8/20/15

LECTURE6:
FUEL AND INDUSTRIAL GASES

CHEMICAL TECHNOLOGY (CH-206)

Dr. Vimal Kumar
Department of Chemical Engineering

INTRODUCTION
The chemical industry depends to a major extent on gases
composed of one or more of the chemical elements of

8/20/15

Carbon

(C)
Hydrogen (H2)
Oxygen (O2), and
Nitrogen (N2).

These gases are used for fuel and for the synthesis of
organic and inorganic chemical compounds.
The raw material for these gases are

Water,
Air,

Coal,

Natural

gas, and
Petroleum.

In India the manufacture of fuel gas is limited to coal as a source of carbon with vary low production.

FUEL GASES: CLASSIFICATION

Kcal/cu m

Producer gas (CO, N2, H2

12001600

Steel industrys heating

requirements (heat treat,
coke oven)

Water gas (CO, H2)

25002700

Heating, Chemical synthesis

Coke oven gas (CO2, CH4,

45008000

Heating, Chemical synthesis

Carburetted or Oil gas

(water gas and pyrolyzed
oil)

40009000

Heating

Natural gas and LPG

(Liquified Petroleum gas)

600014000

Heating, Chemical synthesis

with steam added to

reduce Hnet to zero)

Principal use

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Type

H2)

PERCENT COMPOSITION AND

HEATING VALUES OF VARIOUS
FUEL GASES
NG (mid

NG

Coke oven

Blue water

Carburated

Bituminous

continent)

(Pennysylva

gas

gas

water gas

producer

nia)

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Fuel gas

gas

CO

6.3

42.8

33.4

27.0

CO2

0.8

1.8

3.0

3.9

4.5

H2

53.0

49.9

34.6

14.0

N2

3.2

1.1

3.4

3.3

7.9

50.9

O2

0.2

0.5

0.9

0.6

CH4

96.0

67.6

316

0.5

10.4

3.0

Ethane

31.3

Illuminants

3.7

8.9

Gross (Mj/m3)

36

46

21

11

20

5.5
4

HEATS OF COMBUSTION OF
COMMON NATURAL GASES
8/20/15

Substance

MJ/m3

Btu/ft3

Methane

37.56

1000

Ethane

65.80

1763

Propane

93.65

2510

Butane

121.18

3248

Pentane

149.00

3752

FUEL GASES
PRODUCER (SUCTION) GAS: RAW MATERIAL
Raw material
Coal
Air

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or blast furnace coke

Steam

Reaction (exothermic)
2C + O2+ 3.73 N2 2CO+ 3.73 N2
Quantitative requirements
Basis:

100 Nm3 of producer gas

Coke 2025 kg
or coal 2530 kg
Air 6080 Nm3
Steam 810 kg
Typical plant capacities: 25,000250,000 cubic meter/day

FUEL GASES
PRODUCER GAS: PROCESS
8/20/15

FUEL GASES
PRODUCER GAS: PROCESS
8/20/15

Steam and air mixture injected in bottom of a

watercooled jacketed steel furnace.
The steel furnace is equipped with a rotating
grate to remove fusible ash.
Solid fuel is added from hopper valve on top of
furnace.
Producer gas is cooled by passing through a
waster heat boiler.

FUEL GASES
PRODUCER GAS: MAJOR ENGINEERING ISSUES

Design of suitable gas producer furnace to:

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Keep

uniform fuel surface

Provide adequate gasfuel contact time at high
temperature
Avoid clinkering and provide for proper fused ash
removal

Addition of correct steam quantities to supply net

heat of reaction near zero on a continuous
oncethrough process.

FUEL GASES
WATER (SYNTHESIS) GAS: RAW
MATERIAL

8/20/15

Water gasis comprised ofcarbon monoxideandhydrogen.

The gas is made by passingsteamover a red-hot carbon fuel such
ascoke:
H2O + C H2+ CO (H = +131kJ/mol)

The reaction isendothermicso the fuel must be continually re-heated to

keep the reaction going.
In order to do this, an air stream, which alternates with the vapor
stream, is introduced for the combustion of carbon to take place.
O2+ C CO2(H = 393.5kJ/mol)
(Theoretically, for 6L of water gas, 5L of air is required.)

Alternatively to prevent contamination with nitrogen, energy can be

provided by using pure oxygen to burn carbon into carbon monoxide.
O2+ 2 C 2 CO (H = 221kJ/mol)
(Theoretically 1L of oxygen produces 5.3L of pure water gas.)

