HANDLING THE HEAT

Measuring temperatures within a Claus Thermal reactor is very difficult. Plagued with extreme heat,
thermal shock, vibration, corrosion, shifting refractory, errant flame patterns and quenching, even
instruments specifically designed for the reactor may fail prematurely, suffer from accuracy
problems, or require excessive maintenance.

Following handling and installation procedures properly, and correctly applying ad operating the
protection systems (purges and steam heating) for the instruments can vastly improve the chances
of making an accurate and reliable measurement. But before the measurement systems are
installed, the vessel must be designed with the mounting nozzles placed in the most suitable
locations. The highly-specialised sensors used in this application are subject to a number of
limitations, which make placement critical for accurate and reliable readings.

The operating temperature inside the thermal reactor is measured to ensure that the maximum
refractory design temperature is not exceeded. Refractory hot-face temperature is a reliable
measurement that is most commonly taken. For this reason, it is imperative that the instruments
are not placed in a position of direct flame as impingement will normally occur. Some instruments
attempt to measure the reaction gas temperature, and while this would be ideal, achieving reliable
and accurate measurement of the gas temperature is difficult.

TYPES OF TEMPERATURE EQUIPMENT

The extreme conditions and corrosive environment inside the Claus reactor limit the types of devices
that can be used to measure the tempearure effectively. Currently, the only viable types of
temperature measurement devices for a Claus thermal reactor pressure purged ceramic
thermocouples and optical pyrometers, both of which must be designed specifically for the Claus
reactor.

THERMOCOUPLES

Claus reactor thermocouples are purged noble-metal types (typically type R, S, or B) enclosed in
ceramic thermal wells. The thermocouple is purged with nitrogen to sweep out any process gases
that can diffuse through the thermowell al high temperatures. To insure against intrusion of reaction
gases, the purge must be maintained at a slightly elevated pressure and provide a constant very low
N2 flow. If the thermowell becomes broken, process gases will quickly corrode and destroy the
thermocouple measures the temperature at only a singular point within the reactor.

PYROMETERS

Pyrometers measure the infrared light emitted by the hoot refractory walls to determine
temperature. The pyrometer is aimed at a spot on the refractory, however the indicated
temperature is not necessarily of the refractory brick, about half of the measured infrared (IR)
energy is emitted by the target spot, and the other half is reflected light that was emitted from other
parts of the reactor. Thus, a pyrometer indicates a weighted average of the target area and the
surrounding temperatures.

NOZZLE PLACEMENT LOCATIONS

When considering the positioning of the thermocouples and pyrometers in a Claus reactor, the goals
should be to accurately measure a representative temperature of the reactor and to maximize
reliability, given the inherent vulnerabilities of the devices.

THERMOCOUPLE PLACEMENT

The nozzle for mounting thermocouples should be as short as possible. Nozzles operating below the
freezing point of sulfur (120º C or 248ºF) will tend to form and collect solidified sulfur which could
press against the ceramic thermowell and break it under subsequent expansion and contraction.
Short nozzles are preferable as they keep the forming and solidifying. Preferably, the nozzle flange
should be positioned beneath external thermal protection system shroud.

The insertion length is usually specified so that the thermocouple junction is positioned against the
refractory hot- face. Shorter insertion may cause a lower reported temperature. Longer
insertionwould place more of the ceramic thermowell out into the gas stream, which risks damage
to the thermowell due to exposure to thermal shock during rapidly changing process conditions.

Positioning the nozzle on the top centerline of the reactor, straight vertically downwards is the ideal
position. Positioning a nozzle closer to the sides of the vessel subjects the thermocouple to a greater
chance of damage due to shifting refractory. Radial shifthing is most prevalent at the sides of the
vessel and is nearly non-existent at the top centerline.
Longitudinal shifting is usally checked by the use of expansion joints at multiple intervals.

