I.

Statement of the Design Project

In recent environmental legislations, lower sulfur specifications are required in both gasoline
and diesel fuels. In a refinery in the Delaware Valley, it was anticipated that the new diesel
specification will require an order of magnitude lower of sulfur than currently obtained, which
means that from 0.05 wt% sulfur the new requirement will be 0.005 wt% sulfur content in
diesel. In order to achieve these low sulfur level, a new catalytic hydrodesulfurization (HDS)
system is to be designed. This type of reactor has been in use in the industry for a long time but
never for such a severe service.
This unit will require just two feeds: a liquid feed blend from the refinery, and hydrogen. Since
the refinery does not have a reforming unit (common hydrogen source within a refinery) or a
hydrogen plant, the necessary hydrogen would have to be bought from a third party.
Processing Conditions
In designing the HDS unit, the percent hydrodesulfurization (%HDS) is determined by
Equation 1.

%HDS= 1

( wt %S ) product
100
( wt %S )feed

(1)

The following table shows the conditions of the proposed operation that will be based from
processing data available from an older HDS unit.
Table 1. Conditions of the HDS operation (Quale, 2000)

BASE
OPERATION
1.9
0.05

PROPOSED
OPERATION
1.9
0.005

35
1

35

H2 Circulation, scf/bb

800

1,000 (min.)

H2 Partial Pressure, psi

Start of Cycle Temperature (SOC), F
Aging rate (AR), F/mo

630
632
4.7

800 (min.)
?
?

Feed Sulfur, wt %
Target Product Sulfur, wt %
Reactor Conditions
Feed Rate, TBPD
Space Velocity (SV), hr-1

Page 1 of 35

The circulation and pressure values for the proposed operation are given as minimums to
achieve the necessary product specifications. Increasing these values will improve the catalyst
life, but result in higher capital and operating costs.
For our particular feedstock, the R&D department has done substantial pilot plant work on this
new process and has determined correlations which will assist in designing the HDS reactor.
These correlations are presented in Equations 2 and 3 which were based on the processing data
from an older HDS unit and a reference catalyst. These equations will be used to calculate the
unknown reactor condition values of the proposed operation (Quale, 2000). The terms denoted
with 0 are the baseline data from Table 1 and the values for the constants (A-F) are given in
Table 2. The SOC temperature is given by

T soc=T 0 + A ln

SV
+ B ln
SV 0

( )

[ ]
(
(

S feed
1
S product

S feed
1
S product

)
)

C ln

[ ] [ ]
PH

( P H )0

D ln

H2 .
( H 2 . )0

where Tsoc and T0 are in F and the aging rate is given by

E
PH
1
1
AR= AR 0
exp F

T 0 T soc
( PH )0

[ ] [
2

(2)

)]

(3)

where Tsoc and T0 are in R.

Table 2. Constants used for the correlations of the reaction conditions

Constant
A
B
C
D
E
F

Value
45
44
20
30
1.7
18,000

II. Diesel Fuel

Page 2 of 35

Diesel fuels are distillates with a boiling range of about 149 to 371C and comes in several
different grades, depending upon its intended use. Diesel fuel is not a single substance but a
blend of various petroleum-derived components, including paraffins, isoparaffins, napthenes,
olefins and aromatic hydrocarbons, each with their own physical and chemical properties.
Diesel fuel must satisfy a wide range of engine types, differing operating conditions and duty
cycles, as well as variations in fuel system technology, engine temperatures and fuel system
pressures. It must also be suitable for a variety of climates (Reynolds, 2007). The properties of
each grade of diesel fuel must be balanced to provide satisfactory performance over an
extremely wide range of circumstances. In some respects, the prevailing quality standards
represent certain compromises so that all the performance requirements may be satisfied. By
controlling specifications and properties, it is possible to satisfy the requirements of millions of
compression ignition engines with a single grade of diesel fuel.
Diesel fuel produces power in an engine when it is atomized and mixed with air in the
combustion chamber (UFA Co-operative Limited, 2009). Pressure caused by the piston rising
in the cylinder causes a rapid temperature increase. When fuel is injected, the fuel/air mixture
ignites and the energy of the diesel fuel is released forcing the piston downwards and turning
the crankshaft. Diesel fuel in general are used in diesel engines and its fuel ignition takes place
without spark, as a result of compression of the inlet mixture and then injection of fuel.

DIESEL FUEL QUALITY AND PROPERTIES

A. Cetane Number
Cetane Number is a measure of the ignition quality/delay of a diesel fuel and affects
combustion roughness. It is often confused with the octane number of the fuel. Octane is
a measure of a spark ignition engine fuels (gasoline) ability to resist engine knock (preignition from compression). Diesel cetane ratings work in the opposite direction. Cetane
number is measured in a single cylinder test engine with a variable compression ratio.
The reference fuels used are mixtures of cetane, which has a very short ignition delay,
and alphamethyl naphthalene which has a long ignition delay. The percentage of cetane
in the reference fuel is defined as the cetane number of the test fuel. The higher the cetane

