The document discusses various technologies for producing hydrogen and synthesis gas, including steam reforming, partial oxidation, coal gasification, and water electrolysis. It provides an overview of the main industrial processes used for ammonia synthesis gas production, noting that about 85% is based on steam reforming of natural gas or other light hydrocarbons. Various hydrogen and syngas production processes are also compared in terms of energy consumption, investment cost, and production cost.

1. 1
Presented By,
Prem Baboo
Sr. Manager(Prod)
National Fertilizers Ltd. Vijaipur, India

2. 2
To understand how to utilize feed stock
efficiently
To reduce plant down time
To improve man & machine safety
To reduce pollution level
To reduce capital cost
To optimize the process

3. 3
Various Hydrogen and Syngas
Production Technologies
Gaseous and
Light Liquid
Hydrocarbons
Heavy Oil Methanol Coal Water
Steam &
Autothermal
Reforming
Partial
Oxidation
Reforming Gasification Electrolysis
Hydrogen
and Syngas
Oil Refining
Hydrocracking
Hydrotreating
Ammonia
Methanol
Fischer Tropsch
Fine Chemicals
Oxo alcohols
Acetic Acid
SNG
Ore Reduction
Miscellaneous

4. 4
Main types of production process for ammonia synthesis gas
currently in operation -
– Steam reforming of natural gas or other light
hydrocarbons (Natural Gas Liquids, Liquefied Petroleum
Gas, Naphtha)
– Partial oxidation of heavy fuel oil or vacuum residue
Coal gasification and water electrolysis are no longer in use in
ammonia industry.
About 85% of world ammonia production is based on steam
reforming concepts.
Heavy oil may be attractive under special environmental
concerns, when natural gas is not available and the partial
oxidation process could solve a waste problem (heavy
residues, plastics recycle).

5. 5
Principal Reaction of Hydrocarbons
Reforming and Partial Oxidation
Reforming (strongly endothermic)
CnHm + n H2O n CO + (m/2 + n) H2
CnHm + n CO2
2n CO + m/2 H2
Combustion (strongly exothermic)
CnHm + (n + m/4) O2 n CO2 + m/2 H2O
CnHm + n/2 O2 n CO + m/2 H2
Shift Conversion (mildly exothermic)
CO + H2O CO2 + H2
Carbon Formation
CnHm
n C + m/2 H2 (Cracking)
2CO CO2 + C (Bouduard)

6. 6
Steam/ Air Reforming Process Partial Oxidation Process

7. 7
Relative consumption figures of natural gas reforming, heavy oil
and coal gasification process.
Natural Heavy Coal
gas oil
Energy consumption 1.0 1.3 1.7
Investment cost 1.0 1.4 2.4
Production cost 1.0 1.2 1.7
Drawbacks:
Steam Reforming: Large loss of energy because of endothermic
reaction.
Partial oxidation: Reaction is exothermic and that the optimum
H2/CO ratio of FT reaction, etc. is 2 or less.

8. 8
Block Diagram Of Ammonia
Plant
Gas
Purification
Reforming
Shift
Conversion
Methanation
Ammonia
Synthesis
Steam
Process Air
NG/PN
Ammonia

9. 9
0
100
200
300
400
500
600
700
800
900
1000
B/L HDS ZnO Pre-
Ref
Pri-
Ref
Sec-
Ref
HT LT GV Syn
Units (Converters)
Temperature(°C)
0
20
40
60
80
100
120
140
160
180
200
Pressure(kg/cm²)

10. 10

11. 11
Natural Gas
+
Recycle H2
HDS
(Co-Mo / Ni-Mo)
ZnO-A ZnO-B
S + H2 = H2S H2S + ZnO = ZnS
Co-Mo for Naphtha
Ni-Mo for
Natural Gas

12. 12
 Natural Gas contains both Inorganic and
Organic sulphur.
 Sulfur is poisonous to Reforming Catalyst
Ni + S = NiS
Leads to:
 Low catalyst activity (More CH4 Slip)
 High tube skin temperature

13. 13
 Organic Sulfur can not be removed.
Difficult to analyze.
 Both HDS and The ZnO catalysts are
not fully utilized
 Sulfur slip can only be detected with
lab. Analysis
 Life of catalyst can not be determined
unless lab. tests

