OTC 15354 New Physical Solvent Treating Configurations for Offshore High Pressure CO2 Removal

J.Mak, D.Wierenga, D.Nielsen, C.Graham, Oil and Gas Group, Fluor Enterprises, Inc., Aliso Viejo, California
Copyright 2003, Offshore Technology Conference This paper was prepared for presentation at the 2003 Offshore Technology Conference held in Houston, Texas, U.S.A., 58 May 2003. This paper was selected for presentation by an OTC Program Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper, as presented, have not been reviewed by the Offshore Technology Conference and are subject to correction by the author(s). The material, as presented, does not necessarily reflect any position of the Offshore Technology Conference or its officers. Electronic reproduction, distribution, or storage of any part of this paper for commercial purposes without the written consent of the Offshore Technology Conference is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of where and by whom the paper was presented.

low. Fluor has developed several new FLUOR Solvent configurations (patents pending) that have extended the application of the FLUOR Solvent process to a wider range of gas streams with high CO2 content. In addition, a new configuration (patents pending) has been developed that can be used for the production of liquid CO2 for enhanced oil recovery. This paper discusses the process benefits and the application of these new FLUOR Solvent processes. Offshore Treating Process Requirements From a design and operation standpoint, an offshore gas treating facility requires a different focus than an onshore facility. Daily routine operations that are taken for granted onshore can present serious problems offshore. Operationally, the focus offshore needs to be on safety, simplicity, and reliability. Other offshore considerations are environmental requirements, corrosion mitigation, and operational flexibility. Spills are difficult to clean up and dispose of safely offshore and there are also safety concerns if the solvent is difficult to handle and hazardous. Offshore gas treating facilities also have limited staffing, which makes monitoring and controlling a complex process difficult. Equipment modifications to accommodate an increasing feed gas CO2 content are also more difficult and costly to implement offshore than onshore. From a construction and cost standpoint, an offshore treating plant should have a minimum equipment count. This usually results in a smaller platform footprint and less weight for the jacket to support. In most cases this results in a lower installed cost. Eliminating fired equipment reduces equipment safety spacing requirements and makes the platform footprint smaller. Eliminating a steam or heat medium system reduces the total equipment count and simplifies plant operation. Eliminating amine solution water makeup requirement will eliminate the need for a high quality, low chloride water maker. FLUOR Solvent Process The FLUOR Solvent Process, which was originally developed by Fluor in 1960, is a physical solvent process that uses propylene carbonate for the removal of CO2 and H2S from natural and synthesis gas streams.(1, 2) Propylene carbonate, C4H6O3, is a polar solvent that has a high affinity for CO2.

Abstract This paper describes patent pending, physical solvent based gas treating configurations for removing acid gas from highpressure natural gas streams. The processes are targeted for offshore applications where the feed gas CO2 partial pressure is above 60 psia. These new configurations are based on the physical solvent propylene carbonate (FLUOR Solvent TM ). The advantages of these new configurations include no fired duty for solvent regeneration, high CO2 solubility (scf CO2/gallon solution), no process makeup water requirements, minimal hydrocarbon losses, operational simplicity, and a dry treated gas. Introduction As high quality natural gas resources are being depleted, it is becoming necessary to produce less desirable natural gas reserves. In some cases, the acid gas concentration in these reserves is very high and the economics of producing pipeline quality gas are marginal. As the need to develop these marginal reserves increases, there is a demand for novel processes designed to economically remove acid gases. This paper describes new technology developed by Fluor for removing high concentrations of CO2 from natural gas. The focus of the paper is on the use of this new technology offshore as some producers are now developing deepwater offshore reserves that have a high CO2 content. The FLUOR Solvent process is one of the most attractive processes for offshore gas treating when the feed gas CO2 partial pressure is high and the H2S content is comparatively
FLUOR Solvent is a trademark of The Fluor Corporation

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Propylene carbonate is anhydrous, non-corrosive, non-toxic, biodegradable, and is readily available from several solvent manufacturers. The chemical structure of propylene carbonate is shown in Figure 1.

refrigeration option that can be used for CO2 liquefaction and a solvent stripping configuration that can be used to improve H2S removal. Amine Processes

