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TSP-POGC-NIGC

COURSE
SUBJECT

T.T.F
OIL AND GAS TECHNOLOGY
SULFUR RECOVERY

CODE
P/TM/TRG/P.SU/001

Objectives: Upon completion of the unit the trainees should be able to:

Explain classical Claus process steps.

Describe the effect of pressure, temperature and catalyst on the process plant
efficiency.
Know the main equipment and systems of the Claus plant.

Contents:
1. General introduction
1.1. Function of the unit
1.2. Battery limits of the unit
1.3. Plant capacity and inter connecting
1.4. Feed stock characteristics and capacity
1.5. Properties of H2S and sulfur
2. General description
3. Unit description
3.1. Claus section
3.2. Incineration section
3.3. Water and steam system
3.4. Sulfur degassing and storage section.

TSP-POGC-NIGC
Prepared

Ziabari
b
y

Date
1 July. 2000
SUBJECT

T.T.F
Checked
by

Yeganeh
Larijani

Date
9 July. 2000
SULFUR RECOVERY

Approved
by

T.T.F

Date
CODE
P/TM/TRG/P.SU/001

SULFUR RECOVERY-CLAUS PROCESS


1. GENERAL INTRODUCTION
These documents are extracts from the process package prepared by Elf ep and Lurgi
Bamag according to the design basis for sulfur recovery units for the South Pars field
development phases 2 & 3, onshore facilities.
The process package concerns the Claus units to be installed at Assaluyeh Refinery for
recovery of sulfur from acid gas produced by MDEA sweetening units.
The sulfur facilities of each phase consist of two identical trains, with a capacity of 103 t/d
each.
The sulfur recovery units are designed to achieve an overall recovery of 95%. The absolute
amount of sulfur emission of 95% corresponding to the design case.
Concerning the process arrangements proposed, they have been selected to cope with the
specificities of the design basis with regard to the leanness of the gas feeds (between 21.3
and 31.7% vol. H2S) and the wide range of operating cases (40-105% of design case).
1.1. Function of the Unit
The sulfur recovery units SRUs are designed to recover commercial liquid sulfur from acid
gas streams produced in the amine regenerators. The feed gas contains H 2S, CO2 and
some organic sulfur compounds (mainly mercaptans), together with a small amount of
hydrocarbons and water vapor the SRUs shall recover sulfur from this stream down to the
required specification.
Sulfur recovery units will consist of two identical sulfur recovery trains, each including.
- Air and acid gas feed pre-heaters,
- Thermal reaction furnace,
- Three Claus converters in series,
- One sulfur degassing section.
There is one incinerator for two trains. The incinerator is designed to incinerate the tail gas
at 540C prior to release to atmosphere.
1.2. Battery Limits of the Unit
The sulfur recovery units battery limits include:
- Acid gas inlet facilities (flow control, K.O. drum)
- All equipment necessary for the sulfur recovery operation
- Tail gas incinerator and chimney
- Fuel-gas inlet facilities

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- Steam recovery and Boiler Feed Water (BFW) system facilities including BFW purge,
cooling and steam condensate return pumps
- Sulfur degassing facilities and daily storage.
- Sulfur export pumps to main liquid sulfur storage.
SUBJECT

SULFUR RECOVERY

CODE
P/TM/TRG/P.SU/001

Some items will be common to several SRU trains, as further indicated in process
descriptions.
1.3. Plant Capacity and Interconnecting
- The total sulfur recovery units capacity is the capacity resulting from processing of 2000
MMSCFD of reservoir fluid (dry basis). This capacity is to be treated in 4 parallel identical
trains, each processing 25% of the acid gas from the gas treating units.
- The corresponding acid gas flow rate per SRU train in normal operation is given in this
section with the feedstock composition. A margin of 5% should be added for the design of
each train to take into account the possible fluctuations due to the control system (load
sharing between trains).
- The sulfur recovery units interconnecting philosophy with upstream and downstream units
is pictured in Figure 1.
Basically, two sulfur recovery trains are fed from a common acid gas header receiving the
acid gas of two gas treating trains. The acid gas from this common acid gas header shall be
routed to an acid gas knock-out drum, also common to 2 trains. The acid gas flow is
controlled by flow control for the first train and by pressure control for the second train.
The liquid sulfur from the sulfur recovery units storage and degassing pits (1for 2 trains) will
be sent to a common liquid sulfur storage, from which it is processed in several parallel
sulfur forming trains.
Figure 1
Acid Gas and Liquid Sulfur Interconnecting Piping Philosophy

