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Conversion Efficiency of Biogas to Liquids Fuels through Fischer-Tropsch

Process

Conference Paper · June 2015

DOI: 10.5071/23rdEUBCE2015-3CO.15.5

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 CONVERSION EFFICIENCY OF BIOGAS TO LIQUIDS FUELS THROUGH FISCHER-TROPSCH PROCESS

M. T. Ashraf, J.R. Bastidas-Oyanedel, J. E. Schmidt

Institute Center for Energy – iEnergy, Masdar Institute of Science and Technology,
PO Box 54224, Abu Dhabi, United Arab Emirates
mtashraf@masdar.ac.ae, jbastidas@masdar.ac.ae, jschmidt@masdar.ac.ae

ABSTRACT: Demand for non-fossil liquid transport fuels is increasing and biogas to liquid fuels conversion is one
possible way to produce liquid fuels. Conversion of natural gas to liquid fuels by Fischer-Tropsch synthesis (FT-
synthesis) is an established process applied at industrial scale. Biogas plants have relatively lower throughput and
methane concentration compared to natural gas. Conversion efficiency of carbon in methane to liquid fuel is an
important parameter to benchmark conversion technologies. A biogas to liquid fuel conversion process using
pressurized water scrubbing, dry methane reforming, and FT-synthesis is proposed. The process parameters are
selected by optimization and sensitivity analysis. The process is simulated to calculate the carbon conversion and
energy efficiency. The proposed process has a carbon conversion efficiency of 45% and energy efficiency of 30%.
For the base case of 10,000 Nm3/h of dry biogas the process requires 7.08 MW of power in addition to 35 and 185
GJ/h of heating and cooling duties, respectively. From 4000 kg/h of methane in the biogas feed 1602 kg/h of FT
crude is produced.

Keyword: biogas, Fischer-Tropsch, liquid biofuel, reforming, clean synthesis gas, conversion

