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CONTENTS

1 REFERENCES
2 INTRODUCTION
3 PROCESS THEORY
3.1 CLAUS SECTION
3.2 LIQUID SULPHUR DEGASSING SECTION
3.3 THERMAL INCINERATION SECTION
4 PROCESS DESCRIPTION
4.1 GENERAL
4.2 CLAUS SECTION
4.3 DEGASSING SECTION
4.4 THERMAL INCINERATOR SECTION
4.5 UTILITY SECTION
MOD–PRCa – Rev. 6

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1 REFERENCES

Contractor: KT - KINETICS TECHNOLOGY

Customer: NATIONAL REFINERY LIMITED - NRL
Plant name: SULPHUR RECOVERY UNIT (SRU – U312)
Plant location: KARACHI – PAKISTAN

2 INTRODUCTION

The purpose of this document is to describe the process flow scheme of the first Sulphur
Recovery Unit (U312) to be installed in Karachi, Pakistan, during the Phase 1 of the present
Upgradation Project.

The Sulphur Plant consists of one Claus train designed for 52 t/d of produced liquid sulphur,
which includes the following sections:

 Claus Section;
 Degassing Section;
 Thermal Incinerator Section;
 Sulphur Solidification package.

The unit will process the acid gases coming from:

 Amine Treating Unit (ATU - U310)

 No-Phenolic Sour Water Stripping Unit (NP-SWSU - U311)

This document shall be read in conjunction with Process Flow Diagrams (Doc. No. K131-312-PFD-
0010-001 sheets 1÷5, latest revision).
MOD–PRCa – Rev. 6

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3 PROCESS THEORY

3.1 Claus Section

The process utilized in this section is called “Modified Claus Process” and consists in a
substoichiometric combustion of the acid gas streams taking place in the Thermal Reactor
followed by a catalytic conversion in the Claus Reactors.
In the Claus Section, about one-third of the total H2S is oxidized to SO2 which reacts with the
remaining H2S to form sulphur and water, as shown in the following reactions:

(1) H2S + 1.5O2  H2O + SO2 (oxidation)

(2) 2H2S + SO2  1.5S2 + 2H2O (Claus Reaction)
(3) 3H2S + 1.5O2  3H2O + 1.5S2 (overall)

The goal of the process is to drive the overall reaction to near completion.
In the Thermal Reactor the H2S contained in the acid gas is burnt with air according to reaction
(1) and only one-third of the total H2S is oxidized to SO2. The remaining H2S is then reacted
with the thermally produced SO2 to form elemental sulphur in the thermal stage and in the
subsequent catalytic stages according to reaction (2). The Claus reaction is thermodynamically
limited and has a relatively low equilibrium constant over the catalytic operation region.

During the acid gas combustion a part of the H2S is dissociated to H2 and sulphur as follows:

H2S  H2 + 0.5 S2 (dissociation)

The ammonia contained in the SWS gas reacts with the oxygen according to the following
reaction:

2NH3 + 1.5 O2  N2 + 3H2O (NH3 reaction)

In order to completely decompose the ammonia contained in the SWS acid gas, the furnace
temperature is increased to around 2550°F by using a Thermal Reactor with two-zone
configuration.
The following side reactions, leading to the formation of COS and CS2 are also involved in the
process when CO2 and/or hydrocarbons are present in the acid gas.
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CO2 + H2S  COS + H2O (COS formation)

CO2 + 2H2S  CS2 + 2H2O (CS2 formation)

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CnH(2n+2) + (2n+1)/2 O2  nCO + (n+1)H2O (HC combustion)

CnH(2n+2) + (3n+1)/2 O2  nCO2 + (n+1)H2O (HC combustion)

In order to complete the Claus reactions a suitable residence time is necessary at high
temperature in the thermal reactor.
Usually, 60 to 70% of the total amount of elemental sulphur produced in the Claus process is
obtained in the thermal process step.
In order to boost the sulphur yield up to 98%, the Claus reaction continues in three catalytic
steps with activated aluminium and titanium oxide based catalyst.
The main reaction involved in the catalytic reactors is:

