NOVEL APPROACH FOR ENHANCED H2S RECOVERY FROM SOUR WATER STRIPPERS

Mukesh Kumar Sharma Deputy Manager Indian Oil Corporation Limited (Process Design Engineering Group) New Delhi-110003, India Tel: +91-9871079994, +91-120-2448941 e-mail: sharmamk2@iocl.co.in

Ashis Nag General Manager Indian Oil Corporation Limited (Process Design Engineering Group) New Delhi-110003, India Tel: +91-9999689805, +91-120-2448916 e-mail: naga@iocl.co.in

ABSTRACT
This paper describes a unique process for enhanced recovery of H2S from the Sour Water of Refinery Hydrotreaters by a simple and efficient design.

NOVEL APPROACH FOR ENHANCED H2S RECOVERY FROM SOUR WATER STRIPPERS
Mukesh Kumar Sharma, Indian Oil Corporation Limited, India Ashis Nag, Indian Oil Corporation Limited, New Delhi, India

INTRODUCTION
Stringent environmental regulations emphasize controlling the amount of H2S/SO2 emission, in turn necessitates higher recovery of H2S from sour water in sour water stripper (SWS) unit designs. Usually some amount of H2S is lost along with vent gases of feed stabilization tank of SWS unit. This paper describes a unique process design of SWS to arrest the loss of H2S and recover the same through simple and safe design. Typically the feed stabilization tanks are designed according to API-650/620 to operate at a low pressure of 150-200 mmwc (g). At this pressure considerable amount of hydrogen sulfide (H2S) gets released from the tank due to its high vapor pressure. Traditionally, these vent gases from the tank are routed to the incinerator or stack of sulphur recovery units and are lost. The quantity of the un-recovered acid gas from the feed tank is around 10 % of the sour water feed H2S (depending on operating conditions). Some of the licensors utilize steam jet ejectors on the feed stabilization tank to suck these gases from the tank and recover H2S after employing a small amine scrubber downstream of the ejector with precise tank pressure control system. In such designs, steam is required as a continuous utility for the operation of ejectors and will need a delicate pressure control of the tank, operating at very low pressure. Recently, Process Design Engineering Group of Indian Oil Corporation Limited has developed a new and safe design process called Super Sour for one of its refinery installing a new sour water stripper plant, that ensures minimum H2S loss from the unit and meets the environmental regulations. This process employs installation of an additional hot feed flash drum upstream of cold feed surge drum. The H2S rich vapors from hot flash drum is routed to a small amine scrubber to absorb the liberated H2S. The H2S lean gas containing primarily hydrocarbons is then routed to incinerator of the sulphur recovery unit. The absorbed H2S in rich amine is recovered in the amine regenerator and is fed to the sulphur unit for converting it to sulphur. Liquid hydrocarbon will continue to be separated in cold feed surge drum located downstream to the hot flash drum. The purpose of the hot flash drum is to liberate enough H2S from the feed sour water so that when the same is cooled and routed to feed stabilization tank operating at almost atmospheric pressure, no H2S is lost from the tank. This process does not involve any additional continuous utility consumption (i.e. ejector steam) and precise suction pressure control scheme for the tank-ejector system. This will offer an intrinsically safe, simple and efficient solution to arrest the loss of H2S and recover the same from feed stabilization tank.

BACKGROUND
Refineries that process crudes containing sulfur will liberate the sulfur in various unit operations as hydrogen sulfide. Gas that contains hydrogen sulfide is called sour gas, and water that contains dissolved hydrogen sulfide is called sour water. Additionally sour water may contain other impurities, such as ammonia, phenol, Carbon dioxide and cyanides. Sour water is produced from most of the refinery process units such as atmospheric & vacuum distillation units, hydrotreating units, hydrocrackers, steam crackers, fluid catalytic cracking (FCC) units. Concentrations of both hydrogen sulfide and ammonia contaminants are highest in sour water generated from hydrotreating, hydrocracking and FCC units. Reuse or disposal of such sour water containing hydrogen sulfide, ammonia, phenol & cyanides requires removal of these contaminants from the water by the stripping process. The typical stripping process (Figure 1.0) uses steam at the bottom of the stripper through a reboiler to force both the dissolved hydrogen sulfide (H2S) and ammonia (NH3) out of the water into the gas phase for recovery of H2S in a sulfur recovery unit (SRU). The stripped water is usually reused as process water in other parts of the refinery units or otherwise sent to the Wastewater Treatment Plant for further treatment before reutilization.
SOUR GAS TO SRU SOUR WATER FLASHED GAS TANK VENT GASES

