CA1075906A - Process for preparing methane rich gases - Google Patents
Process for preparing methane rich gasesInfo
- Publication number
- CA1075906A CA1075906A CA237,997A CA237997A CA1075906A CA 1075906 A CA1075906 A CA 1075906A CA 237997 A CA237997 A CA 237997A CA 1075906 A CA1075906 A CA 1075906A
- Authority
- CA
- Canada
- Prior art keywords
- stream
- methanation
- temperature
- recycle
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000007789 gas Substances 0.000 title claims abstract description 87
- 238000004519 manufacturing process Methods 0.000 title description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 33
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 52
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 11
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- 238000011282 treatment Methods 0.000 claims description 5
- 229910002090 carbon oxide Inorganic materials 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 238000004064 recycling Methods 0.000 description 9
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000002816 nickel compounds Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000010742 number 1 fuel oil Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 101100276456 Schizosaccharomyces pombe (strain 972 / ATCC 24843) ssn6 gene Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/06—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen in the presence of organic compounds, e.g. hydrocarbons
Abstract
ABSTRACT OF THE DISCLOSURE
Hydrogen and carbon oxides are reacted to form methane by passing an inlet stream of preheated methanation synthesis gas together with a recycle stream of product gas through a catalyst bed is a adiabatic methanation reactor. The inlet temperature is between 250 and 350°C, the outlet temperature between 500 and 700°C. The recycle stream is withdrawn from the outlet stream after the latter has been cooled to a temperature between 250 and 350°C and being, however, at least 50°C above the dew point. A preferred means for withdrawing the recycle stream is an ejector driven by the inlet stream or by added steam.
Hydrogen and carbon oxides are reacted to form methane by passing an inlet stream of preheated methanation synthesis gas together with a recycle stream of product gas through a catalyst bed is a adiabatic methanation reactor. The inlet temperature is between 250 and 350°C, the outlet temperature between 500 and 700°C. The recycle stream is withdrawn from the outlet stream after the latter has been cooled to a temperature between 250 and 350°C and being, however, at least 50°C above the dew point. A preferred means for withdrawing the recycle stream is an ejector driven by the inlet stream or by added steam.
Description
- iO759~
This invention relates to a process for the production of a methane rich gas by methanation. In such a process carbon oxides and hydrogen are reacted to form methane in the presence of a catalyst. The invention relates particularly to a process for methanation of a gas having a high concentration of carbon oxides.
Methanation processes have been used for many years to remove traces of carbon oxides from ammonia synthesis gas. In recent years methanation processes have become of increasing importance for the production of methane rich gases suitable as substitutes for natural gas.
In this way solid and liquid fossil fuels such as coal and fuel oils can be converted to substitute natural gas by a gasification process followed by methanation.
In such methanation processes the formation of methane from carbon oxides and hydrogen proceeds quickly to equilibrium in the presence of a catalyst and in accordance with either or both of the following reaction schemes:
(1) C0 + 3H2 ~ CH4 + H20
This invention relates to a process for the production of a methane rich gas by methanation. In such a process carbon oxides and hydrogen are reacted to form methane in the presence of a catalyst. The invention relates particularly to a process for methanation of a gas having a high concentration of carbon oxides.
Methanation processes have been used for many years to remove traces of carbon oxides from ammonia synthesis gas. In recent years methanation processes have become of increasing importance for the production of methane rich gases suitable as substitutes for natural gas.
In this way solid and liquid fossil fuels such as coal and fuel oils can be converted to substitute natural gas by a gasification process followed by methanation.
In such methanation processes the formation of methane from carbon oxides and hydrogen proceeds quickly to equilibrium in the presence of a catalyst and in accordance with either or both of the following reaction schemes:
(1) C0 + 3H2 ~ CH4 + H20
(2) C02 + 4H2 ~ CH4 + 2H20 It is not very important to know which of above two reactions is the faster, since there will at the same time be an approach to equilibrium between carbon monoxide and carbon dioxide as follows:
(3) C0 + H20 = 2 2 :' ~0759~6 The net reaction of methane formation whether by reaction (1) or (2) or both will be highly exothermic.
