SULPHUR RECOVERY

PROCESS
SUDHANYA CHOUDHURI
 SULPHUR RECOVERY
WHY ?

1. Sulphur is present in the crude oil in the form

of mercaptans and sulphides. This sulphur is
carried over to all the distillation products.

2. Sulphur is a major pollutant in all the fuels.

3. Sulphur is a poison to catalyst in all the

downstream units.

4. Statutory requirement of the government .

 Goals
Primarily environmental

• government regulations
• emissions, opacity, odour,
• Air , ground level concentration
• Safety & hazards
• increased Sx production
 Euro Norms : Fuel Specification
III IV
1993 1998 2000 2005

MS
S ,%wt 0.05 0.05 0.015 0.005
Benzene (%vol.) 5 5 1 1
Aromatics (%vol.) - - 42 35
Olefins (%vol.) - - 18 ?

HSD
S,%wt 0.20 0.05 0.035 0.005
Cetane 49 49 51 53?
Dist. 0C (T 95) 370 370 360 340
Poly. Arom (% vol) -- - 11 11
 Challenges
Technology as a driver
Technology should be :
 Simple, flexible and reliable.
 Safe
 Environment Friendly.
 Energy Efficient.
 Ease in Adaptability.
 Cost Effective.
 H2S REMOVAL

• ABSORPTION BY REGENERABLE
SOLVENTS

• ADSORPTION ON SOLID BED

• DIRECT CONVERSION TO SULFUR

 Sulphur recovery schematic
Sweet Stack
gas Gas SO2

Gas Modified Tail gas

Incineration
sweetening Claus plant clean-up
Sour Gas

Sour Water
Sour water Sulphur Sulphur
stripping Degassing Forming

Sweet
Water
 Typical Recovery System
Plant Feed Gas
Acid Gas Removal Sweet
Gas Treat Gas

Acid Gas {H2S + CO2}

H2S Recycle

Tail Stack
Claus S.R. Gas Incinerator
gas
Treat

Sulphur
 Claus plant efficiency
• Typical sulfur recovery efficiencies for Claus
plants are 90% to 96% for a two-stage plant
and 95% to 98% for a three-stage plant.

• Most countries require a sulfur recovery

efficiency in the range of 98.0% to >99.9%.

• Therefore, the sulfur constituents in the

Claus tail-gas must be reduced further.
 SRU BLOCK
A typical “Sulpher Recovery Unit” complex
consists of process units like:

• Amine regeneration Unit (ARU)

• Sour Water Stripping Unit (SWS)
• Sulpher Recovery Unit (SRU)
• Tail Gas Treating Unit (TGTU)
 AMINE REGENERATION UNIT

• Simple to understand and operate.

• Difficult to operate well.
• Easiest to mess up.
• The principal aim of operating an Amine
Unit well is to keep the circulating amine
clean. Easier said than done.
 ADSORPTION

• VERY STRONG ADSORPTION OF H2O, CO2,

H2S, SO2, NH3, COS, RSH

• SELETIVE REMOVAL OF H2S IN PRESENCE

OF CO2 POSSIBLE

• ECONOMICAL FOR LOW TO MEDIUM FLOW

GAS CAPACITY & FOR GASES WITH LOW
H2S CONCENTRATION
NON-REGENERABLE ADSORBENTS

350oC
ZnO + H2S ZnS + H2O
(granular form
in packed fixed
bed)
# (H2S LEVEL IN TREATED GAS <0.1 ppm)

REGENERABLE ADSORBENTS
• MOLECULAR SIEVES
( HALDER TOPSØE )

• ZINC TITANATE
Zn-titanate + H2S SULFIDED
SORBENT
air regn.

SORBENT + SRU
SO2
 AMINE ABSORPTION & REGENERATION:
FLOW SCHEME
SWEET FUEL GAS TO
REFINERY NET ACID GAS
V--1

TO SRU

V--2

AMINE AMINE
ABSORBER REGENERATOR

FRESH HX-2

T-1
AMINE
MAKEUP T-2

SOUR FUEL GAS

HX-1

EX UNITS
 Diagram of Amine Regeneration Unit
1.05 KG/CM2
REGENERATOR TO FLARE
92 OC AIR CONDENSER ACID GAS
RICH AMINE
0.95 KG/CM2
FROM UNITS TO SRU

55 OC
104 OC 59 C
O CW

AMINE REGENERATOR COLUMN

RICH SOLVENT

REGENERATOR
REFLUX DRUM
FLASH DRUM
RICH/LEAN REGENERATOR
CW SOLVENT EXCH TRIM CONDENSER
40 OC

59 OC LEAN SOLVENT 72 OC
LEAN SOLVENT AIR COOLER REGENERATOR
TRIM COOLER REFLUX PUMP

127 OC
50 OC RICH AMINE PUMP
LP STEAM
REGENERATOR
REBOILERS

AMINE LP CONDENSATE
127 OC 126 OC
CIRCULATION
AMINE TANK REGENERATOR 8.0 KG/CM2 40 OC
FILTER (785 M3) BOTTOMS PUMP

LEAN SOLVENT LEAN SOLVENT

PUMP TO UNITS
AMINE UNITS: CRITICAL PARAMETERS

• High corrosion / erosion rates.

