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Coal to SNG – The Methanation Process

Christian Wix and Ib Dybkjær, Haldor Topsøe A/S, Lyngby Denmark,
and Niels R. Udengaard, Haldor Topsoe Inc., Houston TX

Presented at the

Twenty-forth Annual International Pittsburgh Coal Conference

September 10-14, 2007, Johannesburg, South Africa

Introduction

Conversion of coal or similar feedstock (petcoke, biomass, etc.) to Substitute Natural Gas (SNG) is
becoming an attractive option in the energy landscape due to high and fluctuating natural gas prices
as well as to political issues. In general, environmental concerns and security of energy supply are
high on the political agenda. Alternative energy sources and flexibility in the conversion and
distribution network are important to reduce the dependency on oil and natural gas.

Oil and natural gas reserves are limited and mainly concentrated at relatively few locations, often
far from the main markets, and often ecologically or politically sensitive. In contrast, coal is
abundantly available, also locally in important energy markets such as China, India, and the USA.
Therefore, coal is now back as an important feedstock with gasification for production of synthesis
gas (a mixture of mainly hydrogen and carbon monoxide) as a key technology.

Fig. 1 shows the main process steps in the conversion of coal or similar feedstock via gasification to
products such as hydrogen, ammonia, methanol, di-methyl-ether (DME), liquid fuels (via Fischer-
Tropsch technology or Topsøe’s TIGAS technology), electric power with carbon dioxide
sequestering, or SNG.

Air
Air
Air separation
Separation
Separation Steam WSATM
WSA TM Sulphuric acid
Unit
unit
Unit
Steam

O2 CO2/H2S

Coal,
petcoke Syngas
Acid
Acid Gas
gas
Gas
or Gasifier Sour
Sour Shift
shift
Shift Removal
removal
Removal
TREMPTM
Synthesis
TREMP TM

biomass

Steam CO2 Steam

Fig. 1. Building Blocks in Coal Synthesis Plants

The main process steps are gasification of the feedstock with oxygen by one of several available
technologies, adjustment of synthesis gas properties as required by the final synthesis process
(mainly the H2/CO ratio) by carbon monoxide conversion, e.g. using Topsøe’s sour gas shift
catalyst type SSK, acid gas removal by e.g. UOP’s Selexol process, sulphur recovery by e.g.
Topsøe’s Wet Sulphuric Acid (WSA) process, and finally conversion of the synthesis gas to the
desired product. When SNG is the product, only partial conversion of carbon monoxide and partial
removal of carbon dioxide is required, since both are reactants in the methanation process.
However, complete removal of sulphur is essential, since it is a poison to the methanation catalysts.

SNG will normally be exported as a product via a natural gas pipeline grid, and it must therefore
comply with relevant gas specifications. A typical SNG specification is shown in Table 1.

Composition Vol%
CH4, 94 - 96
CO2 0.5 - 1
H2 0.5 - 1
CO Nil
N2 + Ar 2-3
HHV, Kcal/Nm3 8900 - 9100

Table 1 Typical SNG Specification

However, there is no general pipeline gas or SNG specification available, and the conditions in the
SNG production process must therefore be adjusted on a case to case basis to fit not only feedstock
properties, but also the relevant product specification.

The Topsøe Recycle Methanation Process (TREMPTM) as described in the following is a cost
competitive process featuring the required flexibility to fit any realistic specification.

The TREMPTM High Temperature Methanation Process

Chemistry and Catalysts

The TREMPTM technology for manufacture of SNG by high temperature methanation was studied
extensively in the 1970’ies (Ref. 1). The technology is today being further developed and optimized
due to the present energy situation. Key challenges in this process are high temperatures and high
concentrations of carbon monoxide in the feed (Ref. 2).