Page 3 of 35

rating, the more easily it ignites or the shorter the interval between the time the fuel is
injected and the time it begins to burn.
Cetane number requirements of an engine will vary depending on engine size, speed and
load variations, starting conditions and atmospheric conditions. Since a diesel engine
ignites the fuel without a spark, proper cetane levels are very important. The air/fuel
mixture is ignited by the combination of compression and heating of the air due to
compression. The fuel is injected into the cylinder at the precise time ignition is desired
to optimize performance, economy and emissions. The importance of cetane number is
very evident as low cetane number usually causes an ignition delay in the engine. This
delay causes starting difficulties and engine knock. Ignition delay also causes poor fuel
economy, a loss of power and sometimes engine damage. A low cetane number fuel can
also cause white smoke and odor at start-up on colder days. White exhaust smoke is
made up of fuel vapors and aldehydes created by incomplete engine combustion. Ignition
delay during cold weather is often the cause. There is not enough heat in the combustion
chamber to ignite the fuel, therefore, the fuel does not burn completely. Typical diesel
fuels have cetane numbers in the low to mid 40's. These are generally satisfactory for
high speed engines while low and medium speed engines may use fuels with lower cetane
number.
B. Volatility
The power and economy of diesel engines are comparatively insensitive to fuel volatility,
unlike spark-ignition engines. There is some indirect impact in that less volatile fuels
have higher heating values (energy content). Conversely fuels with higher front-end
volatility tend to improve starting and warm-up performance and reduce smoke. A
properly designed fuel has the optimum proportion of low boiling components for easy
cold starting and fast warm-up and heavier components which provide power and fuel
economy when the engine reaches operating temperature. Either too high or too low
volatility may promote smoking, carbon deposits and oil dilution due to the effect on fuel
injection and vaporization in the combustion chamber.
The fuel volatility requirements also depend on engine design and size, nature of speed
and load variations, and starting and atmospheric conditions. As an example, more
volatile fuels may provide better performance for fluctuating loads and speeds such as
those experienced by trucks and buses however, better fuel economy is generally
Page 4 of 35

obtained from the heavier types of fuel because of their higher energy content. ASTM D
975 only sets a minimum/maximum range for the temperature at which 90 percent of the
fuel will evaporate. This is referred to as T 90, and the range for No. 2 grades of diesel fuel
is 282C to 338C. This limits the level of high boiling point components that could
lead to increased engine deposits.
C. Viscosity
Viscosity is a measure of a liquid's resistance to flow. High viscosity means the fuel is
thick and does not flow easily. The viscosity of diesel fuel is an important property
which impacts the performance of fuel injection systems. Some injection pumps can
experience excessive wear and power loss due to injector or pump leakage if viscosity is
too low. If fuel viscosity is too high, it may cause too much pump resistance, filter
damage and adversely affect fuel spray patterns.
The viscosity of the fuel affects atomization and fuel delivery rate. The viscosity of
diesel fuel is normally specified at 40C. Fuels with viscosities over 5.5 centistokes at
40C are limited to use in slow speed engines, and may require pre-heating for injection.
For some engines, it is advantageous to specify a minimum viscosity because of power
loss due to injection pump and injector leakage. Maximum viscosity, on the other hand, is
limited by considerations involved in engine design and size, fuel temperature and the
characteristics of the injection system.
D. Fuel Lubricity
Some processes used to desulfurize diesel fuel, if severe enough, can also reduce the
natural lubricating qualities of the diesel fuel. Since engines require the diesel fuel to act
as a lubricant for their injection systems, diesel fuel must have sufficient lubricity to give
adequate protection against excessive injection system wear. Diesel fuel lubricity is a
very important property, since the diesel fuel injection system relies on the fuel to
lubricate moving parts. As with low-viscosity fuels, if lubricating properties are
inadequate, it will lead to increased wear on injectors and pumps.
E. Cold Weather Characteristics
At extreme weather conditions, diesel fuels are blended seasonally and adjusted to
provide ultimate power and performance and minimize cold weather problems which are
inherent to diesel fuel. As diesel fuel is cooled it will reach the "cloud point". This is the
temperature at which paraffin wax falls out of solution and starts to form wax crystals in
Page 5 of 35

the fuel. As the fuel is cooled further, it will eventually reach its' "pour point". This is the
temperature at which fuel will no longer flow or the point at which fuel gels or turns
solid. Another key property of diesel fuel is the "Cold Filter Plug Point" (CFPP). This is
the temperature where fuel can no longer flow freely through a fuel filter, approximately
halfway between the cloud point and the pour point. How critical these factors become in
winter operation depends on the design of the fuel system with regard to fuel line bore,
freedom from bends, size and location of filters and degree of warm fuel recirculation as
well as the amount and kind of wax crystals. Additives are being used successfully to
improve fuel fluidity at low temperatures. These additives, known as wax crystal
modifiers, can result in satisfactory fuel flow on average of 9C to -27C.
F. Flash Point
Flash point is determined by heating the fuel in a small enclosed chamber until the vapors
ignite when a small flame is passed over the surface of the liquid. The temperature of the
fuel at this point is the flash point. The flash point of a diesel fuel has no relation to its
performance in an engine nor to its auto ignition qualities. It does provide a useful check
on suspected contaminants such as gasoline, since as little as 0.5% of gasoline present
can lower the flash point of the fuel very markedly. Shipping, storage and handling
regulations are predicated on minimum flash point of 40C.
G. Sulfur Content
Engine wear and deposits can vary due to the sulfur content of the fuel. Today the greater
concern is the impact that sulfur could have on emission control devices. As such sulfur
limits are now set by the U.S. Environmental Protection Agency (EPA), and those limits
have been incorporated into ASTM D 975. For No. 2 grade low sulfur diesel, the limit is
a maximum of 0.05 percent mass (500 ppm) and, for ultra-low sulfur diesel, it is 15 parts
per million (ppm) maximum.
H. Carbon Residue
Carbon residue gives a measure of the carbon depositing tendencies of a diesel fuel after
evaporation and pyrolysis under prescribed conditions. While not directly correlating
with engines deposits, this property is considered a guide.
I. Ash

Page 6 of 35

Ash forming material may be present in diesel fuel in two forms: (1) abrasive solids and
(2) soluble metallic soaps. Abrasive Solids contribute to injector, fuel pump, piston and
ring wear, and also engine deposits. Soluble metallic soaps have little effect on wear but
may contribute to engine deposits.
J. Acidity
Diesel fuel acidity if not controlled, can cause poor fuel stability, cause corrosion of mild
steel, and it could cause deposit formation in some types of fuel injection equipment.
K. Thermal Stability
Heat transfer is a design function of diesel fuels in many modern diesel engines. Only a
portion of the fuel that is circulated and pressurized by the fuel injection system is
actually combusted. The remainder of the fuel is recycled back to the fuel tank. The bulk
fuel temperature can be well above ambient levels. Inadequate high-temperature stability
of a diesel fuel can result in the formation of insoluble degradation products that can then
cause filter plugging.
In colder temperatures, the recycling of heated fuel back to a colder fuel tank, can cause
condensation problems that could lead to increase in free moisture in the fuel. This
problem could possibly lead to filter plugging and necessitate a higher frequency of fuel
separator filter maintenance and/or drains.

