IBP1219_18

AN INNOVATIVE PROCESS
FOR CO2 REMOVAL
FROM PRE-SALT GASES,
David Schulte1, Bryant Lynch2

Copyright 2018, Brazilian Petroleum, Gas and Biofuels Institute - IBP

This Technical Paper was prepared for presentation at the Rio Oil & Gas Expo and Conference 2018, held
between 24 and 27 of September, in Rio de Janeiro. This Technical Paper was selected for presentation by the
Technical Committee of the event according to the information contained in the final paper submitted by the
author(s). The organizers are not supposed to translate or correct the submitted papers. The material as it is
presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute’s opinion, or that of its
Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Oil & Gas
Expo and Conference 2018 Proceedings.

Abstract

Pre-Salt reservoirs off the southeast coast of Brazil are being developed primarily utilizing
floating production, storage, and offloading (FPSO) units. These reservoirs are characterized
by their high gas-to-oil ratio (GOR) and high CO2 content. The CO2 in the produced
associated gas must be removed to meet the treated gas specifications for fuel gas and export
gas. The separated CO2 typically cannot be vented for environmental reasons and must be
reinjected. This type of gas processing is challenging offshore due to high capital and
operating costs. Despite certain inherent drawbacks, membranes have generally been the
selected technology for CO2 removal. In response to the need for improvements, a
development program is underway to optimize the use of the Fluor SolventTM Process for Pre-
Salt applications. This process, which uses propylene carbonate as a physical solvent, is very
attractive for gas treating when the feed gas CO2 partial pressure is high. The advantages of
Fluor Solvent include no heat for solvent regeneration, high CO2 solubility in the solvent, no
process make-up water requirements, minimal hydrocarbon losses into the CO2 stream,
operational simplicity, and delivery of a dry treated gas. These attributes are critical for
achieving success in an offshore environment. Based on proven experience, updated
thermodynamic models, and new design features, proprietary configurations have been
developed that are ideal for offshore projects. This paper reviews the benefits of using the
enhanced Fluor Solvent Process for a 150,000 BPSD FPSO handling 12 MMm3/d gas
containing 40 to 60 mol% CO2.

Keywords: Gas Production. Gas Treating. CO2 Removal. Gas Export.

______________________________
1
Executive Director, Process Engineering – FLUOR, B.S. in Chemical Engineering from UCLA
2
Process Engineer – FLUOR, B.S. in Chemical Engineering from UCLA
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1. Introduction

Most natural gas CO2 removal processes are based on amines. Amines have a long
and successful track record for CO2 removal in onshore facilities under a variety of
conditions. However, amines are not typically the best choice for offshore CO2 removal when
the CO2 partial pressure and feed gas volumes are high because of the considerable heating
and cooling duties required for amine regeneration. This energy intensity increases the
equipment count, overall footprint, and platform or FPSO cost. In addition, water losses in
the treated gas and the CO2 vent gas can lead to the need for an ample supply of high purity
make-up water. This would also be a costly complication for offshore treating facilities.
Because of these factors and the additional operating and maintenance attention required,
amines are not typically selected for offshore applications when the treated gas must only
meet pipeline gas specifications (maximum 2-5% CO2) and not the tighter LNG specifications
(< 50 ppmv CO2).
Due to the challenges with amines, membranes have become the standard technology
for offshore CO2 removal. In comparison to amines, membranes have the following
advantages:
• Good weight and space efficiency
• Low cost
• Simple to operate and high reliability
• Minimal utility requirements
• Modular design and ease of scale up

While they have been proven in offshore applications, membrane processes also have
some important disadvantages:
• Little economy of scale for large applications
• Sensitive to feed gas contaminants and heavy hydrocarbons
• Meeting a tight H2S specification is a challenge
• High hydrocarbon recovery (i.e. minimal hydrocarbon losses) requires multiple
stages and significant compression power

There is an opportunity to further improve offshore processing of high CO2 Pre-Salt

gases using an alternate technology better suited to the unique combination of requirements.
Recent development work shows that the Fluor Solvent Process can successfully fill this need.
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2. Fluor Solvent Basics

The Fluor Solvent Process, which was originally developed by Fluor in 1960, is a
physical solvent process that uses propylene carbonate (PC) for CO2 and H2S removal from
natural and synthesis gas streams. Physical solvents have an advantage over amine-based
chemical solvents when treating high CO2 partial pressure gases because the acid gas loading
increases proportionally with the CO2 partial pressure according to Henry’s law. PC, C4H6O3,
is a polar solvent that is anhydrous, non-corrosive, non-toxic, biodegradable, and readily
available from several solvent manufacturers. Propylene carbonate also has lower
hydrocarbon solubility than other physical solvents such as SelexolTM. The chemical
structure of PC is shown in Figure 1.

