Simulation of Clause Furnace under HiTAC

Conditions for Enhanced Sulfur Recovery

M. Sassi** S. Ben Rejab** and Ashwani K. Gupta*
The Combustion Laboratory
University of Maryland, College Park
*Email: akgupta@umd.edu
Grad Student: Hatem Selim
** The Petroleum Institute
Abu Dhabi, UAE

International Workshop on Advances in Combustion Science

IIT Kanpur
December 31, 2007 - Jan 2, 2008

Feature Presentation
outline

UMD Information
Air Pollution Control (APC)
Review of the modified Claus process
Process capacity and cost analysis
Chemical equilibrium simulation
CFD simulation
Conclusions and perspectives
2

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Sulfur removal from sour and acid gas
For details: Contact Professor A. K. Gupta, E-mail: akgupta@eng.umd.edu
http://www.enme.umd.edu/combustion/

Combustion Laboratory

Evolution of APC

Combustion Laboratory

Combustion Laboratory

OVERVIEW OF GAS PROCESSING

1
Sour Natural Gas
CH4, H2S, CO2

ALKANOLAMINE
SWEETENING

(Refinery HT)

ACID/BASE

Acid Gas
H2S, CO2

H2S
Recycle
SO2

SO2, H2O, CO2, N2

3
INCINERATION

Sales Gas
CH4, liquid products

2
SULFUR
RECOVERY

TAIL GAS
CLEAN-UP

Air
O2/N2

OXIDATION

1. REDOX
2. OXIDATION

S
4
SOLIDIFICATION

Storage

SULFUR DEGASSING

SOLID
8
STORAGE

MODIFIED CLAUS PROCESS FOR SULFUR RECOVERY

1. Combustion (Reaction Furnace)

H2S + 3/2O2

2H2S + SO2

high T

high T

SO2 + H2O + heat (518 kJ)

3/2S2 + 2H2O HR= + 47 kJ, endothermic

2. Redox (Catalytic Converter)

CAT.

2H2S + SO2

3/8S8 + 2H2O + heat

(108 kJ)

low T

3H2S + 3/2O2

3/8S8 + 3H2O + heat (626 kJ)

OVERALL

SIMPLIFIED PROCESS SCHEME FOR THE CLAUS SULFUR RECOVERY PROCESS

HIGH TEMP.

LOW TEMP.

THERMAL STAGE

CATALYTIC STAGES

RE-HEATER

RE-HEATER

Al2O3

Al2O3

a
ACID
GAS

REACTION
FURNACE

2H2S: SO2
N2, H2O

2H2S: SO2
N2, H2O

WASTE
HEAT
BOILER

CONDENSER
AIR

CONDENSER

Tail gas

CONDENSER

Liq. S8

Liq. S8

Liq. S8

CLAUS PLANT STRAIGHT-THROUGH CONFIGURATION

30% & H2S

Liq. S8

10

PROJECTED WORLD SURPLUS

11
Source: Bill Kennedy, SHELL CANADA LIMITED, Sulphur 2004, Barcelona, Spain, Oct.24-27, 2004

ADNOC HABSHAN PLANT PROBLEM STATEMENT

Design a Sulfur Recovery

Plant with a:
Capacity 800 tonnes/day
Sulfur Recovery of 99%
Using Modified Claus Process +
Tail Gas Unit
Composition of Feed Stream

Feed Stock Conditions

Pressure

1.4 bars

Temperature

30o C

H2S

Mole Percent

CO2 Mole Percent

N2

Mole Percent

60 %
30 %
10 %

12

MODIFIED CLAUS PROCESS

PRACTICAL
LIMIT

THEORETICAL RECOVERY OF SULFUR (%)

CONV 3

CATALYTIC
STAGE

205oC
CONV 2

225oC

CONV 1

305oC

THERMAL STAGE

TGCU

References: Clark Peter, SOGAT Proceedings-Workshop,

Abu Dhabi, UAE, November 29 2005

WHB

(S8)

13

% THEORETICAL CONVERSION TO SULFUR

EQUILIBRIUM SULFUR CONVERSION

HR 108 kJ

HR +47 kJ
responsible for 60-70%
conversion in the furnace

14

EQUILIBRIUM COMPOSITION OF SULFUR VAPOUR

> 95%

S
S

S
S

S=S

15

16

Summary For Cost Analysis of a Sulfur

Recovery Plant Designed on the Process
Simulator HYSYS
Fixed Capital
Investment
@ 2002

Working
Capital
@ 2002

Total Capital
Investment
@ 2006

14.49 M$

2.4 M$

18.75 M$

Total
Catalyst

Total
Utility Cost

Total
Production
Cost

1.02 M$

0.77 M$

3.46 M$
17

CLAUS FURNACE
AIR

Combustion chamber
2500oC
1300oC

600oC

flame zone
Anoxic zone

SOUR
GAS

H2S/O2 Ratio
H2S + 3/2 O2

SO2 + H2O

Products

0.66

Conversion: 100%
Goal 2:1 H2S to SO2 ratio
Air Feed

2502 Kmole/h
18

CLAUS FURNACE - ANOXIC, HIGH T PROCESSES

(SULFUR SPECIES)
O2 (N2)