USES OF DIESEL FUEL

Diesel fuel keeps the world economy moving. From consumer goods moved around the world, to
the generation of electric power, to increased efficiency on farms, diesel fuel plays a vital role in
strengthening the global economy and the standard of living. The major uses of diesel fuel are:
On-road transportation

Farming

Rail transportation

Marine shipping

Electric power generation

Military transportation

Off-road uses (e.g., mining, construction, and logging)

Page 7 of 35

In the United States, on-road transportation, primarily trucks, accounted for nearly 60 percent of
the diesel fuel consumed in 2004. Because diesel fuel is used to move goods from manufacturer
to consumer, its sales are linked to the strength of the economy. Figure 1 shows the percentage
sales of diesel in the U.S.in different sectors.

Figure 1. Diesel Fuel Sales in the U.S. (U.S. Department of Energy, Energy Information
Administration, 2004)

MARKET FOR DIESEL AND ULTRA-LOW SULFUR DIESEL

U.S. refiners produced historically high volumes of distillate fuels and by fine-tuning their
production mix, refineries consistently set record levels of distillate production, topping 5 million
barrels per day (bbl/d) for the weeks ending December 2 and December 16, 2011. In 2011,
weekly distillate production was above the five-year historical range 25 times, and ranked second
highest an additional 19 times. Figure 2 presents the weekly production rate of diesel in America
from the Weekly Petroleum Status Report of U.S. Energy Information Administration.

Page 8 of 35

2006

2007

2008

2009

2010

2011

Figure 2. Diesel Fuel Weekly Production Rate from 2006 to 2011 (U.S. Energy Information
Administration, 2012)

Figure 3 presents the weekly prices of ultra-low sulfur diesel from January 2, 2012, to November
9, 2015 in the East Coast where the state of Delaware is located. These data were reported by the
U.S. Energy Information Administration on their website.

2012

2013

2014

2015

Page 9 of 35

Figure 3. Diesel weekly price in the U.S. East Coast from 2012 to 2015 (U.S. Department of Energy,
2015)

III. Objectives
The main objective of this project is to propose the best design process for the production of
ultra-low sulfur diesel fuel (0.005wt% S). This process takes place in a reactor unit which
contains the supported catalyst for the reaction. For this reason, the reactor unit was chosen as
one of the two equipments that will be designed for this project. After passing through the
reactor unit, the products are separated through the downstream processes. The second
equipment to be designed is a separator equipment that will be used for the downstream
processes.
The project will include the material and energy balances for the whole process and the design
of the reactor and separator units. It will not include the design of the heat exchanger units of
the system, equipment auxiliaries and process control instrumentations. It will also not include
the treatment of the by-products produced.
MAJOR OBJECTIVES
1. Design a reactor that can produce ultra-low sulfur diesel fuel with sulfur content of 0.005
wt%
2. Ensure safe and reliable operations during the production of ULSD.
3. Design a separator that can separate the ULSD from the by-products of the reaction such
as H2S.
4. Establish a material balance at steady-state operation where the total feed mass flow rate
is equal to the total product mass flow rate.
MINOR OBJECTIVES
1. Consider the capital and operating cost for the best possible system that would fit the
product specification
2. Specify process control and instrumentation of the reactor and separation equipment.
3. Provide accurate and detailed utility summary.
IV. Environment, Sustainability, and Safety
Page 10 of 35

ULTRA-LOW SULFUR DIESEL

Ultra-low-sulfur diesel (ULSD) is diesel fuel with substantially lowered sulfur content. As of
2006, almost all of the petroleum-based diesel fuel available in Europe and North America is of
a ULSD type. There is not a single standard set of specifications and as the government
mandated standard becomes progressively stricter so does the definition.
As of 2006, almost all of the petroleum-based diesel fuel available in UK, Europe and North
America is of ultra-low sulfur diesel (ULSD) type. The move to lower sulfur content is
expected to allow the application of newer emissions control technologies that should
substantially lower emissions of particulate matter from diesel engines. This change
occurred first in the European Union and is now happening in North America. New emissions
standards, dependent on the cleaner fuel, have been in effect for automobiles in the United
States since model year 2007. ULSD fuel was proposed by the U.S. Environmental Protection
Agency (EPA) as a new standard for the sulfur content in on-road diesel fuel sold in the United
States since October 15 2006, except for rural Alaska which transferred in 2010. This new
regulation applies to all diesel fuel, diesel fuel additives and distillate fuels blended with diesel
for on-road use, such as kerosene, however, it does not yet apply to railroad locomotives,
marine, or off road uses (American Petroleum Institute, 2015).
ULSD has a lower energy content due to the heavy processing required to remove large
amounts of sulfur from oil, leading to (1 to 2%) lower fuel economy and using it requires more
costly oil. According to EPA estimates, with the implementation of the new fuel standards for
diesel, nitrogen oxide emissions will be reduced by 2.6 million tons each year and soot or
particulate matter will be reduced by 110,000 tons a year (Omidvarbona, Kumar, & Kim,
2014). Sulfur is not a lubricant in of itself, but it can combine with the nickel content in many
metal alloys to form a low melting point eutectic alloy that can increase lubricity. The process
used to reduce the sulfur also reduces the fuel's lubricating properties. The refining process that
removes the sulfur also reduces the aromatic content and density of the fuel, resulting in a
minor decrease in the energy content, by about 1%. This decrease in energy content may result
in slightly reduced peak power and fuel economy. The transition to ULSD is not without
substantial costs. The US Government has estimated that pump prices for diesel fuel will
Page 11 of 35

