PTQ 2014 Q3

SPECIAL FEATURES
INSTRUMENTATION & CONTROL

ROTATING EQUIPMENT
REFINING
GAS PROCESSING
PETROCHEMICALS
PETROLEUM TECHNOLOGY QUARTERLY
ptq
Q3 2014
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2014. The entire content of this publication is protected by copyright full details of which are available from the publishers. All rights
reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means electronic,
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The opinions and views expressed by the authors in this publication are not necessarily those of the editor or publisher and while every care
has been taken in the preparation of all material included in Petroleum Technology Quarterly and its supplements the publisher cannot be held
responsible for any statements, opinions or views or for any inaccuracies.
3 Gas makes the rules
Chris Cunningham

5 ptq&a

17 Tail gas catalyst performance: part 1
Michael Huffmaster Consultant
Fernando Maldonado Criterion Catalysts

31 Selective control for a total reux column
Niyazi Bozkurt Tpra Kirikkale Renery
37 Quality control in biofuels production
Berthold Otzisk Kurita Europe
41 Revamping advanced process control
Stefano Lodolo Aspen Technology
Oleg Vedernikov Isab
49 Design developments for construction projects
Simon Bennett AVEVA Solutions
55 Overcoming corrosion in heat exchangers
Dragon Hao Sandvik Materials Technology
63 Meeting production targets for ultra low sulphur transportation fuels
Bob Leliveld Albemarle
69 Improving a compressor protection regime
Ben Austin Prognost Systems Inc.
72 Avoiding compressor system downtime
Amit Saxena Dresser-Rand
75 Meeting tighter NOx emissions rules
Stephen Harrison, Naresh Suchak and Frank Fitch Linde Gases
81 Cloud point and hydrotreating relationships
Brian Watkins and Meredith Lansdown ART
89 Failure analysis of burner piping
Hyunjin Yoon SK Innovation
97 Microbiological causes of corrosion
Jaya Rawat, Neha Sharma and Apoorve Khandelwal
Bharat Petroleum Corporate R&D Center
105 Albertas crude oil reserves
Mike Priaro Consultant
115 Technology in Action
Suncors Commerce City, Colorado renery where an upgrade has enabled a wider range of oil sands products to be
processed. Photo: Suncor
Q3 (Jul, Aug, Sept) 2014
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T
he European Union has arguably
been the global leader in biodiesel
production and use, with overall
biodiesel production increasing from 1.9
million tonnes in 2004 to nearly 10.3 million
tonnes in 2007. Biodiesel production in the
US has also increased dramatically in the
past few years from 2 million gallons in
2000 to approximately 450 million gallons
in 2007. According to the National Biodiesel
Board, 171 companies own biodiesel
manufacturing plants and are actively
marketing biodiesel.1. The global biodiesel
market is estimated to reach 37 billion
gallons by 2016, with an average annual
growth rate of 42%. Europe will continue to
be the major biodiesel market for the next
decade, followed closely by the US market.
Although high energy prices,
increasing global demand, drought
and other factors are the primary
drivers for higher food prices, food
competitive feedstocks have long
been and will continue to be a major
concern for the development of biofu-
els. To compete, the industry has
responded by developing methods to
increase process effciency, utilise or
upgrade by-products and operate
with lower quality lipids as
feedstocks.
Feedstocks
Biodiesel refers to a diesel-equivalent
fuel consisting of short-chain alkyl
(methyl or ethyl) esters, made by the
transesterifcation of triglycerides,
commonly known as vegetable oils or
animal fats. The most common form
uses methanol, the cheapest alcohol
available, to produce methyl esters.
The molecules in biodiesel are pri-
marily fatty acid methyl esters
(FAME), usually created by trans-
esterifcation between fats and metha-
nol. Currently, biodiesel is produced
from various vegetable and plant oils.
First-generation food-based feedstocks
are straight vegetable oils such as
soybean oil and animal fats such as
tallow, lard, yellow grease, chicken fat
and the by-products of the production
of Omega-3 fatty acids from fsh oil.
Soybean oil and rapeseeds oil are the
common source for biodiesel produc-
tion in the US and Europe in quanti-
ties that can produce enough biodie-
sel to be used in a commercial market
with currently applicable
PTQ Q3 2014 3
Editor
Chris Cunningham
editor@petroleumtechnology.com
Production Editor
Rachel Storry
production@petroleumtechnology.com
Graphics Editor
Rob Fris
graphics@petroleumtechnology.com
Editorial
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Business Development Director
Paul Mason
sales@petroleumtechnology.com

Advertising Sales
Bob Aldridge
sales@petroleumtechnology.com
Advertising Sales Ofce
tel +44 844 5888 771
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Publisher
Nic Allen
publisher@petroleumtechnology.com
Circulation
Jacki Watts
circulation@petroleumtechnology.com
Crambeth Allen Publishing Ltd
Hopesay, Craven Arms SY7 8HD, UK
tel +44 844 5888 776
fax +44 844 5888 667

PTQ (Petroleum Technology Quarterly) (ISSN
No: 1632-363X, USPS No: 014-781) is published
quarterly plus annual Catalysis edition by Crambeth
Allen Publishing Ltd and is distributed in the US
by SP/Asendia, 17B South Middlesex Avenue,
Monroe NJ 08831. Periodicals postage paid at New
Brunswick, NJ. Postmaster: send address changes to
PTQ (Petroleum Technology Quarterly), 17B South
Middlesex Avenue, Monroe NJ 08831.
Back numbers available from the Publisher
at $30 per copy inc postage.
Vol 19 No 4
Q3 (Jul, Aug, Sept) 2014
Gas makes the rules
T
he west Asian Gulf region has established a clear economic lead in the
petrochemicals industry, with the rest trailing in its wake but the US
promising some stiff competition in the near future.
The key to the shape of the industry is cheap gas. Provided natural gas can
be produced and delivered at a suffciently low price, naphtha cracking can-
not hope to compete with ethane cracking as the basis of a proftable petro-
chemicals business. The rules of oil trading, with its transglobal shipments
and benchmarks, determine the price of ethylene from naphtha cracking. Gas
costs whatever it costs on a regional basis.
The best current illustration of this is China, where plans by Sinopec and
PetroChina to build new ethylene plants are being shelved by the day. The
PRCs relative economic downturn is partly to blame, but principally the out-
put of its naphtha crackers is unable to compete with cheaper supplies of
imported ethylene. China is working overtime to generate supplies of gas
and not only for its petrochemicals business. But successful development of
Chinese gas supplies, both conventional and from shale measures, would
still leave the nation at a disadvantage, taking into account the costs of pro-
duction and of infrastructure to connect sources, principally in western
China, to centres of production in the east.
Compare and contrast with the IGCC states where conventional and
well-developed gas felds including Qatars North Field are, relatively speak-
ing, within arms reach. More so, associated gas from the regions oil felds
has a minimal production cost in the raw state and an extensive, inter-state
network of pipelines for delivery. If there is a problem for the regions petro-
chemicals business it is that gas is too cheap. In light of burgeoning demand
from fast-growing populations for other applications, producers will expect
better incentives in other words, higher prices to step up their rates of
output. Setting appropriate prices without punishing a hugely important
industry is a balancing act under way in the UAE at present. It seems
unlikely, however, that the outcome will weigh too heavily in favour of the
gas companies.
So what about that much-touted shale revolution in the US? How will that
impact the Middle Eastern petrochemicals business? Contrary to the hype,
shale gas is not the giveaway that many believe it to be. Fracking is an
expensive activity and the ability of shale gas producers to undercut conven-
tional market prices is regionalised in the US. The chief perceived advantage
to Americans of the shale revolution both gas and oil is the security of
supply afforded by a new wealth of supply. But shale gas can be relatively
cheap; this has led to a rash of new ethane crackers in the US, under con-
struction and planned, with an eye to eastern export markets. Several of
these projects have backing from east Asian sources for just that reason.
Within the next two years, with Middle Eastern pricing issues settled and
American ethylene on tap, the shape of global competition for petrochemi-
cals supply should be clearer.
CHRIS CUNNINGHAM
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Activity, pressure drop, cost... According to Karl Krueger, Criterion research scientist, these among
other factors are critical considerations when selecting a tail gas catalyst. He should know. He and
his colleagues have helped reners all over the world realize lower operating costs and extended
cycle lengths through Criterions range of advanced tail-gas treating catalysts: C-234, C-534 and
C-734. These uniquely different catalysts account for 80% of the worlds installed capacity, proving
the rule that selection success comes from eliminating all but the best.
Theres nothing traditional
about this work. This is real R & D.
Meet Karl Krueger:
Research Scientist. Tail-gas Catalyst Expert.
Leading minds. Advanced technologies.
www.CRITERIONCatalysts.com
criterion.indd 1 05/06/2014 18:56
Q
Using lighter feeds with a higher parafnic content gives
us problems with cold ow properties in our middle distillates.
Will a dewaxing catalyst help with this?
A
Bob Leliveld, Global Director for Applications Technology,
Clean Fuels Technology, Albemarle Corporation, bob.leliveld@
albemarle.com
Long chain normal paraffns have a negative effect on
the cold fow properties of middle distillates. A dewax-
ing catalyst can improve cold fow properties by
selectively converting these paraffns into branched
paraffns or by breaking the longer chains into smaller
fragments. Selection of the optimal dewaxing catalyst
is dependent on the desired degree of cloud point
reduction and the unit conditions and confguration.
For a signifcant reduction in cloud point, a two-stage
process is typically applied which is capable of operat-
ing in both winter and summer mode. For mild
dewaxing applications, the dewaxing catalyst can be
included as a functional layer in the loading scheme of
the ULSD unit. However, when cracking long chain
paraffns, the naphtha make can potentially be a
restriction, depending on the capability of the down-
stream confguration to handle naphtha. There are
various dewaxing catalysts available that can be oper-
ated in sour conditions, while others are more suited
to sweet operations.
A
Sunil Nair, Finished Fuel Additive Director, Dorf Ketal
Chemicals, sunilnair@dorfketal.com
We understand that you want to use dewaxing catalyst
in the hydrotreater reactor, to improve the cold fow
properties. Globally, there are two methods to improve
the cold fow properties:
Using dewaxing catalyst
Using cold fow improver additives.
Usage of cold fow improver additives can help
refners in reducing the cold flter plugging point
(CFPP) and pour point (PP) of middle distillates.
Usage of these additives is cost effective and requires
minimal capex. We suggest that the typical middle
distillate blend is tested on a variety of additives to
screen the most effective additive to meet fnished
middle distillate specifcations.
Q
We have problems with precipitation in the desalter
arising from blends including opportunity crudes. How do we
deal with this?
A
Andrea Fina, Process Technological Unit, Chimec, ana@
chimec.it
Processing heavy crude oils, for example some oppor-
tunity crudes, blended with other crudes, can lead to
desalter upsets. These upsets are commonly caused by
asphaltenes focculation and subsequent precipitation.
The asphaltenes are actually submicroscopic solids at
room temperature dispersed in the oil by the resins.
This asphaltene-resin dispersion is dissolved into
petroleum by aromatics, which are solvents, but
opposed by saturates, which are non-solvents. Thus,
asphaltenes are held in petroleum in a delicate balance
and this balance can be easily upset by adding satu-
rates (such as paraffnic crude oils). Because the
blending of heavy oils with lighter oils can greatly
change the overall concentrations of these molecular
types, it can upset this balance and lead to asphaltenes
precipitation.
The blend induced asphaltene instability has mainly
three negative effects:
Precipitated asphaltenes may cause solids to deposit
within the desalting vessel, thus the oil and water resi-
dence times decrease over the unit run length and the
desalting and dehydration effciency get worse
Agglomerated asphaltenes increase emulsion stabil-
ity inside the desalting vessel
Agglomerated asphaltenes can trap salts, thus avoid-
ing their removal during desalting operation.
There are several strategies to mitigate or avoid
asphaltene precipitation in the desalting system:
1. Blend the crudes in the correct proportion and order
for compatibility. The ratio (saturates + asphaltenes)/
(aromatics + resins) (%wt/%wt), calculated through
S.A.R.A (Saturates, Aromatics, Resins and Asphaltenes)
analysis, gives good indication of the stability of
asphaltenes in the oil matrix:
A ratio lower than 0.7 usually indicates a stable
blend
A ratio from 0.7 to 0.9 indicates an uncertain stability
A ratio higher than 0.9 indicates an unstable blend.
Also, the blending order of two crudes in a tank can
play an important role for asphaltene stability. For
instance, even if the fnal (saturates + asphaltenes)/
(aromatics + resins) ratio is lower than 0.7, during the
blending procedure asphaltenes precipitation may
occur. This phenomenon arises when, for instance, a
heavy crude oil is transferred to/into the tank contain-
ing a paraffnic crude oil. As a result, although the
crudes are blended in the correct proportion for
compatibility, this type of blending order can lead to
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Q&A copy 15.indd 1 09/06/2014 12:12
local asphaltenes precipitation during the mixing of
the two crudes.
2. Add an asphaltenes inhibitor to the crude storage
tank. The asphaltene inhibitor, such as the Chimec
asphaltene inhibitor, acts as an artifcial resin; it
prevents aggregation by shifting the onset of the
asphaltenes focculation point and in this way it
increases the stability of the asphaltene in the blend.
3. Inject an asphaltene dispersant/inhibitor into the
CDU feed. The dispersing and inhibiting action of the
antifouling technology, for instance Chimec antifou-
lant, towards the asphaltenes prevents their
precipitation in the desalting vessel.
A
Marcello Ferrara, President, ITW, mferrara@itw
technologies.com
One of the most common refnery problems is
asphaltenes precipitation in the desalter due to insta-
bility of crude oil blends. Asphaltene instability can
also promote sludge accumulation in the crude storage
tanks and cause accelerated fouling phenomena in the
preheat exchangers, along with a number of additional
problems. Asphaltenes are also well known to stabilise
water-in-oil emulsions. For some crude oil blends,
asphaltene destabilisation can cause emulsion build-up
with subsequent water carry-over and oil carry-under
problems.
Sludge build-up in the desalter can cause sludge
carry-over into the hot preheat train, thereby becoming
an additional source of fouling.
In certain Western Canadian Sedimentary Basin
(WCSB) crudes, the instability is enhanced by the addi-
tion of paraffnic diluent to meet crude oil pipeline
specifcations.
ITW can help in solving the above problems by using
patented asphaltene stabilisers in the crude blend.
Additionally, when sludge accumulates in the
desalter, ITW Online Cleaning can be used to remove
precipitated sludge in as little as 24 hours on an oil-to-
oil basis, without the need to open the vessel and
allow manpower to manually clean it.
A
Parag Shah, Renery Technical Head, Dorf Ketal Chemicals,
paragshah@dorfketal.com
Precipitation in a desalter may be due to the presence of
flterable solids, asphaltenes and/or calcium naphthen-
ate. If the precipitation is caused by flterable solids,
solutions include good tankage preparation, providing
suffcient settling time and use of good desalting aids.
Dorf Ketal has proprietary desalting aids to manage
crude solid content in excess of 1500 ppm. Precipitation
by asphaltenes basically arises due to incompatibility
caused in the crude blending process. This can be over-
come by understanding the compatibility of the crude
to be blended using oil compatibility studies. Dorf Ketal
has the capability to conduct compatibility studies for
more than 200 crudes. If a refner is processing high
calcium crude, the precipitation problem may be due to
scaling arising out of the poor solubility of calcium
salts. Dorf Ketals novel calcium removal approach
includes acid based and a near neutral product
(non-acid based) calcium removal additive (CRA) to
tackle the calcium naphthenate problems.
Q
Are there limits to processing resid in the FCC imposed
by metals content in the feed? Is there an additive to ease the
problem?
A
Bilge Yilmaz, Global Technology Manager, BASF FCC
Catalyst Division, bilge.yilmaz@basf.com
Resid feeds typically contain contaminant metals
including nickel, vanadium, iron, and others. These
metals catalyse a variety of unwanted secondary reac-
tions. Being an especially active dehydrogenation
catalyst, Ni presents a considerable challenge to refn-
ers as it signifcantly increases H
2
and coke yields. In
addition to taking part in unwanted dehydrogenation
reactions, V comes with other major concerns as it is
highly mobile under FCC conditions and its interac-
tion with the zeolite destroys its framework structure,
which manifests itself as increased H
2
and coke yields,
as well as lower zeolite surface area retention. Even
small amounts of contaminant metals in the feed
deposit cumulatively on the catalyst and can result in
high H
2
and coke make during FCC operation, which
is a major concern for the refning industry. Even small
increases in the yields of these relative to the yield of
gasoline or other valuable products can cause signif-
cant practical problems. Development of FCC catalysts
that can withstand the accumulation of contaminant
metals and can help mitigate the negative conse-
quences is of high industrial signifcance.
Several successful strategies have been adopted to
decrease the deleterious effects of Ni within the FCC
unit, including the introduction of antimony, which
forms an inactive alloy with Ni. This strategy is
usually controlled by the refner at the FCC unit and is
adjusted as needed. Incorporation of reactive trapping
materials is a strategy adopted by catalyst manufactur-
ers to address the problem within the catalyst particle
itself. For example, certain specialty aluminas can be
included in the catalyst particle for trapping contami-
nant metals. Mobility of vanadium allows other
possibilities for its passivation, such as the use of sepa-
rate particle V-traps. There are also other novel metal
passivation technologies developed as a result of the
intense research efforts on this feld. All in all, it can be
concluded that with the right catalyst even severe
residual feedstocks can be proftably processed.
A
Carel Pouwels, Global FCC Specialist, Resid, Albemarle
Corporation, Carel.Pouwels@Albemarle.com and Ryan Nickell,
Global FCC Specialist, Additives, Albemarle Corporation, Ryan.
Nickell@Albemarle.com
Metals have a detrimental effect on catalyst perfor-
mance in the FCC unit. The metals most commonly
referred to are nickel and vanadium, while also
sodium, iron and calcium negatively infuence FCC
operations and performance. Vanadium and sodium
are known to increase deactivation of the catalyst
(particularly zeolite) and lower catalyst activity. Nickel,
and also vanadium, on the other hand catalyse dehy-

6 PTQ Q3 2014 www.eptq.com
Q&A copy 15.indd 2 09/06/2014 12:12

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cbi.indd 1 06/06/2014 12:30
1. Contaminant metals levels
2. Amount of high boiling point feed components
3. Unit constraints (wet gas compressor, air blower and
slurry limits).
Deactivation of a catalyst by contaminant metals will
typically occur from zeolite destruction or destruction
of the pore structure of the exterior particle surface.
Furthermore, these contaminant metals can increase
hydrogen, dry gas and coke yields limiting conversion
potential.
A
Vivek Srinivasan, Senior Engineer, Technical Services, Dorf
Ketal Chemicals, viveks@dorfketal.com
There are often concerns of RFCC catalyst deactivation
due to the presence of metals in residue resulting in
substantial costs on fresh catalyst. There are no defned
limits for metal content and these limits are typically
given by a catalyst provider, depending on the catalyst
used in the system. Key metals that are present in the
residue are calcium, sodium, iron, magnesium, nickel
and vanadium. One can reduce the calcium, sodium
and magnesium content by incorporating a desalter
upstream of the RFCC reactor. In addition to desalting,
use of metal removal additives give enhanced metal
removal effciencies. Dorf Ketal has a range of propri-
etary metal removal aids which help in reducing the
metal content including iron (up to 30%). Nickel gener-
ally increases the dehydrogenation reaction resulting in
increased hydrogen production in the off-gas and
reduced valuable products. Nickel passivator additives
are available to reduce the activity of nickel and
improve proftability. Similarly vanadium passivators
are also available that can reduce similar ill effects of
vanadium.
Q
What are the principal issues to address in blending and
storage when high TAN crudes are included?
A
technologies.com
A high total acid number (TAN) crude has the following
properties: high acid value, fewer light components,
high density and viscosity, high asphaltene content,
high salts and heavy metals content, which give rise to
equipment corrosion and severe operating problems.
The main issues for blending and storage a high
TAN crude are in general: blending high TAN with
low TAN crude, primarily the desired product mix,
compatibility between the crudes, and the level of
contaminants in the crudes and their asphaltenic
contents. Blending is also used to reduce the naph-
thenic acid content of the feed and to reduce the
corrosion rate. Blending two different feedstocks may
lead to incompatibility of the heavy crude constituents
(asphaltene) in the more paraffnic light crude oil; for
this reason there are many models claimed to predict
incompatibility.
High asphaltene content, together with incompatibil-
ity, will lead to sludge precipitation in the storage
tanks. ITW can help in solving the problem by using
drogenation reactions and consequently increase
hydrogen yield and coke to some extent. Finally, iron
and calcium can build up on the catalyst surface and
when present in higher amounts form nodules and
block active sites and pores, thereby reducing conver-
sion and increasing slurry yields, and also negatively
infuencing fow behaviour. The effect and magnitude
of each metal is different and depends on the FCC unit
where it occurs. Although Albemarle catalysts have
proven to be effective with highly contaminated feed-
stocks, encountering nickel concentrations in excess of
20 000 ppm and iron content greater than 1 wt%, the
unit limitations, process conditions and economics also
determine the absolute metals limit for a specifc unit.
Regarding additive usage, the answer is again a
mixed bag. The best known and proven additive solu-
tion is the use of antimony to reduce the detrimental
effects of nickel. The effect of antimony depends on the
base catalyst that is used. An example is Coral SMR,
which has exceptional nickel passivation (trapping)
power with its ADM-60 matrix. Antimony, when used
in conjunction with ADM-60, has less of an effect. The
above mentioned record of more than 20 000 ppm was
achieved with Coral SMR and without the use of Sb.
Regarding vanadium and sodium, the most effective
metal traps are highly active matrices such as ADM-20,
which are built into our resid catalysts such as our
Upgrader, Upgrader R+ and AFX series. While these
matrices are predominantly applied for bottoms
conversion, their vanadium tolerance is a welcome
secondary beneft. Some suppliers promote separate
additives to trap vanadium and other elements, but we
have not detected any beneft in a commercial FCC
unit. Albemarle executes continual R&D on metal trap
additives and fnds great benefts only in laboratory
testing; thus, refners that make their catalyst selection
by laboratory testing are the principal users of such
metal traps. This often adds costs to the catalyst, with
minimal or no performance effects. Furthermore, these
are often not even the best catalysts for the unit.
Finally we can address the use of additives for iron
and calcium. The use of additives is typically not neces-
sary when the catalyst is already designed for
feedstocks with high amounts of these metals.
Albemarle catalysts feature high accessibility, which
allows a high amount of iron and calcium to build up
before it has any detrimental effect. Catalysts like
Upgrader and AFX have proven to function perfectly
well under those conditions. However, if a refner is
using a catalyst with a high zeolite-to-matrix ratio,
which often has low accessibility, the effect of iron and
calcium is strong. In such cases an additive with high
accessibility and high matrix activity, such as BCMT has
proven to be a strong remedy. The use of such additive
is the most effective solution for a quick recovery of the
poor bottoms conversion of the poisoned host catalyst.
A
Stuart Kipnis, Marketing Manager, Grace Catalysts, Stuart.
Kipnis@Grace.com
Processing of resid feeds requires an appropriate cata-
lyst which will be infuenced by a number of factors:
Q&A copy 15.indd 3 09/06/2014 12:12
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patented asphaltene stabilisers in the crude blend.
Additionally, when sludge accumulates in the tanks,
patented ITW Online Cleaning can be used to remove
precipitated sludge, without the need for opening the
tank and manually cleaning it. This will avoid or
dramatically reduce downtime and concerns related to
conventional tank cleaning techniques.
The sludge is transformed into a fully reusable prod-
uct and the recovered sludge can be reprocessed
without any concern.
A
Vivek Srinivasan, Senior Engineer, Technical Services, Dorf
Ketal Chemicals, viveks@dorfketal.com
Assuming that the general practice of blending is
followed (no incompatibility issues), high TAN crudes
do not have any issues in blending and storage. The
constraint faced in blending high TAN crude is the
precision required to achieve the desired TAN values
of the overall blend.
Q
We use delayed coking for diesel make at present. Is there
a process option for raising conversion levels, and with what
sort of payback time?
A
Avishek Sengupta, Senior Engineer, Technical Services,
Dorf Ketal Chemicals, avisheks@dorfketal.com
Liquid yield in a delayed coker is mainly driven by
operational parameters like temperature, pressure, recy-
cle rate and the nature of the feedstock. With feedstock
constraints and limited process operating handling,
further improvement in the liquid yield is a big chal-
lenge. However, with advancement in technology, Dorf
Ketal has introduced a proprietary additive range under
the CokerMax brand which helps to improve the liquid
yield by greater than 1%. Based on internal studies and
commercial experience, the CokerMax range does not
affect coke morphology and most of the liquid yield
gain happens in the middle distillate products.
Q
What type of compressor design would you say is the
most reliable with least loss of gas for hydrogen supply to a
hydrocracker or HDS unit?
A
Paul Peyer, Marketing Communications Manager,
Hoerbiger Ventilwerke, paul.peyer@hoerbiger.com
Reciprocating compressors are often the best, most reli-
able and most economic solution for compression of
hydrogen to supply a hydrocracker or HDS unit. They
are fexible, energy effcient and suitable for high pres-
sure applications.
In the past, reciprocating compressors were often
considered unreliable with diffculties in achieving
precise control of their output capacity, and electric
power was wasted because the compressor capacity was
typically controlled by recycle valves (often referred to
as bypass or spillback valves). With todays advanced
control systems (for example, reverse fow control), this
energy waste is a thing of the past and high fexibility in
the variation of gas supply can be achieved.
The same applies for leakages. In the old days, one
of the main leakages in reciprocating compressors was
over the main pressure packing, but with todays tech-
nology (new packing ring design, and so on) leakages
could be reduced to a minimum and in the best case
zeroed out.
Q
The CO
2
content of our sour water stripper gases results
in a high reagent turnover in the caustic scrubber. Solutions
please.
A
technologies.com
Reagent turnover depends basically on stoichiometry
and scrubber effciency. While stoichiometry is related
to gas composition only, operational scrubber eff-
ciency is affected by fouling. Fouling of caustic
scrubbers is quite common, as the composition of
treated gases normally contains unsaturated
compounds. ITW can help to solve the fouling prob-
lems of caustic scrubbers by implementing Online
Cleaning and cleaning the equipment in as little as 24
hours on a process-out/process-in basis.
Q
The exchangers cooling output from our visbreaker have
particular problems with fouling. Can we resolve this upstream
or through exchanger design?
A
Eva Andersson, Market Manager Renery, Alfa Laval, evae.
andersson@alfalaval.com
Fouling mitigation of visbroken residue heat exchangers
Visbroken residue fouling
Visbroken residue is one of the most fouling fuids
among refnery processes. Even with a properly
designed quench, some thermal cracking will still
continue when the fuid enters the heat exchangers
and the resulting cracking products have a special
affnity for metal surfaces, something that is even
further aggravated due to precipitation of asphaltenes.
With high effciency cooling and short exchanger
residence time, the above two fouling parameters can
be minimised but still not completely avoided.
In order to further reduce or even eliminate fouling
problems, high and uniform heat transfer channel
velocity is required and dead zones with low or no
fow must be avoided as much as possible.
Such heat exchanger design is impossible to achieve
in traditional shell-and-tube heat exchangers, where
several long, bulky exchangers are required to carry
out the heat recovery service (visbroken residue versus
feed, crude preheating or even steam generation).
Maldistribution in heat transfer channels is a common
problem and dead areas are present in turning cham-
bers or behind baffes.
Due to this, refneries operating this heat recovery
service with traditional shell-and-tube heat exchangers
all suffer from heavy fouling problems, and run
lengths of those exchangers in between cleaning are
normally short, maybe just a few months.
Q&A copy 15.indd 4 09/06/2014 12:12
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Untitled-1 1 11/03/2014 14:40
such procedure is very easily carried out by means of
HP water-jet, as both heat transfer channels are fully
accessible once the bolted end covers are removed.
Experience with spiral heat exchangers in visbroken service
The frst SHEs operating in visbroken residue/feed
interchanging service were commissioned in 2001 in
order to solve a very high fouling situation in a
European refnery.
Cleaning of the visbroken/tube side of the hot end
shell-and-tube heat exchangers, out of the total 12
exchangers installed for this service, was required
every month and the procedure took almost 30 days,
including drilling of tubes.
The additional fring of the furnace meant the
process cycle length was only around 12 months in
between plant shutdown and decoking of the furnace.
After the shell-and-tube heat exchangers were
replaced by eight SHEs, no cleaning of exchangers was
required in between plant shutdowns and the cycle
length was increased to 18-24 months.
HP water-jet cleaning is only required of the hot end
visbroken residue channel and total time for cleaning
of the exchangers is only fve days.
In addition, SHEs are designed for better heat recov-
ery than the original shell-and-tube heat exchangers so,
when in operation, the energy effciency of the plant is
further improved.
The pay-back time for replacing the original shell-
and-tube heat exchangers was around two years, based
on higher plant availability, reduced process energy
consumption and fewer maintenance and replacement
costs.
Based on the performance of SHEs in this plant and
service, today there are almost 50 units operating in
visbroken residue service in nine different plants
around the world. In total, there are more than 200
SHEs operating in various high fouling refnery
services.
A
Marco Roncato, Process Technological Unit, Chimec,
mroncato@chimec.it
Running visbreaking plants at the maximum possible
severity unavoidably leads to fouling formation: the
more severe the reaction is, the more prone the system
to fouling becomes.
The cause of fouling in process equipment is partly
organic (polymerisation products, destabilisation of
asphaltenes and coke) and partly inorganic (sediment
deposits, sand, corrosion products, salts and sulphide
compounds).
Asphaltene fouling is caused by their destabilisation
in the hydrocarbon matrix and it depends on:
Reduction in resin content
Reduction in the H/C ratio
Agglomeration of asphaltenic micelles.
These being the root causes of fouling, to improve
HEX performance (or, generally speaking, the plants
performance) while running the plant at the maximum
severity, we suggest adopting the following measures:
1. Improvement of the desalters effciency: the lower
Negative aspects of heat exchanger fouling
Cleaning of the visbroken residue heat exchangers can
be a very time-consuming effort. Most of the time,
those exchangers must be fushed with diesel (or simi-
lar hydrocarbon fraction), steam purged and then the
tube bundle must be removed for HP cleaning and
sometimes even drilling. It is not uncommon to have
the exchangers out of service for 10-20 days and some-
times high grade material is needed to make sure the
tube bundles can withstand the severe handling.
Frequent cleaning of those exchangers does not only
lead to high maintenance and replacement cost, but
might also affect the operational cost of the process if
the energy recovered is used to preheat the feed.
With a high fouling rate, giving rise to low heat
transfer effciency, or when having exchangers out of
service for cleaning, the feed inlet temperature to the
furnace is reduced, and more fuel is needed to preheat
the feed to required temperature before the cracking.
This might lead to too high heat fux in the furnace,
something that will shorten the run length of the plant,
as furnace decoking will be required more frequently.
In the worst case scenario, if the furnace capacity is
limited, throughput might even have to be reduced.
So, fouling in visbroken residue heat exchangers for
sure is a very costly problem!
Use of spiral heat exchangers
Many refners have already recognised the anti-fouling
properties of spiral heat exchangers (SHEs) in high
fouling services, such as desalter effuent/feed inter-
changing, (R)FCC main fractionator slurry/feed
interchanging or cooling and of course visbroken resi-
due/feed interchanging.
The spiral channel of the exchanger gives around
three times higher heat transfer effciency than tradi-
tional shell-and-tube heat exchangers, meaning that the
cooling of the residue is quicker and the thermal crack-
ing will stop faster. In addition, due to its fully
counter-current fow, fewer heat exchangers and a
shorter heat transfer channel are required, hence the
hold-up time in the exchangers is minimised.
However, the most important anti-fouling feature of
the SHE is its single channel fow design. There is only
one heat transfer channel for the hot fuid and only
one heat transfer channel for the cold fuid. It means
there is no possibility for maldistribution of fow in the
heat exchangers, the channel velocity is easily
controlled and a certain self-cleaning effect is
achieved. If particles start to settle in the heat transfer
channel, the cross-section in that area is reduced and
the local velocity increased until the particles are
scrubbed away.
The connections, inlets and outlets of those two heat
transfer channels are also designed to avoid dead
zones where fouling could partly or fully plug the heat
transfer channels.
Combined together, all these features give a heat
exchanger with very low or almost eliminated fouling
tendency.
Should fouling still occur and cleaning is needed,
Q&A copy 15.indd 5 09/06/2014 12:12
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burckhardt.indd 1 06/06/2014 15:48
and 2) Can we effectively maximise propylene for both
feeds. Whether we can run both types of feed in the
same process set-up can in general be answered posi-
tively. But unit limitations such as regenerator
temperature or wet gas compressor can determine how
much of each of the feeds can be processed. The total
fresh feed rate can be different or, in the case of
constant fresh feed rate, the blend ratio of either feeds
with VGO can be different. The difference in both
feeds in terms of metals content, hydrogen content,
Conradson carbon and other properties will determine
the crackability and slurry yield on one hand or the
tendency of coke make (such as feed coke or metals
coke) on the other hand. Consequently the yield struc-
ture in both cases will be different. The more refractive
feed will typically lead to lower conversion, more
slurry and more coke. The question now is if propyl-
ene yield can be maximised effectively in both cases.
The typical answer in FCC is It depends. In principle
the propylene yield can be maximised for both cases.
But again unit limitations determine how far the C
3=

yield can be pushed. The case of hydrotreated resid for
instance is expected to lead to higher conversion with
the potential to higher propylene yields. But if the gas
section is strongly limited, the refner can not take the
full beneft and needs to suppress LPG production and
thus C
3=
Important for both feed cases is the choice of the
optimal catalyst. The optimal catalysts for both cases
are not expected to be the same. Your catalyst supplier
can help you further to work out both cases and deter-
mine which is the optimal catalyst design for each
feed. Albemarle has a wealth of experience in process-
ing resid as well as in maximum propylene
applications. For the typical max C
3=
applications of
10 wt% and more, AFX has proven to be very success-
ful in a wide range of feedstocks, including but not
limited to both 100% untreated AR cases 1 as well as
treated resid 2. In the case of lower propylene yields,
Albemarle recommends several resid catalysts ranging
from most coke selective to best bottom conversion:
Coral SMR, Upgrader R+ and Upgrader and which
will be combined with Durazoom for the generation of
the desired level of propylene.
What all these products have in common is the prop-
erty of high or highest accessibility. This physical
property is not only of high importance for resid
processing and leading to the lowest slurry yields, but
is also key for propylene maximisation as it minimises
the unwanted hydrogen transfer reaction. With the
application of this high accessibility, Albemarle has
maximised C
3=
yields, within unit limitations, of FCC
units processing hydrotreated VGO, hydrotreated resi-
due and straight-run residue.
References
1 Amano T, Wilcox J, Pouwels A C, Matsuura T, Process and catalysis
factors to maximise propylene output, PTQ Q3 2012, 17-27.
2 Pouwels A C, Lifting the propylene plateau, Hydrocarbon Engineering,
Jan 2012, 23-29.
the BS&W and the lower the caustic injection in the
desalted crude are, the lower the role of foulings inor-
ganic component in reducing HEX performance will be
2. Close management of the cracking reaction, in order
to avoid fouling peaks: Chimec has developed a
computerised instrument, the Chimec Analyzer, which
allows one to analyse the quantity and quality of the
coke particles in the residue and feed in an optical
way.
The Chimec Value analysis takes only a few minutes
and gives the residue stability value.
The unit reaction severity can be optimised rapidly
according to the Chimec Value analysis and allows a
secure and optimal management of the visbreaking
3. Injection of a suitable chemical in the main fraction-
ator bottom line in front of the exchangers: to face the
above described very complex phenomenon, it is
necessary to use a multifunctional product, providing
different kinds of protection:
Stabilizer for reactive olefns being formed during
the cracking reaction
Dispersing agent for asphaltenes (potential coke
precursors) and inorganics.
During the last three decades Chimec has developed
a specifc line of tailor-made products aimed at manag-
ing and controlling the above mentioned reactions.
A
Parag Shah, Renery Technical Head, Dorf Ketal Chemicals,
paragshah@dorfketal.com
The problem with fouling in the cooling exchangers is
very common in visbreakers across the globe. One
option to control fouling is by increasing the velocity.
Another option is the use of antifoulants which not only
extends the run length but also helps sustain the
conversion since the furnace inlet temperature is main-
tained close to the start of run range with effective
fouling control. Dorf Ketals new generation antifoulants
help in enhancing the visbreaker units proftability.
A
Marcello Ferrara, President, ITW, mferrara@
itwtechnologies.com
ITW Online Cleaning can clean the equipment in as
little as 24 hours on an oil-to-oil basis without extract-
ing the bundles. Additionally, the fractionator lines and
flters will all beneft from Online Cleaning.
By applying ITW Online Cleaning, there is no need
to redesign the exchangers or to revamp the unit (as
far as fouling is concerned) because its regular applica-
tion will allow a run under clean conditions. This is a
mind shift versus the normal run to death mode of
running a unit.
Q
Can we effectively maximise propylene from the FCC with
either hydrotreated resid or straight run resid using the same
process set-up?
A
Carel Pouwels, Global FCC Specialist, carel.pouwels@
albemarle.com
This question can be split up into two questions: 1)
Can we use the same process set-up in an FCC unit
with either hydrotreated resid or straight-run resid;
Q&A copy 15.indd 6 09/06/2014 12:12
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Tail gas catalyst performance: part 1
T
he tail gas unit (TGU) process
has been developed to remove
sulphur compounds from
Claus tail gas in order to comply
with stringent emission regulations.
From the early 1970s to today,
TGUs have been improved to meet
higher levels of performance for
ever tighter environmental require-
ments and to reduce capital or
operating cost. Reactor performance
is a critical parameter in achieving a
TGUs environmental performance.
Conversion of sulphur species to
H
2
S is a function of catalyst activity,
reactor space velocity and tempera-
ture. Assessment of the impact of
these principal variables on both
catalyst bed design and perfor-
mance is the subject of this article
which is presented in two parts. In
the frst part, an introduction to the
ClausTGU sulphur recovery
complex provides a framework for
examining the impact of operating
and design parameters, process
development history, equipment
line-up evolution, catalyst develop-
ments, and reactor chemistry. The
frst part also provides an introduc-
tion to reactor modelling, describes
the reactor pilot plant system, and
examines chemical equilibria which
affect TGU performance. The
second part develops reactor model-
ling and examines the effects of
space velocity and temperature.
Reducing sulphur emissions
TGUs are built for a specifc
purpose increasing the overall
sulphur recovery of the Claus-TGU
sulphur recovery complex to about
99.9% from about 96% achieved on
a Claus plant alone (see Figure 1).
Their sole purpose and economic
The rst part of a two-part account of time and temperature effects on tail gas
catalyst performance provides a background to reaction modelling and pilot studies
MICHAEL HUFFMASTER Consultant
FERNANDO MALDONADO Criterion Catalysts
justifcation is reducing sulphur
emissions, which improves overall
environmental quality. In the
reductive tail gas process addressed
herein, achieving good performance
requires high conversion of sulphur
compounds to H
2
S in the reactor.
Achieving good performance there-
fore requires setting reactor
operating conditions based upon
understanding the infuence of key
operating variables affecting the
catalyst bed.
The key parameters affecting
performance of the catalyst bed are
catalyst kinetic properties, tempera-
ture, and tail gas loading/space
velocity:
A catalysts kinetic properties are
determined by its manufacture,
activation and aging
Temperature affects catalytic
activity and thermodynamic equi-
librium, limiting conversion
Reactor loading directly impacts
space velocity, which controls
conversion.
Tail gas reactor loading and
temperature effects are represented
in frst order reaction mechanics
and thermodynamic equilibrium.
These relationships provide a good
model for understanding the infu-
ence of these operating variables
and show higher gas loading
results in lower conversion. Data
from catalyst testing in Criterions
pilot unit are presented to illustrate
these kinetic effects.
Application and interpretation of
information for assessment of reac-
tor performance and catalyst
activity will be discussed,
including:
Temperature profle observed in
the reactor bed
Changes in conversion, indicated
by increased incinerator emissions
(SO
2
and CO)
Activity evaluation from reactor
inlet and outlet stream composition
and determination of aging,
usually by unit testing and analyti-
cal evaluation results
Measuring physical properties
and/or activity testing for actual
catalyst sample.
This article is intended to help
TGU operators and designers
improve environmental perfor-
mance by understanding these
effects and applying principles to
designs or improving performance
of existing units.
Acid
gas
Claus unit
94-98%
recovery
Tail gas unit
99.8%+
recovery
Thermal
incinerator
H
2
S
COS
SO
2
H
2
S
Recycle H
2
S Trace SO
2
Molten sulphur
Figure 1 Sulphur recovery complex
criterion.indd 1 11/06/2014 10:51
2% to 6%, polluted the environment
as SO
2
.
Reductive tail gas processes
Several types of TGUs were devel-
oped to further mitigate the
pollution released into the environ-
ment by Claus units. The best
performing TGUs utilise a cobalt
molybdenum (CoMo) on alumina
catalyst. These processes, when
properly operated, convert nearly
all of the sulphur species to
H
2
S. The H
2
S is then captured in
an amine circuit and recycled to
the Claus unit. Overall, this
achieves a recovery of 99.9% or
more of the sulphur fed to the
Claus unit, achieving the environ-
mental performance required of
virtually all regulatory settings.
Less than 0.1% of the sulphur in
the Claus feed is released into the
environment.
Principal reactions in the tail gas
reactor are hydrogenation and
hydrolysis of sulphur species (SO
2
,
COS, CS
2
, S
x
) and water gas shift
for CO. Catalysts with high activity
and good selectivity are needed to
accomplish these reactions at
reasonable space velocities and at
moderate temperatures.
The majority of the sulphur
compounds in Claus tail gas are
converted to hydrogen sulphide,
but not completely. Most reactions
are equilibrium limited, causing
several sulphur compounds to
survive at the ppm level. The most
critical is COS because equilibrium
limitations are the most signifcant
for COS, as well as kinetics.
These limit ultimate outlet concen-
tration by equilibrium as well
as limitations for the kinetic reac-
tion function, which result in
conversion around 80-90%. This
means typical residual COS is in
the 10-40 ppm range. The residual
COS is not removed by amine in
the absorber. In some instances,
combinations of high CS
2
feed
concentrations and lower tempera-
ture TGU operation produce
mercaptan compounds. The resid-
ual COS and mercaptan
compounds, in combination with
the H
2
S slip from the removal step
in the absorber, dictate overall
sulphur recovery performance.
The Claus process
The Claus process is the most
signifcant gas desulphurising
process, recovering elemental
sulphur from gaseous hydrogen
sulphide. The multi-step Claus
process recovers sulphur from the
gaseous hydrogen sulphide found
in raw natural gas and from the
by-product gases containing hydro-
gen sulphide derived from refning
crude oil and other industrial
processes. The Claus process
utilised in a sulphur recovery unit
(SRU) recovers 94-98% of the
sulphur in the feed. Used in
conjunction with a reductive tail
gas process, the Claus process
further increases the recovery
achieved in the sulphur recovery
complex to 99.9%.
In the Claus process, a concen-
trated stream of H
2
S is partially
burned to form SO
2
. The SO
2
reacts,
frst thermally and then in subse-
quent steps, catalytically, with H
2
S
to form elemental sulphur. The
produced sulphur is transported as
a melt or as a solid.
H
2
S + 3/2 O
2
SO
2
+ H
2
O + Heat
2H
2
S + SO
2
3S + 2H
2
O + Heat
These reactions to form sulphur
are in equilibrium; therefore,
conversion to sulphur is increased
by condensing the product sulphur
from each stage, reheating the
mixture and taking subsequent
steps to lower reaction tempera-
tures. Higher temperatures limit
sulphur recovery by shifting the
equilibrium towards the reactants.
Increased pressure in the Claus
process requires higher reaction
temperatures in the second and
third stages to maintain margin
above the capillary condensation
temperature of elemental sulphur.
The increased temperatures also
then limit sulphur recovery via this
process.
When the Claus effuent gases
exit the fnal condenser, the major-
ity of the incoming H
2
S gas stream
has been recovered as elemental
sulphur and only residual amounts
of unreacted sulphur dioxide and
hydrogen sulphide and uncon-
densed elemental sulphur remain.
The gas exiting the Claus unit also
contains large volumes of water
vapour, a co-product of H
2
S conver-
sion; hydrogen from H
2
S cracking
and sub-stoichiometric combustion;
and large volumes of nitrogen, if
air is used in the combustion of the
hydrogen sulphide. Additionally,
carbon compounds that enter the
process or form through combus-
tion (CO, CO
2
, hydrocarbons) react
with sulphur species in the reaction
furnace to form carbonyl sulphide
(COS) and carbon disulphide
(CS
2
) some of which remain
unconverted.
The COS and CS
2
in tail gas result
from the quality of acid gas feed to
the Claus unit and are converted in
the frst Claus reactor. In this reac-
tor, it is possible to utilise alumina
catalyst, which can have fairly
rapidly aging or more robust titania
catalyst. Conditions of temperature,
residence time and concentration
infuences how much of these
compounds reach the TGU and, in
concert with environmental perfor-
mance criteria, the degree of
conversion required.
The concentration of these
compounds is governed by
complex equilibrium. This mixture
of dilute sulphur and carbon
compounds in the steam and nitro-
gen stream is labelled as tail gas.
The sulphur species included in the
tail gas comprise 2-6% of the total
sulphur entering the Claus process.
Initially, Claus process operators
were allowed to incinerate the tail
gas mixture to sulphur dioxide, a
less odoriferous compound, and
discharge it to the atmosphere.
Under this scenario, the recovered
sulphur comprised only about 94%
to 98% of the sulphur entering the
process. The balance of the sulphur,
The Claus process is
the most signicant
gas desulphurising
process, recovering
elemental sulphur
from gaseous H
2
S
criterion.indd 2 11/06/2014 10:51
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uop modular.indd 1 06/06/2014 12:27
TGU equipment line-up
The reductive tail gas process
preheats tail gas feed to the TGU
reactor, where sulphur compounds
are reduced to H
2
S. A quench step
removes water formed in Claus and
combustion; the gas is cooled to an
acceptable temperature for amine
use. An amine absorption step
removes H
2
S from the process gas,
and the H
2
S is recycled to the
Claus process. The off-gas is
vented or incinerated. The amine
system is selective toward H
2
S, slip-
ping most of the CO
2
. Amine can
be supplied from a dedicated
regenerator or integrated with an
amine stripper servicing several
systems. Generally, units with a
dedicated stripper achieve lower
H
2
S slip and higher overall sulphur
recovery. A simplifed diagram of a
conventional TGU is shown in
Figure 2.
Equipment in a TGU includes:
In-line heater or reducing gas
regenerator (RGG)
Reactor with CoMo catalyst
HRU (optional)
Quench column and water cool-
ing circuit
Recycle (Start-up) blower or
ejector
Booster blower (optional)
Amine absorber/regeneration
circuit.
For a low temperature TGU, an
indirect heater can be utilised, typi-
cally a steam heat exchanger in
place of a fred heater, which is a
major advantage. This line-up offers
simpler, easier operation, lower
operating cost and fewer upsets or
trips. The remaining portion of a
low temperature TGU is mechani-
cally similar to a conventional TGU.
A simplifed diagram of a low
temperature TGU is shown in Figure
3. There are several advantages with
respect to low temperature TGU
operation, including:
Fuel gas
SRU tail
gas
Air
Steam
Steam
Condensate to SWS
Off-gas to
incinerator
Heater
Reactor
Quench
column
Absorber
Stripper
HRU
Recycle gas to
CLAUS SRU
Figure 2 Simplied diagram for a conventional tail gas unit
HP saturated
steam
SRU tail
gas
Steam
Condensate to SWS
Off-gas to
incinerator
Heater
Reactor
Quench
column
Absorber
Stripper
Recycle gas to
CLAUS SRU
Figure 3 Simplied diagram for low temperature tail gas unit
criterion.indd 3 11/06/2014 10:52
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amount of non-H
2
S sulphur atoms
in the tail gas stream, typically 80%,
and they must be converted to H
2
S.
Also, elemental sulphur must be
converted to prevent accumulation
in catalyst pores and inhibiting
catalyst function. These reactions
are so favourable and strongly
driven by the catalyst that the reac-
tions are not considered
equilibrium limited; that is, the
equilibrium residual is in the parts
per billion range. It is critical,
however, that ample reducing gas
be available for these reactions:
SO
2
+ 3 H
2
H
2
S + 2 H
2
O (1)
SO
2
+ 2 H
2
S + 2 H
2
O (2)
S
x
+ x H
2
x H
2
S (3)
Secondly, the most signifcant
reaction is water with carbonyl
sulphide (COS) and carbon disul-
phide (CS
2
) by hydrolysis. Carbon
disulphide is converted to COS
(Equation 5), followed by subse-
quent hydrolysis of COS (Equation
4). For these reactions, the role
of equilibrium is essential because
the presence of CO
2
and H
2
S estab-
lish a limit for the concentration of
COS.
COS + H
2
O H
2
S + CO
2
(4)
CS
2
+ H
2
O H
2
S + COS (5)
Another important reaction is
conversion of CO by water, referred
to as the water gas shift. This reac-
tion also is equilibrium limited:
CO + H
2
O CO
2
+ H
2
(6)
Although the conversion of CO
does not directly impact sulphur
emissions, it is a useful reaction
(WABT) of 570F (300C), although
this has been extended to as low as
450F (230C) RIT and 480F
(250C) WABT with second genera-
tion catalyst improvements. Low
temperature TGU operation is typi-
cally defned as operation at a RIT
less than 430F (220C) and WABT
less than 465F (240C), and there is
the expectation of seeing a RIT as
low as 390F (200C). A low
temperature TGU operation
requires a high activity catalyst.
Tail gas reactor chemistry
The purpose of the TGU catalyst
reactor is to convert as much of the
various sulphur compounds as
possible into H
2
S so that the amine
absorber can recover sulphur
species in the form of H
2
S. The
catalysts utilised promote hydroly-
sis reactions and hydrogenation
reactions as well as a water gas
shift reaction.
The TGU reactor catalyst has two
types of catalytically active sites
hydrolysis sites driven mainly by
basic support like alumina, and
hydrogenation sites and CO reac-
tion sites driven by the presence of
sulphide compounds of transition
metals like cobalt and molybde-
num. The most important
specifcation relevant to the TGU
catalyst reactor design is the
organic sulphur outlet. This total
organic sulphur outlet, a measure
of how much COS and CS
2
is left
unconverted and also how much
CH
3
SH is formed in the TGU reac-
tor, largely impacts sulphur
emissions.
The most important reaction that
occur in the TGU reactor are the
reactions of hydrogen with SO
2
and
elemental sulphur for conversion to
H
2
S by hydrogenation. These two
species constitute the greatest
Lower costs (capital and
operating)
Reduced TGU tail gas volume
Higher reliability and operating
simplicity
Units with indirect heating
require no combustion controls
Elimination of risk of catalyst
damage by RGG misoperation
Longer catalyst life
Lower production of greenhouse
gases.
TGU catalyst
Catalysts for TGU reactors utilise
alumina base with cobalt and
molybdenum sulphides, which
have active sites for hydrolysis,
hydrogenation and water gas shift.
Catalytic activity is a function of a
catalysts kinetic properties, activa-
tion and operating temperature. At
the low end of the temperature
range, equilibrium related to reac-
tion pathways is not a limitation
but catalysts are challenged to have
suffcient activity. At the upper
range of temperature, catalytic
activity is strong but equilibrium
back pressure increases to become
signifcant. These offsetting trends
impact the selection of an appropri-
ate operating point and ultimate
degree of H
2
S conversion that can
be achieved for sulphur species.
Tail gas catalysts have evolved.
First generation catalysts were
re-purposed hydrotreating cata-
lysts. Second generation catalysts
were specifcally developed as high
activity, high porosity, long-life
catalysts. Third generation catalysts
are contemporary, low temperature
catalysts. The activity of catalysts
has improved, allowing operation
at even lower temperatures. Now,
units are designed with low
temperature catalysts without a
burner for pre-heat. Additional
properties to note are mechanical
strength, bulk density, pressure
drop and resistance to aging. The
general design requirement for
acceptable conversion performance
across this development track is
outlined in Table 1.
Conventional TGU operation is
typically defned as operation at a
reactor inlet temperature (RIT)
greater than 520F (270C) and
weighted average bed temperature