The hydrogenation of carbon oxides to methane takes place over nickel catalysts according to the
following, exothermic reactions:

CO + 3H2 = CH4 + H2O (-∆ H0298 = 206 kJ/mol)

CO2 + 4H2 = CH4 + 2H2O (-∆ H0298 = 165 kJ/mol)

The high heat of reaction results in a large potential adiabatic temperature rise. A key challenge is
therefore to manage the high heat of reaction by having a catalyst that has high activity at low
temperature after long exposure to high temperatures.
Topsøe has developed the proprietary catalysts MCR-2X and PK-7. The MCR-2X catalyst, which is
active at temperatures down to below 300 °C and stable at the very high temperature in the first
methanation reactor, where the outlet temperature may be as high as 700 °C. The PK-7 catalyst is
optimized for operation at low temperature and is always used in the last “clean-up” methanation
reactor, which may operate at inlet temperatures as low as 200 °C. The type of catalyst installed in
the intermediate reactor(s) is chosen on a case to case basis.

Process Layout
A typical process flow diagram for the Topsøe high temperature methanation process (TREMPTM )
is shown in Figure 2.

Feed H2/CO ratio = 3

Steam drum

R1 R2 R3
Recycle
compressor
Feed
preheater

HP
boiler Natural gas product

Super Super- HP
heated heater boiler
steam BFW
HP
boiler BFW
preheater

Process condensate

Figure 2 TREMPTM High Temperature Methanation Process Flow Diagram

A case with only one reactor between the first high temperature reactor and the last “clean-up”
reactor is shown. In some cases, depending on the operating conditions such as pressure as well as
the SNG product specification, a second intermediate reactor is required to obtain sufficient
conversion. The coal-based synthesis gas, which has been passed through a sour shift unit and an
acid gas removal unit for removal of hydrogen sulphide and excess carbon as carbon dioxide, enters
the TREMPTM unit with a value of the stoichiometric ratio M = (H2 – CO2)/(CO + CO2) of about
3.0. In order to protect the methanation catalyst from sulfur poisoning, the feed is first passed
through a sulfur guard bed for removal of traces of sulfur components that have not been picked up
by the acid gas removal unit. The desulphurized feed is then mixed with recycle gas to control the
maximum allowable temperature rise and passed to the first methanation reactor.

The exit gas from the first methanation reactor is cooled by generation of superheated high pressure
steam. After cooling recycle gas is extracted, and the remaining, partly methanated synthesis gas
passes through one or two intermediate methanation reactors in series, before it is passed to the
“clean-up” reactor for complete conversion of the carbon oxides into methane. The process stream
leaving the last methanation reactor is cooled, dried and compressed to meet the relevant pipeline
specification.

The optimal recovery of the substantial heat of reaction from the methanation reactors is important
for an optimized operating economy. The ability of the MCR-2X methanation catalyst to operate at
high reactor exit temperatures makes the production of valuable, superheated high pressure steam
possible. Such steam may be used in steam turbines for driving compressors and pumps or for
production of electric power. It is worth noting that when the steam is produced at 120 Bar g and
520 °C, then it will produce an excess of power compared to the amount required for the production
of oxygen for the gasifier.

The methanation reaction is favored by high pressure and works well with synthesis gas from all
types of coal gasifiers. A typical product specification is given in Table 1. The HHV of the SNG is
typically between 8900 – 9100 Kcal/Nm3. For comparison it may be noted that the HHV of pure
methane is 9494 Kcal/Nm3. Nitrogen and argon in the oxygen from the air separation unit will pass
through the process as inerts and end up in the SNG product. Due to the volume reduction by the
methanation reaction, the concentration of the inerts in the feed will be quadrupled in the SNG
product. Most of the carbon dioxide will be converted to methane. Excess hydrogen in the feed will
result in 0.5-1 vol% hydrogen in the SNG product.

Production & consumption figures will vary and depend on the type of coal gasifier used as well as
other design conditions of each specific plant. An example based on synthesis gas from a GE coal
gasifier is given in Table 2.
 PRODUCTION:
- SNG Product
Flow, Nm3/h 180,000
HHV, kcal/Nm3 9,100

- Superheated HP Steam Export

Flow, kg/h 600,000
Pressure, barg 85
Temperature, oC 485

CONSUMPTION:
- Feed Gas
Flow, Nm3/h 720,000
HHV, kcal/Nm3 2,950

- Power, MWh/h 2.3

- Boiler Feed Water Make-Up, kg/h 485,000

- Cooling Water, m3/h (∆T = 100C) 310

Table 2 Typical Production & Consumption Figures

Process Economy
The production cost of SNG as is shown on the y-axis in Figure 3 has been calculated as the sum of
the following three major components:

1. The production cost of the scrubbed synthesis gas leaving the gasifier including CAPEX and
OPEX of the coal handling & preparation unit, the air separation unit and the gasifier &
synthesis gas scrubbing unit. This cost portion is expressed as the “Synthesis gas Cost” on
the x-axis in Figure 3.
2. The cost of the coal/petcoke feed shown as an indirect variable in Figure 3.
3. The CAPEX and OPEX cost of the sulfur-tolerant shift unit based on the Topsøe Sulfur
Tolerant Shift and COS Hydrolysis technology, the acid gas removal unit, the sulfur
recovery unit based on the Topsøe WSA sulfuric acid technology, and the methanation unit
based on the Topsøe TREMPTM high temperature methanation technology.
The basis for calculating the cost portion under point 3 above is as follows:

1. Capital Cost is based on early 2007 price level.

2. Utility costs:
a. Power $0.05/kWh
b. Cooling Water $0. 1/1000 gallons
c. Boiler Feed Water $1/1000 lbs
d. Export Steam Credit $9.3/1000 lbs
e. Sulfuric Acid Export $40/ST
3. Operating Labor & Maintenance as 3% of Capital Cost.
4. Depreciation & Interest as 15% of Capital Cost.

A depreciation rate & interest of less than 15% will be applicable in countries like China and India
and would result in lower production cost of the SNG product. A depreciation rate & interest of
10% would result in a 20% lower SNG production cost assuming that all other factors are kept the
same.

Price of coal and cost of synthesis gas are the major contributors to the SNG production cost.

9.00
SNG Product Cost, $/MM BTU

Coal/Petcoke -
8.00 $30/ST
Coal/Petcoke -
7.00 $25/ST
(HHV)

Coal/Petcoke -
6.00
$20/ST
5.00 Coal/Petcoke -
$15/ST
4.00 Coal/Petcoke -
$10/ST
3.00
3.00 3.50 4.00 4.50 5.00

Syngas Cost (exit scrubber), $/MM BTU

1 $/MM BTU = 36.1 $/1000 Nm 3 SNG (HHV = 9,100 Gcal/Nm 3)

Figure 3 Production Cost of SNG Product

Influence on Performance of Feed Gas Composition and Operating Conditions

The layout of the TREMPTM process is based on the outstanding capabilities of the MCR-2X
catalyst, which were established in the late seventies. Recent research has confirmed that the
traditional layout is close to the optimum but still may be optimized on a case to case basis
depending on the synthesis gas composition and other parameters.
In order to illustrate the effect of parameter variations, a series of simulations were made. The
simulations were carried out with a fixed number of reactors, with fixed inlet temperatures and
fixed outlet temperatures of the first adiabatic reactor. The effects on recycle compressor power
consumption, high pressure steam production and higher heating value were evaluated. The
reference case in the evaluations is a raw gas with a stoichiometric ratio M = (H2 – CO2)/(CO +
CO2) of 2.99, a carbon dioxide concentration of 1 vol%, and a methane concentration of 0.1 vol%.

Concentration of Carbon Dioxide in the Feed

Variations in carbon dioxide slip from the Acid Gas Removal Unit have been simulated, because
this parameter has an impact on the overall cost of the plant. A higher carbon dioxide slip will
require a lower equilibrium temperature in the Sour Shift Section, and this will require a larger
catalyst volume and lead to a lower production of high pressure steam in this unit. In the Acid Gas
Removal Unit, a requirement for very low carbon dioxide slip is expensive, and a higher slip of
carbon dioxide leads to savings of both in investment and operating cost.

The effect of the carbon dioxide slip on the Methanation Section is shown in figure 4. The
variations of the high pressure steam production and power consumption in the recycle compressor
are shown relative to the base case with 1 vol% carbon dioxide in the feed.

2.0%

1.0%

0.0%
0 1 2 3 4 5 6 7
Variation relative to 1% CO2

-1.0%

-2.0%

-3.0%

-4.0%

-5.0%

-6.0%
CO2 Concentration in Feed Gas, vol %

Recycle Compressor Power Consumption HP Steam Production

Figure 4 Effect of CO2 Concentration in the Feed

It is clear that the optimum does not lie below 1 vol% carbon dioxide, and that the effect on the
recycle compressor is almost linear. Thus an increased carbon dioxide concentration in the feed
reduces the recycle flow. However, at carbon dioxide concentrations above 5 vol% in the feed, the
production of superheated high pressure steam starts to decrease significantly with a corresponding
negative effect on the economics.

