Annual Meeting March 13-15, 2005 San Francisco Hilton Hotel San Francisco, CA

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Review of Cansolv SO2 Scrubbing Systems First Commercial Operations in the Oil Refining Industry

Presented By: John N. Sarlis Vice President, Research and Development Cansolv Technologies Inc. Montreal, QC David K. Stevens Vice President Sulfur Technology Black & Veatch Overland Park, KS Mark R. Tonjes Black & Veatch Overland Park, KS Paul J. Parisi Cansolv Technologies, Inc. Montreal, QC Leo E. Hakka Cansolv Technologies, Inc. Montreal, QC

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This paper has been reproduced for the author or authors as a courtesy by the National Petrochemical & Refiners Association. Publication of this paper does not signify that the contents necessarily reflect the opinions of the NPRA, its officers, directors, members, or staff. Requests for authorization to quote or use the contents should be addressed directly to the author(s)

REVIEW OF CANSOLV SO2 SCRUBBING SYSTEMS FIRST COMMERCIAL OPERATIONS AND APPLICATION IN THE OIL AND GAS INDUSTRY
David K. Stevens and Mark R. Tonjes
Black & Veatch Gas, Oil & Chemicals Division

Leo E. Hakka and Paul J. Parisi

Over the past five years, the CANSOLV system SO2 scrubbing technology has moved from the status of an emerging technology to that of a commercially realized and technically proven process for economical and highly selective regenerable SO2 capture from gas streams. Since May 2002, Cansolv Technologies, Inc. (CTI) has successfully realized startup of three commercial applications of their CANSOLV System SO2 scrubbing technology: 10,000 TPY SO2 Unit in Norandas smelter operations in Quebec 4,000 TPY SO2 Unit for Claus Tail Gas Clean-up at a chemical manufacturing complex in Belgium 3,000 TPY SO2 Unit for Spent Acid Recovery Unit Tail Gas Clean-up at ConocoPhillips Refinery in Los Angeles In addition to these commercial operating units, 12 pilot plant campaigns have been executed for a wide diversity of applications including those in boiler and refinery FCC flue gas desulphurization. In the oil and gas industry, the CANSOLV process has particular merit due to the fact that SO2 removal, in some fashion, is routinely required as a part of the basic oil and gas desulphurizing processes and that a convenient use for the recovered SO2 is found in the ubiquitous Claus sulphur recovery unit.

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INTRODUCTION Two reference plants using the CANSOLV SO2 Scrubbing System Technology aqueous diamine-based regenerable SO2 scrubbing technology and one SO2SAFE plant are now operating in regular commercial production. A unit in Europe is treating tailgas from an incinerator burning a combination of Claus sulphur recovery unit tailgas and a sulphur and chlorine containing waste tar achieving emissions as low as 30 mg/Nm3. A SO2SAFE SO2 Storage System is capturing SO2 from Norandas CEZinc zinc roaster acid plant feed stream into CANSOLV amine absorbent. The rich solution is trucked to another site, Norandas CCR copper refinery, for on-demand regeneration where it is used in a batch chemical operation. The third unit is cleaning the tail gas from a 400 TPD spent sulphuric acid regeneration plant in a California oil refinery to as low as <10 ppmv. This success opens the way for more ambitious applications such as a completely new approach to SRU plant design that promises lower cost and lower emissions.

CANSOLV SO2 SCRUBBING SYSTEM PROCESS DESCRIPTION The CANSOLV SO2 Scrubbing System Technology, as illustrated in Figure 1, is essentially identical to the well-known amine treating process for H2S and CO2 removal from natural gas and refinery streams. The process operates as follows: Prescrubber The feed gas is humidified and cleaned of particulates and strong acids in a water-wash prescrubber. The complexity of this part of the process is a function of the gas being treated. Smelter ventilation gases will typically require a baghouse before the gas is humidified. Metallurgical process gases will need to be of a degree of cleanliness similar to acid plant drying tower feed gas. Absorber Countercurrent contact in a structured packing or dumped packing tower of the lean solvent with the process gas transfers the SO2 to the liquid, producing the rich solvent and a cleaned gas.