CH3

CH O C O

CH2 O

Currently, most natural gas CO2 removal processes are based on amines. Amines have a long and successful track record for CO2 removal under a variety of conditions. However, amines are energy intensive and are not always the best choice for offshore CO2 removal when the CO2 partial pressure and feed gas volumes are high. Generic amine treating processes, such as DGA, DEA, or MDEA, require considerable heating and cooling duties for amine regeneration when treating gas streams with a high CO2 content. On an offshore platform, amine regeneration by steam, hot water, or heating medium requires additional equipment, amine storage capacity, and large piping. This increases platform cost. In addition, fired equipment spacing requirements also increase the platform footprint and cost. The co-absorption of hydrocarbons by these generic amine solvents is very low and the CO2 vent gas stream contains few hydrocarbons. However, this stream usually contains environmentally unacceptable amounts of hydrocarbons and H2S that must be incinerated prior to discharge to the atmosphere. When the CO2 content of the feed gas is high, substantial fuel gas may be required for vent gas incineration. Formulated MDEA processes, enhanced with proprietary activators to accelerate CO2 removal and using heated flash regeneration, can economically achieve high acid gas solution loadings (moles of acid gas/mole of amine). Formulated MDEA processes also have reduced amine regeneration heating and cooling duties in comparison to conventional amine processes. These activated MDEA processes are the most energy efficient amine based processes for CO2 removal when the CO2 partial pressure is high. However, these processes are still very energy intensive when used to treat a high CO2 content feed gas. In addition, the CO2 vent gas stream usually requires incineration to comply with environmental regulations. Even in these state-of-the-art amine processes, sales gas shrinkage is significant when the fuel gas consumption required for solvent regeneration and vent gas incineration is included in the overall energy balance. In addition, in amine units treating high volume, high CO2 partial pressure gas streams, significant quantities of high purity make-up water are required due to water losses in the vent stream. For all of the above reasons, an amine unit requires significant operator attention and maintenance.

Figure 1 Structure of Propylene Carbonate

Fluor has designed and built fourteen FLUOR Solvent plants five treating synthesis gas and nine treating natural gas.(3, 5) Treating pressures in operating plants range from 300 to 2000 psig while CO2 partial pressures range from 53 to 645 psia. FLUOR Solvent plants are inherently simpler and easier to operate and maintain than amine plants.(3, 4) The Selexol Process is an alternate physical solvent process that uses a mixture of the homologues of the dimethylether of polyethylene glycol. Both the FLUOR Solvent and the Selexol processes have been used for removing CO2 from high CO2 partial pressure synthesis and natural gas streams.(7) A comparison of these two processes showed that the FLUOR Solvent process is more suitable for treating natural gas streams where the acid gas is primarily CO2.(7) In these circumstances, FLUOR Solvent plants can operate at lower temperatures than Selexol plants without the solvent becoming too viscous. This, in conjunction with the higher affinity of propylene carbonate for CO2, allows a FLUOR Solvent plant to absorb more CO2 per gallon of solution than a Selexol plant. In addition, the ij values of C1 or C2 to CO2 are higher for propylene carbonate than for Selexol.(7) Therefore, hydrocarbon pickup in the rich solvent and subsequent hydrocarbon losses in the CO2 vent gas stream are lower for FLUOR Solvent than for Selexol. Early FLUOR Solvent plants required minimal maintenance and operator attention. However, these early designs had difficulties with water saturated feed gas streams. Also, despite propylene carbonates low affinity for hydrocarbons in comparison to other physical solvents, hydrocarbon losses from the CO2 vent stream were still higher than from amine processes, especially when the feed gas was rich in C5+ components. Feed gas H2S concentrations were typically restricted to 50 ppmv when a 4 ppmv H2S sales gas specification had to be met. The new FLUOR Solvent process configurations improve upon early designs and now allow plants to efficiently treat richer feed gas compositions. The new configurations also include an internally generated
Selexol is a registered trademark of UOP

