DEFINITION

Mixture of hydrogen (H2 ), carbon monoxide (CO) and carbon dioxide (CO2 ).
• Origin:
– Water gas (CO + H2): water vapor and coal
– Reformed gas (CO + 3H2): CH4 scission with H2O
NOTE that all synthesis gases contain hydrogen.
• Syngas is a key intermediate in the chemical industry. It is used in a number of highly
selective syntheses of a wide range of chemicals
o Methanol
o Formaldehyde
o Formic acid
o Hydrocyanic acid
o Methylamine
o Halogen derivatives of methane
• For fuels, and
• As a source of pure hydrogen ( for ammonia synthesis) and carbon monoxide.
Shift from chemicals to designer fuels
 REFORMING Synthesis Gas
Methane
O2 / H2O
CH4 CO + H2

GTC or GTFC
TECHNOLOGIES
GTL PROCESS

Others

Hydrogen
Methanol Olefins,
FISCHER TROPSCH DME Gasoline
PROCESS MDED

Diesel

Naphtha
PREMIUM PRODUCTS

Lubes
 Coal Synthesis Gas
O2 / H2O
Heavy Oil PARTIAL OXIDATION CO + H2

GTC or GTFC
TECHNOLOGIES
GTL PROCESS

Others

Hydrogen
Methanol Olefins,
FISCHER TROPSCH DME Gasoline
PROCESS MDED

Diesel

Naphtha
PREMIUM PRODUCTS

Lubes
 FEED STOCK FOR SYNTHESIS GAS PRODUCTION

LIGHT HYDROCARBONS HEAVY HYDROCARBONS

Refinery Gases Fuel Oil ( 30%)
LPG (propane, Butane) Vacuum Tar
Natural Gas (48%) Asphalt
Naphtha Petroleum Coke
Bio Sources Coal (18%)
PROCESS PROCESS
Steam Reforming Partial Oxidation
Partial Oxidation -

Natural Gas, LPG, LNG & fuel oil fractions best -> higher H
content
The following is an approximate comparison of the energy consumption, cost of production and
the capital cost of the plants for three the feedstocks.

Natural Gas Heavy Oil Coal

Energy consumption 1.0 1.3 1.7

Investment cost 1.0 1.4 2.4
Production cost 1.0 1.2 1.7
Steam-Methane Reforming
The basic steps leading from the hydrocarbon feed(Natural Gas) to the high purity hydrogen product are:
1. Pretreatment of the raw feed,
2. Reforming to synthesis gas,
3. Conversion to a hydrogen-rich gas, and
4. Purification to hydrogen product specifications.
 Steam Reforming Reactions
The basic reforming reaction for a generic hydrocarbon CnHm may be written as:

CnHm + nH2O nCO + (2m + n)H2

Steam reforming of methane (CH4 ) consists of three reversible reactions: the

strongly endothermic reforming reactions, 1 and 3, and the moderately
exothermic water-gas shift (WGS) reaction 2.

CH4 + H2O CO + 3H2 [ΔH = +206 kJ mol-1] (1)

CO + H2O CO2 + H2 [ΔH = -41 kJ mol-1] (2)
CH4 + 2H2O CO2 + 4H2 [ΔH = +165 kJ mol-1] (3)
• Reaction 1 & reaction 3 (steam reforming) is endothermic and volume
expansion is occurring so, high temperature and low pressure will
shift the equilibrium towards right.
CH4 + H2O CO + 3H2 [ΔH = +206 kJ mol-1] (1)
CH4 + 2H2O CO2 + 4H2 [ΔH = +165 kJ mol-1] (3)

• Reaction 2 is exothermic and hence is favored by low temperature

while pressure has no effect as no volume change occur.
CO + H2O CO2 + H2 [ΔH = -41 kJ mol-1] (2)
Operating Parameters
Following parameters governs the product from the reformer.