2H2S + SO2  2H2O + 3/x Sx (Claus Reaction)

The Claus reaction is an exothermic equilibrium reaction thermodynamically enhanced by low

temperatures.
In the first catalytic reactor, in addition to the Claus reaction, the hydrolysis of COS and CS2 is
achieved:

COS + H2O  H2S + CO2 (COS hydrolysis)

CS2 + 2H2O  2H2S + CO2 (CS2 hydrolysis)

Most chemical reactions in Claus plants occur either in the furnace (Thermal Reactor) or in the
catalytic reactors. The one important exception is sulphur vapour species transformations.
Elemental sulphur vapour can exist as four separate species, namely: S2, S4, S6, S8.
Usually S4 production is negligible; hence, it is important to consider the following equilibrium
reactions, which concern the combustion stage, the catalytic conversion stage and the process
gas cooling stage:

S8(gas)  4S2(gas)
3S8(gas)  4S6(gas)

Most of the sulphur vapour yielded in the furnace exists there as S2. As the gas passes through
the Waste Heat Boiler and Sulphur Condensers (and its temperature drops) the sulphur shifts
partly to S4 and then to nearly all S6 and S8.
MOD–PRCa – Rev. 6

The liquefaction of the sulphur produced in the thermal and catalytic conversion steps is
performed in the Sulphur Condensers according to the following main reactions:

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S8(gas)  8 S1(liquid)
S6(gas)  6 S1(liquid)
S2(gas)  2 S1(liquid)

The sulphur produced is then condensed, separated and sent to the Liquid Sulphur Degassing
Section.

3.2 Liquid Sulphur Degassing Section

The liquid sulphur produced in the Claus section contains soluble H2S and H2Sx (hydrogen poly-
sulfides). Hydrogen poly-sulfide is a weakly bound polymeric combination of hydrogen sulphide
and elemental sulphur:

H2S + S(x-1)  H2Sx

The principle of the degasification process of the liquid sulphur is to release the dissolved H2S gas
and to accelerate the decomposition of the polysulphides to H2S.

H2Sx  H2S + S(x-1) (decomposition of the polysulphides)

(H2S)dissolved  (H2S)gas (desorption of H2S)

For this purpose, instrument air is preheated to 275°F in a conventional steam heater and enters
the bottom of the degassing column.
Air and sulphur enter below the catalyst bed and pass concurrently through the catalyst, which is
Claus plant alumina catalyst able to promote the polysulphide decomposition by the reverse
reaction.
The degassed liquid sulphur overflows just above the top of the catalyst bed while the sweep air
passes through a mist eliminator pad at the top of the column and flows to the Thermal Reactor
Burner in order to improve the sulphur recovery efficiency.

3.3 Thermal Incineration Section

The oxidation of the tail gas produced in the Claus section of the plant is necessary to transform
all sulphur compounds present into SO2.
The oxidation of the sulphur compounds is achieved at high temperature (1470 °F) with excess of
oxygen burning fuel gas.
MOD–PRCa – Rev. 6

The reactions involved in this section are summarized here below:

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S + O2  SO2
H2S + 1.5O2  SO2 + H2O
COS + 1.5O2  CO2 + SO2
CS2 + 3.0O2  CO2 + 2SO2
H2 + 0.5O2  H2O
CO + 0.5O2  CO2
SO2 + 0.5O2  SO3

The flue gases generated have a typical free oxygen content of 25% by vol., which is necessary
to ensure the complete oxidation of sulphur species and hydrocarbons contained in the gas to be
treated.
The design target for the incinerator section is to reach not more than 10 ppm vol. of H2S in the
flue gas.
MOD–PRCa – Rev. 6

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4 PROCESS DESCRIPTION

4.1 General
The process design is based on the KT Claus Technology. The Sulphur Recovery Unit employs
thermal stage and catalytic stages to achieve a sulphur recovery of 98%.
The unit is designed to produce 52 t/d of liquid sulphur with a turndown of 25% of design
capacity.

The Claus Section consists of a Thermal stage, in which H2S is partially burnt with air, followed by
three conventional Claus catalytic reactors.