RIT WABT aGHSV (1/hr)
First generation catalysts 545F 572 625F 1000-1500
285C 300330C
Second generation 445-535F 480-572F 2000-2500
230-280C 250-300C
Third generation 410-430F 445 to 465F 1500-2000
(low temperature) 210-220C 230-240C
Catalyst development for tail gas units
Table 1
criterion.indd 4 09/06/2014 12:45
is to determine the ability of a cata-
lyst sample to perform:
Conversion of SO
2
and elemental
sulphur to H
2
S, hydrogenation
function
Conversion of COS and CS
2
to
H
2
S and CO
2
, hydrolysis function
Conversion of CO to H
2
, water
gas shift function
Minimisation of formation of
COS (sour shift) or mercaptan
(partial hydrogenation).
Additional applications which the
unit design will accommodate with
little to moderate revision are:
SCOT catalyst degradation and
aging
SCOT catalyst passivation or
regeneration
Incineration catalysts for off-gas
Gas phase hydrogenation (up to
300 psig pressure)
Claus catalyst.
The gas metering section is
equipped with 15 Brooks 5280 mass
fow controllers for each reactor;
these regulate fows and blend
gases to prescribed experimental
conditions. Gases are supplied by
cylinder (H
2
S, SO
2
, COS, CS
2
, RSH,
CO, CO
2
, CH
4
) or from house
systems (air, N
2
, H
2
); inlet pressure
to the unit is 60-100 psig (4-6 barg).
The pressure of the outlet gas is
typically 1 psig (~1.0135 bara),
although back pressure up to 15
psig (~1 barg) can be applied.
Reactor modelling
In order to predict the performance
of TGU reactor systems, a basic
framework of chemical equilibrium,
reaction chemistry and catalyst
activity is used. This, in turn,
provides a tool to evaluate the
effects of space velocity and
temperature on reactor
performance.
The requisites for good reactor
design and operation must be met
to achieve good performance. The
assumption in modelling and
predicting performance is that all
the other things are done correctly.
Process selection and design must
include a good design for reactor
hardware including gas distribu-
tion and catalyst support; ample
catalyst (space velocity) to achieve
conversion required for feed
conditions and environmental
via hydrolysis (Equation 5) also is
more strongly competing against
hydrogenation (Equation 8).
SCOT micro-reactor catalyst testing
system R0111
The SCOT (Shell Claus Offgas
Treater) micro-reactor system is
built for analysis and evaluation of
catalysts used in industrial sulphur
recovery applications like SCOT
units or Claus TGU, which repre-
sent most gas plant and refnery
applications. Typically, these cata-
lysts are cobalt-molybdenum on an
alumina carrier, but may contain
other components. The experimen-
tal rig consists of two reactors sets,
with related supply gas fow
controllers, safety system PLC and
HTE control software. This equip-
ment is located in Shell Technical
Center Houston and operated by
CRI/Criterion staff.
The SCOT micro-reactor system
is a bench scale test unit, and each
reactor system is equipped with the
following: gas metering, mixing
manifold, vaporiser for water,
nitrogen saturator for elemental
sulphur, reactor feed pre-heat, and
a reactor with a four heat zone
furnace followed by a cooler,
sulphur/SO
2
indicator and cold
trap. An analysis section with a gas
chromatograph (GC) plus CO by IR
and SO
2
by UV support both reac-
tor trains. All materials exposed to
process gases are 304L or 316L
stainless steel. The two reactor
trains are parallel, independent
systems set inside a negative pres-
sure, ventilated enclosure.
The testing protocol for this unit
that provides hydrogen needed for
hydrogenation. The signifcant
reduction of CO concentration is
important for what may otherwise
be a regulated emission or require
high temperature incineration for
control. As more jurisdictions
around the world adopt CO emis-
sion specifcations, CO conversion
in the TGU reactor becomes more
important.
These six reactions represent the
general chemistry that occurs in the
TGU reactor. There are other reac-
tions that must be considered when
making performance predictions,
particularly when considering a
low-temperature TGU operation.
First is the reaction of CO with H
2
S,
the sour shift. This reaction plays
an important role for CO and COS
conversion, via inter-conversion of
CO and COS. The reaction is
strongly equilibrium regulated, and
as reactor temperature is lowered,
levels of CO increase due to kinetic
limitation of the water gas shift:
CO + H
2
S COS + H
2
(7)
Secondly, the formation of methyl
mercaptan by hydrogenation of CS
2

is important in low temperature
TGU operation. Methyl mercaptan
is an intermediate product of CS
2
hydrogenation to CH
4
. Between the
two expressions (Equations 8 and
9), the latter reaction of hydrogena-
tion of CH
3
SH to methane
(Equation 9) is assumed to be rate
determining:
CS
2
+ 3 H
2
CH
3
SH + H
2
S (8)
CH
3
SH + H
2
H
2
S + CH
4
(9)
This pathway is in competition
with hydrolysis, which becomes
weak at low temperatures. For
low-temperature TGU operation, it
is generally advised to keep CS
2
feed content to the TGU below 250
ppm. This may be accomplished in
the upstream SRU by a combina-
tion of operational and catalytic
approaches. For conventional TGU
operation, mercaptan formation is
typically of little importance. At
higher temperatures, conversion of
CH
3
SH to methane is a strong func-
tion. In addition, CS
2
conversion
In order to predict
the performance of
TGU reactor systems,
a basic framework of
chemical equilibrium,
reaction chemistry
and catalyst activity
is used
criterion.indd 5 09/06/2014 12:46
j matthey.indd 1 06/06/2014 12:32
Chemical equilibrium reaction
model parameters
The equilibrium point for a chemi-
cal reaction determines the ultimate
extent to which a reaction will
proceed, the point at which the
forward reaction rate equals the
reverse reaction rate. The process
chemical equilibrium constant, Kp,
is an expression of that relation-
ship, the ratio of concentration of
reaction products to concentration
of reaction feeds:
[Products]
Kp = ---------------
[Reactants]
For the water gas shift reaction,
the expression is:
[Products] [H
2
] * [CO
2
]
Kp wgs = --------------- = ----------------
[Reactants] [CO] * [H
2
O]
and for COS hydrolysis:

[H
2
S] * [CO
2
]
Kp cos = ---------------
[COS] * [ H
2
O]
The concentration of individual
components is tied to the equilib-
rium constant; when one
component changes, others adjust
to keep the product/reactant ratio
the Kp constant. When the Kp
is available, the expression can be
solved for the concentration of a
reactant if other component concen-
trations are known. For equimolar
reactions there is no pressure
sensitivity.
The equilibrium expressions can
be arranged to provide the compo-
nent equilibrium concentration
value, that is, back pressure or
minimum value, which can be
reached for the component in the
system:

[H
2
] * [CO
2
]
[CO] equilibrium = --------------------
Kp wgs * [H
2
O]
The process equilibrium constant
relates to the driving force for the
reaction, the difference between the
Gibbs free energies of the products
minus reactants at the reaction
Equilibrium considerations will be
addressed frst, then kinetics.
Conversion is a term of frequent
reference in this article. Conversion
for CO (or COS) is expressed as
disappearance across the reactor
and is adjusted for the equilibrium
back pressure of the reacting
component:
CO
out
CO
equilibrium
Conversion = 1 - ----------------------
CO
in
CO
equilibrium
Tail gas reactor temperature
operation has historically ranged
between 200C and 325C. This fts
within the region of active catalyst
functions and meets the required
minimum temperature for catalytic
activity function, about 200C for
low temperature catalyst and
240-300C for conventional tail gas
catalysts. The maximum tempera-
ture is generally limited to 345C
(650F) to avoid sulphide corrosion
of process equipment and acceler-
ated decline in catalyst activity and
surface area by hydrothermal
aging.
The process operates near atmos-
pheric pressure, and most of these
reactions are equimolar. Therefore,
pressure has no-to-small infuence
on equilibrium.
requirements; and quality catalyst
selected, with suitable activity for
intended operating conditions. The
catalyst must be properly loaded,
activated with appropriate proce-
dures, and damaging conditions
avoided. It is critical to have
adequate reducing gas (provided
from Claus, RGG or supplemental
hydrogen) to avoid SO
2
break-
through and severe process
consequences (low quench pH,
sulphur formation in quench water,
amine degradation). With good gas
distribution across the catalyst bed,
acceptable pressure drop for the
process line-up and inlet concentra-
tions within the design boundary,
one can move forward to the
impact of gas rate and time and
temperature on performance.
The infuence of temperature on
performance has competing effects
in kinetics and equilibrium, impact-
ing conversion. The kinetics for
reactions of importance are favour-
ably infuenced by higher
temperature, proceeding to higher
conversion at a given space veloc-
ity. Equilibrium effects from higher
temperature usually result in
higher equilibrium concentrations
for the species, which the system is
designed to destroy, limiting lower
value for outlet concentration.
Temp,C Temp, F COS hydro COS sgs CO wgs
200 392 4697 0.050 236
220 428 3297 0.047 156
240 464 2378 0.045 107
260 500 1757 0.043 75.5
280 536 1326 0.041 54.7
300 572 1020 0.040 40.6
320 608 898 0.039 30.8
Process equilibrium constants, Kp
Table 2
Temperature 390F 480F 570F
(200C) (250C) (300C)

Reaction
SO
2
+ 3 H
2
-> H
2
S + 2 H
2
O 3 E19 3 E17 1 E15
S + H
2
-> H
2
S 4.4 E4 2.1 E 4 1 E4
CS
2
+ H
2
O -> H
2
S + COS 6 E5 2 E5 5 E4
2 H
2
S + SO
2
-> 3/8 S
8
+ 2 H
2
O (Claus) 3 E5 4 E4 5 E3
Equilibrium constants, Kp for non-equilibrium limited reactions
Table 3
criterion.indd 6 09/06/2014 12:46
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biflinger.indd 1 04/03/2014 10:57
water gas shift; intermediate values
can be interpolated.
Note: Kp values for COS hydrol-
ysis derived from JANAF/NIST/
DIPPR are about factor two higher
than historical values of Kp of
Terres and Wesemann, as published
in Kohl and Riesenfeld, and Kp
values for sour gas shift from
NIST/DIPPR are about factor 2
lower. Water gas shift Kp values
are within 5% for the various
sources.
For reference, Table 3 provides
Kp with respect to other, non-
equilibrium limited reactions:
SO
2
equilibrium is very strongly
favoured at TGU reactor operating
conditions, with SO
2
equilibrium at
1E-11 ppm for 300C and 1E-17
ppm for 250C; residual SO
2
is
negligible in either case
Elemental sulphur hydrogenation
is also strongly favoured, although
kinetically limited
CS
2
equilibrium is also strongly
favoured by hydrolysis (forming
H
2
S and COS), making equilibrium
back pressure below 1E-6 ppm for
typical outlet conditions
Claus is favoured, especially at
lower temperatures, and can help
convert SO
2
. At higher temperature
TGU conditions, only a small frac-
tion of SO
2
will react via Claus
before equilibrium limits are
reached.
Equilibrium concentration values
for various components in the reac-
tor outlet are shown in Table 4
under conditions representative of
TGU feeds and outlet conditions.
The COS equilibrium chart (see
Figure 4) shows the concentration of
COS in ppm (wet basis) in equilib-
rium with a tail gas outlet
composition; total carbon refers to
CO plus CO
2
and COS, and
assumes they are in equilibrium. As
total carbon increases, CO
2
increases, and so does COS since
this is hydrolysis.
The CO equilibrium chart (see
Figure 5) shows the concentration of
CO in ppm (wet basis) in equilib-
rium with a tail gas outlet
composition; total carbon refers to
CO plus CO
2
and COS, and
assumes they are in equilibrium. As
total carbon increases, CO
2
increases
and so does CO because this is the
modynamic values for free energies
and Gibbs energies of formation,
entropies and heat capacities of the
components. Higher temperatures
are less favourable as Kp for
(exothermic) reactions decreases.
Table 2 provides Kp values for COS
hydrolysis and sour shift and CO
temperature. The Kp is given by
the Nernst equation (or Gibbs
relationship):

GT = -RT ln Kp
Published data, from JANAF,
NIST and DIPPR, are used for ther-
6
10
9
8
7
5
4
3
2
1

C
O
S

w
e
t
,

p
p
m
0
200 220 240 260 280 300 320 340
Temperature, C
10% carbon
20% carbon
5% carbon
Figure 4 COS equilibrium hydrolysis 34% H
2
O, 1% H
2
S
750
1250
1000
500
250
C
O

w
e
t
,

p
p
m
0
200 220 240 260 280 300 320 340
Temperature, C
10% carbon
20% carbon
20% carbon, 4% H
2
5% carbon
Figure 5 CO Concentration at equilibrium water gas shift 34% H
2
O, 2% H
2
Component Feed 200C 250C 300C
H
2
2.0000 1.7976 1.7937 1.7864
CO
2
7.0000 8.0475 8.0425 8.0360
H
2
S 0.8000 1.2749 1.2748 1.2746
CO 1.0000 0.0024 0.0063 0.0132
COS 0.0250 0.0001 0.0002 0.0004
SO
2
0.4000 0.0000 0.0000 0.0000 LT ppb
CH
3
SH 0.0000 0.0000 0.0000 0.0000 Kinetically limited
CS
2
0.0250 0.0000 0.0000 0.0000 LT ppb
CH
4
0.0000 0.0000 0.0000 0.0000 Kinetically limited
H
2
O 26.0000 25.7275 25.7315 25.7386
N
2
62.7500 63.1500 63.1510 63.1508
Equilibrium values, mole percent
Table 4
criterion.indd 7 10/06/2014 12:33
Fernando Maldonado is the Business
Development Manager Gas Treating Catalysts
for Criterion Catalysts and Technologies,
located in Houston. He has global responsibility
for Criterions gas treating catalyst business.
Prior to joining Criterion Catalysts &
Technologies in 2001, he held positions as a
process design engineer, unit contact engineer,
and an operations superintendent in two US
Gulf Coast reneries. He holds a bachelor of
science degree in chemical engineering from
Texas A&M University.
Email: Fernando.Maldonado@CRI-Criterion.com
Michael A Huffmaster is a process expert
and consultant to industry for gas processing
and treating, rening operation, CO
2
capture,
and related research. His activities regarding
sulphur recovery include amine treating,
Claus, tail gas treating, and tail gas treating
catalyst development, design and operation.
He retired from Shell Oil in 2005 with 36 years
of experience. He holds a bachelor of science
degree in chemical engineering from Georgia
Institute of Technology and is a registered
professional engineer in Texas.
Email: michael.huffmaster@att.net
water gas shift. As noted, hydrogen
is held constant.
If the entire mixture is at equilib-
rium, then COS would be the same
as if for COS hydrolysis or sour
shift. However, outlet mixtures are
not at equilibrium because of space
velocity (limited catalyst inven-
tory). Typically, CO is two or three
times equilibrium even with very
high conversion because inlet
concentrations are fairly high. This
means that the sour shift, for
instance, would express a higher
COS equilibrium value than would
the hydrolysis pathway. As the
expression says, as goes CO, so
goes COS. Figure 6 shows COS for
various concentrations of CO.

Part two
The second part of this article
develops reactor modelling with
a kinetic reaction model, the
effects of temperature and space
velocity, catalyst activation,
catalyst deactivation, and determin-
ing TGU catalyst health from a
commercial unit temperature
profle example.
30
50
60
40
20
10
C
O
S

w
e
t
,

p
p
m
0
200 220 240 260 280 300 320 340
Temperature, C
500 ppm CO
1000 ppm CO
2000 ppm CO
250 ppm CO
Figure 6 COS equilibrium sour gas shift 1% H
2
O, 2% H
2
dust obtained after the second and
third fltration stages is sold to the
paper industry, so the process
delivers zero waste. The roaster
and its fltration system are the
subject of patents.
The hydrometallurgy process
The calcine that was produced
during the roasting process is
treated by hydrometallurgy in three
steps: frst calcine is leached to
produce a slurry containing tung-
sten and molybdenum, depending
on the composition of the catalysts
and their contaminants (which are
mainly phosphorus and arsenic). In
a step using decantation and fltra-
tion, a solid concentrate containing
alumina and silica, along with
oxides of nickel, is produced. This
material is reserved for the pyro-
metallurgical process.
The soluble fraction of the slurry
is purifed to remove phosphorus
and arsenic. These contaminants
are not recycled and are disposed
of as hazardous waste; they repre-
sent less than 1% of the starting
material. Tungsten and molybde-
num are present in the purifed
solution which is mixed with
reagents to precipitate calcium
tungstate or a mixture of calcium
molybdate and tungstate. The yield
of tungsten recovered in one shot is
more than 85%. These metallic
concentrates are calcined and sold
to steelmakers, more particularly to
companies looking for tungsten
units, for example the EuroW
company which produces tungsten
carbide and cemented carbides, or
Erasteel which produces steel and
tungsten alloys. The hydrometallur-
gical process is protected by a
patent.
The pyrometallurgy process
The leaching residues are melted at
a high temperature in a submerged
electrode arc furnace. Nickel alloys
are obtained from this operation;
they are sold to steelmakers while
the silico-aluminate slag produced
is used in roadworks, while dust
produced from the melting stage is
recycled.
Conclusion
The development of a recycling
process for NiW spent catalysts by
Eurecat, LElectrolyse and Valdi
was subsidised by the European
Union and was awarded Best of
the Best project status in 2009.
After several step developments in
the process, in 2013 Valdi success-
fully treated more than 800 tonnes
of spent NiW catalysts. New invest-
ments made in 2011 (a new roaster)
and 2013 (hydrometallurgy capac-
ity) enabled the company to reach
3000 tonnes capacity. With its pyro-
metallurgical and hydrometallurgi-
cal process, the company is able to
recycle a large range of spent mate-
rials, including NiW, NiMo,
NiCoMo and CoMo catalysts.
Jean-Pierre Dufour is the Technical and
Industrial Director of Valdi. He holds a PhD in
metallurgy and has worked for 20 years in the
metallurgical industries.
Sophie Comte is the Laboratory Manager with
Valdi. She started with the company seven
years ago as R&D project manager and holds a
PhD in environmental chemistry.

ww.eptq.com PTQ Q1 2014 145
responses that a high-fdelity model
with a non-complementary control
layer imported from the operating
plant. Use the high-fdelity control
emulation, but be tolerant of the
process model and accept that
some controller tuning is likely to
be benefcial.
OTSs will continue to become
more accurate, but this will not be
achieved through software devel-
opments alone. The more detailed
the simulation, the more data and
understanding that it holds, and,
consequently, the more engineering
effort required. As with any engi-
neering activity, the time and effort
should be assessed against the
value. The best OTS will not be the
best choice for everyone.
Martin Sneesby is an independent dynamic
simulation consultant with more than 20
years of experience in process simulation and
modelling, including many operator training
simulators and detailed engineering studies.
Email: martin.sneesby@apess.co.uk
system is complementary to a plant
or simulation. A low-fdelity
process model with a complemen-
tary (well tuned) control layer
might provide better overall
often need adjustment to work well
with even the most accurate simu-
lation models. Failure to allow for
controller tuning on the simulator
system may be detrimental to the
overall projects success.
Prognostications
High-fdelity process simulation
models are already very accurate, if
built well with the right data and
good engineering assumptions, and
offer a lot of value, particularly for
OTSs. However, not everything can
be modelled perfectly. Modelling
tools and principles can still be
improved. There is still room for
further development to reduce the
granularity of models (such as
smaller volumes, smaller time-
steps, more detailed unit operation
models), although there are dimin-
ishing returns.
The increase in fdelity of DCS
emulation that is achieved by using
real hardware and control confg-
urations is laudable, but it should
be remembered that a control
Green-eld projects share many of the
same characteristics as OTS projects
built for existing plants, but they tend
to be less technically challenging
and more schedule driven. This is
because there is not the same wealth
of detailed knowledge about the
operating plant and assumptions and
estimates become more acceptable.
Data are usually more readily available
and reasonableness will be judged by
less stringent criteria. The project team
generally recognises that value is more
closely linked to the delivery date
(to maximise training time) than it is
to accuracy. Indeed, the incremental
benet of a high-delity OTS for
training is small much can be
achieved with relatively simple, stable
and robust models.
WWW.ZWICK-ARMATUREN.DE
HIGH STANDARD VALVES
FOR NON-STANDARD CONDITIONS.
cat valdi.indd 3 12/03/2014 12:07
criterion.indd 8 09/06/2014 12:54
C M Y CM MY CY CMY K
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rentech.indd 1 05/06/2014 19:43
Selective control for a total reux column
A
selective approach for a total
refux de-ethaniser column is
introduced in this article. The
applied algorithm proposed here is
based on advanced process control
(APC) techniques and implemented
in the amine treating unit of a
de-ethaniser column at Turkish
Petroleum Refneries Kirikkale
refnery. The objective of the
method is to establish appropriate
priorities for controlled variables.
Before implementation, there was
no operational relationship between
refux fow and top temperature.
Following successful implementa-
tion of the application, the refux
fow controller is cascaded to the
top temperature if the refux drum
level is within the secure operating
range. Because this application has
a successful outcome, an algorithm
such as this can be applied to any
total refux column.
The main objective of the de-etha-
niser column is to achieve the best
quality in LPG production. The
de-ethaniser column at Kirikkale
refnery has a total of 30 trays, 10 in
the rectifcation region and 20 in
the exhaust region. The most
important disturbance that occurs
in the column is the feed fow
which is taken from the 11th tray.
Another problem for the column is
the reboiler steam pressure which
was changing too much and too
often. Because of the varying
reboiler steam pressure, the bottom
temperature could not be stabilised
easily. The bottom temperature
affects all operations inside the
column. Another important feature
of the de-ethaniser column at
Kirikkale is that it is a total refux
type.
Operating problems with a de-ethaniser column led to the development of a new
strategy for an advanced process control system
NIYAZI BOZKURT
Tpra Kirikkale Renery
In this work, the control strategy
of the column is improved by
considering in particular the total
refux properties. Selective control
is applied to the top of the column.
In addition, column operation has
become more stable as the bottom
temperature has become stable for
normal operations.
Operation and control of a
de-ethaniser column
The de-ethaniser separates the
overhead stream from the stabiliser
into a C
2
stream, usually used for
fuel gas, and an LPG C
3
/C
4
stream
which is sent to the de-propaniser.
The control scheme is shown in
Figure 1.

Bottom of the column
In the bottom of the column, there
is a fow controller valve for adjust-
ing the amount of reboiler steam.
This fow controller is cascaded to
the columns bottom temperature
controller. Furthermore, the bottom
product temperature is monitored
with the help of a temperature
indicator.
Feed from
debutaniser
To fuel gas
Propane
Butane
Reboil heat
Reflux flow
Column pressure
(target)
O/H accumulator
temp. (minimise)
O/H temperature
Bot. temp.
Pressure
Measured disturbance
C
2
content of
propane
L
CE
F
T
T
P
F
F
Figure 1 Control scheme for a total reux de-ethaniser column
tupras.indd 1 09/06/2014 13:03
Feed to the column
The feed to the column is from the debutaniser and
other units. The feed is taken into the column from the
11th tray by means of a fow controller. The most impor-
tant source of disturbance for the column is the feed.
Top of the column
Refux drum pressure is controlled with a pressure
controller. This pressure value is so important that the
columns operation is overly affected even by small
pressure changes. This is a total refux column. If the
amount of feed is not high enough, there could be
almost no refux inside the column at certain times. The
amount of refux is controlled with a fow controller
valve which is cascaded to the refux drum level control-
ler (LC). The top temperature of the column is not
controlled with a control valve; there is just a tempera-
ture indicator. In short, for our de-ethaniser column, the
top temperature is free and refux fow is controlled
with a refux drum level controller. The main work in
this study is focused on this fact for the purposes of
developing the selective control algorithm.
Separation Index
Reboiler duty or steam fow sets the separation index in
the column by affecting the vapour and
liquid rate. These features set the column traffc and
sharpness of separation.
Effective cut point
This feature is most affected by the mass balance of the
column. The main role of the effective cut point is
concerned with refux drum pressure. As the drum
pressure decreases, the gas product contains more heavy
ends and gas fow increases.
Proposed approach
In this section, the progress of the application is
explained in detail. Furthermore, alternative and recom-
mended approaches which could be implemented in
similar processes are introduced.
Base layer enhancement studies
Here, the control elements of the column are revised to
fx the main operating problems. The problems are
solved and appropriate values for the control parame-
ters (Proportional: P, Integral: I, Derivative: D) are
decided. In addition, the control loops are reviewed,
taking into account the higher resulting effciency of the
column.
Data collection
The data for this application was collected almost one
month before its implementation.
The control element data were collected carefully;
these control elements include the bottom temperature,
As the drum pressure decreases,
the gas product contains more
heavy ends and gas ow increases
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Control_86x270_2014.indd 1 06/03/14 11:36
tupras.indd 2 09/06/2014 13:03
refux fow, top temperature and
refux drum pressure. Quality
values were taken from laboratory
results. These quality results are C
2

at the top and N-C
5
at the bottom
of the column.
Control structure parameters
Manipulated variables
Bottom temperature controller
This control valve affects almost
every operation inside the column
and is required to be stable at all
times. The bottom temperature
controller is in cascade with the
reboiler duty which affects the
separation index in the column.
Reux drum pressure controller
This control valve is particularly
important for the effective cut point
of the column. The product quality
of the column is directly related to
the pressure controller on the refux
drum.
Reux ow controller
The de-ethaniser column is of the
total refux type, so the amount of
refux is crucial to the columns
operation. The refux fow control-
ler is cascaded to the refux drum
level controller in the original
confguration.
Controlled variables
Pressure compensated bottom
temperature
Bottom product quality (C
5
in LPG)
can be estimated and controlled by
the bottom temperature. The
compensating pressure, the only
pressure value in the column, is the
refux drum pressure. The formula
used for this value is the following:
3000 / (3000/ ([Bottom Temperature] +
273.15) - ln(24.5 / ([Reux Drum Pressure])))
- 273.15 (1)
Pressure compensated top temperature
Top product quality (C
2
in gases)
can be estimated and controlled by
the top temperature. The compen-
sating pressure is the refux drum
pressure and the formula used for
this value is the following:
3000 / (3000 / ([Top_Temperature] + 273.15)
- ln(24.5 / ([Reux_Drum_Pressure] + 1))) -
273.15 (2)
Reux drum level
Refux fow is cascaded to the
refux drum level and operation in
the column is affected by the refux
drum level. Furthermore, refux
fow is an important parameter
with regard to the column top
temperature.
Algorithms and alternatives
For a control algorithm, the
controlled variables represent qual-
ity. They are the most important
values in a column. For the de-eth-
aniser column, the proposed
algorithm is based on the expected
controlled variables.
In partial refux columns, refux
fow is cascaded according to top
temperature. Additionally, a fow
controller is positioned at the exit
of the refux drum and this fow
controller is cascaded to the refux
drum level controller.
Previously, the algorithm applied
to the control terminology in the
column was based on refux fow
cascaded to the refux drum level.
There was no connection between
refux fow and top temperature.
This is because of the properties of
total refux.
The main goal for the algorithm
is to build a logical relationship
between refux fow and pressure
compensated top temperature. The
cascaded algorithm between refux
fow and refux drum level is main-
tained during the algorithms
application. In other words, refux
fow will be cascaded either to the
refux drum level or pressure
compensated top temperature.
There will be selectivity between
the refux drum level controller and
the top temperature with respect to
operational conditions. The most
crucial point of this application is
that there will be a wider operating
range for the refux level. If the
refux level is within range, the
refux fow will be controlled by the
top temperature. If the refux level
goes out of the operating range, the
refux fow will be cascaded to the
refux level controller and the main
goal will be to take the level inside
the operating range.
There are two alternatives for
applying the algorithm.
Distributed control system
oriented approach
The operating range for a refux
drum controller is set on the
distributed control system (DCS)
with the help of a software algo-
rithm which could be as follows:
{If (A < Operation Level < B),
then
reux ow will be cascaded to compensated
top temperature indicator
else
reux ow will be cascaded to reux drum
level controller.}
The main disadvantage of this
application occurs when the operat-
ing conditions change or an upset
occurs. At those times, the user will
need to make changes in the engi-
neering computer which may lead
to hazardous results.
Advanced process control
based approach
In Kirikkale refnery, the applica-
tion is achieved by advanced
process control (APC). The main
objective is the operating level stay-
ing within range. For an APC
application, the Priority is set as
follows:
Reux Drum Level Controller Priority >
Compensated Top Temperature
In this application, the refux
drum level controller will operate
in a wider range. Its priority will be
higher than that of the compen-
sated top temperature. In other
words, the refux drum level will
be more important if the refux
drum level controller is not within
the operating range; the compen-
The main goal for the
algorithm is to build
a logical relationship
between reux
ow and pressure
compensated top
temperature
tupras.indd 3 09/06/2014 13:03
Conclusion
In this article, selective control for a
total reux de-ethaniser column is
described. The reux ow controller
selects either the reux drum level
controller or the top temperature as
the master value for control cascade.
The main criterion of such an appli-
cation is to keep the reux drum
level controller within the required
operational range. The algorithm is
APC based and selectivity is
achieved according to the priority
values of the controlled variables.
The reux drum level has a priority
value that is more important than
that of the top temperature. Such an
application can be implemented for
all total reux columns. The main
gain sought from the system is to
have a more stabilised column
process. Furthermore, the company
does not have to purchase any
additional software for such a
control topology.
Thanks to Turkish Petroleum Reneries
engineers and operators, especially the process
control team and crude unit team including
the eld operators.
Further reading
1 Hori E S, Skogestad S, Control structure
selection for the deethanizer column from
Mongstad/Statoil.
2 Amaro C, Requio R, Embiruu M, Dynamic
modeling of a deethanizer column in a natural
gas processing plant, 2011 International
Conference on Modeling, Simulation and
Control, IPCSIT vol. 10 (2011) (2011) IACSIT
Press, Singapore.
3 www.ogj.com/articles/print/volume-100/
issue-12/processing/process-simulator-
effective-in-de-ethanizer-tower-revamp.html
4 Wittgens B, Litto R, Sqrensen E, Skogestad
S, Total reux operation of multivessel batch
distillation, Computers chem. Engng, Vol. 20,
Suppl., S1041-S1046, 1996.
5 Turkish Petroleum Reneries, Kirikkale/
Turkey, Experiences.
Niyazi Bozkurt is Instrumentation and
Control Chief (T) Engineer in the Projects and
Investment Department of Turkish Petroleum
Reneries Kirikkale renery where he has
applied advanced process control techniques
to many renery units. He holds degrees from
the Electrical and Electronics Engineering
Department of Middle East Technical
University, Ankara.
feature the main quality-affecting
properties, which are bottom and
top temperature value. These
parameters are the most important
for the de-ethaniser column process.
As Figure 2 shows, the system
becomes more stable. The standard
deviations of both the bottom and
top temperature values have
smaller values (see Table 1).
Furthermore, the bottom tempera-
ture controllers set value varies
less after implementation of the
algorithm.
sated top temperature will have no
effect on the reux ow controller.
Stabilising and controlling
the column
There may be some additional
applications for this algorithm. To
begin with, the bottom temperature
can be increased to the maximum
allowed value. In this scenario, the
column trafc increases. At this
point, there could be more C
2
at the
top of the column, which is not ef-
cient. To cope with this, the reux
drum pressure is increased. By
doing so, the gas ow decreases
and stabilisation of the column is
achieved.
Application results
The APC based algorithm applied
to the amine treating unit of a
de-ethaniser column in Tupras
Kirikkale renery achieved the
following results. These results
Parameter Standard deviation Standard deviation
of all data after implementation
Bottom temperature process value 4.7665 2.1168
Top temperature process value 6.8278 5.6657
Bottom temperature set value 1.8405 0.5759
Standard deviation changes
Table 1
80
100
90
80
70
130
140
150
120
110
70
60
50
40
30
T
o
p

t
e
m
p
e
r
a
t
u
r
e
B
o
t
t
o
m

t
e
m
p
e
r
a
t
u
r
e
20
10
2
7
/
1
0
/
2
0
1
3
0
8
:
0
0
8
/
1
1
/
2
0
1
3
0
8
:
0
0
2
0
/
1
1
/
2
0
1
3
0
8
:
0
0
2
/
1
2
/
2
0
1
3
0
8
:
0
0
1
4
/
1
2
/
2
0
1
3
0
8
:
0
0
2
6
/
1
2
/
2
0
1
3
0
8
:
0
0
7
/
1
/
2
0
1
4
0
8
:
0
0
1
9
/
1
/
2
0
1
4
0
8
:
0
0
Figure 2 Bottom and top temperature values after the implementation
The reux drum
level has a priority
value that is more
important than that of
the top temperature
tupras.indd 4 09/06/2014 13:04
Sulzer Chemtech
Legal Notice: The information contained in this publication is believed to be accurate and reliable, but is not to be construed as implying any warranty or guarantee of performance.
Sulzer Chemtech waives any liability and indemnity for effects resulting from its application.
Sulzer Chemtech, USA, Inc.
8505 E. North Belt Drive | Humble, TX 77396
Phone: (281) 604-4100 | Fax: (281) 540-2777
TowerTech.CTUS@sulzer.com
www.sulzer.com
Background
Industrial plants use various types of separators and accumulator
drums in many different processes. When unit capacity is pushed
to the limit, this often affects separator performance. Lower
residence time, higher velocities, or a higher rate of either phase
can cause entrainment or decreased separation efciency.
One example is the separation of hydrocarbons and water from
various renery units like column overhead accumulator drums,
inlet separator drums, and wash drums. Water carryover in the
hydrocarbon phase can cause accelerated corrosion, fouling
inside the tower or heat exchanger, as well as foaming issues.