14. 14
 New catalysts are available for Organic
sulfur removal
 ST-101 of Haldor Topsoe
 Synetix(Katalco)-Puraspec-2084
 Sulfur level in ZnO catalyst bed
 TRACERCO, it is probe used from out side to
determine the level of sulfur absorption. (Synetix)
 Sulfur testing coupons inserted at the down stream
of ZnO beds. Analyzed after every 4-8 weeks
(Synetix)

15. 15

16. 16

17. 17
Syngas Production Technologies
Reforming and Partial Oxidation
Pre-Reforming
 Operating temperatures 390 °C - 500
°C
 Catalyst
 Adiabatic
 Low steam/carbon ratio
 Feed: Hydrocarbons up to final
boiling point of 200 °C
 No carbon formation
Steam Reforming
 Operating temperatures 650 °C - 900
°C
 Catalyst
 Heat by external combustion with
air
 High steam/carbon ratio
 No carbon formation
Autothermal Reforming
 Operating temperatures 850 °C - 1000
°C
 Catalyst
 Heat by internal combustion with
oxygen
 High steam/carbon ratio
 No carbon formation
Partial Oxidation
 Operating temperatures 1300 °C -
1500 °C
 Non catalytic
 Heat by internal combustion with
oxygen
 Low steam / carbon ratio
 Carbon formation

18. 18

19. 19

20. 20

21. 21

22. 22

23. 23

24. 24
(Computation Fluid Dynamic)
Heat integration and metallurgy

25. 25
 To reduce High Capital Cost
 To reduce High Stack Losses and Pollution
 To reduce High surface heat loss
 To reduce Large Structure
 To reduce Pressure drop
 To reduce Costly catalyst tubes
 To reduce startup time

26. 26
 To Simplify the process
 To reduce S/C ratio
 To reduce Maintenance cost
 To simplify system heat integration
 To reduce energy for ID & FD

27. 27
 Catalyst
 Catalyst tube material
 Air pre-heater (Modification)
 Pre-Reformer
 Reforming Process (heat integration)
 Design

28. 28
 High activity
 More surface area
 Low pressure drop
 High physical strength
 More stable for poisons

29. 29
 Reforming Catalysts
RING WAGON WHEEL
5-HOLE
DD-RING
Monolithic10-HOLE
Latest by
Synetix

30. 30
 Reformer Tubes
 Concept
To Increase heat transfer
Facilitate more catalyst packing
Increase life and skin temperature
 Thickness reduced, increasing ID, OD kept
Constant.
 Material of construction changed
HK-40 ►IN519 ►Micro alloy (Manu rite)
What has
been
changed?
Latest &
best metal?

31. 31
Grade C Cr Ni Others
HK-40 (1970’s) 0.40 25 20
HP-45Nb 0.45 25 35 1.5Nb
HP-45Nb MA 0.45 25 35 1.5Nb,Ti,Zr
HP-15Nb 0.15 25 35 1.5Nb
IN-519 (1980’s) 0.30 24 24 1.5Nb
IN-657 0.08 50 48 1.5Nb,N
20Cr-32Ni+Nb 0.10 20 32 Nb
35Cr-45Ni,MA(1990’s) 0.45 35 45 1.5Nb,Ti,Zr

32. 32
 Basic reason is to reduce heat loss
through Primary Reformer stack
 To save Fuel and proper combustion.
 ID fan load is reduced.

33. 33
Process
Air
Hydrocarbons
+
Steam
Adiabatic
Pre-Reformer
Primary
Reformer
Secondary
Reformer
Heat Integration (Tri-Reforming)

34. 34
Feed Stock flexibility (Higher hydrocarbons)
Reduced Load on Primary Reformer
Improvement of Primary Reformer catalyst
life
Lower tube skin temperature
As guard for Primary Reformer Catalyst
Easy replacement of catalyst (without
complete plant shut down)

35. 35
Feed 5.4 to 5.6 Gcal/MT NH3
Fuel 1.7 to 2.5 Gcal/MT NH3
Power 0.05 to 0.09 Gcal/MT NH3
Steam + or - Gcal/MT NH3
Total 7.15 to 8.2 Gcal/MT NH3
Steam energy depends on the internal generation & consumption

36. 36
Can Energy be reduced?
Feed Energy
Fuel Energy
Steam Energy
Electrical Power
Yes