FLASH DRUM STRIPPER FEED TANK PUMP AROUND COOLER

HYDROCARBONS

REBOILER

STRIPPED WATER FOR REUTILIZATION

HEAT EXCHANGER

Figure 1.0 (Conventional Sour Water Stripping Unit )

THE CONVENTIONAL PROCESS OF STRIPPING A typical conventional SWS design is illustrated in Figure 1.0. Prior to the stripper tower, sour water feed is first pumped into the flash drum, which has two purposes: (1) to remove hydrocarbon vapors and (2) to remove hydrocarbon liquids. The flash drum is typically operates at low pressure (~0.7-1.0 kg/cm2g) to flash off the lighter hydrocarbons. The flashed vapors are routed to a low-pressure system such as stripper column overhead, incinerator stack of a sulfur recovery unit after burning or acid flare. The liquid hydrocarbons are separated in the flash drum by gravity separation into the drum's hydrocarbon collection compartment. Sour water is then pumped to feed stabilization tank that is used to provide adequate residence time for additional hydrocarbon removal and for minimizing feed composition fluctuations as sour water is produced from different sources in a refinery. Significant composition fluctuations cause poor stripping operation in the tower, resulting in either not consistently meeting product specification or wasting steam by over stripping. The constant feed composition & flow rate from the feed stabilization tank enables better control of the stripper tower and consistent stripped sour water quality. Sour water from the stabilization tank is heated in a feed/bottom heat exchanger by hotstripped water from the stripper bottoms and fed to the tower as feed. As the sour water flows down the tower, hydrogen sulfide and ammonia are stripped off by steam or reboiled vapor from the bottom of the tower. If live steam is used as stripping agent, this will add more water to the tower. Normally low-pressure steam is used in the bottom reboiler to generate the vapors in the tower operating in the range of 0.7 1.2 kg/cm2g top pressure. Hydrogen sulphide, ammonia and steam rise to the tower cooling section, which is controlled at 90oC by pumped around cooler at the top of the tower. Low overhead temperatures below 800C can cause problems due to formation of ammonium salts that may plug process lines. Sour gases containing hydrogen sulfide and ammonia from the top of the stripping tower are routed to the Sulphur Recovery Unit. THE PROBLEM DEFINITION Gujarat Refinery of Indian Oil Corporation limited was installing a new sour water stripper unit as a part of Residue Up Gradation Project in the state of Gujarat, India. Currently the refinery is operating its four old sour water-striping units based on the convectional striping process designs. The process objective of new sour water stripper unit coming under residue up-gradation project was to treat the sour water generated from the Diesel Hydrodesulphurization unit (DHDT), VGO HDT and ISOM unit for removal of hydrogen sulphide (H2S) & ammonia (NH3) to meet stripped water specification below 50 ppmw H2S and NH3. The new unit was to be designed to handle total sour water feed rate of 57402 kg/hr with composition as summarized in the tables (Table 1.0 & Table 2.0) below:

Table1.0. Operating condition of feed to Sour Water Stripper Unit S.N Parameters Unit Value 0 1 Temperature C 55.0 2 Pressure Kg/cm2g 5.0 3 Vapor Fraction 0.0 4 Mol Wt 18.35 Table2.0. Feed Composition of Sour Water Stripper Components Mass Flow Rate Wt% Kg/hr NH3 1058.10 1.84 H2S 2348.60 4.09 Water 53995.30 94.07 Total 57402.00 100.00

S.N 1 2 3

As the Gujarat Refinery is already operating with four conventional units of sour water striping process, the same was considered for the initial design of the new stripper. Figure 2.0 describes the schematic flow diagram of initial design configuration of sour water stripper unit for Gujarat Refinery (as per traditional configuration)
T P 550C 5.0Kg/cm2g

WATER COOLER FLASHED GAS TO STRIPPER OVHD

T P

SOUR GAS TO SRU

900C 1.1 Kg/cm2(g)