Discussion
Separation efciency depends on several factors like droplet
size, residence time, the distance the droplet has to travel
from bulk to the interface, and the difference in densities of
the two phases. Droplet size is inuenced by surface and
interfacial tension along with any shear stress or condensation
processes. Higher velocity in inlet piping creates smaller
droplets, which are more difcult to separate. Smaller droplets
magnify the effect of the density differences between phases
and typically require a longer settling length resulting in the
need for a larger vessel. Higher ow rates decrease residence
time, which decreases the separation efciency.
Separator Internals
Separator efciency can be improved by shortening the distance
that a droplet has to travel or by installing a coalescing device
which increases the average droplet size. Mellaplate W
(shown on right) consists of closely spaced parallel coalescing
plates. This design reduces the travel distance for the coalesced
droplets between plates. Because of this, separation can take
place in a shortened vessel, reducing the required vessel size
and capital costs.
Tower Technical Bulletin
Prot From Quick Improvements For Your Horizontal Separators
The Sulzer Renery Applications Group
Sulzer Chemtech has over 150 years of in-house
operating and design experience in process applications.
We understand your process and your economic drivers.
Sulzer has the know-how and the technology to design
internals with reliable, high performance.
Sulzer Mellaplate
TM
W Coalescer
Typical Horizontal Separator Conguration
Advanced Inlet Devices
Inlet and outlet nozzles are critical to performance and must be
selected and designed with care. Undersized nozzles or non-
optimized inlet devices can lead to the formation of small droplets
and/or stable emulsions which are more difcult to separate.
Depending upon the application, feed devices can vary from a
simple perforated pipe to an advanced gas-liquid distributor like
the Shell Schoepentoeter vane inlet device, or if foaming is an
issue, the Sulzer GIRZ
TM
cyclonic foam breaking device.
Revamp Possibilities
Existing vessels can be retrotted with Mellaplate without any
welding to the shell during a turn-around. Sulzer can provide
supports or special expansion rings and also provide the turnkey
installation of internals or modications inside the vessel. This
simple and cost-effective solution can bring large operational
benets.
sulzer.indd 1 09/06/2014 15:53
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wisely.
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cri.indd 1 28/02/2014 10:24
Quality control in biofuels production
F
ossil fuels are not running out
yet, but bottlenecks of these
natural resources are just a
question of time. Biofuels are clean
fuels which do not produce exces-
sive amounts of greenhouse gases.
They are sustainable and can be
produced from crops and organic
matter. The use of suitable addi-
tives can help to meet product
quality requirements with increased
production capacity and improved
workfow.
Renewable fuels
The increasing use of fossil fuels
leads to higher CO
2
emissions into
the atmosphere, resulting in a
greenhouse effect with climate
change and global warming.
Compared to fossil fuels, renewable
fuels from non-fossil sources have
many advantages and are more
eco-friendly. They produce fewer
greenhouse gases (GHG) and are
environmentally sustainable.
Unfortunately, it is also true that
growing plants and processing the
plants into biofuels still consumes a
lot of energy and that biofuels are
not carbon neutral. Biofuels are
not an invention of modern times
and have been around for decades.
Henry Ford had originally designed
his famous Model T to run with
ethanol and, since the 1930s,
biodiesel has been available
worldwide.
Biofuels are produced from
organic matter in a relatively short
period of time (days, weeks,
months). This is a signifcant differ-
ence when they are compared to
fossil fuels, where formation took
millions of years. The frst step in
biofuels production is obtained
Additives such as emulsion breakers and antioxidants can help to improve the
product quality of biofuels and hence their protability
BERTHOLD OTZISK
Kurita Europe
through a process of biological
carbon fxing. Inorganic carbon
(CO
2
) is converted into organic
compounds. The term biofuels
covers a range of products such as
biogas, bioethanol, biobutanol and
biodiesel.
Raw materials for biofuel produc-
tion are biomass from biological
sources such as products of agricul-
ture and forestry, vegetable oils,
sugar, corn, starch, and so on.
Biofuels can be produced by a
number of commercial processes
and serve as components for blend-
ing into petroleum-based fuels.
Worldwide, more and more new
plants are being built to produce
biofuels, using well-established
technologies or new concepts.
Biofuels represented around 4.7%
of energy used in transport in
Europe during 2012. A number of
European policies like the
Renewable Energy Directive (RED)
and the Fuel Quality Directive
(FQD) have been adopted with a
focus on defned greenhouse gas
savings and reduction in fossil
fuels.
Biomass feedstocks
Biomass to liquids (BTL) is a multi-
step process which can be
accomplished by bioprocessing
technologies such as fermentation,
anaerobic digestion and distillation.
These processes require strong
technical knowledge because the
conversion of useful liquid biofuels
and bioproducts is carried out by
microorganisms. There are a
number of effective biological/
chemical technologies available,
which convert any biodegradable
material such as urban wastes and
agricultural residues into useful
chemicals.
Products which can be economi-
cally produced from biomass are:
Primary alcohols (ethanol,
propanol, n-butanol)
Secondary alcohols (isopropanol,
2-butanol, 3-pentanol)
Organic acids (acetic acid, propi-
onic acid, butyric acid)
Ketones (acetone, MEK, DEK).
For decades, Brazil has converted
sugarcane into ethanol. Research
facilities like the BP Biofuels Global
Technology Centre in San Diego,
California, are developing
innovations like sugar-to-diesel
technology. In the past, it was
uneconomical to break the structure
of cellulose to produce cellulosic
ethanol from agricultural residues.
Promising new biological/chemical
technologies like the Sunliquid
process developed by Clariant are
in operation in Germany where
straw is converted into bioethanol.
New concepts with special microor-
ganisms economically break the
structure of cellulose and provide
sugar molecules. The following
fermentation with another type of
microorganism produces bioetha-
nol. Energy-saving absorption
technologies, rather than distilla-
tion, are used after fermentation.
Around 100 kg of bioethanol can be
produced from 450 kg of straw.
About 60% of the 240 million t/y of
straw produced in Europe could be
used for the production of bioetha-
nol, suffcient to cover up to 25% of
total fuel demand up to 2020.
Biofuels can also be produced
through a thermochemical route,
which is a high energy consuming
process. The biomass is gasifed
kurita.indd 1 09/06/2014 13:12
separation of water and remaining
soapstock at ambient temperature
after treatment with Kurita
EB-4113. A temperature increase
above 30-40C improves the ef-
ciency of water separation and
provides pumpable soapstocks.
Although fatty acids can be recov-
ered from the soapstock with
mechanical separation equipment, a
residual amount has to be disposed
of at high cost.
Quality control
The different commercial processes
and technologies require good
quality control to avoid metal
corrosion and fouling. The presence
of water in biofuels reduces the
caloric value, promotes growth of
microorganisms and increases the
potential for corrosion. The fuel
acidity is directly associated with
corrosion and fuel injector
deposition.
The acid number indicates the
quantity of fatty acids in the
sample. The acidity of bioethanol
covers the determination of total
acidity as acetic acid using
the ASTM D1613 method.
Contamination of bioethanol with
chlorides and sulphates can result
in salt precipitation in lters and
fuel injector nozzles. The European
and US standards for bioethanol
(EN 15376, ASTM D4806, ASTM
D5798) describe the minimum qual-
ity requirements, which are:
pH
Water content, %
Acidity as acetic acid, % m/m
Inorganic chloride, mg/L
Inorganic sulphate, mg/L
Copper content, mg/kg.
Biodiesel is readily biodegradable
and highly susceptible to oxidation.
Unrened vegetable oils contain
natural antioxidants like tocophe-
rols. These antioxidants are
partially lost during rening,
resulting in decreased oxidation
stability. Biodiesel contains C
18
components with several double
bonds and with one or two bis-ally-
lic methylene positions. Contact
with air and metal surfaces results
in the formation of hydroperoxides
through a free radical chain mecha-
nism. This leads to decomposition
into aldehydes, ketones, acids and
and converted to syngas, from
which high quality Fischer-Tropsch
(FT) fuels can be made. Proprietary
new technologies with modied
versions of the Fischer-Tropsch
process are available. They
favour the formation of long chain
waxy molecules and reduce gase-
ous byproducts and unwanted
smaller hydrocarbons. A combined
hydroisomerisation and hydroc-
racking step provides the desired,
lighter products.
Algae biofuels
Another interesting technology
which awaits the next big break-
through is the industrial production
of algae biofuels. It is a process
involving algae growth, biomass
extraction and post-processing.
Algae production does not compete
with high value foods and can
yield more fuel than soy or palm
oil. Nutrient rich water is pumped
into a container with specially
chosen algae. Wastewater or brack-
ish water can be used as growing
medium. By means of photosynthe-
sis the algae produce high
quantities of lipids. The lipids can
be converted into biodiesel and
related fuels. Typically, centrifuges
are used to separate the biomass
from solution, which is why algae
biofuels are expensive.
Biodiesel
Biodiesel is made from animal and
vegetable oil feedstocks and can be
used neat or blended with conven-
tional diesel. Biodiesel offers some
advantages as it is biodegradable
with a high ashpoint. Less net CO
2

is produced if vegetable feeds like
sunowers, soya beans, rapeseed or
palm oil are used. In Europe, mainly
rapeseed oil is used; this is extracted
from the seeds of the rape plant
(Brassica napus oleifera). These seeds
have an oil content of 40 to 45%.
Other plants like Jatropha (Jatropha
curcas) show great promise for the
future as they have high oil contents
as well. They can be grown in arid
regions which are otherwise incapa-
ble of being used for agricultural
purposes.
In 2012 worldwide, approxi-
mately 20 million tonnes of
biodiesel were produced. This
covers around 1% of the planets
total yearly fuel consumption.
Production and the market for
biodiesel are both expanding as oil
prices remain high. In general,
biodiesel can be produced by a
number of commercial processes,
including innovative processes for
the removal of glycerin, methanol
and other byproducts.
A commonly applied technology
to produce fatty acid methyl ester
(FAME) biodiesel is the base
catalysed transesterication of
triglycerides. Methanol reacts with
triglycerides in the presence of a
catalyst such as sodium hydroxide
(NaOH). The transesterication
reaction takes place at a tempera-
ture of about 60-70C at
atmospheric pressure. The free fatty
acid (FFA) chain is broken off from
the triglyceride molecule. The
chemical reaction produces FAME
and byproducts such as glycerin
(glycerol) and soaps. The biodiesel
is washed with mildly acidic water,
which removes the neutralised
catalyst, glycerin, soaps and unre-
acted methanol. High soap levels
can result in emulsication of the
soapstocks. To overcome this
hurdle, an emulsion breaker such
as Kurita EB-4113 can be added to
provide a quick separation into oil,
water and remaining fatty acids.
The ushed soapstock phase
contains byproducts such as phos-
phatides, tocopherols, sterols,
waxes, free fatty acids, chlorophyll
and carotene. Figure 1 shows the
Soap-
stock
Water
Figure 1 Soapstock sample after emulsion
breaking
kurita.indd 2 09/06/2014 13:12
high molecular weight insoluble
polymers, nally resulting in clog-
ging of pumps, lters and fuel
lines. In biodiesel, the acid number
indicates the quantity of fatty acids
and mineral acids. Alkali metals
and alkaline earth metals may be
present in biodiesel after esterica-
tion and further treatment. Both
groups of cations can be deter-
mined accurately with ion
chromatography. The European
and US standards for biodiesel (EN
14213, EN 14214, ASTM D6751)
describe the minimum quality
requirements, which are:
Oxidation stability, h
Iodine value, I2/100g
Water content, mg/kg
Acid number, mg KOH/g
Metals, i.e. Na, K, Ca, Mg, mg/kg
Total glycerin, % mass.
The Rancimat test is a widely
accepted method to determine the
oxidation stability of biodiesel.
Puried air is passed through a
heated biodiesel sample (110C)
and subsequently bubbled into a
measuring cell containing deionised
water (see Figure 2). Oxidation
results in the formation of perox-
ides as the primary reaction
products. After the complete
destruction of the fatty acids,
secondary oxidation products are
formed. These secondary oxidation
products are volatile organic acids
(predominantly formic acid). They
are swept into the measuring cell,
increasing the continually moni-
tored conductivity signicantly.
The induction time is the time that
elapses until these secondary reac-
tion products appear in the
measuring cell, increasing the
conductivity. In Europe and Brazil,
freshly produced biodiesel has to
fulll a six-hour Rancimat test
period. This value will decrease
after a while under common stor-
age conditions.
The oxidation stability of
biodiesel can be improved on a
long-term base by the addition of
fuel antioxidants like Kurita
AO-7206 or Kurita AO-7209. These
products are hindered phenol anti-
oxidants, which provide a
cost-effective solution for less stable
fuels. They trap the radicals formed
in the chain reaction. This inhibits
oxidation to corrosive acids and the
formation of insoluble polymers.
The iodine value measures
unsaturation in organic compounds.
The higher the iodine value, the
higher the number of double bonds.
It is another stability indicator, but
not as accurate as the Rancimat test.
Conclusion
It is a question of time before
production of fuels from fossil oil
leads to bottlenecks. Biofuels are
sustainable and can be produced
from crops and organic matter.
There are many natural sources and
innovative technologies available to
produce clean fuels. Liquid biofuels
such as bioethanol, biobutanol or
biodiesel provide a number of
advantages and do not produce
excess amounts of greenhouse gases.
Additives like emulsion breakers or
antioxidants can help to improve
the product quality, which increases
the protability of biofuels.
Literature
1 Gonzalez R G, Rening biofuels, Biofuels
2007.
2 Blume A M, Hearn A K, The evolution of
biodiesel, Biofuels 2007.
3 Steinbach A, Loyall U, Zumbrgel, B Haider
C, Spinnler G, Schlink R, Wille A, Quality control
of biofuels, Biofuels 2008.
Berthold Otzisk is Consulting Engineer in
the technical department of Kurita Europe,
Viersen, Germany, focusing on renery and
petrochemical applications.
Email: otzisk@kurita.de
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Revamping advanced process control
I
sab, an Italian refner controlled
by Lukoil, recently standardised
Aspen Technologys Advanced
Process Control suite across two
different sites in Priolo, Italy. In the
two years Lukoil has been with
Isab, old, low-performing control-
lers have been replaced or
revamped and new controllers have
been built. This rapid execution
was possible thanks to a set of tech-
nologies implemented with close
collaboration between Isab and
AspenTech. These technologies
have signifcantly impacted the
methodology, development, bene-
fts and sustainability of APC
applications.
The new technologies, collectively
called Adaptive Process Control,
are unique and present a number
of advantages that alter the way
that new controllers are developed
and existing controllers are main-
tained. The overall result is that a
new controller can be deployed just
a few weeks after a project begins,
immediately accruing benefts
while the model is simultaneously
improved on-line. Existing control-
ler benefts are consistently
maintained at peak levels, trans-
forming maintenance from a
reactive process, which is often
neglected, to an automated and
proactive process.
An APC Benchmark comparison
tool designed by AspenTech
demonstrates the results achieved
during the two-year programme.
Improved return of investment
The majority of refneries in
Western Europe are struggling to
improve their margins. Aside from
current capital cost investments
A programme to update a reners APC systems employed a novel approach to
the way new controllers are developed and existing controllers are maintained
STEFANO LODOLO Aspen Technology
OLEG VEDERNIKOV Isab
with a medium to long return on
investment (ROI), they are looking
for initiatives that could permit a
quicker ROI and reduced cost
investments.
APC permits a quick ROI based
on small investments, providing a
good opportunity to improve exist-
ing assets proftably.
Isab runs two integrated refner-
ies in Italy with a combined
processing capacity of 300 000 b/d.
When Lukoil took control of Isab, it
began a number of improvement
initiatives with the overall objective
of improving proftability and
competitiveness within the stagnant
market.
Isab has a long history of APC on
its units, previously adopting three
different technologies with varying
results.
One of the main issues in sustain-
ing the benefts of APC over time is
the specialised skillset, through
internal resources or external
consultants, required to maintain
applications. Sustaining the APC
benefts over time is even more
complicated and expensive when
technology is outdated. Several
technology suppliers offer mainte-
nance solutions but they are
manual activities.
Isab started an ambitious, multi-
year APC programme in order to
cover the main units of the refnery,
standardise on one technology, and
adopt innovative APC solutions.
This initiative allowed it to:
Reduce the skills required to
develop and maintain APC
applications
Automate all possible tasks to
relieve the limited workforce
available
Reduce the labour costs of APC
controller maintenance
Minimise erosion of benefts due
to process, quality, market and
other changes that should trigger
some actions on the APC applica-
tions to restore performance
Return controllers to service
faster after turnarounds.
The APC programme at Isab
The APC programme at Isab was
founded on a master services agree-
ment with AspenTech which
included a medium term plan with
a detailed roadmap.
The plan was developed around
the main refnery units, requiring
old controller revamps or replace-
ments (some with a change of APC
technology supplier) and develop-
ment of new applications.
The main controllers that have
been revamped are related to:
Crude distillation unit
Vacuum distillation unit
Light ends
Fluid catalytic cracking unit.
Some of the new units that have
been covered by APC controllers
include:
One of the main
issues in sustaining
the benets of APC
over time is the
specialised skillset
required to maintain
procedures
aspentech.indd 1 09/06/2014 13:50
large, proftable units has been a
success, creating a new overall
momentum for the entire APC
programme.
APC innovations
Isab determined AspenTechs APC
technology to be the best solution
available, based on the new
Adaptive Process Controller
controller, recently made available
and patented by AspenTech.
APC was designed around the
idea that developing new applica-
tions and maintaining existing
applications should not require the
highest skilled resources, should be
less labour intensive, and should
empower end users.
APC enables customers to:
Start a new APC application
within two to four weeks from
project kick-off meeting
Optimise while step testing the
plant to produce data suitable for
model identifcation
Perform all tasks required to
update controller models without
the need to turn off the controller
Ensure that the controller can
tolerate model mismatch during the
periods between model updates
Handle maintenance as a built-in
and continuous part of the process
and eliminate the need to wait for
turnarounds to revamp controllers
Incorporate control knowledge
within the products and leave it to
the users to leverage their in-depth
knowledge of the production
process.
APC has several advantages over
traditional sustained value
approaches:
The controller model is continu-
ally analysed for accuracy
Poorly performing areas of the
model are identifed
Non-disruptive background test-
ing collects new process data while
the unit is being optimised
New data are monitored in real
time and bad data are automati-
cally identifed and removed
New candidate models are auto-
matically created and presented to
the engineer for review and simula-
tion before on-line deployment.
A key aspect of this technology is
the capability to optimise while
testing. Additionally, this capability
Diesel hydrotreater 1
Diesel hydrotreater 2.
Other units are being covered by
new APC applications:
Gasoline reformer
Hydrogen plant
Hydrogen network optimisation.
More applications will be imple-
mented in the future as per the Isab
APC roadmap.
The frst step in the APC
programme was the replacement of
two existing, outdated APC control-
lers on the CDU and VDU which
were based on a different APC
technology. The revamp of these
M
V
2
MV1
J
optimal
J
JCR
J
actual
Optimum point
Actual point
CV1 limit
CV2 limit
Optimum
area
Figure 1 Adaptive mode optimisation
15
25
30
20
10
5
0
B
e
n
e
f
i
t
s

a
t

e
q
u
i
v
a
l
e
n
t

c
a
p
a
c
i
t
y
,

M
$
/
y
e
a
r
Gap
Today 29% improvement
Average benefits
Pace Setters
at equivalent capacity
Isab average benefits
at site
15
25
30
20
10
5
B
e
n
e
f
i
t
s

a
t

e
q
u
i
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t

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a
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i
t
y
,

M
$
/
y
e
a
r
0
Gap
2 years ago
Average benefits
Pace Setters
at equivalent capacity
Isab average benefits
at site
Figure 2 Benets gap analysis
aspentech.indd 2 10/06/2014 13:36
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is not limited to closed loop step
testing, as the data provided would
be not suitable to identify process
models. Adaptive Process Control
uses a new control algorithm,
combined with enhanced subspace
model identifcation and multi-test-
ing capability which permits
unit operation close to the optimum
and simultaneously generates data
suitable for model identifcation.
Figure 1 illustrates this concept.
When in Adaptive Control Mode,
the optimisation algorithm recalcu-
lates the steady state optimisation
objective function after each run
and stores this cost function (J
optimal
).
It then calculates the objective func-
tion at the current MV targets
(J
actual
) with constraint control only.
It compares the two cost function
values, and calculates the difference
J = J
optimal
J
actual
. Only if J is
larger than the user-specifed toler-
ance (CR: calibration ratio) the
DMCplus engine will generate a
move plan to push the process
towards the new optimal solution.
This process stabilises operation
close to the optimum and creates
some room for very small perturba-
tions that produce data suitable for
model identifcation in a near
closed loop fashion.
In Figure 1, CV1 and CV2 repre-
sent the two active controlled
variables constraints, and MV1 and
MV2 represent two particular
manipulated variables. The technol-
ogy ensures that the two CVs will
be kept inside the shaded triangle
region. In effect, an additional cost
constraint is imposed so that the
cost function will not degrade more
than the user-specifed tolerance.
The engine will generate step
moves for the requested manipu-
lated variables operating within the
shaded triangle that is, close to
the optimum.
Most of the manual, time
consuming tasks required to build
an APC application, including data
treatment (also known as slicing)
and collinearity analysis, are now
automated.
The entire workfow, including
data collection, model quality anal-
ysis, new models identifcation,
simulation and controller deploy-
ment, can be done on-line from a
web interface without the need to
stop running applications.
Isab started evaluating the new
Adaptive Process Control technol-
ogy as an early adopter a few years
ago. The technology was then
incorporated into production
during the APC programmes
execution, achieving signifcant
results.
APC benchmarking and
progress made
To evaluate performance and
provide peer benchmarking,
AspenTech has developed a refnery
APC Benchmarking tool based on
the analysis of many refneries in
Europe, the Middle East and Africa.
Comparisons are made against
pace setters (best performers), simi-
lar sized refneries and all refneries
combined. The main parameters
considered are:
Benefts achieved
Number of APC applications
Total manipulated variables
Applications service factor
Technology breadth
Units coverage
APC maintenance effort
Overall score index.
The APC Benchmarking tool is
used by many refners to compare
performance, identify gaps, and
defne actions and priorities neces-
sary to close the gaps.
Isab was evaluated with the
benchmarking tool before starting
the APC programme and then
again after two years.
12
18
16
14
N
u
m
b
e
r

o
f

A
P
C

A
p
p
l
i
c
a
t
i
o
n
s

P
a
c
e

S
e
t
t
e
r
s
10
8
6
4
2
0
Gap
Number of Applications
Pace Setters
(average of five refineries)
Isab average number of
applications per site
12
18
16
14
N
u
m
b
e
r

o
f

A
P
C

A
p
p
l
i
c
a
t
i
o
n
s

P
a
c
e

S
e
t
t
e
r
s
10
8
6
4
2
0
Gap
2 years ago
Number of Applications
Pace Setters
(average of five refineries)
Isab average number of
applications per site
Figure 3 Applications gap analysis
Most of the manual,
time consuming tasks
required to build an
APC application are
now automated
aspentech.indd 3 10/06/2014 13:36
the APC programme, highlighting
the progress that has been made.
The APC score index accounts for
the benefts achieved related to
refnery assets (capacity, APC
applications, manipulated varia-
bles, manpower and more). It
basically defnes the amount of
value derived from investments.
It is evident that the index tripled
in just two years and Isab is on its
way to join the Pace Setters
community in the near future.
Next steps, overall results, and
benets achieved
The gap analysis and the bench-
marking tools have been used by
Isab to prioritise actions during the
on-going APC programme. Some of
these actions are summarised
below:
1. Improve maintenance and reduce
new project costs using available
technology to automate tasks,
enforce best practices and make
better use of resources available
2. Improve coverage: some addi-
tional units could beneft from
APC applications. Priorities and
expected benefts have been
identifed
3. Revamp the old technology and
outdated applications to obtain
consistent and relevant benefts.
Provide foundation for the hydro-
gen network optimisation which is
a top priority for Isab
4. Take on board a junior APC
engineer to focus on maintenance
of existing applications.
Isab made signifcant progress in
a very short time period. Some 80%
of the benefts delivered by APC
were obtained from the applica-
tions developed or revamped in the
last two years, which translated to
roughly $7.5 million/y with direct
project ROI in just a few weeks.
Benefts achieved were a direct
result of recently developed appli-
cations. A gap in maintenance has
proven that adopting Adaptive
Process Control technology and
dismissing old, outdated tools led
Isab to a sharp change in the right
direction.
Compared to similar refneries
and Pace Setters, there is still room
for improvement. The benchmark-
ing tool has identifed that the
of variables manipulated by APC
controllers and the service factor of
the APC applications have also
achieved signifcant improvements.
These parameters are strictly
related to the economic results
achieved.
Figures 5 and 6 show an overall
APC score index before and after
The bar graphs in Figures 2-4
report the achieved results in
approaching the Pace Setters
community (defned as the fve best
performing refneries in obtaining
benefts from APC technology).
Figures 2-4 demonstrate substan-
tial improvements in several areas.
Others areas including the number
60
90
80
70
T
e
c
h
n
o
l
o
g
y

b
r
e
a
d
t
h

(
P
a
c
e

S
e
t
t
e
r
s
)
,

%
50
40
30
20
10
0
Gap
Pace Setters
technology breadth
Isab Pace Setters
technology breadth
60
90
80
70
T
e
c
h
n
o
l
o
g
y

b
r
e
a
d
t
h

(
P
a
c
e

S
e
t
t
e
r
s
)
,

%
50
40
30
20
10
0
Gap
2 years ago
Pace Setters
technology breadth
Isab Pace Setters
technology breadth
Figure 4 Technology gap analysis
150
250
300
200
100
50
A
P
C

s
c
o
r
e

i
n
d
e
x

(
P
a
c
e

S
e
t
t
e
r
s
)
0
APC score index
Capacity (KBPD)
DMCplus applications
1 2 3 4 5 Average Isab
200 200
209
300
220
16 16
13
26
18
4
24
97
18
82
92
79
117
100
114
186
GAP
2 years ago
Figure 5 Overall APC score: two years ago
aspentech.indd 4 10/06/2014 13:36
in Italy, where he works with customers
across Europe in advanced process control
and energy management. He has around 30
years of eld experience in advanced
process control in the rening, chemical
and petrochemical industries and has
implemented more than 100 MPC and other
automation projects. He holds a masters
degree in chemical engineering from Bologna
University, Italy.
Italy, one of the biggest Lukoil reneries. He
has around 20 years experience in rening,
including Russian (Perm) and American
(Houston) approaches to rening management.
He holds ve patents covering heavy residue
conversion processes, delayed coking in
particular, and a PhD in technical science.
Stefano Lodolo is Senior Advisor and Advisory
Business Consultant with Aspen Technology
number of APC applications and
the number of manipulated varia-
bles could still increase, which
would produce a signifcant gain in
benefts, approaching or exceeding
those of the top performers.
Conclusions
Through the joint commitment of
Isab and AspenTech, the Adaptive
Process Control technology made a
difference at two major sites.
Moreover, these successes proved
that Adaptive Process Control will
change the way new applications
are built and APC proft sustained
at Isab and around the world.
References
1 Harmse M, Zheng Q, Golightly R, An
Enhanced Iterative Process for Maintaining APC
Applications - Adaptive Process Control, Aspen
Technology, Inc.
2 Lodolo S, Harmse M, Esposito A, Autuori A,
Use adaptive modeling to revamp and maintain
controllers, Hydrocarbon Processing, 2012.
Oleg Vedernikov is Deputy General Manager
Technical Director of ISAB Renery, Siracusa,
150
250
300
200
100
50
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1 2 3 4 5 Average Isab
200 200
209
300
220
16 16
13
26
18
8
76
97
18
82
92
79
117
100
114
186
GAP
Today
Figure 6 Overall APC score: today
Reaction Engineering Department, Research
Institute of Petroleum Industry (RIPI), Tehran,
Iran. He holds a PhD in chemical engineering
from Universiti Teknologi Malaysia.
Email: Sadighis @ripi.ir
Reza Seif Mohaddecy is Project Manager,
Catalysis and Nanotechnology Division,
Catalytic Reaction Engineering Department,
RIPI. He holds a MS in chemical engineering
from Sharif University of Technology.
Email: Seifsr @ripi.ir
visbreaking, Ind. Eng. Chem. Res., 43, 2004.
14 Bellos G D, Kallinikos L E, Gounaris
C E, Papayannakos N G, Modeling of the
performance of industrial HDS reactors using
a hybrid neural network approach, Chem. Eng.
Process, 44, 2005, 505515.
15 Abonyi J, Babuska R, Szeifert F, Modied
Gath-Geva fuzzy clustering for identication
of Tagaki Sugeno fuzzy models, IEEE Trans. Syst.
Man Cybern, 32, 2002, 612.
Sepehr Sadighi is Assistant Professor, Catalysis
and Nanotechnology Division, Catalytic
4 Sawarkar A, Joshi J, Pandit A, Kataria K,
Kulkarni K, Tandon D, Ram Y, Petroleum residue
upgrading via visbreaking: a review, Can J.
Chem. Eng., 85, 2007, 1-24.
5 Sadighi S, Ahmad A, An optimisation
approach for increasing the prot of a
commercial VGO hydrocracking process, Can.
J. chem. Eng., 13, 2013, 1077-1091.
6 Sou H.Al, Savaya Z , Moahmmed H, Al-
Azami I, Thermal conversion of heavy Iraqi
residue, Fuel, 67, 1988, 1714-1715.
7 Krishna R, Kuchhal Y, Sarna G, Singh I,
Visbreaking studies on Aghajari long residue,
Fuel, 67, 1988, 379-383.
8 Carlo S.Di, Janis B, Composition and
visbreakability of petroleum residues, Chem.
Eng. Sci., 47, 1992, 2695-2700.
9 Benito A M, Martinez M T , Fernandez I,
Miranda J L, Visbreaking of an asphaltenic coal
residue, Fuel, 74, 1995.
10 Del Bianco A, Panartili N, Anelli M, Beltrame
P, Carniti P, Thermal cracking of petroleum
residues 1. Kinetic analysis of the reaction, Fuel,
72, 1993, 75-80.
11 Trauth D, Yasar M, Neurock M, Nasigam
A, Klein M, Kukes S, Asphaltene and resid
pyrolysis: effect of reaction environment, Fuel
Sci. Technol. Int., 10(7), 1992, 1161-1179.
12 AlHumaidan F, Lababidi M, Al-Rabiah H,
Thermal cracking kinetics of Kuwaiti vacuum
residues in Eureka process, Fuel,103, 2013, 923-
931.
13 Kataria K L, Kulkarni R P, Pandit AB, Joshi J
B, Kumar M, Kinetic studies of low severity
91.5
92.5
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92.0
91.0
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d

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90.0
90.0 90.5 91.0 91.5 92.0 92.5 93.0
Measured viscosity
Training
Validating
Figure 6 Comparison of the measured and predicted data points for the viscosity of
fuel oil
Ivelina Shishkova is R&D Department
Manager with Lukoil Neftohim Burgas. She
holds a MS in organic chemistry engineering
and a PhD in petroleum rening from Soa
Chemical and Technological and Metallurgical
University, and has authored more than 20
technical papers.
Email: Shishkova.Ivelina.K@neftochim.bg
Rosen Dinkov is the Quality Manager in the
Process Engineering department of Lukoil
Neftohim Burgas. His research interests include
crude oil characterisation, bio/conventional
fuels blends characterisation and modelling of
renery distillation processes. He holds a MS
in organic chemistry engineering from Burgas
University and a PhD in the technology of
fossil and synthetic fuels from the University
of Chemical Technology and Metallurgy, Soa.
Email: Dinkov.Rosen.K@neftochim.bg
Vladimir Jegorov is the Sales Development
Manager for Grace in the CIS region. Prior to
joining Grace, he was an FCC process engineer
at the Mazheikiai renery in Lithuania.
Petko Petkov is a full professor and rector
of the Burgas University Assen Zlatarov. He
teaches in the social science department in
the eld of oil rening and lubricants, and has
authored more than 180 scientic papers and
ve books.
Email: PST_Petkov@abv.bg
higher FCC C
4
yield led to higher
production of alkylate, which
resulted in the production of 2%
more premium grade gasoline.
References
1 Watanbe K, Nagai K, Aratani N, Saka Y,
Chiyoda N, Mizutani H, Techniques for octane
enhancement in FCC gasoline, 20th Annual
Saudi-Japan Symposium, Dhahran, December
2010. 17. Montgomery J A, Guide to Fluid
Catalytic Cracking, Part 1, 1993.
Ivan Chavdarov is a Chemical Engineer in
the Process Engineering department of Lukoil
Neftohim Burgas, Bulgaria. His activities are
focused on guiding the operation of the units
of the FCC complex, troubleshooting support
and optimisation of the performance of the
FCC complex.
Email: Chavdarov.Ivan.S@neftochim.bg
Dicho Stratiev is Chief Process Engineer with
Lukoil Neftohim Burgas. He holds a MS in
organic chemistry engineering, and a PhD and
a DSc in petroleum rening from the Burgas
University Assen Zlatarov. He has authored
more than 130 papers.
Email: Stratiev.Dicho@neftochim.bg
Regular A-92
Premium A-95
Super A-98
RVP = 60kPa
1%
28%
71%
RVP = 50kPa
1%
26%
73%
Figure 3 Effect of changing the RVP on
renery gasoline grades produced during
the Resolution catalyst period
MINIDIS ADXpert
Grabner Instruments Messtechnik GmbH | A-1220 Vienna, Austria | Dr. Otto-Neurath-Gasse 1
Phone +43-1-282 16 27-0 | Fax +43-1-280 73 34 | info.grabner-instruments@ametek.at
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ADXpert half page 1.indd 1 06.12.2013 11:46:37
grace.indd 4 11/12/2013 12:49 q2 ripi.indd 5 10/03/2014 14:48
aspentech.indd 5 10/06/2014 13:37
four quest.indd 1 04/03/2014 11:04
Design developments for construction
projects
F
aced with relentlessly increasing
pressures for earlier, consist-
ently on-time delivery of ever
more complex assets, the plant
industries have for many years cast
envious eyes on the performance
gains of the lean manufacturing
revolution. But the key enablers of a
corresponding lean construction
revolution have proved elusive
until now.
The lean philosophy embraces
every aspect of an enterprises oper-
ations, not just engineering. It
comprises three key principles:
Eliminate waste, of whatever
nature
Maximise value-adding effciency
Empower people.
These are deliberately open-ended
concepts; how you apply them
depends on the nature of the enter-
prise and its particular business
processes. The capital engineering
industries have the advantage of
being able to learn from the ways in
which lean manufacturing both
required and drove the develop-
ment of new ways of thinking and
of new types of tools and processes.
Lean construction sees tight inte-
gration of engineering, design and
project management processes
extended to embrace fabrication and
construction in one seamless, closed-
loop process. Recent technology
advances now enable this. Atkins,
for example, one of the worlds
leading design, engineering and
project management consultancies,
has recently chosen Aveva
Everything3D (Aveva E3D) and
Aveva Laser Modeller software to
support lean construction processes.
Atkins has executed many
successful projects using Aveva
Software products enable the principles of lean manufacturing to be applied to
renery construction projects
SIMON BENNETT
AVEVA Solutions
PDMS and is keen to increase its
delivery standards with E3D. Key
capabilities that persuaded Atkins to
migrate to E3D were its BubbleView
laser scan imagery and the tight
integration of Laser Modeller, which
enables laser scans to be readily
converted into intelligent, as-built
3D design models.
Laser scan data that is available
across the entire project life cycle
can greatly reduce discrepancies
between designers, contractors and
fabricators by enabling them to
quickly and correctly respond to
changing circumstances. Engineers
can position new designs and run
clash checks against the existing
plant. This, in turn, will minimise
rework, drive quality and directly
beneft the returns realised across
the project (see Figure 1).
Integrated Engineering & Design
Many project teams still struggle
with a variety of mutually incom-
patible applications for the
engineering and design tasks of the
various disciplines. Apart from
maintaining artifcial barriers within
the project team, this variety creates
opportunities for error through
duplication of information, the
inability to share a common, vali-
dated dataset, and the inability to
control and understand the maturity
of evolving information. Although
the design phase of a project
accounts for only a small fraction of
its total cost, it absorbs costly
resources and the quality of its
deliverables directly affects the
speed, cost and quality of the fabri-
cation and construction phases.
With Avevas solution, it is possi-
ble to import or create engineering
information in a database that forms
part of the projects common data-
set. This, for example, enables
process engineers to create and
maintain control over the develop-
ment of intelligent P&ID schematics,
and to make them visible, at defned
levels of maturity, to the other
project disciplines. Piping designers
can work with this information,
creating 3D layouts that automati-
cally generate material take-off
Figure 1 E3D enables seamless integration of laser scan data into the design environment
aveva q3.indd 1 09/06/2014 13:55
informed decisions made as to how
to eliminate them. Accepted changes
to the steelwork can be readily
incorporated into the master project
model.
Compare & Update is one embod-
iment of the empowerment
principle, because it enables each
discipline to keep control of its own
workfows while collaborating effec-
tively with the rest of the project
team. In contrast, a technology that
sought to rigidly enforce compliance
with design rules at every step, far
from enabling right-frst-time
design, would actually reduce
productivity by requiring designers
to react immediately to every
imposed change while also prevent-
ing them from creating provisional,
non-compliant solutions to require-
ments. Design is an iterative,
evolutionary process and engineers
must have the freedom and fexibil-
ity to set priorities.
Avevas Integrated Engineering &
Design approach improves project
effciency and reduces engineering
and design costs through comple-
information for use by their procure-
ment colleagues. Multi-discipline
collaboration becomes easier and
more transparent.
Another important element in this
is known as the Compare &
Update functionality. Each disci-
pline makes continual changes to its
own work as the design progresses.
This could result in engineers and
designers trying to work under a
blizzard of changes, not all of which
would be of direct relevance to
them. Managing the visibility of
maturity status reduces the blizzard
to a drizzle, but can still leave each
discipline distracted by a great
many changes. Compare & Update
enables a discipline to periodically
compare the status of its own work
with that of others and, importantly,
to decide which changes to accom-
modate, and when. Workfows
become more effcient; non-compli-
ances do not hold up progress but
they remain highlighted until closed
out in an orderly manner.
A typical example is the collabora-
tion between plant layout and
structural steel design. Common
practice is for the basic structural
design to be exported to specialist
steel detailers who use dedicated
software for the purpose. This soft-
ware is usually incompatible with
the 3D plant design solution.
Steelwork must progress in advance
of the rest of the plant, so the two
aspects of the design diverge early
and rapidly. Reconciling changes on
each side is a laborious and mostly
manual procedure with considerable
scope for errors. Often, clashes and
inconsistencies only become appar-
ent during construction, with the
inevitable costs and delays of on-site
rework.
With the incorporation of power-
ful structural steel detailing software
into the Aveva solution, both disci-
plines can work with their own
specialist design tools but the steel-
work can be periodically reimported
for a Compare & Update operation.
Clashes caused, for example,
between gussets on the steelwork
and pipe runs in the plant layout
can be immediately identifed and
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PTQ Q3 2014 (125x178) Jun 2014.indd 1 06/06/2014 11:44:53
aveva q3.indd 2 09/06/2014 13:55
mentary developments that draw on
common processes, disciplines and
deliverables through a single
managed information model. MAN
Diesel & Turbo presented at the
Aveva World Summit in 2013 on its
successful implementation of
Avevas solutions. The implementa-
tion, which started in late 2012,
followed a competitive bid process
and comprised PDMS, Aveva
Engineering, Aveva Diagrams and
Aveva Global.
This implementation created a
fully integrated solution that enables
the standardisation of 2D and 3D
engineering applications across all
disciplines within MAN Diesel &
Turbos Power Plant business unit.
The company launched an internal
project called PIPE (programme for
integrated power engineering) to
target the optimisation of its engi-
neering processes. This programme
addresses a number of market chal-
lenges, including the need to remain
competitive through clearly defned,
measurable and integrated processes
across basic and detailed engineer-
ing. The engineering applications
which the company had been using
had not kept pace with changing
needs. The new software will enable
MAN to cut project times and to
achieve substantial cost savings on
initial deployments.
Laser technology
Empowerment and the elimination
of waste are both made possible by
the advent of technology that
exploits the ease, affordability and
accuracy of 3D laser scanning. This
technology has matured rapidly and
is routinely used for surveying facil-
ities prior to revamp projects, and
for verifying the accuracy of major
plant modules prior to their being
despatched to site. However, it has
now become a practical tool for
creating a feedback loop that
connects fabrication and construc-
tion with design.
Historically, the design offce
essentially pushed deliverables out
to fabrication and construction in
the expectation that the design was
actually 100% accurate and
complete, and that it would be accu-
rately and completely complied
with. Reality often intervened,
however; most construction manag-
ers have bitter experience of on-site
rework crises. This is an example of
open-loop control. The ready availa-
bility of 3D laser scanning now
enables rapid in-process verifcation
at every stage of fabrication and
construction, creating a closed
control loop in which every partici-
pant can actively contribute to the
success of the project. Laser scan
data can be imported into the 3D
design environment and quickly
compared with the design model for
every item, even down to individual
pipe spools. The ability to continu-
ally check and resolve deviations
almost in real time is an important
enabler of lean construction.
For example, many facilities are
built on concrete bases that incorpo-
rate equipment foundations and
other features to accommodate
elements of the plant. You have only
one chance to pour the foundation
so, if the construction team receives
out-of-date information or a site
worker makes a mistake, the
non-compliance becomes literally
cast in concrete (see Figure 2). Now,
the foundation can be laser scanned
as soon as the concrete is suffciently
cured to walk on and the scan
immediately imported into the
design environment for comparison
with the design intent. Informed
decisions can be taken quickly to
deal with any non-compliances,
perhaps by repositioning an
equipment item or modifying
the design of items not yet released
for fabrication. The as-cast founda-
tion becomes an accurate virtual
foundation for the 3D design model.
Laser data import is built into the
E3D solution for plant design.
Remove bottlenecks
When discussing the reduction of
waste with oil and gas EPCs, one of
their most common problems is not
materials waste but wasted time and
effort; this is not surprising when
you consider the cost of even one
days project over-run. One of the
principal causes of delay is the
non-availability of key deci-
sion-makers. Plant projects involve
continual decision making at every
level of detail. Each decision must
be sound and timely to maintain
schedule adherence and create a
Figure 2 The Activity Visualisation Platform enables learning through simulation
aveva q3.indd 3 09/06/2014 13:55
Managing the project
There is, of course, more to project
execution than just engineering and
design. Success is also a matter of
logistics; ensuring that the right
materials turn up at the right time
and in the right place. This is where
Enterprise Resource Management
software can be applied, but it
cannot do so effciently unless it can
work with reliable and complete
information. Not only must the
ERM solution operate with the engi-
neering and design solution as the
source of its information, both must
also work with a common set of
information standards.
If technology now enables lean
methodologies in engineering,
design and resource management,
can it also do so for the construction
stages? Here, the need is to plan the
work and work the plan, but the
widely used project planning solu-
tions, while excellent for high-level
strategic planning, rarely reach the
level of individual work pack sched-
uling, which is where most schedule
adherence problems originate. Work
A design manager using this app,
for example, while waiting in an
airport departure lounge, can
securely log in to a live E3D project,
review its current status, take meas-
urements, add comments (which
are logged in the projects audit
trail) and change the approval
status of any items. His colleagues
in the design offce can immedi-
ately act on this information,
making any necessary changes or
releasing parts for fabrication.
Perhaps the design manager is
actually fying to meet the client or
to visit the construction site. This
same direct access to the live design
model can be invaluable for
presenting project progress, captur-
ing change requirements or
reviewing construction issues.
Potentially critical bottlenecks in
the project schedule can be largely
eliminated. Equally important,
better and more timely decision
making can eliminate both design
rework and the far more costly and
disruptive rework during
construction.
high quality design. But experienced
senior design and project managers
are valuable and highly mobile
people who must split their time
between different locations and are
therefore frequently out of direct
contact with the evolving design.
Responding to this, Aveva has
extended the reach of E3D with the
launch of E3D Insight, the frst
Windows 8.1 tablet app that enables
design decisions to be made directly
into the project model, any time and
anywhere.
E3D Insight provides benefts for
design collaboration, construction
and operations, which rarely
happens in proximity to the offce
desktop. Users can manipulate the
model, measure and inspect as
needed and access status, as well as
other non-graphical information.
Managers and designers can also
take part in a conversation and store
its content directly with the model.
This means that, throughout the
design and fabrication process,
channels of communication can stay
open at all times.
Fits on most rst-response vehicles
Works in up to 13 cm of
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offers signifcant competitive advan-
tage by increasing the value of the
information supplied to the client
and by making the working rela-
tionship more effcient.
Developing a lean strategy
Technology no longer has to be one
of the barriers to developing lean
construction; tools exist that serve
every aspect of project execution.
However, oil and gas projects have
no margin to tolerate disruption of
the business systems that support
them. Introducing new technologies
and workfows must be done in as
risk-free a manner as possible.
Recognising this, Aveva has devel-
oped technology to work alongside
existing business systems. E3D, for
example, can be deployed alongside
PDMS, even on a live project, while
other engineering products can
usually work with (and often
improve the quality of) existing data
assets. Similarly, ERM works with
third-party systems, while NET is
non-invasive, extracting value from
information assets without compro-
mising their integrity.
The lean philosophy has rightly
been described not as an objective to
be reached, but a journey to be
undertaken. Every enterprise must
plan and follow its own journey,
and taking the frst step is often the
hardest part. It is easy to look at a
specifc aspect of lean manufactur-
ing and say That doesnt apply in
this industry; it is harder to look
past the specifcs and see where
general principles such as empower-
ment can be applied in a
project-oriented context. The contin-
uing disappearance of technology
barriers makes it possible to focus
frst on the business areas where the
biggest gains can be made and then
to build outwards. Success in even a
limited area brings both practical
benefts and confdence, making it
easier to change ways of thinking
and working.
Integrated Engineering & Design, AVEVA NET
and AVEVA E3D are trademarks of AVEVA.
Simon Bennett is a Senior Product Business
Manager with Aveva in Cambridge, UK. He
has over 10 years of experience as a software
product manager and was responsible for
launching Avevas Everything3D.
authorities demand increasingly
stringent proof before a facility can
be granted an operating licence.
Again, this is an area where
Aveva has worked with customers
to defne the challenges and create
solutions that enable effcient transi-
tion into safe, nameplate-capacity
production. The companys hando-
ver solution is built on NET a
data-agnostic technology that aggre-
gates, validates, contextualises and
makes readily accessible all types of
information, not just engineering
drawings. This represents a consid-
erable advance beyond the common
requirement for electronic data
handover, which often did little
more than replace the truckload of
uncatalogued documents with a
DVD of the same information.
Today, best practice is for both an
owner operator and its EPC to use
NET for information management,
so that both share the projects infor-
mation asset from the outset.
Information is published to NET as
soon as it has reached a prescribed
level of maturity, whereupon the
owner operators opex team can
begin using it to prepare proce-
dures, populate spares catalogues,
and so on. Handover as a discrete
event is replaced by a process of
progressive transition. The owner
operator automatically acquires a
validated digital information asset
in which incomplete or inconsistent
information is highlighted. Not only
does this transform the speed and
effciency of adopting the new
assets information; equally impor-
tantly, the ability to automatically
generate high quality reports makes
it easier to demonstrate regulatory
compliance and to verify readiness
for start-up. And because NET can
handle all types of information inde-
pendently of its source, the owner
operator does not need to maintain
software licences for the specialist
solutions used by its EPCs or their
suppliers.
The benefts can be considerable.
One major oil and gas owner opera-
tor claims to have achieved 90%
savings in project handover costs
alone. From the EPCs perspective,
far from this technology risking loss
of proprietary IPR or excessive
intrusion by the client, it actually
pack management has therefore
been a topic of considerable interest
for some time.
Analysis has shown that up to
70% of a craftsmans working day is
non-productive: travelling, gather-
ing information, or waiting for
materials or equipment to arrive on
site. As craft labour accounts for
around 40% of construction costs,
there are enormous effciency gains
to be made; it is estimated that work
pack management can cut labour
costs by 25%, or around 10% of total
project cost. Equally important, by
enabling better use of resources, it
can save construction time.
This requires a dedicated solution
that draws on the common dataset
used by other project disciplines
and operates with third-party plan-
ning tools and other business
systems. Aveva provides such a
solution in the form of Enterprise
Resource Management (Aveva
ERM), a modular system that
provides a highly granular level of
planning and work scheduling,
detailed construction planning, and
materials procurement and
management. Additional capabili-
ties are provided by Aveva NET
technology, which harnesses all
types of project or asset informa-
tion for reporting purposes, and
Aveva NET Player, which uses 3D
model and scheduling data to
create animated construction
sequences.
Streamlining project handover
Most particularly in the oil and gas
industry, there is a premium on
speed of achieving full production.
The technologies outlined here offer
benefts in the speed and quality of
creating an asset, but these gains
can be eroded by ineffciencies in
the handover and commissioning
phase. Historically, handover
tended to be a more or less discrete
event involving a handful of keys
and a truckload of drawings and
documents of uncertain reliability or
completeness. Even at frst oil, it
was common for tag data still to be
incomplete, requiring up to two
years further effort to rectify. This is
no longer acceptable practice, both
for economic and business risk
reasons and because regulatory
aveva q3.indd 5 09/06/2014 13:56
heurtey.indd 1 06/06/2014 12:31
Overcoming corrosion in heat exchangers
C
hinas major sources of crude
oil include the Middle East as
well as oil extracted from its
own felds. However, there has
been a gradual decline in the qual-
ity of crude oil in recent years as
some of Chinas old domestic oil
felds have reached the late stages
of extraction. This is resulting in
corrosive phenomena such as
higher sulphur content, heavier
fractions and generally more acidic
conditions.
At the same time, China is
importing large quantities of low
quality oil with high sulphur
content. As crude oil production
intensifes, so too does the chal-
lenge from corrosion which has to
be withstood by oil refnery
equipment.
Renewable energy and reusable
materials will prove essential to
Chinas ongoing growth as an oil
and gas producing nation; leading
analysts predict that it will be 50
years before the Chinese reach the
same standards as the US in this
regard. The heat recovery process is
especially important to refnery
environments, serving as an energy
supply for devices elsewhere.
Problems are arising as tradi-
tional metallic materials fail to cope
fully with the increasingly harsh
corrosive environments, exacer-
bated by the decline in crude oil
quality. Corrosion is a huge prob-
lem for oil refneries the world
over: every year, losses resulting
from corrosion account for approxi-
mately 1-5% of various countries
GDP.
According to The China Greentech
Report 2012, corrosion losses in
China amounted to approximately
Duplex stainless steels are countering traditional materials failure to cope with
corrosion risks aggravated by the declining quality of crude oil
DRAGON HAO
Sandvik Materials Technology
RMB 500 billion ($80 billion) in
2001 and rose to RMB 1.7 trillion
($270 billion) in 2011. Moreover,
corrosion losses account for approx-
imately 6% of the petrochemical
industrys GDP, which is signif-
cantly higher than that of other
industries. Corrosion also impacts
the annual amount of scrapped
metal equipment and materials
globally. Scrap is equivalent to
20-40% of the annual output of
metal, of which 10% is dissipated
due to corrosion and hence cannot
be recycled.
Issues of corrosion pose serious
threats both to production and
security in oil refneries. These chal-
lenges have brought about an
urgent need to adopt a higher level
of anti-corrosion materials to
address these challenges.
Anti-corrosion in standard
materials
To identify materials that exhibit
superior anti-corrosion properties
in harsh heat exchanger environ-
ments, thereby reducing
maintenance needs with more
cost-effective solutions, it is neces-
sary to consider the corrosion
resistance performance of existing
materials. Materials commonly
favoured for these devices include
copper alloys, brass and bronze,
nickel alloys, titanium and stainless
steels. Figure 1 illustrates a perfor-
mance comparison of these
commonly used refnery materials
resistance to corrosion.
Engineers at Sandvik Materials
Technology considered the
complexities of the process environ-
ment in relation to the corrosion
resistance of these materials, focus-
ing on specifc devices: the
overhead condenser, reactor effu-
ent air cooler/bolt locking ring heat
exchanger and reboiler.
For example, the atmospheric and
vacuum distillation unit tower and
its condenser cooling system are
mainly exposed to a highly
15
25
20
10
5
E
r
o
s
i
o
n