• Pick up of iron particulates from piping.
• Monitor amine colour.
Good amine is translucent white. Gray or black amine is Trouble.
• Amine degrades in the presence of oxygen.
• Hydrocarbon condensation in Amine solutions
makes it prone to foaming.
• Amine carryover in acid gas spells doom for the
SRU.
 Amine Unit Troubleshooting

• Respect what is in the pipeline. H2S loaded

amine can blind you.
• Take care not to get drenched in amine.
• Monitoring is a never ending exercise. It must be
done every day, .
• Amine colour & strength are the two most
important parameters - must monitor.
• As amine degrades, it starts to foam at high
temperatures.
 Amine Unit Troubleshooting

• As amine colour begins to deepen, increase the

rate of filtration. The normal rate is 10% of amine
circulation rate. Increase it to 20% for 48 hours.
• Drain oil regularly from the rich amine surge
vessel.
• Maintain gas inlet temperature to absorber at least
6-8 Deg C lower than the amine temperature. This
will prevent hydrocarbon condensation in the
amine.
 Amine Unit Troubleshooting

• Remember, no one knows how to dispose of

amine solutions. The art of operating an Amine
Unit is in keeping the amine clean.
• Foaming in Amine regenerators - To diagnose
foaming, read the column bottom and reflux drum
level indications. If both go high simultaneously,
it’s foaming for certain. Shut down the SRU
immediately. Drain out all the oil from the system.
 MDEA vis- a- vis DEA

1. Around 15 to 20 % capacity increase if existing DEA based plant is converted

to MDEA
2.  Around 15 to 20 % less energy cost compared to DEA system due to
low reboiler duty as less energy is required to break the bond between
acid gas and MDEA.
3.  Around 15 to 20 % less energy required for pumping as MDEA
concentration upto 50 wt % can be kept compared to 25 wt % limitation in
case of DEA, thus circulation rate can be reduced and pumping
requirements will also be reduced accordingly.
4.  Higher acid gas loading in rich amine (0.45 to 0.5 m/m in MDEA system)
compared to 0.35 to 0.4 m/m in DEA system. Lean amine loading is
0.004 to 0.01 m/m in MDEA system as compared to 0.05 to 0.07 m/m in
DEA system.
5.  Selective absorption of H2S over CO2 in MDEA is better compared to
DEA.
 SOUR WATER STRIPPER UNIT

• STRIPS OUT H2S AND NH3 FROM

SOUR WATER GENERATED IN
PROCESS UNITS.

• SIMPLE UNITS TO UNDERSTAND AND

OPERATE. USUALLY OPERATE WELL.
 SOUR WATER STRIPPER: SCHEMATIC
SOUR GAS TO
SRU

CIRCULATING
REFLUX

REBOIL
STRIPPED SOUR STEAM IN
WATER TO ETP

SOUR WATER
FEED CONDENSATE
OUT
 Diagram of Refinery Sour Water Stripper Unit TO FLARE
90 OC
0.9 KG/CM 2
SOUR GAS

SOUR WATER
FROM UNITS TO SRU
65 OC

REFINERY SOUR WATER STRIPPER COLUMN

REFINERY STRIPPER
CR AIR COOLER
SOUR WATER
92.4 OC
SURGE DRUM
FEED/BOTTOMS
EXCHANGER
90 OC
71.6 C
O

REFINERY STRIPPER
CR PUMP
40 OC
123.6 OC
123.8 OC
SWS FEED PUMPS LP STEAM

STRIPPED REFINERY
WATER STRIPPER
STRIPPED WATER REBOILER
TO ETP
40 OC AIR COOLER

LP CONDENSATE
123.8 OC LP CONDENSATE
STRIPPED WATER
TRIM COOLER
REFINERY STRIPPER
STRIPPED WATER TO CDU/DCU BOTTOM PUMP
 ESSENTIAL COMPONENTS
OF SOUR WATER STRIPPER
SOUR WATER FLASH DRUM
FOR REMOVAL OF DISSOLVED HYDROCARBONS FROM
SOUR WATER
FLASHING (FOR VOLATILE HCs)
SETTLING (FOR HIGHER HCs)

