Sulfur Compound Extraction and Sweetening: P A R T 11

Source: HANDBOOK OF PETROLEUM REFINING PROCESSES
11
SULFUR COMPOUND EXTRACTION AND SWEETENING
11.1 Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.
SULFUR COMPOUND EXTRACTION AND SWEETENING
Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.
Source: HANDBOOK OF PETROLEUM REFINING PROCESSES
CHAPTER 11.1
KBR REFINERY SULFUR MANAGEMENT

Michael Quinlan
Kellogg Brown & Root, Inc.
INTRODUCTION
Raw crude oil contains sulfur and nitrogen. During processing, the sulfur and nitrogen are converted principally to H2S and NH3 and, to a lesser degree, organic sulfur (COS and CS2) and mercaptans (RSH). More stringent environmental standards on the emissions of sulfur and nitrogen compounds, together with the low sulfur specifications for petroleum products, have resulted in making sulfur management critical within todays refinery. The importance of sulfur management cannot be overstressed. Todays refineries are processing crudes with higher sulfur contents and are doing more bottom-of-the-barrel conversion. The need for new or revamped sulfur management facilities is expected to grow as demands for cleaner fuels and environment increase and crude oil slates change. As illustrated in Fig. 11.1.1, sulfur management within a refinery consists of four basic processes. Amine treating units (ATUs) remove H2S from recycle gas streams in hydroprocessing operations and from fuel gas/liquefied petroleum gas (LPG) recovery units. The amine is regenerated in one or more amine regeneration units (ARUs). Sour water strippers (SWSs) remove H2S and NH3 from the sour water streams. Sour water is the result of refinery operations using steam in distillation or steam as a means to reduce hydrocarbon partial pressure or where water injection is used to combat potential corrosion or salt buildup. The sulfur in the acid gas from the ARU and the SWS is removed first by a Claus sulfur recovery unit (SRU) that achieves 92 to 96 percent of the overall sulfur recovery and
FIGURE 11.1.1
Sulfur removal/recovery.
KBR REFINERY SULFUR MANAGEMENT 11.4

SULFUR COMPOUND EXTRACTION AND SWEEENING
then by a tail gas cleanup unit (TGCU) that can boost overall sulfur recovery to 99.9 percent. Most refineries now degas the molten sulfur produced. The amine, SWS, SRU, and TGCU processes are discussed in the following chapters.
AMINE
Introduction The sulfur in crude oil that is converted to H2S during processing typically is removed by a suitable amine. Two broad classifications of refinery amine treating applications are recycle gas treating and fuel gas/LPG recovery. In recycle gas treating, shown schematically in Fig. 11.1.2, the product oil from a hydroprocessing unit has an upper specification limit on its sulfur content. The sulfur in the feed oil reacts with H2 at elevated pressure (typically 35 to 150 bar gage) to form H2S. The reactor product stream is flashed, and a recycle gas stream, containing H2, H2S, and some hydrocarbons, is sent to an amine absorber, where the H2S is removed by the circulating amine stream. In fuel gas and LPG recovery units, the off-gases and stabilizer overheads from cracking, coking, and reforming units are sent to gas recovery units. The sour fuel gas has H2S removed at low pressure (3.5 to 14 bar gage typically) by the circulating amine. The LPG stream has the bulk H2S removed by amine at 14 to 21 bar gage, then the remaining H2S plus mercaptans is treated by a caustic solution and a proprietary solvent wash that converts the mercaptans to mercapticides. These washes typically achieve a Copper Strip 1A specification. Figure 11.1.3 shows a typical block flow design illustrating the processing steps.
Process Description Many refineries have multiple amine absorbers served by a common amine regeneration unit. Other refineries have two separate amine regeneration systems, with one system typically dedicated to clean users (such as hydrotreaters) and the other dedicated to dirty users (such as FCC units or cokers). A dual amine regeneration system is illustrated in Fig. 11.1.4. Figure 11.1.5 shows the rich amine streams from the absorbers being combined and sent to the rich amine flash drum to flash off light hydro-
FIGURE 11.1.2
Recycle gas amine treating.

