Treating Technologies of Shell Global Solutions For Natural Gas and Refinery Gas Streams
Treating Technologies of Shell Global Solutions For Natural Gas and Refinery Gas Streams
Treating Technologies of Shell Global Solutions For Natural Gas and Refinery Gas Streams
Treating Technologies of Shell Global Solutions for Natural Gas and Refinery Gas
Streams
By J.B. Rajani
ABSTRACT
Gas / liquid treating is often thought of as being a mature technology with little opportunity for
improvements or innovations. However, changes in requirements from users continue to drive
improvements in technology. These changes include: new and more complex feed sources, more
demanding product specifications, and increasing demands on reliability and other plant performance
improvements.
Technology offerings range from conventional liquid phase absorption, solid bed adsorption, catalytic
gas reaction conversion, to bio-treating of H2S. Owing to our experience across the range of offerings,
Shell Global Solutions can offer solutions based on an integrated combination of processes that takes the
feed stream and deliver the required end product in an optimal manner. Selecting the right technology to
accomplish the objective results in a cleaner environment, improved reliability, and higher margins
R & D work within Shell is geared to these requirements so as to offer the best in treating technologies.
In order to maintain this competitive edge, this paper reviews the traditional treating technologies and
introduces new developments in the Shell treating portfolio.
1. INTRODUCTION
Gas /liquid treating encompasses a wide variety of technologies for the removal of sulphur compounds
and other trace components from gases and light hydrocarbon liquids. Treating is an essential
technology for the application of other core technologies in refineries and in gas plants. In addition,
environmental pressure and more demanding product qualities means that treating units are being given
an increased focus. To maximise refinery and gas plant returns utilisation should not be impaired by the
performance or reliability of the treating units.
Gas/liquid treating is often thought of as being a mature technology with little opportunity for
improvements or innovations. Although this may be the view of those using the technology for their
particular application, Shell Global Solutions see changes driven by user needs for processing new
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streams to meet a variety of product specifications. The fundamental objective in treating is to meet all
outlet stream specifications for a particular feed stream. The variations in feed gas streams are
increasing, and now in addition to traditional streams from refineries and sour gas reservoirs, there is a
need to treat gas streams from: coal or residual oil gasification projects, associated gas from oil
production, bio-gas generation, gas to liquids facilities (such as gas-to-liquid process SMDS), and to
treat natural gas streams on floating platforms. These feed streams come with widely different
temperatures and pressures, but in particular show extremes in composition. Product specifications also
consist of a wide variety of requirements. At the same time, high reliability requirements, reducing
capital and operating costs, and developments from competitors continue to add pressure to ensure that
new developments continue. The process designer is thus faced with applying existing knowledge to
extend the design envelopes of the process. Research efforts within Shell Global Solutions focus on
improved solvent offerings and new applications of technologies. Some step outs work better than
others, but all improve understanding of the processes that are employed and some provide opportunities
for new or improved offerings.
Shell Global Solutions offer an integrated approach to natural gas and refinery gas treating requirements.
In such treating requirements, the removal of sulphur compounds (H2S, COS, mercaptan, sulphides) and
CO2 are often required. In industrial treating applications, feed gas and product streams are often very
diverse and the technology employed is therefore also diverse. Technology offerings of Shell Global
Solutions range from conventional liquid phase absorption, solid bed adsorption, catalytic gas
conversion reactions for HCN and COS to biological gas desulphurisation process recently introduction
to the market as Shell-Paques technology.
This paper reviews Shell Global Solutions treating portfolio and comments on some of the main
developments that have taken place in the treating area over the last two years. Emphasis in the R&D
field has been to widen the Shell treating portfolio so as to encompass as many as possible treating
requirements in industrial processes.
The ADIP process is especially suitable for the removal of H2S from natural gas, refinery gas, synthesis
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gas and SCOT (Shell Claus Offgas Treating Process) offgas and for bulk and deep CO2 removal from
natural gas.
