SULPHUR RECOVERY

UNIT
Unit No. 29

By:
Nishant Baranawal
TOPICS OF DISCUSSION

1 .Introduction to SRU
 Purpose
 Commercial Processes

2. SRU at BORL
 Sulphur Recovery Block
 Flow Description for SRU
 Process Chemistry
 SRU
 TGTU
 Process Variables
 Purpose of SRU

Overhead gases from SWS I , SWS II and ARU contain H2S &
NH3
 H2S can’t be disposed off to atmosphere
 Extremely dangerous, irritant at higher conc.
 Combustion gives SO2 which has a dispoasal limit
(CPCB standard -80 microgm/m3 of air)
 H2S can be treated to produce Sulphur
 NH3 also has a disposable limit of 100microgm/m3 of air(CPCB
standard)
 NH3 is burnt in SRU to N2
 Commercial Processes

Claus process - widely accepted for Sulphur recovery

Low recovery – Approx. 70%
Process was upgraded to increase recovery upto
~99%
Two prevailing commercial methods –
 Maximum Claus Recovery Concept
 Claus Section with extension to Tail gas treatment unit
 Sulphur Recovery Unit
At
Bharat Oman Refineries Ltd.
 Introduction to SRB

Sulphur Recovery Block contains following unit

 Sour Water Stripper – I
 Sour Water Stripper – II

 Amine Regeneration Unit

 Sulphur Recovery Unit

 Tail Gas Treating Unit

 SRB Block Flow Diagram
H2S RICH GAS FLUE GAS
(<10ppmH2S)
475.6 kg/hr
NH3 RICH GAS TAIL GAS
inci
1197 kg/hr
S.W.EX CDU FUEL GAS TGTU
S.W.ex DCU SWS I H2S
S.W.ex ARU Non Hydroprocessing
S.W.ex TGTU Design : 125 T/hr SOUR GAS SRU 2 Trains
90*C
2X180 TPD

14.5t/h 40*C
1670 kg/hr
H2S RICH

ACID GAS
STRIPPED WATER CONDENSATE B/D
GAS

(< 50 ppm H2S ) SWS LIQ. SULFUR

SOUR water Ex RICH AMINE 2X180 TPD
HCU/DHT FG & LPG ATU
SWS II HCU
ARU
Hydroprocessing
SOUR water
Design : 48 T/hr
H2S 481 ppm 470 T/hr
Ex NHT
LEAN AMINE OSBL 45*C
STRIPPED WATER ( <10 ppm H2S)
(< 50 ppm H2S ) 450 T/hr H S 2.5 ppm
2
 Sulphur Properties

Its melting point is 120oC so liq. S temp. in pipeline

should be above 120oC
Sulphur becomes very viscous at temp. above 155oC;
flow will be hampered
Auto ignition temp. is 184oC
Sulphur fires generate SO2
 SRU at BORL

Major Outlines
 Based on the TGTU technology developed by M/s ENGINEERS
INDIA LIMITED along with SINI, Italy
 Punj Loyd has taken contract on LSTK basis
 Capacity – 2*180 MT/day
 Combination of Claus process and the extension of Tail Gas Treatment
Unit
 Feed gas is a mix of acid gas from ARU and sour gas from SWS I & II
 SRU consists of one thermal reactor (Main Combustion Chamber) and
two catalytic Claus converters
Continued…

 Claus off gas which contains H2S, SO2 and traces amount of
COS and CS2, is subjected for hydrogenation reaction in
TGTU
 H2S formed is recovered by amine absorption
 Tail gas is incinerated
 Unit has storage, weighing and loading facilities for liq. S at
site itself
Block Diagram For SRU
Claus Section
Incinerator Section
Sulphur Storage and Loading
 Process Chemistry for SRU
Main Combustion Chamber
 Combined stream of acid gas & sour gas is fed to the burner of Main Combustion
Chamber
 Following reactions are occuring
H2S + 3/2 O2 SO2 + H2O + Heat (1)
2H2S + SO2 2H2O+ 3/n Sn + Heat (2)
2NH3 + 3/2 O2 3H2O + N2 (3)
H2S H2 + 0.5S (4)
 Controlled combustion of H2S takes place(eq 1)
 O2 is limiting and air flow is controlled by an Air Demand Analyser at
downstream of Claus converter II
 Eq 2 is the ‘CLAUS REACTION’ and is slightly endothermic at MCC temp. and
exothermic at Converter temp.
Claus Reaction Kinetics
Continued..

