SPE 49522

Acid/Sour Gas Management in the Petroleum Industry

A.K.M. Jama/uddin, 0.8. Bennion, F.B. Thomas, Hyca/ Energy Research Laboratories Ud. M.A. Clark, University of Ca/gaty
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U.S.A.. f8X01-214-M2-8C35.

Abstract
Due to decreasing world demand for elemental sulphur, the economics of recovering sulphur from sour natural gas has become unfavorable. At the same time, air emission standards and regulations are becoming ina'eaSingiy stringent, increasing the economical strain on oil and gas companies producing sour natural gas. Hydrocarbon producing companies are in search of environmentally-friendly and cost-effective methods for dealing with acid gas, which is produced in association with sour natural gas. In recent years. compressed acid gas re-injection into a porous formation has emerged as a viable alternative to sulphur recovery with the added advantage of eliminating air emissions. As an alternative, some operators also solubilize the sour/acid gas into disposable formation water and dispose acid water into porous formation. In addition, to take advantage of high solubility of acid/sour gas into light hydrocarbon solvent, some operators are also injecting light hydrocarbon solvent containing acid/sour gas into the depleted oil leg as a miscible flood enhanced oil recovery (EOR) technique. Laboratory tests and results will be presented in this paper which illUSb'atethe pros and cons of all these alternative processes to manage the produced acid/sour gas in the petroleum industry.

be "sweetened"to selectively remove the acid gas components beforethe gascanbe transported and sold for commercialuse. Among the sweetening processes, amine extraction processis the most commonly used process in die petrolewn industry. The sweetening process results in die production of acid gas-free "sales" gas,and a rich wastegas streamconsisting of virtually pure carbon dioxide (COJ and hydrogen sulphide ~S). The waste gas streamis commonly referredto as acid gas. The economics of recoveringsulphurfrom acid gas has becomeunfavorablebecause of decreasing world demandfor elementalsulphur.Air emissionstandards and regulationsare becoming increasingly stringent, increasing die needfor anenvironmentally-friendly and cost-effective methodsfor dealing with the acid gas streams.Therearevariousalternatives to dealwith the acid gasmixtures. Thesealternatives are: . Injection of compressed acid gas into the porous formation. . Disposeacid gaswith disposable fonnation water. . Solubilize acid gas into light hydrocarbonsolvent and inject the solvent containing acid gas componentinto the depleted reservoirasa miscible flood enhanced oil recovery(EOR) technique. Acid gascompression andre-injectioninto depleted resuvoirs or disposalzones,similar to producedwater disposal, is a viable alternativeto traditional sulphur recovery processeswith the added advantagesof reducing greenhousegas emissions and providing pressuresupportfor producingreservoirs. 1-4
Acid gas recovered from die amine process contains water, and hence, proper strategic design is essential to address ilie issue of whether an acid gas stream needs dehydration or not The appearance of a free liquid water phase due to changes in temperature and pressure conditions can cause significant operating problems (i.e. compressor damage,corrosion, hydrates formation, etc.). Currently, most injection schemes include dehydration facilities to ensure ilie absence of free

Introduction Sournaturalgasesare producedaseitherfreegasor as liberatedsolution gasfrom sour oil. Thesegases must