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A Comparison of the FLUOR Solvent and Promoted Amine Processes on an Offshore Platform The FLUOR Solvent process has significant advantages over an amine treating process in an offshore environment when treating large gas volumes where the CO2 partial pressure is high. These advantages include: Less complexity Minimal corrosion No solvent regeneration heat requirement Produces a dry product gas Resistant to foaming Reduced winterization requirements No solution concentration monitoring No make-up water requirement Biodegradable solvent

Feed Gas: Component N2 CO2 H2S C1 C2 C3 C4 C5 C6+ Flow rate, MMscfd Temperature, F Pressure, psig Sales Gas: CO2 H2S Temperature, F 2.0 < 4 ppmv 60 Mole % 0.31 19.08 50 ppmv 68.29 5.02 3.52 1.41 0.84 1.53 400 60 1,100

The latest FLUOR Solvent process developments further improve the energy efficiency, hydrocarbon recovery, and operating range of this process. An Example Basis The differences between the promoted MDEA and FLUOR Solvent processes are analyzed in the following example. This analysis is based on the feed gas composition, pressure, temperature, and flow and the sales gas specification given in Table 1. Note that in this example it is assumed that the acid gas from solvent regeneration must be incinerated for destruction of hydrocarbons and sulfur compounds prior to venting to atmosphere. Promoted MDEA Process The promoted MDEA process includes an absorber, a flash drum, a lean/rich exchanger, an amine regenerator, an amine reboiler, an amine regenerator overhead condenser, and a lean solvent cooler and pump. Fluor Solvent Process The FLUOR Solvent process configuration is depicted in Figure 4. The process includes a TEG dehydration unit, an inlet exchanger, a refrigeration cooler, an absorber, and several flash regeneration stages, with the last flash stage operating under vacuum. The TEG dehydration unit removes water from the feed gas and hydrocarbon losses are minimized by recycling hydrocarbon-rich flash gas.

Table 1 Feed Gas and Sales Gas Specifications

Capital and Operating Costs The total installed cost (TIC) was based on an U.S. Gulf Coast 2002 location for an offshore facility. Operating costs are based on natural gas at $2.00 per MM Btu and power is internally generated using a gas turbine drive. Figure 2 summarizes the relative TIC and operating costs for these two processes. In this Figure, the TIC for the promoted MDEA process is assigned a base value of 100. Per Figure 2, the TIC for the FLUOR Solvent plant is 21 percent less than that of the promoted MDEA process due to the reduced number of equipment items and the smaller platform footprint. Operating costs include fuel gas consumption for vent gas incineration, feed gas dehydration, amine solution regeneration, and power generation. While the hydrocarbon losses from the Fluor Solvent process are higher than that from the amine process, these losses are more than offset by the higher fuel consumption required by amine regeneration. Per Figure 2, the annual operating cost for the FLUOR Solvent process has a value of 9 relative to the promoted MDEA process TIC while the promoted MDEA design has a value of 11. Therefore, the FLUOR Solvent plant operating cost is about 18 percent less than that required for the promoted MDEA process.

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Comparison of Key Process Parameters Figure 3 compares several key process parameters. In this comparison, the promoted MDEA case is assigned a value of 100. Solvent Circulation Solvent circulation for the FLUOR Solvent process is about 9 percent higher than for promoted MDEA. Therefore, in this application, the promoted MDEA process has a higher acid gas pickup per gallon of rich solution than the FLUOR Solvent process. Heating Duty The FLUOR Solvent process does not require an external heat source for solvent regeneration. However, the process uses a small amount of waste heat energy from power generation to regenerate the TEG used to dry the feed gas. See Figure 4 for the FLUOR Solvent process configuration. The TEG regeneration heat duty is about 1 percent of the promoted MDEA process heat duty. Air Cooling The process cooling required by the FLUOR Solvent process is for the refrigeration condenser and the recycle compressor aftercooler. The process cooling required by the amine process is for the amine regenerator overhead condenser and the lean amine cooler. The required cooling duty for the FLUOR Solvent process is about 11 percent of the amine process cooling duty. Power The primary power consumers in the Fluor Solvent process are the solvent circulation pumps, the refrigeration unit, the recycle gas compressor, the vacuum pumps, and the air coolers. In this high pressure, high CO2 partial pressure application, most of the refrigeration required by the Fluor Solvent process is generated by the flash regeneration of the rich propylene carbonate solvent. This significantly reduces the mechanical refrigeration load. In the amine unit, the power consumption of the lean amine air cooler, the amine regenerator overhead condenser, and the lean amine pumps is slightly higher than the power demands of the Fluor Solvent process. Per Figure 3, the FLUOR Solvent process requires about 3 percent less power than the promoted MDEA process. Table 2 summarizes qualitative differences between the two example processes. It is difficult to assign a monetary value to most of these items; however, they are important in the operation and design of treating plants. For example, one advantage of using a physical solvent, such as propylene carbonate or Selexol, is that the CO2 loading in the rich solvent increases with increasing CO2 partial pressure. Modifications required for a physical solvent plant to accommodate an increase in the feed gas CO2 partial pressure are minimal. On the other hand, an amine process will require an increase in solvent circulation, fired duty, and cooling proportional to the total increase in the feed gas CO2 partial
Fluor Solvent Promoted MDEA