• The composition of the feed gas,

• The temperature of the reactor,
• The operating pressure, and
• The steam to methane ratio in the reactor (H2O : CH4)
 Steam-methane Reforming at high pressure
Use of high pressure for steam-methane reforming has the following advantages:

1. Hydrogen produced during SMR has to be compressed before it enters the other
manufacturing processes. Since the overall methane reforming reaction increases the total
volume of the gas, a compression ahead of the reforming steps lowers the overall amount of
energy required for compression.
2. The hot gas leaving the CO conversion column, being at a temperature above its dew point
(over 120 -130oC) can serve to heat and regenerate the absorbent solutions used for CO2
removal.
3. Reforming is carried out with an excess of steam, which is recovered downstream as
condensate. The higher the operating pressure, the higher will be the value of the heat
recovered from condensing this steam.
4. High pressure generally leads to more compact equipment with a subsequent general
reduction in investment cost.
5. Natural gas is usually available at high pressure.
H2O: CH4 = 2: 1

Temp Pressure Conversion (vol. %) Dry effluent gas composition

oC atm.
CH4 CO CO2 CO H2 CH4
400 1 23 21.7 11.6 0.3 46.9 41.2
627 1 73.4 33 9.3 11.4 71.7 7.6
5 42.8 27.7 10.8 5.9 61 22.3
10 32.9 23.7 10.7 4.1 55.1 30.1
727 1 95.8 24.9 6.1 17.2 75.6 1.1
5 71.1 26.4 7.8 13.2 70.5 8.5
10 56.6 25.7 8.7 10.5 66.1 14.7
827 1 99.59 19.3 4.7 19.2 76 0.1
5 92.6 20.1 5.1 18.2 74.9 1.8
10 82.2 21 5.7 16.7 72.8 4.8

H2O: CH4 = 4: 1

Temp Pressure Conversion (vol. %) Dry effluent gas composition

oC atm.
CH4 CO CO2 CO H2 CH4
400 1
627 1 91.7 57.3 13.5 7.9 76.7 1.9
5 63.1 46.2 13.8 5 70.2 11
10 50 39.2 13.7 3.7 65.4 17.2
727 1 99.4 49.5 11.1 11.2 77.6 0.14
5 89.6 47.9 11.6 10 76 2.4
10 77.6 44.7 11.8 8.7 73.6 5.9
827 1 99.94 41.7 9.5 13.2 77.3 0.01
5 98.6 41.6 9.5 13.1 77.1 0.3
10 95.2 41.3 9.7 12.6 76.6 1.1
 H2O: CH4 = 6: 1

Temp Pressure Conversion (vol. %) Dry effluent gas composition

oC atm.
CH4 CO CO2 CO H2 CH4
400 1
627 1 97.2 70.5 15.3 5.8 78.3 0.6
5 76.8 59.9 15.3 4.4 74.4 5.9
10 63 51.4 15 3.4 70.7 10.9
727 1 99.8 62.5 13.4 8.3 78.4 0.04
5 96.1 61.1 13.7 7.7 77.8 0.8
10 88.8 58.4 13.8 7 76.5 2.7
827 1 99.98 54.2 11.9 10.1 78 .004
5 99.6 54.2 11.9 10.1 77.9 0.1
10 98.3 53.9 12 10 77.6 0.4

H2O: CH4 = 2: 1 Pressure 30 to 35 atm. H2O: CH4 = 4: 1 Pressure 30 to 35 atm.

Temp oC Dry converted gas composition ( vol. % ) Temp oC Dry converted gas composition ( vol. % )
CO2 CO H2 CH4 CO2 CO H2 CH4
400 11.56 0.31 46.90 41.23 500 15.28 2.06 67.32 15.34
500 12.49 2.41 57.20 27.90 600 14.08 6.60 75.99 3.33
600 10.59 9.08 69.58 10.78 700 11.58 10.42 77.70 0.30
700 6.78 16.03 75.26 1.93 800 9.98 12.51 77.48 0.03
800 5.09 18.65 76.12 0.20 900 8.78 13.99 77.23 0.00
900 4.07 19.89 76.02 0.02
• High percentage of conversion of methane to hydrogen, such as occurs at 899oC with
a methane to steam ratio 1:2, is also achieved at 700oC when the methane to steam
ratio is 1:4.
• Thus reforming conversion for given hydrogen content can be achieved by increasing
the methane to steam ratio at a lower temperature with many benefits, although a
higher methane to steam ratio incurs higher steam generating costs.
• The CO content from methane to steam ratio 1:2 and a temperature of 800oC is about
50% higher then that resulting from methane to steam ratio of 1:4 and a temperature
of 700oC. And since the entire CO in the generator gas must be converted into
hydrogen, the lower the methane to steam ratio during reforming requires more steam
for CO removal.
Reforming reactions 1 and the associated water gas shift reaction 2 are carried
out normally over a supported nickel catalyst at elevated temperatures,
typically above 500oC. Reactions 1 and 3 are reversible and normally reach
equilibrium over an active catalyst, at high temperatures. The overall product
gas is a mixture of carbon monoxide, carbon dioxide, hydrogen, and
unconverted methane and steam.