11.5
FIGURE 11.1.3
Fuel gas/LPG amine treating.
REGENERATOR FLASH GAS Scrubber LEAN AMINE TANK
REBOILERS
RICH AMINE Flash Drum
LEAN AMINE COOLERS
AMINE FILLER LEAN/RICH AMINE EXCHANGERS
FIGURE 11.1.4
Amine regeneration unit.
carbons and to separate entrained hydrocarbons from the amine. This is necessary to minimize hydrocarbon carryover to the Claus SRUs. The flashed gas is treated with a slipstream of lean amine in the flash gas scrubber prior to routing to the fuel gas system. The flash drum is most often operated at 50 to 75 lb/in2 gage so that the flashed amine can be delivered to the top of the regenerator without a pump. Steam from the reboilers using 50-lb/in2 gage saturated steam strips the acid gas (H2S and CO2) from the amine. The overhead is cooled to 38 to 49C to minimize water carryover to the SRU. Provision is made at the reflux accumulator and at the bottom of the regenerator to skim off light and heavy hydrocarbons respectively. The regenerated amine is filtered and cooled, then distributed to the various absorbers.

FIGURE 11.1.5
Amine regeneration unit.
Process Variables Amine selection is normally between monoethanol amine (MEA, 15 to 20 wt %), diethanol amine (DEA, 25 to 33 wt %), and methyl diethanol amine (MDEA, 45 to 50 wt %). MEA, being a primary amine, is highly reactive, but is degraded by COS, CS2, and even CO2. These nonregenerable degradation products require that MEA units employ a semibatch reclaimer. DEA is not as reactive as MEA, but still easily achieves treated product specification. Compared to MEA, DEA is more resistant to degradation from COS, CS2, and CO2, but DEA cannot easily be reclaimed. Generic MDEA reactivity is low and may not meet treated product specification at low pressures. Its increasing use is a result of its selectivity for H2S over CO2 and its lower energy requirements. Formulated MDEA can achieve greater reactivity and still lower energy requirements, but its cost is high. In refineries, DEA is used most often typically as a 25 to 33 wt % solution in water. Sour feeds from cokers and catalytic crackers typically contain acids (acetic, formic, etc.) and oxygen. These contaminants react with the amine to form heat-stable salts (HSS) and to increase the foaming and corrosivity potential of the amine solution. A water wash ahead of the amine absorbers is recommended to minimize acid carryover with the sour feeds. In extreme cases, if the concentration of the HSS exceeds 10 percent of the amine concentration, a slipstream of the amine will need to be reclaimed. Ammonia (from the nitrogen in the crude) can concentrate at the top of the regenerator and cause severe corrosion there. A purge on the reflux return line to the SWS keeps the NH3 at more tolerable levels. For economy, most refineries will employ a common regenerator for the amine treating associated with the main refinery units. TGCUs typically use a selective amine such as MDEA. The size and operation of the MDEA unit is such that it is nearly always kept separate from other refining amine units. The required lean amine acid gas residual is a function of the specifications for the treated products. Typically, recycle gas is treated to about 10 vol ppm H2S, fuel gas H2S is 160 vol ppm or lower, and the treated LPG H2S should not exceed 50 wt ppm. Since the lean amine is in equilibrium with the treated product at the top of the absorber, the required residual at the pressure and temperature conditions can be calculated. Allowable rich amine loadings (moles of acid gas per mole of amine) vary with the chosen amine and are higher for H2S than CO2. At high pressures, high loadings can be