10

FUEL GASES
WATER (SYNTHESIS) GAS: RAW MATERIAL
Raw material
Bituminous,
Air

anthracite coal or coke

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Steam

Quantitative requirements
Basis:

100 cu m of water gas from Carbon (C)

Coke (C)
55 kg
or coal (C) 58 kg
Air
220 Nm3
Steam
80 kg
Typical plant capacities: 250,0001,500,000 Nm3/day

11

FUEL GASES
WATER GAS: PROCESS REGENERATIVE PROCESS
It is comprising of two reactors
One

operates on blow period which heat carbon as follows:

C(s) + O2 (g) CO2 (g)

Other

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HO = 96.5 Kcal

operates on run period where endothermic reaction takes place

C(s) + CO2 (g) 2CO (g) HO = +38.9 Kcal

The process cycle of 46 min is divided as:

Blow

or heatup: 35%
Downrun: 33%
Uprun: 30%
Short purge uprun:
2%

The steel reactor is equipped with refractor lining.

If higher BTU gas is required, an additional high temperature
carburetor section is required for pyrolyzing oil spray and mixing.

12

FUEL GASES
WATER GAS: PROCESS REGENERATIVE PROCESS
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13

FUEL GASES
WATER GAS: PROCESS CONTINUOUS PROCESS
8/20/15

The process was developed in 1940s based on use

of tonnage or low purity grade oxygen made by
air separation procedure.
The correct ratio of steam, oxygen, and coal is
added to the reactor to yield a self sustaining
reaction of approximately zero heat release.
Subsequent innovation allow for ash content >
30%. Therefore, Indian coal can also be used.

14

FUEL GASES
WATER GAS: PROCESS CONTINUOUS PROCESS
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15

FUEL GASES
WATER GAS: MAJOR ENGINEERING ISSUES
8/20/15

Designing suitable ash removal systems for

various grades of coal in continuous processing.
Optimizing cycle for regenerative process.

16

FUEL GASES
COKE OVEN GAS: RAW MATERIAL
Raw material
Coking
Air

coal

Producer

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gas

17

FUEL GASES
COKE OVEN GAS: PROCESS

with alkali to remove CO2,

liquefaction to remove light hydrocarbons, and
scrubbing with liquid N2 to take out CO.

8/20/15

Upgraded coal for coking purpose is fed to a by

product coke oven furnace.
The producer gas is fed for heating the chamber
to 1000 0C for 1220 hours.
The gas is removed continuously and put through
a series of purification steps.
If specifically NH3 synthesis gas is required
further purification operations are needed:

scrubbing

18

FUEL GASES
COKE OVEN GAS: PROCESS
8/20/15

19

FUEL GASES
COKE OVEN GAS: MAJOR ENGINEERING ISSUES

Process Economy Indian Scenario

500 tons of NH3 per day at Rourkela is produced using 1.8
x 106 m3 of coke oven gas in an ammonia synthesis plant.

8/20/15

Suitable grade of coking coal in India. Before

coking typically washing, preroasting, and
solvent extraction are some of the pretreatments
are needed.
Choice of scrubbing liquors for CO and CO are
2
needed.

20

8/20/15

21

CONTINUE.
Natural gas processing

Liquefied Petroleum gas

FUEL GASES
NATURAL GAS
8/20/15

22

FUEL GASES
NATURAL GAS- COMPOSITION
Components of Natural Gas (NG)

Heats of Combustion of common Natural Gases

Substance

8/20/15

MJ/m3

Btu/ft3

Methane

37.56

1000

Ethane

65.80

1763

Propane

93.65

2510

Butane

121.18

3248

Pentane

149.00

3752
23

NG AND LPG TREATMENT PROCESS

Drying

Heavy end removal

Purification
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24

FUEL GASES
NATURAL GAS PROCESSING
excess water
Remove acid gas
Dehydrate
Remove mercury
Remove nitrogen
Separate NGL (ethane, and heavier hydrocarbons)

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Remove

25

FUEL GASES
NATURAL GAS PROCESSING
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26

FUEL GASES
NATURAL GAS PROCESSING
Water removal
Removes

free liquid water and condensate gas

Sends the gas to a refinery
The water goes to waste

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27

FUEL GASES
NATURAL GAS PROCESSING
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28

FUEL GASES
NATURAL GAS PROCESSING
Acid Gases

Hydrogen

sulfide
Mercaptans
Carbon dioxide

8/20/15

Acid gas removal processes

Amine

treating (Monoethanolamine, Diethanolamine,

Diisopropylyamine, Methylethanolamine)
Benfield process
Sulfinol process
others

Hydrogen sulfide goes through a Claus process

29

FUEL GASES
NATURAL GAS PROCESSING: AMINE TREATMENT
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30

FUEL GASES
NATURAL GAS PROCESSING: SULFINOL PROCESS
Used to reduce H2S, CO2, and mercaptans from gases

Great for treating large quantities of gas

Solvent absorbs the sour gas

Sulfolane is used

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31

FUEL GASES
NATURAL GAS PROCESSING: DEHYDRATION
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32

FUEL GASES
NATURAL GAS PROCESSING: GLYCOL DEHYDRATION

Method for removing the water vapor from the

gas

8/20/15

Usable glycols
Triethylene

glycol (most commonly used)