ACID/SOUR GAS MANAGEMENT IN THE PETROlEUMINDUSTRY

SPE 49522

water in die system and reduce corrosion and hydrate concerns. Dehydration facilities comprise a major portion of die capital cost of re-injection facilities. Alternatively, stainless steel materials and med1anol injection are used to combat corrosion and hydrate formation conditions. However, diis alternative is also expensive and poses significant operating problems. An alternative and cost-effective approach would be to keep die water in die vapor phase throughout the injection circuit, eliminating die need to dehydrate. To design an optimized injection strategy widiout dehydrating the acid gas, detennination of thermodynamic properties (i.e. water content, dewpoint, bubble point, and hydrate points) of die acid gas is necessary. The system may also be designed to inject die mixture as a dense phase, above die critical point, reducing die required injection pressure and horsepower requirement due to die hydrostatic head of die colwnn of fluid in die injection wellbore. The hydrate curve information will ensure diat the system never enters die hydrate region, reducing die risk of pipeline plugging. An alternative approach is to solubilize die acid gas in produced or source water in a high pressure contacting tower on the surface, followed by subsequent injection of die sour water.s An understanding of die solubility of die injected gas or insitu water phase is essential in order to quantify die speed of migration of die injected gas (in a direct injection scheme) and to design the contacting apparatus and determine volumes of water required to effect disposal in a sour water disposal scenario. Anodier approach is to solubilize acid gas into light hydrocarbon solvent (taking advantage of high solubility of acid gas into light hydrocarbon solvent), and subsequently, use die light hydrocarbon solvent containing acid gas into die depleted hydrocarbon reservoir as a miscible flood enhanced oil recovery (EOR) tedmique. Experimental tests and results of various processes are discussed in this paper. In addition, advantagesand disadvantages of all diese options are also discussed.

in the injection gas is considerably greater than dlis value. In other instances, the H2S content in the acid gas streams are seen to be lower as well (in die range of 100/0 and the remaining component is COJ. Injection of Compressed Acid Gas into the Porous Formation. Sour natural gases are sweetened by removing H2S and CO2 by absorption with a regenerative solvent in an amine plant. The acid gas mixture of H2S, CO2, and a small amount of light hydrocarbons leaves the sweetening unit saturatedwith water at the amine still conditions of low pressure and high temperature. The gas mixture is then compressed in 3 to 4 stages. After each stage, the gas mixture is cooled, without entering the two-phase region. Condensed water is removed after each stage. After the last stage,the mixture travels down the pipeline into the disposal well. Ideally at the fmal compressor discharge pressure, the mixture will be supercritical. Further cooling in the pipeline will increase the density without a phase change, increasing the hydrostatic head of fluid in the well and reducing the required injection pressure. The operator must ensure d1at the mixture does not cool below its water saturation temperature, especially in the hydrate region, to avoid corrosion and hydrate plugging of the pipeline and wellbore. Corrosion and hydrates may occur when the gas is saturated with water. Due to the safety hazard associated with acid gas equipment failure, most injection schemes currently include dehydration facilities to ensure the acid gas is undersaturated throughout the system. Unfortunately, dehydration facilities and stainless steel comprise a major portion of the capital cost of re-injection facilities. Methanol injection is an option to combat corrosion and hydrate fonnation, but can significantly increase operating expenses. Although there is little experimental data on acid gas mixture, the solubility of water in pure H2S and CO2 lead to some interesting hypotheses. The ability of the pure c0mp01Dldsto hold water in the vapor phase decreases as the pressure increases up to about 3000 kPa (400 psi) for H2S and 6000 kPa (900 psi) for CO2. At higher pressures dte water holding capacity of the gases increases, corresponding to a higher water absorption capacity in dte liquid phase or dense phase compared to the vapor phase. In both cases,inaeasing the temperature allows more water to be absorbed in the gas phase. Small amounts of methane substantially reduce the water absorption ability of both components. It is assumed d1at solubility of water in the gas mixtures mimics the trend of dte individual components, then a minimum water holding capacity

Characteristics of Acid Gas Streams

A summary of basic characteristics of acid gas components are summarized in Table 1.6.7 As seen in the table, bodt gases have diatomic structme and exhibit high propensity for solubilizing in both aqueous and hydrocarbon solutions, a fact which can be used to our advantage in some disposal operations. Composition ofdte injected acid gasescan vary widely and is a direct function of the acid gas content of the oils/gases which are acting as the feedstocks for the sweetening process. In general, most acid gas blends contain at least 4Q8/.H.,S and often dte fraction ofHzS