increase between $.05 and $.25 per gallon as a result of the transition. And, according to the
American Petroleum Institute (2015), the domestic refining industry has invested over $8
Billion to comply with the new regulations.
ISSUES ON DIESEL FUEL
A. Diesel Engine Smoke
Diesel engine smoke is caused by incomplete combustion.
White smoke is caused by tiny droplets of unburned fuel resulting from engine misfiring
and low temperature. This smoke should disappear as the engine warms up.
Black smoke could be caused by a faulty injector, insufficient air and overloading and/or
over fueling the engine.
Blue gray smoke is the result of burning lubricating oil and is an indication the engine is
in poor mechanical condition
B. Diesel Fuel Contamination
One of the more common contaminants in fuel is water. Water gets into diesel fuel
storage and vehicle tanks in several ways including condensation during transportation,
by leakage through faulty pipes or vents and by careless handling. Water can cause
injector nozzle and pump corrosion, bacteria and fungi growth and fuel filter plugging
with materials resulting from corrosion or microbial growth. Both vehicle and storage
tanks should be checked frequently for water and drained or pumped as necessary. In
extreme cases, biocides may be required to control bacterial growth.
In cold winters, ice formation in fuel containing water creates severe fuel line and filter
plugging problems. Regularly removing the water is the most effective means of
preventing this problem; however, small quantities of a water dispersing diesel fuel
treatment may be used to help prevent line and filter freeze-ups. Most new diesel engines
require almost daily draining of water separators to avoid excessive or critical moisture
build-up.
Dirt is another common contaminant of fuel and may cause poor performance and
extreme wear in fuel pumps. Fuel tank caps, dispensing nozzles and hoses should be kept
clean to eliminate potential sources of contamination.
C. Diesel Fuel Color
There is no relationship between natural diesel fuel color and such desirable diesel fuel
qualities as BTU/gallon, viscosity, cloud point, cetane number or distillation range.
Page 12 of 35

Diesel fuel color varies with the crude source, refinery methods and the use of dyes.
However, if the fuel color darkens during storage, this could indicate oxidation and/or
other sources which can cause operating problems.
D. Blending Lubricating Oil into Diesel Fuel
It was a common practice to blend lubricating oil into diesel fuel to provide added
lubricity for fuel pumps and injectors. This practice may adversely affect fuel quality
features and could lead to fuel system and piston deposits, increased exhaust emission,
and fuel filter plugging. This practice may also result in the diesel fuel being out of
compliance with federal regulations or other specifications. Todays seasonal blends of
ultra-low sulfur diesel fuel are monitored at the refinery level to ensure adequate
lubricity.
Water and sediment contamination is by far the most probable cause of fuel system
failure

WHY DIESEL FUEL IS REGULATED

The amount of sulfur in diesel fuel is directly linked to the amount of pollutants produced when
the fuel is burned in an engine. Higher levels of sulfur increase pollutants. When diesel fuel is
burned in engines, the emissions that result contributes to air pollution that has serious human
health and environmental effects.
Pollutants from diesel exhaust includes:

Soot or particulate matter (PM);

Oxides of nitrogen (NOx) which contributes to the production of ground-level ozone

(smog) and acid rain;

Hydrocarbons (HC);

Carbon monoxide (CO); and

Page 13 of 35

Other hazardous air pollutants (HAPs) and air toxics.

This air pollutants can cause heart and lung disease and a range of other health effects. It can
also damage plants, animals, crops, and water resources.
ULSD LEGISLATIONS
It has been critical to the successful development of diesel fuel and diesel-powered vehicles to
have consensus among refiners, vehicle and engine manufacturers, and other interested parties on
the characteristics of diesel fuel necessary for satisfactory performance and reliable operation. In
the United States, this consensus is reached under the auspices of ASTM International (formerly
American Society for Testing and Materials. The name was changed to ASTM International to
reflect the fact that many of the specifications are used in other parts of the world.) The European
Union has also developed specifications for diesel fuels. These specifications are used
extensively in Asia and the Pacific basin countries, with modifications to fit local supply, crudes,
and regulations (Chevron Corporation, 2007).
The required properties of diesel fuel as stated by ASTM D 975 are listed in the Table 3. It sets
the limits (requirements) for the values of its properties. Seven grades of diesel fuel are defined
by the specification where the fuel grades S15, S500, and S5000 refer to the maximum sulfur
content allowed in the fuel expressed in ppm by weight (e.g., S15 refers to diesel fuel with a
maximum sulfur content of 15 ppm). Specification D 975 also contains the standard test methods
used to measure the values of the properties.
Table 3. ASTM D 975 Requirements for Diesel Fuel Oils (Chevron Corporation, 2007)

Property
Flash Point, C (F), min
Water and Sediment, % volume,
max
Distillation Temperature, C (F),
90% Volume Recovered:
min
max

Test
Method
D 93
D 2709
D 1796
D 86

S15, S500,
S5000
No. 1-D
38 (100)

S15, S500,
S5000
No. 2-D
52 (125)

55 (130)

0.05

0.05

No. 4-D

0.5

288 (550)

282 (540)
338 (640)
Page 14 of 35

Or
Simulated Distillation, C (F)
D 2887
(Does not apply to No. 1-D S5000
or No. 2-D S15)
90% Volume Recovered:
min
300 (572)
304 (572)
max
356 (673)
Kinematic Viscosity, mm2/sec at
40C (104F):
D 445
min
1.3
1.9
5.5
max
2.4
4.1
24
Ash, % mass, max
D 482
0.01
0.01
0.10
Sulfur, ppm (g/g), max
D 5453
15
15
% mass, max
D 2622
0.05
0.05
% mass, max
D 129
0.5
0.5
2.0
Copper Strip Corrosion Rating,
D 130
No. 3
No. 3
max
After 3 hours at 50C (122F)
Cetane Number, min
D 613
40
40
30
One of the following must be met:
(1) Cetane Index, min
D 967-80
40
40
(2) Aromaticity, % volume, max
D 1319
35
35
Cloud Point, C (F), max
D 2500
Varies
Varies
Ramsbottom Carbon Residue, max
(% mass on 10% Distillation
D 524
0.15
0.35
Residue)
Lubricity, 60C, WSD, microns,
D 6079
520
520
max
Diesel fuel specifications in the European Union are similar, but not identical, to those in the
U.S. For example, the minimum cetane number in Europe is higher and there is a density range
requirement. The EN 590 had been introduced along with the European emission standards. With
each of its revisions the EN 590 had been adapted to lower the sulfur content of diesel fuel
since 2007 this is called ultra-low sulfur diesel and is presented in the Table 4.
Table 4. EN 590 Diesel Fuel Requirements and Test Methods (Chevron
Corporation, 2007)
Diesel Specification Parameter
Units
Limits
Test Method
Cetane Number
51.0 min
EN ISO 5165
Cetane Index
46.0 min
EN ISO 4264
820 min to 845
EN ISO 3675
Density at 15C
kg/m3
max
EN ISO 12185
Polycyclic Aromatic Hydrocarbons % (m/m)
11 max
EN 12916
Page 15 of 35