120 100 Relative Cost 80 60 40 20 0 Total Installed Cost Annual Operating Cost 9 11 79 100

Figure 2 - Comparison of FLUOR Solvent and Promoted MDEA Relative Costs

Fluor Solvent 120 100 Relative Value 80 60 40 20 0 Solvent Circ. 1 Heating Duty 109 100 100

Promoted MDEA 100 97 100

11

Air Cooling

Power

Figure 3 - Comparison of FLUOR Solvent and Promoted MDEA Process Parameters

pressure. The modifications required to accommodate these changes are significant. Another advantage of the FLUOR Solvent process is minimal winterization requirements. Propylene carbonate freezes at 57 F in comparison to about 20 to 30 F for many amine processes. Other advantages, as summarized in Table 2, are plant simplicity and ease of operation, all carbon steel construction with no stress relieving, no fired heat duty required for solvent regeneration, minimal solvent foaming tendency, no corrosion, and minimal environmental impacts due to the use of a biodegradable solvent.

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Case Equipment Count Operational Complexity Stainless Steel Materials Stress Relieving of Carbon Steel Fired Heat Required Modification for Increasing CO2 in feed Vulnerable to Solvent Foaming Winterization Required Solvent Concentration Monitoring Non-Toxic and Biodegradable Solvent Produces Dry, Cold Treated Gas Hydrocarbon Content of Acid Gas Feed Gas Shrinkage Delivered Sales Gas

FLUOR Solvent Lower Lower No No No Minimal No No No Yes Yes Higher Lower Higher

Promoted MDEA Higher Higher Yes Yes Yes Substantial Yes Yes Yes No No Lower Higher Lower

applications were limited to feed gas streams low in C5+ hydrocarbons (usually less than 0.5 mole percent) and with a low H2S content. Early configurations also had two other shortcomings. The first problem was the difficulty of maintaining a water balance around the unit. Early designs typically used glycol injection at 0 F or higher for feed gas dehydration and hydrate control upstream of the FLUOR Solvent unit. As the level of water removal was limited, water accumulated in the solvent. When the propylene carbonate water content is greater than about 5 weight percent, the solvent treating capacity decreases significantly. The second difficulty was that, when treating a rich gas with more than 0.5 mole percent C5+ hydrocarbons, heavy hydrocarbon absorption by the solvent and hydrocarbon losses from the CO2 vent gas stream were substantial. These shortcomings have been resolved by several new FLUOR Solvent process configurations. Three of these new configurations are reviewed in the following discussion. These new configurations have been developed for treating: A low to medium CO2 content feed gas A high CO2 content feed gas A feed gas with more than 50 ppmv H2S.

Table 2 Qualitative Comparison of the FLUOR Solvent and Promoted MDEA Processes

Other New FLUOR Solvent Configurations The early FLUOR Solvent process configurations were limited to treating a narrow range of feed gas compositions. That is,

These configurations have been simplified for illustration purposes. Variations in these configurations are often necessary when treating specific feed gases.