existsat somepressure. I In a re-injection facility, over

each compression stage, dte pressure and temperature

increase and after each compression stage die gas is cooled. Initially, die water holding capability of die gas decreasesfrom stage to stage, until d1eminimum water holding capacity is reached. Ifdle condensed water is removed at this point. the gas will be undersaturated widl water throughout die rest of compression. Stainless steel will not be required in the compressors or coolers after die second last stage. If die temperature of die compressed gas does not drop to the new water saturation temperature in the pipeline or wellbore, dehydration can be eliminated and stainless steel materials and methanol injection will not be necessary. It is understood that dehydration may not be completely eliminated due to a particular set of conditions, for example in an extremely cold climate, die experimental data will still be beneficial. The operator will know the inlet water content and the conditions of the lowest water solubility of die system. The glycol contactor tower, regenerator and circulation system can then be designed appropriately. Aldlough experimental data is available for pure H2Sand CO20little work has been done determining die water content. density, phase behavior and hydrate formation conditions of acid gas mixtures.1-12 Currently, estimates of the density, water content and phasebehavior of acid gas mixtures are being predicted with equation of state models, as experimental data is unavailable. The equations can produce considerable error and result in over or underdesigned facilities. Experimental data results in proper decisions on the equipment and materials required for each particular set of conditions, which can lead to considerable cost savings. In this section of the paper, the results of a study in which water content. dew point. bubble point and hydrate formation conditions are presented. The example acid gas mixture contains 100/0 H2S/900/o CO2 and a minor amount of methane. The mixture was saturated with water at 2800 kPa and 24OC(400 psia and 75F). Experimental procedure and apparatus. The apparatus consists of a temperature controlled air bath. a high-pressure cell widl sight glass, a positive displacement pump, a gas volume meter, a cooled water trap, a mass balance and a Hewlett Packard 5890 gas chromatograph (GC). The sight cell has an internal volume of approximately 80 cm] (5 in]) and a maximum working pressure of 70 MPa at 1500c (10000 psi at 3000F). The 2.5 cm (I in.) dlick sight glass located on the front and back of the cell allows visual observation of the cell contents dtroughout experimentation. As shown in Figure I, the high pressure sight cell is mounted in the centre of the oven as are the cylinders containing gas mixtures and distilled water. The oven can be heated up to 1500c

(3000F) and the temperature is measuredand controUed to within %IOC (2F). The sight ceU volume and pressureare controlled by the addition and withdrawal of mercury through a port at the bottom of the sight ceU. Sample fluids are pumped in and out of a port at the top of the cell. The pump measures volume displacement with a precision of %0.02 an) (0.001 in2). A dead-weight calibrated digital pressure gauge is connected to the pump outlet. The oven is connected to a motor via a steel arm. The motor rotates the ann, rocking the oven and its contents in a 1800arc. The mercury in the sight cell agitates the fluids and enhances the fluids and enhances mixing when the oven and cell are rocked. The apparatus is contained in a sour gas laboratory. The lab is continuously flushed with fresh air pumped in from die ceiling and drawn out of vents located in the bottom four comers of the room to an incinerator stack. A pem1anentH~ monitor is located close to the floor, below the apparatus. If the monitor detects 10 ppm H~, an alarm sounds outside the sour gas lab and the incinarator fires up. At 20 ppm the main lights in the lab shut off and emergency lights flash. Personnel working in die lab with supplied air breathing apparatus (SABA) may not hear the alarm and the flashing lights ensure their evacuation. The lab is equipped with a video camera for continuous remote monitoring of personnel performing dangerous work. An "H2S Panic Button" which summons emergency rescueand medical services is located immediately outside the sour gas lab. A gas mixture is synthesized from pure components in the laboratory using partial pressures. Concentrations are verified using the GC. The system is purged and gas is transferred to the sight cell. The gas in die cell is saturated with water at the desired temperature and pressure and allowed to equilibrate while rocking. At equilibrium. usually reached within a few hours. a stable free water phase should be visible in the cell. ensuring the gas is fully saturated. Water content analysis is performed by flashing a sample of gas dtrough a valve to a cooled water trap while maintaining constant ceU temperature and pressure. The trapped. condensedwater is weighed and the dried gas volume is measured. The average water content is obtained over several samples. This method of water content analysis has not proved reliable due to the very small quantities of condensed water being measured. The water content data obtained for this report can be regarded as accurate only within an order of magnitude. A control experiment with pure CO2 was within 200/0of accepted values and the average difference between samples was %200/0. ExperimentJ. The objective of this study was to establish the phase behavior, water content and hydrate conditions of an acid gas mixture saturated at die