The Sulfinol process is highly suited for the removal of both H2S and CO2 and especially COS,
mercaptans and organic sulphides. This makes it the process of choice for treating natural gas and
synthesis gas from coal/oil gasifiers and steam reformers.
Integrated approach for optimal operation of ADIP and Sulfinol units includes optimal designs, full
process monitoring including chemical analysis of solvent, advice on solvent quality management such
as reclaiming, filtration, active carbon beds, etc.
The ADIP (Figure 1) process is highly suitable for the following applications:
$ Removal of H2S and CO2 from natural gas, synthesis gas and refinery gas streams
$ Removal of H2S and COS from light liquid hydrocarbon streams (LPG and NGL)
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Figure 1: Typical process flow scheme of the Shell ADIP and Sulfinol Process
The process can be used over a wide range of operating pressures (units are in operation at pressures up
to 180 bar) and contaminant levels.
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$ 5 ppms (LPG/NGL)
$ Removal of H2S, CO2, COS, mercaptans and organic sulphides from gas streams
$ Deep removal of CO2 from syngas and LNG plant feed gas
The process can be used over a wide range of operating pressures (units are in operation at pressures of
up to 80 bar) and contaminant levels.
$ 5 mg S/Nm3
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There are over 200 Sulfinol units in operation. In spite of such success in the use of ADIP and Sulfinol
processes in the gas / liquid treating, Shell Global Solutions has continued to invest in improving these
processes. This has lead to the following two new additional processes in the Shell technology portfolio.
The Shell ADIP-X process is a regenerable amine process for acid gas removal utilising a mixture of
two or more alkanolamines, in general a base amine such as MDEA (methyl di-ethanolamine) and an
accelerator. The process achieves a higher loading capacity compared to single amine solvents. This
leads to the design of smaller absorber columns with reduced number of trays when compared with
generic MDEA solvent.
$ Removal of H2S and CO2 from natural gas, refinery gas and synthesis gas streams
$ Particularly suitable for natural gas field with CO2 content in the excess of 5 %v in the feed gas.
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The Shell Sulfinol-X process is a regenerable amine process for acid gas removal utilising a mixture of
two or more alkanolamines, in general a base amine such as MDEA or DIPA and an accelerator. As the
process uses a mixture of water, Sulfolane and one or more alkanolamine, removal capacity of COS,
mercaptans and organic sulphides from gas streams is excellent by virtue of the improved physical
solubility of these compounds in the solvent. The process achieves a higher loading capacity thus
enabling a design of smaller absorber columns with reduced number of trays when compared to the
Sulfinol process..
$ Removal of H2S, CO2, COS, mercaptans and organic sulphides from gas streams
Gas streamH2S
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$ 5 mg S/Nm3
Shell Global Solutions licenses all the above mentioned treating processes. A significant advantage of
Shell processes is that the client is able to buy the chemicals on the open market and is not locked in to a
single supplier.
3. SULPHUR PROCESSES
Depending on gas flow and H2S concentration, the most favourable choice can be made between four
main processing options, as shown in the figure below.
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If H2S is present in the feed, sulphur emissions will be subject to local legislative restrictions. The most
appropriate process to convert the H2S and organic sulphur to elemental sulphur is mainly dependent on
the quantity of sulphur present in the feed.
To minimise Claus unit size (Figure 2) and maximise efficiency the feed gas can be enriched by
selectively removing the H2S from the regenerator off-gas. For very low H2S levels in acid gas there are
also other processes available, e.g. Selectox that replaces the thermal stage of a conventional Claus plant
with a direct oxidation stage. There is little experience with such units at commercial scale natural gas
processing plants.
For lower quantities of sulphur (< 5-20 t/d) the Claus unit can be replaced by a redox type process, such
as the SulFerox process or the new biological Shell-Paques process which are not restricted by a
minimum H2S content in the feed gas.
As stated above it is important to identify the best integrated and economic solution to the overall
treating needs. The SCOT tail gas technology can readily be integrated with the main amine gas
treatment, with or without an acid gas enrichment step and, if necessary, treatment of regeneration gas
from molecular sieve regeneration.