A Thermal Incinerator for the oxidation of the tail gas is used to convert the residual sulphur
compounds to SO2 before the flue gases are released to the atmosphere via a dedicated stack.

The produced undegassed liquid sulphur is collected into the undegassed compartment of the
sulphur drum and, then, it is sent to the degassing column. From the storage compartment of the
sulphur drum, the degassed liquid sulphur is pumped continuously to the storage tank.
Finally, the liquid sulphur is transferred from the sulphur tank to the solidification package.

4.2 Claus Section

The unit feedstocks are the acid and sour gases produced in the new Amine Treating Unit U310
(ATU) and No-Phenolic Sour Water Stripping Unit U311 (NP-SWSU).
The Amine Acid Gas and the SWS Acid Gas from the battery limits enter the Amine Acid Gas
Separator (312-V-0001) and the SWS Acid Gas Separator (312-V-0002) respectively.

Separators are installed to prevent any liquid, resulting from upstream operational upsets, from
being entrained in the acid gases to the Thermal Reactor (312-F-0001). Any sour water or other
liquids collected in the separators are discontinuously pumped off via Sour Water Pumps
(312-P-0001A/B/C) on level control. The pump C is the common spare for pumps A and B.

The SWS Acid Gas, which contains NH3, is fed to the Thermal Reactor Burner 312-ME-0001, while
the Amine Acid Gas coming from ATU unit is fed partly to the Thermal Reactor Burner 312-ME-
0001 (about 70-75% of the whole flowrate) and partly (up to 30% max.) to the second zone of
the Thermal Reactor 312-F-0001.
With this arrangement it is possible to reach, in the first zone of thermal reactor, a temperature
of about 2550 °F which ensure the compete ammonia destruction.
The thermal reactor temperature is monitored by two pyrometers, one in the first zone and one in
the second zone.

The acid gas streams are burnt in 312-ME-0001 by means of combustion air supplied by the
Combustion Air Blowers 312-K-0001A/B (one operating and one spare) and preheated in the
Combustion Air Preheater 312-E-0001.

The H2S/SO2 ratio is the most important parameter for the sulphur conversion efficiency. The
quantity of combustion air is controlled in order to maintain such parameter in the ratio 2:1 by a
MOD–PRCa – Rev. 6

combination of feed forward and feedback control.

The amine acid gas and SWS acid gas streams to the Thermal Reactor are metered to determine
the combustion air requirement. This value is used to control the main air valve under feed

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forward control. A separate automatic trim air controller is used for fine tuning control. The trim
air controller operates automatically and independently of the main air controller and receives a
signal from the H2S/SO2 tail gas analyzer that monitors the residual H2S and SO2 in the tail gas
leaving the Final Sulphur Condenser (312-E-0005).
The main air controller is reset as necessary to keep the trim air controller within the effective
operating range.

The process gas produced in the Thermal Reactor (312-F-0001) passes through the Waste Heat
Boiler (312-E-0010) where high pressure saturated steam is generated at 348 psig under
pressure control.

Any sulphur that may condense in the WHB can be drained (Normally No Flow line) via the 1st
Hydraulic Seal (312-ME-0003) into the Sulphur Drum (312-V-0006).

The process gas from Waste Heat Boiler enters the First Sulphur Condenser (312-E-0003); here
sulphur is condensed, separated and collected to the Sulphur Drum via the 2nd Hydraulic Seal
(312-ME-0004). The process gas, leaving the first condenser, still contains a high percentage of
H2S and SO2. In order to convert it into sulphur, the process gas is conducted through three
Claus Reactors in series, on alumina and titania catalyst beds.

Prior to entering the First Claus Reactor (312-R-0001), the process stream is heated up to the
optimum temperature for the catalytic conversion (about 464°F) in the 1st Claus Reactor
Reheater (312-E-0004).

The process gas temperature is automatically controlled by a temperature controller on the

process gas to the First Claus Reactor, acting on the flowrate of the heating steam entering 312-
E-0004.