compression inlet conditions of2.8 MPa (400 psi) and 24C (75F). A mixture of 100/0H2S and 900/. CO2 was prepared. A small amount of CH. was added and the exact composition verified with dte OC. The mixture was saturated widt water at 2.8 MPa (400 psi) and 24 C (75F). After several hours of rocking, dte average water content was detennined. Several isodtenns were obtained to establish the phase envelope. The cell temperature was set and allowed several hours to equilibrate. The cell mercury volume was increased incrementally, resulting in 15-30 psi pressure steps. Transient and stabilized phase behavior was observed and recorded. The change in mercury volume was recorded as a function of pressure. At pressures close to dte dew and bubble points, dte volume/pressure increment was reduced. By taking a series of data points immediately above and below the appearance and disappearance of the twophase region, the dew and bubble points were established. Isobaric cooling experiments were perfonned to establish the hydrate fonnation conditions for this acid gas/water mixture. The oven temperature was raised to 50C (122 oF) and dte gas was pressurized to between 9000 kPa (1305 psia) and 17700 kPa (2567 psia) and allowed to stabilize. Since the gas was saturated widt water at 2800 kPa (400 psia) and 24 C (75 oF) and dte water content was not changed as the temperature and pressure were raised, the gas was undersaturated at dte conditions of high temperature and pressure. The temperature was dten reduced in 1.6C (3 OF) steps every 30 to 45 minutes until a hydrate was visually observed in dte cell. The hydrate fonnation temperature measured in this manner differs from dte traditional hydrate temperature obtained by cooling gas in contact widt a liquid water phase. When liquid water is present, hydrate fonnation is predicted to occur at elevated temperatures in dte order of 20C (68F) at 9000 kPa (1305 psia). When dte gas is not in contact widt a water phase and is undersatw'ated, hydrates cannot fonD until dte temperature drops sufficiently dlat dte gas can no longer bold all the water in solution and wfreew water is available for dte fonnation of hydrates. Hydrates fonD preferentially to a liquid water phase, since dte gas is already below its satmated hYdratetem perature at these conditions. Res"lts, observations and discussion. As recorded in Table 2, dew points were observed at 7c/41 00 kPa, 9C/4342 kPa, 15C/5045 kPa, 26C/6355 kPa, 34 C/7479 kPa and 37C/7955 kPa. Bubble points w~ observed at 7c/4528 kPa, 9C/4755 kPa, 16C/55 10 kPa, 27C/6900 kPa and 34cn844 kPa. Above 37.5C (99.5 OF), a stable two-phase region was not observed. Some droplets, and elongated