1 INTRODUCTION conversion efficiency, heat and power requirement of the

process are calculated by process simulation in Aspen
Our global industrialized society development has Plus. The process is modeled for the base case of 10,000
been based on fossil fuels, 66% of total energy Nm3/h of dry biogas with the nominal composition
consumption in 2012 came from fossil fuels [1]. Fossil shown in Table I.
fuels use results in increase of greenhouse gases (GHG)
emission, with detrimental effects to our environment [2], Table I: Composition of biogas, adapted from [8] and [9]
[3]. Total global energy consumption has increased from
4,671 Mtoe (Millions of tonnes of oil equivalent) in 1973 Landfill This
to 8,980 Mtoe in 2012 [1]. In 2012, refined oil products, Component Units AD Biogas Biogas Study
e.g. liquid fuels, accounted for 40.5 % of the total energy CH4 vol% 53-70 30-65 60
consumption, while bioenergy (biofuels and waste-to- CO2 vol% 30-50 25-47 38
energy) represented 12.4% [1]. N2 vol% 2-6 <1-17 2
In this environmental context, biofuels have the O2 vol% 0-5 <1-3 0
potential to mitigate GHG emissions [4]. Biofuels H2 vol% NA 0-3 0
availability, to contribute meeting the projected fuel H2S ppm 0-2000 30-500 2000
demands, is a global priority for a sustainable social and NH3 ppm <100 0-5 100
economic development, reducing GHG emissions. Total Chlorine mg/Nm3 <0.25 0.3-225 0
Biogas is produced by a biological process, anaerobic Siloxane µg/g-dry <0.08-0.5 <0.3-36 0
digestion, that uses organic matter, e.g. agro-residues,
food wastes, animal manure, organic fraction of
municipal solid waste and industrial wastes [5]–[7]. 2 PROCESS DESCRIPTION
Table I shows the typical biogas composition. Biogas
production advantages not only rely on the environmental 2.1 Biogas cleaning
viewpoint, reducing GHG emissions, but also on the Apart from major components CH4 and CO2 raw
robustness of the technology, its capacity to use diverse biogas has impurities: H2S, NH3, N2, and siloxanes.
raw materials/applications, it can be use in remote These impurities can cause corrosion, toxicity, catalyst
locations [5], and its financial aspects [6]. deactivation, and reduction of heating value. Removal of
For markets where there is a demand for sustainable these impurities to certain levels is required depending on
liquid biofuels, biogas can be converted to liquid fuels downstream utilization. For production of synthesis gas
using FT-synthesis. One processing route can be of presence of H2S effects the activity of catalyst and
following steps: 1) biogas cleaning to remove impurities reduces the conversion of CH4 and CO2. Chattanathan et
2) biogas reforming to produce synthesis gas (syngas) 3) al. [10] studied the effect of 0.5 mol% H2S impurity on
syngas upgrading to remove CO2 4) Fischer-Tropsch biogas reforming using commercial catalyst (Reformax®
synthesis (FT-synthesis) for liquid fuel production. The 250) and reported decrease in CH4 and CO2 conversions
energy required for reforming can be provided by from 67% and 87% to 19% and 22%, respectively.
biomethane oxidation. Removal of H2S is necessary for all biogas reforming
The objective of this study is to evaluate feasibility of technologies. Removal of CO2, called biogas upgrading,
FT-synthesis process, which is conventionally used for improves the biogas heating value. However this step is
natural gas to liquid fuel conversion, for relatively small energy intensive as CO2 is the second major component
scale biogas to liquid fuels conversion (10,000 Nm3/h dry in biogas, hence reforming technologies that can tolerate
biogas). A process topology is developed from the high levels of CO2 are preferred.
available technologies based on literature survey, and Commonly used biogas cleaning technologies are
thermodynamic and first principles analysis. Carbon pressurized water scrubbing, pressure swing adsorption
(PSA), membrane permeation, and chemical absorption
with amine [8]. There are 249 industrial scale biogas
cleaning plants, water scrubbing has the highest market
share with 43% followed by 22% PSA and 21% chemical
absorption [11]. PSA removes N2 and CO2 gases while
H2S and NH3 can get irreversibly attached to adsorbent
and hence requires their removal before PSA use [11].
Chemical absorption has high selectivity for CO2 and is
mostly used for bulk removal of CO2. Water scrubbing
has the advantage over other technologies that it can
simultaneously remove H2S, NH3, siloxanes, and
halogenated compounds [11], [12]. It has the drawback of
high water requirement, however pilot scale test by
Läntelä et al. [12] has shown that complete recycle is
possible by regeneration. Due wide scale application and
ability to clean multiple impurities simultaneously
pressurized water scrubbing is selected here for biogas
cleaning. For the fine removal of H2S required for
reforming catalyst activated carbon impregranted with
ZnO is very efficient [13]. Adsorption over packed bed of
ZnO impregranted carbon is used as final step to remove
H2S to <10 ppb.
2.2 Biogas reforming
Synthesis gas (syngas) is a mixture of H2 and CO
which is a precursor for various long chain hydrocarbon