r
e
s
i
s
t
a
n
c
e
,

m
/
s
0
Stainless Cu-Ni
70-30
Cu-Ni
90-10
Al-brass Brass Copper
Figure 1 A performance comparison of commonly used renery materials resistance to
corrosion
sandvik q3.indd 1 09/06/2014 14:15
condense into liquid water at the
same rate at which it evaporates
thereby causing serious corrosion
in equipment in water or during
catalysis.
It is when dew point corrosion
takes hold, caused by the formation
of hydrochloric acid from the
condensates absorption of HCl,
that uniform corrosion and local-
ised corrosion are common in
standard grades. Evaporation
temperatures in different refneries
are illustrated in Table 1.
Hydrochloric acid initiates dew
point corrosion, pitting corrosion
generated by chlorides, and
under-deposit corrosion from
ammonium chloride. The chemical
interaction between HCl and H
2
S
has also been observed to cause
corrosion of equipment. These
factors pose serious threats to
devices used in distillation, hydro-
treating and catalytic reforming of
crude oil.
Naphthenic acid in crude oil is
among the primary initiators of
tube corrosion. Corrosion by naph-
thenic acid does not occur at 220C
(428F) but actually occurs at its
greatest potential under tempera-
tures of 270-280C (518-536F).
The corrosion rate of naphthenic
acid has been shown to decline
at temperatures above 280C
(536F) and rise rapidly again
at 350C (662F), stopping corrosion
at temperatures above 400C
(752F).
Moreover, corrosion by naph-
thenic acid is most intense in
environments with elevated
temperatures and without water.
This is intensifed by sulphur diox-
ide and corrosion rates vary under
different temperatures a major
factor for China as it imports large
quantities of low quality oil with
high sulphur content. Trends relat-
ing to global crude oil gravity and
sulphur content are further illus-
trated in Figure 2, including data by
the American Petroleum Institute
(API), and different fractions of
sulphur levels are shown in
Table 2.
Sulphide does not decompose at
temperatures below 120C (248F)
but H
2
S is generated at tempera-
tures between 240-340C
corrosive aggregation of hydrochlo-
rides, hydrogen sulphide and water
(HCl + H
2
S + H
2
O). Standard mate-
rials have exhibited both
advantages and disadvantages in
these circumstances.
Carbon steel undergoes serious
uniform corrosion in such environ-
ments and typically needs to be
replaced every two years. Standard
austenitic stainless steels are prone
to stress corrosion cracking (SCC)
and exhibit weak localised corro-
sion resistance and SCC resistance
in chloride solutions. Copper alloys
are prone to erosion and other
material related problems; and
copper-nickel alloys are more
resistant to brine and sensitive to
H
2
S and sulphur, but are vulnera-
ble to overhead gas corrosion.
Nickel alloys, meanwhile, can result
in higher costs.
Titanium is an unsuitable mate-
rial for retubing of existing heat
exchangers, especially those that
have been retubed numerous times
before. This is because titanium is
unsuitable for dissimilar welding
into copper nickel (CuNi) alloys or
brass tube sheets, nor is it suitable
for gross expanding into enlarged
holes.
Typical recommended steel
grades include Alloy 825 in API
932A/B which is useful against
corrosion caused by ammonium
chloride (NH
4
Cl) and ammonium
hydrosulphide (NH
4
HS). For poly-
thionic acid corrosion,
neutralisation cleaning can be
avoided with the use of the stain-
less steels of 347 type which are
composed of 18% chromium (Cr)
and 11% nickel (Ni). The regenera-
tion tower reboiler should be made
of special steels according to the
API 945 standards, yet ASTM 304L
and ASTM 316L are generally used
domestically instead.
Sources of corrosion
The main sources that cause corro-
sion in refnery equipment include:
the corrosive media present in
crude oil; the additives added in
the transportation and production
process; the corrosive medium
produced in the refning process;
and the large amounts of corrosive
additives added due to oil feld
tertiary oil recovery applications.
Furthermore, the presence and
interaction of these media exacer-
bate the complexity of the
environment in which the refning
equipment is placed.
Tube corrosion in oil is primarily
initiated by naphthenic acid,
sulphides, chlorides, nitrides,
hydrochloric acid, polythionic acid,
oxygen and heavy metals. These
elements react under the dew
point temperature at which
constant barometric pressure
causes water vapour in air to
36.0
36.3
36.2
36.1
35.9
35.8
35.7
35.6
35.5
Q
u
a
l
i
t
y

o
f

c
r
u
d
e

o
i
l

a
n
d

c
o
n
d
e
n
s
a
t
e
,

A
P
I

d
e
g
r
e
e
s
35.4
1.30
1.40
1.35
1.25
1.20
1.15
1.10
1.05
S
u
l
p
h
u
r
-
c
o
n
t
a
i
n
i
n
g

a
m
o
u
n
t
1.00
2000 2005 2010 2015 2020 2025 2030
Weighted average yield (API degrees)
Sulphur-containing amount
Figure 2 Trends of global crude oil gravity and sulphur content
<32.2 (<90) Butane/light oil
32.2-104 (90-220) Gasoline fraction
104.157.2 (220-315) Naphtha fractions
157.2-232 (315-450) Kerosene
232-426 (450-800) Gas oil
426 (800) Residue
Different renery fractions
evaporation temperatures
Table 1
sandvik q3.indd 2 09/06/2014 14:15
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(464-644F) and then starts to
corrode the equipment. This corro-
sion is exacerbated by temperature
increases, reaching its highest level
when the temperature reaches a
range of 420-430C (788-806F).
Practically speaking, the heavier
the oil the higher the boiling point.
Corrosion at high temperatures has
caused carbon steel equipment to
fail in meeting expected usage
requirements, often resulting in
unplanned shutdowns and even
accidents.
Anti-corrosion properties of duplex
stainless steels
Sandvik assessed its fndings and
concluded that materials that are
resistant to low temperatures
should be used as the main basis of
selection of materials. In order to
ease corrosion problems which
occur in oil refneries each year, it
recommends the use of duplex
stainless steels.
Duplex stainless steels are more
resistant to stress corrosion crack-
ing and pitting corrosion and have
superior processing performance in
comparison to austenitic steels of
ASTM 304 and ASTM 316 types.
Their yield strength is double that
of the ASTM 304L and ASTM 316L
austenitic stainless steels which can
effectively reduce tube wall thick-
ness. With these qualities, duplex
grades are used in the harshest
corrosive environments within
temperature ranges of -50C to
300C (58-572F).
Today, a range of duplex stain-
less steels is available; each
possesses a combination of corro-
sion resistance and high mechanical
properties and contributes to a
reduction in wall thickness and
lower processing costs. These
grades include Sandvik SAF 2205,
SAF 2304, SAF 2507 and SAF 2707
HD (UNS S32707), the earlier grade
Sandvik 3RE60 (UNS 31500) and
Sanicro 28. All have brought the
advantages of operational uptime
to oil refneries around the world.
A comparison of these materials
resistance to SCC alongside stand-
ard AIS 304 and 316 grades is
shown in Figure 3.
Figure 3 clearly demonstrates the
sustainability of SAF 2304 for use
in the -50C to 300C (-58F to
572F) temperature range in which
H
2
S starts to corrode refnery
equipment. The grade is character-
ised by similar corrosion resistance
to ASTM 316L but with distinct
cost advantages and, due to these
advantages, it is included in
numerous equipment manufactur-
ers preferred procurement list.
Development of duplex grades
Development of duplex stainless
steels began in the 1930s. The frst
generation of duplex stainless steels
contained chromium, molybdenum,
a high carbon content, and had low
weldability.
These grades include Sandvik
3RE60, the properties of which
were demonstrated in 1969 when a
German oil refnery company used
the material to replace the carbon
steel tubing in its feed water heater.
The refnerys existing carbon steel
300 (570)
200 (390)
100 (210)
T
e
m
p
e
r
a
t
u
r
e
,

C

(
F
)
0 (32)
AISI 304 and 316
Sandvik SAF 2707 HD
Sanicro 28
Sandvik SAF 2205
Sandvik SAF 2507
Sandvik SAF 2304
0.00001 0.0001 0.001 0.01 0.1 1 10
Chloride ion concentration, %
Figure 3 A comparison of commonly used materials resistance to stress corrosion cracking (SCC)
Fractions Gasoline Kerosene Diesel fuel Gas oil Residue
Sulphur levels, % <0.8 <5.2 6-15.5 13.5-44.5 43.6-76
Source: Equipment corrosion status in renery plant and solution (part 1)
Different fractions of sulphur levels
Table 2
Typical process condition:
Temp: 35-150C (95-302F)
Pressure: 0.1013-20.7665 MPa
(0.1033-20.1687 kg/) of absolute
pressure
Chlorides, amines: SCC, general
corrosion
Materials:
Commonly used: carbon steel.
Austenitic 304, 316
Sandvik recommends:
Duplex grades
Corrosion at high
temperatures has
caused carbon steel
equipment to fail in
meeting expected
usage requirements
sandvik q3.indd 3 09/06/2014 14:15
corrosive heat exchanger environ-
ments. The grade is an enhanced
alternative to SAF 2205 with supe-
rior anti-sulphide and chloride SCC
resistance and crevice corrosion
resistance capabilities compared to
most other alloys. These qualities
are essential for processing low
quality oil with high sulphur
content.
SAF 2507 is a duplex (austenitic-
ferritic) stainless steel with high
mechanical strength and toughness.
The material is especially resistant
wall thickness was also reduced
from 16 BWG (42.272mm) to 14
BWG (36.988mm). In another case,
the service life of SAF 2205 in a
crude oil desalting feed water
heater can be seven or eight years
without any problems.
Anti-sulphide properties
In response to the exacerbating
effects of crude oil quality decline
on modern corrosion phenomena,
SAF 2507 is recommended as a
suitable choice of material for
tubes were prone to rapid corrosion
and needed repairs within just
12-18 months of service. Likewise,
the companys ferritic ASTM 410
alloy tubes also exhibited pitting
corrosion and were rapidly losing
effectiveness.
After installation, Sandvik 3RE60
lasted for 17 years, while the entire
unit of carbon steel tubes was grad-
ually replaced due to excessive
corrosion. Based on this perfor-
mance, the German plant
subsequently relied on replacement
3RE60, alongside heat exchangers
manufactured from SAF 2205.
Later duplex stainless steels
developed during the 1970s
contained reduced levels of carbon,
while alloy elements that improve
corrosion resistance such as molyb-
denum, copper, silicon and
especially nitrogen were enhanced.
This led to the formation of the
second generation of new nitrogen
containing duplex stainless steels,
including the 18Cr-type, 22Cr-type
and 25Cr-type.
So-called super duplex stainless
steels were introduced in the 1980s.
These generally have a low carbon
content but with increased amounts
of molybdenum and nitrogen. The
ferrite content is about 50% or
slightly lower. Some of these grades
are characterised by a pitting resist-
ant equivalent (PRE=%Cr +
3.3x%Mo + 16x%N) value of at
least 40. PRE is a tool for ranking
stainless steels with regards to their
pitting and crevice corrosion
resistance.
A further demonstration of
3RE60s enhanced properties took
place in 1981 when a renery in
Sweden looked to replace the tube
in its reaction efuent air coolers
due to the failure of ASTM 321
materials. The replacement grade
3RE60 was implemented and
remained in use for more than 15
years. The material was subse-
quently replaced with Sandvik SAF
2205.
Today, use and availability of the
SAF 2205 grade accounts for more
than 80% of applications of duplex
stainless steel grades. The Swedish
plants replacement tube remained
in service for many years. Due to
the high mechanical strength, tube
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sandvik q3.indd 4 09/06/2014 14:15
found a good connection of the
pipes tube plate. The tubes inte-
rior had not been subjected to
corrosion and examination of the
exterior found no under-deposit
corrosion of crude oil. In contrast,
general corrosion on the old carbon
steel tube plate was observed.
Between the years 2000 and 2011, a
total of four new heat exchangers
were subsequently put into use, all
using the duplex material.
Similarly, a refnery in Italy
required replacement tubes in its
six overhead condenser system heat
exchangers. Each heat exchanger
comprised 1298 tubes made from
ASTM A179 steel. After two years
of use, multiple tubes in the bundle
experienced early onset of failure.
SAF 2507 was installed in the
heat exchangers in 2003. An inspec-
tion in 2006 revealed the heat
exchangers to be in good condition,
despite serious decomposition seen
in the tube plates and shell passes.
It was not until 2008 that, with
moderate concentrations of
hydro-cleaning, some signs of
corrosion were found.
Higher temperature operations
Engineers at Sandvik also turned
their attention to the fracture of
production tubular steel caused by
corrosion attack resulting from a
lack of oxygen.
Low oxygen levels prevent corro-
sion resistant alloys from
developing an oxide flm which
further protects against corrosion
attacks such as SCC and sulphide
stress cracking (SSC). These are
critical considerations in high pres-
sure and high temperature felds
whenever H
2
S and CO
2
gases are
present in wet conditions. Such
factors have many implications, not
the least of which is lost production
with expensive consequences for
the operating company.
Sanicro 28 was initially devel-
oped for pipes and heat exchangers
in sulphuric acid and phosphoric
acid production, as a high alloy
multi-purpose austenitic stainless
steel designed for service in highly
corrosive conditions.
This was demonstrated in a refn-
ery in New Zealand which was
experiencing problems with its
ing 951 steel pipes, each measuring
19.05 x 1.65 x 6096 mm. These were
used to process crude oil and were
subjected to many of the situations
that cause corrosion in refnery
equipment, including H
2
S, dew
point corrosion, chloride pitting,
NH
4
Cl, and under-deposit
corrosion.
The existing pipes were made of
carbon steel and were exhibiting a
maximum service life of two to
three years when subjected to
condensation of hydrocarbons and
H
2
O in small amounts (30-100 ppm
Cl and 200-1000 ppm H
2
S) gener-
ally at pH levels of 6-7, 45-55C
(113-131F) inlet temperatures, inlet
pressures of 0.0780.12 MPa (0.8-1.2
kg/cm
2
), and outlet temperatures
of 60-75C (140-167F).
SAF 2507 was identifed as a suit-
able replacement material. An
inspection carried out in April 2000
revealed that the tubes were still in
good condition. A visual inspection
to CO
2
corrosion and has resistance
to acid corrosion at a low partial
pressures of H
2
S, with physical
properties that offer design advan-
tages such as the ability to undergo
cold and hot processing and good
weldability.
Figure 4 shows a comparison of
corrosion resistance between SAF
2507 and other materials, and
demonstrates its enhanced proper-
ties over 2205 alloys.
Since the early 1990s, the use of
SAF 2507 has proved effective in
refning, whether for retubing
purposes or in new heat exchang-
ers. It is an optimal material when
ammonium hydrosulphide
(NH
4
HS) forms 2-8% of the middle-
range concentration, as shown in
the joint industry programme (JIP)
to address NH
4
HS corrosion in
H
2
S-dominated sour waters
typically found in refneries (see
Figure 4).
The grade can also be used in
high temperature heat exchangers
containing either chlorinated or
non-chlorinated water. It is now
established as a cost-competitive
alternative to materials that are
traditionally favoured in oil refner-
ies, such as expensive nickel alloys
and titanium.
Application in heat exchangers
A refnery was experiencing corro-
sion problems in its overhead
condensers. The system comprised
four heat exchangers each contain-
Alloy 2205
Alloy 20Cb-3
Alloy 825
Alloy 2507
Alloy 625
Alloy C-276
UNS N08367
Alloy 600
Alloy 800
304 SS
316 SS
410 SS
Alloy 400
Carbon steel
Least
resistant
Most
resistant
S
a
n
d
v
i
k

S
A
F

2
5
0
7

n
e
x
t

b
e
s
t
Figure 4 Comparison of corrosion resistance in Sandvik SAF 2507 and other materials
A summary of results from
a joint industry program
(JIP) to address ammonium
hydrosulphide (NH
4
HS)
corrosion in H
2
S-dominated
sour waters, typically found
in reneries.
Duplex stainless
steels and high alloys
are solving many
corrosion-related
problems faced
by the oil rening
industry
sandvik q3.indd 5 09/06/2014 14:18
reactor effuent air coolers due to stress corrosion
cracking initiated by high chloride content, erosion and
under-deposit corrosion caused by NHHS. The refn-
erys existing materials included ASTM 321, Alloy 825
and Alloy 625. These were subjected to temperatures of
380C (716F) input and 250C (482F) output. Such
conditions create the threats of naphthenic acid corro-
sion and polythionic acid corrosion against which the
traditional AISI grades were failing due to cracking.
In normal circumstances, Sandvik duplex stainless
steels are ft to be used in the temperature range -50C
to 300C (-122F to 572F). Because the New Zealand
refnery had a maximum operating temperature of
454C (849.2F), high alloyed Sanicro 28 was instead
recommended. With higher contents of the alloying
elements chromium, nickel and molybdenum, the mate-
rial exhibits excellent resistance to acid, stress corrosion,
inter-granular corrosion, pitting corrosion and crevice
corrosion in a variety of corrosive environments.
Sanicro 28 is complementary to duplex grades and
an alternative for tube materials. It proves especially
effective in the temperature range 300-550C (572-
1022F), under which refneries are in a shutdown state
and must withstand threats posed by naphthenic acid
and other corrosion.
The replacement Sanicro 28 tube exhibited high
corrosion resistance in strong acids, along with very
good resistance to SCC and intergranular corrosion in
various environments where hydrogen sulphide is
present together with chlorides. In addition, the mate-
rial yielded higher resistant to stress corrosion and
better resistance to sulphuric acid corrosion than the
traditional AISI materials.
Conclusion
There is a pressing need to ease the corrosion risks in
oil refneries, especially as these risks are aggravated
by the decline in crude oil quality and traditional
metallic materials failure to cope with harsh corrosive
environments. Duplex stainless steels and high alloys
are solving many corrosion-related problems faced by
the oil refning industry.
These duplex grades are shown to offer cost-effective
solutions as they demonstrate superior corrosion resist-
ant properties in harsh environments with excellent
mechanical properties. Moreover, their processing
performances are good and have shown highly
competitive cost advantages due to the long service
life. Hence, they are increasingly gaining attention
from oil refneries.
Sandvik SAF 2205, Sandvik SAF 2304, Sandvik SAF 2507, Sandvik SAF
2707 HD, Sandvik 3RE60 and Sanicro are marks of Sandvik.
Dragon Hao is Technical & Development Manager, responsible for the
technical activities of tube products, at Sandvik Materials Technology
in Shanghai, China. He was educated at Zhengzhou University, focusing
on metals, and the University of Science and Technology, Beijing,
specialising in the microstructure of super alloys. Prior to working at
Sandvik, he was an Engineer in the R&D centre of Baoshan Iron & Steel
Co, Ltd Special Steel Branch.
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Uiou|, anc (alai lelioleum counl on lince lnineeiin:
ex|eili:e loi leail U!l in (alai.
ln 2OO6, lince wa: awaicec wilh lhe luinkey conliacl lo
builc eihl laie aii :e|aialion |lanl: loi lhe leail U!l |lanl
in ka: lallan lncu:liial Cily, (alai. when leail U!l - lhe
woilc: laie:l U!l lacilily - wenl on :lieam in 2Oll, (alai
became lhe lobal U!l ca|ilal.
!he eihl aii :e|aialion |lanl: |iocuce 86O,OOO cubic
melie: ol oxyen |ei houi, which aie u:ec lo conveil
l4O,OOO baiiel: ol naluial a: inlo liquic hyciocaibon:. A:
:uch, leail U!l i: lhe laie:l inleialec com|lex ol il: kinc
in lhe woilc.
wilh lhi: |io|ecl, lince cemon:liale: once aain lhal il i:
ie:|oncin lo lhe challene ol |iocucin cleanei luel: anc
eneiy lo meel inciea:in woilcwice cemanc. luilheimoie,
lhe com|any conliim: il: leacin |o:ilion a: a lechnoloy
|iovicei anc llC conliacloi.
hega aii sepaiaIion uniIs Ioi Ihe woilds
laigesI gasIoliquids (uJL) piojecI in aIai.
00094_ADV_Quatar_EN.indd 1 11.06.14 15:49
linde.indd 1 11/06/2014 16:06
Meeting production targets for ultra low
sulphur transportation fuels
A
re increasingly stringent spec-
ifcations for transport fuel
sulphur a challenge or an
opportunity? The answer depends
on many variables, including refn-
ery confguration, operating strategy
and catalyst technology. Even with
the latest high activity catalyst tech-
nologies, refners face accelerated
catalyst deactivation and thus more
frequent catalyst changeouts. This
leads to shorter unit run lengths and
higher operating costs. Although
meeting new transport fuel sulphur
regulations will add to their costs
for most refners, the application of
new catalyst technologies may help
to lessen the impact and to give
some of them a competitive
advantage.
The amount of sulphur allowed in
transport fuels has been reducing
across the world. For example, the
United States Environmental
Protection Agencys Tier 3 specifca-
tions, which come into effect in
2017, will reduce gasoline sulphur
content to 10 wppm from the Tier
2 maximum of 30 wppm. At the
same time, demand for diesel trans-
port fuel is increasing, as light-duty
diesel vehicle sales increase to meet
Corporate Average Fuel Economy
standards.
For refners without FCC naphtha
post-treatment capabilities, the
greatest impact of Tier 3 and similar
ultra low sulphur gasoline (ULSG)
regulations will be on FCC-PT unit
operations. These refners are likely
to experience signifcant reductions
in FCC-PT unit cycle lengths and
have higher operating costs. This is
because the more severe processing
required for the heavy FCC-PT feed
will result in accelerated catalyst
Increasingly stringent sulphur regulations and diesel price premiums are prompting
reners to draw a broad process envelope for yield, quality and economic assessment
BOB LELIVELD
Albemarle
deactivation and more frequent
catalyst changeouts.
FCC gasoline typically contains
57% of the sulphur content of the
hydrotreated FCC vacuum gas oil
(VGO) feed. Thus, if the VGO prod-
uct from the FCC-PT unit contains
12001500 wppm sulphur, the FCC
naphtha that results generally
contains 60100 wppm sulphur (see
Figure 1). For a refnery meeting the
Tier 2 gasoline specifcations of 30
wppm, this implies that the FCC
naphtha going to the gasoline pool
can be 3050% of the overall pool.
Most FCC-PT units operating in
constant hydrodesulphurisation
(HDS) mode (about 70% of refner-
ies worldwide) can achieve these
VGO product sulphur limits easily
and many achieve cycle lengths of
two and a half years or more.
Consequently, many FCC-PT units
undergo two turnarounds for each
FCC unit turnaround.
To meet Tier 2 gasoline specifca-
tions with the FCC feed and
naphtha product sulphur allow-
ances cited, many refners without
FCC naphtha post-treatment capa-
bilities must achieve 9095% HDS
in their FCC-PT units. To meet the
Tier 3 ULSG specifcations, the
allowable sulphur content of FCC
naphtha will need to be 2035
wppm. This will generally mean
that the VGO feed to the FCC unit
should contain 400600 wppm
sulphur, which translates into
9798% HDS for the same FCC-PT
unit.
Reduced unit cycle lengths
Albemarle has used its proprietary
hydroprocessing catalyst (HPC)
process model to simulate units
operating under three different
pressure regimes to predict the
likely impacts of Tier 3 ULSG regu-
lations on different types of FCC-PT
unit operation. These screening
studies assumed 100% hydrotreat-
ment of FCC feed and were for
illustrative purposes only. The
actual impacts of the Tier 3 specif-
cations will depend on a refnerys
1000
10 000
100
10
F
C
C

g
a
s
o
l
i
n
e

s
u
l
p
h
u
r
,

p
p
m
1
0.01 0.1 1 10
FCC feed sulphur, wt%
FCC gasoline sulphur is
5-7% of FCC feed sulphur
for hydrotreated feeds
Unhydrotreated feed
Figure 1 The impact of VGO FCC-PT product sulphur on FCC naphtha sulphur content
q3 albemarle.indd 1 11/06/2014 16:01
include these units in their process
envelope.
As a result of the higher severity
of FCC-PT operations, most refners
will face increased challenges when
trying to coordinate FCC-PT operat-
ing cycles with FCC unit
turnarounds. The present conven-
ient ft of two FCC-PT operating
cycles for each FCC unit turnaround
will no longer be possible. At the
same time, many refners will be
trying to increase their output of
ultra low sulphur diesel. Faced with
this dual challenge, it seems likely
that many operators will investigate
alternative FCC-PT operating strate-
gies to help them optimise their
overall operations and product
slates.
Those refners with the fexibility
to implement alternative modes of
FCC-PT operation, such as mild
hydrocracking (MHC), may opt to
evaluate alternative operating strate-
gies, and their projected impacts on
overall refnery yields and qualities
of intermediate and fnished prod-
uct streams. This option may be
especially important for refners that
are trying to increase their ultra low
sulphur diesel yields.
Refners with FCC naphtha
post-treatment capabilities may fnd
that operating their FCC-PT unit at
a higher severity to lower the
sulphur content of FCC naphtha
helps them to meet Tier 3 ULSG
regulations with similar octane
losses to those incurred in meeting
Tier 2 specifcations.
In general, refners will incur
higher costs for their FCC-PT units
to meet Tier 3 sulphur regulations.
Loading higher activity catalysts,
such as ultra high HDN activity KF
861 NiMo catalyst, will help to
lengthen cycles compared with
using current catalysts. However,
more frequent changeouts, even
with these new catalysts, are likely
to result in annualised fll costs up
to 30% higher than those currently
incurred. Shorter cycles mean that
the cost of turnarounds and spent
FCC-PT catalyst disposal will also
increase.
Additionally, higher hydrogen
consumption for the early portion of
the operating cycle (until the
maximum aromatics saturation
specifc feed compositions, unit
capabilities and constraints, and
FCC-PT operation strategies.
For units operating in constant
HDS mode at low to moderate
hydrogen partial pressure (4070
bar), meeting Tier 3 gasoline speci-
fcations is projected to shorten the
FCC-PT cycle length by 2040%,
even if very high-activity CoMo or
NiCoMo VGO HDS catalysts are
used (see Figure 2). The hydrogen
consumption at the start of run is
likely to increase by roughly the
same amount because the weighted
average bed temperature will have
to be higher and will begin close to
the maximum aromatics saturation
temperature for the feed and oper-
ating pressure.
For moderate to high pressure
FCC-PT units currently operating
in maximum aromatics saturation
mode, the effects of the new specif-
cations are harder to quantify.
Initial simulations suggest that the
decrease in cycle length could be
50% or more and that the operation
may have to switch to constant
HDS mode early on to achieve and
maintain greater than 98% HDS
(see Figure 3).
What are the options?
In assessing their options for meet-
ing Tier 3 ULSG regulations,
refners will need to draw a broad
process envelope for yield, quality
and economic assessments to
account for the overall effects on
the bottom line. Specifcally, as a
minimum, the assessments will
need to include the FCC-PT and
FCC units performance. Refners
with FCC naphtha post-treatment
capabilities will also need to
760
800
780
740
720
700
680
660
W
A
B
T
,

F
640
96
100
98
94
92
90
88
86
H
D
S
,

%
84
0 5 10 15 20 25 30 35
Months on stream
Tier 3: 97% HDS
Tier 3 WABT
Tier 2 WABT
Tier 2: 92% HDS
Figure 2 A low pressure FCC-PT unit in constant HDS mode is predicted to have cycle
lengths 16 months shorter
760
800
780
740
720
700
680
660
W
A
B
T
,

F
640
96
100
98
94
92
90
88
86
H
D
S
,

%
84
0 5 10 15 20 25 30 35
Months on stream
Tier 3: 98% HDS
Tier 3 WABT
Tier 2 WABT
Tier 2: 94% HDS
Figure 3 A moderate pressure FCC-PT unit in constant HDS mode is predicted to have
cycle lengths more than 10 months shorter
q3 albemarle.indd 2 09/06/2014 14:21
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merichem.indd 1 28/02/2014 10:28
temperature is reached) will increase
the operating costs for that part of
the cycle. It is also more critical that
there is full hydrogen availability at
the start of cycle to avoid hydrogen
starvation of the catalyst. The over-
all impacts of these factors will be
highly dependent on a given refn-
erys specifc supply and unit
considerations.
Taking advantage of low cost
hydrogen through volume swell
Increased gas production from
hydraulic fracturing shale forma-
tions in North America has led to a
substantial fall in natural gas and
hydrogen prices. These prices are
likely to remain relatively stable
over the coming years, which makes
hydrotreating an attractive option
for boosting ULSD volumes.
Adding hydrogen to aromatic
distillate feedstocks signifcantly
increases liquid volume and
improves product quality. The larg-
est gains in liquid volume come
from increased hydrogen addition
to the most aromatic distillate
streams, such as light crude oil
(LCO), but, for a moderate to high
pressure ULSD unit, gains are possi-
ble even when processing typical
feedstocks.
This approach requires a clear
understanding of hydrogenation
kinetics and a catalyst system
designed to manage hydrogen
consumption. Albemarles Stars,
Nebula and Stax technologies
provide a complete solution for
creating economic value from low
cost hydrogen. The Stars catalysts
were the frst commercially availa-
ble HPCs to deliver 100% Type II
active sites for enhanced activity
and Nebula catalysts can signif-
cantly increase hydrogen addition.
Stax uses a modelling tool to
simulate the reactions taking place
in different parts of the hydrotreater.
For example, easy sulphur species
are removed near the top, organic
nitrogen is removed in the middle
and refractory sulphur species are
removed in a nearly nitrogen-free
zone at the bottom. The simulation
leads to the use of different combi-
nations of Stars and Nebula catalysts
to optimise the hydrotreating
process.
Deploying an optimum combina-
tion of activity for HDS, HDN and
hydrogenation can push the unit
operation against its constraints
while increasing margin upgrade
and/or volume swell.
For example, in one refnery, a
moderate pressure diesel hydro-
treater producing ULSD has a
reasonably high outlet partial pres-
sure of hydrogen (ppH
2
) of 5560
bar, but is limited by hydrogen
availability. The unit processes a
mix of straight-run and cracked
(LCO) diesel. A substantial increase
in hydrogen uptake would signif-
cantly decrease the outlet partial
pressure.
Despite signifcant constraints, the
reasonably high outlet ppH
2
offered
opportunities for economic improve-
ment by adjusting the catalyst
system. The refnery objectives were
to increase the intake of cracked
feed to 15% and the intake of
aromatic extract to 10%.
Albemarle designed a catalyst
system that would increase HDN in
the middle of the reactor in order to
increase the hydrogen consumption.
The enhanced performance of the
ULSD unit signifcantly increased
the overall refnery proftability and
prompted the refner to choose the
same catalyst system for the subse-
quent cycle.
A second refnery operates a
moderate pressure diesel hydro-
treater with an outlet ppH
2
of 5055
bar. The feedstock is a blend of
straight-run and cracked (LCO)
diesel. This unit has hydrogen
supply constraints and a marginal
outlet partial pressure for mono
aromatic saturation. Although
volume swell would be economi-
cally advantageous, the units
capabilities are such that the main
beneft would be from increased
LCO intake.
Albemarle optimised the catalyst
system design to manage the
marginal hydrogen availability. The
unit has a relatively low liquid
hourly space velocity, which helps
to keep the deactivation rate reason-
able, even with low hydrogen
availability. Comparing the cracked
and heavy feed intake with the
previous cycle showed an increase
from 11% to nearly 14%. The hydro-
gen uptake averaged nearly 8%
higher.
The refnery averaged 23 g/L
lower ULSD density compared with
previous runs. In combination with
the additional cracked and heavy
feed intake, the changes to the cata-
lyst system generated a positive
return on investment.
Revamping units
Commissioning new processing
units can help to increase the yield
and quality of ultra low sulphur
transport fuels. However, some
refners may have the opportunity
to convert existing FCC-PT and
diesel units into MHC units with
relatively low investment.
One refnery was able to increase
diesel yields and quality by revamp-
ing an existing hydrotreater to
become a MHC unit. This unit,
which uses Stars catalysts, has
successfully achieved >50, 340C
conversion in all of its fve cycles,
with a product density reduction of
48 g/L and 15ppm sulphur content.
In the frst cycle, additional revenue
of over $44 million a year was
reported, which means the payback
time for the revamp was less than a
year. In subsequent cycles, the
refner has reduced fll costs by
using regenerated React Stars
catalyst.
Summary
Albemarle is using its technology
expertise and proprietary HPC
process model to help refners get
the most out of the prevailing situa-
tion, for example, boosting ULSD
volumes with low cost hydrogen for
hydrotreating and designing unit
revamps. It is also helping refners
to prepare to meet new sulphur
specifcations as economically as
possible by working with them to
develop an optimised combination
of operating conditions and catalyst
systems.
Bob Leliveld is Director of the Application
Technology group in Albemarles Clean Fuels
Technology (CFT) division. In this role, he and
his team are responsible for the development
and marketing of CFT technologies. He holds a
PhD in inorganic chemistry and catalysis from
the University of Utrecht, The Netherlands.
q3 albemarle.indd 3 09/06/2014 14:21
enersul.indd 1 06/06/2014 12:30
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WORLD STANDARD COMPRESSORS
ariel.indd 1 09/06/2014 14:57
Improving a compressor protection
regime
C
ompressor crosshead frac-
tures are costly, leading to
unplanned outage of the
system and loss of production.
Prognost Systems claims that the
development of fractures in the
motion work, especially on the
crosshead, can be detected by
using segmented peak-to-
peak piston rod position analysis.
The company also recommends
this as a mandatory parameter
and for safety interlock. This claim
was proven to be true by a
complete fracture of a crosshead
which could have been avoided
if the automatic interlock had
been activated by the operator.
The experience of this case also
motivated the operator to improve
their site shutdown philosophy.
The installation
At a renery in the US, a Nuovo
Pignone reciprocating compressor
was put into operation in 2004.
Since the initial start-up, a Prognost
system had been used to detect
Analysis of the build-up to the fracture of a compressor crosshead led a rener to
revise its approach to performance monitoring
BEN AUSTIN
Prognost Systems Inc.
common faults such as valves,
riders, rings and others. The
compressors overall reliability had
been very good. No failures in the
motion works components
occurred; no Prognost safety alert
or alarm limit of CHS vibration
(active) or rod position (inactive)
had been reached.
Failure history
In 2011, the compressor had its rst
major overhaul in seven years due
to a knock. Several parts such as a
rst stage connecting rod, bearings,
crosshead pin and the main bearing
liners were replaced. The crosshead
failure described here occurred 11
months after these service works
2|29|2012 17:55 8tatus Ha|n A|arm (2HP} for '6200-A' act|vated !!!
2|29|2012 17:55 8T 2 V 6h8 8T2 8tatus Ha|n A|arm dead center act|vated !
2|29|2012 17:55 8T 1 V 6h8 8T1 8tatus Ha|n A|arm dead center act|vated !
2|29|2012 17:55 8T 1 0amage c|ass: '6rosshead | P|ston Rod| P|ston' 8T 1 corre|at|on: 100.0 7
2|29|2012 17:51 8T 1 R0 8T1 5:51:00 PH Rod drop cy||nder 8T1 Peak-Peak over 8 8eg. ..45 degrees 8egment: 4 [
2|29|2012 17:31 8T 1 R0 8T1 5:28:00 PH Rod drop cy||nder 8T1 Peak-Peak over 8 8eg. ..45 degrees 8egment:
2|29|2012 17:28 8T 1 R0 8T1 8afety Unsafe R0 8T1 - Peak-Peak over 8 8eg. ..45 degrees: safety p|ausab|||ty v|o|at|on
2|29|2012 17:51 8T 1 R0 8T1 5:4:00 PH Rod drop cy||nder 8T1 Peak-Peak over 8 8eg. ..45 degrees 8egment: 7 [ 5:45:00 P
2|29|2012 17:41 8T 1 R0 8T1 5:38:00 PH Rod drop cy||nder 8T1 Peak-Peak over 8 8eg. ..45 degrees 8egment: 8 [ 5:38:00 P
2|29|2012 17:55 8T 2 V 6h8 8T2 8tatus Pre-A|arm 8afety ||m|ts v|o|ated |n the fo||ow|ng segments: 32 34 35 3
2|29|2012 17:55 8T 1 V 6h8 8T1 8tatus Pre-A|arm 8afety ||m|ts v|o|ated |n the fo||ow|ng segments: 32 34 35 3
2|29|2012 17:55 8T 1 V 6h8 8T1 8tatus Pre-A|arm 8afety ||m|ts v|o|ated |n the fo||ow|ng segments: 5
2|29|2012 17:54 8T 1 V 6h8 8T1 8tatus Pre-A|arm 8afety ||m|ts v|o|ated |n the fo||ow|ng segments:
Figure 1 The logbook of the last 30 minutes before the fracture illustrates the sequence
from the rst diagnostic messages (green) to pre-alarm (orange) to the main alarm (red)
124
132
130
134
128
126
122
120
118
116
114
D
i
s
p
l
a
c
e
m
e
n
t
,

m
i
l
112
0.4
1.2
1.0
0.8
0.6
0.2
0
0.2
0.4
0.6
A
c
c
e
l
e
r
a
t
i
o
n
,

g
0.8
TDC BDC
0 20 40 60 80 100 120 140 160 180 200
Rotation angle,
220 240 260 280 300 320 340 360
V CHS vibration signal
V CYL vibration signal
Figure 2 The normal online signature of the compressor seven days prior to the event (CHS RMS vibration = blue; piston rod position =
red curve)
prognost.indd 1 10/06/2014 09:57
had been carried out by a non-OEM
contractor.
Development of the crosshead
fracture
At the time the event started, the
compressor was running steadily at
a normal load of 75%:
Twenty-nine hours prior to the
break, the Prognost-NT system
issued the rst diagnostic message.
It reported the following damage
class: Crosshead/Piston Rod/Piston
Stage 1 with a correlation of 100%
During the following minutes,
there was a steady increase from
the rst diagnostic message
(pre-alarms) to alarm (shutdown).
In addition, the vibration safety
limits of the crosshead slide were
violated in several segments
Sixty seconds before the cross-
head failed, the rst stage piston
7.50
10.00
8.75
6.25
5.00
3.75
2.50
1.25
V

C
H
S

r
m
s

v
a
l
u
e
s
,

g
0
29/2/2012
4:58:00PM
29/2/2012
5:10:00PM
29/2/2012
5:20:00PM
29/2/2012
5:30:00PM
29/2/2012
5:40:00PM
29/2/2012
5:50:00PM
29/2/2012
6:00:00PM
Figure 3 The crack development is visible in the RMS short term trend two minutes prior to the fracture, but only in four segments (33,
34, 35, 36). Six were needed for the trip
22.60
30.20
26.40
18.90
15.10
11.30
7.55
3.77
R
D