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With a SCOT unit an overall sulphur recovery efficiency of higher than 99.8% can be achieved, with a
SUPER SCOT the recovery can be increased up to 99.95%. The SCOT process has a great tolerance to
variation in the tailgas composition of the upstream Claus unit.
It has a turndown ratio to less than 10% of the design throughput. The unit can be integrated with the
refinery amine treating units. Capital costs are thus reduced, as no dedicated regenerator is necessary for
the SCOT amine absorber. The unit requires little operational attention and has a very high (>99%)
record of reliability.
• The unit is robust and forgiving when compared to most other tailgas treating units. The overall
sulphur recovery efficiency of the Claus - SCOT configuration remains about the same within a
relatively large operating window of the upstream Claus unit.
• The sulphur recovery efficiency in the upstream Claus unit is not critical for the performance of the
SCOT unit and the overall sulphur recovery efficiency of the Claus SCOT combination. A Claus unit
with two catalytic stages is sufficient.
• The SCOT unit is not sensitive to ammonia and does not require complete ammonia destruction in
its upstream Claus unit for trouble free operation.
• The overall sulphur recovery efficiency is consistently very high when compared to other tailgas
treating units.
Shell Global Solutions International has a number of proven solutions for integrating new SCOT unit
and existing Claus unit(s), including interaction of the amine absorber as a cascaded design.
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The process is based on contacting a gas stream containing hydrogen sulphide with an aqueous soda
solution containing sulphur bacteria in a scrubber. The hydrogen sulphide is absorbed in the soda which
is transferred to a regenerator. The regenerator consists of an aerated atmospheric tank where hydrogen
sulphide is biologically converted to elemental sulphur. The sulphur is removed from the tank in the
form of a slurry, which can be worked up to a dry powder or to a molten sulphur with the same high
purity as Claus Sulphur.
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$ Synthesis gas
$ Oxygen containing waste gases like vacuum offgas, which cannot be successfully treated with other
solvents.
The main advantages of the Shell Paques process when compared to conventional schemes are:
$ Simple and reliable and safe unit design that is very easy to operate.
$ Very low H2S contents can be achieved in the treated gas (less than
5 ppmv).
$ No plugging and blocking problems due to the hydrophilic nature of the biological sulphur.
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The process is most competetive in the 0.1-15 tonne/day sulphur capacity range. Thanks to its unique
patented chelate chemistry, the SulFerox process can maintain an aqueous solution of iron in high
concentrations.
As a result the amount of liquid circulated is low and the equipment is surprisingly small, resulting in
significantly lower investment cost. The SulFerox process is particularly attractive for natural gas
treatment, when low H2S and high CO2 contents would normally make conventional amine-based units
uneconomic. The small equipment size makes the process very attractive for offshore applications.
SulFerox has the following advantages over absorption based treating processes :
$ Very low H2S contents can be achieved in the treated gas (less than 5 ppmv).
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More than 30 SulFerox units are currently in operation covering a wide range of gas treating
applications.
3.6. Incineration
Incinerators are installed to convert H2S in the tailgas to SO2 before discharge to atmosphere. The two
main types of incinerators are thermal and catalytic. A thermal incinerator downstream of a Claus/SCOT
usually operates at a temperature of 650 - 850 °C, oxidising all sulphur components, as well as CO and
H2. A catalytic incinerator operates at about 300 °C with the sulphur components (only) being
selectively oxidised to SO2.
Shell developed catalyst (Criterion 099, previously known as C 099 and S 099), was by 1990 in use in
over 30 catalytic incinerator units worldwide. It is characterised by a high activity for the oxidation of all
sulphur components to SO2 and excellent selectivity, within the specified temperature range no SO3 is
formed and no oxidation of CO and H2 occurs.