Refractory bricks are usually installed to fit somewhat loosely so that they are not crushed by
thermal expansion during start up. As the reactor heats up, bricks expand and are pushed outward,
moving to fill gaps that were intentionally left for this purpose. Upward movement of bricks on the
side of the vessel could potentially break the ceramic thermowell of any side-mounted
thermocouple. Therefore, to minimize the risk of breakage from shifting refractory, thermocouples
should be installed on the top centerline of the thermal reactor vessel. Mounting the thermocouple
on top of the vessel also makes installation easier and reduces the chance that the thermocouple
will be broken during installation.

Thermocouples should not be installed in an area of direct flame impingement as this could cause
cracking of the ceramic thermowell due to thermal shock. Unfortunately, this region is likely to be
where one is most interested in making a temperature measurement. A pyrometer may be a better
choice for measuring in these areas.

The thermocouple location should not be directly downstream of any bypass nozzle, as
temperatures there may not be representative of the overall reactor temperature. The optimum
thermocouple location along the length of the vessel is best determined by computational fluid
dynamic (CFD) modelling of the thermal reactor and burner. Lacking that, for a typical two-zone
thermal reactor, it is common to place one thermocouple two-thirds to three-quarters of the way
into zone 1 and another thermocouple two-thirds to three-quarters of the way into zone 2 (Figure1).

PYROMETER PLACEMENT

Unlike thermocouples, pyrometers are not prone to damage due to refractory shift. However, they
are susceptible to inaccuracy due to blockages of the sight path. This could be caused by deposition
of sulfur or another material in the nozzle bore or on the viewport window, or by significantly
shifting firebricks that might partially obscure the view through the borehole into the reactor.
Because of the potential for sight path blockage, the pyrometer should be placed in a location that
allows easy access for inspection of the sight path, verification, calibration, cleaning, and alignment
while the reactor is in operation. The side of the vessel is usually he most convenient mounting
location.

The nozzle should slope slightly downward to allow any condensed sulfur or other materials to fall
out the nozzle into the vessel. The pyrometer nozzle does not have to be near the target spot, it
could be anywhere a line of sight of the target spot. The pyrometer is aimed at a specific spot in the
reactor but, due to reflectivity, the indicated temperature is a weighted average of the and the
surrounding temperatures, as previously mentioned. However, the temperature of the target spot
does affect the measurement and so the target spot should not be directly downstream from a
bypass nozzle or on some other location whose temperature is not representative of the overall
temperature. If the nozzle is to be mounted at an angle to the vessel to, for example, aim towards
the tube sheet or checker wall, the angle should not be less than 45º from the long axis of the
reactor. Shallower angles create a large elliptical hole in the refractory that can cause hot spots at
or around the nozzle.

Like the thermocouple, the target spot for a pyrometer is best determined using a CFD simulation
of the reactor. And likewise, lacking such a simulation, it is common to position a pyrometer two-
thirds to three-quarters of the way into zone 1 and another two-thirds to three-quarters of the way
into zone 2.

NOZZLE DESIGN

For both thermocouple or pyrometer installations, the ideal nozzle should be as short as possible,
leaving sufficient space beneath the flange to remove frozen studs at turnaround time.
The shorter nozzle will operate at a much higher temperature, minimizing the possibility of sulfur
forming in the nozzle, or in the case of a pyrometer, forming on the inside of the viewport glass,
which has historically required frequent cleaning to restore accuracy. The added heat will also
minimize the possibility of corrosion. Although impossible to attain, the ideal nozzle would operate
at the same temperature as the vessel shell and remain corrosion free. In spite of the benefits of a
short nozzle, it is essential to consider the equipment manufacturer’s maximum ambient and nozzle
temperature ratings.