Therefore, the temperature of the reactants and products will increase during the passage through a catalyst bed in an adiabatic reactor. On the other hand, such increasing temperature will tend to displace the equilibrium towards lower methane concentration. Consequently, complete or close to complete reaction will only be possible if the temperature increase is limited by cooling the reacting gas in one way or another, for instance by recycling of cooled product gas.
Recycling of cooled product gas for the purpose of reducing the temperature increase in an adiabatic methanation reactor has been used previously. For instance, the product gas has been cooled to a temperature of about 50 C or lower with subsequent removal of the steam condensate before recycling. Cooling to low temperatures is necessary since otherwise a conventional compressor could not be used ; for the recycling. However, such complete cooling of the product gas before recycling will result in a poor energy economy of the methanation process.
On the other hand, if the recycle gas is only moderately cooled, the recycle compressor should be designed so as to operate at high temperatures, for instance at 300C.
At such a temperature the energy economy would be good since steam condensation would not occur and the heat removed during the cooling could be efficiently utilized for high pressure steam production. However, a simple and yet safe compressor design for temperatures substantially above 150C is hardly known, and in any case would be complicated and expensive. Therefore, recycling of product gas at 300C would give compressor problems.
lo~ssn6 It is an object of the present invention to provide a methanation process in whlch the reactor is maintained cooler by recycling of cooled product gas without a preceding steam condensation and without the use of a compressor.
Accordingly, we provide a process for the production of a methane rich gas by adiabatically passing methane synthesis gas together with a stream of hot recycle product gas through at least one catalyst bed in which process the recycle gas stream is withdrawn from the product gas stream after having been cooled to a temperature above the condensation point of the product gas and in which process the recycle gas stream may be recycled by means of an ejector.
More specifically, we provide a process for the production of a methane rich gas in at least one adiabatically operated methanation reactor by combining an inlet stream of a preheated methane synthesis gas containing hydrogen and carbon oxides, especially carbon monoxide, and a recycle stream consisting of product gas from the methanation reactor, passing the combined streams through a bed of a methanation catalyst contained in the methanation reactor, and dividing the outlet stream into the recycle stream and a stream of product gas which may be passed on for further processing, or which may be collected and cooled for direct use, for instance as a substitute natural gas. The above objects of the invention are achieved if the methanation reactor is operated to provide the outlet stream at a temperature of between 500C and 700C after which the outlet stream is cooled to a temperature between 250C and 350C and being at the same time at least 50C above the
Therefore, the temperature of the reactants and products will increase during the passage through a catalyst bed in an adiabatic reactor. On the other hand, such increasing temperature will tend to displace the equilibrium towards lower methane concentration. Consequently, complete or close to complete reaction will only be possible if the temperature increase is limited by cooling the reacting gas in one way or another, for instance by recycling of cooled product gas.
Recycling of cooled product gas for the purpose of reducing the temperature increase in an adiabatic methanation reactor has been used previously. For instance, the product gas has been cooled to a temperature of about 50 C or lower with subsequent removal of the steam condensate before recycling. Cooling to low temperatures is necessary since otherwise a conventional compressor could not be used ; for the recycling. However, such complete cooling of the product gas before recycling will result in a poor energy economy of the methanation process.
On the other hand, if the recycle gas is only moderately cooled, the recycle compressor should be designed so as to operate at high temperatures, for instance at 300C.
At such a temperature the energy economy would be good since steam condensation would not occur and the heat removed during the cooling could be efficiently utilized for high pressure steam production. However, a simple and yet safe compressor design for temperatures substantially above 150C is hardly known, and in any case would be complicated and expensive. Therefore, recycling of product gas at 300C would give compressor problems.
lo~ssn6 It is an object of the present invention to provide a methanation process in whlch the reactor is maintained cooler by recycling of cooled product gas without a preceding steam condensation and without the use of a compressor.
Accordingly, we provide a process for the production of a methane rich gas by adiabatically passing methane synthesis gas together with a stream of hot recycle product gas through at least one catalyst bed in which process the recycle gas stream is withdrawn from the product gas stream after having been cooled to a temperature above the condensation point of the product gas and in which process the recycle gas stream may be recycled by means of an ejector.