Steam reforming process is divided into two steps: a section at high

temperature and pressure (typically 800-1000C and 30-40 bar) in which the
reforming and water gas shift reaction occurs, followed by an additional two-
step shift section at a lower temperature (typically at 200-400C) in order to
maximize the CO conversion.
PRIMARY REFORMING
REFORMING FURNACES
• Primary reformer is a heat exchanger
• Its purpose is to heat up the process gas
• Catalyst and reactions are in tube side
• Combustion on the shell side
• Dominant heat transfer by radiation
• Multiple fuel supply points
 The primary reformer furnace consists of two principal sections:
1. The radiant fire box containing burners and tubes packed with catalyst.
2. The convection section containing a series of heat exchangers designed
to recover the maximum possible heat from the flue gases leaving the
fire box.

REFORMING FURNACES
REFORMING FURNACES
REFORMING FURNACES

The overall design of reforming furnaces may be divided into two parts:
1. The process design, which is concerned with the tubes and their
contents, and
2. The furnace design, which is concerned with the furnace installation
surrounding the tubes
 PROCESS DESIGN OF REFORMING FURNACE:

• Tube walls have thickness of 0.4 to 0.9 inch.

• Depending upon the pressure, the inside diameter of the tube ranges from 3 to 6 inches.
• The pressure drops through the catalysts filled tubes might vary from 20 to 75 psi. Higher
allowable pressure drops permit longer tubes.
• Higher velocities inside the tubes lead to lower tube-wall temperatures and smaller
furnaces.
• After their passage through the hundreds of primary reformer furnace tubes, the hot
process gases are collected into one stream at a relatively high temperature and velocity.
The combination of high temperature, high reducing potential of the hydrogen and high
velocity requires careful attention to protecting the inside surface of the transfer line to
avoid erosion.
The thermal efficiency of the radiant section of modern furnaces varies
between 45 % and 49 % of the fuel’s lower heating value, the convection
section to recover most of the remaining energy by
o Preheating process air and air for combustion
o Preheating the feed stock
o Superheating steam at one or more pressure levels
o Generating steam
o Preheating steam boiler feed water

By arranging various convection sections the overall efficiency can be as high as

91 % of the fuel’s lower heating value.
REFORMING FURNACE DESIGN

Most important design variables are

• Life-time of reformer tubes (high Cr alloy),
• Catalyst activity,
• Service life,
• Heat transfer and
• Pressure drop.

Material deterioration occurs due to the alternating thermal and mechanical

stress, external and internal oxidation and carburization.
The radiant fire box handles the process fluid in three sections
o An inlet header, which feeds the catalyst filled tubes
o The catalyst filled tubes, and
o An outlet header, which is connected to each of the catalyst tube