TSP-POGC-NIGC

SUBJECT

T.T.F

SULFUR RECOVERY

CODE
P/TM/TRG/P.SU/001

1.4. Feedstock Characteristics and Capacity


The three acid gas qualities, used as basis of the design, correspond to the following cases:
- Design case, corresponding to the maximum H2S-content in the plant (31.6% H2S), and
therefore, to the maximum sulfur production rate (98 t/d).
- Sensitivity case, corresponding to the minimum H2S content in the plant main gas
feedstock, and therefore to a reduced sulfur production capacity (84.6 t/d) and H 2S
concentration (26.8% H2S) in the feed to the SRU.
The turn down case is related to the operation of the gas treating units at their minimum
capacity (40%) corresponds to the minimum H2S concentration (21.3% H2S) that can be
expected in the SRU acid gas feed stock and the minimum sulfur rate (33.7 t/d) in
continuous operation.
These cases represent the extremes of the expected acid gas compositions.
The unit shall operate the acid gas feeds from this three cases.
The definition and composition of design and operating cases are given below.
- Acid gas feed compositions and conditions at battery limit
Pressure and temperature of acid gas are the same for all cases, design values are:
Pressure (max.)
Temperature

bar g
C

0.8
55

Sulfur recovery units feedstock characteristics

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T.T.F
Normal Operation
Design case
Sensitivity case
(High H2S)
(Low H2S)

Turndown
Operation

B.L. Conditions

Pressure
bar abs
Temperature (C)
H2S normal flow rate
per train (kmole/h)
Composition (dry basis)

H2S
CO2
COS
Mercaptans
Hydrocarbons
Total train (dry basis) *

Water Content

1.8 max.
55 max.

1.8 max.
55 max.

1.8 max.
55 max.

134.5*
mole %
kmole/h*
34.2
134.5
64.7
254.3
Traces
0.1
1.0 max.
4.1
100.0
393.0

115.9*
mole %
kmole/h*
29.0
115.9
69.9
279.4
Traces
0.1
1.1 max.
4.3
100.0
399.7

46.3*
mole %
kmole/h*
23.1
46.3
74.8
150.0
Traces
0.1
2.1 max.
4.2
100.0
200.6

Saturation @ GTU
reflux drum conditions

Saturation @ GTU
reflux drum conditions

Saturation @ GTU reflux


drum conditions

SUBJECT

SULFUR RECOVERY

CODE
P/TM/TRG/P.SU/001

* The molar flow rates indicated are for normal capacity. For SRU design, a margin of 5%
shall be added in each case.
1.5. Properties of H2S and Sulfur
- Properties of gaseous H2S
Density relative to air :

1.19

Heat value

3820 cal/kg

Spontaneous ignition :

260C

Explosive mixture between 4.3 and 46% by volume in air (0C-760mm)


Soluble in water (water can absorb as much as 3 times its volume at ambient temperature)
Mud tend to absorb H2S
Agitation or temperature increase produces toxic gas liberation
At high concentration, gas is less odorous (therefore you cannot rely on your sense of
smell)
After a 10 minutes exposure, the nose cannot perceive the odor.
Burns with a blue flame to evolve SO2
Colorless

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- Properties of sulfur
124 C
132 C
150 C
156 C
159.9 C
159.1 C
159.4 C
160 C
160.3 C
165 C

10.94 cp
8.66 cp
7.09 cp
7.19 cp
7.59 cp
9.48 cp
14.45 cp
22.83 cp
77.32 cp
500.00 cp

Density: 1.78 g/cm3 at 150C (302 F)


Melting point: 119C (246 F)
Normal handing temperature for liquid sulfur: 145C-155C (293-311F)
SUBJECT

SULFUR RECOVERY

CODE
P/TM/TRG/P.SU/001

- Final SRU product specification:


Purity on dry basis:
Color:
Organic matter:
Ashes:
H2S content:

Min 99.8% wt.