CH3 CH CH2

O O
C

O
Figure 1. Structure of Propylene Carbonate Figure 2. Woodward Oklahoma Fluor Solvent Plant

To date, fifteen Fluor Solvent plants have been constructed treating both natural gas
feeds and synthesis gas feeds. Figure 2 above shows one of these facilities (4 MMm3/d
capacity with 22 mol% CO2 in the feed gas). Operating experience spans the following range:
• Treating pressures from 20 to 140 barg
• Inlet CO2 from 5 to 55 mol%
• Train sizes from 0.3 to 7.7 MMm3/d

Fluor has made continuous improvements to the technology over the last 50 years.
Recent work includes additional solvent testing to improve predictions of Vapor-Liquid-
Liquid Equilibrium (VLLE) and physical properties. This enhanced data set and associated
updated simulation tools have allowed new innovations applicable to Pre-Salt gases to be
developed. These proprietary designs include: 1) optimized configurations with solvent
temperatures as low as -30°C to reduce circulation, 2) designs for treating richer feed gases
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with minimal hydrocarbon losses, 3) new schemes using internally generated refrigeration for
CO2 liquefaction, and 4) a solvent stripping configuration for improved removal of higher
levels of H2S. Two examples are described below. Note that these configurations have been
simplified for illustration purposes. Variations are often necessary for specific feeds.

2.1. Medium to High CO2 Content Gas with CO2 Production for Sequestration or EOR

Figure 3 depicts a Fluor Solvent design that can be used to treat feed gases with
medium to high levels of CO2 (feed pressures between 50 and 85 barg with CO2 levels
ranging from 20 to 60 mol%). The feed gas is first dried using glycol or molecular sieves to
avoid hydrate formation in the absorbers. In addition to allowing lower solvent temperatures,
dehydration upstream of the Fluor Solvent Process also results in a dry treated gas and dry
CO2 stream because the solvent is anhydrous. The dried gas is combined with recycle gas and
cooled by the treated gas and the flashed solvent. Liquid condensate is removed in a separator
prior to entering the absorber. If the feed gas contains a significant amount of C5+
hydrocarbon, removal of the condensate is necessary to reduce the hydrocarbon losses in the
CO2 stream and eliminate the possibility of forming a second liquid phase in the absorber.

CO2 to
Recycle
Sequestration
Compressor
Semi-Lean Lean
Absorber Absorber

Refrig HP Drum MP Drum

Vac.
Drum

Feed Gas Inter-

Drying Pump
LP Drum
Cond.

Hydraulic Solvent Pump

Treated Gas Turbine

Figure 3. Process Configuration for Medium to High CO2 Content Gas

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CO2 absorption is accomplished in a two-stage absorber system. This typically done

for offshore applications to minimize the height of the towers and reduce the center of gravity.
The high pressure feed gas is first scrubbed in the Semi-Lean Absorber using the semi-lean
solvent from the Lean Absorber. The semi-lean solvent, which has been heated by CO2
absorption in the Lean Absorber, is cooled for re-use in the Semi-Lean Absorber. By cooling
the semi-lean solvent from the Lean Absorber, both absorbers can operate at a uniformly
lower temperature. The residual CO2 in the overhead gas from the Semi-Lean Absorber is
scrubbed with the lean solvent, to meet the sales gas specification. The absorbers contain
packing that is used for heat and mass transfer in the CO2 removal process.
The rich solvent from the Semi-Lean Absorber is letdown in pressure in the Hydraulic
Turbine, which cools the solvent. The Hydraulic Turbine is an energy efficient device as it
produces shaft work to operate the Solvent Pump while also producing cooling. The flashed
solvent from the Hydraulic Turbine is separated in the HP Drum, which produces a methane
rich vapor that is recycled back to the absorber. The flashed liquid is letdown to the MP
Drum, resulting additional cooling and producing a second flashed vapor, which is also
recycled back to the absorber. With this type of recycle scheme, hydrocarbon losses are
minimized. Flashed liquid from the MP Drum is heated in the feed exchanger, which
promotes solvent regeneration, while at the same time, cools the feed gas and the semi-lean
solvent. This innovation significantly improves the operating efficiency of the Fluor Solvent
Process. The heated solvent is further letdown in the LP Drum at close to atmospheric
pressure, producing a CO2 stream above 97 mol% purity. The LP flashed solvent is further
letdown and flashed to vacuum pressure. The CO2 streams can be further compressed for
enhanced oil recovery (EOR) or CO2 sequestration.
For a medium CO2 partial pressure process, external refrigeration is needed to meet
process cooling requirements. The amount of refrigeration generated by rich solvent flash
regeneration increases with increasing feed gas CO2 partial pressure. At very high CO2
partial pressures, the refrigeration from flash regeneration eventually exceeds the cooling
demand required for CO2 absorption. The excess refrigeration can be used to cool and
partially or completely condense the CO2 vent stream from the atmospheric and vacuum
flashes after this stream is compressed to a suitable pressure. The condensed CO2 is then
pumped to a higher pressure, if necessary, and used for EOR or disposed of in a suitable
formation.
Figure 4 shows a typical offshore layout for the configuration.
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Figure 4. Platform Layout for High CO2 Content Gas