11.7
employed without exceeding a 70 percent approach to equilibrium at the absorber bottom. However, high loadings need to be weighed against the increased corrosiveness of the rich amine solution when it is depressurized at the separation drum and beyond. Acid gas loadings typically vary from 0.2 to 0.5 mol/mol. In LPG liquid treaters, lower loadings may be necessary because of enhanced LPG-amine contact and tower hydraulics.
Operating Considerations The major operating considerations for amine units are maintaining the condition of the amine solution, minimizing losses and preventing hydrocarbon carryover to the sulfur plant. Solution cleanliness is achieved by 100 percent particulate filtration and a 10 to 20 percent slipstream filtration through a carbon bed absorber to remove hydrocarbons, foaming, and heat-stable salt precursors. Amine temperatures at the bottom of the regenerator should not exceed 126C. If high back-pressure from the Claus and TGCUs makes this difficult, the possibility of lowering the amine concentration or of a pumparound regenerator cooling system should be investigated. While the carbon bed absorber may remove some of the precursors that lead to heatstable salt formation, the HSS in the amine solution should not be allowed to exceed 10 percent of the amine concentration. Water washes at the top of the absorbers are an effective way to reduce amine losses, and excess water can be bled off at the reflux purge to the SWS. The rich amine separator drum is a three-phase separator with 20 to 30 minutes residence time provided to separate the hydrocarbons. Additional hydrocarbon skims also may be provided at the reflux accumulator and at the regenerator tower bottom surge chamber.
Economics The cost of an ARU is strongly dependent on the circulation and, to a lesser degree, the stripping steam (reboiler size) requirements. Full-flow particulate filtration and large carbon bed adsorbers increase capital cost, but are justified by significantly reduced operating costs and downtime.
SOUR WATER STRIPPING

Sour water in a refinery originates from using steam as a stripping medium in distillation or from reducing the hydrocarbon partial pressure in thermal or catalytic cracking. Also, some refinery units inject wash water to absorb corrosive compounds or salts that might cause plugging. This steam or water comes in contact with hydrocarbons containing H2S; sour water is the result. The NH3 present in sour water comes from the nitrogen in the crude oil or from ammonia injected into the crude fractionator to combat corrosion. In addition to H2S and NH3, sour water may contain phenols, cyanide, CO2, and even salts and acids. Process Description A conventional SWS design is illustrated in Fig. 11.1.6. The sour water passes through a flash/separation drum and/or tank to flash off dissolved gases and to remove hydrocarbon oils and solids. The stripper feed is then heated by exchange with the stripper

FIGURE 11.1.6
Conventional sour water stripper.
bottoms water. Steam is provided to the bottom of the stripper through a reboiler or by direct steam injection if the reboiler is out of service. The stripped H2S and NH3 vapors pass through a cooling/dehumidification section at the top of the stripper. A pumparound cooler removes the heat. The acid gases, plus the uncondensed water vapor, flow to the sulfur plant at a temperature of 82 to 93C. The stripped water is cooled by exchange with the feed and is further cooled by air or water, if necessary, before being reused or sent to a biological treating unit.
Process Chemistry The chemistry assumes that NH3 and H2S are present in the aqueous solution as ammonium hydrosulfide (NH4HS), which is the salt of a weak acid (H2S) and a weak base (NH4OH). The salt hydrolyzes in water to from free NH3 and H2S, which then exert a partial pressure and can be stripped. The aqueous phase equilibrium is NH4+ + HS H2S + NH3 Increasing the temperature shifts the equilibrium to the right, and makes it easier to strip out H2S and NH3. H2S is much less soluble and is therefore more easily stripped. When acidic components such as CO2 or CN are present, they replace HS in the above equations, and the NH3 becomes bound in solution as a salt such as (NH4)2CO3. The free NH3 formed by hydrolysis is small. Thus, the H2S removal is higher than predicted, while the NH3 removal is lower.
Process Variables Steam, fuel gas, and air are all possible media to strip the sour water. To meet stripped water specifications, steam normally is required and is almost exclusively used in refinery sour water treatment. A typical stripped water specification limits H2S to 1 to 10 wt ppm and NH3 to 30 to 200 wt ppm. Normally, it is the NH3 specification that governs the stripper design, since it is much more difficult to strip than H2S. Some stripper designs use caustic to free the bound ammonia, particularly when the feed has appreciable CO2 or cyanides. The presence of phenols and cyanides in the sour water also can have an impact on the number of strippers. Nonphenolic sour water strippers process sour water with H2S and