bubbles appearedduring a volume/pressure change and while the system was stabilizing, but upon reaching equilibrium, the system was single phase at all pressures. At 37.5C (99.5 oF) and 8253 kPa (1197 psia), the critical point was observed. At all other temperatures the contents of the cell were clear and colorless in the vapor, liquid and two-phase regions. In the critical region, a small change in pressure (3-5 psi) resulted in the entire cell contents becoming a murky, grey cloud and then stabilizing out into a variety of shades of yellow. Above 8303 kPa (1205 psia) the contents were single phase, clear and colorless. At about 8274 kPa (1200 psia), the see-through single phase took on a slightly yellow tint. At the critical point of 8253 kPa (1197 psia), two phases appeared with an indistinct thick yellow interface, a darker yellow color at d1e bottom of the cell and a lighter yellow color on top. At 8212 kPa (1191 psia) the bottom half of the cell was a distinct dark orange liquid and the top half a colorless vapor. At 8198 kPa (1189 psia) the liquid phase faded to yellow and below 7957 kPa (1154 psia) the cell contents were again a colorless single phase. In Figure 2, the calculated equation of state phase envelope is plotted along with the experimental data. The widths of the two phase envelopes are similar, but the calculated envelope falls below and to the left of the experimental data. The calculated critical point occurs at 34.9 C and 7633 kPa (94.8 of, 1107 psia), 2.6C and 620 kPa below the experimentally determined critical point of 37.5C and 8253 kPa (99.5F, 1197 psia). The deviations between actual and calculated phase behavior emphasize the importance of obtaining an experimental data set for acid gas mixtures. The equation of state was regressed to fit d1ephasebehaviour data obtained experimentally. The regressed curves and critical point match the measured data within the experimental error. The modified equation of state allows some extrapolation to different conditions, but experimental verification will be necessary until more data becomes available and a general regression is completed. The Sa11D'ated water content of the gas mixtW"Cat 2860 kPa and 24C (415 psia and 75F) over four samples was measured to be 0.6 mole percent or 270 Ib water/MMSCF. This value is over three times d1e value that analysis of accepted pure component data and equation of state calculations predict. The difference is attributed to experimental error and reflects on inaccuracies inherent in dte gravimetric water content measurement. Figure 3 summarizes dte phase behavior and hydrate formation data obtained for dtis acid gas mixture. The two-phase region can be avoided during compression by cooling the gas to a minimum of

SPE49522

A.KM. JAMALUDOIN. D.B. BENNION. F.B. THOMAS.MA CLARK

37.5C between compression stages. The fluid is in the supercritical, dense phase above 8253 kPa and above 37.5C. The hydrate formation temperature is below the traditional hydrate temperature since the gas is not in contact with a liquid water phase. With undersaturated gas, hydrate fonnation is expected to coincide with dte water saturation temperature. In this study, hydrates were observed at temperatures above the expected water saturation temperature of the gas. At 9000 kPa (1305 psia) and 17700 kPa (2567 psia) predictions basedon pure component water saturation data indicate the gas will be saturated at approximately -9C (15F) and -18C (0 oF), while hydrates were observed at -2 C (28F) and 8C (46F). The difference can be attributed either to experimental error or the inaccuracies inherent in predicting mixture saturation temperatures from pure component data. In either case, since the observed hydrates occurred at higher temperatures than expected, a conservative design would not require dehydration of the gas unless the temperature in the pipeline or wellbore dropped below the observed hydrate formation temperature.

acid gas Sb'eam. This reduces the cost. volume and H2S

content of the remaining residual gas which subsequently will be processed by more conventional means. Solubility of acid gasesin aqueoussolution is a function of the following parameters:

. . . .

Acid gas composition Contacting pressure Contacting temperature Water salinity

Disposal of Acid Fonnation Water

Gas with

Disposable

Sour water injection has advantages and disadvantages in comparison to direct injection. The technique results in better containment of the sour gas as it is dissolved in the injected aqueous phase and, excepting diffusive forces which act very slowly in porous media, the sour wattt moves only as the injected phase spreads into the reservoir. This also lessenssafety concerns with respect to rate of release and volume of release in the event of blowout of a sour disposal well. Compression costs are reduced, as the effluent is pumped down the well as a liquid phase using conventional equipment (with appropriate corrosion inhibition). Disadvantages include concerns about corrosion in the surface and injection equipment, hydrate in the contacting equipment, cost and safety of the surface contacting equipment, and the fact that the phase behaviour of the sour water must be precisely detem1medto ensure that sour gas is not liberated from solution as temperature increases as the fluid is heated by contact with the fonnation. The water-contacting process also suffers from the fact that it is not a perfect method for removal of acid gases and preferentially tends to adsorb H2S over CO2. A relatively large volume of water is also required to dissolve an acid gas stream of any appreciable volume. The technique can still be advantageous in systems where a large volume of produced water is available and must be disposed in any event, and can be used as a technique to extract a large fraction of the sour gas component from a rich

