LNG/GAS PROCESSING DEVELOPMENTS SPECIALREPORT

Select optimal schemes

for gas processing plants
Careful process evaluation helps meet
product requirements and environmental standards
M. MALEKI and M. KHORSAND MOVAGHAR,
Energy Industries Engineering and Design Co., Tehran, Iran

G
as processing plants are an essen- gas treating of the feed gas using amine The original scheme designed to meet
tial part of the energy industry is necessary. The amine unit is designed the product specifications from a sour
and provide one of the cleanest- for total H2S removal and total or partial feed containing high concentrations of
burning fuels and a valuable chemical feed- CO2 removal. This article will investigate H2S, CO2 and mercaptans is depicted in
stock. The importance and complexity of the reason for partial CO2 removal, which Fig. 1.
gas processing plants have increased over is no longer required due to the recent The gas processing facility has a feed gas
the years due to their use as a feedstock advances in sulfur recovery technology treating unit (GTU) using amine for total
source and their integration with petro- used in gas processing plants, including H 2S removal and partial CO 2 removal.
chemical plants. South Pars gas plants. The facility also includes utilities, offsites
Important factors that drive the pro- and necessary infrastructure. The functions
cess selection and design of gas process- Partial CO2 removal scheme. Over of the main process units can be summa-
ing plants are environmental and safety a span of 20 years, the process design of rized as follows:
regulations, capital and operating costs, each gas processing plant has been modi- • Feed reception and gas/liquid separa-
and process efficiency. Therefore, selecting fied to some extent. The main reasons for tion
an optimized process scheme during the the changes are more stringent environ- • Total H2S removal and partial CO2
project feasibility study is vital to ensure mental regulations for newer projects and removal from gas
that the project is technically feasible, cost- higher ethane purities required for petro- • Dehydration using molecular sieve
effective and profitable. chemical plants. technology

PROCESS SCHEME SELECTION

The process selection study usually Flue gas
begins with a design basis to specify the
general configuration of the plant and its Incinerator
outline requirements. These requirements
consist of: Claus unit Sales gas
Sales gas
• Feed characteristics, especially H2S, Sulfur compressor
CO2 and mercaptan concentrations
• Product specifications, including Ethane
Reception Gas treating Dehydration Ethane treatment Ethane
maximum concentrations of sulfur and facilities unit (with unit recovery unit with DEA
CO2 in the products. MDEA) and drying
The criteria to be optimized for the pro-
cess scheme selection include: C3 liquid
Gas condensate NGL C3 treatment
• Environmental and safety compli- stabilization fractionation and drying
ance with local regulations for effluents
from incinerators, flare stacks, wastewater
treatment, etc. C4 treatment
and drying
• Flexibility and performance
C4 liquid
• Cost
• Energy consumption. Stabilized condensate
The maximum H 2 S concentration
allowed in the sales gas is 4–5 parts per FIG. 1 Original scheme for sour gas treating plant.
million by volume (ppmv); therefore,