Bright yellow (in solid form)
500 ppm wt max.
200 ppm wt max.
10 ppm wt max.

2. GENERAL DESCRIPTION OF SRU PROCESS.


- Classical Claus Process Step
Sulfur recovery by the Claus process involves conversion of a poisonous waste by-product
of natural gas treating operations, namely acid gas into saleable sulfur and a relatively
innocuous off gas suitable for discharge to the atmosphere. A net credit of the process is
useful heat in the form of steam generation. In chemical terms, the object is to oxidize the
H2S in the acid gas to S plus H2O while still burning any hydrocarbons present to sulfur-free
products without soot formation. The overall net result of the process may be represented
by the following equation:
2 H2S + O2

2 H2O + S2

This is not a reaction which occurs at any one place; the process is carried out by burning
one third of the acid gas stream mixed with the total amount of air required according to the
above equation, producing SO2 and H2O.
H2S

+ 3/2 O2 SO2

2 H2S + SO2

+ H2O

3/n Sn + 2 H2O

+ 124 kcal/mole

(1)

- 11 kcal/mole for S2 gas

(2)

+ 35 kcal/mole for S8 liq

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The reaction (1) takes place in the reaction furnace by burning one third of the total acid
with air.
The reaction (2) between H2S and SO2 to form sulfur begins immediately in the combustion
zone of the reaction furnace, but requires further contact of the process gas with a Claus
catalyst at controlled temperatures, in converters following in series, to carry the reaction
towards completion.
The sulfur vapor formed by the reaction (2) is condensed and recovered as liquid sulfur
after each step of the reaction (reaction furnace and catalytic converters).
- COS-CS2 Formation
Acid gas containing hydrocarbons and carbon dioxide may undergo side reactions to form
carbonyl sulfide (COS) and carbon disulphide (CS 2). The main reactions capable of forming
these compounds that occur in the reaction furnace are the following:
SUBJECT

CH4

SULFUR RECOVERY

+ 2S2
H2S

CS2

2H2S

H2

CO

H2 O

CO2

+ H2

CO

+ S2 COS

CODE
P/TM/TRG/P.SU/001

The sulfur compounds undergo partial hydrolysis in the catalytic converters tanks to the
high water vapor content in the process gas. This hydrolysis is most noticeable in the first
converter tanks to the higher temperature. These hydrolysis reactions are the following:
H2O

COS

CS2

+ H2O

H2S

COS +

CO2
H2 S

- H2S/SO2 Ratio
The control of the H2S to SO2 ratio, as close as possible to the exact stoichiomeric ratio of 2
throughout the unit is essential for maximum conversion and thus minimum sulfur losses in
the tail gases.
The air flow rate for oxidation of one third of H 2S must be set at the best to optimize the
reaction (2):
-an air deficiency entails additional sulfur losses of H2S
-an air excess entails additional sulfur losses of SO2
- Principle of Sulfur Degassing Process
Elementary sulfur produced by the Claus process always contains dissolved H 2S and
chemically combined H2S under the form of polysulphides H2SX.
H2SX

H2S + (x-1) S

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The degassing process can be schematized as follows:


H2Sx sol

H2S sol. + (x-1) S H2S gas + (x-1) S

Polysulphide

H2 S

Decomposition

degassing

As H2S is removed from the system, the above equilibrium is driven to right resulting in
further breakdown of hydrogen polysulphides with subsequent degassing of more H 2S. The
decomposition reaction is promoted by the use of the AQUISULF catalyst.