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Regenerator The SO2 is stripped from the rich solvent in the regenerator with steam produced by the boiling aqueous solvent in the reboiler. Most of the water is removed from the regenerator overhead stream by condensation, leaving water saturated SO2 as the byproduct. The condensed water is returned to the tower as reflux.

Treated Gas to Stack

Impurities to Blowdown AMINE PURIFICATION UNIT

SO 2 Product 99.99% (dry basis)

ABSORPTION COLUMN
Rich Amine Water Feed

REGENERATION COLUMN
HEAT EXCHANGER

PRESCRUBBER
Feed Gas LEGEND Gas Phase Liquid Phase Amine Blowdown

Steam

Lean Amine

Condensate

Figure 1 Block Flow Diagram of the CANSOLV SO2 Scrubbing Process Technology

Amine Purification The quality of the solvent is maintained by removing strong acids from a small slipstream of lean solvent in the absorbent purification unit. Streams containing SO2 generally also contain sulphuric acid mist that passes the prescrubbing stage and is captured by the amine solvent, producing heat stable salts, which if not removed would eventually neutralize the scrubbing capacity of the solvent. An electrodialysis heat stable salt removal unit replaces the heat stable sulphate anions from a slipstream of lean amine with bisulphite, which is regenerable. A full description of the CANSOLV SO2 Scrubbing System Technology and its applications may be found at www.Cansolv.com.

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CANSOLV SO2 SCRUBBING SYSTEM PROCESS CHEMISTRY The aqueous amine solvent used in the CANSOLV System process is very stable and highly selective for SO2. In water solution, dissolved SO2 undergoes reversible hydration and ionization to produce bisulphite and sulphite according to the following equations: SO2 + H2O H+ + HSO3 (1)

Adding a buffer, such as an amine, to the water increases the quantity of SO2 dissolved. The buffer drives the above equilibria to the right by reacting with the hydrogen ions to form ammonium salts. R3N + H+ + HSO3 R3NH+ + HSO3 (2)

Reaction 2, the overall reaction, indicates that as the concentration of SO2 in the feed gas increases, the equilibrium moves to the right, i.e. the quantity of SO2 dissolved in the rich solvent increases. Thus, the scrubbing of more concentrated gas streams requires a less than proportional increase in solvent circulation rate. Since the gas volume, and therefore the gas side equipment, remains constant, a relatively small total cost increase is caused by an increase in feed SO2 concentration. Steam stripping of the SO2 loaded solvent in a counter-current multi-stage column will force the equilibrium of reaction (1) to the left and consequently, reactions (1) - (2) are reversed, regenerating the absorbent. The CANSOLV System process is based on a unique class of diamine absorbents that optimally balance the ability to absorb and regenerate sulphur dioxide. One absorbent molecule has two amine functionalities. One of the amine functionalities is strongly basic and non-heat-regenerable. Once it has reacted with SO2 or a stronger acid, it remains in salt form in the scrubbing process. The resulting monoprotonated amine in reaction (3) is the CANSOLV System lean amine that scrubs the SO2. The second amine functionality is less basic than the first and is referred to as the "sorbing nitrogen". It operates in the buffering range that gives the optimal balance for absorption and regeneration of SO2 in reaction (4). This amine functionality is the essence of the CANSOLV system technology. NRlR2R3NR4R5 + HX H+ NRlR2NR3R4R5N + X(3) (4)

H+ NRlR2NR3R4R5N + SO2 + H2O H+ NRlR2NR3R4R5N H++ HSO3-

Expressed in other terms, the absorbent used in the CANSOLV System process is a diamine, one amine function always being in salt form. This prevents volatilization and therefore loss of solvent to the cleaned gas, as well as avoiding contamination of the byproduct SO2 with the solvent. Through an optimum balance of SO2 absorption and

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desorption tendencies, the process is able to achieve high purity in the treated gas while using a minimum of regeneration energy. The CANSOLV System process is very robust and easy to operate. Sulphur dioxide removal to <100 ppmv can easily be obtained in most applications and treated gas purities of <10 ppm are usually attainable, at a slight increase in capital expense and regeneration steam use. The CANSOLV System amine absorbents provide the following significant advantages: No losses to vapour since the absorbent is in salt form and therefore non-volatile Selectivity of SO2 over CO2 by factor of 50,000 High thermal and chemical stability, even in the presence of oxygen in the treated gas High water solubility, giving a homogeneous liquid absorbent of relatively low toxicity (no mortality at 20.0 g/kg, rats) Low foaming tendency (due to lack of conditions responsible for foaming)