production through syngas fermentation, Fischer-Tropsch
synthesis, and methanol to gasoline technology (MTG)
[11], [14]. Reforming of biomethane to syngas is critical
step in converting biogas to liquid fuels. Following
technologies are available for methane reforming: dry
reforming, steam reforming, partial oxidation, and
autothermal reforming. Selection of the reforming
technology depends on the feed biogas composition
(CH4/CO2 ratio) and downstream syngas utilization
process. Biogas has often higher CO2 content as
compared to natural gas and the reforming technology
should be able to utilize the carbon content of CO2 for
syngas production. Hence a technology that converts CO2
to CO along with conversion of CH4 to CO and H2 will
be more suitable for biogas reforming. Based on lab scale
studies dry and steam reforming can directly use the
clean biogas containing CH4 and CO2 while partial
oxidation requires removal of CO2 [11]. Removal of CO2
adds additional cost in the biogas upgrading stage and
results in loss of carbon which can be converted to liquid
fuels. Steam methane reforming is a mature technology
mostly used for hydrogen production from methane [15].
But it produces higher syngas ratio (H2/CO=3) compared
to that required for FT-synthesis [16]. Dry reforming is
more feasible for biogas utilization as it produces a lower
H2/CO ratio and tolerate varying concentration of CO2
associated with biogas [17], [18]. Taking these into
consideration dry reforming is selected for analysis.
2.2.1 Dry reforming
Dry reforming is the reaction between CO2 and CH4
to produce syngas Eq. (1) as a result high content of CO2
are advantageous in this case. Dry reforming produces a
lower syngas ratio (H2/CO=1), as compared to steam
reforming, which is preferred for Fischer-Tropsch
synthesis [19]. H2/CO ratio is also influenced by water
gas shift reaction (WGS), Eq. (2), which lowers the ratio
due to reverse reaction converting H2 to H2O [19].
However H2/CO ratio can be controlled between 1 and 2
by the partial oxidation reaction of methane, Eq. (3) [18]
and by feeding water to promote the water gas shift
reaction in forward direction. Partial oxidation being
exothermic also helps in lowering the energy demand of
the process, Eq. 3.
𝐶𝐶𝐶𝐶4 + 𝐶𝐶𝐶𝐶2 ⇄ 2𝐶𝐶𝐶𝐶 + 2𝐻𝐻2 +247 kJ/mol (1)
𝐶𝐶𝐶𝐶 + 𝐻𝐻2 𝑂𝑂 ⇄ 𝐶𝐶𝐶𝐶2 + 𝐻𝐻2 +41 kJ/mol (2)
𝐶𝐶𝐶𝐶4 + 1⁄2 𝑂𝑂2 → 𝐶𝐶𝐶𝐶 + 𝐻𝐻2 -38 kJ/mol (3)
Two types of catalyst have been studied for dry
reforming: noble metal based and Ni based. Noble metal
based catalyst like Rh and Ru offer better activity and
stability but have higher cost which limits their industrial
application [20], [21]. Ni based catalyst, like Ni/Al2O3,
are most commonly used due to low cost, high H2 yield
and fast turnover rates [22], [23]. Ni/Al2O3 is selected
here due to low cost and readily availability.
Apart from its suitability for biogas dry reforming has
the drawbacks of catalyst deactivation and high energy
demand. Carbon deposition is the major cause of catalyst
deactivation which results due to methane decomposition,
Eq. (4), and CO disproportionation or Boudourad
reaction, Eq. (5). Dry reforming has higher tendency for
carbon deposition due to lower O/C and H/C ratio in the
feed [24]. The process requires high energy as the
reforming reaction is endothermic, Eq. (1), and requires
to be operated at high temperatures of 850 to 1000 °C to
obtain better conversion and to minimize carbon
deposition [25]. External energy demand can be reduced
through partial oxidation, Eq. (3), by introducing air in
the feed however this will reduce syngas quality by
complete oxidation reaction of CH4, CO and H2.
Introduction of air also reduces the coke formation [18].
In this study air added to make the process thermally-
neutral and steam is added to improve the H2/CO ratio by
promoting reverse water gas shift reaction. Dry reforming
is modeled here by Gibbs energy minimization
considering all the reatants and products in Eq. (1) to Eq.
(5).
𝐶𝐶𝐶𝐶4 → 𝐶𝐶 + 2𝐻𝐻2 +75 kJ/mol (4)
2𝐶𝐶𝐶𝐶 → 𝐶𝐶 + 𝐶𝐶𝐶𝐶2 -172 kJ/mol (5)
2.3 Upgrading of syngas
Syngas produced from dry reforming has CO2 which
need to be removed before it can be fed to Fischer-
Tropsch reactor. Amine absorption has high selectivity
for CO2. The technology was originally developed to
separate CO2 from flue gas and later was used on
industrial scale for natural gas cleaning and biogas
upgrading [11]. Commonly used solvents for absoption
are alkanolamines, such as monoethanolamine (MEA),
diethanolamine (DEA) or methyldiethanolamine
(MDEA), among which MEA is the most widely
employed solvent for low pressure absorption, and is
selected for this study.
2.4 FT-synthesis
Fischer-Tropsch synthesis (FT-synthesis) is a process
to polymerize the carbon and hydrogen atoms in syngas
into long chain molecules. FT-synthesis reaction
competes with methanation (reverse of methane
reforming) and is commonly run over iron or cobalt
catalyst at a pressure of 20-30 bar [14]. Overall FT-
synthesis reaction is exothermic, Eq. (5) [26], where CH2
polymerizes to make long chain hydrocarbons called
syncrude.
𝐶𝐶𝐶𝐶 + 2𝐻𝐻2 → ∙∙ 𝐶𝐶𝐶𝐶2 ∙∙ +𝐻𝐻2 𝑂𝑂 (5)