Solubility increases with increasing H2S concentration and increasing pressure (although solubility generally levels out near the critical pressure of the mixture (about 7000-10000 kPa). Solubility is reduced by inaeasing temperature and increasing salinity of the contacted water. Figure 4 provides an illustration of the solubility of pure carbon dioxide in fresh and salt water at various pressures at 100C. There are virtually no published data on the solubility of mixtures of acid gases in water. Table 2 provides a summary of some limited selected solubility data available for different concentrations of acid gases at varioustem perature and pressure contacting conditions. Detailed experimental solubility studies should be conducted prior to any acid gas injection study. This will quantify the compatibility and expected solubility of the target acid gas stream in the specific aqueous phase present in the reservoir or contemplated for coinjection. Problems may be associated with solubility of hydrogen sulphide into water. Water solutions containing H2S are not stable and reaction with adsorbed oxygen can cause the precipitation of elemental sulphur\) and turbidity. This may result in plugging of the injection zone by the suspended solid precipitate. The turbidity can be reduced by filtration or stabilized with various inhibitors (ie. glycol), but both techniques may increase the cost of the injection operation significantly thus reducing the economic viability of d1esour water injection operation. Solubilize Acid Gas into Light Hydrocarbon Solvent and Inject the Solvent Containing Acid Gas Component into tbe Depleted Reservoir as a Miscible Flood Enhanced Oil Recovery (EOR) Technique. Rich acid gases exhibit extreme solubility in liquid hydrocarbons at elevated pressures (gas-oil ratios of acid gases in hydrocarbons. particularly light condensates.can be in excess of300 m3/m3).Solubility of pure CO2 in 40 API gravity oil at 100C is provided in Figure 4. Many potential injection zones contain a residual mobile or immobile liquid hydrocarbon saturation. This would include depleted oil reservoirs. transition zones containing an immobile oil saturation. watertlooded zones at a residual oil

saturation, depleted gas reservoirs containing an initial

irreducible or sub-irreducible oil saturation, and

depleted retrograde condensategas zones containing a trapped irreducible or sub-irreducible critical condensate saturation. Two potential concerns arise with respect to the contact of these hydrocarbon liquids with the acid gas as follows: Compatibility. Many oils may de-asphalt when contacted with diatomic gases such as CO2 and H2S. The precipitation of granular solid asphaltenescan lead to plugging of the pore system and restricted injectivity in the near wellbore region. If injection into a zone containing liquid hydrocarbons is contemplated, detailed compatibility testing should be conducted between the live hydrocarbon liquid and the proposed injection gas over the range of expected downhole injection conditions to ensure that destabilization of asphaltenes from the liquid hydrocarbon phasedoes not

occur. Swelling. Due to the extremesolubility exhibited by rich acid gases in most hydrocarbons a large
formation volume factor increase(expansion of the size of the liquid hydrocarbon phase) occurs when the acid gas contacts the insitu oil. If pressure is sufficient, the acid gas may actually be miscible with the insitu crude which will result in miscible displacement of the residual oil saturation away from the wellbore area, potentially creating an advantageous increase in relative permeability to the injected acid gas and an increase in injectivity. In many situations, the composition of the acid gas, liquid hydrocarbon gravity and downhole temperature and pressure conditions are not conducive to the establishment of miscibility. In this situation, a portion of the injection gas is absorbed into the trapped liquid hydrocarbon phase, causing a large increase in formation volume factor of the oil. Figure 5 provides a pressure-composition diagram for a typical insitu retrograde condensate phasewith a molecular weight of approximately 110 when contacted with a 50% H2S/500/oCO2 acid gas stream at 10000 kPa and 60 C. It can be seen at the saturation point (ie. point where the saturation pressure of the liquid is equivalent to the injection pressure of 12000 kPa representing the maximum degree of swelling expected to occur) that an increase in condensate volume of over 27% occurs due to solubility effects. If the expanded oil saturation is already at the irreducible level, the problem may not be significant. When the oil saturation expands, it is basically akin to increasing the oil saturation, and the portion of the increased liquid hydrocarbon saturation in excessof the irreducible value should be mobilized and displaced deeper into the formation. Problems may occur if the original oil saturation is relatively small and is at a subirreducible level. This often occurs in depleted gas