11.9
NH3 only. The stripped water is usually suitable for recycle to process units as injection wash water. Phenolic sour water contains phenols and other pollutants from catalytic crackers and cokers, and stripped water from phenolic sour water strippers is corrosive and may poison catalysts if used as injection wash water. In conventional single-stage strippers, an acid gas containing H2S and NH3 is produced. This means that the SRU must be designed for NH3 burning. An alternative is to use a twostage stripper (such as Chevrons WWT) that produces separate NH3 and H2S product streams. It is desirable to recycle as much of the stripped water as possible. Stripper water may be reused in the crude desalter, as makeup water for coker/cruder units, as wash water for the hydrotreaters, and occasionally, as cooling tower makeup water. The use of segregated strippers and the specifications of the stripped water determine the extent by which the stripped water can be reused.
Operating Considerations Major operating considerations for sour water strippers are the foul service and corrosive environment. Some reboilers may last only 6 months to a year without cleaning, and provision for direct steam injection is advisable. The use of pumparound cooling instead of overhead condensing reduces corrosion. Extreme care is needed in metallugy selection.
Economics The cost of sour water strippers is strongly dependent on the sour water flow. As would be expected, stripped water specifications and installed tankage capacity also affect the capital costs.
SULFUR RECOVERY
SRUs convert the H2S in the acid gas streams from the amine regeneration and SWS units into molten sulfur. Typically, a two- or three-stage Claus straight-through process recovers more than 92 percent of the H2S as elemental sulfur. Most refineries require sulfur recoveries greater than 98.5 percent, so the third Claus stage is operated below the sulfur dew point, it is replaced with a selective oxidation catalyst, such as Superclaus,* or a TGCU follows the Claus unit. It is becoming increasingly popular to degas the produced molten sulfur. Shell, Elf Aquitaine, and others offer proprietary processes that degas the molten sulfur to 10 to 20 wt ppm H2S. Process Description The Claus process, illustrated in Fig. 11.1.7 and photographed with a TGCU in Fig. 11.1.8, consists of a thermal recovery stage followed by two or three stages of catalytic recovery. In the thermal recovery zone, the acid gas is burned in a reaction furnace with the appropriate amount of air to combust approximately one-third the H2S plus all
*Trademark of Stork Comprimo.

FIGURE 11.1.7
Two-stage Claus SRU.
the hydrocarbons and ammonia in the acid gas feed. The SO2 from the combustion reacts with the uncombusted H2S to form elemental sulfur. The products of combustion are cooled in the waste heat boiler and thermal sulfur condenser. Steam is raised at the steam drum associated with the waste heat boiler. Typically, 60 percent or more of the sulfur is recovered in the thermal recovery section of the Claus unit. Following the thermal stage are two or three catalytic stages, each consisting of reheat (reheater), catalytic conversion (converter), and cooling with sulfur condensation. The sulfur is run down from each of the condensers into a sulfur pit, where optionally the sulfur is degassed. If the overall sulfur recovery requirement is between 96 and 99 percent, the last stage of the three-stage Claus unit can be replaced by a selective oxidation catalyst (such as Superclaus) or by a sub-dew-point reactor [such as Sulfreen* (Elf Aquitaine), CBA (Amoco), or MCRC (Delta-Catalytic)].
Process Chemistry H2S + 32O2SO2 + H2O (thermal) (thermal and catalytic) H2S + 12SO2 32S + H2O Process Variables Refineries generally require two or more Claus units to assure continued refinery unit operation during upsets, maintenance, or loss of one of the SRU. The choice between two or three is largely one of economics versus flexibility. Some Claus units can now be designed to use oxygen or enriched air when the other Claus unit is down so that only two Claus units are required. SWS acid gas contains ammonia unless a two-stage SWS is employed. This ammonia can significantly increase the size of the Claus unit and can cause Claus operating problems if the ammonia is not fully destroyed in the thermal reactor zone. The design of burners and the reactor furnace configuration are strongly dependent on whether the Claus unit must have ammonia-burning capabilities. If all of the acid gas is not sent to the burner, the amine acid gas should be water-washed to remove traces of ammonia. Replacing air with enriched air or oxygen significantly enhances the capacity of a Claus unit. This can be particularly attractive when a Claus unit is down or when an existing refinery needs to be revamped to handle higher sulfur capacity.
*Trademark of Elf Aquitaine.
REGENERATOR
HYDROGENERATION REACTOR
ABSORBER
REHEATER
WASTE HEAT BOILER
ACID GAS K.O. DRUM
INCINERATION STACK
CONVERTER
FIGURE 11.1.8
REACTION FURNACE
Claus unit and TGCU.
STEAM DRUM