There are four main reactor types used for FT-

synthesis; multi-tubular fixed bed, circulating fluidized
bed, fixed fluidized bed, and slurry reactor. Slurry
reactor is selected in this study which has higher single
pass conversion efficiency of 80% as compared 40%
from traditional fixed-bed reactors [27]. It is preferred
due to low capital cost, low catalyst consumption rate, Figure 1: Sour water equilibrium reactions.
better heat removal, and less pressure drop [26], [28].
Sasol and Shell are leading companies in this technology 3.2 Modeling of dry reforming
with large scale commercial plants [14]. Typical reaction The process is simulated in Aspen Plus using RGibbs
conditions for the slurry reactor are 200-300°C, 20-30 reactor block, Figure 3. RGibbs calculates the reaction
bar, and syngas H2/CO ratio of 1-1.8 [27]. products by minimizing the Gibbs energy of the system.
Components considered in the RGibbs model are: H2, O2,
N2, H2O, CH4, CO, CO2, and Coke (defined as pure
3 MODELING DETIALS AND ASSUMPTIONS carbon). Air is added at 200°C in the reactor to reduce the
coke formation and provide heat needed for the
3.1 Modeling of pressurized water scrubbing reforming reaction. Steam is added to control the H2/CO
Solubility of sour gases H2S and NH3 in water is ratio to desired value optimum for FT-synthesis. For the
many times higher than solubility of CH4 in water [29]. feed biogas shown in Table I sensitivity analysis is made
Pressure water scrubbing consist of absorption column to see effect of reaction temperature, pressure, steam to
operating at 9-12 bars, an intermediate flash vessel at 3-4 CH4 ratio, and O2 to CH4 feed ratio. Results of the
bars to recycle absorbed CH4, and an air stripping sensitivity analysis are used to set and optimized the
column operating 1 bar to regenerate absorption water operating condition for the dry reformer.
[11], [30]. Absorption and stripping columns are modeled
in Aspen Plus as Radfrac distillation blocks using
ELECNRTL property method. Absorption of the all the
gas components in water is accounted by Henry
coefficients and dissolution of H2S and NH3 in water is
considered using equilibrium reactions shown in Figure
1. Henry coefficient and equilibrium constants used are
the default values available in “sour” electrolyte property
insert available in Aspen Plus package [31]. Biogas feed
is compressed to 12 bar and cooled to 40°C before feed at Figure 3: RGibbs reactor model for dry reforming.
the bottom of packed absorber column. Absorption
column is operated at 12 bars, intermediate flash at 3 bar 3.3 Modeling of amine absorption
and stripping column at 1 bar. Water is added at the top Monoethanolamine (MEA) is used as absorption
of the column and cleaned biogas leave the column from solvent which can dissolve higher amount of CO2 per unit
top and impurity rich sour water leaves from column volume as compared to water [29]. Desulphurization is a
bottom. Sour water is flashed at 3 bar in the flash vessel prerequisite for amine absorption, rest of the processing
to remove absorbed CH4 and then sent for regeneration in scheme is similar to water scrubbing; an absorption
striping column. Stripping column operates at 1 bar and column for CO2 removal from syngas and stripping
air is used as stripping medium. Figure 2 shows the column to regenerate solvent by removing CO2.
pressurized water scrubbing model with important Absorption column operate at pressure of 6 to 7 bar.
process parameters. Value of water flowrate is selected Syngas is cooled to 50°C and compressed to 7 bar before
after a sensitivity analysis made to analyze the effect of
feeding to absorption column. Upgraded syngas leave at
water flowrate on H2S removal.
the top of absorption column while CO2 rich MEA leaves
at the bottom. MEA
To Figure 7 regeneration column
operates at lower pressure
of 1.4 bar where MEA is
regenerated by heating at
120-160 °C [30]. A heat
exchanger is used to
reclaim heat from
regenerated MEA by
preheating rich MEA
coming from absorption
column. Process is modeled
in Aspen Plus using
Radfrac distillation column
and MEA absorption
reactions from “kemea”
data package available in
Aspen Plus [31].
Figure 2: Pressurized water scrubbing model (legend description in the Appendix).
3.4 Modeling of FT-synthesis The products from FT synthesis are water and syncrude
The polymerization of CH2 and its kinetics are which is classified according to chain length as follow:
independent of the products formed, therefore C1-C4 lights, C5-C9 naphtha, C10-C16 kerosene, C17-C22
selectivities can be predicted based on simple statistical diesel, and C22+waxes.
distributions calculated from chain growth probability
and carbon number [26]. Anderson–Schulz–Flory (ASF)
model, Eq. (6), is widely used to predict selectivities [32].
It relates the mole fraction of FT-synthesis products with
carbon number (n) and chain growth probability factor
(α). However selectivities change with temperature and
feed syngas H2/CO ratio. Vervloet et al. [33] proposed a
process condition dependent α-model, Eq. (7), which
represented the experimental product distribution well.
The model has three parameters: ka is the ratio of rate
constants for the termination over propagation reactions,
β is the syngas ratio power constant, and ΔE is the
difference in activation energies for the propagation and
termination reactions.