Each of these sections requires extreme care in designing for stresses

resulting from high temperatures and pressures. The main problems in
the mechanical design arise with respect to support and thermal
expansion.
• The tubes are some time supported by an arrangement of multiple counter weights that
allows the differential movement of the tubes which prevent the variation in longitudinal
stresses as the tube expands upward. The same effect may also be achieved through a
constant support spring hanger. Keeping the tubes in tension at all the times reduces any
tendency for then to bow.
• Vertical expansion of catalysts filled tubes varies between 7 to 10 inches, depending on
metal temperature and tube length.
• While the tube is expanding upward by this distance, the inlet manifold also expands
horizontally along its length as a function of its temperature.
• The horizontal expansion of outlet manifold can be as much as19 inches for a larger
reformer.
• Carbon steel or 1.25Cr-.5 Mo steel is used for inlet manifold while centrifugally cast pipe
of HK-40 or HT material is used for outlet manifold.
Types of Reformer
Top fired reformer
• Firing occurs at one level. No of burner per tube is less than side fired.
• Radiation efficiency is higher than other design
• Burner is located in close to the coldest point
• Less structural steel is needed
• But heat input is adjustable only a limited degree
• Difficult to adjust the heat release along the length of tube, which leads to
form carbon in the upper part of the tubes ( where cold gas inside the tubes
is exposed to a thermal shock by the high rate of heat release)
• The greatest heat fluxes occur at the tops of the tube
• A number of fuels can be used
Terraced Wall Type Reformer
 Developed by Foster Wheeler company and is intermediate between the
side fired and bottom fired
 Heat flux of any location can be controlled because of the position of the
burner ( very even heat flux distribution)
 Wide choice of fuels
 It takes in the account the variations in the process heat demands from inlet
to outlet of the tube, with the heat flux in the upper part is higher then in
the lower.
 It takes into account the need for uniform distribution of heat flux around
the circumference of the tubes
 Higher investment cost but more economical on long run
Side Fired Reformer
 Provide very uniform heat distribution along the length of the catalyst tube
and can be adjusted by control for the individual burner
 The larger number of burners makes fuel and preheated combustion air
distribution more complicated and more expensive.
 Radiation efficiency is lower than top fired
 Lower residence time of flue gas can favor NOx formation
 Tubes are bottom supported. Holes are provided in the ceiling for free
upward expansion
 Advantages and disadvantages are same as terrace wall furnace
Primary Reformer (PRF)
Furnace Zone
• Convert the hydrocarbon mainly Methane (CH4) to CO, CO2 and H2.
• Nickel (Ni) catalyst is used.
• This is an endothermic reaction.
• A part of PNG is used as fuel in the furnace.
• Other part of PNG is used for steam reforming.
• Fuels are supplied using tubes. There are 100 tubes in each side, so in total 200 tubes are
used in the primary reformer.
• Tubes are designed to absorb certain temperature (T) and pressure (P). In primary
reformer vacuum is maintained.
• 480 burners are used in. The height of the furnace is 12m. In the upper 3m there are pre
reformed catalysts.
• In the PRF N2 blanket is used to protect reduced catalyst from being oxidized.
Primary Reformer (PRF)
Heat recovery in Convection Zone
• There is a convection zone in the upper part of the furnace.
• Only about 50% of the energy produced in the Furnace Zone is used for reforming
reaction.
• To recover the rest of the energy this convection zone is required.
• This energy is used for various purposes such as heating the process streams,
• process steam,
• process air,
• boiler feed water etc.
• Around 35-40%energy can be recovered. Two induced draft fans (IDF) are used to
emit the exhausts of the PRF. The exhaust temperature is generally 185ºC. The
temperature of these gases should not be less than 100ºC. If temperature is less
than 100ºC mist can form which can damage the IDF coil.
Secondary Reformer (SRF)
• In PRF 100% conversion is not achieved.
• So another reformer is used to convert the rest of the saturated
hydrocarbon.
• Ni catalyst is also used in this section.
• Here an additional reaction takes place.
• This additional reaction is combustion reaction of H2 and O2.
Catalyst for Steam Methane Reforming
• Methane can be reformed without a catalyst but at a very high
temperature of about 1300 to 1400 C

• In non catalytic process, methane not only reacts with steam but also
with its thermal decomposition products.
CH4 H2 + C2H6
CH4 CH3 + H
H + CH4 CH3 + H2
2CH3 C2H6
Primary Reformer Catalyst Requirements
1. High and Stable Activity
• Low methane slip
• Lower tube wall temperature
• Reduced Fuel usage
2. Low Pressure Drop
• Savings in Compression Power / Fuel
• Possible Throughput increase
3. Good Heat Transfer
• Reduced tube wall temperatures
• Smaller catalyst particles improve heat transfer from wall to bulk gas
• Smaller particles increase pressure drop
• Catalyst shape should be optimized for high heat transfer with low PD

4. High resistance to Carbon Formation

5. High Strength
6. Robust Formulation / Simple Operation
Primary Reformer Catalyst

Active Metal Surface

Investigated Catalysts
• Noble metal catalysts
Supported Rh, Pt, Pd, Tr, Ru, Re catalysts
• Non noble metal catalysts
Ni based catalysts (most investigated catalysts)
• Precious metals are more active then Ni as catalyst for steam reforming but Ni has been
recognized as the most active and reliable metal for commercial catalyst for steam
reforming.
• The noble metals have an activity of this order:
Rh>Pt>Pd>Ru