Diethylene glycol
Ethylene glycol
Tetraethylene glycol

Absorption of water with glycol

33

FUEL GASES
NATURAL GAS PROCESSING: GLYCOL DEHYDRATION
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34

FUEL GASES
NATURAL GAS PROCESSING: PRESSURE SWING
ADSORPTION

8/20/15

Adsorbent material is used

Gas and material go under high pressure
Material adsorbs the gas ( H S, mercaptans, CO )
2
2

Disadvantages
Requires

high pressures
Slow cycle times

35

FUEL GASES
NATURAL GAS PROCESSING: MERCURY REMOVAL
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36

FUEL GASES
NATURAL GAS PROCESSING: MERCURY
REMOVAL

Current Processes
Activated

carbon through chemisorption. Activated

has extremely high surface area

8/20/15

Mercury can damages aluminum heat

exchangers
Those

used in cryogenic processing plants

Those use in liquefaction plants
37

FUEL GASES
NATURAL GAS PROCESSING: NITROGEN
REJECTION

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38

FUEL GASES
NATURAL GAS PROCESSING: NITROGEN
REJECTION

Cryogenic process
Common

refrigerants used
Most common method for removal of impurities such
as nitrogen
Disadvantages

8/20/15

Must reach extremely low temperatures

Only useful for large scale production

Absorption process (using lean oil or solvent)

Lean

oil is fed countercurrent with the wet gas

Temperature and pressure are set to allow for the
greatest absorption of unwanted gases

Membrane separation
Adsorption process (activated carbon)

39

FUEL GASES
NATURAL GAS PROCESSING: DEMETHANIZER
8/20/15

40

FUEL GASES
NATURAL GAS PROCESSING:
DEMETHANIZER
The next step is to recover the NGLs

Process

Cryogenics

8/20/15

using a turbo-expander can be used

This is the most common

Lean

oil adsorption can be used here

41

FUEL GASES
NATURAL GAS PROCESSING: CRYOGENIC PROCESS
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42

FUEL GASES
NATURAL GAS PROCESSING: NGL RECOVERY
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43

FUEL GASES
NATURAL GAS PROCESSING: NGL RECOVERY
The rest of the liquid is fed to three units
Deethanizer

8/20/15

Debutanizer

Depropanizer

Process

Separation

using distillation column

44

FUEL GASES

NATURAL GAS PROCESSING: NGL SWEETENING

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45

FUEL GASES

NATURAL GAS PROCESSING: NGL SWEETENING

Merox Processes
Mercaptan

oxidation
Removes mercaptans from

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Propane
Butane
Larger hydrocarbons

46

FUEL GASES

NATURAL GAS PROCESSING: NGL SWEETENING

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47

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48

LPG PROCESSING

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49

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50

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51

SYNTHESIS GASES

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52

FUEL GASES: SYNTHESIS GAS

INTRODUCTION

Synthesis Process

CO/H2

Catalysts

Temp. OC

Products

atms.

ratio
Methane

Pres.,

8/20/15

It is generally considered as a variable mixture of CO and H2 for

synthesis of organic compounds.
In some applications CO is not needed, such as: ammonia synthesis gas
(3H2 + 1N2) and hydrogenation of alcohols (H2 only)

Ni

205500

FischerTropsch

0.50.2

Co, Ni, Fe

180300

130

Paraffinic & olifinic

hydrocarbons varying from
methane to waxes and small
quantities of oxygenated
products

Synol

0.30.5

Fe

185225

1530

Straight chain normal alcohol

0.3

ZnO, CuO,
Cr2O3

250350

100
300

Methanol

Fe + alkali

400500

100
300

Alcohols from C1 to Cn

100
300

Saturated branched
hydrocarbons

Methanol
Higher alcohol
synthesis
Isosynthesis

0.5

ThO2, ZnO,
Al2O3

400450

CH4

53

FUEL GASES
SYNTHESIS GAS: PROCESSES
From petroleum hydrocarbons
Reforming

(ICI steamnaphtha reforming process)

Partial combustion

8/20/15

From coal or coke

Water

gas
Coke oven gas

54

FUEL GASES

SYNTHESIS GAS: REFORMING (ICI STEAMNAPHTHA

REFORMING PROCESS)

(a)

Reforming reaction (endothermic and exothermic reaction)

C n H 2n 2 nH 2 O Ni (2n 1)H 2 ;

8/20/15

H o 52 Kcal for n 1
H o 238 Kcal for n 6

(b)

CO 3H 2 CH 4 H 2 O;

H o - 52.0 Kcal

55

FUEL GASES

SYNTHESIS GAS: REFORMING (ICI STEAMNAPHTHA

REFORMING PROCESS)
Raw material

Refinery naphtha or offgases

Air (optional)
Steam
Catalysts (nickel and promoted iron oxide)
Solvents (ethanolamine, and ammoniacal cuprous formate)