Reheat may be accomplished by in-line burners (using amine acid gas or fuel gas), hot gas bypass, external heating by steam, etc. These methods vary in cost, reliability, and maintenance requirements. External heating is usually the preferred method, but often the available heat source may not be hot enough to achieve the required reheat temperatures, particularly during catalyst rejuvenation periods. The purpose of the Claus unit is to assist in achieving the environmentally mandated sulfur recovery requirement. Since the Claus unit often cannot do this alone, the design of the Claus unit (number of stages, selection of last stage between Claus, sub-dew-point and selective oxidation) has to be coupled with TGCU design when sub-dew-point or selective oxidation catalysis in the final SRU stage cannot meet the overall sulfur recovery requirements.
Operating Considerations Best operating results are achieved when feed flows and compositions are maintained constant. Additionally, hydrocarbon carryover to the Claus unit must be minimized. These objectives are met by designing features into the amine and SWS units, such as large rich amine flash drums, and by providing sour water tankage. When a unit is operated in the pure Claus mode, it is vital to keep the H2S/SO2 ratio in the tail gas at 2/1, since slight deviations cause significant loss in recovery. Superclaus units ahead of the Superclaus reactor should have a H2S/SO2 ratio of 10/1 or greater. Running Claus units at low turndown should be avoided because of instrumentation limits and greater corrosion potential.
Economics The cost of an SRU is strongly dependent on the sulfur capacity and the number of catalytic stages. Ammonia-burning capabilities and low H2S feed concentrations can significantly increase costs. The H2S/CO2 ratio in the feed also affects costs, although most refineries have a relatively rich aggregate acid gas feed. Degassing costs are almost totally dependent on sulfur capacity.
TAIL GAS CLEANUP

Overall sulfur recovery requirements at most refineries in the United States, Germany, etc., are higher than 99 percent, requiring that a TGCU follow the SRUs. The tail gas from the Claus unit contains H2S, SO2, CS2, S vapor and entrained S liquid. Most tail gas cleanup processes hydrogenate/hydrolyze the sulfur compounds to H2S, and then either recover or convert the H2S. The H2S recovery is usually by a selective amine. The H2S conversion may use a liquid redox or catalytic process. The most popular TGCU processes are the Shell Claus Offgas Treating/Beavon Sulfur Reduction-MDEA (SCOT/BSR-MDEA) units and their clones. These are representative of the H2S recovery processes and are capable of achieving overall recoveries of 99.9 percent of the sulfur in the acid gas to the SRUs.
Process Description Figure 11.1.9 illustrates a SCOT-type TGCU. (Some of the major equipment items also are visible in Fig. 11.1.8.) The tail gas from the Claus unit is heated in the hydrogen-