It has also been said that Nickel (Ni) at higher loadings is equally effective with Rh,
Pt, and Pd. Nickel based catalysts widely used, although nickel-based catalysts require a
high reaction temperature and an excess amount of steam to prevent coke deposition on
the catalyst surface.
 Disadvantages of Ni Based Reforming Catalyst
• High temperature reaction induces sintering of catalyst.
• Carbon deposit formed makes catalyst deactivated rapidly – major
problem
• Two possible pathways for carbon formation:
• methane dissociation
CH4 C + 2H2
• CO disproportionation (esp., favored at temperatures b/w 600 – 800 oC):
Un-sintered Catalyst

Sintered Catalyst
The heterogeneous catalytic steam reforming reaction could possibly
follow the general path
CH4 C + 2H2
C + H2O CO + H2

CH4 + H2O CO + 3H2

This possibility finds some confirmation in methane decomposition

promoted by reforming catalysts as well as carbon deposits that occur
when the ratio of steam to methane is low.
At the same time it has been established that methane reforming with
twice or more the theoretical steam requirement is associated with no
carbon deposit on the active nickel catalyst.
Primary Reformer Catalyst

Three key factors in catalyst design:

• Geometric surface area
• Heat transfer from tube to gas
• Pressure drop

Also of concern:
• Packing in the tube
• Breakage characteristics
Catalyst activity largely depends upon
1. Its metal surface area i.e., the number of active sites.
The catalytic activity of a given metal benefits from a high dispersion of the metal
particles. For Ni catalysts, the dispersion of the metal particle is 2- 5%, with metal
particles of 20-50 nm. It has been shown that a loading of 15-20 wt. % of Ni does
not produce any increase in activity.
2. The structure of the available surface area.
It has been noticed that close packed surface of nickel is less active than the more
open surface. It has been shown that some lattice distortion is required to play a
role in the catalytic reaction. The activity per unit metal surface area decreases
with increasing dispersion. The reason for this is due to a decrease of large
ensemble landing sites on the smaller particles.
Primary Reformer Catalyst

Reforming reaction is Diffusion Limited Reaction

Diffusion Limitation
• The reforming reaction is very fast on the Ni sites
• Reaction limited to catalyst surface (<0.1mm)
• Reaction rate controlled by film diffusion
• High geometric surface area gives high activity
 Key Reaction Steps

1. Diffusion of the molecules in the bulk gas phase----------------- FAST

2. Diffusion of the molecules through the gas film------------------ SLOW

3. Diffusion through catalyst pores -------------------- SLOW

4. Absorption of the molecules onto the Ni sites ----------- FAST

5. Chemical reaction to produce CO2 and H2 ------------- FAST

Primary Reformer Catalyst

Reaction Rate:

• Reaction rate controlled by film diffusion

- Most of the reaction takes place on the catalyst surface <0.1mm
- Pore diffusion not limiting as film diffusion controls the overall rate
- Catalysts with higher geometric surface area (GSA) per unit volume of
catalyst will have a higher activity.
- Pore size/distribution is not significant for most commercial grades of
reforming catalyst
 Catalyst Heat Transfer

 Reforming involves large heat flows into tubes

 Absolute requirement to keep tubes cool
 Major limitation is at the tube wall
 Need to minimize thickness of stationary gas film at tube wall
 The catalyst acts as a heat transfer enhancer to improve heat transfer from tube wall to gas
 Promotes turbulence at the wall
 Promotes gas mixing from walls to tube centre
 Smaller catalyst particles improve heat transfer from wall to bulk gas and hence reduce tube
wall temperatures
 Catalyst Heat Transfer

 Heat transfer to catalyst normally very good (high GSA)

 Minor limitation is radially in the catalyst
 Catalyst also improves radial heat transfer
 Smaller pellets improve wall transfer
 Larger pellets improve radial transfer
 Smaller usually better overall
 BUT smaller particles increase pressure drop
 Catalyst shape needs to be optimized for high heat transfer with low PD
 Catalyst Shape

 The traditional catalyst shape is a ring

 Smaller rings give higher activity and heat transfer but higher pressure drop

 Shape optimised catalysts offer high GSA and heat transfer with low PD

 Important that shape also provides good packing and breakage characteristics
 Catalyst Design Criteria
Conclusions