S
T
1

a
m
p
l
i
t
u
d
e
,

m
i
l

p
k
-
p
k
0
41.50
49.10
45.30
37.70
34.00
29/2/2012
5:05:00PM
29/2/2012
5:15:00PM
29/2/2012
5:24:00PM
29/2/2012
5:33:00PM
29/2/2012
5:42:00PM
29/2/2012
5:51:00PM
29/2/2012
6:00:00PM
Figure 4 The curve of the dynamic piston rod position shows a rapid increase within
the later revolutions. Each line (blue, green, red and so on) represents one of the eight
segments into which the 360-degree crank-angle is divided
60
80
70
50
40
30
20
10
V
i
b
r
a
t
i
o
n

s
i
g
n
a
l
,

g
0
RD ST1 proximity signal ZT 6001
P HE ST1 pressure signal S 67-PT-2005 V CHS ST1 vibration signal VT 6001
P CE ST1 pressure signal S 67-PT-2006
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
CA
Figure 5 The green curve indicates the loss of pressure within the compressor caused by separation of the crosshead
prognost.indd 2 10/06/2014 09:58
rod position reached trip levels
After the crosshead parted and
the vibration alert conditions on
both crossheads were reached,
automatic shutdown was initiated
on the crosshead slide vibration
On previous trips, the operators
had seen the low oil pressure
annunciator on and assumed that
was the cause of the shutdown,
when in reality this is one of the
alarms that comes in when the
machine is tripped ofine and is
coasting down. They checked the
oil system, found it to be good, and
restarted the compressor 32
minutes after the safety shutdown.
A log of the 30 minutes leading
up to the fracture is shown in
Figure 1.
Data analyses showed that the
crosshead slide vibration and the
rod position were both giving a
normal online signature seven days
prior to the failure (see Figure 2).
The crosshead vibration safety limits
were set between 2.0g and 2.3g.
Sixty minutes before the event,
the crosshead vibration and the rod
position were well below the safety
limits. Two minutes prior to the
fracture, development of the crack
was visible in the CHS vibration
RMS analysis in four segments (see
Figure 3). For the safety shutdown,
violations in six segments were
needed.
Compared to the crosshead, the
rod position increased 10 minutes
earlier, averaging 51.23 mils 60
seconds prior to the trip. Some 15
seconds before the trip, the rod
position reached 71.2 mils, exceed-
ing 90 mils during the last three
revolutions (see Figures 4-6). The
sequence of events is shown in
Table 1.
Taken together, all of the gath-
ered data fully illustrated the
reaction of the system shortly
before the separation of the cross-
head as well as what happened
when the operator team overruled
the shutdown initiated by the
Prognost system. The shutdown
settings from the site acceptance
test (SAT) protocol showed the
detailed safety limits and criteria
for the activation of pre-alarm
and main alarm. It also proved the
disabling of analyses by resetting
the safety alarm if the machine
stops.
A new safety shutdown philosophy
After the complete fracture of the
crosshead, the data analyses led to
several conclusions on the opera-
tors side. First of all, Prognost
monitoring showed that the devel-
opments of this type of crosshead
fracture cannot be detected at an
early enough stage by using the
crosshead vibration alone. The use
of piston rod position measure-
ments has proven to be a reliable
factor for safety protection.
As a result, the monitoring of
piston rod measurements is now
part of the site shutdown philoso-
phy on machines equipped with
Prognost at the renery. In addi-
tion, operators are no longer
permitted to restart a compressor
tripped by a Prognost system.
Thus, the Prognost-NT system now
helps to avoid costly damages to
rotating equipment, lowering
outage and securing productivity at
the renery.
Ben Austin works in Customer Support with
Prognost Systems Inc., Houston, Texas. He is
an ISO Certied Category III Vibration Analyst
with the Vibration Institute with over 17 years
experience with rotating equipment.
Time Event Cause
SAT Crosshead RMS safety limits settings between 2.0g and 2.3g
-7 days Crosshead RMS ~0.4g, rod position ~18 mils
-29 hrs Diagnostic message Crosshead, Stage 1, 100%
-10 min Rod position ~22 mils
-120 sec Crack development visible CHS RMS vibration (4 of 6 segments)
-60 sec Prognost main alarm 1st stage piston rod position (51.24 mils)
(automatic trip deactivated by customer)
Pre-alarm 1st stage CHS RMS vibration
-15 sec Rod position 71.2 mils
Last 3 revs Rod position exceeded 90 mils
Crosshead parted
Pressure curves show crosshead separation
17:55 hrs Compressor tripped RMS crosshead vibration Stage 1 and 2
(5:55pm)
+32 min Restart by operators on deck
Immediate shutdown by Prognost-NT
Sequence of events leading to shutdown
Table 1
TDC 36 TDC 36
TDC 36
29/2/2012
5:31:00 PM
29/2/2012
5:57:00 PM
29/2/2012
6:31:00 PM
V CHS ST1
RD ST1
BDC 18
TDC 1
BDC 18
51.24 mil
0 18 36
mil
54 72 90
Figure 6 3D Waterfall trend of one hour. The blue surface represents the RMS of
crosshead vibration over a 360-degree crank-angle: reaction after the operator overruled
the trip released by the Prognost system
prognost.indd 3 10/06/2014 09:58
Avoiding compressor system downtime
T
he Compressed Air and Gas
Institute (CAGI) estimates that
industrial facilities in the US
waste up to $3.2 billion every year
on energy costs due to poorly
designed and maintained compres-
sion systems. Compressors are the
key drivers of many of these
systems and damage to them can
often result in costly maintenance
expenditures, increased downtime
and an overall drop-off in system
effciency. With energy prices on
the rise, the need for new and inno-
vative control technologies that can
help cut operating expenditures
and boost process effciency are
more critical than ever.
Understanding surge
Surging is one of the most common
causes of compressor damage.
Because it is highly dependent on a
number of different variables, its
occurrence is diffcult to predict
accurately. Even with anti-surge
measures in place, many compres-
sors have to be used rather
conservatively in order to prevent
damage to equipment. This results
in wasted energy and decreased
productivity, making process opti-
misation virtually impossible to
achieve.
Surging occurs when insuffcient
fow into the compressor and/or an
increasing pressure rise across the
compressor causes a condition in
which forward fow is unable to be
sustained. This results in a tempo-
rary reversal of fow within the
impeller, causing a decrease in the
discharge pressure and/or an
increase in the suction pressure.
This rise in suction pressure
allows the compressor to
Developments in anti-surge technology make it possible to maximise process
efciency and optimise compressor function
AMIT SAXENA
Dresser-Rand
re-establish forward fow but, when
it resumes, the resulting pressure
differential again reaches a point
where the compressor becomes
unstable, fow is reversed and this
cycle is repeated. This continues
until a change is made in the
process and/or compressor
conditions.
Surging can cause serious physi-
cal damage to pumps, fttings,
valves, pipes, and other ancillary
pieces of equipment. Rotor shifting
caused by the surge cycle can also
destroy thrust bearings and, in
many cases, operating temperatures
can exceed allowable limits, caus-
ing compressors to overheat.
Because of this, it is always impor-
tant to have effective anti-surge
measures in place.
Surge can be prevented either by
blow-off or recirculation of fow in
order to keep the pressure differen-
tial across the compressor at a level
in which reversal cannot occur. The
moment at which either of these
actions need to take place is deter-
mined by the controller, which is
designed to predict the point at
which surging is imminent (i.e., the
surge line) by measuring a function
of pressure rise versus fow.
The challenge, however, is being
able to defne accurately the surge
line over a wide range of operating
conditions. Because this is so diff-
cult to do, engineers generally have
to err on the side of caution and
use compressors in a very conserv-
ative manner, resulting in
decreased throughput and low
operating effciencies.
The key to maximising compres-
sor effciency is to determine the
surge line with a high degree of
accuracy. In doing so, the workable
limits of the compressor can be
clearly defned and unnecessary
recirculation of fow can be kept to
an absolute minimum.
Current surge technology
The technology that drives many of
the anti-surge applications used
today is based upon the premise
that for any given rotational speed
the compressor surge limit fow will
correspond to fxed values of poly-
tropic head and volumetric suction
fow. This generally holds true for
single-stage compressors, but many
multi-stage compressors deviate
from this theory. This methodology
also produces surge control maps
with coordinate systems that are
only partially invariant to inlet gas
molecular weight, temperature and
compressibility.
Due to the volume ratio effect,
which affects the polytropic head
suction fow relationship, the
temperature and molecular weight
of incoming gas can signifcantly
change the point at which surge
occurs in a multi-stage compressor.
As a result, anti-surge algorithms
that fail to produce surge control
maps with coordinate systems that
are completely invariant to changes
in the properties of an incoming
fuid are subject to a wide margin
of error.
Surging is one of
the most common
causes of compressor
damage
dresser rand.indd 1 09/06/2014 18:08
the operating point of the compres-
sor reaches the back-up line a
certain number of times within a
specifed period of time. When this
occurs, the control set point is
shifted to the right via Dresser-
Rands Set Point Shift Logic. The
fow set point continues to be
shifted until the cause of instability
can be corrected. This action estab-
lishes a larger margin of safety
from the surge line.
The third control is a variable
proportional gain action that takes
effect when normal PI control
response is unable to prevent fow
from dropping below the control
line during rapid system upsets.
To prevent surge under these
circumstances, Dresser-Rands
Floating Proportional Control
Algorithm is initiated and surge
valves are opened before the oper-
ating point reaches the control line.
When the upset has been stabilised,
normal PI control is resumed.
Amit Saxena is Senior Control Systems
Engineer at Dresser-Rand.
If an anti-surge controller that
was unable to compensate for the
difference of two gases with differ-
ent molecular weights is used on a
particular compressor, it would
either not be able to prevent surge
under all conditions, or it would
produce a control line located so
far to the right that the compressor
would be highly ineffcient when
dealing with heavier gases.
Solving the surge problem
Dresser-Rands Universal
Performance Curve Coordinate
System is an anti-surge technology
that makes it possible to maximise
process effciency and optimise
compressor function by eliminating
unnecessary fuid recirculation
and/or blow-off.
The system automatically
compensates for changes in molec-
ular weight, temperature, pressure,
compressibility, and rotor speed to
produce a surge control map that is
accurate across all possible
scenarios.
Under normal operating condi-
tions, proportional integral (PI)
control is used to operate the
compressor. The PI control loop is
used to compare the control set
point to the operating point of the
compressor and provides an output
to the surge valve to prevent fow
from decreasing below the control
line. Under these conditions, surge
control action is initiated at the
control line by opening the surge
valve. This prevents a further shift
of the operating point to the left
towards the surge line.
In the case of rapid reductions in
fow, such as process upsets, three
additional controls are imple-
mented to prevent surge from
occurring. The frst control is a
back-up line, which is located
between the control line and the
surge line on the surge control
map. In the event that the operat-
ing point reaches this line,
Dresser-Rands Open Loop Step
Logic quickly forces the surge valve
open to increase forward fow
through the compressor.
The second control takes effect if
9
th
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CONFERENCE FOCUS:
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SPECIAL FEATURE:
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September 10, 2014
September 11-12, 2014 Hofburg, Vienna - Austria
For Programme and Online Registration: www.recip.org
9
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h

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EFRC_Advert_PTQ.indd 1 20.02.2014 16:32:47
dresser rand.indd 2 11/06/2014 12:51
Process
Ideal Stage or Mass Transfer...
Which Model Should Be Used?
Insight:
The design and optimization of separation processes is
carried out using process simulators, which utilize various calcula-
tion approaches. Two techniques that are widely used for modeling
distillation are the ideal stage model and the mass transfer model.
IDEAL STAGE MODELS
The ideal stage model requires a minimum amount of
dataonly equilibrium relationships and enthalpy data for the heat
balance. The assumptions of the ideal stage approach are: 1) that
the vapor and liquid are both perfectly mixed so that the vapor and
liquid leaving a stage are at the same composition as the material
on the stage and 2) that thermodynamic equilibrium is obtained on
each stage. The equilibrium assumption also means liquid and va-
por leaving a stage are at the same temperature. Ideal stage mod-
els can also account for non-ideal column performance through the
use of reaction kinetics as is done for amine sweetening columns.
Obviously, the main disadvantage of the ideal stage
approach is just thatthe use of ideal stages to model real trays
or packing depths. However, for most processes encountered in
gas processing and other industries, the overall effciencies are
well established for proper operating conditions of the column. For
systems that are unavailable, similar systems often exist to allow for
effciency estimation. If not, the mass transfer approach is available
as an option.
MASS TRANSFER MODELS
For the end user, the notable feature made available via
the mass transfer approach is the ability to model a column with the
actual number of trays in the unit or the actual depth of packing.
However, there are still several assumptions that are made in this
approach that can have a signifcant impact on results. Two that are
worth mentioning include the mixing model for trayed columns and
the discretization of the packing depth for packed towers.
Application of the mass transfer model to random or
structured packing requires the column height to be discretized into
vertical segments or stages. For trayed columns, various mixing
models can be used for the liquid and vapor phases. The most
basic assumption is that of complete mixing in both the liquid and
vapor phases. However, the concentration gradients that develop
on a tray can signifcantly impact the predictions made by this model
since this gradient is the driving force for mass transfer. As the
column diameter becomes larger, the perfectly mixed fow model is
less applicable.
For modeling both liquid phase chemical reaction and
mass transfer, the use of the enhancement factor technique may be
considered. The enhancement factor describes the increased rate
of absorption due to the effect of a chemical reaction. The material
balance requires kinetic rate expressions for all chemical reac-
tions occurring in the system. As with equations for a non-reacting
system, an appropriate model for interface behavior must be used.
Mass transfer models require data necessary to calculate
interphase mass and heat transfer coeffcients and interfacial area
based on correlations of the following transport and thermal proper-
ties: diffusivities, viscosities, densities, heat capacities, thermal
conductivities, etc. Furthermore, mass transfer models require
detailed information on the column internals. For trays, this includes
information such as weir heights and fraction active area. For pack-
ing, this includes surface area per unit volume and void fraction.
If the simulator allows the user to select from various
alternatives for these parameters, knowing the correct selection
may be problematic. Further, the prediction of multicomponent
mass transfer coeffcients is of questionable accuracy. These facts
prompt the recommendation that columns modeled with the mass
transfer approach be checked against an ideal stage model with
an expected effciency until suffcient experience with the particular
application is achieved.

CONCLUSIONS
When performed properly, both the ideal stage and mass
transfer approach as implemented in ProMax 4.0 can calculate ac-
curate results for a variety of separation processes with and without
reactions. The ideal stage approach can be used initially to deter-
mine appropriate equipment sizes and operating conditions. More
detailed studies can be performed using the ideal stage approach,
the mass transfer approach, or both. Although signifcant operat-
ing experience provides reasonable effciency estimates for most
processes, the empiricism in scaling up from ideal to real stages or
ideal stages to real bed lengths can be a disadvantage when ac-
curate overall effciencies or HETPs are unavailable.
The mass transfer approach requires more equipment
design details and does not make use of overall effciencies or
HETPs. More detailed composition and temperature profles are
produced by this method at the expense of longer calculation time.
The mass transfer approach may appear more predictive in nature,
but is not necessarily more accurate. It relies on more parameters
that must be estimated, as both require thermodynamic data to
model equilibriumfor the tray composition in the ideal stage
approach and for the interface composition in the mass transfer
approach. Many of these mass transfer parameters are of limited
accuracy but also may be of limited sensitivity in some systems.
Both techniques are useful tools in process simulation.
For more information about this study, see the full article at
www.bre.com/support/technical-articles.aspx.
ProMax process simulaton sofware by Bryan Research & Engineering, Inc.
EngineeringSolutonsfortheOil,Gas,Refning&ChemicalIndustries
sales@bre.com
www.bre.com
979 776-5220
US 800 776-5220
bre.indd 1 12/09/2013 11:21
Meeting tighter NOx emissions rules
R
equirements for reducing air
pollution emissions have been
evolving over the past couple
of decades and today are an intri-
cate mix of limits, targets and caps.
In many parts of the world, indus-
tries emitting pollutants must not
only comply with rigid emission
limits, but also need to provide
emissions data to numerous differ-
ent agencies and bodies in order to
comply with disparate legislative
formats and reporting systems at
regional, national and international
level and legislation is going to get
increasingly stringent. The global
community is working to improve
cooperation between emitting
sources, monitoring systems and
the legislation they support in
order to reduce the number of seri-
ous pollutants being released into
the air, soil and water to help miti-
gate the negative impacts on human
health and adverse affects on the
environment in coming years.
In 2007, the EU, acknowledging
that existing legislation on industrial
pollution was complex, sometimes
inconsistent and not far reaching
enough, adopted new legislation to
strengthen the provisions already in
force and reduce further industrial
emissions. The new directive aims
to improve the uptake and imple-
mentation of Best Available
Technologies (BAT), which maxim-
ise the use of technology in plant
design, build and operation in order
to drive down emissions. Critically,
it also tightens current minimum
emission limit values for large
combustion plants and introduces
minimum provisions on environ-
mental inspections of installations
and incentives for the development
A low temperature oxidation technology uses ozone to remove very low levels of
nitrogen oxide from renery gases
STEPHEN HARRISON, NARESH SUCHAK and FRANK FITCH
Linde Gases
and employment of environmentally
friendly technologies.
Nitrogen oxides, mainly consist-
ing of nitric oxide (NO) and
nitrogen dioxide (NO
2
), and
commonly referred to as NOx, is
among one of the major criteria
pollutants listed under the Clean
Air Act by the US Environmental
Protection Agency and is also
monitored by several other coun-
tries, notably China. NOx deriving
from stationary combustion sources
makes a major contribution to total
emissions and proper control of
NOx emissions could result in
signifcant environmental benefts,
especially when combusting oil and
coal.
In most cases, NOx is a product
of the combustion of fossil fuels or
industrial processes and contributes
to the formation of smog, acid rain
and other health hazards. NOx
undergoes chemical and photo-
chemical reactions in the
atmosphere and reacts with volatile
organic compounds (VOCs) in the
presence of sunlight to form smog
and ground level ozone. The effect
is very signifcant and harmful in
the summer months to children and
people with lung diseases such as
asthma, causing damage to lung
tissue and a reduction in lung func-
tion. NOx also reacts with
ammonia, moisture, and other
compounds to form small particles
capable of penetrating deeply into
sensitive parts of the lungs and
causing or worsening respiratory
diseases such as emphysema and
bronchitis, also aggravating existing
heart and lung disease. In addition,
NOx interacts with oxygen in the
atmosphere to produce the atmos-
pheric pollutant low level (or
tropospheric) ozone, which impacts
on human health. NOx emissions
also contribute to the formation of
damaging acid rain, eutrophication
and oxygen depletion degrading
water quality and harming wildlife
and plant life.
High levels of industrial activity
and increasing vehicle emissions
have elevated ambient NOx and
ground level ozone levels in several
critical geographies, particularly in
the US, Europe and China. In
response, environmental authorities
are tightening their regulations
governing NOx emission manage-
ment and applying sector specifc
parameters. However, control of
NOx from each source is a complex
process affected by factors that
include the amount and distribu-
tion of air in the combustion
process, temperature, unit load and
burner design.
The largest output of NOx emis-
sions in stationary sources is from
coal fred boilers, especially those
in the power generation segment.
Other major sources of NOx emis-
sions include kilns and furnaces
Proper control of
NOx emissions could
result in signicant
environmental
benets, especially
when combusting oil
and coal
linde.indd 1 09/06/2014 14:27
post-combustion and the most
commonly specied technique for
the removal of high levels of NOx
is selective catalytic reduction
(SCR), a technology designed to
facilitate NOx reduction reactions
in an oxidising atmosphere. It is
called selective because it reduces
levels of NOx using ammonia as a
reductant within a catalyst system.
The reducing agent reacts with
NOx to convert the pollutants into
nitrogen and water. SCR has been
adopted effectively in lowering
NOx emissions from gas red clean
ue gas streams. However, in treat-
ing dirty gas streams from
industrial processes involving kilns,
furnaces and combusting coal or oil
with SCR possess a risk of the cata-
lyst being compromised by
chemical poisons in the ue gas, or
blinded by the dust and particulate
matter also resident in the ue gas.
SCR must be integrated into a
high temperature region of the
process, so if it is not included in
the original design of the furnace,
later installation will require a
major rework of the process. The
intermediate technology selective
non-catalytic reduction (SNCR) is
also applicable in the high tempera-
ture regions impacting the process.
SNCR does not make use of a cata-
lyst, but requires a highly dened
temperature region to provide a
reaction with ammonia. This tech-
nology is capable of achieving a
50-60% NOx removal.
The effective temperature for
reduction in NOx through a SCR
catalyst is in the range 200-400C
and for SNCR to be effective,
ammonia injection and reduction
need to be in the range of
900-1100C. Additionally, retrot-
ting NOx reduction solutions such
as SCR or SNCR can often be
disruptive to the industrial process
and can have negative implications
with respect to operations and
costs.
Lindes LoTOx technology, which
stands for low temperature oxida-
tion, has been specically
developed for the control of NOx
emissions. LoTOx, which works on
dirty exhaust gas streams to
oxidise and then capture NOx, is a
selective, low temperature oxida-
from the cement, lime, ferrous and
non-ferrous metals industries.
However, petrochemical processes
also produce large amounts of NOx
and other airborne pollutants,
primarily originating from utility
boilers, cogeneration units, process
heaters, steam methane reformers,
ethylene cracking furnaces and
uid catalytic cracking (FCC)
regeneration units. Consequently,
the NOx emission levels specied
for this sector are among the lowest
in industry, highlighting the need
for efcient NOx removal.
While some industry sectors
claim there is no effective means to
remove NOx from their emissions
or rather, no cost effective means to
sustain the economic viability of
such an operation there is a spec-
trum of conventional and more
recently introduced technologies
available in the market to address
this important obligation.
A common approach to
controlling NOx emissions is to
modify the basic combustion
process within the furnace. By using
oxygen instead of air in the produc-
tion process, which removes the
nitrogen ballast, energy efciency is
not only increased, but one of the
most important benets is the very
signicant reduction of both direct
and indirect greenhouse gas emis-
sions, including CO
2
and NOx. CO
2

emissions can be reduced by up to
50% and, for NOx, emissions levels
of below 50 mg/MJ can be reached.
However, since emissions vary
widely according to changes in
temperature and air/fuel mixing,
modications to the combustion
process impact not only the emis-
sions, but very frequently also the
efciency and operability of the
furnace. This renders NOx control a
technically challenging undertaking
that calls for understanding of
complex issues around combustion
chemistry and plant operations, as
well as the economic issues related
to plant fuel consumption and
maintenance. NOx reduction by
combustion modication is limited,
typically in the 30% to 50% range
and must be implemented where it
is effective and applicable without
signicant de-rating of the combus-
tion furnace. Alternatively,
replacement of the existing combus-
tion equipment can be done but
this is obviously capital intensive.
NOx can also be treated
Combustion or
other NOx gas
emissions source
Raw NOx,
NO and NO
2
Ozone
NOx, SOx, HCI,
particulates and
heavy metals
Oxygen/ozone
supply
New or existing
scrubber
Analysers and
controls
Figure 1 The LoTOx process is applied at a controlled temperature zone within the
scrubbing system
LoTOx is a versatile
NOx removal process
but is ideally suited
when the level of
removal required is
greater than 80%
linde.indd 2 09/06/2014 14:27
tion technology that uses ozone to
oxidise NOx to water soluble and
very reactive nitric pentoxide
(N
2
O
5
). The process is applied at a
controlled temperature zone within
the scrubbing system (see Figure 1).
It does not require additional
scrubbers but can leverage those
already installed to remove other
pollutants such as SOx. Dirty gas
means gas with other targeted
pollutants, typically particulate
matters, SOx and other acid gases.
Irrespective of NOx removal, for
control of these pollutants, air
pollution control devices such as
wet and dry scrubbers are required
to remove those pollutants.
Integrating the LoTOx process
within such air pollution control
devices is relatively simple and acts
as a multi-pollutant removal
system.
Inside a wet or dry scrubber,
N
2
O
5
forms nitric acid that is subse-
quently scrubbed by aqueous spray
and neutralised by the alkali
reagent. The conversion of higher
oxides of nitrogen into the aqueous
phase in the scrubber is rapid and
irreversible, allowing an almost
complete removal of NOx, in the
region of 90-95% even as high as
98% from fue gases. The low
operating temperature allows stable
and consistent control, regardless of
variation in fow, load or NOx
content, and acid gases or particu-
lates have no adverse effect on the
performance of the process.
LoTOx is a versatile NOx removal
process but is ideally suited when
the level of removal required is
greater than 80% or where stack
emissions must be below 20 ppm.
The process offers inherent fexibil-
ity in NOx removal. In most gases,
simply increasing the amount of
ozone injection may meet increas-
ingly stringent regulations or
limiting tiered NOx emissions.
The benefts of this technology
include increased capacity, greater
fexibility in the choice of feeds,
increased conversion rates and
reduced emissions. Since the tech-
nology is a post-combustion
solution that treats the fue gas at
the end of the process, it does not
interfere with the process in any
way. The system does not utilise a
fxed catalyst bed and does not
impact system hydraulics, making
it robust and reliable, capable of
operating without maintenance for
periods of two to three years
between refnery shutdowns. It is
Dry FGD
Very reactive Very soluble
O
2
O
3
N
2
O
5
NOx
Capture and
removal
Wet FGD
Capture and
removal
Ozone generation
O
2
O
3
Mixing and oxidation
NOx + O
3
N
2
O
5
Figure 2 LoTOx uses ozone to oxidise NOx
to water soluble nitric pentoxide (N
2
O
5
)
OGT 128 ProTreat Half Page Horizontal PTQ Q3 2014.indd 1 6/4/14 9:24 AM
linde.indd 3 09/06/2014 14:27
required during start-up and upset
conditions. Once a record of
consistent performance has been
established, air emissions from
stacks should be visually monitored
for opacity at least once every eight
hours. Annual emissions monitor-
ing of combustion sources should
be carried out for SOx, NOx and
organics, with fuel sulphur content
and excess oxygen maintained at
acceptable levels during normal
operations.
Monitoring data should be
analysed and reviewed at regular
intervals and compared with the
operating standards, so that any
necessary corrective actions can be
taken in a timely manner.
Monitoring records should be kept
in an acceptable format for submis-
sion to the responsible authorities
and relevant parties, as required.
The automation enabled by tech-
nological advances favours
continuous emission monitoring
systems (CEMS), while emission
measurement instruments are
becoming smaller and less expen-
sive. This has heralded the way for
gas phase measurement and gas
phase calibration from gas cylin-
ders, with a move away from
manual and people-intensive wet
chemistry measurement.
Government institutes used to
carry out much of the emissions
measurement themselves, but have
now outsourced this function to a
large extent. There is a distinct
trend of moving from control to
compliance. Metrology has been
commercialised and the establish-
ment of primary calibration
standards has moved from the
government domain into that of the
major oil and gas companies. Such
a development has been enabled by
improved international standards
and by global recognition of these
standards, such as ISO Guide 34
and the emerging ISO 17025.
However, many pockets of local,
national and regional requirements
are still in place, for instance the
GBW standards in China and the
US-centric EPA.
Technology for monitoring and
detection
With the growing importance and
by the process of reducing NOx.
This marginally increases the
amount of caustic solution used by
the scrubber for removing particu-
lates and sulphur oxides.
A further, unexplored beneft of
recent interest is the LoTOx
systems ability to reduce mercury
emissions as part of a complete
multi-pollutant control solution.
More recently, Lindes engineer-
ing division has developed a new
NOx removal technology for use
with carbon sequestration and stor-
age, called Liconox.
Monitoring, detection and reporting
Environmental concerns have come
a long way since the 1970s, when
acid rain caused by sulphur dioxide
and nitrogen oxides prompted
power stations to install sulphur
dioxide scrubbers and SCRs for
nitrogen oxide reduction and motor
vehicles were ftted with catalysers.
Emissions measurement was
carried out for compliance, result-
ing in fnes for those who
overstepped the mark. Today,
however, as legislation and action
plans grow in number and strin-
gency, the importance of
monitoring and quantifying emis-
sion pollutants in an accurate and
transparent manner is becoming a
priority. Day-to-day emissions
measurement has serious fnancial
implications and compliance to
measurement is absolutely critical.
Real-time and on-line reporting
systems will be the aim for most
large sources.
Frequent sampling may be
also able to manage unit upsets
without impacting overall reliabil-
ity and mechanical availability.
The ozone required is produced
from oxygen on site in response to
the amount of NOx present in the
fue gas generated by the combus-
tion process and the fnal NOx
emission required (see Figure 2).
Some 40 LoTOx installations have
been commissioned to date 30 of
them in petroleum refneries
through Lindes LoTOx licensee for
refnery applications, DuPont Belco.
Installations are almost equally
divided between the US and, nota-
bly, China, which is advancing its
NOx control regulations due to
heavy industrialisation and chal-
lenging air quality issues. There are
two more installations in progress,
one in Romania and another in
Thailand, indicating stricter envi-
ronmental regulations on the
horizon.
LoTOx is attracting a reputation
for being able to bypass some of
the problems associated with the
dirty fue gases that impact the
effective operation of SCR. It is
suitable for both new and retroft
applications and is the only post
combustion technology of its kind
in industry today, set apart by its
method of treating fue gases with
ozone and the fact that most of the
other oxidation and reduction
processes take place at high
temperatures.
To control costs, LoTOx is
frequently recommended in combi-
nation with a lower end
combustion modifcation technol-
ogy to remove a certain level of
NOx, before it takes out the
remaining NOx to a low level.
Operating costs derive from the
power, oxygen and cooling water
associated with ozone generation
and each of these costs is directly
proportional to the levels of NOx
being treated. In comparison to the
ammonia storage and handling
issues associated with SCR or
SNCR, LoTOx produces ozone on
demand by passing oxygen through
a conventional industrial ozone
generator, as required and on site.
The other operating cost relates to
the addition of caustic solution to
neutralise the nitric acid produced
With the growing
importance and
prioritisation
of monitoring
and quantifying
emissions, accuracy
and reliability
in measurement
calibration is critical
linde.indd 4 09/06/2014 14:27
Stephen Harrison leads Lindes global Specialty
Gases & Specialty Equipment business from
Munich, Germany. He is a British Chartered
Engineer (MIChemE) with a career in industrial
gases spanning 20 years, 10 of which have been
focused in the area of specialty gases. He has
worked in an international capacity for both
Linde Gases and previously BOC, and holds a
masters degree in chemical engineering from
Imperial College, London.
Naresh Suchak is Senior Project Manager with
Linde Gases Division. For the past 20 years
he has worked in technology development
from concept to commercialistion of
innovative processes in the elds of chemical
manufacturing and pollution control. He
has been granted seven US patents and has
been responsible for the development and
commercial implementation of LoTOx NOx
control technology. He holds a MS and PhD in
chemical engineering from Bombay University.
Frank Fitch is Senior Project Manager with
Linde Gases Division and is the product lifecycle
manager for the Linde NOx control technology
LoTOx. For more than 30 years he has worked
in materials/technology development for the
chemical industry. He has been granted 34 US
patents, is the author of 36 papers, and holds
a BSc and PhD in chemistry from Imperial
College, London.
ured. In the US, the EPA has
defned shelf lives for protocol
gases as between six to 36 months
depending on the gas and concen-
tration and similar shelf life
standards exist in the ISO frame-
work for reference materials.
Notwithstanding these interna-
tional protocols, Lindes range of
HiQ 60 specialty gas products have
an extended fve-year shelf life a
signifcant advance in the supply of
calibration gases. Previously, gas
suppliers offered product expira-
tion guarantees generally limited to
36 months, with many products
available with only 12 or 24 months
of shelf life. Gas products with
these more limited shelf lives can
impact measurement accuracy, as
gas stability in terms of consistency
and quality can change over time.
Where consistency or purity of the
gas has been compromised, this can
result in expensive system recali-
bration procedures, additional
cylinder changeovers and wasted
human resource time.
prioritisation of monitoring and
quantifying emissions, accuracy
and reliability in measurement cali-
bration is critical. The demand for
stable, accurate measurement is the
cornerstone of emissions analysis.
However, calibration standards for
low level reactive mixtures, typi-
cally those with levels below 5
ppm, can prove to be unstable over
time and can result in incorrect
measurements, lost productivity
and with emissions monitoring
potential legislative fnes.
To keep pace with increasingly
stringent legislative requirements,
calibration gas mixtures are now
being delivered with state-of-the-art
packaging technology so that they
even exceed the demanding
requirements for consistency and
stability down to part-per-billion
levels.
With any gas used for calibration
purposes, the most important
requirement is that it can accurately
and repeatedly report values of the
relevant instrument being meas-
together with spent catalyst. In the
roaster, the temperature and rate of
air injection are adjusted in order to
remove sulphur (as sulphur diox-
ide), to burn hydrocarbons, and to
oxidise the metallic elements.
A stream of compressed air sends
the gas into a post-combustion
chamber which treats it for oxides
of carbon. The fumes pass through
three levels of ltration; the gas
rejected is devoid of particles and
does not exceed 50 mg/m
3
/hr of
sulphur dioxide. These three stages
of ltration are performed by sieves
with different cut-off points: the
rst stage retains sublimated metal
particles, the second and third
stages treat the gas. Dust captured
in the rst stage of ltration is
treated at the hydrometallurgy
stage with the roasted calcine. The
tungsten or just tungsten. In the
rst case (including the presence of
molybdenum), the recycling
process is completed by a further
step involving the removal of phos-
phorus and arsenic.
Recovery of both molybdenum
and tungsten from spent catalysts
involves a combination of pyromet-
allurgical and hydrometallurgical
processes (see Figure 3).

The roasting step
First of all, a new roaster that began
operations at Valdi in 2011 is used
Table 1
Composition of NiW(Mo) spent catalysts
Characteristics Wt%
Moisture 3.5
Oil 13
C 14.8
S 4.9
W 7.8
Mo 2.5
Ni 2.9
P 0.5
As 0.02
Fe 0.39
Al
2
O
3
26.3
The average composition of NiW
catalysts received in 2013
CaWO
4
AS + P
Spent NiW
catalysts
Roasting
Roasted
catalysts
Filtration Filtration
Calcination
Purification
Precipitation
Pyro-
metallurgical
process
Hydrometallurgical process
Filtration
Leaching
Product
Slag
Alloy
Garbage
Dusts
Product
Filtration
Liquid
Solids
Gas
<50mgSO
2
/m
3
/hr
Figure 3 Recycling process for spent nickel-tungsten catalysts
grip-type tube fttings will not back
off with thermal cycling or vibra-
tion, unlike the threaded fttings
used with carbon steel.
The third objective maintaining
temperature within a certain range
is achieved by heating the
impulse lines. You can insulate your
impulse lines manually feld
tracing or purchase tubing that
has been insulated in the factory
and encased in a polymeric jacket.
Pre-insulated bundled tubing comes
ready to install in coiled lengths. It
can be heated with steam or left
unheated, as the application
requires. It is important with pre-in-
sulated tubing bundles to follow the
manufacturers instructions for seal-
ing the insulation when splicing into
or cutting into the pre-insulated
tubing bundle.
Manifold
The manifold consists of a set of
valves whose bodies are machined
from a single block of metal,
usually stainless steel. The mani-
fold mounts to the side of the
transmitter and serves a critical
function, enabling calibration or
service of the transmitter.
Quality is especially important in
a manifold. During calibration or
normal operation, at least one of
the valves in the manifold is in the
off position. If the shut-off is less
than complete, the result is an inac-
curate reading from the transmitter.
For example, when calibrating a
transmitter in a standard differen-
tial pressure setup, the technician
closes the two isolation valves and
opens the equalisation valve (see
Figure 4). This procedure results in
the transmitter being zeroed out
for calibration. If one of the two
isolation valves is leaking, however,
the calibration will be unsuccessful
and all subsequent readings will be
inaccurate.
Further, after calibration, the
operator will close the equalisation
valve and open the two isolation
valves, placing the transmitter back
in service. If the equalisation valve
does not achieve a positive shut-off,
high pressure will leak across the
seat to the low pressure side,
rendering the differential reading
inaccurate.
Why would these valves leak?
One cause is debris, either scaling
HP LP
To
transmitter
To
transmitter
Isolation
valves
Equalisation
valve
Figure 4 A manifold, consisting of three
needle valves, enables the technician to
isolate and calibrate the transmitter in
the eld
yield selectivity, in particular the
propylene yield. The higher the
hydrogen content, the higher the
propylene yield.
For the types of crude oil that
have been considered here, the
typical CCR content of atmospheric
residues is about 12-14 wt%, and
metals are 80-90 wtppm. Thus,
pretreatment of the feed is required.
The ARDS unit is a specially
designed hydrotreater that pretreats
the feed to the RFCC unit to reduce
contaminants including sulphur,
nitrogen, organometallic metals and
CCR. Additionally, it increases the
hydrogen content of the atmos-
pheric residue, thus improving the
crackability and selectivity of the
residue. For a typical ARDS HDS
rate of 90%, the CCR reduction is
about 65-70% and the metals reduc-
tion (HDM rate) is about 85-90
wt%. The HDT RFCC feed will
then have a CCR content of less
than 6 wt% and metals content of
less than 10 wtppm.
Due to the feed rate, nature of the
feed, and processing objectives, a
relatively high pressure and low
space velocity design is required
compared to other hydroprocessing
technologies. Even so, the cycle
length of the ARDS unit is typically
only one year. For the case evalu-
ated and ARDS operating
objectives, at least two reactor
trains, each with three to fve very
large and thick-walled reactors, will
be required. Consequently, both the
initial investment and on-going
catalyst replacement cost will be
much higher than for most hydro-
processing units.
The other key features of this
confguration to maximise the
production of petrochemicals are:
Process straight-run light naph-
tha along with light catalytic
naphtha (LCN) in the steam cracker
Process heavy straight-run naph-
tha in a catalytic reforming unit
(CRU) to produce reformate
Process heavy catalytic naphtha
(HCN), pygas and reformate
through the aromatics complex to
produce paraxylene and benzene
The C
4
s with relatively high
olefns content are either sold or
recycled to the second riser of the
FCC (directly or through oligomeri-
sation) to maximise propylene
production
Products from the RFCC unit and
steam cracker are combined in a
single light ends recovery section to
produce ethylene and propylene,
minimising the capital investment
Hydrogen from the CRU and
steam cracker is supplemented by
further hydrogen production from
steam reforming to be used in the
hydrotreaters.
Complex conguration with
HCU + VRDS + RFCC
The intention of this refnery confg-
uration is to increase the production
of middle distillate at the expense of
petrochemicals. Relative to the frst
confguration of ARDS + RFCC, the
LVGO fraction of the crude is
routed to a VGO hydrocracker
(HCU) to shift the yields in the
desired direction. Figure 2 shows a
schematic of the refnery.
The key features of this refnery
confguration are:
A vacuum tower is installed to
produce a diesel-type cut to be
processed in the distillate hydro-
treater, a LVGO cut to be processed
in a two-stage, almost full-conver-
sion hydrocracker unit oriented
towards the production of middle
distillates
The HVGO is combined with
vacuum residue to be pretreated in
the vacuum residue desulphurisa-
tion (VRDS) unit before processing
it in the RFCC unit
Depending on the quality of the
combined vacuum residue and
HVGO feed to the VRDS unit, a
slip stream of vacuum residue
could be taken and blended with
diluents such as RFCC decanted oil
(DCO) and light cycle oil (LCO) to
produce some fuel oil. The VRDS
unit would then be able to reduce
the CCR to the levels required by
the RFCC feed, especially when the
CCR content of the feed to the
VRDS unit exceeds 24 wt%.
Complex conguration with
SDA + DCU + HCU + RFCC
The refnery confgurations illus-
trated above, where residue
hydrotreaters reduce the feed
Max Ovchinnikov is a Senior Research Chemist
with Criterion Catalysts and Technologies
based in Houston, Texas. He is primarily
engaged in the research and development of
catalysts for hydroprocessing applications and
has 12 years of experience in heterogeneous
catalysis and rening technologies. He has co-
authored over 20 technical publications and
holds a PhD degree in organic chemistry from
Iowa State University.
2 Dekkers C, Daane R, Oil & Gas J., 1999, 97,
145.
3 Puri B K, Irgolic K J, Environ. Geochem. Health,
1989, 11, 95.
4 Nielse B, Villadsen, Appl. Cat., 1984, 11, 123.
5 (a) Internal communication, Criterion
Catalysts & Technologies; (b) Merryeld R N,
Gardner L E, Parks G D, Catalyst Characterization
Science, ACS Symposium Series 1985, 1.
6 Bhan O K, Arsenic removal catalyst and
method for making same, US Patent 6759364.
requires increased process unit
capabilities in a number of refning
process units, particularity hydro-
processing assets. The magnitude
of impact, of course, depends on
the particular feed processed, the
inherent fexibility of the facilitys
operations and the ability to
offset this increased processing
requirement.
In making this move, proper
selection requires a good under-
standing and modelling of the
facility as well as a strong knowl-
edge of the sources and processing
requirements of the available
crudes. With the continued devel-
opment and increased availability
of such feeds, this knowledge needs
to be continuously updated to
ensure minimal operational
surprises. Reviewing TBP curves
and bulk properties of whole crude
or even the individual cut-point
ranges does not
necessarily characterise the feed
diffculty or indicate the full impact
on the individual processing units.
References
1 Henke K R, Arsenic, Environmental Chemistry,
Health Threats and Waste Treatment, Wiley,
2009, 186.
30
50
60
40
20
10
N
o
r
m
a
l
i
s
e
d

H
D
S

t
e
m
p
e
r
a
t
u
r
e
,

F
Base
Alternative feed Current feed
Temp. 1 Temp. 2 Temp. 3 Temp. 3 Temp. 2 Temp. 1
check-
back
Temp. 1
Catalyst age
DN-3651 alternative feed DN-3551 alternative feed
DN-3651 current GO DN-3551 current GO
Figure 15 DN-3651 and DN-3551 normalised HDS temperature
increased water in the sulphur
plant feed and thus more condensa-
tion in the sulphur plant feed NH
3

gas knock-out drum (and thus
water that has to be recycled back
to the sour water stripper).
The design shown in Figure 2
was common in the 1960s.
However, it also suffers from the
same heat balance drawbacks and
needless complications as seen in
Figure 1. In other words, a lot of
equipment is added to generate
reux when no fractionation is
required between the feed and
overhead product. Again, the only
purpose of the tower is to strip out
the NH
3
and the H
2
S.

Correct stripper design
In 1969, while working for the now
vanished Amoco International Oil
(1)
(8)
(15)
Sour
water
feed
90F
Low NH
3
water
to desalters
Steam
250F
E-1
P-1
13 PSIG
Ammonia gas
to sulphur plant
190F
Medium content
NH
3
water to
hydrotreaters
Figure 4 Two-stage sour water stripper design without feed preheat
Company in the UK, I designed a
sour water stripper that eliminated
the unnecessary features of the unit
shown in Figure 2.
Figure 3 shows the essentials of a
correct sour water stripper design.
Feed is brought in at ambient
conditions (70-100F, 21-38C) from
the sour water feed tank. To heat
the feed from 90F (32C) to 250F
(120C) requires about 16 wt%
steam ow, or about 1.3-1.4lb of
steam per gallon of stripper
bottoms, which is close to a typical
design stripping steam ratio for
sour water strippers. The E-1 feed
preheater, reux pump (P-2) and
the reux cooler (E-2) shown in
Figure 2 are all eliminated. How,
then, does one know that the
design shown in Figure 3 will
work? Because it was built this way
(at the Amoco renery in Milford
Haven, Wales, UK) in 1970, where
it worked just as well as the
conventional design shown in
Figure 2.