37. 37
 Steam-Methane-Reforming (SMR)
 Auto thermal Reforming (ATR)
 Non-Catalytic Partial Oxidation
(NCPOX)
 Catalytic Partial Oxidation (CPOX)
 Combined Reforming (CR)

38. 38
CONVENTIONAL STEAM REFORMING
Process Air
Natural Gas
+
Steam
Reformed Gas
Fuel

39. 39
STEAM REFORMER TOP
FIRED

40. 40

41. 41
Steam-Methane Reforming
 Advancements
 Reduction in numbers of catalyst tubes
 Primary Reformer size reduction
 Elimination of FD fan
 Dual fuel firing system
 To improve combustion, improved burner designs

42. 42
Combustion Air
Suction duct
Reformer furnace height is large
Normally ID fan is at the top

43. 43
Auto Thermal Reformer
 Auto thermal reformer is a pressure vessel similar to
that of Secondary Reformer.
 Catalyst is advanced, resistance to high temperature.
 It can be operated up to a pressure of 50kg/cm²G.
 Start up time is minimum as compared to
conventional reforming.
 It is economic if used in large capacity
plants(1800MTPD & above)
 CH4 conversion is more than 99%

44. 44

45. 45
Auto Thermal Reforming Route
ATR technology is offered by three Process Licensors
M/s Lurgi, Germany
M/s KBR, USA
M/s HTAS, Denmark

46. 46
KBR
ATR/ KRES (KBR Reforming Exchange System)
Purifier Technology

47. 47

48. 48
Kellogg’s Advanced Auto Thermal
Reformer
1. Being vertical in shape can be
accommodated in small area
2.Capacity is very high
3. Reduced NOx and Sox
4. Carbon conversion more than 99%

49. 49
Lurgi G-POX
Low cost non-catalytic partial oxidation

50. 50
Lurgi C-PoX
Catalytic partial oxidation

51. 51
Lurgi’s Auto Thermal Reformer
(ATR)

52. 52
HTAS
The key elements of the technology are the design
of the burner, the catalyst formulation, and
refinement of the operating conditions.
Topsøe’s proprietary burner design has been
developed on the basis of computational fluid
dynamics, hydraulic simulation, pilot plant
testing, and feedback from industrial operation.

53. 53
Secondary Reformer
 Critical parts
 Burner (gun)
 Catalyst and top bricks
 Insulation material
 Material of construction

54. 54
Combined Reforming
 In this process the heat generated in
Secondary Reformer has been used in
Primary Reformer
 Type of Combined Reformers
 Gas Heater Reforming (GHR)
 Heat Exchange Reforming (HER)
 Heat Integrated Reforming (HIR)

55. 55

56. 56
ICI – Heat Exchange Reformer

57. 57
Some Facts & Figures
Process Feed
Gcal
Fuel
Gcal
Total
Gcal
Steam Reforming 5.29 1.72 to 2.15 7.01 to 7.44
Excess air
Reforming
5.60 1.08 to 1.72 6.68 to 7.32
Auto thermal
Reforming
5.93 0.86 to 1.72 6.79 to 7.65
Partial Oxidation 6.89 1.29 to 2.15 8.18 to 9.04
Energy = Gcal/MT Ammonia

58. 58
Brand
Name
GREENCAST 94
TRL
KAST-O-LITE 97
L TRL
SiO2 0.1 0.16
Al2O3 94.6 95.2
Fe2O3 0.1 0.1
CaO 4.9 4.16
MgO Traces Traces
TiO2 Traces Traces
Na2O+K2O 0.2 0.3
Trange 1850°C 1900°C

59. 59
 Advanced Burner for Secondary Reformer
ICI Burner Haldor Topsoe Burner

60. 60
MPG - LURGI MULTI PURPOSE GASIFCATION
•Multi Purpose Gasification "MPG" is a process for the
partial oxidation of hydrocarbons delivering a synthesis gas
composed mainly of carbon monoxide and hydrogen.
•Different -even unmixable- hydrocarbon-containing feeds
can be gasified: ranging from
•Natural gas,
•Tars,
•Other coal gasification residues,
•Refinery residues,
•Asphalts
•Slurries and chemical wastes

61. 61
Waste Utilization Centre at SVZ (Sekundärrohstoff Verwertungs Zentrum
Schwarze Pumpe)