8/20/15

Quantitative requirements

Basis: 100 Nm3 of hydrogen of 99.0 % purity

Naphtha
21.9 kg
Steam
560 kg
Fuel (as naphtha)
22.3 kg
Cooling water
6.5 tons
Electricity
1.4 KWH
Typical plant capacities: 10 200 tons/day of H2

80,0001,680,000 Nm3/day of synthesis gas

56

FUEL GASES

SYNTHESIS GAS: REFORMING (ICI STEAMNAPHTHA

REFORMING PROCESS)
Reforming for preparation of synthesis gas containing H 2
with or without CO.

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57

Ammonia Gas

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58

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59

FUEL GASES

SYNTHESIS GAS: REFORMING (ICI STEAMNAPHTHA

REFORMING PROCESS)
Reforming for preparation of ammonia synthesis gas.

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60

FUEL GASES

The hydrocarbon is mixed with steam and fed to the

reforming furnace.

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SYNTHESIS GAS: REFORMING (ICI STEAM

NAPHTHA REFORMING PROCESS)

The nickel catalyst is packed in vertical tubes of 34 inches

in diameter and about 2025 feet long.
Heat for the endothermic reaction is supplied by
combustion gas.
The reaction temperature is maintained in the range of
7001000 OC; high temperature alloy steel is used for the
tubes and the steel wall of the furnace is refractory lined.
A space velocity of 500600 /hr is maintained.
Depending on the required product there are three
alternate processes after the reformer.

61

FUEL GASES
SYNTHESIS GAS: REFORMING (ICI STEAM
NAPHTHA REFORMING PROCESS)
For COH2 synthesis:

The effluent reformer gas is cooled to 35 OC and pumped to a

hot potassium carbonate scrubbing system to remove CO 2.

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For H2 gas:

Stream is mixed with product gas and fed to shift converter to

produce more H2 from CO.
Reformer gas is quenched with steam to give 350 OC input gas to a
catalytic converter using iron oxide catalyst promoted with
chromium oxide.
A space velocity of 100200 /hr is maintained.
CO2 is scrubbed using amine absorption process and traces of CO
are removed by methanation reaction.
For high purity hydrogen, one or two additional stages of the shift
converter, CO2 absorption combination are added with either
ammonical cuprous formate or molecular sieves used added to
remove residual CO and CO2 down to 10 ppm or less.

62

FUEL GASES
SYNTHESIS GAS: REFORMING (ICI STEAM
NAPHTHA REFORMING PROCESS)
For NH3 synthesis:
The

correct amount of nitrogen is added via air and

the oxygen is burned out by hydrogen in a Ni
catalyzed combustion chamber inserted immediately
following the reformer.
Gases are cooled to 350 OC using water quenching
tower and then passed to the shift converter.
Except for additional N2 which passes through, the
remainder of the process is same as for hydrogen
preparation.

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63

FUEL GASES
SYNTHESIS GAS: MAJOR ENGINEERING ISSUES

Sulfur contamination of reforming catalyst (sulfur content

in the naphtha should be 5 ppm)

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Design of an efficient reformer furnace to economically

supply endothermic heat of reaction.
Avoid carbon formation on catalyst by use of highly specific
catalyst.
Removal of CO2 and CO.
The bulk of the CO2 is removed by the absorption
process using either potassium carbonate or
monoethanolamine (MEA).
Final traces of CO and CO2 can be removed by
methanation process (reverse refoming process):
(a)

CO 2 4H 2 Ni CH 4 2H 2 O;

(b)

CO 3H 2 Ni CH 4 H 2 O;

300 - 400 O C, 8 - 10 atm

64

FUEL GASES

SYNTHESIS GAS: PARTIAL COMBUSTION

8/20/15

Chemical reactions
(a)

CH 4 2O 2 CO 2 2H 2 O

(b)

CH 4 H 2 O CO 3H 2

(c)

CH 4 CO 2 2CO 2H 2

Net reaction : 3CH 4 2O 2 3CO H 2 O 5H 2 ;

H 0

The CO:H2 ratio can be lowered by adding extra steam to give the
water gas shift reaction:
CO H 2 O CO 2 H 2
65

FUEL GASES
SYNTHESIS GAS: PARTIAL COMBUSTION

8/20/15

66

FUEL GASES

SYNTHESIS GAS: PARTIAL COMBUSTION

Raw material

Low purity natural gas or cheap liquid hydrocarbons

Tonnage oxygen (low purity grade)
Steam
Catalysts (promoted iron oxide shift converter catalyst)
Solvents (ethanolamine, and ammoniacal cuprous formate)

8/20/15

Quantitative requirements

Basis: 100 Nm3 of hydrogen of 99.0 % purity

Naphtha
29.2 kg
Steam
104 kg
Oxygen
26 Nm3
Cooling water
8 tons
Electricity
0.7 KWH
Typical plant capacities: 10 200 tons/day of H2

100,0001,600,000 Nm3/day of synthesis gas

67

FUEL GASES

The process feed and oxygen are preheated separately.