Two-stage sour water stripper
Figure 4 shows a sour water strip-
per with a side draw-off. The partly
stripped sour water is extracted
from tray 8 and directed to the
hydrotreaters for use as make-up
water in the salt (NH
4
HS) removal
step of the reactor efuent.
Completely stripped water from
the sour water stripper bottoms is
sent to the crude desalter. While
communicate where the module
will be installed on the plot plan.
Connections between the modules
are designed to be similar in confg-
uration so that construction is
relatively straightforward. Ventech
estimates that, with modularisation,
approximately 70% of a project is
already complete even before the
modules are shipped from their
facility. This greatly decreases feld
construction time to deliver an
operational facility (see Figure 1).
These methods also facilitate easy
disassembly and relocation, if
necessary, at some point in the
future. For example, a remotely
located gas processing facility could
be easily taken apart and moved to
a new natural gas source if an exist-
ing supply was depleted in its
current location.
Applying modularisation to refn-
ery construction has advantages
with regard to productivity, prod-
uct quality and ensuring the safety
of construction personnel. Since the
modules are built in a well-lit,
climate-controlled environment,
work can continue around the clock
regardless of weather conditions,
for greater productivity and easier
quality control. Since module height
is restricted, safety is enhanced, as
workers build at limited heights
within the fabrication facility.
Modularising GTL
The same advantages of modular
construction of refneries are being
applied to the construction of
distributed GTL plants. The GTL
process involves two operations: the
conversion of natural gas to a
mixture of carbon monoxide (CO)
and hydrogen (H
2
), known as
syngas, followed by a Fischer-
Tropsch (FT) process to convert the
syngas into paraffnic hydrocarbons
that can be further refned to
produce a wide range of
hydrocarbon-based products, includ-
ing clean-burning, sulphur-free
diesel and jet fuel. Speciality prod-
ucts including food-grade waxes,
solvents and lubricants can also be
produced from the paraffnic
hydrocarbons.
Large, commercial-scale GTL
plants, including the Sasol Oryx and
the Shell Pearl plants (both located
in Qatar), have been built at enor-
mous capital cost. The Oryx plant,
designed for production levels of
34 000 b/d, cost around $1.5 billion
to build. The Shell Pearl plant, with
an ultimate design capacity of 140
000 b/d of GTL products and 120
b/d of natural gas liquids, cost
around $18-19 billion. Conventional
GTL plant designs rely on econo-
mies of scale to drive positive
fnancial returns and are viable only
where there are large supplies of
low-priced natural gas.
However, another option being
developed smaller-sized and
distributed GTL plants shows
promise for deriving value from
smaller accumulations of unconven-
tional gas that would otherwise be
left underground, such as shale gas,
tight gas, coal bed methane and
stranded gas (gas felds located too
far from existing pipeline infra-
structure). A small, modularised
GTL plant has the fexibility to be
installed close to the trapped
resource and then used to process
that resource locally. Associated gas
(gas produced along with oil) is
another area of opportunity for
modularised GTL plants. This gas
is typically disposed of either by re-
injection, at considerable expense,
back into the reservoir or by the
wasteful and environmentally
damaging practice of faring, which
is subject to increasing regulation.
Modularised GTL plants enable this
otherwise wasted gas to be
converted into additional revenue.
In the larger economic picture, a
modular GTL capability can be the
key factor that enables the construc-
tion of upstream projects that
would otherwise be cancelled
because of poor results derived
from economic models. For exam-
ple, some shale gas discoveries are
being hampered by high develop-
ment costs, which result in marginal
economics due to gas prices that
are often low. These projects can be
enhanced by converting the gas to
higher-value clean fuels produced
in the GTL process.
ITW
Innovative
Technologies
Worldwide
ITW is a fast growing Company, marketing and implementing unique and patented Production Units Online
Cleaning, Tank Cleaning, Decontamination and Reclamation technologies, along with Specialty Chemicals.
Given the considerable success, ITW is expanding its markets and activities and is looking for experienced
professionals worldwide. The candidates should have minimum a 5 years experience in at least one of these
fields:
refining/petrochemicals process specialty chemicals sales
refining/petrochemicals process technology, operations, maintenance, turnaround
and should be willing to travel nationwide and worldwide, along with being prone to hard working and sales.
Having a technical degree and good market knowledge is also required.
The available positions will cover: technical sales, implementation of ITW technologies on the field,
sales and operations management.
Interesting compensation plans will be given along with serious career possibilities. Please contact:
ITW S.r.l. S.Cusumano 96011 Augusta - Italy jobs@itwtechnologies.com www.itwtechnologies.com
HIRING EXPERIENCED PROFESSIONALS WORLDWIDE
velocys.indd 2 10/12/12 14:27:56
lieberman.indd 3 08/03/2013 16:02
cri.indd 10 10/06/2013 16:38
f wheeler.indd 3 12/09/2013 13:40
from corrosion (as mentioned
earlier) or other debris, such as
burrs. Burrs are a byproduct of the
machining process during manufac-
turing. A critical step during
manufacturing and installation
should be the removal of all burrs
from all wetted surfaces. Otherwise,
they can dislodge when the mani-
fold is in service and catch in or
scratch the valve stem or seat,
preventing a positive shut-off. Burrs
may also be an issue in monofanges
and other globe pattern needle
valves.
Seat seals in needle valves
Another reason why valves leak is
poor design. Most needle valves
employ a metal to metal seal. The
metal tip of the stem moves down-
ward to seal against a metal seat of
matching shape. The tip of the stem
may be shaped like a ball or a vee.
In either case, it is important that
the tip does not rotate with the
stem. If it does, it may grind into
the seat, scoring it and creating a
pathway for leakage.
There are two main design
approaches to achieving a non-
rotating stem tip. In the case of a
vee tip, there may be a knuckle
joint that enables the upper stem to
turn while the lower stem remains
stationary, except for axial (up and
down) movement.
In the case of a ball tip, a ball
foats in the stem tip, like in a ball-
point pen. Among ball tips, there
swagelok.indd 3 11/12/2013 14:52
to produce calcine, which provides
feedstock for the following step.
This roaster is specic; it was
developed by Valdi to deliver
highly effective desulphurisation
and decarbonation, good produc-
tivity and very low cost of treat-
ment. It was designed to be capable
of treating all categories of spent
catalyst. The conditions of roasting
are controlled and the gas treat-
ment is also closely monitored.
Screening at the head of the furnace
and at its output enables the extrac-
tion of ceramic materials found
cat valdi.indd 2 12/03/2014 12:07
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turbo machinery.indd 1 09/06/2014 15:51
Cloud point and hydrotreating
relationships
A
s the distillate markets allow
for increased distribution
worldwide, refners need to
be more aware of the additional
product specifcations that can be
present at the various locations.
One product property that is diff-
cult to modify with general
hydrotreating is the ability to
improve (lower) the cloud point
and cold flter plugging point of the
diesel. Cold fow properties are
determined by the wax or crystals
that are formed as the diesel is
cooled. The formation of these crys-
tals can plug flters and lead to
poor engine performance.
There are various approaches to
meeting cold fow targets, the
simplest of which is the blending of
lighter material (kerosene or jet)
into the fuel. Other options include
the use of additives, solvent dewax-
ing, or adding a separate
isomerisation reactor. All of these
options have disadvantages, includ-
ing high costs or yield losses.
Diluting with blending stocks, such
as kerosene, has the added compli-
cation that the blending stocks
must separately meet all of the
same requirements, such as
sulphur, of the fnished ultra low
sulphur diesel (ULSD) and could
require the blending stock to
undergo additional hydrotreating.
This also involves taking a higher
value fuel, degrading its value by
blending it into diesel, and will
have volume limits in order to stay
within distillation and fash point
specifcations for diesel fuel.
The ability to modify the cold
fow properties of the diesel in the
hydrotreater can have signifcant
and obvious economic advantages
There is a complex interaction between dewaxing and hydrotreating in ultra low
sulphur diesel applications
BRIAN WATKINS and MEREDITH LANSDOWN
ART
that the other options do not
provide. Use of a specialty catalyst
is required in order to do catalytic
or hydro-dewaxing (HDW) to
improve the cold fow product
properties within the ULSD hydro-
treater complex and to avoid
making changes to naphthenes or
iso-paraffns that already have
acceptable cold fow properties.
Understanding the cold fow
requirements frst is necessary to
create an individually tailored
process and avoid the pitfalls asso-
ciated with inappropriate quantities
of HDS catalyst such as yield losses
and not having the fexibility to
meet market demands. Figure 1
shows some simple reactions that
can effectively improve the cold
fow properties of the diesel prod-
uct. The resultant products contain
some olefnic material due to the
cracking mechanism and require
proper catalyst staging to achieve
process goals.
The typical process of dewaxing
utilises a ZSM-5 type catalyst. The
structure of ZSM-5 is such that only
straight chained hydrocarbon mole-
cules (normal paraffns or
n-paraffns) ft inside the cage
structure and are cracked into
smaller, lighter molecules. These
molecules have signifcantly lower
cloud and pour point characteris-
tics. Table 1 shows some of the
various n-parrafns present in a
C
+H
2
+
C-C-C-(C)
n
-C-C-C C-C-C-(C)
n
-C-C-C C-C=C + C-C-C=C + C-(C)
n
=C
H
2
+H
2
+
C-C-C-(C)
n
-C-C-C C-C-C-(C)
n
-C-C-C C-C=C + C-C-C=C + C-(C)
n
=C
H
2
+H
2
+
C-C-C-(C)
n
-C-C-C C-C-C-(C)
n
-C-C-C (C)
n-1
+ C-C=C + C-C-C=C
H
2
C
Figure 1 Mechanisms for dewaxing in a hydrotreater
Table 1
Boiling point, F Melting point, F
Dodecane C
12
421 15
Tetradecane C
14
489 43
Hexadecane (Cetane) C
16
549 65
Octadecane C
18
601 83
Eicosane C
20
649 98
Docosane C
22
695 112
Tetracosane C
24
736 129
Hexacosane C
26
774 134
Octacosane C
28
809 148
Melting and boiling points for n-parafns
art.indd 1 09/06/2014 14:39
simulate the feed rate over a dewax
bed in a hydrotreater. This work
was completed over the entire
range of temperatures for a ULSD
hydrotreater from start of run to
end of run. As the fgure shows,
there is very little change in prod-
uct values. The cloud point of the
product is improved only slightly
and this corresponds with a small
increase in bromine number which
is expected based on the reactions
listed in Figure 1. It is important to
note that it also shows that there is
very little sulphur and nitrogen
removal, and interestingly enough
there is actually a slight increase in
the volume percent for mono and
polyaromatic species in the prod-
uct, as indicated by a negative
percent change.
Decreasing the LHSV over the
dewax catalyst bed produces simi-
lar trends for the total and
polyaromatics conversion as well as
the HDN and HDS conversions (see
Figure 4). There are only a few
degrees change in cloud point and
almost no change in the bromine
number from the higher LHSV.
This clearly indicates that it is
important to provide some level of
hydrotreating in advance of the
HDW catalyst in order to be able to
utilise the zeolitic function. It is
also important to note that there
needs to be enough hydrotreating
catalyst available in the system in
order to meet the other product
specifcations such as sulphur and
aromatics since the HDW catalyst
provides no sulphur or nitrogen
removal.
One of the keys to successfully
combining a dewaxing catalyst
with an HDS system is an under-
standing of the tradeoffs between
dewaxing and HDS activity as the
amount of dewax catalyst is
changed. ART completed a number
of pilot plant tests with two differ-
ent amounts of dewax catalyst and
ARTs NDXi, a premium nickel
molybdenum catalyst for ULSD
applications. The pilot plant work
consisted of testing loadings of 10%
and 20% dewax.
The frst set of data examines the
ability of the system to meet 10
wppm sulphur in the diesel at both
low pressure (500 psi hydrogen
typical diesel boiling range. The
melting point is what impacts the
cloud point of the diesel if left
unconverted and, of course, the
higher the carbon content, the
higher the boiling point.
Due to the nature and structure
of the zeolite, choice of catalysts is
important as these structures can
easily be poisoned by nitrogen and
olefns present in the feed. Even in
high-pressure applications hydro-
treating has only a small impact on
product cloud point. Figure 2 shows
the effect of hydrotreating on cloud
point at 1400 psi hydrogen partial
pressure and with a feed containing
50% cracked material. This fgure
examines the cloud point improve-
ment across a wide range of
product sulphur and operating
temperatures. Even at high temper-
atures, well beyond that required to
produce ULSD, there is little
change in product cloud point.
Typically, the target market for
these products requires much more
than several degrees decrease in
cloud point below the value of the
feed. This suggests the use of HDW
in conjunction with the ULSD unit
is desirable.
As was mentioned previously, for
HDW catalyst to perform most eff-
ciently it requires some
hydrotreating frst since it is
susceptible to poisoning from the
organic sulphur and nitrogen pres-
ent in the feed. Figure 3 shows pilot
plant results from operating a
system using untreated feed over
dewax catalyst at 5.75 LHSV to
4
6
2
0
2
4
6
I
m
p
r
o
v
e
m
e
n
t
,

N
u
m
b
e
r

o
r

%
8
C
l
o
u
d

p
o
i
n
t

i
m
p
r
o
v
e
m
e
n
t
B
r
o
m
i
n
e

n
u
m
e
r
i
c
a
l

i
n
c
r
e
a
s
e
H
D
S

%
H
D
N

%
H
-
D
A

%
H
-
P
N
A

%
Figure 2 Hydrotreating and cloud point improvement
Figure 3 Dewax catalyst with untreated feedstock at high LHSV
6
10
9
8
7
5
4
3
2
1
C
l
o
u
d

p
o
i
n
t

i
m
p
r
o
v
e
m
e
n
t
,

F
0
1000
10000
100
10
P
r
o
d
u
c
t

s
u
l
p
h
u
r
,

w
p
p
m
1
550 600 650 700 750
WABT, F
Cloud point
Product sulphur
art.indd 2 09/06/2014 14:39
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fw.indd 1 11/06/2014 10:08
partial pressure) and at a higher
pressure (975 psi hydrogen pres-
sure). Figure 5 compares the two
systems and the base case is the
10% dewax system at low pressure.
This base condition is for producing
10 wppm product sulphur and is
the zero point on the temperature
axis. As expected, the higher pres-
sure system outperforms the low
pressure application by almost 30F.
At lower pressure, the difference
between the systems shows a 10F
higher temperature required with
the increased dewax catalyst
volume. The additional temperature
required to meet ULSD also needs
to be considered as this could mean
a debit of four to eight months in
cycle life if too much HDW catalyst
is loaded into the hydrotreater.
The ability to determine product
cloud point and how it is expected
to change over time is also impor-
tant. Similar to a hydrocracking
reactor, as the temperatures are
increased over the bed of HDW
catalyst, the ability to break the
n-paraffns increases. There is a
clear difference in the ability to
make a cloud point change based
on not only LHSV over the dewax
bed, but also the operating pressure
of the unit, much like that for
producing ULSD. In Figure 6, the
base case is again the 10% dewax
bed, and the zero point on the
chart is the point at which 10
ppm sulphur is produced. Moving
from left to right is changing
the WABT relative to the expected
SOR temperature for 10 wppm
sulphur.
Once the temperature is high
enough to begin dewaxing, the
kinetic response for converting the
n-paraffns is linear for both cata-
lyst systems. In these cases, with
the combination of hydrotreating
catalyst and dewax catalyst
(HDT-HDW), there is still a
requirement for the removal of
sulphur and nitrogen in order for
the system to perform well. At 20F
below the expected SOR tempera-
tures, the system is still capable of
decreasing the cloud point 5-7
numbers with the remaining
sulphur to the HDW catalyst
between 60-100 wppm. Increasing
the residence time over the HDW
catalyst has a signifcant impact on
the product cloud point. At the
temperature required to produce 10
ppm product sulphur the 20%
HDW case results in 8-10 degrees
5
10
0
5
C
l
o
u
d
/
b
r
o
m
i
n
e

i
m
p
r
o
v
e
m
e
n
t
,

n
u
m
b
e
r
10
C
l
o
u
d

p
o
i
n
t

i
m
p
r
o
v
e
m
e
n
t
B
r
o
m
i
n
e

n
u
m
e
r
i
c
a
l

i
n
c
r
e
a
s
e
H
D
S

%
H
D
N

%
H
-
D
A

%
H
-
P
N
A

%
more cloud point reduction
compared to the 10% HDW case.
Similar trends are observed when
the two catalyst systems are oper-
ated at higher pressure as shown in
0.1
0.01
0.001
P
r
o
d
u
c
t

s
u
l
p
h
u
r
,

w
t
%
0.0001
100 80 60 40 20 0 20 90 70 50 30 10 10 30
Change in temperature, F
10% HDW at HP
10% HDW at LP
20% HDW at LP
20% HDW at HP
Figure 4 Dewax catalyst with untreated feedstock at low LHSV
20
35
30
25
15
10
5
0
5

c
l
o
u
d

p
o
i
n
t
,

F
10
120 100 80 60 40 20 0 20 40 60
10% HDW
20% HDW
Figure 5 Changes in LHSV and pressure over the HDW catalyst system
Figure 6 HDW performance at low pressure
art.indd 3 09/06/2014 14:39
(121C) plus boiling material. There
is a clear importance to under-
standing the limits of placing too
much HDW catalyst into a hydro-
treater. Tailoring a system to be
able to control the activity of the
HDW catalyst is important so that
as EOR temperatures are reached,
the system is capable of being
controlled so that the yield losses
are within expectations. Note that
the high pressure system, regard-
less of the percent of HDW catalyst,
is able to maintain better liquid
yields benefting from an environ-
ment in the hydrotreater that
allows it to be highly selective in
what molecules it will work on.
This is also due to the ability of the
NiMo catalyst to saturate and
modify the hydrocarbon molecules
before it has a chance to be
converted by the HDW catalyst. In
the lower pressure system, ring
saturation does not occur as easily,
and the HDW catalyst is unable to
be as selective in which molecules
it is converting and results in a
greater liquid yield loss.
ARTs extensive pilot testing has
shown that there is a complex inter-
action between dewaxing and
hydrotreating in ULSD applica-
tions. There is a balance between
dewaxing activity and HDS activ-
ity, which needs to be understood
when designing a catalyst system.
Furthermore, the liquid yield needs
to be considered at both SOR and
EOR as this is highly dependent on
the amount of dewax catalyst in the
system. ARTs technical services
staff can work with refners in
order to provide the right catalyst
system tailored for maximum refn-
ery proft.
Brian Watkins is the Manager for ARTs
distillate pilot plants and Technical Service,
providing customer support and monitoring
globally. He has 19 years of experience in
hydroprocessing and has held a variety of
technical research and research management
positions at Grace and Advanced Rening
Technologies. He holds a BS degree in
chemistry from Western Illinois University in
Macomb Illinois. He has written and presented
numerous technical papers at the AFPM, the
CLG symposiums and various other locations
in North America.
compared to the 10% case at 10
ppm product sulphur.
As discussed earlier, the HDW
function is to break the n-paraffns
into smaller molecules in order
create less waxy molecules in the
fnished diesel product. This chain
breaking reaction, although some-
what selective, does have the
potential disadvantage that it can
convert diesel boiling range mate-
rial into naphtha or possibly lighter
materials. These materials, if the
refnery is able to tolerate and
utilise them, can be considered
quite valuable as well. One concern
is that if a signifcant volume of
diesel is converted to lighter prod-
ucts, the downstream equipment
might not be capable of handling
excess light materials.
Figure 8 compares the two load-
ings and the two pressures in terms
of liquid volume yields of 250F
Figure 7 for both 10% and 20%
HDW catalyst systems. The zero
point on the x-axis is where the
10% HDW system is able to
produce 10 ppm product sulphur.
The important item to note is that
the total cloud point improvement
is much greater in this application
than at lower pressures. In this
case, the 20% HDW case 20-25F of
cloud point improvement is
achieved at the temperature
required for 10 ppm sulphur.
Similar cloud point reduction was
achieved for the 20% HDW case at
10 ppm sulphur at low pressure,
but as shown in Figure 5 there is
20-30F difference in WABT for 10
ppm sulphur between low and
high pressure. The impact of resi-
dence time in the dewax bed is a
little larger at high pressure as well.
The 20% dewax system gives about
10-12F more cloud point reduction
95
110
120
100
90
85
L
i
q
u
i
d

y
i
e
l
d
,

v
o
l
%
80
70 50 30 10 10
cloud point, F
10% HDW high pressure
20% HDW high pressure
20% HDW low pressure
10% HDW low pressure
Figure 7 High pressure effects on HDW performance
Figure 8 Yield loss and HDW
60
100
90
110
80
70
50
40
30
20
10

c
l
o
u
d

p
o
i
n
t
,

F
0
10
100 80 60 40 20 0 20 40 60 80 100
10% HDW
20% HDW
art.indd 4 09/06/2014 14:55
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KALDAIR
j zink.indd 1 05/06/2014 19:39
Failure analysis of burner piping
T
ypically, huge damage is
involved when a fre occurs at
a refnery. However, the
industry keeps repeating the same
old mistakes with the same results:
leaks, fres and process upsets. In
order to help reduce the risks of
fatal or catastrophic incidents, this
article will describe failure analysis
investigations of burner piping. It
also discusses the corrosion assess-
ments and remedial measures such
as burner piping design criteria
including the recommendations in
specifcations. The focus is to learn
lessons from a prior incident, which
has been thoroughly investigated
and the results shared.
The incident whose causes are
analysed here occurred during the
start-up of a fred heater immedi-
ately after a turnaround. There was
a severe fre around the burner
piping which led to catastrophic
incidents involving neighbouring
equipment and huge unscheduled
downtime, mainly due to fre
damage of instrumentation cables.
Investigation after the fre was put
out showed that fexible hoses for
fuel gas were leaking. Just like most
refnery fres, the incident started
with a single problem of piping
leakage.
Specications of exible hose and
burner tip
A fexible hose is specially designed
to achieve several objectives in pipe-
work design. These include
avoidance of absorption or vibra-
tion, to operate effectively under
high pressure, and to adjust or
correct for misalignment. Flexible
hoses are generally used in burner
piping (fuel oil, atomising steam,
Investigation of the causes of a severe renery re leads to recommendations for
burner piping design to prevent such incidents
HYUNJIN YOON
SK Innovation
fuel gas), specially for the purpose
of positional adjustment of the
burner gun. They permit a very
economical installation against the
rigid piping in diffcult locations,
such as complicated burner piping.
It is easy to adjust the elevation or
orientation of a burner gun without
any mechanical modifcations to the
burner piping. The inside tube is
made from stainless steel strip, an
annularly corrugated tube manufac-
tured by continuously processing
the material on a high speed auto-
matic forming machine. The
geometry of the corrugations gives a
metal hose excellent hoop strength,
providing superior resistance to
collapse when exposed to high pres-
sure. After this processing step, it is
annealed in a furnace without
oxidation to completely eliminate
residual stresses. The outer covering
is made from stainless steel wire
braid which provides the necessary
protection from abrasion.
The burner typically combines oil
and gas fring and is designed to
operate both liquid and gas fuels.
The burner in question had been
operated with either oil or gas
during normal operation. The fuel
gas burner tip is made of a higher
temperature metal alloy casting,
because it is typically exposed
directly to heat (fame) in the radi-
ant box of the fred heaters. The
burner components, including the
burner tip, are designed in accord-
ance with the minimum
requirements shown in Table 13 of
API standard 560 (Fired Heaters for
General Refnery Service).
1
Table 1

Material Specication Remarks
Flexible hose AISI Type 304 Size 1/2in, 0.26mm thickness AISI Type 304
strip annularly corrugated tube
w/ AISI Type 304 wire braid See Fig. 1
Burner tip 300 series stainless steel Casting (1800C resistant) See Fig. 2
Specications for exible hose and burner tip
Table 1
Figure 1 Flexible hose: a stainless steel
construction of core bellows tube with
wire braid outside
Figure 2 Burner tip (new): the proper size
of drill bits used to make the ports (size
and orientation) in the tips as specied on
the burner drawing. The back side of a drill
bit is used for this purpose
sk.indd 1 09/06/2014 14:48
Material composition
The chemical composition of the
corrugated tube was reviewed
Metallurgical analysis of the
failed tube satisfed the ASTM
specifcation (AISI Type 304).
Visual inspection
Many small pin holes were
noticed on the surface of the
bottom of the corrugated tube
Liquid stagnation marks were
noticed at the bottom of the corru-
gated tube
Severe thinning and pitting were
noticed at the bottom area of the
internal surface of the corrugated
tube
The region near the pits, which
was thinned due to corrosion,
showed layers of deposits over the
surface
The failed portion of the tubes
contained pit holes, which had
perforated the tube, initiating from
the inside surface. The perforations
made holes of 1-2mm diameter,
surrounded by thin pits (see Figure
3)
The top part of the gas tip was
melted out and there was severe
coke build-up inside the gas tip
(see Figure 4)
The gas tip holes were melted,
plugged and eroded.
Energy-dispersive X-ray
spectroscopy
EDX is an analytical technique used
for the elemental analysis or chemi-
cal characterisation of a sample.
EDX studies were carried out to
determine the elemental composi-
tions of the matrix and the
deposits/scales on the failed tubes:
The EDX profle of the failed tube
(see Figure 6) shows iron, sulphur
and chromium in very high concen-
trations. Sulphur and chloride
cause corrosion, while Cr, Fe and
Ni were released as a result of
corrosion
The results of EDX studies indi-
cate that there is substantial
incorporation of sulphur comp-
ounds in the corrugated tube
during operation
Pitting corrosion is caused by the
effects of sulphur and chloride,
especially when they are present in
hydrous solution.
The detail specifcations of fexi-
ble hose and burner tip are
described in Table 1.
Morphology of damage
Many small pin holes were found in
the fexible hose bellows (corrugated
stainless steel tube), especially at the
bottom side (see Figure 3). Corrosion
is characterised by localised metal
losses in the form of pits.
Additionally, the top of the fuel
gas tip was melted and the gas tip
holes were severely plugged and
eroded (see Figure 4). Following a
review of the maintenance history,
it was found that the fuel gas
burner tips had been frequently
replaced during operation, as a
result of severe damage. In general,
as burner tips are custom designed
in number, size and angle of tip
holes (see Figure 2) for specifc
applications, the damaged burner
tip will result in undesired fame
characteristics (length, size and so
on), as well as poor performance in
operation, including environmental
problems (NOx emission levels).
The process details for the burner
are as follows:
Operating fuel gas pressure:
1.2-1.5 kg/cm
2
Operating fuel gas temperature:
30-60C
Fuel gas composition: H
2
69%,
C
2
H
6
10%, C
3
H
8
8%, others 13% (no
critical toxic components)
Operating scheme: designed to
operate either oil or gas (not to oper-
ate on both fuels simultaneously).

Probable reasons for failure
The failure of the bellows tube may
have occurred due to any one of, or
a combination of, the following:
Wrong material of construction:
an incorrect material (abnormal
composition) was selected
Improper installation: due to
kinking or excessive bending, the
corrugated tube was damaged
Corrosion: even if the correct
material is used, corrosive chemi-
cals could have been present
Process upset: a higher tempera-
ture or pressure than design
conditions.
A review of the material compo-
sition of the corrugated tube was
made in accordance with the ASTM
specifcation. Visual inspection was
carried out in order to identify the
main clues behind material failure.
Since the corrosion pits were found
on the corrugate tube, it was neces-
sary to carry out energy-dispersive
X-ray spectroscopy (EDX) to inden-
tify the components of corrosion
from the scale deposited on the
inside of the tube.
Scale
Deposit
Figure 3 Failed exible hose (corrugated tube)
Outer surface Inner surface
Figure 4 Plugged burner tip: plugged
tips will lead to unstable ames, ame
impingement and pollution problems
EDX is an analytical
technique used
for the elemental
analysis or chemical
characterisation of a
sample
sk.indd 2 09/06/2014 14:49
A number of key issues arose
from the EDX analysis including
the presence of a lot of sulphur,
although the fuel gas contains no
sulphur at all. This implies that the
main cause of the corrosion may
not be related to the fuel gas itself.
In this regard, engineering failure
analysis is needed to identify the
main causes of corrosion. There
was a need to go further and ask
ourselves how and from where the
sulphur is generated. Engineering
failure analysis has two major
objectives: to determine the failure
mechanism; and to determine the
failures root cause. The failure
mode is the basic material behav-
iour that results in failure, for
instance pitting corrosion. Root
cause is the fundamental condition
or event that caused the failure
material defects, design problems,
or improper use.
Failure analysis
Chemical analysis conrmed that
the material of construction of the
exible hose tube is Tp304, which is
correct for the design fuel gas
composition. No abnormality was
noticed in the tubes metallurgy.
Tube failure due to the wrong mate-
rial of construction is ruled out.
It is not unusual to provide exi-
ble hose for burner piping in the
petrochemical industry. It is well
recognised that, especially for the
purpose of easily tting burner
piping during installation making
allowance for minor misalignment
of components and also for conven-
ience during maintenance exible
hose is generally applied. The size,
thickness and anges were within
the design specication (ANSI
LC1-2005, CSA 6.26-2006, Fuel Gas
Piping Systems Using Corrugated
Stainless Steel Tubing).
There was no evidence of wrong
installation, such as kinking or
twisting of the exible hoses. In
accordance with API RP535 Burners
for Fired Heaters in General
Renery Services, the exible hoses
were installed within their design
radius of curvature.
Condensate
Flue gas
Fuel gas
Air
Oil Steam
Fuel gas
Damper control
Pilot gas
Figure 5 Burner details: the ue gas condensate stays in the exible hose as an illustration
0 1 2 3 4 5 6 7 8 9 10
Fe
Al
SS
Cr
C
1
Ni
Fe
Fe
Cr
Figure 6 EDX prole of external deposits collected form the failed tubes
Detail A
sk.indd 3 09/06/2014 14:49
striking features of this combustion
process is that the fue gas pene-
trates through the idling fuel gas tip
holes, and collects inside the corru-
gated tube. In approaching the issue
of fue gas fow mechanisms, we
would do well to begin with a
theory of gas volume Charless
Law. (At constant pressure, the
volume of a given mass of an ideal
gas increases or decreases by the
same factor as its temperature on
the absolute temperature scale.) Hot
fue gas is continuously fowing
into the burner gun and corrugated
tube due to the difference in gas
volume between the hot burner tip
area and the cold fexible hose area.
Once the fue gas stays inside the
corrugated tube, then the gaseous
fue gas becomes condensate as the
temperature falls below dew point.
As the fuel oil contains sulphur at
0.3 wt%, the fue gases may also
contain a small amount of sulphur
oxides in the form of gaseous
sulphur dioxide (SO
2
) and gaseous
sulphur trioxide (SO
3
). The gas
phase SO
3
then combines in the
vapour phase water to form gas
phase sulphuric acid (H
2
SO
4
), and
some of the SO
2
in the fue gases
will also combine with water
vapour in the fue gases to form gas
phase sulphurous acid (H
2
SO
3
):

H
2
O + SO
3
H
2
SO
4
(sulphuric acid)
H
2
O + SO
2
H
2
SO
3
(sulphurous acid)
The fue gas collected (gaseous
acid) at the fexible hose between
the gas tip and the isolation valve
will start to condensate into liquid
acid, because the burner piping
located outside of the furnace is at
room temperature, which is far
below the sulphuric acid dew point
of the fue gas (about 120C for 0.3
Stagnation of fuel gas condensate
during heater operation may
increase the corrosivity of the envi-
ronment, reduce the stability of the
protective surface flms and
increase susceptibility to metal loss.
Attack of the material is affected by
chemical concentration, tempera-
ture and the type of material from
which the corrugated tube is manu-
factured. In accordance with the
corrosion resistance charts
published by NACE (National
Association of Corrosion
Engineers), it is not recommended
that Tp304 should have service in
sulphuric acid and sulphurous acid.
Most stainless steels form a protec-
tive flm of stable oxides on the
surface when exposed to oxygen
gas. The rate of oxidation is
dependent on temperature. At
ambient temperatures, a thin flm
of oxide is formed on the stainless
steel surface. Since there is virtually
no sulphur (only 10 ppm) in the
fuel gas which is always supplied
at ambient temperature, there is no
chance of corrosion from the fuel
gas condensate. Tube failure due to
fuel gas is ruled out.
Could the problem be due to
sulphur from the fue gas? In
approaching the corrosion issue, we
must look into the fue gas side as
well as the fuel gas itself. It is
crucial to understand the mecha-
nism of fue gas acid dew point
corrosion. It is very important not
to cool the fue gas below its acid
dew point because the resulting
acid condensed from the fue gas
can cause serious corrosion prob-
lems for equipment. During oil
fring, the gas burner is not in oper-
ation, however the gas guns are
placed in the burner and the gas
tips are exposed to the hot fue gas
in the radiant box. One of the most
Recommendations
Burner piping specication Rigid piping is preferred to exible hose in order to prevent fuel
gas leak due to acid dew point corrosion of ue gas.
A low drain point with a slope is preferred in order to prevent the
burner tip plugging due to liquid carryover.
Code (API RP535) The requirement for preventing ue gas acid dew point corrosion in
burner piping should be clearly specied.
Recommendations for burner piping in an oil-gas combination burner
Table 2
www.eptq.com
dynamic simulation exceeded the
available capacity of the existing
PSV. Mitigation approaches were
studied by lowering the initial liquid
level in the overhead drum to 55%
volume. As a result, the relief loads
were further reduced by 26% and
18% for the TPF and refux pump
failure cases, respectively. With the
recommended mitigation approach,
the new predicted relief loads are
within the capacity of the existing
PSV. Therefore, the risk and cost of
modifying the existing relief and
fare systems are minimised and
potentially avoided.
References
1 Chittibabu H, Valli A, Khanna V, Calculating
Column Relief Loads, PTQ, 55-65, Q2 2010.
2 API RP 520: Recommended Practice for the
Design and Installation of Pressure Relieving
Systems in Reneries, Part I (Sizing and
Selection, 2008) and Part II (Installation, 2003),
American Petroleum Institute, Washington D.C.
3 Sengupta M, Staats F Y, A new approach to
relief valve load calculations, 43rd Proceedings
of Rening Section of American Petroleum
Institute, Toronto, Canada, 1978.
Harry Z Ha is a Senior Process Engineer/
Specialist with Fluor Canada Ltd, Calgary,
Alberta, Canada. He holds a masters degree
in environmental engineering from Hong
Kong University of Science and Technology
and a PhD in chemical engineering from the
University of Alberta.
Email: Harry.Ha@Fluor.com
Abdulla N Harji is an Executive Director of
Process Technology, at Fluor Canada. He holds
a BSc degree in chemical engineering from
Loughborough University, UK.
Jonathan Webber is a Process Engineer with
Fluor Canada. He holds a PhD in process control
from Dalhousie University and a masters in
biotechnology from McGill University.
changes on the trays and the
system volumes contribution to the
transient availability of cooling and
heating. They also ignore the time,
temperature and pressure depend-
ency of heat input or heat removal
from the system. In the cases of
plant revamp or debottlenecking,
conservative relief loads from
conventional methods will likely
call for the addition of PSVs and/or
the modifcation of the existing
fare system, which adds substan-
tial cost and risk to the project.
Dynamic simulation simulates the
actual composition and inventory
changes inside the column and
accumulator and provides more
accurate predictions on relief loads.
Typically, the relief loads predicted
by dynamic simulation are less
than those calculated by conven-
tional methods. Depending on the
system, the reduction in calculated
relief loads can be signifcant (by
>50%). For plant revamp or debot-
tlenecking projects, this reduction
in relief loads can result in signif-
cant savings for the project.
This case study illustrated such an
example. Employing dynamic simu-
lation for an existing deisobutaniser
has reduced the calculated relief
loads by more than 35% for both
TPF and refux pump failure cases,
compared to the conventional meth-
ods. This study also demonstrated
that the initial liquid level in the
overhead accumulator is a key
parameter in relief load calculation.
When the initial liquid level is set at
70% volume (as it is in current oper-
ation), the relief loads predicted by
300
500
450
400
350
250
200
150
100
50
R
e
l
i
e
f

l
o
a
d
,

1
0
0
0

l
b
/
h
0
30
35
25
20
15
10
5
P
S
V

s
i
z
e

r
e
q
u
i
r
e
d
,

i
n
2
0
0 5 10 15 20 25 30
Time, minutes
PSV Size
Relief load
Figure 6 Reux failure relief loads of dynamic simulation at 55% initial volume
Our new clean-fuels
plant is straining the
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How can we boost their capacity
without major construction?
Read more on this topic at
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TO MEET CLEAN FUELS
requirements for gasoline, a medium-
sized Midwestern renery added a low-
sulfur fuels technology plant. Gasoline
throughput was unchanged. However,
the sharp increase in sulfur removal
required more hydrogen from the
hydrogen unit and sent more sulfur
gases to the amine treaters and
downstream sulfur units. These
auxiliary units became bottlenecks,
overdriven at the cost of product
purity and amine consumption.
On studying the hydrogen, amine,
and sulfur units, AMACS found many
opportunities for improving separation
efciency and capacity. The problems
were solved without major construction
by applying modern technology to mist
eliminators, liquid-liquid separators,
and tower trays and packing. Results
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reduced amine consumption. Now a
diesel clean-fuels plant is being added.
Phone: 713-434-0934 Fax: 713-433-6201
amacs@amacs.com
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fluor.indd 5 12/03/2014 12:04
sk.indd 4 09/06/2014 14:50
USA
THINK GERMAN,
ACT LOCAL.
VIBRATIONS TROUBLING THE
NATURAL GAS MARKET?
NEA UNDERSTANDS MOTOR DYNAMICS
TO REDUCE DRIVE TRAIN VIBRATIONS
Motor dynamics have a major impact on torsional
vibrations especially on shaft torque and electric
current pulsations. Thats why for NEA it is
mandatory to include motor electro-magnetic
characteristics in drive train simulations. NEA
compressors are made in Germany, and we have
local engineering, packaging, service and parts
to deliver reliable, vibration free solutions.
NEUMAN & ESSER USA, Inc.
Located in Katy, Texas
www.neuman-esser.com
Contact me for Latin and North America:
Swamy Subramanyam
Vice President of Technical Management
and Procurement
ssubramanyam@neuman-esser.com
Direct Phone: +1 713-554-9636
NEA GROUP Headquarters in Germany
JOIN US FOR DISCUSSIONS AT
TURBOMACHINERY SYMPOSIUM, BOOTH NO. 737
AND GMC, BOOTH NO. 716.
BLUESTROKE
COMPRESSOR
SYSTEMS
PTQ A4-Subramanyam 2014-06.indd 1 06.06.14 13:19 neuman esser.indd 1 06/06/2014 12:48
be chemically resistant to the media
to which it will be exposed. One of
the main drawbacks of exible hose
is that it may be too thin (0.26mm
thickness), so that the life of corru-
gated tube becomes too short once
corrosion is initiated. For this
reason, the use of corrosion resist-
ance charts published by
manufacturers of piping compo-
nents, such as pipe ttings, anges,
and so on is not recommended for
corrugated metal hose; other piping
components generally have wall
thicknesses much heavier than
those of corrugated metal hose, and
therefore may have allowable
corrosion rates that would be unac-
ceptable for exible hose.
As for a cost comparison between
exible hose and rigid piping, espe-
cially for 1in burner piping, the
price of stainless exible hose is
about twice that of carbon steel
rigid piping. However, the installa-
tion cost of rigid piping is about
three times that of exible hose
since it requires special tting and
welding. Although exible hose
may be economically advantageous
for installation, the cost of mainte-
nance and safety must be taken
were no out-of-specications in the
listed items. Nonetheless, there is a
need to focus on the condensate
from ue gas. It is important to
recognise that the collected conden-
sate will be carried over to the gas
tip as soon as the fuel gas is pres-
surised and put into service. Under
continuous normal operating condi-
tions, this may not be a problem
because the tips are sufciently
cooled by high velocity fuel gases
owing through the gas tips. Upon
switching from oil ring to gas
ring, the condensate which stays
inside the exible hose will auto-
matically be delivered to the hot
gas tip. This will lead to abrupt
evaporation of liquid inside the hot
gas tip, which then results in plug-
ging due to hydrocarbon coke
build-up, and nally to melting of
the gas tip. Overheating the burner
tips can cause carbon in the fuel to
thermally crack, giving rise to
severe coking inside the tips, which
leads to plugging of the holes.
Recommendations
Compared with rigid piping, ex-
ible hose (corrugated tube) is made
of thin-walled tubing, and it must
wt% fuel oil, depending on the
concentrations of sulphur trioxide
and sulphur dioxide). Eventually,
the liquid phase sulphurous and
sulphuric acid can both lead to
severe corrosion.
This theory may be a cause for
some confusion, because it is gener-
ally thought that the amount of ue
gas owing through the small gas
tip holes should be almost negligi-
ble. However from actual eld
operation tests, especially during
winter time when the exible hose
is dismantled after one week of
operation (fuel oil ring only no
fuel gas ring), it is interesting to
note that more than 50cc of conden-
sate was observed inside each 1in
exible hose. There is no doubt that
failure was the result of corrosion
by ue gas condensation (see Figure
5, Detail A)
Liquid carryover liquids, partic-
ulates, unsaturated hydrocarbons
and H
2
S in fuel gas cause most
plugging problems. In order to
indentify the material causing the
tip plugging, a fuel gas analysis
and a design review of the knock-
out drum which removes liquids
from fuel was carried out; there
Fuel gas
Air
Oil
Steam
3
/
4
in
drain
Fuel gas
Damper control
Pilot gas
3
/
4
in
drain
1in
pipe
Figure 7 Recommended fuel gas burner piping
Detail B
sk.indd 5 09/06/2014 14:49
mechanical requirement for exible
hoses Flexible hoses require
special attention to avoid failure due
to kinking it is highly recom-
mended that the detail requirement
for preventing ue gas acid dew
point corrosion should be clearly
specied.
Further reading
1 API Std. 560, Fired Heaters for General
Renery Service, 3rd Edition.
2 Combustion Technology Manual, IHEA, 4th
Edition.
3 Marcus P, Corrosion Mechanisms in Theory
and Practices, 3rd Edition.
4 Craig B D, Handbook of Corrosion Data, 2nd
Edition.
5 Young J, Corrosion by Sulphur, Ch 8,
Hyunjin Yoon is a Stationary Equipment
Engineer with SK Innovation at Ulsan
Complex, South Korea. With over 25 years
of petrochemical industry experience, he
has wide experience in red heater design,
troubleshooting and maintenance works. He
is credited with major roles and involvement
in the development of standard specications
and various maintenance procedures of
stationary equipment. He graduated with a
MS degree in material science and engineering
from Stanford University, USA.
the potential for re accidents in a
plant. Also, in order to identify fail-
ure earlier, close visual monitoring
is necessary. Corrosion of a corru-
gated metal hose can be spotted by
looking for signs of chemical resi-
due on the exterior of the assembly,
or pitting of the metal hose wall.
The braid wires may become
discoloured from chemical attack
and may begin to fracture.
In order to prevent fuel gas tip
damage due to liquid carryover, a
drain system at the nearest available
point from the burner gun should
be provided at the lowest point of
the fuel gas piping between the rst
block valve and burner tip (see
Figure 7). It is also important that
liquid drain before gas ring should
be strictly specied in the burner
operation manual.
Considering the huge risk of
damage by re due to leakages from
burner piping, more consideration
needs to be given to the revision of
the code or specication. In the case
of API RP535 2nd edition Burners
for Fired Heater in General Renery
Services, in addition to the current
into account if there is any possibil-
ity of corrosion.
Considering all of this, it is
strongly recommended that fuel gas
piping for combination type burner
operation, which will eventually
result in ue gas condensation in
the exible hose, should be designed
as rigid piping (size 1in Sch.40:
3.4mm thickness) which is about 13
times thicker than a bellows tube
(see Figure 7). Little is known about
the corrosion failure characteristics
of rigid burner piping which is thick
enough to withstand dew point
corrosion caused by ue gas
condensation.
For gas ring burners, this appli-
cation should also be made in the
case of intermittent gas ring burn-
ers using high sulphur fuel gas. If
the use of exible hose is inevitable,
then the material of construction of
the bellows tube should be Inconel
625, which is sufciently resistant
to sulphur corrosion, or stainless
steel lined with PTFE liner and
ared through end ttings. A peri-
odic soap-bubble test on the surface
of the exible hoses can eliminate
To keep pace with the demanding
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use analytical technology is required.
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Determination of Sulfur and other
elements at-line and in the laboratory
sk.indd 6 10/06/2014 14:10
sandvik.indd 1 05/06/2014 18:57
Microbiological causes of corrosion
M
icrobiologically induced
corrosion has a potential
impact on a wide range of
industrial operations, including
refning. Problems associated with
MIC affict water handling opera-
tions and manufacturing processes
in oil and gas production, pipelin-
ing, refning, petrochemical
synthesis, and other industrial
sectors. Most of the commercially
used metals and alloys such as
stainless steels, nickel and alumin-
ium based alloys and materials
such as concrete, asphalt and poly-
mers are readily degraded by
Many of the most serious problems with corrosion of renery equipment have a
microbiological basis
JAYA RAWAT, NEHA SHARMA and APOORVE KHANDELWAL
Bharat Petroleum Corporate R&D Center
microorganisms. Protective coat-
ings, inhibitors, oils and emulsions
are also subject to microbial degra-
dation. Quality research and
analyses of corrosion failure have
provided deeper understanding of
the causes of microbial corrosion.
Microbiologically induced corro-
sion is not in itself a form of
corrosion, but rather a process that
can infuence and even initiate
corrosion. It can accelerate most
forms of corrosion, including
uniform corrosion, pitting corro-
sion, crevice corrosion, galvanic
corrosion, intergranular corrosion,
dealloying, and stress corrosion
cracking. MIC deteriorates pipes,
tanks or vessel surfaces by pitting
corrosion. The formation of slime
or tuberculation nodules can cause
blockages or reduce fow. Low fow
or stagnant conditions make
systems more susceptible to micro-
bial growth. Microbiologically
induced corrosion can degrade or
cause to fail many different types
of system. The ultimate effect is the
premature failure of metal compo-
nents. To understand the causes
and effects, it is necessary to under-
stand the chemical, metallurgical
Genus/species pH Temp.,C O
2
requirement Metals Metabolic process
Desulphovibrio 4-8 50-105 Anaerobic Iron, steel, stainless steel, Use hydrogen in reducing SO
4
2-
to S
2-
and H
2
S;
aluminium, zinc, copper alloys promote formation of sulphide lms