mg/kg

50.0 max
10.0 max

>55

EN ISO 20846
EN ISO 20847
EN ISO 20884
EN ISO 2719

% (m/m)

0.30 max

EN ISO 10370

% (m/m)
mg/kg
mg/kg

0.01 max
200 max
24 max

EN ISO 6245
EN ISO 12937
EN 12662

class 1

EN ISO 2160

g/m3

25 max

460 max

EN ISO 12205
EN ISO 121561

mm2/sec

2.00 min to 4.50

max

Sulfur Content
Flash Point
Carbon Residue (on 10% Dist.
Residue)
Ash Content
Water Content
Total Contamination
Copper Strip Corrosion (3 Hours at
50C)
Oxidation Stability
Lubricity, WSD at 60C
Viscosity at 40C
Distillation
Vol. Recovered at:
250C
350 C
95% Point
Fatty Acid Methyl Ester (FAME)
Content

EN ISO 3104
EN ISO 3405

% (V/V)
% (V/V)
C
% V/V

<65
85 min
360 max
5 max

EN 14078

V. Design Data
A. Desired Production Rate
The feed rate, as stated in the problem in Table 1, is 35 thousand barrels per day (TBPD). From
the mass balances (which will be shown in Task 2), the production rate was determined to be
1,820,085.41 tons ULSD/year. With a density of 845 kg/m 3 (European Standard EN 590:2009),
the volumetric production rate is about 2,153,947,231 L/year of ULSD.
B. Desired Product Purity
The ultra-low sulfur diesel to be produced has a sulfur content of 0.005 wt%.
C. Reaction Conditions and Kinetic Data
Page 16 of 35

As stated previously, in designing the HDS unit, the percent hydrodesulfurization (%HDS) is
determined by Equation 4. From the sulfur content of the diesel feed (1.9 wt. %) and of the
desired product (0.005 wt%), the %HDS was found to be 99.737%.
( wt %S ) product
%HDS= 1
100
( wt %S )feed

(4)

The reactor conditions of the proposed operation that will be based from processing data
available from an older HDS unit is shown in Table 1.
The diesel blend contains various sulfur compounds as presented in Table 5. The reaction of
these compounds with hydrogen is exothermic and forms H2S which is separated from the
diesel product by the downstream processes.

Table 5. Sulfur compounds of diesel fuel (Axens IFP Group Technologies, 2010)

Sulfur compound
Mercaptans

Structure
RSH

Disulfides

RSSR

Sulfides

RSR

Thiophenic

Benzothiophenic

Page 17 of 35

Dibenzothiophenic

Benzonaphtothiophenic

Benzodibenzothiopheni
c

In HDS, the most refractive sulfur compounds in the diesel blend are the alkyl-substituted
dibenzothiophenes (DBT) in which the substituents are in the 4 and 6 positions. Consequently,
these least reactive sulfur compounds determine the overall desulfurization rate in producing
ULSD (Knudsen, Cooper, & Topsoe, 1999). The desulfurization reaction of DBT is used as the
representative for all the desulfurization reactions for the rest of the discussion as this is the
rate limiting step.
There are two pathways for hydrodesulfurization reaction: direct sulfur extraction pathway
(hydrogenolysis) and the pre-hydrogenation pathway. Figure 4 shows the hydrodesulfurization
of dibenzothiophene.

Figure 4. Hydrodesulfurization of dibenzothiophene (Knudsen, Cooper, & Topsoe, 1999)

Page 18 of 35

Direct sulfur pathway or hydrogenolysis, involves adsorption of the sulfur compound on the
catalyst surface through the sulfur atom followed by a C-S bond scission. It has a relatively low
hydrogen partial pressure dependency. On the other hand, the hydrogenation pathway involves
saturation of one aromatic ring of DBT through hydrogenation followed by the extraction of
the sulfur atom. This pathway is equilibrium limited which results in low activation energy for
HDS. It also exhibits a high hydrogen partial pressure dependency.
The DBT hydrodesulfurization reaction as shown in Figure 5 is a gaseous reaction where 2
moles of product is produced from 3 moles of reactant.

Figure 5. Hydrodesulfurization reaction of dibenzothiophene

A change in density is expected because of the change in the number of moles during reaction.
However, since the components that actually react in the reactor comprises only about 1.9 wt%
of the feed it can be assumed that the expansion factor is equal to zero.
Kinetic studies have usually indicated that simple first-order kinetics with respect to sulfur are
the predominant mechanism by which sulfur is removed from the organic material as hydrogen
sulfide (Ancheyta & Speight, 2007). The rate of reaction then can be described by Equation 5.
r=k C S

(5)

For first order reaction with plug flow regime, the performance equation is given by Equation 6
where k is the rate constant (hr-1gcatalyst-1), and Xs is the %HDS (Levenspiel, 1999).
k ' ' =( 1+ s ) ln

( 11X ) X
s

(6)