condensate reservoirs or some gas reservoirs which have been created by gas migration over geological time into previously oil bearing strata. As the liquid saturation increases in value, it still remains below the irreducible value and hence is not mobilized, but expands and occludes space previously available for gas to be injected. The end result can be a significant reduction in gasphaseinjectivity if the configuration of the gas phase relative penneability curve is very steep at low liquid saturation values. Figure 6 provides an illustration of this phenomena. This problem is very difficult to diagnose without direct field or lab testing. Conventional gas-liquid relative penneability curves can provide some insight, but the parameters and configuration of nonnal gasliquid relative penneability curves are generally significantly altered when considering an acid gas-oil or acid gas-water system. Dissolution of the acid gas in the liquid phase significantly reduces its viscosity (by an order of magnitude or more for some hydrocarbon liquid systems) and also can substantially reduce interfacial tension between the gas and liquid phases. Potential Side Benefits. Acid gas re-injection may have potential side benefits in addition to the direct disposal of unwanted sour gas. Some of these factors have been alluded to previously, but will now be discussed in greater detail. They include: Potential stimulative nature caused by carbonate dissolution. In the absence of adverse precipitation effects and dissolution induced fmes mobilization and plugging, long-term acid injection may actually improve injectivity in some disposal wells due to low pH induced dissolution effects. Desiccation. In most direct acid injection projects, the injected acid gas will have been dehydrated to minimize hydrate problems at surface. Due to higher downhole temperatures, hydrate formation willl&ely not be problematic, but the dry nature of the injection gas may result in a gradual desiccation of the trapped irreducible or connate water saturation from the region adjacent to the injection zone. This is analogous to a phenomenon which often occurs during injection of conventional dry gas into gas storage reservoirs. The reduction in initial water saturation can cause an increase in injectivity due to a lessening of adverse relative permeability effects associated with the presence of the initial water saturation in the porous media. This effect may also be damaging if the insitu water being desiccated is highly saturated with soluble salts (for example, in a typical deep carbonate formation). Desiccation of fluid by the injection gas results in precipitation of these soluble salts within the pore system which may have a counteracting effect on the expected increase in penneability due to water

saturation removal, depending on the location of the reprecipitation within the pore system. limited Or Fun Miscibility with In-situ Oil Most acid gas streams represent excellent miscible injection solvents (from a phase behaviour point of view) and very low or zero interfacial tension can be obtained with these gases with many oils at relatively low pressures. This makes these gases potential EOR injectant candidates for the miscible displacement of oils (which are generally in and of themselves already sour). Due to the supercritical nature of the gas, actual volume available for injection is usually too small to be an effective consideration for voidage replacement for an EOR process. Situations do exist. however, where the rich acid gas, extracted from produced solution gas from a large oil reservoir or directly from a sour gas reservoir, could be used to miscibly inject into adjacent smaller oil pools or isolated zones of the source oil pool. Detailed lab and numerical studies would be required in this situation to confinn miscibility with the insitu crude, pressure required to maintain low 1FT/miscibility and potential compatibility concerns with the gas-crude system and injectivity issues as discussed previously. Contingency plans for premature ultra-sour gasbreakthrough at a producing well are also a necessity in this situation.

References
1.

Wichert,E. andT. Royan,"Sulphur Disposalby Acid Gas Injection," SPE 35585, Gas Technology Conference, Calgary, Alberta,
Canada, May 1996.

2.

Keushnig, H., "HydrogenSulfide - If You Don't Like It, Put It Back," Journal of Canadian
Petroleum Technology, 34(6), June 1995, 18-20.

3.