WHB

Combustion chamber
1300oC
2500oC

600oC

flame
Anoxic zone

acid gas
zone

Products
3/2 S2 + 2 H2O

2 H2S + SO2

S2 + 2 H2O
2 H2S

H2S + H2 + SO2 (favoured)

2 H2 + S2
19

2 H2 + SO2

2 H2O + 1/2 S2

CHEMICAL MODEL OF THE REACTION FURNACE

large number of
possible reactions

20

CLAUS FURNACE THERMOCHEMICAL EQUILIBRIUM

we have used the

STANJAN Code to explore
the influence of varying the
following parameters on the
sulfur recovery in the Claus
furnace :
- inlet hydrogen sulfide
content in the H2S / CO2
mixture
- combustion temperature
- inlet temperature
-O2 content in the air

STANJAN interface

21

Numerical Effort

Species Included in the equilibrium

kinetics mechanism
H2

CH4

O2

H2O

CO

CO2

CH3

OH

HO2

N2

AR

NH

NO

NO2

SH

H2S

SO

SO2

SO3

HSO2

HOSO

HOSO2 SN

S2

HOSHO COS

HSNO

HSO

HOS

HSOH

H2SO

H2S2

H2SO4

HS2

CH

CS

22

Case 1: Varying H2S Content

80

1600

1500

75

1300
65
1200

60

TEMPERATURE, K

70

Temperature, K

1400

H2S conversion,
%
H2S CONVERSION, %

we increase the H2S

content from 25% to
100% in the inlet sour
gas and see the
evolution of the
chemical equilibrium
state.

1100

55

1000

50

900
25%

30%

35%

40%

45%

50%

55%

60%

65%

70%

75%

80%

85%

90%

95%

100%

H2S CONTENT

H2S content
Sulfur recovery as a function of H2S inlet content

We notice an increase in sulfur conversion with CO2 decrease.

23

Case 2: Varying Temperature

We consider a mixture of 50% H2S and 50% CO2 reacting with air: 21% O2
and 79% N2 in the furnace at varying combustion temperatures.
80

70

It is shown that an
optimum sulfur
recovery is
obtained for a
furnace
temperature
around 1500K

H2SH2Sconversion,
CONVERSION, % %

60

50

40

30

20

10

0
900

1200

1500

1800

2100

2400

2700

3000

TEMPERATURE, K
Temperature,
K

Sulfur recovery as a function of temperature

24

Case 3: Varying Inlet Temperature

In this case, we are just varying the inlet temperature of the reactants. 50% H2S /
50% CO2 and air: 21% O2 / 79% N2 are reacting in the furnace.
80

3000

70
2500

40

1500

30
1000

EQ TEMPERATURE, K

2000
50

Temperature, K

H2SH2S
conversion,
%
CONVERSION, %

60

20
500
10

0
300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 2100 2200 2300 2400 2500 2600
INLET TEMPERATURE, K
Inlet
temperature, K

Sulfur recovery as a function of inlet temperature

Despite the increase of the inlet temperature, we remark that the sulfur recovery is
25
decreasing.

Case 4: Varying Oxygen Content in the Air

2100

74

72

EQ TEMPERATURE, K

1700

Temperature, K

70

H2S conversion, %

we vary the oxygen

content in the air,
starting from 21% until
100%, which reacts
with a 50% H2S and
50% CO2 mixture at
an inlet temperature
equal to 300K.

1900

68

1500
66

1300
64

1100

62

60

900
21

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

O2 CONTENT, %
Sulfur recovery as a function of O2 content

Even though the oxygen enrichment is supposed to increase recovery, we notice

that the H2S conversion decreases.
26

Equilibrium calculations [3H S + 1.5O

2

+ 5.64N2 3H20 +1.5 S2 + 5.64 N2 ] 41 species

Mass fraction of molecular sulfur for the mole fraction case of:
( H2S= 29.58%, O2= 14.79%, and N2= 55.62%)
0.24

0.76
0.74

0.23

S2 Mass fraction

0.70

0.21

0.68

0.20

0.64

0.66
0.62

0.19

0.60
0.58

0.18

0.56
0.17

Conversion efficiency

0.72

0.22

0.54
0.52

0.16
1000

1200

1400

1600

1800

2000

2200

2400

0.50

Temperature (K)

Reactor temperature versus equilibrium mole fraction of S2

Conversion efficiency = (Mass of S2)/(Mass of sulfur in H2S)

Temperature around 1600K provides high sulfur removal efficiency

27

Equilibrium calculations [3H S + 1.5O

2

+ 5.64N2+ CO23H20 +1.5 S2 + 5.64 N2 + CO2] 41 species

Mass fraction of molecular sulfur for the mole fraction case of:
(H2S= 26.9%, CO2= 8.97%, O2= 13.46%, N2= 50.62%).
0.200

