The conversion of gaseous hydrocarbons to hydrogen can be achieved in many ways. Partial oxidation with air is one of the options. In this process methane in the biogas with oxygen in air to form hydrogen in a bed of catalyst.
Principle
This commercial process route is basically the result of sequential combustion reactions in which the gas is burnt with deficit oxygen (nearly 30 % of stoichiometric requirement). Depending on the feed -stock the product gas may require purification of sulphur compounds and CO2 - removal. The advantage of dispensing with an external heat source favours the partial oxidation step, since the oxidation of CO supplies the necessary heat.
Process flow
The biogas containing 55-60 % methane , 40 % CO2 and traces of H2 S is first dehydrated and then purified from H2 S. The gas is then sent to the partial oxidizers to form hydrogen. Depending on the composition of the outlet gas from the oxidizer methanation of residual carbon oxides can be incorporated. Finally a Co2 scrubber may be added depending on the type of fuel cell to be used in the power plant.
Process
The process occuring in the partial oxidizer is
CH4 + 0.5 O2 = Co + 2H2
The process requires oxygen, which may be separated and supplied from air and is favoured by moderately high pressure. It is understood that due to residence time limitations, the process approaches equilibrium leaving some residual methane and carbon in the product gas. Hence CO2 needs to be scrubbed and recycled in the plant (Balthasar).
Need for pure oxygen
If air is used instead of oxygen the separation of hydrogen from nitrogen is difficult. Hence oxygen at a purity of at lease 95 % and has to be used in large scale systems. Pressure of notrogen could be accepted in small scale fuel cell applications. After all the cathode gas (air) contains 80% nitrogen. The process has thus to be modified for operation on air in this particuler study.
Factors controlling the process
As the partial oxidation proceeds through a flame reaction, it is necessary to moderate the flame temperature, preferably by means of steam. The raw gas composition is controlled by the oxygen to methane ratio and by the steam addition. In order to reduce the oxygen consumption for the oxidation step the biogas and steam has to be preheated and have to be metered precisely to the reactor.
The operating conditions vary with the non-catalytic reactors.
Pressure: 60 to 90 bar. Reaction temperature: 1200 to 1370 C.
Under catalytic partial oxidation a commercial process, topsoe SBA has specified the following conditions.
Pressure: up to 30 bar or more. Temperature: 90c.
Catalyst: Ni
Feed-stock gas and super heated steam are mixed and preheated to 60c and mixed with oxygen
Reactor
The reactor may be a refractory lined stainless steel vessel with one or more burners. In order to initiate the reaction part of the gas has to be burnt inside the reactor. Johnson Matthey Ltd. report in their patent a reactor made of SS tube with entry for gas at the middle of the reactor and exit for product gas from the end. As gas entry is made near the middle of catalyst bed, they have observed a higher temperature of 450 c at the tip and a uniform temperature of 280 c surrounding the hot zone. This is claimed to be superior to at once through reactor. The reactor may then have multiple (4 or 5 entries from the sides).
A theoretical model developed by Opris et. al describes the temperature and product distribution profiles along the length of the reactor. This fits well with the commercial data. The reactor requires a minimum length for complete partial oxiation of methane leading to a continuous supply of hydrogen at a fixed concentration.
Catalysts
The catalyst used by Johnson Matthey let. in their Hot Spot TM reactor contained 0.01 to 5 wt % platinum and from 1 to 15 wt % chromium oxide supported on a refractory solid such as silica. The support may be monolith honeycomb or particles with a maximum size of 1.5 mm.
Catalyst deactivation
The successful economic and technical utilization of the process depends on the avoidance of free carbon deposition which decreases the catalyst surface area resulting in lower reaction rates. It is suggested that carbon deposition shall be avoided by operational techniques rather than by inhibition.
Product gas
The hot product gas is expected to have the following composition on a dry basis.
Hydrogen and CO, 93 % by volume
Carbon dioxide, 5 % by volume
Nitrogen and argon, 1.5 % by volume
Methane, 0.6 % by Volume
The reactor effluent needs rapid cooling to freeze the gaseous equilibria established at the high temperature reactor by a direct water quench or by heat exchange. The product gas then has to be washed free of carbon-sulphur compounds, carbon dioxide and inert gases.