The versatility and regenerability of the CANSOLV System process enables its application to scrubbing almost any gas stream containing SO2. COMMERCIAL UNIT OPERATING EXPERIENCE The three full-scale commercial reference plants began operation in 2002. The first commercial plant is located at the CEZinc smelter in Valleyfield, Quebec and operates under the patented SO2SAFETM process. The SO2SAFETM process, which is an extension of the CANSOLV System process, reduces the hazard of SO2 storage and transport by dissolving the gas in a high capacity solvent, instead of compressing it to liquid state, thereby limiting the release of gaseous SO2 in case of a leak or spill. The SO2 is regenerated from the solvent in an automated unit on demand at the user's site, in this case, CCR copper refinery, some 90 kilometres from the site of the CANSOLV unit. This process is less expensive than other liquid SO2 replacements and the
Figure 2 Cansolv SO2SAFETM Unit at Noranda Zinc Smelter in Valleyfield, Quebec

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high capacity of the solvent allows for economical transportation. The second commercial plant incorporating the CANSOLV System process, which started up in May 2002 at a chemical plant in central Europe, desulphurizes the flue gas from an incinerator burning sulphur recovery unit (SRU or Claus unit) tail gas and waste tar. The recycle of SO2 to the SRU expands its sulphur recovery capacity by reducing the thermal stage combustion air requirement, while controlling total sulphur emissions to less than 100 ppmv and as low as 20 ppmv. The operation of the plant has been stable and operators attest to the robustness and trouble-free nature of the CANSOLV System process. The degradation of the solvent has also been less than expected, indicating a very low makeup requirement. The performance, operability and cost advantages of SRU tail gas treatment by regenerable SO2 recovery are significant and will no doubt lead to wide commercial use of this process option. The third commercial unit operating the Cansolv SO2 Scrubbing System was started up in late September of 2002 in California. The unit treats tail gas from a 400 tpd spent acid sulphuric acid plant. The recovered SO2 is sent back to the front end of the acid plant for conversion to sulphuric acid. This unit has been operating for 1 year. Due to higher than specified strong acid in the feed gas, additional heat stable salt removal capacity had to be brought on site until this problem can be corrected during the next acid plant turnaround. The Cansolv SO2 Scrubbing unit has exceeded the guaranteed cleanup of 50 ppmv in the tail gas with normal operation resulting in a concentration between 10-20 ppmv. Steam guarantees have also been easily met. The process has proven itself to be robust and easily adaptable to changing conditions. Recently, due to increased production in the acid plant, the SO2 load on the Cansolv unit was 50% over design. The unit was able to easily maintain the cleaned gas SO2 concentration below 20 ppmv during this period. The three initial commercial applications of the CANSOLV System SO2 scrubbing process have exceeded expectations regarding cost, Figure 3 Cansolv Acid Plant removal efficiency, energy consumption, and Tail Gas Unit in California solvent stability. The range of commercial TM applications, namely SO2SAFE , desulphurizing flue gas from an incinerator burning SRU and Claus unit tail gas and waste tar, and treating sulphuric acid plant tail gas to less than 10 ppmv, bear witness to the versatility of the CANSOLV System SO2 scrubbing process. Performance to date has far surpassed current benchmark technology.