SOUR WATER STORAGE

FOR HCs THAT ARE EMULSIFIED AND REQUIRE DAYS TO
SETTLE
FEED/BOTTOMS EXCHANGE AND STRIPPED
WATER COOLING
FOR ENERGY RECOVERY
 ESSENTIAL COMPONENTS
OF SOUR WATER STRIPPER
• SOUR WATER STRIPPER
– 40 TO 60 TRAYS
– STAINLESS STEEL COLOUMN FOR CHLORIDE LEVELS
WITHIN ACCEPTABLE LIMITS
– NO PACKING
• STRIPPER BOILER
ONCE THROUGH REBOILER
STEAM AT 50 TO 150 psig
• STRIPPER OVERHEAD CONDENSER
– ALUMINIUM OR TITANIUM TUBES
– PUMP AROUND STRIPPER WITH 4 TO 10 ADDITIONAL
TRAYS
 CW Diagram of Hydroprocessing Sour Water Stripper Unit TO FLARE
90 OC
SOUR HYDROPROCESSING 0.9 KG/CM 2
WATER FEED MIX COOLER SOUR GAS
FROM
HCU/ SOUR WATER
DHDT SURGE DRUM TO SRU
65 OC

HYDROPROCESSING SOUR WATER STRIPPER COLUMN

40 OC
HYDROPROCESSING
STRIPPER
CR AIR COOLER
94.5 OC

FEED/BOTTOMS
EXCHANGER
90 OC
65.5 OC
HYDROPROCESSING
STRIPPER
123.6 OC CR PUMP
123.8 OC
40 OC
SWS FEED PUMPS LP STEAM
SOUR WATER
STORAGE TANKS
HYDROPROCESSING
STRIPPED WATER CW STRIPPER REBOILER
TO ETP

HYDROPROCESSING STRIPPED
LP CONDENSATE
WATER COOLER 123.8 OC

STRIPPED WATER
TO HCU/DHDT
 Typical Acid Gas Feed Composition ARU

Component Mole %
Hydrogen 0.04-.06
Water 7.5- 8.5
Hydrogen Sulphide 86-92
Hydrocarbons 0.01- .03

Typical Sour Gas Feed Composition

SWS
Component Mole %
Water 40-43
Hydrogen Sulphide 15-171
Ammonia 38-42
Hydrocarbons 1-2
 Diagram of Sulphur Recovery Unit
HP STEAM (42 Kg/cm2)

1400 OC LP STEAM
ACID GAS KOD

322 OC 180 OC
REACTION FURNACE WASTE HEAT BOILER

BFW BFW
IST CONDENSER
SOUR GAS KOD

232 OC 208 OC 2ND CONVERTER

IST CONVERTER
TAIL GAS
TO TGTU
132 OC
HP STEAM
HP STEAM
AIR BLOWER 2ND REHEATER
IST REHEATER
LP STEAM
TO INCINERATOR 287 OC HEATED BFW
173 OC
233 OC
DEGASSING
CONTACTOR
2ND CONDENSER BFW BFW
FINAL CONDENSER

BFW

DEGASSED SULPHUR TO YARD

SULPHUR PIT
REACTION
FURNACE
 CLAUS PROCESS – 1st Stage
Reaction Furnace: Expectations

• Oxidize all hydrocarbons to CO2 and

water.
• Oxidize all NH3 to Nitrogen.
• Convert 1/3rd of the H2S to SO2.
 Reaction furnace

Function

• Burn 1/3 of the H2S

• Produce sulphur directly

• Destroy feed contaminants

Reaction Furnace with Wasteheat Exchanger
(Modified Claus Process)

Air Main Process

Stream Steam HGBP
Start-up Refractory
Fuel Gas lining

2nd pass tubes

1st pass tubes

Acid Gas
Ceramic
Burner
Ferrule
Saddle Sulphur
drain BFW
 Wasteheat Exchanger

Functions

• Cool process stream

• Recover energy in useful form

Feed Impurities
• Inert gases

• CO2

• hydrocarbon

• ammonia
 Actual reactants and products

Modified Claus Process Reaction Furnace

HO
RS CO
Steam
2

H C
HC O2 N
NH 2 H
ydr 2 NH
oca
rbo 3
n
H2S
Free Flame H2S SO2 H2O
Reaction Furnace S2 S3
and N2 Ar CO2 S4 S5 S6
Wasteheat S7 S8
O2 Exchanger COS CS2 H2 CO

n ts
a O
l l ut H 2
Po CO 2
r BFW
A
N2
Catalytic
Converters
 Claus Process
Patented 1884-06-30
Carl Friedrich Claus

• Chemist of Mark Lane, London.