CW CO2

Recycle Compressor Vacuum Pump Flash Drums

Absorber Treated Gas

LP

Vac MP Refrig. Feed Gas TEG Atm HP

Water

Condensate Hydraulic Turbines Circulation Pump

Figure 4 Low to Medium CO2 Content FLUOR Solvent Application

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Low to Medium CO2 Content FLUOR Solvent Application Figure 4 depicts a FLUOR Solvent process design used to treat feed gases containing moderate levels of CO2. The CO2 partial pressure is between 60 and 120 psia and the feed gas is at 1000 psig and ambient temperature. Per Figure 4, the feed gas is first dried in a TEG contactor to remove almost all of the water. This prevents water buildup in the solvent. The dehydrated feed gas is then cooled by cold treated gas from the absorber and is further cooled by external refrigeration. In a typical application, the feed gas can be cooled to as low as 35 F. When feed gas is chilled to this low temperature, most of the C5+ heavy hydrocarbons are condensed and can be removed from the system as condensate that can be further processed to produce a valuable product. The removal of heavy hydrocarbons prior to the solvent contactor is beneficial as it minimizes the co-absorption of heavy hydrocarbons by the solvent. This reduces the recycle gas flows and hydrocarbon losses in the CO2 vent gas. An additional benefit of a low feed gas temperature is that the cold feed gas cools the rich solvent inside the absorber. This cooling minimizes the temperature rise in the bottom of the absorber caused by the heat of solution of CO2. This results in a close to isothermal absorber temperature profile. The near isothermal temperature profile improves both mass transfer and rich solvent CO2 loading in comparison to early designs where the temperature profile was much more pronounced, being much colder at the top of the absorber and much warmer at the bottom. With the more uniform temperature profile of these new configurations, the surface tension and viscosity of the solvent, which control heat and mass transfer, are more uniform and the temperature at the bottom of the absorber is lower. This results in increased solvent loading in the rich solvent and more uniform mass transfer throughout the absorber. The CO2 rich solvent is regenerated by a series of flashes. The flash drums are stacked one on top of the other to reduce the treating plant footprint. This reduces the cost for both onshore and offshore applications. The flash gases from the high-pressure, medium-pressure, and low-pressure flash drums are recycled back to the front end of the plant via a recycle gas compressor. Flash gas recycle typically reduces hydrocarbon losses to less than 0.5 percent of the feed gas. Losses can be reduced further with an increase in recycle compression horsepower. The solvent depressurization process can be used to generate power or to directly drive the solvent pump. The use of hydraulic turbines for power production is particularly

advantageous because, in addition to power generation, the extraction of internal energy from the solvent results in significant solvent chilling. Over 90 percent of the CO2 is desorbed in the atmospheric flash and residual CO2 is desorbed in a vacuum flash. The vacuum pressure that can be achieved with the use of a liquid ring vacuum pump is typically 2 to 7 psia. With the advent of larger and more efficient vacuum pumps, a vacuum pressure of 2 psia is often economical. Centrifugal compressors are also an option. A 2 psia vacuum flash will reduce the residual CO2 in the lean solvent and lower both the solvent circulation and the sales gas CO2 content. A lean solvent pump directs the lean solvent back to the absorber. In this scheme, no additional refrigeration is required other than that used in the feed gas chilling section. The balance of the cooling duty comes from desorption of CO2 from the rich solvent. High CO2 Content FLUOR Solvent Application Figure 5 depicts a FLUOR Solvent process configuration used to treat a high CO2 content feed gas. The feed gas pressure in this case varies from 400 psig to 1200 psig with the CO2 content varying from 30 to 70 mole percent. When the feed gas CO2 content increases, the amount of refrigeration produced by flash regeneration of the solvent increases correspondingly. At very high CO2 partial pressures, the cooling effect from flash regeneration will exceed the cooling required for acid gas absorption. Also, at low temperatures, the surface tension and viscosity of propylene carbonate increase dramatically and the absorber mass transfer rate drops drastically. This negatively impacts the process. In these circumstances, solvent overcooling must be avoided by removing excess refrigeration. The FLUOR Solvent process configuration depicted in Figure 5 was developed to harness this excess refrigeration. In this application, refrigeration generated from flashing the rich solvent from high to medium pressure is used to lower the absorption column temperature via a side cooler. This allows the absorber to operate at a lower temperature and increases the solvent loading. The flashed gases are compressed and recycled to reduce hydrocarbon losses in the CO2 vent gas stream to a minimum. Excess refrigeration, generated by flashing of the rich solvent flowing to the first stage flash drum, is used to cool and condense the CO2 vent stream from the atmospheric and vacuum flashes. The condensed CO2 can then be used for EOR or disposed of by injecting the liquid into an underground formation. Supplementary refrigeration may be required if the feed gas pressure and CO2 partial pressure are low.