Concentration of Methane in the Feed

Some gasifiers are known to form methane (e.g. E-Gas, BGL and the HTW gasifier). This is a
disadvantage when the final product is chemicals such as ammonia, methanol, or synthetic fuels.
However, for SNG-production it would be surprising if the presence of methane is a disadvantage.

100% 101.4%

95% 101.2%

90% 101.0%
Power Consumption, HP Steam Prod.

Higher Heating Value of the SNG

85% 100.8%

Power Consumption
80% 100.6% HP Steam Prod.
HHV, SNG

75% 100.4%

70% 100.2%

65% 100.0%

60% 99.8%
0% 2% 4% 6% 8% 10% 12%
Methane Concentration out of Gasifier, Dry Vol %

Figure 5 Effects of Methane Concentration, Relative to 0.1% Methane

Figure 5 shows that an increased methane concentration leads to reduced recycle ratio and reduced
steam production, but that the product quality is improved.

Temperature Increase in the First Methanation Reactor

The MRC-2X catalyst allows a wide temperature range in the first adiabatic reactor. High outlet
temperature facilitates the production of the superheated steam, which is generated in the TREMPTM
process. The standard temperature of the superheated steam is 520°C, and it is possible to superheat
much more steam to this temperature than generated in the TREMPTM section itself (e.g. steam from
the gasifier cooling train and/or the shift section).

The temperature increase over the first reactor is proportional to the conversion of carbon monoxide
and carbon dioxide to methane. It is known that low inlet temperatures may result in problems with
nickel carbonyls. However, high outlet temperatures make the equipment more expensive.
A parameter variation has been made where the temperature increase over the first reactor has been
increased by 4.3% by either increasing the outlet temperature or decreasing the inlet temperature.
The effect on recycle compressor power requirement and steam production was studied.

8.0%

7.0%

6.0%

5.0%

4.0%

3.0%

2.0%

1.0% Reduction of Power Consumption

0.0%
Reduction of HP Steam Prod.

Higher Outlet Temperature

Lower Inlet Temperature

Figure 6 Effects of 4.3% Temperature Adjustments in the 1st Methanator

The results of the equal variations of inlet and outlet temperature are shown in figure 6, and it is
clear that the low inlet temperature brings down the power consumption, but also the production of
high pressure superheated steam. If the inlet temperature is kept constant and the outlet temperature
is increased, then the same positive effect on the power consumption is seen with almost no impact
on the steam production.

Conclusions

The TREMPTM high temperature methanation process is a robust, simple, and economically
competitive process allowing production of SNG meeting pipeline specifications from synthesis gas
with varying composition. The process is based on the use of the catalyst MCR-2X, which allows a
large temperature increase over the first methanation reactor. This minimizes equipment size and
cost, reduces power consumption for recycle and facilitates production of superheated high pressure
steam. The process is flexible, and layout and operating conditions may be adjusted on a case to
case based to obtain the optimal result.
The optimization of the methanation section should be made together with the entire SNG plant,
because the composition of the feed gas has a significant impact on the design of the methanation
section. It is clear that a methane rich feed gas is an advantage for the methanation section, and the
effect methane has on the Acid Gas Removal and the Shift Section should be examined.

The carbon dioxide slip of the Acid Gas Removal Section should be more that 1-3%, but less that
5% to reduce the power consumption in the recycle compressor. This concentration range does not
have any significant effect on the steam production.

The high temperatures in a TREMPTM plant ensure a high production of superheated high pressure
steam, which potentially corresponds to a power production close to 1 kWh / Nm3 SNG.

References

1. Udengaard, N.R., Olsen, A., Wix-Nielsen, C. ”High Temperature Methanation Process –

Revisited”, Pittsburg Coal Conf. 2006

2. Rostrup-Nielsen J.R., Sehested. J. in Proc. 20 North Amer.Cat.Soc. Meeting, Houston, June

2007 , Paper O-S6-10.