Over various types of catalysts used (i.e. Mo/Al 2O3, CoMo/Al2O3, or NiMo/Al2O3), it appears
that there is no fundamental difference in the reaction pathway or the mechanism (i.e.
Mo/Al2O3, CoMo/Al2O3, or NiMo/Al2O3) (Topsoe, Clausen, & Massoth, 1996). Also, under
Page 19 of 35

typical HDS conditions, dibenzothiophenes are much more stable than thiophenes and
benzothiophenes and so deep HDS of the high dibenzothiophene content distillates will require
more active catalyst than that of the distillates containing predominantly thiophenes and
benzothiophenes. (Furimsky, 1997). For this reason, rate constant, k, of alkyldibenzothiophene
is used.
D. Correlations
The relevant correlations to be used for the forthcoming calculations is the start-of-cycle
temperature as shown in Equation 2 and the aging rate as shown in Equation 3. The constants
used to determine the start-of-cycle temperature (Tsoc) are listed in Table 2.
E. Equilibrium Data for Flash Vaporization
In a conventional hydrodesulfurization plant, after the products leave the reactor, the gas-liquid
mixture goes to a gas-liquid separator equipment. These are pressure vessels designed to divide
a combined liquidgas system into individual components that are relatively free of each other
for subsequent disposition or processing. To separate the liquid and gas components, the H 2Sdiesel mixture undergoes flash evaporation.
Hydrogen Sulfide
Equation 7 presents the Antoine Equation parameters for the hydrogen sulfide component

log 10 ( P )=A

B
T+C

(7)
where P is the vapor pressure in bar, T is the temperature in K and the constants are listed in
Table 6.

Table 6. Antoine Constants for H2S (Stull, 1947)

Temperature (K)
138.8-212.8
212.8-349.5

A
4.43681
4.52887

B
829.439
958.587

C
-25.412
-0.539

Page 20 of 35

Diesel
There are various components in the diesel fuel, majority of which are hydrocarbons. The
average chemical formula for common diesel fuel is dodecane (C 12H23), ranging
approximately from C10H20 to C15H28 Invalid source specified.. Thus, the equilibrium data as Antoine
parameters are based from dodecane as shown in Table 7.
Table 7. Antoine Parameters for Dodecane Invalid source specified.

Temperature

Pressure

(K)

(Pa)
0.615

263.57 - 658

1.822x10

C1

C2

C3

C4

C5

137.47

-11,976

-16.698

8.090x10-6

These constants are used for Equation 8 to determine the vapor pressure, Ps.

Ps=exp C 1+

C2
+ C 3 ln T +C 4 T C 5
T

(8)

F. Raw Materials
Diesel Blend
The primary feed of the HDS system is the diesel blend with the composition presented
in Table 8 in the properties section.
Table 8. List of Properties of the Feed Blend Invalid source
specified.

Cetane Number
Density @ 15C (kg/m3)
Sulfur, wt%
Total Nitrogen, ppmw
Boiling range (C)

30 40
913.9
1.9
200
232-350

The availability of the diesel blend is convenient since it is produced by the company which
is then directly fed to the HDS system to reduce its sulfur content.
Hydrogen

Page 21 of 35

Hydrogen reacts with the sulfur compounds of the diesel blend and thus decreases the sulfur
content of the blend. Since the refinery does not have a hydrogen plant, it is necessary to buy
hydrogen from a third party. There will be three companies that will supply the hydrogen
needed for the HDS process. Table 9 presents the composition of the hydrogen supplied by
the three suppliers.
Table 9. Composition of Hydrogen from Different Suppliers

Main Supplier

Secondary Supplier

Third Supplier

SEFIC (Shanghai Eternal

Huixian Tianli Machinery Co.,

Faith Industry Co., LTD)

Ltd

Company Name

Linde Industrial Gases

Plant Location

Blue Bell, PA, USA

Shanghai, China

Henan, China

Hydrogen Purity

99.9% vol

99.99% vol

99.99% vol

Price

$6-15 per kg

$5-24 per kg

$0.35-6.42 per kg

http://www.sefic.com.cn/

http://m.hxtljx.en.alibaba.com/

Website

http://www.lindegas.com/en/index.html

The primary supplier, Linde Industrial Gases, is conveniently located in Blue Bell which is 109
miles (via I-95 N route) or 121 miles (via DE-1 N route) from Delaware as shown in Figure 6.
The Linde Group is a world leading supplier of industrial, process and specialty gases. Their
products can be found nearly in every industry in more than 100 countries.

Page 22 of 35

Figure 6. Location of Linde Industrial Gases from Delaware (Google Maps)

To ensure availability of hydrogen feed should there be any conflicts with the primary supplier,
back-up suppliers are also available which are located in Shanghai, China and Henan, China.

Catalyst
The catalysts used in hydrodesulfurization (HDS) consist of a metal hydrogenation component
on an amorphous, porous support material. The hydrogenation component comprises a
transitional metal usually selected from Groups VIA and VIIIA. Some of the most common
catalysts for hydrodesulfurization are the NiMo and CoMo catalysts. Hydroprocessing catalysts
are widely available since they are essential for effective and optimal hydrodesulfurization of the
diesel feed. Some of the companies that sell hydroprocessing catalysts are the Haldor Topsoe
(Denmark), Axens (France), Johnson Matthey (United Kingdom), Criterion (USA), Sd-Chemie
(Germany), Albemarle (USA), Grace Davison (United Kingdom) and ExxonMobil Chemical
(USA).
Catalyst Support
The main role of a support in catalysis is to disperse the active phase in order to increase the
specific activity of the catalyst and also makes the catalytic nanoparticles stable and obtain
Page 23 of 35

optimal performance. Some of the most common supports for catalysts are alumina,
silica, titania, zirconia and carbon.