SOUR WATER 1 FEED

5 3
T P 400C 1.1 Kg/cm2g

VENT GASES TO SRU INCINERATOR STACK 4

T 400C P 150 mmH20(g)

FLASH DRUM (COLD)

STRIPPER PUMP AROUND COOLER FEED TANK

HYDROCARBONS

T P

400C 8.0 Kg/cm2(g)

T P

750C 15 Kg/cm2(g) T P

REBOILER
126 C 1.4 Kg/cm2(g)
0

STRIPPED WATER FOR REUTILIZATION 6 WATER COOLER

HEAT EXCHANGER

Figure 2.0 (Conventional Sour Water Stripping Unit at Gujarat Refinery)

THE PROBLEM ENVISAGED IN ADOPTION OF CONVENTIONAL DESIGN In this design, the sour water feed to unit is received in the flash drum after cooling from 550C to 400C. The feed is cooled to reduce the vapor pressure of sour water to minimize H2S loss from storage tank. The flash drum is floated with stripper column overhead, which is operating at pressure of 1.1 kg/cm2g. After flashing off hydrocarbon vapors in the flash drum, feed enters to feed stabilization tank operating at almost atmospheric pressure condition (i.e. at 150 mmwc (g) pressure). The tank is designed according to API-650. At this low pressure, considerable amount of H2S gets released from the storage tank due to its high vapor pressure. The vent gases from the tank are routed to incinerator of Sulfur Recovery Unit and are lost. The loss is around 7.5% of the feed H2S as shown in Table no 3.0. Environmental regulations do not allow the emission of these vent gases containing hydrogen sulfide to incinerator stack or atmosphere as the same leads to higher emission of H2S /SO2. Table3.0 Stream summary of Conventional Sour Water Stripper Unit (Simulated Results)
S.N Stream No. 1 Feed 3 Flashed Gas from Cold Flash drum 40.0 1.1 4 Vent Gas from Tank 40.0 0.015 5 Sour Gas from Stripper to SRU 90.0 1.1 6 Stripped Water from Sour water Unit 40.0 8.0

1 2

3 4 5

Temperature Pressure Component Flow Rate NH3 H2S H2O Total

C Kg/cm2g

55.0 5.0

Kg/hr Kg/hr Kg/hr

1058.10 2348.60 53995.3 57402.0

0.122 45.0 0.854 45.976

0.19 178.20 6.80 185.19

1056.79 2124.4 1300 4481.19

<50 ppmw <50ppmw 52687.65 52689.65

A NEW DESIGN CONFIGURATION OF SOUR WATER STRIPPER TO ARREST THE H2S LOSS FROM FEED TANK Process Design Engineering Group of Indian Oil Corporation Limited has developed a new process design configuration called Super Sour for sour water stripping. This process ensures minimum or no H2S loss from the unit resulting in enhanced recovery of H2S compared to the traditional designs. This process (as shown in Figure 3.0) employs installation of an additional small diameter hot feed flash drum (essentially, a typical vapor-liquid separator) upstream of cold feed surge drum. The purpose of the hot flash drum is to liberate enough H2S from the feed sour water, so that, when the same is cooled and routed to feed stabilization tank (operating at almost atmospheric pressure) will not bleed any H2S from the tank and resulting in no loss of H2S from the tank. In this design, the hot flash drum is kept at around 60 0C by heating the sour water feed with hot-stripped water coming from outlet of feed/bottom exchanger. This requires no additional hot utility. The H2S rich vapors from hot flash drum is routed to a small amine scrubber to

absorb the liberated H2S. The lean gas from absorber containing primarily hydrocarbons is then routed to incinerator of the Sulphur Recovery unit. The absorbed H2S in rich amine is recovered in the amine regenerator and is fed to the sulphur unit for converting it to sulphur. Flashed feed from hot drum is cooled to 400 C before being routed to the cold feed surge drum for effective separation of hydrocarbon oil from water. This also reduces the vapor pressure of sour water. After separation of liquid hydrocarbon in cold feed surge drum, sour water is routed to the stripper tower through feed stabilization tank. Cold surge drum & feed tank pressure is maintained by the nitrogen make-up.
TO SRU INCINERATOR
T P 550C 5.0Kg/cm2g