Desulphotomaculum 6-8 50-105 Anaerobic Iron, steel, stainless steel Reduce SO
4
2-
to S
2-
and H
2
S
(some at 115-165)
Desulphomonas 6-8 50-105 Anaerobic Iron and steel Reduce SO
4
2-
to S
2-
and H
2
S
Acidithiobacillus 0.5-8 50-105 Aerobic Iron and steel, copper alloys, Oxidises sulphur and sulphide to form H
2
SO
4
thiooxidans concrete
Acidithiobacillus 1-7 50-105 Aerobic Iron and steel Oxidises ferrous ions (Fe
2+
) to ferric ions (Fe
3+
)
ferrooxidans
Galionella 7-10 70-105 Aerobic Iron, steel, stainless steel Oxidises (Fe
2+
) to (Fe
3+
) and manganous (Mn
2+
) to
manganic (Mn
3+
) ions, promotes tubercle formation
Siderocapsa - - Microaerophilic Iron, carbon steel Oxidises iron
Leptothrix 6.5-9 50-95 Aerobic Iron and steel Oxidises (Fe
2+
) to (Fe
3+
) and manganous (Mn
2+
)
to manganic (Mn
3+
) ions
Sphaerotilus 7-10 70-105 Aerobic Iron and steel and stainless Oxidises ferrous ions (Fe
2+
) to ferric ions (Fe
3+
) and
steel manganous (Mn
2+
) to manganic (Mn
3+
) ions,
promotes tubercle formation
Sphaerotilus natans - - - Aluminium alloys -
Pseudomonas 4-9 70-105 Aerobic Iron, steel, stainless steel Some strains reduce Fe
3+
to Fe
2+
Pseudomonas aeruginosa 4-8 70-105 Aerobic Aluminium alloys -
Common microorganisms found in conjunction with MIC
Table 1
bpcl6.indd 1 10/06/2014 09:54
Parameters affecting the develop-
ment of bioflms include:
Temperature of the system or
ambient temperature
Water fow rate past the surface
Nutrient availability
Surface of the substratum
pH of water in the system
Effectiveness of biofouling reme-
dial measures.
Bioflm formation is the result of
an accumulation process not
necessarily uniform in time or
space that starts immediately
after immersion of metal in the
aqueous environment. The growth
of bioflm is considered to be a
result of complex processes involv-
ing transport of organic and
inorganic molecules and microbial
cells to the surface, adsorption of
molecules to the surface and initial
attachment of microbial cells
followed by their irreversible adhe-
sion facilitated by production of
extracellular polymeric substances
(EPS). Once attached, the organisms
begin to produce material termed
extracellular biopolymer, or slime
and microbiological aspects of
microbial corrosion.
Microbial activities act as a driv-
ing force for biocorrosion.
Microbiologically induced corro-
sion causing organisms are
sulphate reducing bacteria
(Desulphovibrio, Desulphotomaculum,
and Desulphomonas sp.), iron reduc-
ing bacteria (Gallionellea ferrugine
and Ferrobacillus sp.), acid produc-
ing bacteria (Pseudomonas,
Aerobacter, and Bacillus), and
sulphur oxidising bacteria
(Thiobacillus sp.).
Microorganisms are ubiquitous in
nature and grow at very rapid rates
in soil, water and air. They show
extreme tolerance to varying envi-
ronmental conditions such as acidic
and alkaline pH, low and higher
temperatures as shown in Table 1.
Microorganisms and their meta-
bolic products, including enzymes,
exopolysaccharides, organic and
inorganic acids, and volatile
compounds, such as ammonia or
hydrogen sulphide, can alter elec-
trochemical processes at the
bioflm-metal interface. Both aero-
bic and anaerobic organisms play
an important role in the initiation,
propagation, and inhibition of
corrosion in different ways by their
different energy deriving
pathways.
Fungi and algae may also be
involved in metal deterioration. In
fuel and oil storage tanks, fungal
species such as aspergillus, penicil-
lium and fusarium may grow on
fuel components and produce
carboxylic acids which corrode
iron.
Role of biolms
The term bioflm refers to the
development of microbial commu-
nities on submerged surfaces in
aqueous environments. Bioflm
infuences the physic-chemical
interactions between metal and
environment, frequently enhances
corrosion, and leads to deteriora-
tion of the metal. Bioflm induces
many changes in the type and
concentration of ions, pH values,
and oxidation reduction potential.
stages into a process that typically
runs at 70-90% load of the rated
capacity. When considering pneu-
matic suction valve unloaders and
spillback valve control, a four-
cylinder compressor with two
cylinders per compression stage
would be required to enable at
least 25% load increments to run,
relatively effciently, at loads
between 70% and 75%. However,
between 100% and 76% load, the
dispensable process gas still needs
to be recycled through the spill-
back valve. In this worst case, up
to 24% of the rated compressor
power is wasted. Additionally,
installed fxed clearance pockets
would improve the situation
slightly, but the control logic
would become more complicated
and access to the compressor for
maintenance impeded. However,
two cylinders per stage are still
required as compared with stepless
control.
The same application with a step-
less full-range fow control system
would require only one cylinder
per compression stage (two cylin-
ders in total for the compressor)
of automation allows for precise
plant control and fne-tuning of
process parameters, such as gas
pressure, hydrogen/feed ratio and
gas fow rate.
The following example explains
the impact on the compressor
arrangement based on the chosen
capacity control system. A recipro-
cating compressor shall compress
process gas in two compression
of the compressor, the number of
cylinders per stage can be reduced.
Hence, the capital costs and foot-
print of the compressor are
minimised. Furthermore, fewer
cylinders mean reduced mainte-
nance costs, shorter shutdown
periods for overhauls, and fewer
spare parts to be kept in stock. The
higher effciency reduces electric
power costs, and the high degree
60
100
90
80
70
50
40
30
20
10
I
n
d
i
c
a
t
e
d

p
o
w
e
r
,

%
0
0 10 20 30 40 50 60 70 80 90 100
Capacity, %
Step control
Reverse flow control
Ideal control system
Energy savings
Figure 6 Comparison of the compressor power consumption between step control and
reverse ow control as a function of the compressor capacity
3 Respini, Jones, Spanu, Sesselego, Avoiding foul
play, Hydrocarbon Engineering, Nov 2006.
Matteo Virzi is Senior Technology Manager
with ISAB Priolo renery in Italy. He is an
expert in distillation and thermal conversion
processes. With more than 20 years of
experience in technology, operations and
automation, he holds a degree in chemical
engineering from the University of Palermo.
Email: mvirzi@isab.com
Marco Respini is a Senior Technology Expert
with Baker Hughes Downstream Chemicals,
specialising in renery and petrochemical
process improvements in fouling control.
He has 15 years of rening experience and
is currently involved in developing new
technologies for improving renery conversion
processes. With extensive experience in
asphaltene related problems in oil production
and rening, he is an inventor of ve US patents
and has published 10 technical papers and
seven conference papers on visbreakers and
heavy fuel oil stability problems. A graduate
of Milan University with a degree in industrial
chemistry, he has been a Research Fellow in
the eld of organometallic catalysts and is a
registered professional chemist in Italy. He is
also a member of ACS and NACE.
Email: marco.respini@bakerhughes.com
which provided refnery personnel
with the right information to be
able to constantly keep the unit at
the best process severity for any
processed feed.
VisTec is a mark of Baker Hughes Incorporated.
References
1 Petralito G, Respini M, Achieving optimal
visbreaking severity, PTQ, Q1, 2010.
2 A Phase Separation Kinetic Model for Coke
Formation, Preprints ACS, Div. Pet Chem, 38,
428-433, 1993.
result in better handling of fouling,
and at the same time increase
HVGO directly (less gasoil recycled
as wash oil). Figure 17 shows the
trend of wash oil rate.
The decrease in wash oil rate
was continuously optimised. The
HVGO was analysed on a daily
basis with respect to the level of
contaminants, using the VCI tech-
nique that measures the coke
particles entrained within the
HVGO (thus not removed by wash
oil).
Also, the rate of antifoulant on
the wash oil was optimised and
increased when needed.
Conclusions
This article describes an example of
high conversion visbreaking with
increased run length when
compared to typical visbreaker run
lengths.
This successful result was made
possible by coupling Baker Hughes
VisTec anticoke/antifoulant treat-
ments with monitoring technology,
A controlled decrease
in wash oil can result
in better handling of
fouling, and at the
same time increase
HVGO directly
B
e
s
t
V
a
lv
e
s
s
in
c
e
1
8
6
7
baker hughes.indd 8 13/12/2013 11:38
hoerbiger.indd 5 10/03/2014 13:40
bpcl6.indd 2 10/06/2014 14:26
for short. The amount of EPS
produced can exceed the mass of
the bacterial cell by a factor of 100
or more. The extracellular polymer
that is produced provides a more
suitable protective environment for
the survival of the organism. The
EPS in bioflm consists of lipids,
polysaccharides, proteins and
nucleic acids. The content of these
macromolecules in EPS varies,
depending on bacterial species and
growth conditions. One of the
important properties of EPS is their
ability to complex with metal ions.
This initial flm is able to alter the
electrostatic charges and wetability
of the metal surface, facilitating its
further colonisation by bacteria.
For example, in a marine environ-
ment the presence of a bioflm can
accelerate corrosion rates of carbon
steel by several orders of magni-
tude. After colonisation and
formation of bioflms, maintenance
and operational problems arise,
including a reduction in fow, heat
transfer rates, fouling, corrosion,
and scale.
Anaerobic sulphate-reducing
bacteria, such as Desulphovibrio sp.,
is the most often considered bacte-
ria for microbial corrosion.
Anaerobic regions develop beneath
the bioflm, even in aerobic bulk
water environments, thus allowing
sulphate reducing bacteria a very
favourable environment for growth.
This organism will seek out and
colonise areas defcient in oxygen,
such as those found within porous
corrosion tubercles, within bioflms,
and under debris. This bacterium is
responsible for severe metal loss in
industrial water systems. This type
of corrosion is easily recognisable
from the characteristic sulphide
by-product present within the
corrosion cell. Sulphate reducing
bacteria primarily cause corrosion
by utilising the molecular hydrogen
produced at the cathode, thereby
depolarising it.
The mechanisms of microbial
corrosion of metals may be site
specifc and tend to vary with the
environment, type of organism,
type of metallurgy and the surface
characteristics of the metal.
Microorganisms may induce corro-
sion processes directly or indirectly.
Various mechanisms have been
proposed to explain the active
participation of microbes in corro-
sion. Some microbes can produce
metabolites that are acidic (for
instance, sulphuric acid by sulphur
oxidising bacteria) or facilitate the
local depassivation or dissolution
of the protective flms or corrosion
products on the metal surface (for
instance, biogenic sulphides desta-
bilising the copper oxide flm on
Cu-Ni alloys, a marine Vibrio
reducing insoluble corrosion prod-
uct to soluble Fe
2+
).
Microorganisms can consume
substances in bioflm and lead to
formation of concentration gradi-
ents of chemical species that are
important for their metabolic activi-
ties, which are also electrochemical
reactants (oxygen and protons)
relevant to the underlying substra-
tum. Mechanism on the basis of
type of organisms can be classifed
into two categories.
Anaerobic corrosion
Pipelines, offshore oil platforms
and underground structures are
found to be quite vulnerable to
microbial corrosion which is
assumed to be mediated with
different groups of microorganisms
respiring with oxidised compounds
such as sulphide and nitrite.
Sulphate reducing bacteria are
proposed to be mainly responsible
for anaerobic corrosion, specifcally
in environments with high sulphate
concentrations such as seawater.
Von Wolzogen K uhr and van der
Vlugt in 1934 frst postulated the
most widely accepted theory for
the mechanism of corrosion of iron
and steel by cathodic depolarisa-
tion. These organisms reduce
sulphate to sulphide. Cathodic
hydrogen formed on a metal
surface by active corrosion can
specifcally promote growth of
organisms, including sulphate
reducing bacteria that are able to
use hydrogen in their metabolism.
Severe corrosion cells develop as
sulphide, produced by the micro-
bial reduction of sulphate,
combines with ferrous ions,
released by the corrosion process,
to produce insoluble black iron
sulphides
Aerobic corrosion
Bioflms, which form under aerated
conditions, cause corrosion by the
formation of differential aeration
cells or concentration cells. Thus
aerobic corrosion occurs when the
oxide flm is damaged, or oxygen is
kept from the metal surface by the
microorganisms and rapid pitting
or corrosion occurs under the
bioflm.
Pseudomonas species and other
slime forming bacteria are found to
be involved in microbial corrosion.
Exopolymeric substances (EPS) by
these bacteria may contain organic
acids and salts at high concentra-
tions, which may stimulate metal
deterioration. Some group of bacte-
ria produce inorganic acids and
becomes very corrosive towards
metal surface. For instance,
Thiobacillus sp. produce sulphuric
acid by oxidising sulphur species.
Other group of bacteria, including
Gellionella, Leptothrix and
Sphaerotilus are also involved in
microbial corrosion. Formation of
tubercle in the iron steel is a
common type of corrosion by these
bacteria.
MIC in water systems
Generally, it is bacterial bioflms
that are most problematic in indus-
trial water systems, since they
are responsible for the blockage
and fouling of heat transfer
equipment. Biofouling of industrial
water systems is the phenomenon
whereby surfaces in contact
with water are colonised by micro-
organisms, which are ubiquitous
in our environment. The conditions
in cooling water systems are
quite favourable for bacterial
growth. Microbial bioflm and
corrosion in cooling systems are the
most common problems that
damage expensive equipment,
cause loss of production and
increased maintenance cost. Bioflm
is a population of cells embedded
in a thick mucilaginous matrix of
EPS.
Sulphate reducing bacteria
bioflm (see Figure 1) isolated from
an aeration basin inlet water
sample from a refnery cooling
water network is studied for its role
in biocorrosion in carbon steel.
bpcl6.indd 3 10/06/2014 14:25
are of iron, steel, copper, alumin-
ium and its alloys. It appears that
almost any system with free water
present can host microbial activity,
provided there is a source of nutri-
ents and an absence of toxic
material. Favoured locations for
failures include locations where
water can collect in piping, dead-
end or shut-in piping, tank bottoms
at the interface between liquid
hydrocarbons and underlying
water, or areas heavily fouled with
surface deposits. Identifcation of
MIC sites on metal surface can be
done on based on three types of
evidence:
Metallurgical: appearance of
corrosion damage
Biological: cell counts for bacte-
rial populations
Chemical: identifcation of corro-
sion products and other deposits.
Galvanised steel is frequently
used in the construction of cooling
towers and water containers owing
to its good corrosion resistance,
mechanical workability and resist-
ance to biofouling. In spite of the
ent sources, reproducing and
generating intra- and extracellular
organic and inorganic substances in
water. The present trend in indus-
trial water systems is to minimise
both water consumption and water
discharge by recirculation. This
results in the concentration
of dissolved and suspended
substances promoting growth of
waterborne microbes, and shifting
the microbial community to more
copiotrophic conditions.
Most failure analyses reported
SEM studies of the metal surface,
after removal of bioflm, revealed
pitting attack (see Figure 2) and
increased corrosion rate due to the
presence of sulphate reducing
bacteria.
In industrial systems, biodegrad-
able materials, such as some of the
hydrocarbons found in oil and gas
operations or susceptible compo-
nents of coating materials, can
provide a source of nutrients for
microbial growth. Microbes are
capable of utilising available nutri-

Figure 1 Sulphate reducing bacteria biolm formation on metal surface
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bpcl6.indd 4 10/06/2014 09:55
The major applications where
MIC has attacked aluminium alloys
have been in fuel storage tanks and
aircraft fuel tanks. Pitting corrosion
due to sulphate reducing bacteria is
reported in few cases. A report has
suggested susceptibility of alumin-
ium towards fungus.
Mitigation methods
Biocides, cathodic protection, and
corrosion inhibitors are various
chemical measures to mitigate and
control MIC. Selection of method of
control considers factors such as
cost, effcacy, cleanliness of the
metal/solution system to be
treated, and environmental concern.
Cleaning of the system can be done
on a regular basis by different
methodologies including pigging,
hydraulic methods, thermal back-
wash and ultrasound methods.
Frequent cleaning is found to be
signifcantly effective in improving
the effcacy of chemical treatment.
As far as the use of corrosion
inhibitors is concerned, the envi-
ronmental toxicity of organic
corrosion inhibitors has prompted
the search for green corrosion
inhibitors as they are biodegradable
and do not contain heavy metals or
other toxic compounds. Because, in
addition to being environmentally
friendly and ecologically accept-
able, plant products are
inexpensive, readily available and
renewable, investigations of the
corrosion inhibiting abilities of
tannins, alkaloids, organic, amino
acids, and organic dyes of plant
origin are of interest. Inhibition of
bioflm formation is the simplest
way of biocorrosion prevention.
interrupted. If related bacteria are
present, or there are elements like
chlorides or sulphides in the initial
solutions contacting the metal, the
passive or protective layers on the
metal surface form other complex
chemical compounds rather than
copper oxide. The problem with
these complex chemical compounds
are their strength; they are typically
much weaker than copper oxide
and break down at lower fow rates
allowing a variety of mechanisms
to attack or degrade the substrate.
Copper alloys fnd use in seawa-
ter piping systems and heat
exchangers, which are susceptible
to microbially infuenced corrosion.
Microbial products that can be
harmful to copper alloys include
carbon dioxide (CO
2
), hydrogen
sulphide (H
2
S), ammonia (NH
3
),
organic and inorganic acids, and
other sulphides. Sulphate reducing
bacteria has also been known to
attack copper alloys, causing deal-
loying of nickel or zinc in some
cases.
well-known anticorrosive and anti-
fouling properties of galvanised
steel, few investigations have
reported its failure due to microbial
corrosion in simulated cooling
systems and pipework. Microbially
infuenced corrosion is a potential
contributor to sporadically occur-
ring failures in galvanised steel
systems containing water. A few
investigations have reported accel-
erated corrosion of galvanised steel
due to heterotrophic bacteria
bioflm and failure of a galvanised
steel metalworking lube due to
microbial corrosion.
Stainless steels corrode at an
accelerated rate, primarily through
pitting or crevice corrosion, which
occurs in low lying areas, joints,
and at corner locations. Also,
microbially infuenced corrosion in
stainless steels occurs adjacent to
welds; consequently, microorgan-
isms readily attack areas around
welds due to the inhomogeneous
nature of the metal. Analysis of
stainless steel heat exchanger due
to MIC has been reported. Another
report has stated that bacteria
belonging to a Pseudomonas species
dominate the microbiological corro-
sion of stainless steel 304 in a
potable water system.
Carbon steel is a relatively unre-
sistant material to microbially
infuenced corrosion so that when
it is corroded, the voluminous
corrosion products thus produced
can create areas of local low and
high oxygen partial pressures so
that areas with low partial pressure
of oxygen become anodes and
those having a relatively high
partial pressure can form cathodes.
In this way, by establishment of
differential aeration cells, the corro-
sion of the steel is initiated and/or
accelerated. A report has suggested
the MIC assisted embrittlement of
the steel in biotic media (carbon
steel in 3.5% chloride solution
containing sulphate ions and
sulphate reducing bacteria) along
with fractography.
Copper base alloys are most
susceptible to microbially infu-
enced corrosion because they are
soft and can incur impingement
that causes erosion and other wear
problems if their passive layer is
Figure 3 Pit in carbon steel coupon in the
presence of sulphate reducing bacterial
biolm

Figure 2 Micrograph of pits on a metal surface exposed to sulphate reducing bacterial
medium for 24 days
bpcl6.indd 5 10/06/2014 09:55
12 Ford T E, Maki J S, Mitchell R, Involvement
of bacterial exopolymers in biodeterioration
of metals, Proceedings of the Seventh
International Biodeterioration Symposium,
Elsevier Applied Science, 1988, 378384.
13 Jaiyeola G A, Microbiologically
Inuenced corrosion of galvanized steel by a
metalworking lube, Journal of Failure Analysis
and Prevention, Vol13, 2, 2013, 136-139.
14 Ghazy E A, Mahmoud M G, Asker M S,
Mahmoud M N, Abo Elsoud M M, Abdel Sami
M E, Cultivation and detection of sulphate
reducing bacteria (SRB) in sea water, Journal
of American Science, 7, 2, 2011.
15 Huttunen-Saarivirta E, Honkanen M,
Lepist T, Kuokkala V T, Koivisto L, Berg C G,
Microbiologically inuenced corrosion (MIC)
in stainless steel heat exchanger, Applied
Surface Science, 258, 2012, 6512-6526.
16 Ilhan-Sungur E, otuk A, Microbial
corrosion of galvanized steel in a simulated
recirculating cooling tower system, Corrosion
Science, 52, 2010, 161171.
17 Jack T R, Biological corrosion failures,
American Society for Microbiology (ASM)
Handbook-Failure Analysis and Prevention, Vol
11, 2002.
18 Kakooei S, Ismail M C, Ariwahjoedi B,
Mechanisms of microbiologically inuenced
corrosion: a review, World Applied Sciences
Journal, 17, 4, 2012, 524-531.
19 King R A, Microbiologically induced
corrosion and biolm interactions, Journal of
Pipeline Engineering, 2008, 225-230.
20 Javaherdashti R, Singh Raman R K, Panter
C, Pereloma E V, Microbiologically assisted
stress corrosion cracking of carbon steel in
mixed and pure cultures of sulphate reducing
bacteria, International Biodeterioration &
Biodegradation, 58, 2006, 2735 .
21 Xianming Shi, Ning Xie, Jing Gong, Recent
progress in the research on microbially
inuenced corrosion: a birds eye view through
the engineering lens, Patents on Corrosion
Science, 1, 2011, 118-131.
Jaya Rawat is Manager, R&D, in the Corporate
R&D Centre of Bharat Petroleum Corporation
Ltd, Surajpur, India. She holds a doctorate
degree in corrosion science from Z H College
of Eng. & Technology AMU Aligarh (India).
Email: jayarawat@bharatpetroleum.in
Neha Sharma is Project Assistant in the
Corporate R&D Centre of Bharat Petroleum
Corporation Ltd, Surajpur, India. She holds a
MSc degree in biochemistry.
Email: nehaa.anand@gmail.com
Apoorve Khandelwal is Deputy Manager,
R&D, in the Corporate R&D Centre of Bharat
Petroleum Corporation Ltd, Surajpur, India. He
holds BTech & MTech degrees in biochemical
engineering and biotechnology from IIT Delhi.
Email: apoorvekhandelw@bharatpetroleum.in
Future developments will be
centred on the potential of innova-
tive technologies that increase the
effectiveness and competitiveness
of eco-friendly approaches to
microbially induced corrosion and
signifcantly reduce or completely
eliminate the need for biocides and
other traditional methods. The
research and development in this
area are ongoing.
Further reading
1 Antony P J, Chongdar S, Kumar P, Ramana
R, Corrosion of 2205 duplex stainless steel
in chloride medium containing sulphate
reducing bacteria, Electrochimica Acta, 52,
2007, 39853994.
2 Beech I B, Gaylarde C C, Recent advances
in the study of biocorrosion an overview,
Revista de Microbiologia, 30, 1999, 177-190.
3 Beech I B, Zinkevich V, Hanjangsit L,
Gubner R, Avci R, The effect of pseudomonas
NCIMB 2021 biolm on AISI 316 stainless
steel, Biofouling, 15 (1-3), 2000, T3-12.
4 Beech I B, Corrosion of technical materials
in the presence of biolms current
understanding and state-of-the art methods
of study, International Biodeterioration &
Biodegradation, 53, 2004, 177-183.
5 Rosalesa B M, Iannuzzi M, Aluminium
AA2024 T351 aeronautical alloy: Part 1.
microbial inuenced corrosion analysis,
Materials Science and Engineering: A, Vol
472,12, 15 Jan 2008, 1525.
6 Bolton N, Critchley M, Fabien R, Cromar
N, Falloweld H, Microbially inuenced
corrosion of galvanized steel pipes in aerobic
water systems, J Appl Microbiol, 109, 1, 2010,
239-47.
7 Castaneda H, Benetton X D, SRB-biolm
inuence in active corrosion sites formed at
the steel-electrolyte interface when exposed
to articial seawater conditions, Corrosion
Science, 50, 2008, 11691183.
8 Coetser S E, Cloete T E, Biofouling and
biocorrosion in industrial water systems,
Critical Reviews in Microbiology, 31, 2005,
213232.
9 Dogruz N, Minnos B, Ilhan-Sungur E,
otuk A, Biolm formation on copper and
galvanized steel surfaces in a cooling water
system, Istanbul University Faculty of Science
Journal of Biology, 68, 2, 2009, 105-111.
10 Huttunen-Saarivirtaa E, Honkanena M,
Lepista T, Kuokkalaa V-T, Koivistob L, Berg
C-G, Applied surface science microbiologically
inuenced corrosion (MIC) in stainless steel
heat exchanger, Applied Surface Science, 258,
2012, 6512 6526.
11 Enning D, Venzlaff H, Garrelfs J, Dinh H T,
Meyer V, Mayrhofer K, Hassel A W, Stratmann
M, Widdel F, Environmental Microbiology, 14,
7, 2012, 17721787
Use of naturally produced
compounds such as plant extracts
could be used as effective biocides.
For instance, ginkgo biloba leaf
extracts, hexane extracts of
Capsicum pepper plants and
molybdate are found to be effective
inhibitors of sulphate reducing
bacteria. Lignin and its derivatives
(lignosulphonates, acetylated
lignin), and neem extract are also
found to be effcient against
sulphate reducing bacteria.
Beside chemical methods, some
non-chemical or physical methods
can be taken into consideration
since they are more environment
friendly. Ultra fltration, UV radia-
tion and ultrasound treatments are
also found to be effective against
microorganisms.
Economic losses
Biocorrosion leads to increased
corrosion rates of metals inducing
important material losses. There are
no offcial fgures for the cost of
microbially induced corrosion, but
some indication of its importance
can be gained from individual
companies or sectors of industry.
The direct annual cost of microbi-
ally induced corrosion has been
estimated at $16-17 billion dollars
per annum in the US alone. Damage
caused by microbially induced
corrosion in the production, trans-
port, and storage of oil amounts to
some hundred million dollars per
year in the US. The damage caused
can be unexpectedly enormous. It is
almost impossible to quantify
economic losses because many of
them are not recognised as microbi-
ally infuenced even though they
are. It is estimated that about 20%
of all corrosion damage of metals
and building materials is microbi-
ally infuenced and enhanced. Metal
deterioration due to biocorrosion
may lead to unexpected ruptures
and blockages in plants, particularly
in those plants where heat exchang-
ers generally use river water or
ground water as cooling fuid. In
the case of buried pipelines, unex-
pected leakage may occur due to
metal pitting and degradation
which, in turn, can be the source of
considerable environmental
pollution.
bpcl6.indd 6 10/06/2014 09:55
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PROCESS
CONSULTING
SERVICES,INC.
upsets from water slugs and
other unpredictable situations
that have damaged internals,
resulting in diluent losses and
high vacuum unit overhead con-
densable oil. Diluent is neither
cheap nor plentiful, and high
vacuum column operating pres-
sure will reduce overall liquid
volume yields. And if the design
of the delayed coker fractionator
is based on todays experience
with conventional heavy feed-
stocks you will be lucky to run
six months.
What all this means is that
special process and equipment
designs are needed to satisfy
the special demands of pro-
cessing oil sands crudes. Such
processes are not generated by
computer based designers who
have little or no experience and
never leave the office. They are
developed only by engineers
with know-how who have real
experience wearing Nomex
suits
and measuring true unit per-
formance in Northern Alberta.
Shouldnt this be kept in mind
by those considering long term
supply agreements?
Oil Sands Crude
Profits and
Problems?
Canadian bitumen production
currently runs about 1 MMbpd,
with some being sold as Synbit
and Dilbit. Over the next 10-12
years output is expected to
increase to 3.5 MMbpd and more
refiners will begin investing to
process it and come to depend
on the Synbit and Dilbit for a
significant part of their supply.
Few today, however, have ever
processed these feeds at high
blend ratios, and are unaware
that conventional process and
equipment designs are not up
to the job. Canadian oil sands
feedstocks are extremely hard
to desalt, difficult to vaporize,
thermally unstable, corrosive, and
produce high di-olefin product
from the coker. If you intend to
lock into a long-term supply,
therefore, it is imperative that you
consider reliability and run length
from a particular design.
Too low tube velocity in the
vacuum heater tubes will lead to
precipitation of asphaltenes. Too
fast a flow rate will erode the
tube bends. If coil layout, burner
configuration and steam rate are
not correct, run length will be
measured in months, not years.
Diluent recovery unit designs
must take into account possible
For a discussion of factors
involved in designing refinery units
to process difficult oil sands feed-
stocks, ask for Technical Papers
#234 and 238.
10 PTQ 01:10 01 PC PTQ 0107 ADF 10/19/07 4:42 PM Page 1
pcs 2.indd 1 1/6/12 21:05:28
Albertas crude oil reserves
T
he Western Canada
Sedimentary Basin
(WCSB, see Figure 1)
extends from the Williston
Basin, which straddles the
Canada-US border, north to
the Mackenzie Basins, west
to the Rocky Mountains and
east to the edge of the
Precambrian Shield.
The WCSB has long been
considered gas-prone and
large volumes of conven-
tional gas have been
shipped, mainly to eastern
Canada and the western
US, for more than 50
years. Very recently
1
, the
Alberta Energy Resources
Conservation Board (ERCB),
now the Alberta Energy
Regulator (AER), along with
the Alberta Geological
Survey (AGS) estimated
3424 tcf (trillion cubic feet)
of original gas in place and 59
billion barrels (bbl) of original
natural gas liquids (NGLs) in place
in just six of 15 Alberta tight shale
and siltstone formations that were
evaluated and are just starting to
be developed.
Signifcant production of conven-
tional oil, defned as crude light
enough to be pipelined, lighter than
~20 API, started in the WCSB with
the discovery of oil at Turner
Valley in the 1930s, expanded
greatly with discovery of the Leduc
reef trend by Imperial Oil in 1947,
and peaked at 1.4 million bbl/d in
1973.
Over 200 years ago, the frst
Europeans noted bitumen seeps
along the banks of the Athabasca
River in northern Alberta. The local
Recovery factors achieved by improved recovery techniques indicate that
crude oil reserves in Albertas bitumen sands are the largest on earth
MIKE PRIARO
Consultant
people had long been using bitu-
men to waterproof canoes. Bitumen
is crude with a specifc gravity
greater than fresh water (less than
10 API) and is a thick, semi-solid
fuid at room temperature that does
not fow at commercial rates to a
wellbore under normal reservoir
conditions.
Karl Clark, a scientist with the
Alberta Research Council in the
1920s, pioneered experiments with
a hot water fotation process. He
mixed bitumen sand with hot water
and aerated the resultant slurry
which would then separate into a
foating froth of bitumen and a
clean layer of sand that settled to
the bottom of the tank. The hot
water fotation process was used to
produce bitumen for roofng and
road surfacing at a plant
north of Fort McMurray. In
1936, Abasand Oils plant
west of Fort McMurray
produced diesel oil from
the bitumen sands until it
burned down in the 1940s.
In 1962, the Government of
Alberta announced a policy
to provide for the orderly
development of the bitu-
men sands and Suncors
Great Canadian Oil Sands
project came on stream in
1967 to become the worlds
frst large scale bitumen
sands project.
Albertas bitumen sands
Shallow, bitumen satu-
rated, unconsolidated sand
and hard-rock carbonate
reservoirs are now known
to underlie 54 132 square
miles of land in northern
Alberta in the Alberta Basin portion
of the WCSB (see Figure 2).
Depending on depth beneath the
surface, raw bitumen is produced
either by surface strip mining or by
various in situ techniques using
wells.
In the surface mineable area (see
Figure 3), estimated at 1854 square
miles, bitumen sands reservoirs are
generally thick and high quality
and lie less than about 250ft below
the surface, allowing bitumen to be
extracted economically by strip
mining with recovery factors often
exceeding 90%. In this method,
vegetation is stripped, overburden
is removed, bitumen sands are
mined by excavation, and raw bitu-
men is separated from mined
material using the hot water

Figure 1 Western Canada Sedimentary Basin
Source: Alberta Energy Resources Conservation Board report ST98-2013
Priaro.indd 1 10/06/2014 12:40
pipelined or refned. Upgrading
means removing carbon by decok-
ing or adding hydrogen to carbon
to produce a lighter product requir-
ing some additional processing to
produce a sweet syncrude that is
more valuable and desirable as
refnery feedstock.
The eight surface strip mining
projects currently operating and
under active development are
CNRL Horizon, Suncor Fort Hills,
Imperial/ExxonMobil Kearl, Shell
Muskeg River, Shell Jackpine,
Suncor, Syncrude, and Total Joslyn
North. The just commissioned
Kearl project and the in develop-
ment Fort Hills project are the frst
surface strip mines without upgrad-
ers. Kearl is also the frst to use a
solvent process to separate bitumen
from sand.
At greater depths, in situ recovery
of bitumen is done using enhanced
thermal recovery techniques of
cyclic steam stimulation (CSS) or
steam assisted gravity drainage
(SAGD).
In CSS, the frst in situ enhanced
recovery method developed, high
pressure steam is injected into a
well for a period of months and
then produced back from the same
well for another period of months.
The cycle is then repeated.
In SAGD, pairs of parallel hori-
zontal wells, one about 15ft or 20ft
above the other, are drilled from a
pad. High pressure steam is contin-
uously injected into the upper well
to heat the reservoir and reduce the
viscosity of the bitumen, allowing it
to continuously drain into the
lower horizontal wellbore for
production. SAGD is currently the
technique of choice for almost
every in situ project under develop-
ment. There are literally dozens of
operational, under development, in
approval, or planned in situ SAGD
projects.
The Alberta Energy Resources
Conservation Board (ERCB) fore-
casted
2
bitumen production
doubling to 3.8 million b/d from
2012 to 2022 with an ever increas-
ing percentage of in situ production
(see Figure 4).
A June 2013 forecast
3
by the
Canadian Association of Petroleum
Producers (CAPP) forecasted
process. In the surrounding
Shallow Thermal Area there is
increased risk of high pressure
steam and heated bitumen break-
through to surface for in situ
projects.
The raw bitumen is then either
diluted with condensate to allow
pipelining as dilbit (~20 API) or
upgraded to synthetic crude oil
(SCO or syncrude, ~30 API and
higher) which can then either be

Figure 2 Albertas bitumen deposits and areas Source: ERCB ST98-2013

Figure 3 Bitumen sands surface mineable area Source: AER
Priaro.indd 2 10/06/2014 12:40
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the same increase by 2022 (see
Figure 5).
Recovery factors
The frst commercial SAGD project
was initiated in 1996 at Foster
Creek and achieved commercial
production only in 2001. In situ
thermal enhanced recovery technol-
ogy for bitumen production is still
at an early development stage
improvements in effciency as
measured by recovery factor will
most assuredly continue to occur.
Recovery factors measure how eff-
ciently original oil in place (OOIP)
is recovered by production
technology.
In a 2006 presentation,
4
Eddie Lui
of Imperial Oil said that in the
portion of the reservoir (net pay)
being targeted by CSS, typical
recovery rates are about 35-45%.
This translates to a recovery rate
of 25-30% of the entire bitumen
bearing zone (gross pay). Net
pay is reservoir thickness deemed
to contribute to production of
technically recoverable reserves.
Gross pay measures the total
thickness of reservoir containing
any measurable quantities of
crude.
Improvements in technology such
as co-injection with air and chemi-
cal additives, use of solvents,
inclined and horizontal drilling,
and fracturing of the formation
have been highly successful,
improving CSS recovery factors to
40% of gross pay.
5
Recovery factors for SAGD typi-
cally exceeding 50%
6
and
sometimes reaching 70-80%
7
are
well documented but are not yet
adequately recognised by the
ERCB.
2
Here are some examples of new
technology under development by
just one company, Imperial/
ExxonMobil, to further improve in
situ bitumen recovery factors and
reduce greenhouse gas (GHG)
emissions intensity:
After more than 10 years of
research and pilot testing,
Imperial/ExxonMobil is deploying
a new technology called LASER
(liquid addition to steam to
enhance recovery) that uses co-in-
jection of low concentrations of
pipeline diluent (natural gas
condensate) and steam. The diluent
helps reduce bitumen viscosity,
helping it to fow, and increases the
amount of bitumen extracted per
unit of steam. This decreases GHG
emissions intensity of bitumen
extraction by more than 25% and
will likely increase bitumen recov-
ery factors.
Imperial/ExxonMobil has also
piloted continuous infll steam
fooding to increase bitumen recov-
ery in mature projects. Results from
the pilot showed increased in situ
bitumen recovery factors and
reduced GHG emissions intensity
of in situ bitumen extraction by up
to 30%.
Imperial/ExxonMobil is construct-
ing a $100 million feld pilot,
expected to start up in 2014, to test a
cyclic solvent in situ bitumen extrac-
tion process. Using solvent instead of
steam to extract bitumen is expected
to reduce GHG emissions intensity
by about 90% by virtually eliminat-
ing water use.
Reducing GHG emissions
600
700
500
400
300
200
100
P
r
o
d
u
c
t
i
o
n
,

1
0
3

m
3
/
d
0
3776
4405
3146
2517
1888
1259
629
P
r
o
d
u
c
t
i
o
n
,

1
0
3

b
b
l
/
d
0
2002 2004 2006 2008 2010 2012 2014 2016 2018 2020 2022
Surface mining
In situ
6
8
7
5
4
3
2
1
P
r
o
d
u
c
t
i
o
n
,

m
i
l
l
i
o
n

b
b
l
/
d
0
Oil sand operating
and in construction
Eastern Canada
Conventional light
Pentanes
June 2012 forecast
Conventional heavy
Oil sands growth
2
0
0
6
2
0
0
8
2
0
1
0
2
0
1
2
2
0
1
4
2
0
1
6
2
0
1
8
2
0
2
0
2
0
2
2
2
0
2
4
2
0
2
6
2
0
2
8
2
0
3
0
Actual Forecast
Figure 4 Alberta crude bitumen production Source: ERCB ST98-2103
Figure 5 Bitumen and oil production forecast
Source: Crude Oil Forecast, Markets and Transportation, CAPP report, June 2013
In situ thermal
enhanced recovery
technology for
bitumen production
is still at an early
development stage
Priaro.indd 3 10/06/2014 12:40
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In contrast, Albertas Grosmont
bitumen carbonate deposit with a
productive area of 17 650km
2
has a
volumetrically determined OOIP of
406 billion bbl.
2

The Grosmont carbonate contains
bitumen with properties very simi-
lar to that in the bitumen sands but
in reservoir rock having very differ-
ent rock properties from the
unconsolidated bitumen sands.
The term unconsolidated sand-
stones, widely used in the
Saudi Arabias super giant
Ghawar oil feld is undisputedly
the worlds largest conventional oil
reservoir. With a productive area of
2800km
2
, the highest published esti-
mates of Ghawars OOIP are
250-300 billion bbl and 140 billion
bbl for its original recoverable
reserves (International Energy
Agency, 2008). This implies recov-
ery of about 51% of OOIP.
Volumetric estimates place
Ghawars OOIP at 190 billion bbl.
8
intensity refers to reducing GHG
emissions per barrel of bitumen
extracted. Depending on how much
bitumen extraction volumes
increase, total GHG emissions
could actually increase even though
emissions intensity has decreased.
Albertas bitumen sands reserves
In 2013, the ERCB estimated 1270
billion bbl of OOIP in Albertas
bitumen sands, 406 billion bbl of
OOIP in Grosmont bitumen
carbonates, and another 168 billion
bbl OOIP in other bitumen
carbonate formations such as the
Nisku to give total bitumen OOIP
in Alberta of 1844 billion bbl.
2
The ERCB, technically competent
but cautious to a fault, used an
average recovery factor of about
22% to recognise ultimate recovera-
ble reserves of 277 billion bbl in the
bitumen sands and only about 7%
to recognise ultimate recoverable
reserves of 38 billion bbl in the
bitumen carbonates.
The ERCB also estimated initial
established reserves of 177 billion
bbl in the bitumen sands indicating
an average recovery factor of only
about 14% of OOIP and recognised
no initial established reserves in the
bitumen carbonates whatsoever.
The ERCB estimated that 7% of
the OOIP in the bitumen sands is
ultimately accessible by surface
strip mining and 93% by in situ
methods.
2
Applying a recovery factor of
90% to strip mine accessible bitu-
men sands and a moderate
recovery factor of 45% to in situ
accessible bitumen sands to total
OOIP of 1270 billion bbl in the bitu-
men sands indicates 575 billion bbl
of technically recoverable reserves
in Albertas bitumen sands, after
deducting 6% shrinkage (see
Table 1).
Albertas bitumen carbonates
Bitumen saturated carbonate forma-
tions are found just below Albertas
bitumen sands formations. Figure 6
details bitumen net pay in the
Grosmont carbonate formation,
which extends over an area of 6816
square miles (or 17 650 km
2
), reach-
ing a net pay thickness of up to
394ft (120m).
Extraction OOIP Recovery OOIP OOIP Reserves after
accessible by factor of recovered by recovered by 6% shrinkage
each method
1
each method each method each method method
% % % billion, bbl billion, bbl
Strip mine 7 90 6.3 80 75
In situ 93 45 41.9 532 500
Totals 100 - 48.2 612 575
Source: Mike Priaro and ERCB
Alberta bitumen sands crude oil reserves
Table 1