Principle
This commercial process route is basically the result of sequential combustion reactions in which the gas is burnt with deficit oxygen (nearly 30 % of stoichiometric requirement). Depending on the feed -stock the product gas may require purification of sulphur compounds and CO2 - removal. The advantage of dispensing with an external heat source favours the partial oxidation step, since the oxidation of CO supplies the necessary heat.
Process flow
The biogas containing 55-60 % methane , 40 % CO2 and traces of H2 S is first dehydrated and then purified from H2 S. The gas is then sent to the partial oxidizers to form hydrogen. Depending on the composition of the outlet gas from the oxidizer methanation of residual carbon oxides can be incorporated. Finally a Co2 scrubber may be added depending on the type of fuel cell to be used in the power plant.
Process
The process occuring in the partial oxidizer is
CH4 + 0.5 O2 = Co + 2H2
The process requires oxygen, which may be separated and supplied from air and is favoured by moderately high pressure. It is understood that due to residence time limitations, the process approaches equilibrium leaving some residual methane and carbon in the product gas. Hence CO2 needs to be scrubbed and recycled in the plant (Balthasar).
Need for pure oxygen
If air is used instead of oxygen the separation of hydrogen from nitrogen is difficult. Hence oxygen at a purity of at lease 95 % and has to be used in large scale systems. Pressure of notrogen could be accepted in small scale fuel cell applications. After all the cathode gas (air) contains 80% nitrogen. The process has thus to be modified for operation on air in this particuler study.
Factors controlling the process
As the partial oxidation proceeds through a flame reaction, it is necessary to moderate the flame temperature, preferably by means of steam. The raw gas composition is controlled by the oxygen to methane ratio and by the steam addition. In order to reduce the oxygen consumption for the oxidation step the biogas and steam has to be preheated and have to be metered precisely to the reactor.
The operating conditions vary with the non-catalytic reactors.
Pressure: 60 to 90 bar. Reaction temperature: 1200 to 1370 C.
Under catalytic partial oxidation a commercial process, topsoe SBA has specified the following conditions.
Pressure: up to 30 bar or more. Temperature: 90c.
Catalyst: Ni
Feed-stock gas and super heated steam are mixed and preheated to 60c and mixed with oxygen
Reactor
The reactor may be a refractory lined stainless steel vessel with one or more burners. In order to initiate the reaction part of the gas has to be burnt inside the reactor. Johnson Matthey Ltd. report in their patent a reactor made of SS tube with entry for gas at the middle of the reactor and exit for product gas from the end. As gas entry is made near the middle of catalyst bed, they have observed a higher temperature of 450 c at the tip and a uniform temperature of 280 c surrounding the hot zone. This is claimed to be superior to at once through reactor. The reactor may then have multiple (4 or 5 entries from the sides).
A theoretical model developed by Opris et. al describes the temperature and product distribution profiles along the length of the reactor. This fits well with the commercial data. The reactor requires a minimum length for complete partial oxiation of methane leading to a continuous supply of hydrogen at a fixed concentration.
Catalysts
The catalyst used by Johnson Matthey let. in their Hot Spot TM reactor contained 0.01 to 5 wt % platinum and from 1 to 15 wt % chromium oxide supported on a refractory solid such as silica. The support may be monolith honeycomb or particles with a maximum size of 1.5 mm.
Catalyst deactivation
The successful economic and technical utilization of the process depends on the avoidance of free carbon deposition which decreases the catalyst surface area resulting in lower reaction rates. It is suggested that carbon deposition shall be avoided by operational techniques rather than by inhibition.
Product gas
The hot product gas is expected to have the following composition on a dry basis.
Hydrogen and CO, 93 % by volume
Carbon dioxide, 5 % by volume
Nitrogen and argon, 1.5 % by volume
Methane, 0.6 % by Volume
The reactor effluent needs rapid cooling to freeze the gaseous equilibria established at the high temperature reactor by a direct water quench or by heat exchange. The product gas then has to be washed free of carbon-sulphur compounds, carbon dioxide and inert gases.
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