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SPECIALREPORT LNG/GAS PROCESSING DEVELOPMENTS

• Ethane recovery for production of • Lower sulfur content requirement in nolamine (DEA) generally provide maxi-
sales gas and gaseous ethane propane and butane products. mum CO2 concentrations of 100 ppmv
• NGL separation for production of This article investigates the best pro- in the treated gas.
liquid C3, C4 and gas condensate cess scheme for the new conditions and Changes in the sulfur recovery unit.
• Sales gas export compression compares total CO2 and H2S removal for The acid gases (H2S and CO2 ) removed
• Sulfur recovery the GTU vs. partial CO2 removal. It also in the amine unit are sent to the SRU.
• Ethane treatment for CO2 removal examines the impact of this change on The SRU is based on the modified Claus
and drying. other units in the plant. process for recovering elemental sulfur
Gas treating unit. The GTU uses from acid gas. The chemistry of reac-
Restrictions affect design. New amine for H 2 S and CO 2 removal. tions involved in the Claus process may
environmental standards have influenced Although we assume that readers are famil- be described in a simplified form with
product specifications and have led to iar with amines, it is important to note the following two equations: the first is
changes in the gas plant design. The main that three types of amines are already used a simple combustion of one-third of the
changes that have altered the design are: in most gas refineries, as summarized in hydrogen sulfide; the second is the reac-
• Improved sulfur recovery efficiency Table 1.1, 2 tion of SO2 produced with the remaining
in the sulfur recovery unit (SRU), result- When the GTU is designed for total two-thirds of H2S, according to the fol-
ing in less sulfur being burned in the H 2 S and CO 2 removal, normally the lowing reactions:3
incinerator CO2 can be reduced to less than 5 ppmv. H2S + 3/2 O2 t SO2 + H2O – 519
• Lower CO2 content requirement in However, because of design limitations, kJ/mole (–124 kcal/mole)
the ethane product guaranteed figures using generic dietha- 2 H2S + SO2 t 3/n Sn + 2 H2O – 143
kJ/mole (–34 kcal/mole)
TABLE 1. Amine technology process capabilities Feed gas composition. The acid gas
from the GTU regenerator column consists
Amine Features Regeneration duty of H2S and CO2 that is fed to the Claus
Diethanolamine: • DEA is for complete H2S and CO2 removal. High unit. The Claus process efficiency is largely
(DEA)2HN(CH2CH2OH)2 • Yields low degradation products and corrosion rates. dependent on the H2S/CO2 ratio, and it is
MDEA: CH3N(C2H4OH)2 • Used selectively for deep H2S removal, with only Low difficult to maintain at a high value when
moderate CO2 removal. the H2S content in the acid gas drops below
• Yields significantly low degradation products and 36%–40%. This difficulty is due to the fol-
corrosion rates.
lowing factors:
Activated MDEA • Used for complete CO2 removal; H2S removal also Low • CO2 is an inert gas that dilutes the
(aMDEA) occurs due to enhanced reaction kinetics.
process gas and, consequently, reduces the
• High-performance solvent with reduced energy
requirements, high acid loadings, minimal corrosivity
conversion efficiency by lowering the par-
and negligible degradation products. tial pressure of reactants. Furthermore, in
the reaction furnace (where the thermal
Claus reaction takes place), the conversion
Flue gas efficiency is limited due to resulting low
flame temperature.
Incinerator
• The low H2S content may present
challenges to sustaining the flame in the
Acid gas
Claus unit
Tail gas reaction furnace, where only one-third of
enrichment treatment the acid gas should be burned to achieve
Sales gas
Sulfur the stoichiometric H2S-to-SO2 ratio of 2
Regeneration required by the Claus reaction.
Sales gas gas treatment
compressor with DEA • Carbon dioxide may react with a sul-
fur species to form carbonyl sulfide (COS)
Ethane and carbon disulfide (CS2) or a dissociate,
Gas treating treatment Ethane
Reception Dehydration Ethane which may result in reduction of the overall
unit (with with DEA
facilities unit recovery unit
MDEA) and drying sulfur recovery, unless adequate precautions
are taken for the design of the reaction fur-
C3 liquid
nace and the catalytic converters.
Gas condensate NGL C3 treatment • Due to the above reasons, limitations
stabilization fractionation and drying
in the Claus process on the maximum
CO2 content require a ratio of 60:40 for
C4 treatment CO2:H2S for the acid gas from the GTU.
and drying Lower H2S concentrations can be accepted
C4 liquid using special measures (such as enriched air
Stabilized condensate and fuel gas co-firing), but at the expense of
lower conversion efficiencies. However, to
FIG. 2 Sour gas treating plant with partial CO2 removal. minimize the Claus unit size and maximize
efficiency, an acid gas enrichment using