In the First Claus Reactor, the catalytic conversion is carried out on alumina catalyst (10% of
catalyst bed) and on a titania catalyst (90% of catalyst bed) capable of maximizing the hydrolysis
of COS and CS2. The catalytic reaction is exothermic.

The process gas leaving the First Claus Reactor enters the Second Sulphur Condenser
(312-E-0003) where sulphur is condensed, separated and collected to the Sulphur Drum via the
3rd Hydraulic Seal (312-ME-0005). First and Second Sulphur Condensers have a common shell.

The process gas leaving the second condenser is heated up in the 2nd Claus Reactor Reheater
(312-E-0006) and enters the Second Claus Reactor (312-R-0002).

The process gas inlet temperature is automatically controlled by a temperature controller on the
process gas to the Second Claus Reactor, acting on the flowrate of the heating steam entering
312-E-0006.

The process gas leaving the Second Claus Reactor (312-R-0002) enters the Third Sulphur
Condenser (312-E-0005) where sulphur is condensed, separated and collected to the Sulphur
Drum via the 4th Hydraulic Seal (312-ME-0006). Third and Final Sulphur Condensers have a
MOD–PRCa – Rev. 6

common shell.

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The process gas leaving the third condenser is heated up in the 3rd Claus Reactor Reheater
(312-E-0007) and enters the Third Claus Reactor (312-R-0003).

Also in this case, the process gas inlet temperature is controlled by a temperature controller
acting on the steam flowrate.

Finally, the process gas enters the Final Sulphur Condenser (312-E-0005) where sulphur is
condensed, separated and collected to the Sulphur Drum via the 5th Hydraulic Seal (312-ME-
0007). The tail gas resulting from the Claus section is sent to the Incinerator 312-F-0002.

In the 1st and 2nd Sulphur Condenser (312-E-0003), low Pressure steam is produced at 51 psig
for internal use.
In the 3rd and Final Sulphur Condenser (312-E-0004), very low pressure steam is produced at 17
psig. Such steam is used as stripping medium in the Deareator (312-V-0009).

Boiler feed water is supplied under level control to the Sulphur Condensers 312-E-0003 and
312-E-0005.

In case of shut-down of the Claus section, all the feedstocks to the Thermal Reactor will be cut-off
and some nitrogen shall be sent to the Thermal Reactor for cooling and purging purposes.

During the Claus section heating up, fuel gas is burnt in the Thermal Reactor Burner, in order to
reach certain minimum temperatures before admitting acid gas to process lines and equipment.
The fuel gas to be burnt in the Thermal Reactor Burner and in the Incinerator Burner, prior to
being fed to the burners, flows into the Fuel Gas Separator (312-V-0007), where possible
condensates are separated.

Whenever any sulphur is present in the plant, the combustion of fuel gas has to be carried out in
stoichiometric conditions, in order to avoid catalyst and plant damages.

Stoichiometric combustion conditions are defined as: oxidizing all the H2 and hydrocarbons
contained in the fuel gas to CO2 and H2O, with no excess oxygen in the flue gas.
During the stoichiometric combustion of fuel gas it is necessary to moderate the flame
temperature by using low pressure steam as a quenching agent. Quench steam can be blown into
the Thermal Reactor Burner for this purpose.

4.3 Degassing Section

The produced liquid sulphur is degassed by means of the KT degassing process, in order to
decrease the H2S content in the liquid sulphur down to 10 ppm by weight.

The liquid sulphur from the hydraulic seals is fed to the undegassed compartment of the Sulphur
Drum (312-V-0006).
Liquid sulphur is sent, by means of pump 312-P-0002A/B (one operating and one spare), to the
degassing column (312-C-0001) where H2S is stripped in co-current by degassing air. The
MOD–PRCa – Rev. 6

degassing air is preheated at 275°F in the Degassing Air Preheater (312-E-0008) where LP
steam from internal header is used as heating medium.

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The Degassing Column is a packed tower with a bed of alumina catalyst.