PLACING MULTIPLE INSTRUMENTS

In a typical two-zone reactor, the use of at least one temperature instrument in each zone is
recommended, since there is often a difference in temperature between the zones.
Additional instruments may be desired for redundancy. The use of both thermocouples and
pyrometers in each will provide improved reliability by protecting against common-cause failures.
 CREATING A SMALLER FOOTPRINT
Ensuring reliable energy supplies but with reduced carbon emissions is of global importance.
Changing to lees carbon-intensive energy sources is well under way in most nations, but there are
considerable technical and economic challenges. Effective energy generation systems need to be
evaluated with urgency (as investment cycles are long), developed and taken to “technology ready”
status to meet carbon emission targets. Focusing on the UK, this article will discuss why hydrogen is
a leading decarbonisation solution.

Progress to decarbonsation

Reducing carbon emissions to the atmosphere is of paramount importance in avoiding the increased
global temperatures and consequential effects of climate change due to escalating atmospheric
carbon levels. For most developed nations this has meant reduced coal use for electricity generation
and increased use of natural gas, nuclear and renewable energy for both industrial and domestic
use.

The UK is typical of many countries in having legislation to meet a 2050 target for carbon emissions
(Climate Change Act 2008). The UK aims to achieve at least 80% reduction from 1990 levels.
Deregulation of the gas market in the 1990s led to gas being used for power generation with
resultant decarbonisation. The country now imports over half of its gas demand, and, for strategic
reasons, has multiple methods of electricity generation. Renewables and nuclear power generation
are important in a diversified mix of low-carbon energy supply. Of the 140 million toe consumed in
2016, 17%of primary energy came from low-carbon sources, with nearly half of that from nuclear
and a third from bio-energy. Changes in electricity generation, a decline in energy-intensive
manufacturing and greater energy efficiency have helped reduce carbon emissions by 42%since
1990(compared to the Climate Change Act target of 26% reduction by 2020), while GDP has risen
by 67%. The use gas for electricity generation (instead of coal) has risen dramatically (Figure 1).
Other countries are applying similar principals to decarbonize. However, much more needs to be
done to meet carbon emissions targets.

Natural gas

Natural gas is a suitable “bridging fuel” for decarbonisation from coal whilst other methods of large-
scale energy generation are developed. With the recent opening of major LNG production terminals
in Australia, the US and Russia, many nations can now access plentiful, low-cost natural gas without
needing pipeline supply. For countries such as the UK, and others with pipeline supply and well-
established natural gas infrastructure, gas should be an affective source of low-carbon electricity,
as well as for industrial and domestic heating.

“New” energy generation technologies

To meet global climate change targets, alternative energy sources must be developed at competitive
cost. Both wind and solar power are being used more for electricity generation as technology has
progressed. It is likely that costs will continue to fall. However, both require some form of energy
storage to ensure that generated electricityia obtainle on demand and large-scale solutions are
currently not available. While renewables may support electricity generation, crucially they do not
help in heating or act as a raw material to produce chemicals and petrochemicals as natural gas
does.

Hydrogen

The UK has an expensive gas distribution network but a decarbonized replacement is needed. This
leads to the question of how to decarbonize whilst whilst effectively utilizing this countrywide
network and existing gas reserves (and relatively low-cost imported gas)? This promotes the use of
hydrogen, derived from natural gas, whilst alternative methods of providing low- carbon, low-cost
industrial and domestic heating can be developed. Hydrogen deserves detailed consideration as a
replacement for natural gas and work must start now to meet 2050 emissions targets.
Reforming of natural gas to produce hydrogen for electricity generation is currently significantly
cheaper than using wind or nuclear power and could save the UK €160 billion compared to other
alternatives.

A primary feature of pure hydrogen as a fuel is that when it burns, only water is produced and there
is no direct carbon burden, However, reforming natural gas produces carbon dioxide. The effective
capture. The effective capture and disposal (or usage) of this carbon dioxide is of key importance to
the potential use of hydrogen as a fuel source.