Longworth,H.L., G.C. Dunn andM.Semchuck, "Underground Disposalof Acid Gasin Alberta, Canada: Regulatory Concerns and Case Histories," SPE 35584, Gas Technology Conference, Calgary, Alberta, Canada, May 1996. Clark, M.A., W.Y. Svrcek, W.D. Monnery, A.K.M. Jarnaluddin. D.B. Bennion, F.B. Thomas, E. Wichert, A. E. Reed, and D.J., Johnson, "Designing and Optimized Injection Strategy for Acid Gas Disposal widtout Dehydration," paper presented at dte 11m Annual Convention of dte Gas Processors Association,Dallas,Texas,March 16-18,1998. Duckworth, G.L., D. Kopperson,S. Home, G. Kohn, D. Romansky, and C. ChaD,"Dispoal of Acid Gases with Oilfield Produced Water," paperpresented at the 7~ Annual Convention of the Gas Processors Association, Dallas, Texas,March 16-18,1998. "Natural Gas Processors Association Handbook," Gas Processing Suppliers Organization,Tulsa, O.K., 1980.
"Merck Chemical Index, " Ill" Edition. Merck & Co. Inc., Rahway, N.J., USA, 1983.

4.

Summary

5.

Acid gas or water injection has proven to be a viable technology for the disposal of large volumes of waste acid gas. For compressed acid gas injection, either as a disposal or miscible solvent, the operating company must avoid the two-phase region during compression. Water condensation and hydrate formation in the postcompression equipment must be prevented to ensure a safe, cost-effective operation. Experimental data on the water content, density, hydrate and phase behavior of acid gas mixtures is therefore necessary. In the case of the studied acid gas mixture of 9.90/0H2S, 89.5% CO2 and 0.6% CR., dehydration is not required unless the temperature drops below 8 C at 17700 kPa. The twophase region will be avoided during compression by maintaining the gastemperature above 37.5 C between stages. Acknowledgments The authors would like to thank Union Pacific Resources Company for permission to publish the experimental data. The authors also express appreciation to Vivian Whiting for her assistance in the preparation of the manuscript and figures.

6.

7.
8.

Song,K. and R. Kobayashi,"Water Contentof CO2in Equilibrium with Liquid Water and/or Hydrates", SPE Formation Evaluation, December1987,500-508. Selleck,F.T., L.T. Cam1ichael and B.H. Sage, "Phase Behaviorin the HydrogenSulfide-Water System", Ind Eng. Chem., September,1952, 44(9),2219-2226.

9.

ACID/SOUR GASMANAGEMENT IN THE PETROLEUM INDUSTRY

SPE 49522

10. Carroll, J.J. and A.E. Mather, "Phase Equilibrium in die SystemWater-Hydrogen
Sulfide: ExperimentalDetenn ination of die LL V

Locus", Canadian Journal of Chemical Engineering.,67, June,1989, 468-470. Ng, H., D. Robinson and A. Leu, "Critical Phenomena in a Mixture of Methane,Carbon Dioxide and Hydrogen Sulfide", Fluid Phase Equilibria, 19, 1985,273-286.

12.

Huang. S.. A.D. Leu. H.J. Ng and D.B. Robinson. " The Phase Behavior of two mixtures of Methane. Carbon Dioxide. Hydrogen Sulphide. and Water". Fluid Phase Equilibria. 19. 1985. 21-32.

13.

Mussumeci,A., "Computationin Gas Hydrate Fonnation", SPE 21112, presented at die SPE Latin America Petroleum Engineering Conference,Rio de Janeiro,Oct. 14-19,1990. Dodds, W.S. et aI, "CO2 Solubility in Water", Chern.Eng. Data Series1, 1956,p. 92. Munjal, P. and P.B. Stuwart, "Solubility of Carbon Dioxide in Pure Water, SynfueticSea Water and SynfueticSeaWaterConcentrates at -5C to 25C and 10 to 45 ATM Pressure", Journal of Chemical Engineering Data, 15,

14.
IS.

1970,67. 16.
Simon, R. and D. Graue, "Generalized Correlationsfor PredictingSolubility, Swelling and Viscosity Behavior of CO2-Crude Oil Systems",Journal of Petrolewn Technology, Ian 1965,p. 102.

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