The degassed liquid sulphur, after overflowing above the bed and draining through the hydraulic
seal 312-ME-0008, is stored into storage compartment of the Sulphur Drum.
The Sulphur Drum is kept slightly below atmospheric pressure by means of Steam Ejector 312-J-
0001A/B (one operating and one spare).

The off-gas, containing some H2S, is sent from the steam ejectors to the Incinerator (312-F-
0002).

From the Sulphur Drum, the liquid sulphur is continuously pumped to the Sulphur Tank 312-S-
0001 by the Degassed Sulphur Pump 312-P-0003A/B (one operating and one spare).
From the Sulphur Tank, liquid sulphur is sent to the Sulphur Solidification Package (312-X-0005)
by means of pumps 312-P-0005A/B (one operating and one spare).

4.4 Thermal Incinerator Section

A Thermal Incinerator 312-F-0002 is provided for the combustion of the following streams:

 Tail gas from Final Sulphur Condenser

 Vent gas from Sulphur Degassing Package
 Sweep air from Steam Ejector

The Incinerator Burner 312-ME-0002 is a forced draught type.

Combustion air is provided by the Incinerator Air Fan 312-K-0002A/B (one in operation and one
spare) and is fed to the incinerator burner.

Fuel gas is burnt in the Incinerator Burner, in order to allow the complete oxidation of H2S to
SO2. The ratio between combustion air and fuel gas is automatically controlled.

The flue gas is discharged to the atmosphere through the Stack (312-ME-0009) where an oxygen
analyzer is located, in order to monitor the amount of excess air.

The operating temperature of the incinerator is normally maintained at 1472°F, in order to reach
the maximum allowable value of 10 ppm vol. of residual H2S in the flue gas (on a dry basis and
with 3% excess oxygen)

The flowrate of the fuel gas, that is necessary to support the combustion of tail gas in the
Incinerator, is automatically controlled by a temperature controller in the combustion chamber,
resetting a flow controller on the fuel gas stream to the burner.

Due to the large amount of heat generated by the oxidation, the Thermal Incinerator Section
incorporates a Waste Heat Recovery System (312-E-0009) to further reduce operating costs by
generating HP steam at 696 psig.
MOD–PRCa – Rev. 6

The HP steam produced in Incinerator WHB Steam Drum (312-V-0008) is partially fed to the
Claus Reactor Reheaters; partially used for steam tracing and the balance is mixed to the HP

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steam produced in the Thermal Reactor WHB. The resulting amount of produced steam is then
superheated in the superheating section of 312-E-0009.
HP steam at 320 psig and 696 °F is exported to the Refinery HP Steam Header.
The steam export temperature is controlled by means of HPS Desuperheater (312-DS-0001).

4.5 Utility Section

In the SRU Unit, the heat given-off by the process gas and the condensation heat involved during
the liquid sulphur production are utilized to produce high or low-pressure steam. In particular,
high pressure steam is produced in:

 Thermal Reactor WHB (312-E-0010)

 Waste Heat Recovery System (312-E-0009)

Low pressure steam and low-low pressure steam are generated respectively from:

 1st and 2nd Sulphur Condensers (312-E-0003)

 3rd and Final Sulphur Condensers (312-E-0005)

The total amount of the required feedwater for the steam production is internally produced by
stripping demineralized water in the Deareator (312-V-0009). Boiler feed water is supplied under
level control to each boiler/condenser by means of the Boiler Feed Water Pumps 312-P-0004 A/B
(one operating and one spare).

All the steam condensate coming from internal users is recovered by flashing-it in the Deareator
hold-up drum, while LP steam from battery limits is used as stripping medium in the Deareator
degassing tower.

The HP boiler blowdown from the Thermal Reactor WHB and from the Incinerator WHB is sent to
the HP Blowdown Flash Vessel (312-V-0003) in order to recover low pressure steam by flashing it
at 51 psig.
The remaining boiler blowdown, leaving the 312-V-0003, is joint to the LP blowdown coming from
312-E-0003 and 312-E-0005 and it is collected and cooled down with Cooling Water in the Blow
Down Cooler (312-V-0005), before being discharged to sewer at 140°F.
MOD–PRCa – Rev. 6

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