There are major cost saving available by reforming natural gas to separate carbon dioxide from
hydrogen, compared to capturing carbon dioxide that is highly diluted in flue gas from natural gas
combustion as has been the main focus of carbon capture schemes to date. Reforming makes it
much easier to obtain pure carbon dioxide. Flue gas carbon capture has been evaluated extensively
(mostly based on solvent) with little success in reducing cost, whereas carbon capture from
hydrogen at an elevated pressure opens up a broad range of proven gas purification technologies.

The use of hydrogen will require long-term strategic planning as well as government support and
subsdy particularly for the incentivisation of carbon capture and storage. A national benefit from
greater availability of hydrogen could be the uptake of fuel-cell electric vehicles (FCEVs), which react
stored hydrogen and oxygen from the air to produce electricity to power the vehicle. This
opportunity to reduce carbon emissions from transport requires further assessment and
incentivisation, and is supported by the UK government’s Clean Growth Strategy. Economic
comparison with greater use of electric battery vehicles, with their need for regular charging, would
be valuable. The latter will need electricity grid reinforcement.

Pure hydrogen can be sourced by using a direct current for the electrolysis of water. This also
produces pure oxygen as a byproduct, which has several important industrial uses. Large-scale
electrolysis is currently more expansive than natural gas reforming, but deserves more evaluation
and may be relevant to smaller applications. Costain is currently engaged in assessing the round trip
afficiency for a UK project to address the economics of hydrogen production by electrolysis for
energy storage.

Although gasification of biomass or domestic waste is a source of hydrogen, it generates much more
carbon dioxide than reforming natural gas.

Natural gas reforming

Hydrogn production through the high temperature reforming of natural gas with steam has been
practiced for almost a century, to provide a synthesis of gas for the manufacture of chemicals such
as methanol and ammonia, and produce high purity hydrogen for refinery operations including
hydrotreating and hydrodesulfurisation. Over 90% of industrial hydrogen is produced in this way.
Reformer technology is mature and well-proven

The amount of hydrogen needed for large-scale heating is much more than that currently produced
for chemicals manufacture and refinery use, which presents challenges on whether the maximum
size of reformers can be scaled-up reforming with steam is performed using a catalyst according to:

Ecuacion

The carbon monoxide is then converted into carbon dioxide by the water gas shift reaction:

Ecuacion

The reforming reaction is highly endothermic and needs a lot of heat. High temperature heat raising
from hot exhaust gas increases energy efficiency to very high levels.

Steam methane reforming (SMR) gives (on a dry basis) approximately 70% hydrogen and up to 10%
carbon dioxide (before carbon monoxide “shift” to carbon dioxide and hydrogen). Autothermal
reforming (ATR) uses oxygen in lieu of air to produce higher pressure hydrogen (up to 100 bar) at
up to 1000ºC. This technology is economical at the large capacities of today’s methanol, ammonia
and gas to liquids (GTL) plants, but produces significantly more carbon dioxide. SMR is therefore
preferred, but studies on optimal and lower cost carbon capture technology may mean that ATR will
be favoured for some applications in the future. More work is needed on this.

The carbon dioxide can be removed from the hydrogen by several well technologies- by solvent,
pressure swing adsorption (PSA), semi-permeable membrane and cryogenic. Costain has designed
many hydrogen related facilities, including for synthesis gas purification and for hydrogen recovery.
A hydrogen purity of 99+% can be economically achieved.

Large-scale carbon dioxide capture from hydrogen has been demonstrated industrially but there are
opportunities for technology development and optimisation of the purification technologies such
as chemical looping and hybrid process schemes of PSA, membrane and cryogenic technology.