8/20/15

SYNTHESIS GAS: PARTIAL

COMBUSTION
The preheated feed and oxygen are mixed at 550 OC and fed
to a burner in a refractory lined furnace labeled gas
generator.
After wash quench the product gas is routed for different
routes depending upon the required products:
H2 route

Steam is mixed with product gas and fed to shift converter to

produce more H2 from CO.
Amine absorption of CO2 is followed by caustic scrubbing.
Traces of CO and CO2 can be removed by either ammonical cuprous
formate or liquid nitrogen scrubbing.
The purified H2 after mixing with N2 can be used for further
production of NH3.

68

FUEL GASES

SYNTHESIS GAS: PARTIAL COMBUSTION

CO + H2 route:
The

shift converter is by passed and scrubbed with

amine to remove CO2.

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Acetylene route:
The

product gas is treated with dimethyl formamide

to remove acetylene and polymer before further CO
H2 processing.

69

FUEL GASES
SYNTHESIS GAS: MAJOR ENGINEERING ISSUES
Proper design of burner for flame stabilization in gas
generator

Removal of trace impurities of CO and CO2.

Handling of deposited carbon on the catalyst.

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70

AMMONIA SYNTHESIS
Feed

Steam

Ammonia
Synthesis

SteamMethane
Catalytic Reforming

Methanation

Shift
Conversion

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Sulfur
Removal

Carbon Dioxide
Removal

Ammonical
Product

Operating pressure for:

The steam reforming, shift conversion, carbon dioxide removal and methanation:
25 to 35 bar,
71
The ammonia synthesis loop 60 to 180 bar (depending upon the proprietary
design used)

Steam reforming

AMMONIA SYNTHESIS
SULFUR REMOVAL

The gaseous hydrogen sulfide is then adsorbed and

removed by passing it through beds ofzinc oxide
where it is converted to solidzinc sulfide:
H2S + ZnO ZnS + H2O

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Sulfurcompounds are removed from the feedstock

because sulfur deactivates thecatalysts used in
the synthesis of ammonia.
Catalytichydrogenationis carried out to convert
sulfur compounds in the feedstocks to gaseous
hydrogen sulfide:
H2+ RSH RH + H2S(gas)

72

AMMONIA SYNTHESIS

CATALYTIC STEAM REFORMING, SHIFT

CONVERSION & CO2 REMOVAL
The sulfur free feedstock is then passed into a
catalyticsteam reformerto produce hydrogen pluscarbon
monoxide (synthesis gas):

8/20/15

CH4+ H2O CO + 3H2

The mixture of CO and H2 is then proceeds to the

catalyticshift converter to convert the carbon monoxide
tocarbon dioxideand more hydrogen:
CO + H2O CO2+ H2

The carbon dioxide is then removed either by absorption in

aqueousethanolaminesolutions or by adsorption
inpressure swing adsorbers(PSA).

73

AMMONIA SYNTHESIS
CATALYTIC METHANATION

Further the catalytic methanation is carried out

to remove any small residual amounts of carbon
monoxide or carbon dioxide from the hydrogen:
CO + 3H2 CH4+ H2O

8/20/15

CO2+ 4H2 CH4+2H2O

To produce ammonia, the hydrogen is then

catalytically reacted with nitrogen (derived from
process air) to form anhydrous liquid ammonia
(ammonia synthesis loop also referred to as
theHaber-Boschprocess):
3H2+ N2 2NH3

74

AMMONIA SYNTHESIS
CATALYTIC METHANATION

8/20/15

Due to the nature of the (typically multi-promoted

magnetite) catalyst used in the ammonia synthesis
reaction, only very low levels of oxygen-containing
(especially CO, CO2and H2O) compounds can be
tolerated in the synthesis (hydrogen and nitrogen
mixture) gas.
Relatively pure nitrogen can be obtained byAir
separation, but additional oxygen removal may be
required.
Since relatively low single pass conversion rates
(typically less than 20%), a large recycle stream is
required. This can lead to the accumulation of
inerts in the loop gas.