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I JANUARY 2012 HydrocarbonProcessing.com
 LNG/GAS PROCESSING DEVELOPMENTS SPECIALREPORT

selective amine is generally used to produce ular sieve beds are regenerated using sales In more recent projects, environmental
“enriched” acid gas suitable for conven- gas that is then sent to the fuel gas system. regulations allow for fewer SO2 emissions
tional Claus SRUs.4 The regeneration gas must be CO2-free, from the SRU incinerator, which requires
• Another option is to use an amine as requested by the LPG guard bed ven- an increase in the conversion of sulfur
absorption process, which is suitable for dor. Therefore, if partial removal of CO2 recovery from 97.5% to 99.5%. Thus,
H2S concentrations within the range of is considered for the GTU design, then to achieve higher overall sulfur recovery,
1%–30 vol%. 5 They offer less complex another DEA absorber must be installed acid gas enrichment and tail gas treatment
designs and the same sulfur quality as for total CO2 removal from the regenera- units must be used. The acid gas enrich-
the Claus process, but have the disadvan- tion gas. However, if the CO2 is totally ment unit consists of selective H2S removal
tage of providing lower sulfur recovery of removed in the GTU, then molecular from the acid gas in the presence of CO2
96%–97%. sieve guard beds can be used instead of a (i.e., partial CO2 removal from the acid
Sulfur recovery efficiency. Typical sul- DEA absorber. gas). This is accomplished by including an
fur recovery efficiencies for Claus plants amine unit using a generic MDEA solvent
are 90%–96% for a two-stage reactor Evaluation of existing GTU. The that selectively absorbs H2S. The offgas
and 95%–98% for a three-stage reactor. CO2 specifications for sales gas fed to a leaving the top of the amine absorber
However, new environmental regulations consumer network should be less than 2 is sent to the incinerator to convert the
limit sulfur recovery efficiencies to 98.5%– mol%—the maximum limit to prevent residual H2S to less harmful SO2, while the
99.9%. This limitation has led to the devel- general corrosion and pitting in pipelines. sour gas reaching the required H2S:CO2
opment of a large number of tail gas units This limit will be achieved if the CO2 con- ratio from the amine regeneration unit is
based on different concepts to remove the tent in the treated gas from the GTU is less sent as feed to the Claus reactor.
last remaining sulfur species.6 than 1 mol%. In fact, the latter quantity Therefore, by making a gas enrichment
was obtained by back calculation using the unit part of the sulfur gas recovery unit,
Changes in ethane quality. Due to ratio of 60:40 for CO2:H2S in the acid it is no longer a requirement to specify an
partial CO2 removal in the current design, gas to the SRU and a sulfur recovery of outlet CO2 of 1 mol% in the treated gas
the ethane product—which is separated 97.5%. Therefore, partial CO2 removal from the GTU. Based on these results,
from the treated gas in the ethane-recov- in the GTU was dictated by the process two alternatives exist for the gas process-
ery section—contains CO2. Therefore, it requirements in the SRU. ing plant scheme:
becomes necessary to add an ethane decar-
bonation unit (EDU) to reduce the CO2 TABLE 2. Effect of CO2 removal on heating value of two sales gases
level to the specified maximum of 50 parts
per million by weight (ppmw) prior to Heating value (Kcal/Nm3) Heating value (Kcal/Nm3)
with CO2 (max. 2 mol%) without CO2 % change
export. DEA is used to remove CO2 from
ethane in the EDU before it is dehydrated Gas A 8,228.05 8,396.48 2.04
using molecular sieve beds. Gas B 8,548.01 8,635.24 1.01
In the case of total CO 2 removal in
the GTU, the ethane cut from the ethane
recovery section will contain very little to Flue gas
virtually no CO2. In fact, ethane will con-
Incinerator
tain around 500 ppmw if CO2 is lowered to
100 ppmv in the GTU using DEA, which
can be removed by molecular sieve beds. Acid gas Tail gas
Also, there is no need for a separate drying Claus unit
enrichment treatment
unit if molecular sieve beds are used, which
Sulfur Sales gas Sales gas
provides an advantage in terms of cost, ease
compressor
of operation and maintenance. Therefore, Regeneration gas
in the case of total CO2 removal, even the
molecular sieve bed is just a CO2 guard. Gas treating
Ethane
Changes in LPG product quality. The Reception Dehydration Ethane treatment Ethane
facilities unit (with unit recovery unit with mole
environmental specification for the total DEA or aMDEA)
sieve beds
sulfur content in LPG products (C3 and
C4) has been lowered from 80 ppmw to 10 C3 liquid
ppmw; this was the case for LPG products Gas condensate NGL C3 treatment
stabilization fractionation and drying
from South Pars gas plants.
Sulfur species in LPG are essentially
mercaptans, which are removed by direct C4 treatment
and drying
oxidation with air in the presence of a pro-
prietary catalyst, using a caustic soda-wash C4 liquid
process. The LPG product is then dried Stabilized condensate
before export.
A molecular sieve sulfur guard is FIG. 3 Sour gas treating plant with total CO2 removal.
installed after the LPG dryers. The molec-
HYDROCARBON PROCESSING JANUARY 2012
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SPECIALREPORT LNG/GAS PROCESSING DEVELOPMENTS