2.2. Improved H2S Stripping Configuration

Figure 5 depicts a Fluor Solvent process configuration that has been developed to treat
feed gas streams with higher H2S content. Early Fluor Solvent configurations were typically
limited to treating feed gases with less than 50 ppmv H2S in order to still be able to meet a 4
ppmv H2S sales gas specification. The new configuration has the capability to produce a lean
solvent with a very low H2S content that permits treating gases with H2S concentrations up to
about 200 ppmv. The exact limit depends on the feed gas composition and pressure.
In this new configuration, a stripper, containing random packing and operating under
vacuum, is used to regenerate the solvent. The stripping gas is a portion of the treated gas
from the absorber. This gas, which is essentially H2S free, is a good medium for stripping
H2S from the solvent. The vacuum stripper produces an ultra-lean solvent, depleted of H2S,
that can be used to absorb H2S to meet pipeline sales gas specifications. The vacuum stripper
overhead can be combined with the flash gas from the atmospheric flash drum for re-injection
for disposal or incineration. The amount of H2S that can be removed with this process is a
function of the amount of stripping gas used.
There are other iterations of this innovation where a lean / ultra-lean configuration is
used. The bulk of the solvent from the LP Flash Drum is returned to a midpoint of the
absorber and only a portion is sent to the stripper. The stripped ultra-lean solvent is then sent
to the top of the absorber to polish the gas.

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CO2

Expander

Compr
Compr.
Absorber

Stripper

Feed Gas

Mixer
H2O
Treated Gas TEG
Contactor Hydraulic
Turbines

Ultra Lean Solvent

Stripping Gas

Figure 5. Process Configuration for High H2S Content Gas

3. Pre-Salt Case Study

Fluor has screened the gas from a representative Pre-Salt Project for Fluor Solvent
applicability. In this Case Study, the treating section of a 150,000 BPSD FPSO handles 12
MMm3/d of gas containing high levels of CO2 and 60 ppmv H2S. The processing objective
was to produce export gas with less than 3 mol% CO2 and H2S below 5 ppmv. The pressure
at the inlet to the Fluor Solvent unit was assumed to be 65 barg.
The overall Block Flow Diagram for the system is shown in Figure 6. This analysis is
based on the use of TEG to dehydrate the gas. The water content of the gas from the TEG
unit is assumed to be reduced to 3 lbs/MMscf (about 70 ppmv). This provides a sufficiently
low water dewpoint to avoid hydrate formation in the downstream hydrocarbon recovery and
Fluor Solvent units. Fluor Solvent will further dehydrate the inlet gas with about 90% of the
inlet water ending up in the CO2 stream. Depending on the water specifications for the Sales
Gas and CO2, it may be necessary to use mole sieves for dehydration instead of TEG.

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CO2
COMPRESSION
CO2 TO INJECTION

INLET TEG FLUOR

HC RECOVERY
SEPARATION DEHYDRATION SOLVENT
WELL FLUID SALES GAS

CONDENSATE
STABILIZATION
CONDENSATE

Figure 6 Process Configuration for High H2S Content Gas

The majority of the C4+ is assumed to be removed from the gas in the liquids recovery
unit. The extent of the heavy hydrocarbon removal would depend on the vapor pressure
limits of the condensate product and the hydrocarbon dewpoint specification for the export
pipeline. The main impact of having higher C4+ levels in the feed to the Fluor Solvent unit
would be an increase in hydrocarbon losses and possibly an increase in solvent circulation if
operating temperatures need to be increased to avoid formation of a second liquid phase in the
system.