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OIL AND GAS INDUSTRY APPLICATIONS In the oil and gas industry, the CANSOLV process has particular merit due to the fact that SO2 removal, in some fashion, is routinely required as a part of the basic oil and gas desulphurizing processes and that a convenient use for the recovered SO2 is found in the ubiquitous Claus sulphur recovery unit. Areas where CANSOLV is most applicable in the oil and gas industry are: Hydrogen Sulphide Based Power Generation: A key to harnessing hydrogen sulphide for power generation is the removal of SO2 produced in the process. CANSOLV SO2 capture is the best solution for these processes involving re-injection of sulphur dioxide as is currently being investigated for large-scale sour gas processing projects. FCC/Fluid Coker Wet Gas Scrubbing: As an alternative to traditional practice of caustic-based or other non-regenerable processes. Flue Gas Scrubbing for High-Sulphur Fuel Boilers and Heaters: Flue gas desulphurization of utility/cogeneration boilers or fired heaters enables the firing of low-value sulphur rich fuel gases and oils. Claus Tail Gas Treating Technology: As an alternative to the current conventional practices, CANSOLV readily meets a 10 250 ppmv total SO2 emissions specification and benefits the Claus plant with SO2 recycle for increasing available capacity. Lean Acid Gas Processing: When optimally integrated with Cansolv SO2 removal, the scope and cost of a Claus unit can be shrunk considerably. The entire thermal reaction and conventional tail gas unit become unnecessary. In this case, the SO2 required for the Claus reaction is generated from the direct combustion of a nominal one-third of the acid gas. The CANSOLV process is used to capture and concentrate the SO2 as the reactant for the balance of the H2S in the acid gas. This novel approach is most applicable for lean acid gas with low hydrocarbon content such as those associated with gasification facilities. Problematic Acid Gas Processing: As CANSOLV can readily capture and recycle SO2, the process is well-suited for scrubbing combustion products of any streams containing sulphur-bearing compounds which would not be readily accomplished in a conventional Claus plant, e.g., high hydrocarbon content acid gas, ammonia-bearing sour water stripper gas, disulfide oils, etc. In this case, the problematic stream is combusted in the Claus plant tail gas incinerator, scrubbed with CANSOLV, and the removed SO2 recycled to the front of the sulphur plant.

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CURRENT OIL AND GAS INDUSTRY PROJECTS Several new projects in the oil and gas industry are in the early stages of design. A major project is underway for the application of a CANSOLV system SO2 scrubbing process at a refinery for FCC wet gas scrubbing. A second new project involves the addition of a CANSOLV unit for Claus tail gas treating at a refinery sulfur complex. Additional new projects are currently being executed for CANSOLV units processing problematic sulfur-bearing hydrocarbon streams and for SO2 removal application in a new process for sulfur recovery applicable in the gas processing industry. Refinery FCC Wet Gas Scrubbing Unit This project involves the installation of a CANSOLV SO2 scrubbing system on a refinerys fluid catalytic cracker (FCC). The CANSOLV system will be used to remove SO2 from the FCC offgas and recycle the SO2 to the refinerys sulfur recovery units. It is a large-scale application of CANSOLV where a gas flow of ~2,000,000 lb/hr is treated for removal and recycle of ~4000 lb/hr of SO2. Removal of SO2 in the treated gas to less than 25 ppmv is required. As this is a FCC application, particulate removal is also a major process requirement. Process Overview The hot FCC off-gas (650F) enters the bottom of a tower in the Prescrubber section where the gases are cooled by multiple layers of water sprays. The water sprays remove particulates and cool the gas. The gas is cooled by evaporation of the water provided by the sprays. The extent of the cooling by evaporation is limited to the adiabatic saturation temperature, in this case 155F. Any further cooling beyond these temperatures must be provided by means other than the evaporation of water. The saturated gas from the Prescrubber flows through a proprietary gas cleaning system for further removal of particulates and entrained water. The cooled, filtered, off-gas then enters the absorber where the SO2-laden gas is contacted with the CANSOLV amine solvent for SO2 removal. The performance of the solvent is dependent on the temperature. The lower the contacting temperature, the better the SO2 removal, and the lower the SO2 slip from the absorber. Depending on the contacting temperature and the solvent performance, the gas from the absorber may be treated, or polished with caustic for further SO2 removal to meet the emissions limits. The rich CANSOLV amine solvent leaving the absorber is regenerated in a stripper and the recovered SO2 sent to the refinery sulfur recovery unit where it is recovered as elemental sulfur. Additional infrastructure, such as a purge treatment unit for quench water particulate removal and waste water neutralization, is also required.