LEAN AMINE SLIP STREAM Amine Scrubber

T 600C

SOUR WATER FEED

1 FEED HEATER

2 RICH AMINE TO REGENERATOR 5

T 900C

2 P 1.1 Kg/cm g

SOUR GAS TO SRU

HOT FLASH DRUM VENT GASES TO SRU INCINERATOR STACK 3 N2

T

WATER COOLER
T 400C

2 P 1.1 Kg/cm (g)

N2
400C 150 mmH20(g)

P 0.9 Kg/cm2g

COLD FLASH DRUM

STRIPPER FEED TANK HYDROCARBONS PUMP AROUND COOLER

400C

T P

750C 15 Kg/cm2(g) T 1260C

REBOILER

P 8.0 Kg/cm2(g)

STRIPPED WATER FOR 6 REUTILIZATION WATER COOLER

HOT STRIPPED WATER

1.4 Kg/cm2(g)

HEAT EXCHANGER

Figure 3.0 (Super Sour Unit Configuration)

The above design configuration results in no loss of H2S from feed stabilization tank, as it is evident from the stream summary given in Table no.4.0. The results shown in the Table 4.0 are simulated numbers. The electrolyte package of Chemstations, USA (Chemcad ver 6.1) was used to model and simulate the sour water stripper unit. At the elevated temperature of around 600C of hot flash drum, the ammonia (NH3) going to the gas phase from the hot drum will be very marginal (shown in the Stream no 2 of Table 4.0) due to its high solubility in water as compared to the H2S. Thus the NH3 build up in the amine regenerator due to this approach will be insignificant. However, a NH3 purge stream from the Amine overhead accumulator back to the cold surge drum of Sour water stripper is already considered in the process design to knock off NH3 build up, if any. Figure 4.0- may be referred for partial pressure of ammonia over aqueous solution.

Table4.0 Stream Summary of Super Sour Stripper Unit (Simulated Results) 3 4 5 6 S.N Stream No. 1 2
Feed Hot Flash Vapor To Amine Scrubber 59.1 1.1 Flashed Gas from Cold surge drum 40.0 1.1 Vent Gas from feed Tank 40.0 0.015 Sour Gas from Stripper to SRU 90.0 1.1 Stripped Water from Sour water Unit

1 2

1 2 3

Temperature Pressure Component Flow rate NH3 H2S H2O Total

C Kg/cm2g

55.0 5.0

40.0 8.0

Kg/hr Kg/hr Kg/hr

1058.10 2348.60 53995.3 57402.0

0.380 228.0 12.0 240.38

0 0 0 0

0 0 0 0

1056.72 2119.6 1300 4476.32

<50 ppmw <50ppmw 52683.3 52685.3

Figure 4.0 Chart Showing Partial Pressure of Ammonia over Aqueous Solution

In another alternate configuration developed, vapors from the hot flash drum containing primarily H2S may be directly routed to the stripper overhead line for recovery of sulphur along with the stripper overhead vapors. This configuration does not require installation of small amine scrubber column for absorbing the H2S from Hot flash drum vapors. Figure 5.0 shows the schematic flow diagram of this configuration. This configuration can be adopted where the likelihood of lighter hydrocarbon coming along with sour water is minimum or nil. Otherwise these hydrocarbons may find its way to sulphur recovery unit, which will be detrimental for the operation of sulphur recovery unit.

T P

550C 5.0Kg/cm2g

SOUR WATER FEED

1 FEED HEATER
T 600C

FLASHED GAS TO STRIPPER OVHD

SOUR GAS TO SRU

2 P 1.1 Kg/cm g

HOT FLASH DRUM VENT GASES TO SRU INCINERATOR STACK 3 N2

T

5
T 900C

WATER COOLER
T 400C

2 P 1.1 Kg/cm (g)

N2
400C 150 mmH20(g)

P 0.9 Kg/cm2g

COLD FLASH DRUM

STRIPPER FEED TANK HYDROCARBONS PUMP AROUND COOLER

400C

T P

750C 15 Kg/cm2(g) T 1260C

REBOILER

P 8.0 Kg/cm2(g)

STRIPPED WATER FOR REUTILIZATION 6 WATER COOLER

HOT STRIPPED WATER

1.4 Kg/cm2(g)

HEAT EXCHANGER

Figure 5.0 (Alternate Super Sour Unit Configuration)