75

ACKNOWLEDGEMENT
Slides are developed from the following references:
Austin

G. T., "Shreves Chemical Process Industries",

Fifth edition, Tata McGraw Hill, NY.
Kent J.A., "Riegel's Handbook of Industrial
Chemistry, CBS Publishers.
Gopala Rao M. & Marshall Sittig, "Drydens Outlines of
Chemical Technology for the 21st Century", Affiliated
East West Press, New Delhi.
Mall I. D., "Petrochemical Process Technology",
Macmillan India Ltd., New Delhi.
NPTEL (online)
http://encyclopedia.che.engin.umich.edu/Pages/Separatio
nsChemical/Adsorbers/Adsorbers.html

8/20/15

76

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77

SUBSTITUTE NATURAL GAS

FUEL GASES: SUBSTITUTE

NATURAL GAS
CO + H2 mixture from coal and steam by
gasification process
Lowheat

content (3.7 to 7.5 MJ/m3, having 50% N2)

Mediumheat

8/20/15

content

The lowheat content gas is used mainly as an

onsite
Industrial

fuels, and
Intermediate in the production of formaldehyde and
ammonia

The mediumheat content gas is used to produce

substitute natural gas after methanation.

78

COAL GASIFICATION PROCESS

TECHNOLOGIES
Technology

Coal Feed,

Location

t/day
Fixed bed
Lurgidry ash
British Gas/Lurgi Slagging

2nd generation

600800
3800
200

Worldwide
Westfield, Scotland
Noble County Ohio
York, Pa.

Fluidized Bed
Hygas
Ugas

2nd generation
2nd generation

75
2800

Chicago, Ill.
Memphis, Tenn.

Entrained Bed
Kopper Totzek
Texaco

1st generation
2nd generation

150
1000
200

Worldwide
Germany
Barstow, Cailf.
Muscle Shoals, Ala.

Shell - Koppers

2nd generation

150

W. Germany

Combustion Engineering

2nd generation

150

Windsor, Conn.

ATC/Wellman

Status1981

1st generation
2nd generation

8/20/15

Gasifier

79

LURGI PRESSURE GASIFIER

(PROCESS)

It has a pressurised moving bed (~2800 kPa) system, therefore it cannot

use caking coals and operated with either air or oxygen.
8/20/15

Devolatilization takes places as the

coke flow downward due to gravity
Devolatilization and gasification of the
resulting char takes place at 620 OC
760 OC temperatures.
The crude gas leaves the gasifier at
temperatures between 370 OC and 595
O
C, depending upon the type of coal.
The crude gas contains tar, oil,
naphtha, phenols, ammonia, and
traces of coal and ash dust.
The crude gas is passed to a scrubber and
washed with a circulating gas liquor and
then cooled to a temperature at which the
gas is saturated.
The gas leaving the gasifier after
scrubbing are CO2, CO, CH4, H2, and H2O.

80

PROCESS FLOWSHEET OF SASOLLURGI

GASIFICATION PROCESS
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81

WINKLER GENERATOR FLUIDIZED BED

GASIFIER
8/20/15

It has the advantage of uniform temperature distribution and

excellent solid gas contact.
It can handle wide variety of coals without a significant loss of
efficiency.

Crushed and fine coal is fed

into the top and oxygen and
steam into the bottom of the
reactor.
The oeprating temperature is
higher, 800 OC 1000 OC.
The exit gas have high dust
contents and it must be
removed before further
processing

82

KOPPER TOTZEK ENTRAINED BED

GASIFIER

It can handle wide variety of coals and produce a gas free of tars and
phenols.

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It has the advantage of higher capacity and gas production as

compared to other processes.

The Pulvarised coke, steam

and oxygen are fed together
and the coal is gasified in
suspension.
The operating temperature is
very higher 1900 OC. Further it
needs high amount of oxygen.
No pretreatment is needed as the
flowing gas separates the
particles and they are gasified so
rapidly that they cannot
agglomerate.

83

COMPOSITION OF TYPICAL PRODUCT

GASES
(DRY BASIS MOLE %)

Lurgi

Kopper-Totzek

Winkler

H2

38.0

36.7

41.8

CO

20.2

55.8

33.3

CO2

28.6

6.2

20.5

CH4

11.4

0.0

3.0

C2H6

1.0

0.0

0.0

H2S or COS

0.5

0.3

0.4

N2

0.3

1.0

1.0

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Component

84

TEXACO GASIFICATION PROCESS

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It also uses entrained flow technology for gasification of coal.

It gasifies coal under relatively high pressure (2085 atm) by
injection of oxygen (or air) and steam with concurrent gas/solid flow.
Fluidized coal is mixed with either oil or water to make it into
pumpable slurry.
This slurry is pumped under pressure into a vertical gasifier, which
is basically a pressure vessel lined inside with refractory walls.
The slurry reacts with either air or oxygen at high temperature.
The product gas contains primarily CO, CO 2, and H2 with some
quantity of methane.
Because of high temperature, oil or tar is not produced.
This process is basically used to manufacture CO-rich synthesis gas.

85

TEXACO GASIFICATION PROCESS

8/20/15

86

The gasifier operates at around 11001370C and a pressure of 2085 atm.