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Liquid sulphur from Claus units still contains about 250 - 300 ppmw hydrogen sulfide and hydrogen
polysulfides (H2Sx). To meet environmental and safety restrictions, the liquid sulphur should contain
less than 10 ppmw H2S. In the Shell Sulphur Degassing process (Figure 6) the sulphur is circulated over
a stripping column, open in top and bottom, by bubbling air through the sulphur.
By agitating the sulphur this way the H2S is released. The whole system is located in a separate vessel or
in the intermediate sulphur storage.
The new Shell Sulphur Degassing process has been developed to decrease residence time (and
consequently capital expenditure) while still meeting the sulphur product specification of 10 ppmw H2S
without the utilisation of a catalyst or any equipment employing moving parts. The process provides a
reliable and safe operation, with very little attention required.
Currently more than 120 Shell Sulphur Degassing units are in operation, at capacities ranging from 3 to
4000 tons of sulphur per day.
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adsorption process. Two types of adsorbents given below are routinely applied in such processes.
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units is their reliability as has been shown by Shell Global Solutions involvement in monitoring the
dehydration units of three Shell advised LNG plants.
Shell Global Solutions has conducted test runs on two mole sieve units at a gas plant in Scotland in the
fall of 1999 and identified a problem with the top half of one of the dryers. The test run data was also
used to optimize the run cycle time and predict the capacity available. The predicted capacity was less
than that required to meet the peak demand expected for the winter of 2000. This provided justification
for replacement of the mole sieve during the summer of 2000.
Another example for mol sieve reliability service has been a design review of the Canadian gas plant
mole sieve unit. Data indicated that the upstream knockout vessel was grossly undersized relative to our
design specifications and current plant throughput. This has been identified as the major contributor to
short life of the mole sieve material and recommendations for improvements are being evaluated.
Shell Global Solutions also has developed sophisticated mathematical models for the prediction of free
water formation during regeneration of mol sieves. If free water is formed, the uptake water capacity of
the sieve is drastically decreased over a short period of time. This leads to premature change out of the
mol sieve inventory and thus production losses due to unscheduled shut down. Such optimization of
regeneration procedures and cycle time has been carried out at other LNG locations in Brunei, Malaysia
and Australia.
Shell Global Solutions can provide a basis of design, proprietary catalyst, and operating guidance for
this process. Figure 8 shows the process scheme for a typical HCN/COS hydrolysis unit.
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7. Technology selection
Simple rules for the selection of the most effective treatment technology are difficult to arrive at given
the array of possibilities in feed gas conditions and resultant requirements for one or more of stage gas
treatment (one or two stages), acid gas enrichment, mercaptan removal, sulphur recovery technology,
Claus tail gas treatment, high pressure operation, low temperature operation etc. Added to this are other
considerations such as reliability record, corrosion performance, quality of process guarantees and
availability of professional after sales technical service.
Given the magnitude of the investment in a treating facility it is appropriate to carry out a rigorous
treating process selection study to identify the most cost effective and fit for purpose treatment package.
The consultant chosen to do the study must be experienced in the field of gas treatment design, familiar
with all the technologies available, able to discern effective integration options and ideally be able to
draw upon actual operating experience to identify a robust operating line up. The investment in a high
quality consultant to provide process selection will be well rewarded with a reliable fit for purpose and
cost effective treatment package.
8. Conclusions
Up until recently the levels of CO2 and sulphur encountered in natural gas developments have allowed a
fairly open selection of solvent based treatment technology although preference has most often been
given to well proven technologies. However with increased sulphur levels, mercaptans and more
extreme operating requirements the available choices for a cost effective integrated treating package
narrow dramatically. Additionally environmental constraints to waste streams have to be taken in
account. Use of the Shell ADIP and Sulfinol technology can be the decidedly more attractive option in
these cases. It is critical that each new gas development undergoes a rigorous selection study to identify
the most cost effective and fit for purpose treating package.
Shell Global Solutions offer a portfolio of treating processes that can assist in solving treating problems
effectively. Shell Global Solutions shall be more than happy to discuss any specific situation and
determine in which areas Shell Global Solutions can assist in overcoming design or operational problem
(s).
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