1. Partial CO2 removal in the GTU— tages that can be easily prevented by total tion and a longer time for bed regenera-
similar to the old scheme, regardless of the CO2 removal in the GTU, which can be tion. Therefore, it could be expected that,
changes in the SRU, as shown in Fig. 2. achieved using DEA or activated MDEA in the case of total CO2 removal, the bed
2. Total CO2 removal in the GTU—an (aMDEA) in the GTU. When the GTU is adsorption capacity will be increased while
optimized gas processing plant scheme based designed for both H2S and CO2 removal the bed regeneration time and energy con-
on changes in the SRU, as depicted in Fig. 3. (down to 3 ppmv and 100 ppmv, respec- sumption are decreased. This is an item
Effects of total CO2 removal on sales tively) in the treated gas using DEA, the that needs further investigation by opera-
gas quality. The sales gas from gas process- CO2 content in the sales gas ranges from tors and vendors.
ing plants can contain a maximum of 2 100 ppmv–200 ppmv.
mol% of CO2, as stated in the previous Effects of CO2 removal on sales gas Overall optimized scheme. Fig. 3
section. Carbon dioxide is an inert gas that heating value. When modifying the sales shows the optimized scheme for total CO2
only uses energy to be heated to the flame gas composition by total CO2 removal, it removal, where the ethane treatment with
temperature, without any heat input con- is important to check the heating value to molecular sieve beds should only be con-
tribution to the combustion. Therefore, its ensure that the changes are not significant sidered if the treated gas from the GTU
presence at a relatively high amount in the enough to require burner change in the will provide an ethane product with a CO2
sales gas is a waste of energy. consuming furnaces. Two sales gases were content higher than 50 ppmw.
In addition to the above, environmen- studied for this purpose; the results are
tal agencies of many countries continue presented in Table 2. As the table shows, SOLUTION
to implement more stringent emissions the effect of total CO2 removal on sales gas Before selecting a scheme for a gas pro-
standards requiring companies to report heating value and its possible consequences cessing plant, it is necessary to construct
their greenhouse gas emissions. Thus, many on burner design—as well as adverse effects a clear and complete picture of the entire
customers buying sales gas want CO2 lev- on the operation of existing burners—is facility. The requirements of each unit
els in the gas to be minimized. Also, the insignificant. within the plant must be understood before
CO2 present in the sales gas is distributed Effects of total CO2 removal on the they are integrated into the whole scheme.
through many users, although it can be dehydration unit. If CO2 is present in the The process scheme selection is car-
recovered for industrial use when totally feed gas to the dehydration unit after the ried out during the conceptual stage of a
captured at the gas plant source. GTU, it might be partially co-adsorbed project and should take into account new
These negative aspects of CO2 presence by the molecular sieve beds, resulting in technology developments for each unit in
in the sales gas are some of the disadvan- a reduced active area for water adsorp- the plant. Such an approach will deliver an
optimized process for the plant that is cost
effective, energy efficient, and meets local
environmental and safety regulations. HP

LITERATURE CITED
Complete literature cited available online at
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