62. 62
Gasifiers operated at SVZ (Sekundärrohstoff Verwertungs
Zentrum Schwarze Pumpe)
•Fixed bed gasifiers (FBG)
•British Gas/Lurgi gasifier (BGL)
•Multi Purpose gasifier (MPG)

63. 63
MPG Gas-gasification
Gasification occurs in the empty, refractory-lined reactor at temperatures between 1200°C
and 1400°C
A water-scrubbing tower removes traces of soot, HCN and NH3
Soot formation in the process is extremely low, so that no special filtration is necessary
with the wastewater passing to a sour-water stripper and final treatment
A desulfurization unit can be located either upstream or downstream of the gasification,
depending again on the heat utilization and on the material selection for the equipment in
areas prone to metal dusting.

64. 64
ATR Gas-MPG
pressure [bar] 35 70
temperature inlet [°C] 750 500
temperature outlet [°C] 950 1400
O2 / natural gas [mol/mol] 0.4 0.7
steam / natural gas [mol/mol] 1.5 … 1.7 0.05…0.2
Comparison of Lurgi´s catalytic and non-catalytic partial
oxidation processes

65. 65
0 1 2 3 4 5 6 7 8
MPG
Autothermal
Reforming
Steam
Reforming
H2/CO Molar Ratio
Process
Syngas Production Process Comparison
H2 / CO Ratios

66. 66
 The reaction
 CO + H2O  CO2 + H2 (exothermic) Water Shift reaction.
 HT Shift Reaction : Iron Oxide Cromia Catalyst
300 – 450 oC
CO Conversion : 90 – 95 %
 LT Shift Reaction : CuO – ZnO Catalyst
200 - 300 oC
 Present process is highly stable and well proven.
 The drawbacks of the process are:
 High pressure drop
 Degree of conversion
 Bottom most catalyst remains half utilized

67. 67
 Isothermal reactors were tested to improve the
CO conversion but failed.
 Reasons
 High pressure drop
 Mechanical failure of inter bed exchangers
What is successful ?

68. 68
 Radial flow converter
 Advantages:
 Low pressure drop
 Low CO slip
 More than 80% of the
catalyst utilization
Casale Radial-Axial Flow
Shift Converter

69. 69Axial-Radial distribution concept

70. 70
Process
 Chemical absorption
 Benfield, GV, Glycine, Catacarb, MEA.
 Physical absorption
 Methanol (Rectisol), Sulfolane (Sulfinol),
Dimethyl ether of propylene Glycol (Selexol)
 Adsorptive Purification
 Zeolites (PSA)
 Membrane Seperation
 CMS (Carbon molecular Sieves): hydrogen
permeation
 Nanoporous Carbon membranes: Carbon
dioxide permeation

71. 71

72. 72

73. 73

74. 74

75. 75

76. 76
 Advancements Why?
 High loop pressure
 Low conversion per path
 Compressor Recycle stage Efficiency Low
 High pressure drop across the loop
 High Compression power

77. 77
 Advancements What?
 Improved catalyst activity
 Reduce pressure +drop
 Increase conversion per path
 Reduce synthesis gas compressor size and
increase efficiency.

78. 78
 Synthesis gas purification (eliminate CH4,
Ar)/Reduction in gas volume
 Latest Ruthenium catalyst (Reduced loop
pressure)
 Using catalyst in multi-beds with inter-stage
cooler.
 Drying and cooling synthesis gas
 Eliminate inter cooler separators (or make
compact)
 Improved design

79. 79
 Haldor Topsoe
 Kellogg(KRES)
 Kellogg-Braun-Root(KAAP, KBR)
 Foster Wheeler
 Krupp-Uhde
 ICI, LeadingConcept Ammonia (LCA)
Most widly used Technologies

80. 80

81. 81

82. 82

83. 83

84. 84

85. 85
Iron Catalyst
Ruthenium

86. 86

87. 87

88. 88

89. 89

90. 90

91. 91

92. 92

93. 93
Ammonia Casale Axial Radial
Converter:
Annular top bed is left open at the top to permit a
part of the gas flow radially through the catalyst
bed.
The Brown & Root Braun Adiabatic
Converter:
Two adiabatic converters in series each
containing a single catalyst bed.

94. 94
19.14-21.53
G C al/ MT
11.24-12.68
07.89-10.05
06.46-07.89
05.74-6.22

95. 95