Page 24 of 35

VI. Input-Process-Output Diagram

Flue Gas

Hot water

Hydrogen Feed

Off Gas

HYDRODESULFURIZATION

Diesel Fuel Blend Feed

Ultra-Low Sulfur Diesel

Supported Catalyst

Supported Catalyst

Fuel

Cooling Water
Page 25 of 35

VII. Functional Block Flow Diagram

Hydrogen
Diesel Blend

Off Gas
Feed
Pre-Treatment

Conversion

Separation
Ultra-Low
Sulfur Diesel

Page 26 of 35

VIII. Battery Limits and Basic Assumptions

A. Battery Limits
An industrial process of catalytic hydrodesulfurization of diesel involves the pretreatment of
the feedstock, the catalytic hydrogenation of compounds and the downstream processes. This
proposed equipment design is mainly focused on the catalytic reactor and the gas-liquid
separator after the reactor. It will include the selection of the materials of construction,
sizing/design of reactor and separator units and the power requirements.
The inside battery limit refers to the processes, units and services included while the outside
battery limit refers to those units, processes and services not included for the design of the
catalytic reactor and the gas-liquid separator.
Table 10. Inside and Outside Battery Limits
Inside Battery Limits
Perform an overall and component material and
energy balances for the whole process
Conduct chemical engineering design on reactor
and gas-liquid separator

Outside Battery Limits

Produce Diesel Blend

Recover hydrogen

Conduct mechanical design on reactor and gas-

Construction of reactor and separator

liquid separator

units

Specify equipment auxiliaries (pumps, pipings,

valves)

Design of heat exchanger to utilize the

heat of the products after the reaction
step
Design of piping and instrumentation

MATERIALS ENTERING AND LEAVING THE BATTERY LIMITS

Page 27 of 35

The first equipment in the battery limit is the reactor, in which gasified fuel blend and hydrogen
enters in it. The desulfurization reaction of the fuel blend takes place with the help of a catalyst.
The amount of catalyst that will be used is part on the chemical engineering design of the reactor.
After the reaction, the heat of the product stream is utilized to preheat the reactant. After it
passed the heat exchanger some of the products are already liquid. The product stream will then
be feed into a gas-liquid separator. The gas-liquid separator is used to separate the hydrogen
sulfide which will comprise the gas phase from the fuel blend which comprises the liquid phase.
The further treatment of the hydrogen sulfide and the fuel blend are already outside of our
battery limits.
Table 11. Definition of Incoming and Outgoing Streams
Stream
Definition

Incoming Streams
The diesel blend is provided by the
companys petroleum refinery. The diesel
Diesel fuel blend feed

blend

contain

several

hydrocarbons

(biphenyl, pentane, n-dodecane, pyridine,

etc.). The most dominant component in the
diesel fuel is the n-dodecane.
The hydrogen feed is 100% pure which is

Hydrogen Feed

used to react with the sulfur compounds in

the diesel fuel
The catalyst may be homogeneous or

Catalyst

heterogeneous. It acts as an active site for

the reaction.

Fuel

Fuel is a utility used to operate fired heaters

for the feed pre-treatment process
Cooling Water is a utility used in heat

Cooling Water

exchangers to cool down the products from

high temperatures

Table 11 continued

Page 28 of 35

Outgoing Streams
The off gas consist of gas components that
is vent off after the whole process.
Specifically, it consists of the following
components:
Unreacted Hydrogen - An excess of
hydrogen is fed to ensure conversion of
sulfur compounds to Hydrogen Sulfide.
Thus, unreacted hydrogen is included in the
off gas stream
Impurities

in

Hydrogen

Feed

The

hydrogen feed has a purity of 99.99 vol%.

The 0.01 vol% consists of the impurities,
namely, O2, N2, CO, CO2, CH4 and H2O.
These components are assumed to be inert
Off Gas

and are vented off in the off gas stream

Hydrogen Sulfide - The by-product in the
hydrodesulfurization

reaction

which

contains the sulfur from the diesel fuel

Ammonia

The

by-product

in

the

hydrodenitrogenation reaction. Aside from

hydrodesulfurization,

this

reaction

also

occurs
Hydrocarbons These consist of small
traces of n-Dodecane, Dibenzothiophene,
Biphenyl, Pyridine and Pentane. The nDodecane is the major component found in
the diesel feed, dibenzothiophene is the
dominant sulfur compound present in the
diesel feed, and Pyridine is the dominant
nitrogen compound
Page 29 of 35

Table 11 continued

in the diesel feed while Biphenyl and

Pentane

are

products

of

the

hydrodesulfurization

and

hydrodenitrogenation

reactions,

respectively.

Ultra-Low Sulfur Diesel

The

desired

product

to

be

obtained

containing 0.005 wt% sulfur.

When the catalyst degenerates with time, it

Catalyst

would eventually be replaced. The catalyst

life could be determine through its aging
rate.

Flue Gas

Flue gas is considered as a waste product

from the fuel
The cooling water from the heat exchangers

Hot Water

becomes hot water after heat transfer occurs

between the cooling water and the hot
product streams.

Given in the problem statement, the Delaware Refining Company produces 35,000 barrels of
diesel fuel blend per day that is needed to meet the product specification of the sulfur content of
the diesel which is 0.005 wt % sulfur.
B. Basic Assumptions
The following are the assumptions to be considered in the subsequent material and energy and
design calculations:
1. The process is operating in steady state condition.
Page 30 of 35

2. The sulfur compounds in the diesel feed can be represented by dibenzothiophene, which is
the rate-limiting reactant.
3. The hydrocarbons in the diesel feed can be represented by n-dodecane.
4. All gas components follow the ideal gas behavior.
5. The impurities in the hydrogen feed which consist of 0.01 vol% are inert compounds that
will not contribute to the reaction and would just be vented off in the off gas stream.
C. Overall Process Operational Mode and Stream Hours
The typical plant operational modes are the batch and continuous operation. For the batch
process, the diesel blend and hydrogen mixture is fed one batch at a time and the products are
also taken one at a time. This type of operational mode is suitable for slow reactions and those
that have a flexible production rate. It has a relatively simple and low capital costs and easy to
clean and maintain. However, this is only suitable for a plant capacity of less than 4,500 tons
per year (Coulson & Richardson, 2005; Douglas, 1988; Towler, 2013) . Since the production rate of
this project is 2,153,947,231 L/year which is about 13,550 thousand barrels/yeat (1 barrel =
159 L), the suitable process operational mode for this project is the continuous mode operation.
The feed is continuously fed to the reactor and the products are continuously taken. It is more
energy efficient and can be automated.
Petrochemical plants conduct shutdown regularly for maintenance. During maintenance
shutdown, the production is halted, the materials are removed from the site, all cleaning of the
permitted equipment and storage equipment is completed and equipment are inactivated. For
this project, the duration of maintenance shutdown operation is 1 month (around 30 days)
yearly. This is in comparison of the shutdown operation of Petron which is 2-3 months. Since
our refinery plant has a much lower plant capacity, it is decided that a month of shutdown will
suffice. Hence, the stream hours that would meet the yearly rate of production is 8040 hours
per year (335 days per year).