SUBJECT

SULFUR RECOVERY

CODE
P/TM/TRG/P.SU/001

3. UNIT DESCRIPTION
3.1. Claus Section
The unit is schematized on the attached process flow diagram. The acid gas from the
sweetening unit is routed to the acid gas knock-out drum 108-D-101. The liquid carry over
is removed and sent back to acid gas removal unit or water treatment. The acid gas K.O.
drum 108-D-101 is common to two trains. The acid gas flow to the two trains is controlled
by flow control for the first train, and by pressure control for the second train.
The process air for reaction furnace is supplied by air blowers 108-K-101 A/B. The second
blower is common spare for two trains.
Prior to entering reaction furnace 108-H-101, the acid gas and the air are preheated up to
220C by HP steam in the 108-E-107 and 108-E-108 exchangers.
The acid gas then passes through the reaction furnace burner 108-H-101 where it is burnt
with a controlled amount of air:
The air to acid gas control is ensured by means of two control valves in parallel on the air
circuit:
- one main air valve which controls the primary air flow rate,
- one trim air valve which adjusts the balance of air.
The main valve is controlled by an air to acid gas flow ratio controller (feed forward control).
The trim valve is actuated from a cascade control system from the H 2S/SO2 analyser, which
presets the trim airflow a controller (feed back control). When the signal to the trim air flow
controller entails a full opening or closing of the trim air valve, an incremental signal is sent
back to the main air to acid gas ratio valve ratio controller to decrease or increase its ratio
accordingly. This control system device allows to keep the trim air valve position within its
operational range at all times.
Due to the high variations of acid gas composition the reaction furnace burner is fitted with
fuel gas tips to burn continuously a small amount of fuel gas.

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The fuel gas burner is acting as pilot flame to maintain acid gas flame in case of
perturbation.
The fuel gas flow is set to 50-75 Nm 3/h, and will be adjusted from acid gas feed to achieve
a reaction furnace temperature up to 925C.
The unit is provided with an acid gas bypass line to split a small part of acid gas feed
(10-15%) downstream reaction furnace to be routed directly to the first condenser
108-E-101.
That allows to burn the acid gas on reaction furnace burner with a higher air to gas ratio
than Claus ratio and then to achieve a higher flame temperature to get a good flame
stability.
The acid gas bypass is used only during start-up or turn down period or when acid gas
quality coming from sweetening unit is less than 28%.
SUBJECT

SULFUR RECOVERY

CODE
P/TM/TRG/P.SU/001

The process gas is cooled in passing through the reaction furnace boiler 108-B-101 where
LP steam is generated.
The process gases flow to the 1 st condenser 108-E-101 where the gases are cooled and
sulfur formed in the reaction furnace is condensed. LP steam is generated in the shell side
of condenser 108-E-101.
The condensed sulfur is removed from 108 E 101 through a bottom seal drain to the sulfur
degassing pit 108-T-101.
Then, the process gases are routed the 1st catalytic stage.
The process gas passes through the auxiliary burner 108-H-102, where they are reheated
up to 235C before entering the first catalytic reactor 108-R-101.
During normal operation (design and sensitivity case) the auxiliary burner is operated by
burning a split stream of acid gas feed.
The acid gas is burnt under substoichiometric conditions to avoid oxygen going through
catalytic beds.
During turn down operation the variation and lower H2S-content in acid gas make the
control of substoichiometric combustion difficult. For turn down operation the auxiliary
burner is operated with fuel gas instead of acid gas, in order to get a correct control of the
substoichiometric combustion.
When the H2S- content of the acid gas is decreasing below 25%, fuel gas will be
progressively introduced to the auxiliary burner.
The temperature controller of process gas at the outlet of auxiliary burner 108-H-102 is
setting the air amount to the auxiliary burner. The air flow rate feeding the burner is
controlling in cascade mode the acid gas and / or fuel gas demand via a ratio controller
according to the substoichiometric ratio defined for both fuels.
The gases flow downwards through the catalytic bed where the sulfur formation reaction
and hydrolysis reaction of COS and CS2 are carried on.