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Key Design Factors Several of the key design factors considered for this installation are discussed in the following sections. Absorber Solvent Contacting Medium There are several options for contacting the scrubbed off-gases with the CANSOLV solvent: (1) (2) (3) (4) (5) An open spray tower Grid type structured packing Conventional structured packing Random packing Trays
Stack

Transition

Open Spray Towers Open spray towers offer the best resistance to particulate fouling. However, the flow in an open spray tower is not truly counter-current and would require more stages versus other types of contacting devices. Additionally, the HETP for an open spray tower stage is higher versus the HETP for packing. Therefore, the tower size required to accommodate the large number of stages plus the associated gas cleaning system required for entrainment removal, would be tall and expensive. Grid Type Structured Packing Grid type structured packing is a very open style of packing that offers excellent resistance to fouling and has a high capacity and a low pressure drop. It has been used in similar applications with success. However, the efficiency is quite low compared with conventional structured packing. This is considered a viable option requiring further investigation, if conventional structured packing is considered to be too prone to fouling. In similar applications, grid packing has been used upstream of more conventional packing and/or trays to knock out particulates

Liquid Distribution Caustic Polishing Section Chimney Liquid Distribution Absorption Section 2 Collector Liquid Redistribution Absorption Section 1

Liquid Distribution Scrubbing / Recirc Section Vap Distr. Disengaging Space

316L 6Mo

Conventional Structured Packing Conventional Inlet Duct 6Mo structured packing offers the highest efficiency 316L versus other devices. However, it is less resistant to particulate fouling versus grid style packing and Figure 4 Cansolv Absorber there is less experience with conventional packing Figure 6.1 Tower in this particular service. This is considered a viable option but requires a design that mitigates the potential for particulate fouling.

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Random Packing Random packing is generally less efficient and of lower capacity than conventional structured packing, especially at the low liquid loading rates encountered in this application. Random packing is also less fouling resistant than structured packing, because the liquid flow on structured packing more efficiently sweeps the packing surface. It is also more difficult to maintain adequate liquid distribution with random packing versus structured packing. For these reasons, structured packing is considered superior to random in this application and random packing is not considered. Trays Trays are not considered a viable option because of their high pressure drop and will not be considered further. Packing Options Summary For this project, only open grid packing and conventional structured packing were considered for the contacting medium. The main trade-off is between the additional cost of the increased tower height to accommodate the grid style packing versus the reliability risk (plugging) with structured packing. Regeneration Pressure The SO2 regenerated from the solvent must be sent to the Sulfur Recovery Units for further processing and conversion to elemental sulfur. The required delivery pressure at the SRU is expected to be 10 to 12 psig, depending on the eventual modifications that are made to the SRUs and the upstream amine units. The delivery pressure will also depend on the ultimate injection point for the SO2 stream (reaction furnace, first reactor inlet, etc.). There are two options for meeting the required delivery pressure. The first option is to use a blower to boost the SO2 stream to the required pressure. The second option is to operate the Regenerator at a sufficient pressure that a blower is not required. Since the Regenerator reboilers use low pressure steam (nominal 35 psig), increasing the Regenerator pressure from 4 psig to 12 will significantly reduce the temperature driving force in the reboilers and require significantly more heat transfer area. Also, providing a dedicated blower will result in greater operating flexibility with regards to future SRU upgrades. Since the blower savings are expected to be minimal, low regeneration pressure is the preferred option. Material Selection There are several corrosive process streams within the Regenerative SO2 Scrubbers. These corrosive streams have one or more of the following the following conditions: low pH high chloride content high solids content which promote erosion and deposit formation high temperature

Prescrubber Vessel and Quench Water Loop The pH of the circulating quench water is 1.0 to 2.0. Chloride concentrations in the prescrubber water depend on chlorides in the makeup water, caustic, and in the flue gas and is expected to be approximately 1000

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ppm. The Prescrubber is designed to prevent solids buildup by keeping all of the internal surfaces wetted. A summary of the material selection for the various piping and equipment items is given below. Vessels Pumps Piping Valves Heat Exchangers Tubes Header Boxes 6Mo SS Rubber-lined Cast Iron 6Mo SS Large: rubber lined; Small: Hastelloy