 H2S Dissociation – 6-7 % of total H2S feed

 Sulphur formed takes different allotropic forms
3S2 S6 + Heat
4S2 S8 + Heat
 Some other reactions that are occuring
CH4 + 2O2 CO2 + 2 H2O (6)
CO2 + H2S COS + H2O (7)
COS + H2S CS2 + H2O (8)
2H2S 2H2 + S2 (9)
 Presence of hydrocarbons in feed also increases COS & CS2 formation with
increase in air requirement
Continued…

 NH3 combustion requires higher temperature

 MCC Adiabatic flame temp. – 1350 – 1450 0C
 At higher NH3 conc., formation of solid nitrogenous salts
such as ammonia sulfate and sulfides which get deposited
in the downstream units
 To ensure complete NH3 destruction, acid gas is burnt in
two zones which maintains flame temp. above 1350 0C
Continued…

CLAUS CONVERTERS
 Less temperature favors claus reaction in the catalytic converters
 Converter temp. should be above S dew point
 Small quantities of CS2 and COS are formed
 There destruction improves S recovery
 1st converter temp is higher(around 300*C) to ensure maximum
destruction
COS + H2O H2S + CO2
CS2 + 2H2O 2H2S + CO2
 2nd Converter temp. subsequently is lower
Continued…

Liquid Sulphur Degassing

 Liquid sulfur absorbs hydrogen sulfide and forms hydrogen
polysulfudes
H2S + (x-1)S ↔ H2Sx
 Solubility of H2S - H2Sx in liquid sulfur depends on the partial
pressure of H2S and temperature of liquid sulfur
 Increase in temp. favors H2S in liq. S
 Total H2S is in the range of 540ppmw to 590ppmw within temp.
range of 125 – 140 0C
 Liq. Sulphur goes to pit and H2S above S is swept with steam ejectors
Continued…

 Process is further accentuated by mechanical agitation and

presence of catalyst like CATDEGAS
 H2S levels of < 10 ppmw can be achieved
 Moreover, sweeping ensures that H2S content is below
3.7%(LFL)
 Process Chemistry For TGTU

 Remaining S in Claus off-gases is recovered as H2S

 Tail gas at min. temperature of 280oC enters Hydrogenator
where H2S production takes place as
SO2 + 3H2 H2S + 2H2O
S + H2 H2S
CO + H2O H2 + CO2
COS + H2O H2S + CO2
CS2 + 2H2O 2H2S + CO2
COS + 4H2 H2S + CH4 + H2O
CS2 + 4H2 2H2S + CH4
Continued …

All reactions are exothermic

Hot gases are cooled in Waste Heat Boiler and sent
to water removal tower
MDEA solvent selectively absorbs H2S
H2S + (C2H5)2CH3N (C2H5)2CH3NH+ + HS-
H2S is stripped off in regenerator and sent to Claus
train
Tail gas from absorber is incinerated alongwith NH3
 Stream Data for BORL
Component Acid Gas Sour Gas from H2S Rich Gas NH3 Rich Gas
SWS I from SWS II from SWS II

Kmol/hr(%) Kmol/hr(%) Kmol/hr(%) Kmol/hr(%)

H2S 404.75 + 15.36 7.22 (35.22) 46.43 (90.51) 1.34 (1.98)

(ARU) (TGTU)
(91.1)