Page 31 of 35

C. Plant Location
The Delaware Refining Company is located at 4550 Wrangle Hill Rd, Delaware City, DE 19706,
United States.

Figure 7. Delaware Refining Company Location (Google Earth)

IX. Economic Margin

The economic feasibility of the design project can be determined by considering the costs of the raw
materials that are to be used (diesel blend, hydrogen, and supported catalyst) and the price of the
main product (ultra-low sulfur diesel). Since the diesel blend comes from the plants refinery, there is
no need to consider its cost as it will not be bought. The hydrogen and supported catalyst are to be
bought from suppliers near the state of Delaware and the prices of the said raw materials are taken
from the reports of Linde Industrial Gases and PenWell Corporation. The annual consumption are
estimates based from the supply and demand data around the U.S. East Coast.

Page 32 of 35

Table 12. Summary of Main Raw Material and Product Costs

Annual Consumption
(ton/year)

Unit Price
($/ton)

Annual Value ($/year)

Hydrogen

38,160c

400a

15, 264, 000

Supported Catalyst

29.35b

15432.34b

452, 939.2

Main Raw Material

TOTAL
Annual Consumption
(ton/year)

Main Product
Ultra-Low Sulfur Diesel

1, 700, 000c

Unit Price
($/ton)
900c
TOTAL

15, 716, 939.2

Annual Value ($/year)
1, 530, 000, 000
1, 530, 000, 000

Linde Industrial Gases, http://www.linde-gas.com/en/index.html

PenWell Corporation. (2005). Catalyst prices, demand on the rise. Oil & Gas Journal.
http://www.ogj.com/articles/print/volume-103/issue-39/special-report/catalyst-prices-demand-on-the-rise.html
c
U.S. Department of Energy. (2015, November 9). Petroleum and Other Liquids. Retrieved from U.S. Energy Information
Administration: Independent Statistics & Analysis: http://www.eia.gov/petroleum/
b

The economic feasibility of the project is determined by considering the economic margin which
is given in Equation 8.
=

(8)

= $ 1, 530, 000, 000 $ 15, 716, 939.2

= $ 1,514,283,060.8

It is implied from the obtained economic margin above that the product that will be produced by
this design project has a greater economic value than the raw materials that are to be bought.
This would mean that the operation would be profitable and thus making this design project
feasible for construction and operation.

X. References
Page 33 of 35

American Petroleum Institute. (2015). Ultra Low Sulfur Diesel. Retrieved from Oil & Natural
Gas
Overview:
http://www.api.org/oil-and-natural-gas-overview/fuels-andrefining/diesel/ulsd
Ancheyta, J., & Speight, J. G. (2007). Hydroprocessing of Heavy Oils and Residua. Florida,
USA: CRC Press.
Axens IFP Group Technologies. (2010). Hydro-Treating/Hydro-Processing. Industry-Academia
Workshop on "Refining & Petrochemicals". Petroleum Federation of India NIT Jalandhar
& Lovraj Kumar Memorial Trust.
Chevron Corporation. (2007). Diesel Fuels Technical Review.
Furimsky, E. (1997). Selection of catalysts and reactors for hydroprocessing. Applied Catalysis,
177-206.
Kabe, T., Akamatsu, K., Ishihara, A., Otsuki, S., Godo, M., Zhang, Q., & Qian, W. (1997). Deep
Hydridesulfurization of Light Gas Oil. 1. Kinetics and Mechanisms of Dibenzothiophene
Hydrodesulfurization. Ind. Eng. Chem. Res., 5146-5152.
Kim, J. H., Ma, X., & Song, C. (2004). Kinetics of Two Pathways for4, 6Dimethyldibenzothiophene Hydrodesulfurization over NiMo, CoMo Sulfide, and Nickel
Phosphide Catalysts. Energy & Fuels, 353-364.
Knudsen, Cooper, & Topsoe. (1999). Catalyst and process technologies for ultra low sulfur
diesel.
Levenspiel, O. (1999). Chemical Reaction Engineering. New York, USA: John Wiley & Sons,
Inc.
Omidvarbona, H., Kumar, A., & Kim, D.-S. (2014). Characterization of particulate matter
emitted from transit buses fueled with B20 in idle modes. Journal of Environmental
Chemical Engineering, 2335-2342.
Quale, M. J. (2000, January). Mobil Technology Company.
Reynolds, R. (2007). Changes in Diesel Fuel - The Service Technician's Guide to Compression
Ignition Fuel Quality.
Sakanishi, K., Ma, X., & Mochida, I. (1994). Hydrodesulfurization Reactivities of Various Sulfur
Compounds in Diesel Fuel. Catalysis Today, 218-222.
Topsoe, H., Clausen, B. S., & Massoth, F. E. (1996). Hydrotreating Catalysis. In J. e. Anderson,
Calysis. Berlin Heidelberg: Springer-Verlag.
U.S. Department of Energy. (2015, November 9). U.S. Energy Information Administration:
Independent Statistics & Analysis. Retrieved from Gasoline and Fuel Update:
http://www.eia.gov/petroleum/gasdiesel/
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U.S. Energy Information Administration. (2013). Retrieved from Distillate Fuel Oil Consumption
Estimates,
2013:
http://www.eia.gov/state/seds/data.cfm?
incfile=/state/seds/sep_fuel/html/fuel_use_df.html&sid=US
UFA Co-operative Limited. (2009). Diesel fuel characteristics and resources.
Retrieved from Petroleum:
http://www.ufa.com/petroleum/resources/fuel/diesel_fuel_resources.html

Page 35 of 35