Figure 6 Alberta Grosmont carbonate bitumen net pay thickness Source: ERCB ST98-2013
Priaro.indd 4 10/06/2014 12:41
reserves are as yet offcially
recognised.
Applying 45% recovery to
Albertas bitumen carbonates OOIP
totalling 574 billion bbl indicates
technically recoverable crude oil
reserves in the bitumen carbonates
of 243 billion bbl after deducting
6% shrinkage.
Applying 10% recovery of 424
billion bbl of OOIP for Alberta tight
oil shales and siltstones indicates
an additional 40 billion bbl in tech-
nically recoverable reserves.
Adding these reserves to the
previously calculated 575 billion
bbl of reserves for strip mining and
in situ bitumen sands indicates total
recoverable reserves of oil in
Alberta of 858 billion bbl (see Table
2). Note that cumulative produc-
tion from the bitumen sands to year
end 2013 is 10 billion bbl.
The provinces remaining estab-
lished light, medium, and heavy
conventional crude oil reserves of
1.7 billion bbl are tiny in compari-
son though there has been a
reversal from decline to small
increases in the last three years.
Are Albertas oil reserves larger than
Saudi Arabias and Venezuelas?
A 2009 US Geological Survey
study
10
estimated mean OOIP of
1300 billion bbl in Venezuelas
Orinoco oil belt and applied a 45%
recovery factor for Orinoco heavy
oil and shrinkage of 6% to estimate
technically recoverable reserves of
550 billion bbl. The US EIA
currently recognises a lower fgure
of 298 billion bbl for Venezuelas
proven reserves.
11
OPEC listed Saudi proved oil
reserves of 260 billion bbl in 2012
12
.
With total production of 125 billion
bbl since the discovery of oil in
Saudi Arabia and OOIP of 716
billion bbl, the Kingdom claims a
recovery factor of about 54%.
Table 3 shows that Albertas
remaining crude oil reserves are the
largest based on recent indications
of improved recovery factors and
new reserves in bitumen carbonates
and tight oil shales.
Crude oil reserves
Table 3 is a conservative compari-
son of Albertas crude oil reserves
carbonates for the frst time,
recently completed successful
commercial scale pilots. Both are
now proceeding to step by step full
scale development of their bitumen
carbonate leases. Note that the vast
majority of the remaining mineral
leases in the best parts of the
Grosmont bitumen carbonate
deposit are held by Shell, Suncor,
and Husky Energy.
Grosmont carbonate core lab tests
show recovery factors of 30-60%
9
under SAGD which compares
favourably to bitumen sands core
lab tests.
The ERCB estimates an additional
424 billion bbl of OOIP in Albertas
tight oil shales.
2
These contain
conventional light crudes in a vari-
ety of different formations but little
development has occurred to date
and no technically recoverable
petroleum industry, refers to sand-
stones, or sands, that possess no
true tensile strength arising from
grain to grain mineral cementation.
Such materials are friable, which
means an intact sample can be
easily broken apart with the hand
into individual grains.
The Grosmont carbonate forma-
tion consists of competent reservoir
rock of limestone and dolomite
uniquely characterised by large
vugs, open fractures, and signif-
cant porosity in the matrix rock.
This results in high, but transient,
initial fracture and vuggy produc-
tivity followed by lower, but stable,
matrix productivity.
In the 1980s, pilot projects in
the Grosmont carbonate were
conducted using CSS in vertical
wells with some of those wells
producing promising amounts of
bitumen. However, these trials
ended in 1986 when the price of oil
dropped to $10/bbl making further
development uneconomic. Since
then, application of recently devel-
oped technologies such as horizontal
drilling, SAGD and 3-D seismic
have dramatically improved recov-
ery factors in both the bitumen
sands and bitumen carbonates.
OSUM Oil Sands and Laricina
Energy, both applying the new
technologies in the bitumen
Alberta Bitumen and oil deposits OOIP Recovery Recoverable Reserves
factor crude oil after 6%
reserves shrinkage
billion bbl % billion bbl billion bbl
Bitumen sands strip mining 89 90 80 75
Bitumen sands in situ 1181 45 531 500
Bitumen carbonates in situ 574 45 258 243
Tight oil shales 424 10 42 40
Totals 2268 - 912 858
Source: Mike Priaro and ERCB
Table 2
Jurisdiction OOIP Remaining crude oil reserves Average recovery
billion, bbl billion, bbl after shrinkage
%
Alberta 2268 848 38
Venezuela 1300 550 42
Saudi Arabia 716 260 54
Source: Mike Priaro, Industry, OPEC, ERCB
Crude oil reserves
Table 3
Cumulative
production from the
bitumen sands to
year end 2013 is
10 billion bbl
Priaro.indd 5 10/06/2014 12:41
www.eia.gov/cfapps/ipdbproject/IEDIndex3.
cfm?tid=5&pid=57&aid=6
12 OPEC Annual Statistical Bulletins, www.
opec.org/opec_web/en/publications/202.htm
13 Cumulative bitumen production of 10
billion bbl to the end of 2013 was deducted.
Mike Priaro has worked in facilities, production,
operations and reservoir engineering, as
engineering consultant, area superintendent,
and in engineering management in Albertas
oil patch for 25 years for companies such as
Amoco and PetroCanada. He holds a BEngSc
in chemical engineering from the University
of Western Ontario.
america/north-american-crude-oil-and-ngls/
thermal-insitu-oilsands/
7 Cenovus, Telephone Lake Project, Vol 1
Project Description, Dec 2011, 4-25, www.
cenovus.com/operations/docs/telephone-
lake/Volume%201/V1_Sec4.pdf
8 www.geoexpro.com/articles/2010/04/
the-king-of-giant-elds
9 Macquarrie Equity Research, Feb 2010,
26, www.sunshineoilsands.com/uploads/les/
macquarie_report_01_10.pdf
10 US Geological Survey study, An Estimate
of Recoverable Heavy Oil Resources of the
Orinoco Oil Belt, Venezuela, pubs.usgs.gov/
fs/2009/3028/pdf/FS09-3028.pdf
11 US Energy Information Administration,
in that it shows a lower average
recovery factor to estimate Albertas
crude oil reserves than is used for
either Venezuela or Saudi Arabia.
The table also uses the highest
published estimates of reserves for
Venezuela and Saudi Arabia.
The fgure of 848 billion bbl
13
for
Albertas remaining crude oil
reserves does not include any natu-
ral gas liquids in shale gas reserves
and in as yet unmeasured bitumen
sands extending into the Athabasca
Basin in the adjacent province of
Saskatchewan.
It also does not include substan-
tial developed, undeveloped and
potential crude oil reserves in the
rest of the WCSB including the
northern part of the Williston Basin
and the Athabasca Basin in
Saskatchewan, the Intramontane
and Pacifc Basins of the province
of British Columbia, basins in the
Yukon Territory, the Mackenzie
Basins and Delta, the Beaufort Sea,
Canadas Arctic Islands archipel-
ago, as yet unmeasured bitumen
sands deposits indicated by a 60
mile long outcrop on Melville
Island in Canadas Arctic, and
offshore Eastern Canada.
Estimating reserves is often as
much art as science and, in the
case of OPEC and even Alberta, can
be more politics than science.
Reserves estimates generally
change over time as new informa-
tion becomes available. There are
also differences in defnitions of
reserves, for example, technically
recoverable versus proved reserves.
And most certainly, reserves esti-
mates are subject to interpretation,
professional opinion, agendas, and
politics.
References
1 See ERCB/AGS Open File Report 2012-06,
Oct 2012.
2 ERCB Report ST98-2013.
3 Canadian Association of Petroleum
Producers Jun 2013 report Crude Oil Forecast,
Marketing, and Transportation, www.capp.ca/
getdoc.aspx?DocId=227308&DT=NTV
4 Imperial Oil, www.imperialoil.ca/Canada-
English/les/News/N_S_Speech060608.pdf
5 Alvarez J, Han S, Current overview of cyclic
steam injection process, Journal of Petroleum
Science Research, Vol 2, 3, Jul 2013.
6 www. cnr l . com/ oper at i ons / nor t h-
Priaro.indd 6 10/06/2014 12:41
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Chevron Lummus Global worked closely with a private
rener in China to dene a processing scheme that
would upgrade low value, opportunistic feedstocks
such as Merey 16 crude or high sulphur fuel oil streams
to high value, all-liquid products; the rener did not
want to produce petcoke because of current oversupply
and low pricing of even anode grade coke in China.
The most important technology selection criteria were
robustness proven through commercial experience and
the ability of the licensor to deliver nished products
from residue hydrocracking through integration of
appropriate technologies. Utilising the companys
process planning modelling capabilities, CLG quickly
evaluated multiple potential technologies and technol-
ogy platforms after pinpointing the exact nature of the
feedstocks and product demand pattern and narrowed
down the processing route as shown in Figure 1.
The LC-Max reaction platform (see Figure 2), built on
the proven LC-Fining technology platform, is based on
the philosophy that eliminating the heaviest
asphaltenes from the conversion process effectively
eliminates the most common and persistent fouling
issues related to residue hydrocracking while at the
same time signicantly reducing hydrogen consump-
tion (not wasted in heavy asphaltenes saturation and
hydrocracking), reactor volume, and catalyst addition
rate.
The vacuum gas oils from the LC-Max unit are sent
to an Isocracking unit for conversion to heavy naphtha
and diesel. The catalyst system in the two-stage hydroc-
racking unit is designed for maximum conversion to
heavy naphtha while still retaining the capability to
produce a signicant quantity of diesel. Integrated
within the same high pressure loop as the Isocracking
unit is an Isotreating unit that utilises the excess hydro-
gen available in the hydrocracker circuit and the
available high hydrogen partial pressure to hydrotreat
the naphtha and diesel range material from the crude
distillation section and residue hydrocracking.
Integration saves at least 30% of the capital compared
to a standalone distillates hydrotreating unit.
Technology in Action

Residue hydrocracking for value
addition
Future imported
fuel oil
Crude
AR
SR diesel
Whole naphtha
Light naphtha
Pitch
Isomerate
Heavy naphtha
Hydrogen
SRVGO
LCFVGO
SR diesel
LCF diesel
SR naphtha
LCM naphtha
VR
Desalter
CDU
VDU
Isom.
CCR
Benzene
extraction
Naphtha
splitter
Isocracking
with
integrated
isotreating
Gasifier
Sour fuel gas
Euro V diesel
Gasoline pool
Benzene
Sour LPG
LC-MAX
unit
Mixed
xylenes
To ARU
To ARU
Figure 1 Processing scheme to upgrade low value feedstocks
case studies copy 8.indd 1 10/06/2014 13:21
then subjecting the coke through calcination and rigor-
ous testing to prove its suitability for use as anode
coke.
For more information: BSRI@chevron.com
Sulzer was contacted by two separate refners who
noted a continued fouling problem and short run
lengths on their wastewater strippers. The confgura-
tion of the units was very similar, with both strippers
processing wastewater from the desalters, coker blow-
down, and various waste sumps from around the
refnery.
Refner A was operating a retroftted column,
formerly utilised as a coker main fractionator. It wanted
to install new internals to ft within the existing tray
support rings to avoid welding on a stress-relieved
vessel. The refner targeted an increase in run length
from eight weeks to six months.
Refner B had noted its fouling problem becoming
worse with opportunity crudes being processed. They
were batching fow to the stripper, with a surge tank
upstream. Refner B was controlling stripping steam
injection to maintain a middle tray temperature target.
It had planned to replace the trays in kind, but wanted
to investigate other options before the next outage for
cleaning.
The strategy
Benzene stripper columns, built so that refneries can
meet the US National Emissions Standards for
Hazardous Air Pollutants (NESHAP), operate with
Hydrogen production
Natural gas is very expensive in China and, in particu-
lar, at this refners location. Many of the recent projects
have a natural gas price of $16-18/MMBtu. At these
prices, gasifcation to produce hydrogen starts becom-
ing economically attractive and is an excellent outlet for
the pitch from the LC-Max unit. The gasifer will
process a blend of pitch and coal. CLG is working with
a third party to produce the pitch in a form that is
suited to most gasifers. In addition to hydrogen from
gasifcation, hydrogen is recovered from the catalytic
reforming and propane dehydrogenation units that also
form part of the refnery complex.
Project schedule
The refner is driven to complete the detailed engineer-
ing on the entire project within 24 months and to start
up the unit within 36 months. To this end, long-lead
items such as reactors and compressors were ordered
very soon after project kick-off.
Increased interest
Since licensing this unit in late 2013, CLG has seen a
spate of inquiries from other refners for both grass-
roots and revamp options utilising LC-Max. For those
refneries with existing delayed coking units or those
that are contemplating producing anode grade coke for
use in aluminum smelters, incorporating a LC-Fining
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attractive option, especially for those refners process-
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demonstrated that anode grade coke can be produced
from unconverted oil derived from a high conversion
LC-Fining unit by coking the unconverted residue and

Wastewater stripper fouling cured
Figure 2 LC-Max block ow diagram
Vacuum
resid feed
Make-up H
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team, working with the customer, discovered control
systems with improper confguration, broken valves,
faulty instruments, and controller tuning that was far
from the optimum.
In its refnery operations, too, the company was
searching for a way to stabilise operations, increase
production, improve yields and qualities. There had
been earlier attempts to solve performance issues with
other loop control tools, but with no success.
Cooperation between the company and Metso started
with limited-scope trial installations in refning and
upstream operations with clearly defned success crite-
ria. Metso also provided the company with training
and support in identifying major issues.
A key part of the Control Performance Solution is to
prioritise the action items, according to their economic
beneft. The highest priority items were addressed
immediately, delivering the fast return on investment.
Currently, the team is focused on resolving the remain-
ing high priority issues. The company has understood
that additional on-site technicians and engineering
personnel are needed. An emphasis on continued
monitoring of control performance will ensure that the
benefts are sustainable.
Software and specialists
The foundation for Metsos Control Performance
Business Solution is Metso ExperTunes PlantTriage
software. The software is used by Metsos control
performance specialists, who collect and analyse real-
time performance data, identify the root cause of
underperforming loops, prioritise corrective action
recommendations and manage the resolution of issues.
These specialists are trained to recognise the economic
value of control improvement so they can focus on the
most important issues and report on their impact in
business terms.
Typically 30% of all plant controls are not fully
performing, with the result that plant performance is
signifcantly impacted. The challenge is to correctly
identify the underperforming controls, identify the root
several unique conditions low vapour rates, high
liquid loads, and a high tendency toward fouling make
designing well-balanced, effective internals diffcult.
Benzene steam stripper columns tend to have very
low vapour rates because the refner seeks to minimise
energy consumption and steam usage. The vapour load
on the top trays is primarily stripped hydrocarbon,
with much of the steam having condensed on the lower
trays. The low vapour rates are coupled with high
liquid rates, which can make a good, balanced tray
design tricky.
Without the appropriate stripping steam, the
top vapour loads can be non-existent. Sulzer
starts with a simple heat balance in the column. A
signifcant amount of latent heat from the steam is
transferred to sensible heat in the water and unable to
be used to strip the benzene. Steam injection must be
suffcient to where enough steam remains in the
vapour phase or no tray design will be successful in
this application.
An anti-fouling tray design should be considered.
There are several features that Sulzer implements in
many services to reduce fouling accumulation like a
deck design to reduce stagnation zones, high perfor-
mance downcomers to enhance liquid disengagement,
and large fxed valves like the Sulzer V-Grid LVG trays.
The solutions
Presented with an anti-fouling tray option or a less eff-
cient shed deck option, Refner A chose to equip their
column with V-Grid LVG trays and channel baffes in
order to create an active area with adequate sweep of
liquid and adequate valve density to maintain effciency.
For Refner B, Sulzer recommended an alternate
control scheme to maintain a stripping steam to feed
rate ratio, ensuring that the system had adequate duty
to strip out benzene. Refner Bs stripper was equipped
with antifouling trays, featuring sloped downcomers to
keep a higher velocity in order to sweep solids from
the exit.
For more information: TowerTech.CTUS@sulzer.com
A global oil and gas company was facing major chal-
lenges in both its upstream and refning processes.
High levels of process variability were leading to issues
with stability of operations and were limiting produc-
tion. Many of these problems could be traced to
fundamental performance issues with instrumentation,
valves, and process control. Upon initial inspection, it
was unclear which devices were underperforming,
leading to instability in the production process.
How could the company increase production and stabi-
lise its operations? There had been several earlier
attempts to solve the performance issue with no
success.
In 2013, the company turned to Metso and was
informed about Metsos Control Performance Business
Solution. This customised service program helps to

Control issues resolved
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Sponsored by:
Register at www.europetro.com - conferences@europetro.com - tel: +44 20 7357 8394
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3
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ASIA TECHNOLOGY FORUM 2014
8 & 9 OCTOBER 2014, KUALA LUMPUR
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CONFERENCE HIGHLIGHTS
KEYNOTE PRESENTATIONS
Refining & Petrochemicals Perspectives: Feedstock and Crude Price Trends
Journey to a Successful Project - Make Every Step Count
Petronas' Approach to Asset Management Excellence
PROFITABILITY, MANAGEMENT & ENERGY EFFICIENCY
ONGC's Strategic Development Model for Business Growth and Sustainability
Energy Reduction Plans for Refiners: Significant Cost Savings
Integration of Planning & Scheduling Tools to Optimise Refinery Assets
FOCUS ON CLEAN FUELS
Petronas Melaka's Experience with Lubes VDU
Alpha-Olefins Production Expertise
Profiting from Sour Water in Changing Global Climate
Sinopec's Integrated Clean Fuel Production Technology
NEW! PROCESS SAFETY FOCUS SESSION
Integrating Culture and Leadership into Process Incident Prevention
Leveraging Systems to Build High-Functioning Organizational Culture
Integrated Fire, Safety and Security Design Concept
Helping the Plant Safety Team Manage Incidence and Mitigate Risks
RESIDUE-UPGRADING STREAM
Solvent Deasphalting - the Key to High Conversion
Superior DCU (Delayed Coking) Reliability and Safety
Revamping Your Crude Distillation Unit for Maximal Energy Efficiency
PETROCHEMICALS STREAM
Capturing Value with Advanced ParamaX Technologies and Services
Alternate Feedstock Routes to Produce Olefins
Enhanced Aromatics Recovery Process from FCC Gasoline
asia tech.indd 1 05/06/2014 19:01
resistance to stress corrosion cracking (SCC) in
chloride bearing environments and in environments
containing hydrogen sulphide (H
2
S). It also has high
resistance to general corrosion, pitting and crevice corro-
sion, along with erosion corrosion and corrosion fatigue.
The enhanced microstructure of Sandvik SAF 2205
provides the material with superior corrosion proper-
ties and toughness, confrmed with ASTM A262
Practice E (Strauss test) without reservation. Its high
strength is roughly twice the proof strength of austen-
itic stainless steel, making the material an attractive
alternative to austenitic steels in structures that are
subjected to heavy loads.
These good mechanical and corrosion properties
make SAF 2205 an economical choice in many applica-
tions by reducing the lifecycle costs of equipment. The
grades physical properties and good weldability imbue
the material with design advantages over austenitic
stainless steels in equipment comprising both carbon
steel and stainless steel.
With duplex stainless steels, pitting corrosion resis-
tance depends on the pitting resistance equivalent
(PRE) value. PRE is a tool for ranking stainless steels
with regards to their pitting and crevice corrosion resis-
tance, depending on the levels of chromium,
molybdenum and nitrogen (PRE=%Cr + 3.3x%Mo +
16x%N). The minimum PRE value for SAF 2205 seam-
less tubes is above 35, signifcantly higher than PRE
values for typical duplex stainless steels like UNS
S31803 and Alloy 825.
Practical advantages of the grade are particularly
evident at high temperatures. When exposed to
temperatures exceeding 280C (540F) for prolonged
periods, under which H
2
S typically starts to corrode
standard refnery equipment, resulting microstructure
changes do not necessarily affect the behaviour
of the material. The result is that duplex stainless steel
heat exchanger tubes can be used at considerably higher
temperatures and chloride contents than ASTM TP304
and ASTM TP316 grades, without pitting. For these
reasons, SAF 2205 is far more serviceable in chloride
bearing environments than standard austenitic steels.
During the tender process, Sandvik established a rela-
tionship with key fabricators and those responsible for
engineering procurement and construction (EPC). The
Sandvik Production Unit mill in Zhenjiang
was formally audited by the project team accompanied
by the fabricators, for whom technical training
was arranged. Situated approximately 250km northwest
of Shanghai, the mill serves the rapidly growing Asian
markets with tubes for heat exchangers.
These are made in either straights or U-bends in lengths
of 3000mm up to 24 500mm, to suit each specifcation.
After lengthy discussions regarding the projects tech-
nical aspects, the fabricators and EPC recommended
Sandvik tube products to the oil and gas company at
the very beginning of the project. Additionally, upon
examination of the facilitys advanced production tech-
nologies, knowledge resources and processes for
manufacturing advanced stainless steel tubes for heat
exchangers and hydraulic and instrumentation systems,
cause and implement the corrective measures.
When process controls are working well, they
respond swiftly to any disturbances, applying just the
right amount of correction. When controls are not
performing correctly, the inappropriate response will
add to the process variability, or may even create an
unstable situation.
For more information: aija.kalander@metso.com
Duplex stainless steels are becoming increasingly relied
upon in oil refneries around the world. Sandvik
Materials Technology has been developing advanced
duplex grades since the 1930s which are generally char-
acterised by lower levels of carbon (C) and increased
amounts of molybdenum (Mo) and nitrogen (N). They
are shown to provide superior resistance to stress corro-
sion cracking (SCC) and pitting corrosion compared to
standard duplex grades.
A Chinese oil and gas company, with technical
support from a leading global manufacturer and
marketer of differentiated chemicals, wanted to
construct a large-scale propylene oxide chemical green-
feld project located in Nanjing, China. The project
entailed installing more than 450 tonnes of duplex
tubes, including both straight and U-bend, in its heat
exchangers.
Propylene oxide is a high added value petrochemical
product used in the production of polyurethane insula-
tion in varied applications from building construction
to the automotive industry.
Corrosion resistant materials for superior processing
performances are increasingly critical to Chinas refner-
ies which face intensifying corrosion phenomena such
as high sulphur content, heavier factions and more
generally acidic content. These corrosion media are
exacerbated by a gradual decline in quality of Chinas
crude oil as its domestic oil felds reach the late stages
of extraction.
Given these factors, and the nature of the project, cost
was an essential factor. After a year of tough negotia-
tions and competition from local tube producers,
Sandvik was formerly awarded the contract for the heat
exchanger tubes in the last week of 2013.
The tender process involved a number of technical
meetings, including at the Beijing Tsinghua Urban
Planning & Design Institute, and concluded with two
rounds of tough price negotiation. Sandvik offered an
extra value of 15-22% against its competitors, due
largely to the cost and lifecycle advantages of its
advanced duplex stainless steels over standard duplex
grades.
SAF 2205 material grade was specifed as the material
for the project, supplied in U-bend tube. It is a member
of the family of duplex stainless steels
by Sandvik whose chemical composition is balanced in
such a way that the reformation of austenite in
the heat affected zone, adjacent to the weld, takes
place quickly. The grade is characterised by high

Duplex steel for exchanger tubes
www.eptq.com PTQ Q3 2014 121 122 PTQ Q3 2014 www.eptq.com
Environmental soundness. The audit process and
subsequent report by feld technicians and engineers,
builds on know-how covering compressors from every
major manufacturer. The audit is rigorous and detailed,
yet the follow-up report sets out its conclusions in a
straightforward way that makes it easy for plant
managers to act on the information.
Mina Al-Ahmadi, with a 730 000 b/d throughput
capacity, is one of three refneries operated by Kuwait
National Petroleum Corporation (KNPC), the others
being Mina Abdulla and Shuaiba. KNPC is Kuwaits
biggest refnery operator and has the largest refning
capacity in the Middle East.
Hoerbiger has worked with KNPC for more than 15
years and supplies the company with reciprocating
compressor spares and services through its offces in
Kuwait and the UAE.
The state-owned company supports current govern-
ment programmes to reduce emissions, conserve
energy and use environmentally friendly processes, and
new initiatives at KNPC sites must adhere to an estab-
lished change management process. KNPC managers
had previously considered whether to optimise the
compressors but were not clear whether this would
contribute to the companys overall goals.
KNPC has to pay world market prices for the energy
it consumes in the production of diesel fuel and gaso-
line, which is incentive enough to produce as effciently
as possible.
Zhenjiang was approved as the clients preferred mill.
The audit concluded that Sandvik duplex stainless
steels in heat exchanger tubes can be used at higher
temperatures, without any problems.
Overall, the Nanjing project will consume more than
400 tonnes of duplex tube including U-bend tube, with
reduced use of the standard 904L grade. The frst batch
of supply from Product Unit Zhenjiang will commence
in October 2014, with the remainder being delivered in
early 2015.
For more information: sara.liu@sandvik.com
A thorough performance review of 40 reciprocating
compressors at the Mina Al-Ahmadi refnery in Kuwait
will form the basis for future upgrades to improve
energy effciency and environmental performance,
according to compressor specialist Hoerbiger. The refn-
ery, which dates back to 1949, uses reciprocating
compressors primarily to handle hydrogen for hydroc-
racking and hydrotreating.
Hoerbiger used a proprietary process known as REE
auditing to assess the operation of each compressor and
show how its performance could be improved through
measures ranging from new valves and packings to a
complete overhaul.
REE stands for Reliability, Effciency and

Compressor review leads upgrade
primary reformer tubes during 30 years: failures,
avoiding problems, and improving performance.
4 Nielsen N K, Is hot restart jeopardizing plant
safety?, AIChE 2012.
5 Cotton B, Broadhurst P, Common problems
on primary reformers, AIChE 2004.
6 Webb G M, Taylor W K, Reformer tubes: not a
commodity, AIChE 2006.
7 Rani B, Catastrophic failure of reformer tubes
at Courtright ammonia plant, AIChE 2006.
8 Rogers M, Lessons learned from an unusual
hydrogen reformer furnace failure, AIChE 2006.
9 Brightling J, Roberts M, Catalyst catastrophes
II, AIChE 2005.
Oliver J Smith IV is the Global Process Lead
for the Hydrogen and Syngas business with Air
Products and Chemicals, Inc. He holds a BChe
from the University of Delaware and a PhD in
chemical engineering from Carnegie Mellon
University. He has authored over six patents
and numerous journal articles in the areas of
process optimisation and asset utilisation.
Bill Cotton supports Johnson Matthey Leading
Edge Customers by direction of technical
support and development programmes. He has
worked in a variety of technical and techno-
commercial roles covering methanol, ammonia
and hydrogen plants covering technical
support, plant operations and plant revamps.
He holds a BEng in chemical engineering from
Loughborough University of Technology.
Conclusions
A CatTracker offers a range of bene-
ts to the operators of synthesis gas
plants across many unit operations
including reformers, shift and
synthesis converters. For the rst
time, operators can now accurately
measure the process gas tempera-
tures within a reformer tube and
gain an insight into something that
has been previously hidden from
view. The unique features of system
also allow for application to radial
ow converters.
There are endless possibilities for
application of single and multiple
units with a variety of designs and
sensing point locations.
CatTracker is a registered trade mark of Daily
Instruments Corporation. Daily Thermetrics is a
division of Daily Instruments Corporation.
References
1 Cotton W J, Fisher B R, A complete analysis
of your reformer, AIChE 2002.
2 Davies M, Fisher B, Cotton W J, Advanced
modelling tools and techniques for primary
reformers, AIChE 2004.
3 Atef Hassan Saad El-Din, A.F.C. experience in
points are in the bed. Furthermore,
the location of the sensing points
can be biased to allow for highly
accurate remnant life calculation
and therefore maximisation of cata-
lyst charge. For poison-susceptible
applications (for instance, low
temperature shift) some of the sens-
ing points can be biased to the inlet
of the bed, allowing for close moni-
toring of the rate of poisoning to
help determine the poisoned
volume and hence catalyst change-
out timings.
For radial/axial ow applications
(points 2 and 3), it is important to
understand whether there is good
ow distribution across both the
ow planes within the bed. A
CatTracker can be designed such
that a single unit can provide
temperature measurements in both
the radial and axial planes.
Conventional thermocouples strug-
gle to provide such data as they
cannot be bent into the complex
shapes required for such monitor-
ing. A CatTracker can be bent into
any appropriate shape.
We make technology work.
www.hoerbiger.com
Like musicians set the tone,
HOERBIGER sets standards in
the Oil and Gas Industry.
Image_ad_KT_2014.indd 1 06.03.2014 15:46:22
j matthey.indd 7 10/03/2014 13:06
observed. When the iron content is high enough it
seals off the catalyst interior by forming a nodular
shell-like layer at the catalyst surface that inhibits
hydrocarbon diffusion into and out of the catalyst parti-
cle interior. Zeolite and matrix active components at
the core of the catalyst particle are unaffected by iron,
but are no longer readily accessible due to the barrier
formed on the outer surface. Often refners will try to
tackle iron poisoning with an increased fresh catalyst
make-up rate or use of added equilibrium catalyst to
dilute the iron by fushing it out of the FCC unit.
Cat-Aid is an effective trap for vanadium and other
contaminants such as iron. Vanadium is a permanent
poison that accumulates on the catalyst where it causes
catalyst deactivation by increasing the rate of destruc-
tion of the zeolite component, and promotes
undesirable dehydrogenation reactions, leading to
increased coke and gas make. Cat-Aid was originally
designed to capture vanadium thereby protecting the
base catalyst and greatly improving its performance.
For more information: Bart.deGraaf@Matthey.com
Refnery proftability may be improved by operating
with a cheaper crude oil diet though, in practice, this is
harder than it sounds. Cheaper crudes are cheaper for a
reason: they are generally heavier, sourer and more
contaminated than refners would normally consider
ideal. Consequently, converting them into premium
grade products at high yields and without undermin-
ing plant reliability presents a considerable challenge.
It is clearly possible, however. One North American
refner, for instance, has successfully processed large
volumes of diffcult, discounted crude oil to return an
impressive product slate of clean fuels that meet the
highest international specifcations. This refners
success is partly due to the close attention it pays to its
hydroprocessing assets, the way that it operates them
and its ability to respond positively to challenges as
they arise. An example of this is the way that the
refner, with help from Criterion, tackled the acute drop
in performance of one of its two kerosene hydrotreat-
ers, ultimately turning the problem around and
generating business benefts in terms of increased cycle
length and enhanced operational fexibility.
The site hydrotreats straight-run kerosene at rela-
tively low pressure (<500 psi) in two units. The frst of
these tends to receive higher grade kerosene to make jet
fuel, with its tight colour and colour retention specifca-
tions. It is mainly hydrodenitrifcation (HDN) and
saturation taking place in this reactor. The second unit
is assigned the tougher kerosene and it generally makes
an ultra low sulphur diesel (ULSD) specifcation prod-
uct for blending purposes.
Hydrodesulphurisation (HDS) is the prime objective
here. Colour is not so important for this product;
its value lies in its ability to improve the ULSD
pool in terms of volatility, gravity and viscosity.
Once Hoerbiger developed the concept of a REE
audit, even before the actual audit had been carried
out, it was obvious that the process would provide a
structured way to assess the potential to support
KNPCs business objectives through selective compres-
sor upgrades.
So in February 2013 the Austrian REE team went to
work at Mina Al-Ahmadi, spending four days on site.
After analysing the results, the team returned a month
later to present their fndings.
The REE audit showed that the 40 motor-driven
reciprocating compressors consume 55 MW of electric
power under current operating conditions, with a 20%
margin to cover production variations and future
expansion. The study also showed that continuous
stepless reverse fow control could cut power consump-
tion by 10%.
The audit team demonstrated how much more
knowledge could be extracted from the operating data
and inspection of every machine. Now the refnery has
40 detailed analyses indicating numerous ideas for
sustainable improvements.
Over the next few years KNPC will work with
Hoerbiger to choose and prioritise upgrade options for
the sites 40 reciprocating compressors, based on
the information from the REE audit. The resulting
energy savings and performance improvements
will help KNPC meet its energy and environmental
goals, while potentially bringing process improvements
too.
For more information: paul.peyer@hoerbiger.com
Residue and shale oil feeds often contain high levels of
contaminants that can create a number of challenges for
refners today. In recent commercial applications,
Johnson Mattheys Intercat
JM
catalyst enhancement
additive Cat-Aid has been found to be able to reverse
the effects of iron poisoning of the FCC catalyst. By
breaking down the nodular iron-rich shell on the
surface of the catalyst, Cat-Aid opens up access to the
inner core of the catalyst, allowing it to become avail-
able for cracking once more. This signifcantly increases
the proftability of the FCC operation by relieving oper-
ating constraints, improving product yields, and
reducing fresh and fushing equilibrium catalyst
consumption.
Metal contaminants such as vanadium, nickel, iron,
calcium, sodium and potassium can limit the refners
ability to process residue and shale oil feeds and
signifcantly impact the proftability of the FCC. Iron
poisoning, specifcally, can have a devastating effect on
FCC performance; iron typically lowers conversion,
increases slurry, coke, dry gas selectivity and increased
regenerator fue gas SOx emissions. In addition, unit
constraints such as impaired fuidisation may lead to
operational diffculties.
Most fresh catalysts are capable of handling up to
+0.3 wt% add-on Fe
2
O
3
before detrimental effects are
Reversing catalyst poisoning
Upgrading hydroprocessing
performance
www.eptq.com PTQ Q3 2014 123 124 PTQ Q3 2014 www.eptq.com
Centera technology platform. The new catalyst had
already demonstrated outstanding HDS and HDN
activity and stability in other low to medium pressure
ULSD units running difcult feeds.
Given the uncertainty surrounding the quality of the
feed to the unit, the team was unable to predict accu-
rately the effect of the new operating strategy and
catalyst on cycle length. It was hoped, however, that
the changes would add at least four months to the 12
months achieved previously.
The unit was loaded with Centera DC-2618 and
restarted with 100% kerosene from synthetic crude,
which had been held in storage during the shutdown.
The start of run WABT was as predicted. After this
poor quality kerosene had been processed, the WABT
fell by 6C, and it became clear from the subsequent
rate of temperature rise that the catalyst was retaining
its activity better than its predecessor, even though the
unit continued to be fed kerosene of variable quality.
Data obtained during the rst months of operation
led the team to revise its estimate of the cycle length.
Technologists at the renery began to believe it would
be possible to reach the 24-month mark, which is
double the length of the last run.
The enhanced performance of the unit has been put
down to the catalysts outstanding HDN activity. While
levels of 6070% were typical during the previous run,
analysis of data from the unit shows that the DC-2618
catalyst is achieving an HDN level of 9095%. This
means there is less nitrogen inhibition of the catalyst;
Unfortunately, the practice of using the second unit to
treat low-grade kerosene ran into difculties. This was
soon after the renery had begun to import more
opportunity and synthetic crudes. The kerosene
distilled from these synthetic crudes had higher
sulphur and nitrogen levels and challenging API gravi-
ties. All this kerosene was directed to the second unit,
which had just been loaded with fresh catalyst,
Criterions Ascent DC-2533. The impact of the feed
change was felt almost immediately. The renery had
to increase the operating temperature of the unit by
811C to meet the ULSD specication. And the catalyst
deactivation rate tripled. The renery technologists
tried to manage this by establishing a weighted average
bed temperature (WABT) budget and reducing the
throughput of the unit.
However, despite the reners best efforts, the cycle
length was curtailed 12 months after its start. Given the
likelihood that synthetic crudes would continue to
feature strongly in the crude diet through the course of
the next cycle, the renery approached Criterion for
help in devising the best way of maximising the cycle
length. A team of hydroprocessing specialists from the
renery and Criterion was assembled to examine the
composition and properties of the feed and to formu-
late the best operating strategy for the hydrotreating
unit and the crude distillation unit used to process the
synthetic crude. As part of this exercise, Criterion team
members proposed switching to a new-generation
CoMoalumina catalyst, DC-2618, based on Criterions
Kurita Europe GmbH
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Industriering 43
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41751 Viersen
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Germany
Phone: +49 2162 95800
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www.kurita.de
Permanent research and development form the core of our innovative products for chemical water and process management. As a worldwide market
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blending properties to those of ethanol and alkylate.
Compared to ethanol, isobutanol has a much lower
RVP and about 30% more energy content. The blend
octane of isobutanol is high as well (although slightly
lower than ethanol). Isobutanol also has less oxygen
content than ethanol, so more isobutanol can be
blended into gasoline for a given oxygen content. And
more blend volume plus more energy content means
more renewable identifcation number (RIN)
generation.
Isobutanol overcomes the regulation blend wall
limitation of ethanol blending. It is substantially
similar to gasoline at a 2.7 vol% oxygen content
(or up to 12.5 vol% blend). This is a conservative
frst step for blending for refners, and generates
16.25 RINs per gallon of fnished product. E10 has
3.5 vol% oxygen, which is the currently accepted limit
of oxygen content by automobile engine manufacturers.
For this same 3.5 vol% oxygen, a US EPA
211(b) waiver exists that would allow isobutanol blend-
ing to 16.1 vol%, yielding 20.93 RINs, more than twice
the RINs as E10 for the equivalent oxygen content.
Unlike ethanol that is fully miscible in water, isobuta-
nol has very limited water solubility (about 8.5%).
Isobutanol also does not cause stress corrosion cracking
in pipelines. These factors result in major advantages in
terms of blending logistics. Isobutanol can be blended
as a drop-in renewable fuel at the refnery and shipped
in pipelines to fuel terminals via existing infrastructure
which prospectively eliminates the need for segregated
tankage or pipelines. This also affords refners the
opportunity to once again produce a fnished spec
gasoline rather than a sub-octane blendstock for
oxygenate blending.
Taking the bio-isobutanol and processing it further to
iso-paraffnic kerosene (IPK) bio-jet has now been
demonstrated at Gevos hydrocarbon plant in Silsbee,
Texas.
To make IPK bio-jet from bio-isobutanol involves
three sequential steps:
1. Dehydration of the renewable isobutanol to mainly
isobutylene
2. Oligomerisation of the isobutylene to mostly
trimers/tetramers to produce C
12
and C
16
molecules
3. Hydrogenation of olefns to iso-paraffnic kerosene
(IPK) bio-jet
These processes present opportunities for retrofts
of existing under-utilised refning/petrochemical
assets in some cases and commercialisation and inte-
gration into an existing process plant should be
straightforward.
Depending upon economics, the overall process also
has the fexibility to make more or less iso-octene and/
or iso-octane byproduct streams (which make good
renewable gasoline blending components). It should be
noted that both renewable gasoline blendstocks (isobu-
tanol and iso-octene) are not tied to crude oil
processing, so these are not likely to carry crude oil
price volatility effects.
This bio-jet process has been demonstrated in a
small 10,000 gal/month (feedstock design capacity) unit
consequently, the required HDS level can be achieved
at reduced temperatures. This is highly signifcant: it
has improved the colour and colour stability of the
product from the second unit to the extent that it may
be used as a jet fuel component.
Detailed performance studies by the team, taking into
account feed quality and various operational scenarios,
indicate that it should be possible to run for 24 months
with high volume fractions of diffcult kerosene feeds.
At the same time, the refnery has gained the fexibility
to swing between ULSD and jet fuel production,
depending on the prevailing product market
economics.
The refnery has a strong record of using its hydro-
processing assets to process less favoured crudes and
achieve good margins. Therefore, the company is work-
ing with Criterion to increase the cycle length beyond
the projected 24 months. It is also looking at other feed
and product possibilities that have opened up as a
result of the improved performance of the second unit
with Centera catalyst.
For more information: Kevin.Carlson@criterion.com
Bio-isobutanol has many valuable characteristics that
allow it to:
Be used as is, as either a solvent or as a gasoline
blendstock
Be readily converted, through known processes, to a
variety of hydrocarbons for use in the petrochemical
and/or refning industries
Be effciently and effectively used in existing produc-
tion, distribution, marketing and end user assets.
The pathway to make bio-isobutanol is via fermenta-
tion, paired with an integrated separation technology to
optimise production. In May 2012, Gevo announced
that it had started up the worlds frst commercial bio
based isobutanol production plant in Luverne,
Minnesota, a planned 18 million gal/y facility.
Bio-isobutanol fermentation is quite similar to the
existing ethanol process; ethanol plants can be modifed
and repurposed to make isobutanol relatively easily
and cost effectively. And this was the case for Luverne.
One of the main reasons that converted plants have
such good projected economics is that bio-isobutanol is
so versatile as a platform molecule. In the chemicals
arena, it can be: sold as solvent product itself (for
paints) and/or through dehydration to isobutylene,
converted into materials such as butyl rubber and
paraxylene and other derivatives for use in market
applications such as tyres, plastic bottles, carpets and
clothing. For fuels applications, isobutanol can be
blended in as a low vapour pressure gasoline compo-
nent and/or used as feedstock to make other
transportation fuels (for instance, iso-paraffnic kero-
sene for use as bio-jet) or other renewable products
(including renewable heating oil).
Bio-isobutanols properties as a gasoline blendstock
can best be understood by comparing some of its

Bio-isobutanol: a versatile molecule
19thAnnual Meeting
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The meeting place for the international refining industry
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Crangrejera, Mexico. The project was initiated due to
the decreasing availability and reliability of the three
compressors, built by a third party manufacturer in
1978 after more than 200 000 operating hours.
As turnkey contractor, Burckhardt Compression
was in charge of the entire project and site management
as well as the engineering and manufacturing aspects.
The preparation time of eight months
including manufacturing and part delivery as well
as the timeline of 24 days per line for each
revamp turned out to be a challenge. By the end of
2013, the revamp was successfully fnished on schedule.
For more information: bettina.freihofer@burckhardtcompres-
sion.com
The Habshan Sulphur Granulation Plant, located about
16km southeast of the existing Habshan Gas Complex
in Abu Dhabi, is about to be the worlds largest sulphur
forming plant when measured by capacity. The plant
also includes extensive storage, blocking, and rail car
loading capabilities.
In early 2011, Dodsal Engineering and Construction,
the UAE based contractor, awarded Enersul, located in
Calgary, Alberta, a contract for 12 of Enersuls GXM1
sulphur granulation units as well as block pouring
towers and other equipment.
Sulphur granulation is a size enlargement process.
Liquid sulphur is sprayed onto small sulphur seeds
undersized granules and cooled to solidifcation.
With repeated application of liquid sulphur, the seed
increases in volume and weight. As the granule is
enlarged, each coating of liquid sulphur is fully and
structurally bonded to the layer beneath. This ensures
a spherical granule, entirely dry and completely free
of voids.
The process occurs in a rotating drum. Undersized
granules, which serve as seeds, are fed into the
granulating drum and lifted by fights attached
to the inside of the rotating drum. The result is a
continuous falling curtain of sulphur granules.
Liquid sulphur is sprayed onto the seed curtain
by a series of spray nozzles along the length of the
drum. The cooling process is achieve by the evapora-
tion of water, which is sprayed throughout the length
of the drum from the process water system.
As such, the GX process produces a spherical formed
product completely void of fat surfaces resulting in
lower friability and fugitive dust. The GXM1 is
Enersuls high capacity sulphur granulation unit,
which can produce 1500 t/d with higher throughput
being achieved through multiple process lines. The 12
Habshan units will produce 15 000 t/d of premium
formed sulphur.
The Habshan project was unique in that it featured a
staged delivery schedule with the frst four GXM1 gran-
ulation units to be delivered in 56 weeks, the second
four in 62 weeks, and the fnal third in 68 weeks.
For more information: pwories@enersul.com
product has been sold to the US Air Force as part of the
Alternative Fuel Certifcation Division (AFCO) process.
Again, isobutylene, iso-octene and iso-octane are side
products that can also be drawn off as products and
used as feedstock for production into other renewable
petrochemical products such as renewable paraxylene,
which now has also has been demonstrated at Gevos
site at Silsbee.
For more information: Richard.kolodziej@mustangeng.com
Pakistan Refnery Limited (PRL) is using process tech-
nology and modular equipment from Honeywells
UOP to help it meet growing domestic demand for
gasoline. The technology will be used to convert naph-
tha, which PRL currently exports, to high octane
gasoline. The refner will use Penex process technology
to produce isomerate gasoline blending component.
The use of isomerate will also help PRLs efforts to
produce cleaner fuels.
PRL selected UOP to deliver the process unit in
modular form to help ensure it is built to specifcation
and delivered on time and on budget.
Refnery process units are usually built in the
feld by third party engineering, procurement and
construction (EPC) companies. UOPs modular
units are built at an offsite fabrication shop where
adverse weather and wind conditions do not
cause delays. The modular units are inspected prior to
delivery. Reduced onsite installation time can
potentially result in earlier start-up, further
optimising project economics. UOP offers modularised
equipment for refning, petrochemical and gas process-
ing units.
In addition to licensing and modular equipment,
UOP will provide catalyst, adsorbent, engineering, tech-
nical support and a drier regeneration control system
for extended catalyst life for PRLs Penex unit, which
will process 5000 b/d of light naphtha. The unit is
expected to start up by mid-2015.
The Penex process enables refners to upgrade light
naphtha feedstock to produce gasoline blendstock
which does not contain benzene, aromatics or olefns.
In addition, the process uses UOPs high activity isom-
erisation and benzene saturation catalysts to remove
benzene. To date, the company has sold more than 220
Penex units, and its isomerisation catalysts have been
loaded into more than 300 units.
Pakistan Refnery Limited is a hydro-skimming refn-
ery which processes 50 000 b/d of crude oil. It is
located on the coastal belt of Karachi, Pakistan.
Pemex Petroquimica chose Burckhardt Compression as
turnkey contractor for the general revamp and
modernisation project of three Hyper Compressors at
the companys low density polyethylene plant in

Modular process for isomerate

Compressor revamp

Worlds biggest sulphur forming site
4th Opportunity Crudes Conference IBC
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ABB Consulting 50
Aerzener 59
Air Liquide Global E&C Solutions IFC
AMACS Process Tower Internals 92 & 114
Ariel Corporation 68
Asia-Tech 2014 120
Axens OBC
BASF Corporation, Catalysts Division 11
Bilnger Water Technologies 27
Bryan Research & Engineering 74
Burckhardt Compression 13
Cat Tech 22
CB&I 7
Chevron Lummus Global 9
Clariant 119
ContiTech Schlauch 61
CRI Catalyst 36
Criterion Catalyst & Technologies 4
Delta Valve 113
EMCOR Industrial Services 110
Enersul 67
ERTC Annual Meeting 126
Everlasting Valve Company 103
ExxonMobil Research & Engineering 16
ExxonMobil Research & Engineering/UOP Alliance 15
Flexim 39
Foster Wheeler 84
Four Quest Energy 48
GE Water & Process Technologies 40
Grabner Instruments 47
Heat Exchange Engineering Middle East 2014 100
Heurty Petrochem 54
Hoerbiger Kompressortechnik Holding 122
ITW Technologies 57 & 79
Johnson Matthey Process Technologies 25
John Zink Hamworthy Combustion 88
KBC Advanced Technologies 2
Kurita 124
Linde 62
Man Diesel & Turbo 44
Merichem Company 65
Metso Automation 117
Neuman & Esser Group 93
OHL Guttermuth 98
Optimized Gas Treating 77
Process Consulting Services 104 & 107
Prognost 87
Rentech Boiler Systems 30
Sabin Metal Corporation 43
Sandvik Materials Technology 96
Spectro Analytical 95
Streamlight 52
Sulzer Chemtech 35
ThyssenKrupp Industrial Solutions 108
Turbomachinery Symposium 80
UOP 19 & 21
Wood Group Mustang 83
Yokagawa Europe 32
Zwick Armaturen 29
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axens.indd 1 6/12/12 13:17:48

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