The above Super Sour design configuration is implemented at Gujarat Refinery of Indian Oil Corporation limited in year 2010. OTHER AVAILABLE DESIGNS OF SOUR WATER STRIPPER TO ARREST THE H2S LOSS FROM FEED TANK Some of the licensors utilize steam jet ejectors on the feed stabilization tank to suck these gases from the tank and recover H2S after employing a small amine scrubber downstream of the ejector with precise tank pressure control system as shown in Figure 6.0. In such designs, steam is required as a continuous utility for the operation of ejectors and will need a delicate pressure control of the tank operating at very low pressure. Such tanks are designed in accordance with API-620.

TO SRU INCINERATOR
T P 550C 5.0Kg/cm2g

LEAN AMINE AMINE SCRUBBER SOUR GAS TO SRU

T 900C 1.1 Kg/cm2(g)

SOUR WATER FEED RICH AMINE WATER COOLER STEAM EJECTOR LP STEAM VENT GASES TO SRU INCINERATOR STACK
T 400C

400C

1.1 Kg/cm2g P

COLD FLASH DRUM

P 0.14 kg/cm2(g) PC

STRIPPER PUMP AROUND COOLER FEED TANK HYDROCARBONS

400C Kg/cm2(g) T P 1260C

REBOILER

P 8.0

STRIPPED WATER FOR REUTILIZATION

1.4 Kg/cm2(g)

WATER COOLER

HEAT EXCHANGER

Figure 6.0 (Other Available Design of Sour Water Stripping Unit)

CONCLUSION
The process Super Sour developed by Process Design Engineering Group of Indian Oil Corporation Limited is an intrinsically safe & simple solution to arrest the loss of H2S from feed stabilization tank and thus result in enhanced recovery of H2S (7-10 wt% of H2S in feed) from Sour Water Strippers. This design is more applicable for treating sour water from the refinery hydrotreaters and in other processes having high concentration of H2S in water.

References
1. Robert A. Meyers, Handbook of Petroleum Refining Processes, 2nd edition 2. Sour Water Design by Charts (Part-1, Part-2 & Part 3), Hydrocarbon processing, September 1991, October 1991 & November 1991.

AnnexureI
Economic&SocialImpactoftheinnovativedesignofSuperSourprocess
A) Costbenefitoftheprocessdesign Sourwaterstrippingunitcapacity H2SinFeed H2SrecoverybyconventionalSWSunit H2SrecoverybySuperSourDesign ThusadditionalH2Srecovery bySuperSourdesign

:57402.0kg/hr :2348.0kg/hr :2169kg/hr :2347kg/hr

:178kg/hr (7.5wt%onfeed) :167.5Kg/hr :167.5x8000/1000 :1340tonsperanum :Rs4000pertonsuphur :Rs4000x1340 :Rs53.6lacsperanum

AdditionalsulphurproductionfromSRU (Considering99.9%sulphurrecoveryinSRU) Additionalannualsulphurproduction (Considering8000hrsofoperationperyear) CurrentmarketpriceofSuphur Netannualsavingsduetoadditionalrecovery

 B) Social&Environmentalbenefitoftheinnovativedesign a. This design helps in meeting Stringent Environmental Regulation of SO2emission&reducesacidrain. b. Recovers additional H2S which is otherwise burnt in incineration and releasedtotheatmosphereintheformofSO2. c. Every ton sulphur recovered will eliminate 2 tons of SO2 going to atmosphere. Thus this design reduces around 2680 tons of SO2 emissionperannum. C) Acceptabilityofthedesign a. The super sour design was selected in Laurence Reid Gas Conditioning Conference as a novel design in year 2009. The paper was published & presented in Laurence Reid Gas Conditioning ConferenceheldinOklahoma,USA. b. The same design was also published in Oil & Gas Journal (May 09 issue). Oil & Gas Journal is a part of PenWell Petroleum Group, HoustonUSAsince1902. c. Any existing conventional SWS Unit can easily be retrofitted to SuperSourdesignConfiguration. d. The first grass root unit of Super Sour unit configuration has been put into operation in year 2010 at Gujarat refinery of Indian Oil CorporationLimited.
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