CO2 0.89 (0.2) - - -

NH3 0.67 (0.14) 7.17 (35.19) 0.05 (0.097) 45.28 (66.88)

H2O 38.29 (8.3) 6.15 (30) 4.86 (9.47) 21.03 (31.12)

HC as C1,C2 0.89 (0.2) - - -

Total flow 460.90 20.50 51.30 67.7

Continued…

Component Process Gas from Tail Gas from Tail Gas to

MCC both trains to incinerator
Train A TGTU
kmol/hr(%) Kmol/hr(%) kmol/hr(%)
H2S 46.21 (4.95) 10.1 (0.606) 0.20 (0.02)
CO2 0.85 (0.09) 1.74 (0.104 ) 1.97 (0.18)
H2 28.11 (3.01) 56.22 (3.37) 41.75 (3.82)
CO 0.27 (0.03) 0.54 (0.033) 0.05 (.005)
H2O 268.4 (28.72) 619.18 (37.13) 72 (6.6)
N2 487.36 (52.16) 974.72 (58.45) 974 (89.31)
COS 0.015 (0.002) 0.00 -
SO2 22.99 (2.46) 4.82 (0.29) -
S2 78.11 (8.36) 0.26 (0.02) -
S6 2.02 (0.216) - -
 Operating Conditions

Feed Stream Variation

 Feed to SRU includes acid gas, H2s rich gas & NH3 rich gas
1 – Load Variation
 Acid Gas from ARU is major feed and there is a turndown for it
 Sour gas from SWS may vary from 0-100%
 Increase in NH3 concentration requires more O2
 Formation of solid salts like Ammonium sulphate, Ammonium
bisulphate,Ammonium sulphide is possible at low temperature
2 – Composition Variation
Hydrocarbons
 Increased hydrocarbon increases O2 consumption
 Formation of CS2, CO, COS
 Carbon formation over Claus catalyst also occurs
Continued…

Steam
 Diluting agent
 Causes flame instability
Entrained Liquid
 Flame stability affected
 Corrosion of Acid Gas lines
3 – Pressure & Temperature
 Increased temp. of feed indicates more steam content
 High Pr. of feed may lead acid flare routing of gases
 Process Variables

1 - Main Combustion Chamber

 Pressure fluctuation can be due to feed variation
 High Pressure leads to high Temp. due to more feed
 Quench steam is used for temp. above 1450 oC
 For low temp. below 1300 oC, NH3 is routed to incinerator
 High Pr. due to blockage of a downstream unit will route
the feed gases to acid flare
 Further, there is provision of routing process gases from
condenser I to incinerator
Continued…

2- Air/Acid Gas Ratio

 Air is required to burn 1/3rd of total H2S, all NH3 and HCs
for efficient plant operation
 For monitoring air flow, Air Demand Analyser is located at
downstream of Condenser III
 It checks for H2S/SO2 ratio, which must be at or above a
min. value
 Below this ratio, there is excess air, more SO2 formation
which may lead to catalyst Sulphation
 Chances of SO3 formation and hence, corrosion
Continued…

3 – Claus Converters
 Inlet temp. of process gas to Claus converter is crucial for S recovery
 1st Claus converter temp. is around 300 oC to ensure COS, CS2 destruction and
better rate of reaction
 Increased temp. of converters decreases S recovery
 Temp. below dew point of S may lead to S deposition over catalyst, so that
should be avoided
Continued…

4 - Incinerator
 Fuel gas firing maintains the temp.
 O2 content in outlet flue gas should be 2 % mol (wet basis)
 At high temp., incinerator has a trip
 Tail gases however are sent to atmosphere for some
minutes to restore temp.
 Comparison With BPCL Unit

Parameter BPCL BORL SRU

RMP SRU

Capacity 2*70 T/day 2*180 T/day

Process Involved MCRC sub dew Claus with TGTU

point process

Recovery 99.5 % 99.9%

(design basis)
THANK YOU