COAL GASIFICATION: SUMMARY

The low and medium heat syngas produced from coal can be
converted to a high heat content gas (30 37 MJ/m 3) by the
following reactions:
(1) C + H2O CO + H2

(gasification)

(2) CO + H2O CO2 + H2 (water gas shift reaction

to give CO:H2 = 1:3)
(3) C + CO2 2CO

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controlled

(Boudouard reaction)

At sufficiently high pressure the hydrogen from reactions (1) and

(2) will hydrogenate some of the carbon to yield methane:
(4) C + 2H2 CH4
(5) CO + 3H2 CH4 + H2O (methanation)

Before methanation the sulfur and CO 2 are removed from the gas

87

COAL GASIFICATION: SUMMARY

Operating pressure:

Operating temperature: 800 OC to 1650 OC

atmospheric to 6.9 MPa

The higher pressure and lower temperature result in the

formation of large amount of methane.

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88

COAL GASIFICATION: SUMMARY

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89

IN-SITU COAL GASIFICATION (UCG)

8/20/15

In situ gasification, or underground gasification,

is a technology for recovering the energy content
of coal deposits that cannot be exploited either
economically or technically by conventional
mining (or ex situ) processes.
Coal reserves that are suitable for in situ
gasification have low heating values, thin seam
thickness, great depth, high ash or excessive
moisture content, large seam dip angle, or
undesirable overburden properties.

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IN-SITU COAL GASIFICATION

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91

CLAUS PROCESS

TheClaus processis a catalytic chemical process

that is used for converting gaseous hydrogen sulfide
(H2S) into elemental sulfur (S).

8/20/15

The process is commonly referred to as asulfur

recovery unit (SRU)and is very widely used to
produce sulfur from the hydrogen sulfide found in:
raw

natural gas,and
the by-product sour gases containing hydrogen sulfide
derived fromrefining petroleum crude oiland other
industrial facilities.

In 2010, the world wide production of by-product sulfur was 68 M metric tons,
majorly from petroleum refiningandnatural gas processing plants.

92

CLAUS PROCESS: HISTORY

8/20/15

In nineteenth century, there were many alkali manufacturing plants

in England producing sodium carbonate (Na 2CO3) by the Leblanc
process.
The original Claus process was developed by Carl Friedrich Claus, a
chemist working in England, for the purpose of recovering sulfur
from the waste calcium sulfide (CaS) generated by the Leblanc
process.
As a catalyst, he chose a bog iron ore and later bauxite (a mineral
with a high alumina content).
In 1883, Claus was granted a British patent for the process.
During the next 53 years, the Claus process underwent several minor
modifications.
In 1936, I.G. Farbenindustrie a (German conglomerate of chemical
companies) introduced a modification of the process that utilized a
thermal conversion step followed by catalytic conversion steps, which
is the basically the concept currently used in modern Claus sulfur
recovery units.

93

CLAUS PROCESS: FEED GAS

COMPOSITION
8/20/15

94

CLAUS PROCESS: REACTION

MECHANISM

The Claus reaction to convert H2S into elemental sulfur

requires the presence of one mole of SO2for each two
moles of H2S:
2H2S + SO23S + 2H2O

8/20/15

To provide that ratio of components, the first step in the

Claus process is the combustion of one-third of the H 2S in
the feed gas:
H2S + 1.5 O2SO2+ H2O
The overall process reaction, combining reactions (1) and
(2), is:
2H2S + O22S + 2H2O

95

CLAUS PROCESS: PROCESS

DESCRIPTION

The feed gas to a is burned in a reaction furnace using sufficient

combustion air to burn only one-third of the H 2S it contains.

8/20/15

The furnacetemperature and pressureis maintained at about 1000

OC and 1.5 bar gauge (barg).

At those conditions, the Claus reaction occurs thermally in the reaction

furnace (i.e., without requiring any catalyst).

About 70% of the H2S in the feed gas is thermally converted into
elemental sulfur in the reaction furnace.
The hot reaction product gas, containing gaseous sulfur, is used to
produce steam in a waste heat boiler (or boiler) which results in
cooling the gases.
The gas is then further cooled and condensed in a heat exchanger
while producing additional steam.
The condensed liquid sulfur is separated from the remaining
unreacted gas in the outlet end of the condenser and sent to product
storage.

96

CLAUS PROCESS: PROCESS

DESCRIPTION
8/20/15

The separated gas is then reheated and enters

the first catalytic reactor maintained at an
average temperature of about 305 C, where
about 20% of the H2S in the feed gas is converted
into elemental sulfur.
The outlet product gas from the first reactor is
cooled in another condenser while also producing
steam.
The condensed liquid sulfur is separated from the
remaining unreacted gas in the outlet end of the
condenser and sent to product storage.