18 BWG Hastelloy or 14 BWG 6Mo SS 6Mo SS, seal welding is not required

Prescrubber Inlet At the Prescrubber gas inlet where the inside surface can alternate between wet and dry, Hastelloy X is recommended. Prescrubber Outlet through Absorber Inlet The duct work from the Prescrubber outlet to the Absorber inlet should be 6Mo SS. The duct is designed to prevent dry surfaces and solids buildup which accelerate corrosion. Absorber Inlet Area The portions of the bottom of the Absorber shell that are not continuously wetted by amine may be exposed to low pH quench water carry-over. These areas should also be 6Mo SS. This includes the portion of the absorber vessel above the low-low liquid level up to one foot above the elevation of the packing supports. The vapor distributor, packing support grid, and associated support beams should also be 6Mo SS. Absorber and Solvent System The rich CANSOLV solvent pH will be 4. The lean solvent pH will be 5 to 6. For solvent at a pH of 4, the maximum recommended chloride level for Type 316L SS is 100 ppm. For the Absorber, Stack, Regenerator, and all equipment and piping in the solvent loop, Type 316L SS is sufficient. Solvent storage tanks may be either Type 316L SS or lined CS. In order to prevent localized high chloride concentrations under solid deposits, full stream rich solvent filtration should be provided. Development of a suitable filter system design is critical to minimizing fouling and associated under-deposit corrosion in the Regeneration Unit.

Regenerator Overheads The regenerator overheads will have a low pH of 1.0 and a maximum temperature of 230F. Chloride content will be extremely low. Therefore,

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Type 316L stainless steel is adequate for the overhead condenser, reflux drum, reflux pump, SO2 blower, and associated piping. Absorber Design The major design issues for the Absorber are the potential plugging problems; the number of stages and determination of the packing HETP; and proper liquid distribution due to the large size of the tower (>20 ft dia.). Design Issues Flooding Limits CANSOLV has lower foaming tendencies versus traditional gas treating amines. For this study, the following tower sizing parameters are recommended. System factor of 0.85 80% flood limit Maximum pressure drop of 0.25 in. H2O per foot of packing height

Reliability The reliability for both units must be very high. The required run length between turn-arounds is 5 years for the FCCU. Hence, the importance of the plugging issue. Pressure Drop The pressure drop through the tower must account for all losses including the inlet ductwork, the various gas and liquid distributors within the absorber, the various packing support grids and hold downs, and the vent stack. The total pressure drop through the entire unit from the CO boilers through the Absorber is a critical issue and is limited to 50 in. w.c. HETP For aqueous amine absorption systems, with a high viscosity and high surface tension liquid, HETP is typically 50-100% higher than for a typical hydrocarbon system. Design Recommendations The preliminary recommended tower design is illustrated in Figure 4 and summarized below. Inlet Area A vapor redistributor located underneath the bottom packed section is required for good vapor distribution in the tower. This is due to the combination of high velocity in the inlet duct, low gas pressure drop in the bottom bed, and the large tower diameter. The bottom of the vapor redistributor is typically located 1.5 duct diameters above the centerline of the inlet duct. Bottom Wash Section The purpose of the bottom wash section is to knock out large particulate from the off-gas prior to contact with the structured packing in the Absorption section. The wash section protects the structured packing from plugging.

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Absorption Section The purpose of the absorption section is bulk removal of SO2 from the off-gas by absorption with CANSOLV solvent. The recommended packing selection is conventional structured packing. Caustic Polishing Section The purpose of the caustic polishing section is removing additional SO2 that is not picked by the solvent. Compared to the Absorption section, the structured packing should be larger and more open due to the potential fouling caused by the formation of carbonates at high pH. The caustic system should be designed to control the pH of the recirculating dilute caustic stream at 6.0 7.0 to prevent carbonate formation. The typical control strategy is to control the caustic makeup rate based on maintaining the pH of the circulating caustic stream; controlling the water makeup rate based on solution density; and blowing down spent caustic based on liquid level on the chimney tray. Liquid Distributors For the sections of the tower where liquid carry-over must be minimized, gravity liquid distributors are preferred over spray distributors. This includes the liquid distributors at the top of the caustic polishing section and at the top of each of the two absorption beds. The liquid distributor at the top of the solvent wash section may be either a spray or gravity type.