Design of catalyst shape is a complex optimization of:

- Higher GSA (Needed for activity - diffusion control)

- Higher HTC (Needed for cooler reformer tubes)

- Lower Pressure drop (Plant Efficiency / Capacity)

Need also to consider breakage characteristics

and loading pattern inside the reformer tube
VULCAN
VSG-Z101

VULCAN
VSG-Z102
 Catalyst Breakage

 Catalyst breaks up in service

 Main mechanism due to startup / shutdown
 The tube when cooling exerts massive forces (several tonnes)
 Forces exerted by carbon formation immeasurable
 Pressure drop rises about 10% per year
 Minimum Catalyst strength for handling & charging approx. 10 kgf
 The key is to ensure the catalyst does not fragment into small bits/dust.
 Careful charging essential
Packing Characteristics
Catalyst Support
• Support plays an important direct or indirect role in the reaction steps involved in a
catalytic process.
• The same active metal on different support produces different conversion and yields.
• The support determines the dispersion of the catalytically active metal particles and the
catalyst’s resistance to sintering.
• In general, the role of the support is literally to provide a surface support for dispersing
the catalytically active metal, in order to obtain a stable and high activity metal surface.
• Support plays a crucial role since it determine the final particle size of the metal, with its
pore structure, morphology, and phase transitions that it can undergo.
• In addition, a support can have a chemical role as well, by activating one or more reaction
steps.
• The strong interaction between metal and support would make a catalyst more resistant to
sintering and coking, which would create a more stable catalyst.
• During the initial development of the reforming process, Ca-Al-Si
base catalysts were used, but now have been replaced as they generate
volatile silica which acts as fouling agent in downstream heat
exchangers
400 oC 600 oC 700 oC 800 oC 900 oC
Silica Conc. In steam at 1.0 7.0 15.0 26.0 40.0
180 psig (ppm w/w)

50 psig 200 psig 300 psig 400 psig 500 psig

Silica Conc. In steam at 5.2 21.4 31.6 41.7 52.5
750 oC(ppm w/w)

Most common supports for methane reforming are α- and γ-Al2O3,

MgO, MgAl2O4, SiO2, ZrO2 and TiO2. These supports have good
porosity, which allows larger surface area.
• Ni-Ni bonds for Ni/MgO catalysts can be stabilized by NiO-MgO
solid solution. In addition it can prevent carbon diffusion into nickel
particles. The support also influences the catalyst activity by varying
the electron donating ability of the reduced nickel surfaces. Supports
with a basic nature, such as MgO, are known to enhance the activation
of steam, and dissociation of steam into OH and H species. Carbon
deposits can lead to active site blocking and affect the catalyst
reactivity and stability. The support can also play a role in suppressing
carbon deposition.
• ZrO2 and CeO2 have been known to be able to oxidize deposited
carbon. Further, they are capable of participating in the catalytic
reaction by oxidizing or reducing reaction intermediates.
Different catalysts are required for different duties of primary and
secondary reforming and for different feed stocks.
Component 57-1 46-1 54-1
NiO 32 21 18
CaO 14 11 15
Al2O3 54 32 67
MgO - 13 -
K2 O - 7 -
Service PRF of CH4 at P at PRF of higher SRF of PRF gases
least 30 atm. and T hydrocarbons at 30 atm. And T up
up to 850 oC other than to 1000 oC
methane

The Al2O3 and MgO in these compositions act as promoters for active
nickel catalyst.
Aluminate base catalysts are now being used, which have following
advantages
1. No shrinkage with use
2. Activity at low temperatures ( 540 o C )
3. High crush strength in oxidized state
4. More uniform strength among the catalyst ring
5. But aluminate base catalyst has low crush strength after reduction
and loses its activity due to formation of nickel aluminate.
Possibility for the improvement of Ni-containing catalysts
• Controlling the size of the ensembles of Ni atoms on the surface
inhibits carbon deposition
• Controlling the Metal-Support Interface of Ni Catalysts
• Using metal oxide support with strong Lewis basicity can suppress the
carbon formation
• The structure-sensitivity of carbon formation provides the possibility
for inhibition of the carbon deposition by the modification of the
catalyst surface