Hydrogen projects

Due to the large scale of hydrogen deployment, it must be considered in a staged way by
geographical area, with arising technical and financial know-how being made available for future
use. This approach was employed in the UK for two front-end engineering and design (FEED)
projects for carbon capture and storage, one at Peterhead in Scotland (post combustion capture
downstream of an existing gas-fired power plant) and the White Rose projects at Drax, North
Yorkshire (Carbon capture from new oxyfuel coal-fired power plant). Both intended to ultimately
store carbon dioxide in North Sea reservoirs. In November 2015, the government’s financial support
was withdrawn and the projects were abandoned. However, the 2017 Clean Growth Strategy is an
opportunity for project developers, techno-economic consultants and engineering companies to
develop a more compelling case for government funding for hydrogen use and for carbon capture,
usage and storage.
Leeds, one of the UK’s largest cities, has been proposed as the first area in the country to potentially
use pure hydrogen as a fuel source for industrial and domestic heating. Hydrogen would be supplied
by pipeline from four SMRs on Teesside, with 1.5 million tpy of carbon dioxide piped to the North
Sea for storage. Salt caverns would be used for hydrogen ‘buffer’ storage. This project could be used
as a template for the wider implementation of hydrogen through the 2030s.

An alternative approach has been proposed by Cadent11 for the North West England conurbation.
Three 260 MW SMRs will provide a reliable source of hydrogen to local chemical manufacturers and
industrial heat consumers (which together consume over 5% of the UK’s energy) through a new
hydrogen pipeline system and by supplementing the existing natural gas network to a hydrogen
content of 10%. This content is significantly more than current limits for UK natural gas and the
effects of such a change are being assessed. A concurrent evaluation, termed ‘HyDeploy’, is
assessing the viability of natural gas containing 20% hydrogen.12 Carbon dioxide from the North
West ‘Cluster’ is intended to be piped to the soon to be depleted Hamilton gas field in Liverpool Bay
to store about 1.5 million tpy of carbon dioxide (including some industrial emissions currently sent
to atmosphere).

The proposed North West ‘Cluster’ would have an advantage over the proposed Leeds scheme in
not requiring modification to existing gas systems. It only provides partial decarbonisation of the
gas network but would demonstrate some key elements of a fully decarbonised scheme. The
economic feasibility of changing industrial and particularly domestic systems and burners from
natural gas to suit hydrogen, which is important to the Leeds scheme, is currently being evaluated.

Technical issues with hydrogen use

The advantages of large-scale production and utilisation of hydrogen (over other proposed carbon
reduction technologies) include:

Most of the key technology elements and equipment are well established and understood by the
leading process engineering consultants with reliable design methods and engineering procedures
in place.

Leading engineering companies already have corporate strengths in gas processing and
transportation, design safety capability, understanding of key legislation, economic modelling
capability, and the ability to deliver large scale technology intensive projects.

Established supply chain for critical equipment.

As an example of necessary skills now being in place, Costain has worked extensively on the national
gas grid and on underground gas storage; undertaken plant design and supply projects for hydrogen
and for carbon dioxide capture; has intellectual property to reduce the cost of carbon capture from
hydrogen; worked on hydrogen injection into the national gas grid; identified optimal locations for
carbon capture and storage in offshore UK depleted gas fields; and defined optimal carbon dioxide
transportation schemes.

Some technical concerns with hydrogen include:

It is volatile and highly flammable and has inherent safety concerns that require key management
and mitigation, including prediction of dispersion.
As hydrogen has such low density, pipelines and infrastructure for hydrogen transport are more
likely to leak than with natural gas.

It can lead to pipeline embrittlement (though the UK low pressure gas distribution system should
be 100% polyethylene pipe by 2032).

The characteristics of hydrogen in terms of its combustion characteristics (such as flame speed) are
different to natural gas (though Wobbe Index is within 10% that of natural gas).

High flame temperatures with hydrogen promote NOX formation.

The technical and engineering issues associated with high-pressure transportation and hydrogen
use need detailed evaluation to provide confidence.

Conclusion

Technology consulting and engineering capabilities exist to progress hydrogen deployment. Today’s
challenge is organising and managing the key techno-economic studies and evaluations that are
required to optimise hydrogen-based energy supply on a local and national level. There is an urgent
need for this to happen to ensure critical targets for carbon dioxide emissions can be met.