3.1. Simulation Results

The Fluor Solvent unit is configured as 2 x 50% trains, each processing 6 MMm3/d of
gas. The train configuration is very similar to the lean / semi-lean arrangement shown in
Figure 4. The high-pressure flash stage operates at about 27.5 bara, and vacuum flash stage is
set at 0.3 bara.
Two CO2 cases were evaluated: 40 mol% and 60 mol%. The process performance for
the two feed gas cases is summarized in Tables 1 and 2.

Table 1. Process Performance – Stream Summary

40 mol% 60 mol%
Parameter
CO2 Case CO2 Case
Treated Gas CO2 2.7 mol% 2.9 mol%
Treated Gas H2S 4.7 ppm(mol) 3.8 ppm(mol)
Treated Gas H2O 6.1 ppm(mol) 4.9 ppm(mol)
Treated Gas Pressure 59.5 bara 59.5 bara

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40 mol% 60 mol%
Parameter
CO2 Case CO2 Case
Hydrocarbon Recovery 92% 90%
CO2 Stream Purity 97% 99%
H2S in CO2 Stream 145 ppm(mol) 98 ppm(mol)
H2O in CO2 Stream 170 ppm(mol) 114 ppm(mol)
CO2 Stream Battery Limit Pressure 3.2 bara 4.6 bara
Total Solvent Losses per Train 0.2 kg/hr 0.2 kg/hr

Table 2. Process Performance – Equipment Summary (per Train)

40 mol% 60 mol%
Parameter
CO2 Case CO2 Case
Solvent Circulation 690 m3/hr 690 m3/hr
Absorber Diameter 3.5 m 3.5 m
Hydraulic Turbine (890) kW (1,110) kW
Recycle Compressor 900 kW 1,680 kW
Circulation Pumps 1,800 kW 1,800 kW
CO2 Compression 1,370 kW 2,180 kW
Refrigeration 460 kW None
Total Power 3,640 kW 4,550 kW

The same solvent circulation can be used for both the 40 mol% and 60 mol% CO2
gases due to the increase in the solvent absorption capacity related to the Henry’s Law
benefits of higher CO2 partial pressure. The main difference between these two cases is the
power consumption of the recycle gas compressor and CO2 compressor. More CO2 is flashed
off with the high CO2 gas, and hence the load on the recycle compressor is higher. The power
can be lowered if higher hydrocarbon losses can be tolerated. The power required for the CO2
compressor is higher due to the higher flow rate.
For the high CO2 case, sufficient refrigeration is generated from the flash operation
and no external refrigeration is required. There is actually excess refrigeration available that
could be used to chill other streams. For the lower CO2 gas case, less gas is flashed off and
hence less cooling is produced, which means a small refrigeration unit would be required for
the heat balance.

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4. Conclusions

Treating of natural gas offshore presents several challenges for conventional

membrane or amine based CO2 removal processes. Initial analysis of Pre-Salt gas
applications shows that Fluor Solvent is ideal for CO2 removal:
• No heating medium required or make-up water required
• Compact footprint – conducive to modularization
• Produces a dry gas
• 5 ppmv H2S specification can be met without a downstream fixed bed polisher
• Increased hydrocarbon recovery compared to one and two stage membranes
• Can process 40 mol% to 60 mol% CO2 in the feed gas without increasing solvent
circulation

Although the Fluor Solvent process has not been installed offshore, over 50 years of
onshore of Fluor Solvent experience is transferrable. The main issues related to the impact of
wave motion on the performance of the absorber and managing the solvent inventory would
be similar to those for a TEG dehydration system. Fluor Solvent is an attractive economic
alternative to membrane technology and does not compromise safety, reliability, or
operational simplicity. The use of Fluor Solvent could play a key role in improving offshore
design and enabling Petrobras, IOCs, and others to unlock the potential of Pre-Salt reserves.

5. References

GRAHAM, C., MAK, J., NIELSEN, R., and ZHANG, I., Fluor Solvent – A Flexible CO2
Removal Process. Laurence Reid Gas Conditioning Conference, Oklahoma, 2010.
GRAHAM, C., MAK, J., NIELSEN, D., WIERENGA, D., New Physical Solvent Treating
Configurations for Offshore High Pressure CO2 Removal. Offshore Technology
Conference, Texas, 2003.
KOHL, A., NIELSEN, R. Gas Purification, 5th ed., Gulf Publishing Company, Houston, TX,
1997.
MAK, J. Configurations for Improved Acid Gas Removal. US Patent No. 7,192,468.
MAK, J. Configurations and Methods of Acid Gas Removal. US Patent No. 7,424,808.
MAK, J., NIELSEN, R., SCHULTE D. An Update of the Fluor Solvent Process. Laurance
Reid Gas Conditioning Conference. Oklahoma, 2007.
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