𝑊𝑊𝑛𝑛 = 𝑛𝑛(1 − 𝛼𝛼)2 𝛼𝛼 𝑛𝑛 −1 (6)

1 Figure 4: Water flowrate versus H2S concentration in
𝛼𝛼 =
𝐻𝐻2 𝛽𝛽 ∆𝐸𝐸 1 1 (7) the clean gas leaving the absorption column.
1 + 𝑘𝑘𝑎𝑎 ( ) exp⁡( ( − ))
𝐶𝐶𝐶𝐶 𝑅𝑅 498.15 𝑇𝑇
3.4 Overall process simulation
Overall process is simulated using the results of
In this study slurry reactor is modeled using Ryield
sensitivity analysis and optimization.
reactor block in Aspen Plus with CO conversion of 80%
[34]. The reaction temperature and H2/CO ratio are
4 RESUTLS
optimized to maximize kerosene and diesel fraction using
solver function in MS Excel. For 80% conversion H2/CO
4.1 Pressurized water scrubbing
ratio > 1.6 is required. FT product distribution is
Feed biogas has 2000ppm of H2S. Figure 4 shows the
estimated from the feed synthesis gas based on ASF
effect of water flowrate over H2S in the clean gas leaving
model with α-model parameters from Kruit et al. [35].
(a) (b)

(c) (d)

Figure 5: Sensitivity analysis of dry reforming. (a) effect of temperature at 1 bar, 0 air and steam feed (b) effect of
pressure at 950°C, 0 air and steam feed (c) effect of air at 950°C, 1 bar, and 0 steam (d) effect of steam at at 950°C, 1
bar, and 0 air
 (a)
Figure 6: Sensitivity analysis of FT-crude product distribution. (a) H2/CO ratio at 250 °C, (b) at H2/CO ratio of 1.8.
the absorption column. It can be seen that beyond 550
m3/hr there is no significant decreases in H2S
concentration. At 650 m3/hr of water H2S concentration
of <100 ppm is achieved. For fine removal of H2S
activated carbon impregnated with ZnO is used.
Resulting clean biogas has < 10ppb of H2S and NH3 with
99% and 76% recovery of CH4 and CO2. Recovery of
CO2 is low as it is more soluble in water than CH4 and is
not fully recovered in the intermediate flash vessel
resulting in its loss with in the stripping column.
Operating cost of the process is associated with power
required for compression and makeup of water lost in
stripping column. For the base case of 10,000 Nm3/hr of
dry raw biogas compressor power is 1.85 MW and
makeup water needed it 0.36 m3/hr.
4.2 Dry reformer
Figure 5 shows the results of sensitivity analysis
made to analyze the effect of process conditions on CH4
conversion, syngas H2/CO ratio and coke formation
(Coke/CH4in ratio).
CH4 conversion increases with increase in temperature
while both H2/CO ratio and coke formation decreases,
which means higher temperature is feasible. Increases in
pressure have opposite effect to increase in temperature
hence a lower value is preferred. Gopaul and Dutta [36]
made an optimization study on dry reforming for range of
biogas composition and reported optimum value 950°C
temperature and 1 bar pressure. These value are in
agreement with sensitivity results of this study and are
selected as operating condition for reformer reactor.
Introduction of air in the feed to reformer lowers the
From Figure 2
Figure 7: Simulation flowsheet of biogas dry reforming, syngas upgrading, and FT-synthesis (legend description in the
Appendix).
(b)
external energy demand and coke formation. Avoiding of
coke formation is critical for long life of the reformer.
Also by controlling the air input reformer can be made
thermally-neutral [36]. This mean reactor will not require
external heating source resulting in lower operating and
capital cost. However this lowers the syngas quality by
reducing H2/CO ratio which can be improved by
introducing steam. Figure (d) shows the effect of steam
on H2/CO ratio, with increase in steam the H2/CO ratio
increases. Based on these analysis two design spec blocks
are used to control the thermal-neutrality and optimum
syngas ratio by varying the feed air and steam flowrate,
respectively.
4.3 FT-synthesis model
Selectivity of FT-crude products depends on H2/CO
ratio in the syngas and reaction temperature. Figure 6
shows the results of sensitivity analysis on syncrude
product distribution. Minimum H2/CO ratio analyzed is
1.6 which is the least required for 80% conversion of CO
to syncrude. It can be seen that with increase in H2/CO
ratio from 1.6 to 3 lights increase from 6% to 70% while
diesel and kerosene decrease from 27% and 24% to 3.5%
and 0.1%, respectively. With increase in temperature
similar trend of increase in lighter fractions and decrease
in heavier fractions is observed. It can be concluded that
lower values of H2/CO ratio and temperature a favorable
for heavier fractions. The reaction temperature and feed
syngas H2/CO ratio are optimized between 200-300°C
and 1.6-2, respectively, for the objective of maximizing
kerosene and diesel fractions in the syncrude. Results of
the optimization are given in Table II.
Table II: Optimization results of FT reaction conditions 6 CONCLUSION