• British Patent No. 5958
 Claus Reaction
3 H2S + 3/2 O2 3/x Sx + 3H2O

• 200 - 3500C (392 - 6620F) - catalytic

• energy release 620 kJ (588 BTU)
 Claus Process
H2S O2

170 - 3500C
Catalytic Converter (340 - 6600F)

130 - 2000C
LP Steam Sulphur Condenser (270 - 3900F)

S liquid
Further Treatment
 Claus Reactions
Modified
3 H2S + 3/2 O2

SO2 + 2 H2S + H2O + 520 kj

3/x Sx + 2 H2O + 93 kj
 Modified-Claus Process
H2S O2

Free flame reactor

925-12500C
HP steam Wasteheat exchanger (1700-23000F)

170-3500C
Catalytic converter (340-6600F)

LP steam Sulphur condenser 130-2000C

S liquid (270-3900F)

Further treatment
 SRU Reactor Details

1200 mm
3600 mm

150 mm
6100 mm

POROCEL MAXCEL 727 DESIGN PR DROP 0.035 KG/CM2

R-1LINED BY A 65 MM REFRACTORY
POROCEL DUROCEL 242 LAYER WHEREAS R- 2 IS NOT.
Typical Claus Plant Converter
(Two beds in one vessel)

Gas in Gas in
Partition Inlet
Manway plate gas
deflecto
Catalyst bed r

Bed 1 Bed 2

IP
IP

Catalyst Support Screens and

support layer Gas beam grating Gas out
out
Thermowell
IP = Inspection port
 Catalytic Converters

Functions

• catalyze H2S : SO2 reaction

• catalyze COS and CS2 reactions
 Catalytic Reactions

2H2S + SO2 3/x Sx + 2H2O

COS + H2O H2S + CO2

CS2 + 2H2O 2 H2S + CO2

EQUILIBRIUM vs. KINETICS
• KINETICS IS FAVORED AT HIGH TEMP.
SECOND STEP OF THE REACTION TAKES PLACE
RAPIDLY ABOVE 1200 OC.

• EQUILIBRIUM IS FAVORED AT LOW TEMP.

TO ENHANCE RECOVERY, REACTION IS CARRIED OUT
AT LOW TEMPERATURE OVER CATALYST BEDS.

• CATALYTIC CONVERSION
USE OF CATALYST RETARDS THE REVERSE REACTION
IN THE SECOND STEP AND PUSH REACTION IN
FORWARD DIRECTION.
 Modified Claus Reactions

Reactants H2S + 3/2 O2

T = 925 TO 1200 0C

Thermal

Intermediates 2H2S + SO2 + H2O

T = 170 to 370 0C
Catalytic

Products 3/x Sx + 3H2O

 Sulphur Condenser

Steam
Process
Process gas out
gas in Vapour Demister &
space dry pipe Baffle
plate Demister
pad

Tubesheet Tube
Boiler Rundown to
feedwater seal pot
Saddle
 Sulphur Condenser

Functions:

• condense sulphur to liquid phase

• separate liquid from the process gas
stream
 Sulphur Condenser

Operating Limits:

• above sulphur melting / freezing

point
– 1190C (2460F)

• below inlet sulphur dewpoint

– depends on sulphur vapour content
 Sulphur Condensers

• vessel slope
• mass velocity
• seamless 10BWG carbon steel tubes
• mist eliminator
• rundown and seal pot
TAIL GAS
CLEAN-UP
 Different sulphur recovery processes normally
followed after the thermal reaction ( 1st Stage)

For achieving 99% (wt) sulphur recovery

• SuperClaus
• Maximum Claus Recovery Concept (MCRC)
• CBA

For achieving 99.9 % (wt) sulphur recovery

• SCOT / ARCO (Tail Gas Treating unit)
 Alternatives

Sub-dewpoint processes
• capable of 99.55
Commercial technologies
• Sulfreen, CBA, MCRC, Clinsulf, IFP
(Clauspol), Crystausulf
Incineration
 INCINERATION - OVERVIEW

PROCESS HP
GAS STEAM

FUEL
GAS

INCINERATOR
STACK
BOILER FEED
WATER
AIR
PROCESS
GAS

FUEL TIC T

GAS

FIC INCINERATOR

20% 10%
80%
STAGED
AIR
AIR PRIMARY SECONDARY
AIR AIR
Typical Operating Conditions

• Incinerator temperature 600-7500C

(1100-13800F)
• stack exit temperature 5400C
(10000F)
– may be regulated
• “excess” oxygen : 2 to 6+ mole% in
stack
 SULPHUR
DEGASSING
CHEMISTRY OF LIQUID SULPHUR
DEGASSING
Gas Phase

Air Air

Air H2S

H2SX+1 H2S + SX

Liquid Phase
Thank