97

CLAUS PROCESS: PROCESS

DESCRIPTION
The separated gas from the second condenser is sent to another
reheater and the sequence of gas reheat, catalytic reaction,
condensation and separation of liquid sulfur from unreacted gas is
repeated for the second and third reactors at successively lower
reactor temperatures.

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About

5% and 3% of the H2S in the feed gas is thermally converted into

elemental sulfur in the second reactor and third reactors, respectively.

The remaining gas (or tail gas) separated from the last condenser
is either burned in an incinerator or further desulfurized in a "tail
gas treatment unit" (TGTU).
In a Claus sulfur recovery plant having three catalytic reactors, an
overall conversion of at least 98% can be achieved.
In fact, the latest modern designs can achieve up to 99.8%
conversion of hydrogen sulfide into product sulfur that is 99+%
saleable "bright yellow sulfur".

98

CLAUS PROCESS: PROCESS FLOW

DIAGRAM
8/20/15

99

CLAUS PROCESS: REHEAT

METHODS
The various methods used for the reheating
required upstream of each catalytic reactor
include:

gas-fired heaters using fuel gas and designed

to operate at sub-stoichiometric conditions to prevent
any oxygen (O2) from getting into the reactors which
can damage the catalyst.
Gas-to-gas heat exchangers in which cooled gas from
a condenser exhanges heat with the hot gas from the
upstream reactor.
Steam-to gas heat exchangers in which the cooled gas
from a condenser is heated with high-pressure steam.

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Direct

100

CLAUS PROCESS: OTHER DESIGN

FEATRUES
8/20/15

Older Claus sulfur recovery units were designed using only two
catalytic reactors.
Such units will typically convert only about 97% of the H 2S in the feed
gas.
Because of stringent environmental regulatory requirements in the
United States as well as many other nations, many of those older units
have been upgraded to include three reactors.
The tail gas from those that have not been upgraded is very probably
desulfurized further in a tail gas treatment unit.
When the feed gas to a Claus unit includes ammonia and
hydrocarbons(such as in the overhead gas from a petroleum refinery
sour water stripper), special designs of the reaction furnace burner are
available to provide complete combustion of those feed gas components.
To obtain higher reaction furnace temperatures and/or reduce the gas
volume to be processed, pure oxygen may be used to enrich the reaction
furnace combustion air.

101

CLAUS PROCESS: CATALYST

8/20/15

The catalytic reactors each contain a bed of catalyst (porous

aluminum oxide (Al2O3) or also referred as alumina) with a depth
of about 90 to 120 cm.
The catalyst not only increases the kinetics (i.e., the rate of
reaction) of the Claus reaction equation (1), but it also hydrolyzes
the carbonyl sulfide (COS) and carbon disulfide (CS 2) that is
formed in the reaction furnace:
COS + H20H2S + CO2 (4)

CS2+ 2H202H2S + CO2 (5)

The H2S formed as per the hydrolysis equations (4) and (5) is then
converted into elemental sulfur as per the Claus reaction (1).
Most of the hydrolysis occurs in the first Claus reactor.

102

CLAUS PROCESS: CATALYST

Other Claus catalysts based on titanium dioxide
(TiO2) are also used.

The titanium dioxide catalysts are produced

fromanatase, one of the three naturally occurring
mineral forms of titanium dioxide.
Titaniacatalysts and are said to be more resistant to
thermal aging than the alumina catalysts.
They are also said to have a higher activity for the
hydrolysis of COS and CS2which allows the first
Claus reactor to operate at lower temperatures
compared to alumina catalysts.
However, they are significantly more expensive than
the alumina catalysts.

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103

CLAUS PROCESS: REFERENCES

8/20/15

J.H. Gary and G.E. Handwerk(1984),Petroleum Refining Technology and

Economics, 2nd Edition, Marcel Dekker, ISBN 0-8247-7150-8.
Fundamental and Practical Aspects of the Claus Sulfur Recovery Process P.D.
Clark, N.I. Dowling and M. Huang, Alberta Sulfur Research Ltd., Calgary,
Alberta, Canada
The SuperClaus process

Sulfur production report by the United States Geological Survey

Gas Processors Suppliers Association(GPSA) (1987),Gas Processors Suppliers

Association Engineering Data Book, 10th Edition, Gas Processors Suppliers
Association. (See Volume II, Section 22)
The Role of Claus Catalyst in Sulfur Recovery Unit Performance Terry
McHugh, Ed Luinstra and Peter Clark,presented at Sulphur 98 conference in
Tucson, Arizona, November 1998.
Arthur Kohl and Richard Nielson (1997),Gas Purification, 5th Edition, Gulf
Professional Publishing, ISBN 0-88415-220-0.
Howard F. Rase (2000),Handbook of Commercial Catalysts:Heterogeneous
Catalysts, 1st Edition, CRC Press, pp. 240 - 242, ISBN 0-8493-9417-1.
British patent 5,958 (1883)

104