0.73
0.72
0.71
0.70

0.190

0.69
0.68

0.185

0.67
0.66

0.180

0.65
0.175

0.64
0.63

0.170

Conversion efficiency

S2 Mass fraction

0.195

0.62

0.165
1000

0.61
1100

1200

1300

1400

1500

1600

1700

1800

1900

2000

Temperature (K)

Reactor temperature versus equilibrium mole fraction of S2

Hydrogen sulfide conversion to S2 maximum at temperature ~1500K

CO2 affects the process by reducing the optimum temperature

28

Sample Kinetics Calculation at 1600K

Major Species behavior with distance (time)

H2S as well as O2 mole fraction decreases with time (both curves are related)
SO2 mole fraction increases due to the reaction between O2 and H2S
S2 mole fraction increases due to the reaction between SO2 and H2S
29

Sample Kinetics Calculation at 1600K

Minor Species behavior with distance (time)

General trend for minor species with distance (time)
Species show peak behavior at the beginning, then get consumed during the
terminating reactions

30

Detailed Kinetics Calculation

Effect of Reactor Pressure

Effect of the reactor pressure on S2 mole fraction

Atmospheric pressure is favorable
High pressure reduces S2 formation
31

Detailed reaction pathways

Reaction pathways for H2S-O2 reaction

32
(Click in the box and observe changes in color & width of arrows)

CFD SIMULATION OF THE CLAUS FURNACE

FLUENT is a CFD code dedicated to
the simulation of fluid flow, heat and
mass transfer, and a host of related
phenomena involving turbulence,
reactions, and multiphase flow. We
have used it to simulate the
combustion process in the Claus
furnace.

Turbulence Model:

Meshed geometry

Standard k - model
Wall

Turbulence- Chemistry Interaction Model:

EDC
Velocity
inlet
Pressure
outlet

Boundary conditions:
Velocity
inlet

Boundary Conditions

33

CFD Results
Four cases are treated:
Case 1

Case 2

Air inlet

Temperature:

300 K

Velocity:

0.1 m/s

H2S inlet

Temperature:

300 K

Velocity:

85 m/s

Case 3

O2 inlet

Temperature:

300 K

Velocity:

100 m/s

H2S inlet

Temperature:

300 K

Velocity:

0.1 m/s

Temperature:

300 K

Velocity:

100 m/s

Temperature:

1000 K

Velocity:

0.66 m/s

Case 4

O2 inlet

Temperature:

300 K

Velocity:

100 m/s

H2S inlet

Temperature:

300 K

Velocity:

0.2 m/s

Air inlet
H2S inlet

34

Case 1:

H2S + 1.5 [O2 + 3.76 N2]

2 H2S + SO2

Pure H2S inlet

Temperature:

300 K

Velocity:

85 m/s

SO2 + H2O + 5.64N2

1.5 S2 + 2 H2S

Q=0

Air inlet
Temperature:

300 K

Velocity:

0.1 m/s

35

Case 1

36

Case 1

37

Case 2:

H2S + 1.5 O2

SO2 + H2O

2 H2S + SO2

1.5 S2 + 2 H2O

Pure H2S inlet

Temperature:

300 K

Velocity:

0.1 m/s

Q=0

Pure O2 inlet
Temperature:

300 K

Velocity:

100 m/s

38

Case 2

39

Case 2

40

Case 3:

[H2S + CO2] + 1.5O2

2 H2S + SO2

SO2 + H2O + CO2

1.5 S2 + 2 H2O
Q=0

H2S/CO2 inlet
Temperature:

300 K

Velocity:

0.2 m/s

Pure O2 inlet
Temperature:

300 K

Velocity:

100 m/s

41

Case 3

42

Case 3

43

Case 4:

[H2S + CO2] + 1.5 [O2 + 3.76 N2]

2 H2S + SO2

SO2 + H2O + 5.64N2 + CO2

1.5 S2 + 2 H2O
Q=0

H2S/CO2 inlet
Temperature:

1000 K

Velocity:

0.66 m/s

Air inlet
Temperature:

300 K

Velocity:

100 m/s

44

Case 4

45

Case 4

46

Temperature Distribution under Normal

HiTAC and Condition

47

Summary
The Claus process for sulfur recovery has been known and used in the
industry for over 100 years. It involves thermal oxidation of hydrogen sulfide
and its reaction with sulfur dioxide to form sulfur and water vapor. This process
is equilibrium-limited and usually achieves efficiencies in the range of 94-97%,
which have been regarded as acceptable in the past years. Nowadays strict air
pollution regulations regarding hydrogen sulfide and sulfur dioxide emissions
call for nearly 100% efficiency, which can only be achieved with process
modifications. A detailed literature survey revealed that most of the early
studies have focussed on the Claus catalytic stages and/or the tail gas
treatment unit. While very little work has been devoted to explore the possible
improvements to the combustion process in the Claus furnace. In this study we
presented numerical simulation results of the combustion and thermal stage of
The Claus furnace burner. We specifically explored the improvements that
Could be made on the process by oxygen enrichment, reactants pre-heating,
and injection port exchange between fuel and oxidant in the burner.

HiTAC is attractive for this process

48

The End

49