Optimization Starting Results of the simulation show that it is technically

Lower Upper Results
Objective Value possible to convert biogas to liquid fuels on a small scale.
Maximize Conversion efficiency can be improved by coming up
Kerosene + Diesel 2.7% 52.2% with low temperature reforming process and reducing
Decision Variable impurities in biogas production. The heating and cooling
H2/CO ratio 2 1.6 2 1.62 duties and their corresponding temperatures ranges
Temperature (°C) 290 200 300 270 indicate a potential for heat integration that will reduce
the overall energy requirement of the process. This will
4.4 Overall process further improve the carbon conversion efficiency. For the
Using the optimum and selected value from results of proposed process a more detailed study using kinetic
sensitivity analysis process for biogas FT-synthesis is reactor models and heat integration is in the prospective.
simulated. Figure 2 and 7 shows the process flowsheet This will highlight the potential of this process for small
with important process parameters block and stream scale biogas utilization and encourage pilot scale
name description are given in the Appendix. demonstration.
Carbon coming with CH4 in the feed biogas is 3000
kg/h (250 kmol/h), and the carbon in FT-crude is 1358
kg/h making an overall carbon conversion efficiency of 7 REFERENCES
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 10 APPENDIX

Table IV: Simulation block and stream legend

description

Simulation
Description
Block
D-1 Dummy block to saturate dry biogas
with water
C-1 Feed biogas compressor
H-1 C-1 after cooler
ABS-1 Water scrubbing absorption column
FLASH Intermediate flash vessel to recover
CH4
STRIP-1 Stripping column to regenerate
absorption water
P-1 Water recirculation pump
H-2 Clean biogas heater
H-3 Feed water heater
H-4 Feed air heater
DR Dry reformer (RGibbs)
H-5 Syngas cooler
C-2 Syngas compressor
H-6 C-2 after cooler
ABS-2 MEA absorption column
H-7 Rich MEA and Lean MEA heat
exchanger
STRIP-2 MEA regeneration column
C-3 Upgraded syngas compressor
H-8 C-3 after cooler
H-9 Water condenser
P-2 MEA recirculation pump
FT FT-synthesis reactor (RYield)
FRACT FT-crude separation
Streams Description
DRY-BG Biogas feed (dry basis)
LEAN-WAT Regenerated water
SOUR-WAT Water with absorbed sour gases (H2S,
NH3)
CL-BG Clean biogas
WATER Water feed to dry reforming
AIR Air feed to dry reforming
SYNGAS Synthesis gas
U-SYNGAS Upgraded synthesis gas
FT-CRUDE FT-synthesis product
VENT-2 CO2 vent
LEAN-MEA Regenerated amine
RICH-MEA MEA with absorbed CO2

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