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The catalytic bed is composed of a first layer of AM 4.8 promoted catalyst on the top, and
an under layer of CR 3S activated alumina catalyst.
In the reactor 108-R-101, additional sulfur is produced and carried over in vapor phase by
the process hot gases. The exothermic Claus reaction results in a temperature rise across
the reactor. The inlet temperature should be set in such a way that the outlet temperature
exceeds 300C in order to favour the hydrolysis of COS and CS2.
The hot gases leaving the 1st reactor are cooled in the 2nd condenser 108-E-102 by
generating LP steam. The condensed sulfur flows through a seal pot to sulfur degassig pit
108-T-101.
The gases leaving the second condenser 108-E-102 are reheated up to 215C passing
through the tubes of the re-heater 108-E-105. Gases are heated by condensing saturated
HP steam in the shell side.
The catalytic bed in the 2nd reactor 108-R-102 consists of CR 3S activated alumina.
SUBJECT

SULFUR RECOVERY

CODE
P/TM/TRG/P.SU/001

The hot gases leaving the second converter are cooled in the 3 rd condenser 108-E-103 by
generating LP steam. The condensed sulfur flows through a seal pot to the sulfur degassing
pit.
Process gases leaving the third condenser are reheated up to 200C by means of HP
steam, in the exchanger 108-E-106, prior to entering the 3rd catalytic reactor 108-R-103.
The process gases pass downwards through the catalyst bed of third reactor 108-R-103
loaded with CR3S, activated alumina, on the top and CRS 31, titanium dioxide, underneath.
Then the gases are cooled to 130C in the last condenser 108-E-104 in order to condense
the sulfur and to decrease sulfur losses by vapor pressure in the tail gas. The last
condenser ensures cooling of gases by generating very low LP steam, which is condensed
in an air cooler.
Prior to being incinerated, the gases through the final separator 108-D-105 at the outlet of
the last condenser, where entrained droplets of liquid sulfur are retained.
The residual H2S and SO2 contained in the tail gas are analyzed to control the H 2S/SO2
ratio through the trim air valve at unit inlet.
3.2. Incineration Section
The tail gases leaving the final condenser 108-E-104 are routed together with the tail gases
from the second train to the incinerator, where all remaining sulfur compounds are
converted into SO2 by incineration at 540C before release to atmosphere through the
stack.
This temperature is reached by burning fuel gas with a slight excess of air, which is
introduced into the incinerator burner by natural draft.
3.3. Water and steam systems
The sulfur unit is producing LP steam only in reaction furnace boiler and sulfur condensers.
LP steam is send to LP steam network at B.L..

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HP steam from B.L. is used to heat up air and acid gas feeds and to reheat process gas at
the inlet of 2nd and 3rd reactors.
HP condensate from air and acid gas pre-heater is recovered in HP condensate drum 108D-103 and then send to steam drum 108-D-102. HP condensate from 2nd and 3rd stage
re-heaters are directly routed to steam drum 108-D-102.
To be adequate for sulfur reheating, the pressure of LP steam is reduced to 2.5. bar g
before feeding steam jackets (liquid sulfur lines) and unit tracing system. LP steam is
desuperheated by injection of boiler feed water.
LP condensate from both units are recovered in LP condensate flash drum 108-D-106 and
cooled down by recirculation through air cooler 108-A-102. By pump 108-P-105 LP
condensate production is routed to B.L.

SUBJECT

SULFUR RECOVERY

CODE
P/TM/TRG/P.SU/001

3.4. Sulfur degassing and storage section


The sulfur degassing pit is common for two trains.
The liquid sulfur produced in both units in all sulfur condensers is routed to sulfur degassing
and storage pit 108-T-101.
The degassing pit includes 2 compartments working in series.
The liquid sulfur is routed to the first compartment of degassing section, where sulfur is
sprayed in the gas space by a re-circulating pump 108-P-102.
Liquid sulfur flows to the second compartment by an opening at the bottom of dividing wall,
where the sulfur degassing is completed by spraying with the second re-circulating pump
108-P-103. The degassed liquid sulfur is transferred by level control to the storage section
by means of a control valve on the discharge line.
An injection of AQUISULF catalyst is carried out at the suction of both re-circulating pumps.
The catalyst is injected from catalyst tank 108-T-102 at preset flow rate by the volumetric
pump 108-P-104.
To remove the H2S released during the process, the gaseous phase of the pit is swept by
air. This sweeping gas is discharged to incinerator by a steam ejector 108-J-101. A
continuous analyzer monitors the H2S content in the air.

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