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CW

Recycle Compressor Absorber Treated Gas Vacuum Pump

LP

Vac MP Atm HP

Feed Gas

TEG

Water Condensate Hydraulic Turbines Circulation Pump CO2 to EOR Refrig. CW Injection Compressor

Figure 5 High CO2 Content FLUOR Solvent Application

CW

Recycle Compressor

CO2

Absorber

Treated Gas

LP Atm MP Vacuum Pump

Feed Gas

TEG Refrig. water

HP

Vac Stripper

Condensate Solvent Circ Pump Hydraulic Turbines

Figure 6 High H2S Content FLUOR Solvent Application

High H2S Content FLUOR Solvent Application Figure 6 depicts a FLUOR Solvent configuration that has been developed to treat high H2S feed gas streams. Early

FLUOR Solvent configurations were typically limited to treating feed gases with less than 50 ppmv H2S in order to meet a 4 ppmv H2S sales gas specification.

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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 flash gas from the medium pressure flash drum. This flash gas, which contains mostly CO2 and some light hydrocarbons, is substantially H2S free, and is a good choice for stripping H2S from the solvent. The vacuum stripper produces an ultra lean solvent, depleted of H2S, which 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 reinjection, can be separately incinerated, or treated in a sulfur recovery unit before venting to atmosphere. The amount of H2S that can be removed with this process is a function of the amount of stripping gas used. The stripping gas leaves the process with the vent gas and, therefore, hydrocarbon losses will increase with increasing feed gas H2S content. Conclusion Treating of natural gas offshore presents several challenges for conventional CO2 removal processes. This paper presents some new FLUOR Solvent process configurations that can achieve energy efficient, cost effective CO2 removal for a wide range of CO2 content feed gases and applications. In many cases, the FLUOR Solvent process is an attractive economic alternative to conventional and promoted amine CO2 removal processes. The example described in this paper shows that for a feed gas with a CO2 content of 19 mole percent at 1100 psig (a CO2 partial pressure of 209 psia) the FLUOR Solvent process has both operating and capital cost advantages over amine treating processes. This advantage over amine processes increases proportionately as the CO2 partial pressure increases. In addition, the FLUOR Solvent process provides safety, environmental, operational, and maintenance advantages in an offshore environment.

References
1. Kohl, A. L., and Miller, F. E., 1960, U.S. Patent 2,926,751 2. Kohl, A. L., and Miller, F. E., 1960, U.S. Patent 2,926,753 3. Kohl, A. L., and Nielsen, R. B., 1997, Gas Purification, 5th ed., Gulf Publishing Company, Houston, TX. 4. Kohl, A. L., and Buckingham, P. A., 1960, Fluor Solvent CO2 Removal Process, Petroleum Refiner, Vol. 39, No. 5, pp. 193196. 5. Buckingham, P. A., 1964, Fluor Solvent Process Plants: How They Are Working, Hydrocarbon Processing, Vol. 43, April, pp. 113-116. 6. Freireich, E., and Tennyson, R. N., 1977, Increased Natural Gas Recovery from Physical Solvent Gas Treating Systems, Proceedings Gas Conditioning Conference, University of Oklahoma, Norman, OK, March 7-9. 7. Bucklin, R. W., and Schendel, R. L., 1985, Comparison of Physical Solvents Used for Gas Processing, in Acid and Sour Gas Treating Processes, S.A. Newman, editor, Gulf Publishing Company, Houston, TX, pp. 42-79.