11.13
erator reactor to the hydrogenation bed inlet temperature by an in-line burner. Fuel gas is combusted substoichiometrically with steam to generate a reducing gas (H2, CO) and to heat the tail gas. In the reactor, all the sulfur compounds are converted to H2S according to the process chemistry described below. The reactor products are cooled to generate steam, then further cooled to 38 to 49C by a circulating quench water system. A bleed stream from the circulating quench water is sent to the SWS. The gas from the quench tower overhead is then sent to an amine unit. (The absorber and regenerator of the amine section of the TGCU can be seen in Fig. 11.1.8.) The amine is selective but otherwise the flowsheet is almost identical to that described in Chap. 2.2. In SCOT, the absorber operates at low pressure, and there are no hydrocarbons in the tail gas. Thus, a rich amine flash drum is not needed. The filtration of the amine is usually upstream of the regenerator.
Process Chemistry SO2 + 3H2 H2S + 2H2O COS + H2O H2S + CO2 CS2 + 2H2O 2H2S + CO2 Svap + H2 H2S Process Variables In the Claus unit burner, typically 5 to 6 percent of the H2S dissociates into H2 and sulfur. Depending on the Claus sulfur recovery, it may not be necessary to generate additional reducing gas, enabling the tail gas to be heated externally to hydrogenation bed inlet temperature requirements. Alternatively, a makeup H2 stream, available elsewhere in the refinery, may negate the need for reducing gas. The amine is usually a selective amine. Its selection depends on the H2S specification from the absorber. If the H2S specification is 10 vol ppm, the absorber vent gas can be vented, thereby saving considerable fuel gas at the incinerator. However, achieving low H2S levels requires a proprietary formulated MDEA, since generic MDEA will reduce H2S to only 150 to 250 vol ppm depending on MDEA temperature. More recently, some refineries have had to meet total sulfur content in the absorber treated gas. This is not usually a problem when the CO2 in the Claus tail gas is low, but
FIGURE 11.1.9
SCOT/BSR-MDEA (or clone) TGCU.

equilibrium constraints can cause COS levels from the hydrogenation reactor to be a problem when CO2 levels are high. In such cases, a COS hydrolysis reactor downstream of the reactor effluent cooler may be warranted.
Operating Considerations When the hydrogenation/hydrolysis catalyst loses activity, there is a danger of SO2 breakthrough. This can cause corrosion in the circulating quench water circuit, and the SO2 poisons the amine. Catalyst activity and pH levels of the circulating water should be carefully monitored. Maintenance of the MDEA solution is imperative. It is best to filter the MDEA upstream of the regenerator.
Economics The cost of a SCOT or BSR/MDEA or equivalent clone is usually 75 to 100 percent of the parent Claus unit without degassing.

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Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

SULFUR COMPOUND EXTRACTION AND SWEETENING

SULFUR COMPOUND EXTRACTION AND SWEETENING

Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

KBR REFINERY SULFUR MANAGEMENT

KBR REFINERY SULFUR MANAGEMENT 11.4

Recycle gas amine treating.

KBR REFINERY SULFUR MANAGEMENT

Fuel gas/LPG amine treating.

REGENERATOR FLASH GAS Scrubber LEAN AMINE TANK

RICH AMINE Flash Drum

LEAN AMINE COOLERS

AMINE FILLER LEAN/RICH AMINE EXCHANGERS

Amine regeneration unit.

KBR REFINERY SULFUR MANAGEMENT 11.6

Amine regeneration unit.

KBR REFINERY SULFUR MANAGEMENT

SOUR WATER STRIPPING

KBR REFINERY SULFUR MANAGEMENT 11.8

Conventional sour water stripper.

KBR REFINERY SULFUR MANAGEMENT

KBR REFINERY SULFUR MANAGEMENT 11.10

Two-stage Claus SRU.

KBR REFINERY SULFUR MANAGEMENT

WASTE HEAT BOILER

ACID GAS K.O. DRUM

Claus unit and TGCU.

KBR REFINERY SULFUR MANAGEMENT 11.12

TAIL GAS CLEANUP

KBR REFINERY SULFUR MANAGEMENT

SCOT/BSR-MDEA (or clone) TGCU.

KBR REFINERY SULFUR MANAGEMENT 11.14

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