Refinery Claus Tail Gas Treating Unit The objective of this CANSOLV application is two-fold: first, the refinery is required to install a new tail gas unit in order to satisfy environmental requirements and second, the overall Claus sulfur recovery capacity needs to be increased by 25%. Both objectives can be met by installation of a new CANSOLV Claus tail gas treating unit. As the CANSOLV system is unique in its capability to remove and recycle SO2, the oxidant in the Claus process, a Claus sulfur recovery capacity increase is realized with a CANSOLV tail gas treating unit, i.e., by recycling SO2 instead of H2S by a conventional tail gas unit, the oxygen (air) requirement for Claus sulfur recovery is reduced. If a conventional H2S-recycle based tail gas unit would have been employed, the 25% increase in Claus sulfur recovery capacity would have to be achieved by conventional air-based debottlenecking or the use of oxygen enrichment. Process Overview The following is a general description of the CANSOLV tail gas treating unit being installed in this refinery application. Tail gas from the Claus sulfur recovery unit is first processed in a conventional tail gas incinerator to convert all the remaining reduced tail gas sulfur compounds (H2S, COS, CS2 and elemental sulfur) to SO2. This is accomplished by the conventional practice of combusting natural gas with excess air with the Claus tail gas to a temperature of 1200 to

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1500F. The incinerated offgas is then cooled to 600F in a fire-tube waste heat boiler generating high-level steam. The gas is further cooled and saturated with water by direct water contact in a recirculation quench system similar to that of the typical SCOT process. However, a major difference between the CANSOLV TGU and SCOT is that the pH of the CANSOLV TGU recirculating quench water is quite acidic (due to the presence of SO2) and acid resistant materials of construction are required. The quenched gas is processed in the CANSOLV absorber where the SO2 is selectively removed by the solvent. Absorber offgas, containing less than 150-200 ppmv of SO2, is directly vented to the atmosphere. No post-incineration of absorber offgas is required. Key Design Factors In order to recycle enough SO2 from the CANSOLV TGU to the Claus SRU for a 25% increase in Claus SRU capacity, additional refinery acid gas is bypassed around the Claus SRU and incinerated directly with the Claus tail gas in the CANSOLV TGU incinerator. Directly processing a fraction of the refinery acid gas in the CANSOLV TGU incinerator also has the advantage of reducing the incinerators natural gas fuel requirement for temperature achievement and reduces the volumetric throughput through the CANSOLV TGU (i.e., reducing the required equipment size). For this project, bypassing ~10% of the total refinery acid gas around the Claus SRU and processing directly in the CANSOLV TGU provides enough SO2 for a net 25% increase in total Claus SRU capacity. CONCLUSION The last 18 months has shifted CANSOLV technology from being a promising curiosity to a proven established process ready for application in the oil and gas industry. Increasingly stringent environmental regulations will push the industry towards solutions that effect nearly complete fixation of SO2 emissions. References 1. 2. 3. L. Hakka and J. Sarlis, Scrubbing Sulphur Dioxide, Hydrocarbon Engineering, December, 2002, 53-54. V. Lveill, CANSOLV Sulphur Dioxide Scrubbing System, Americana 2003 Conference, Montreal, Canada, 2003, 19-21. L. Hakka, Smelter and Acid Plant Applications of CANSOLV System Technology, Sulphur 97 Conference, Vienna, Austria, 1997.

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4.

L. Hakka, SO2 Recirculation as an Economic Alternative to Double Absorption, Sulphur 2000 Conference, San Francisco, California, USA, October 2000. L. Hakka and W.K. Boyd, Sulphuric Acid Plant Tail Gas Cleanup With CANSOLV System SO2 Scrubbing Technology, American Chemical Society Convention, Division of Fertilizer and Soil Chemistry, Las Vegas, Nevada September 8, 1997. J.P. Lacoursire J. Sarlis and P. Ravary, The SO2Safe Technology For Storage And Transport Of Sulphur Dioxide, AIChE 32nd Annual Loss Prevention Symposium, New Orleans, 1998. U.S. Patent 5, 019,361, Leo E. Hakka, May 28, 1991.

5.

6.

7.

BLACK & VEATCH

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