The document details the procedures and considerations for the start-up, activation, and reduction of methanation catalysts in refinery processes. It emphasizes the importance of controlling gas composition and temperature during catalyst reduction to ensure proper functionality and safety. Additionally, it includes disclaimers about the information's reliability and the potential liabilities involved in reliance on these procedures.

1. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
GBH Enterprises, Ltd.
Methanation Catalyst Start-up Procedures
Process Information Disclaimer
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2. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
VULCAN Series VSG-N101/102
Methanation catalysts are almost always manufactured and transported in the
oxidized form, and therefore they must be reduced in the reactor to give nickel
metal in order to make them active. The reduction is usually carried out in
process gas and occurs by the two reactions:
NiO + H2 ---> Ni + H2O H25oC = +2.6 kJ mol-1
NiO + CO ---> Ni + CO2 H25oC = -30.3 kJ mol-1
Since neither reaction is strongly exothermic, the reduction process itself does
not cause a large temperature rise in the catalyst bed. However, once some
metallic nickel has been formed by reduction with process gas, methanation will
start.
The exothermic heat of reaction will augment the temperature and accelerate
reduction of the catalyst. The temperature rise must not be excessive, and for
this reason the gas used for reduction should contain as little carbon monoxide
and carbon dioxide as possible, and preferably not more than 1% in total.
It is worth making checks to ensure that the concentration of carbon oxides does
not increase during the reduction; for example, as a result of malfunction of the
carbon dioxide removal unit. These precautions protect not only the catalyst, but
also the methanation vessel.
Although most methanation catalysts can withstand temperature excursions, the
maximum design temperature for the converter itself is frequently about 450o
C.
In the later stages of reduction, it is advantageous to raise the temperature to
about 400o
C, because this will increase the proportion of reduced nickel.
To achieve this temperature, it may be necessary to increase the carbon
monoxide or carbon dioxide content of the inlet gas by a controlled bypassing of
the low-temperature shift catalyst or of the carbon dioxide removal system.
These techniques are often the only means for providing extra heat to the
catalyst when the gas entering the methanator is heated by exchange with the
exit gas.
Progress of the reduction can be monitored by following the rapid fall in the exit
carbon monoxide and carbon dioxide to the design level, which is normally less
than 5 ppm CO + CO2.

3. Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology – Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology – Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
The complete procedure from beginning the heat-up to passing methanator exit
gas to the ammonia synthesis loop can be completed in less than 12 hours, and
less than 24 hours is normal, but this does depend on the catalyst used.
CAUTION: Great care must be taken during the heating up or cooling down of
methanation catalyst in the reduced state to avoid formation of highly toxic nickel
carbonyl.