More specifically, we provide a process for the production of a methane rich gas in at least one adiabatically operated methanation reactor by combining an inlet stream of a preheated methane synthesis gas containing hydrogen and carbon oxides, especially carbon monoxide, and a recycle stream consisting of product gas from the methanation reactor, passing the combined streams through a bed of a methanation catalyst contained in the methanation reactor, and dividing the outlet stream into the recycle stream and a stream of product gas which may be passed on for further processing, or which may be collected and cooled for direct use, for instance as a substitute natural gas. The above objects of the invention are achieved if the methanation reactor is operated to provide the outlet stream at a temperature of between 500C and 700C after which the outlet stream is cooled to a temperature between 250C and 350C and being at the same time at least 50C above the
- 4 -.
, 107590~;
dew point of the outlet stream (i.e. the condensation temperature of the steam present in the outlet stream) at the actual pressure and composition thereof, the recycle stream being withdrawn after this cooling from the outlet stream and combined without further treatment with the inlet stream.
In effect this means that the improved process according to the invention for producing a methane rich gas in at least one adiabatically operated methanation reactor containing a bed of a methanation catalyst comprises, in combination, the steps of ta) supplying to the methanation reactor an inlet stream of a preheated methanation synthesis gas containing hydrogen and carbon monoxide (and often also carbon dioxide), the inlet stream being combined with a stream of a recycle gas and being passed through the catalyst bed, (b) operating the methanation reactor so as to provide an outlet stream having a temperature between 500C and 700C~ (c) cooling the outlet stream to a temperature between 250C and 350C and being at least 50C
above the dew point of the outlet stream at the actual pressure and composition of that stream, (d) after the cooling withdrawing said recycle stream from the outlet stream and combining it without further treatment with the inlet stream and (e) passing the outlet stream on for further processing or for cooling and use as a desired ultimate product.
According to the invention it is very convenient to withdraw the recycle stream from the outlet stream by means of an ejector.
'~' _ 5 -.. . - .. . . ~
107590~j This may be carried out in various ways. Firstly, it is possible according to the invention to withdraw the recycle stream from the outlet stream by means of an ejector driven by the inlet stream. Secondly, it is possible according to the invention to withdraw the recycle stream from the outlet stream by means of an ejector driven by steam. In any of these situations, it is advantageous according to the invention to preheat the inlet stream to a temperature approximately the same as the temperature to which the outlet stream is cooled before the withdrawal of the recycle stream therefrom.
A methane synthesis gas suitable for methanation in a process according to this invention may have a dry gas composition within the following ranges, expressed in percent by volume: 10-50% carbon monoxide, 0-35% carbon dioxide, 40-80% hydrogen, and vsrying concentrations of methane depending upon the source of the synthesis gas.
Gases containing hydrogen and carbon monoxide are manufactured in large quantities by gasification of coal and by gasification of fuel oils. In such processes, the coal and fuel oil, respectively, is reacted at high temperatures with oxidizing gases containing oxygen, air, and/or steam. Depending upon its composition, the crude gas obtained from such processes must be subjected to various treatments before it is suitable for use as a methane synthesis gas. It will, normally, have to be purified for dust, tar products, solids, sulphur compounds, etc.
Furthermore, if the composition of the crude gas is far from being stoichiometric with respect to methane formation, it has been necessary in hitherto known processes ~;
~)75~Q6 to adjust the gas composition, for instance by converting part of its carbon monoxide with water to carbon dioxide and hydrogen according to reaction scheme (3) and by complete or partial removal of its carbon dioxide and steam, etc. However, it is an advantage of the process of this invention that it is rather flexible with respect to composition of the methane synthesis gas. This flexibility is in particular achieved because the process can be operated in such a way that the carbon monoxide conversion can take place in the methanation reactor simultaneously with the methanation reactions, and because a hot recycle is used.
In this way, it is possible to compensate for deviations from stoichiometry by varying the concentration of steam present in the methane synthesis gas. Accordingly, a much wider range of synthesis gas composition can be used in the ; process of this invention than hitherto known processes.
This means an improved economy of the process.
In cases where a product gas is desired which is equivalent to natural gas~ i.e. rich in methane, the process of this invention should preferably be operated ! on a methane synthesis gas having a slight excess of carbon oxides. If appropriate operating conditions are selected, this excess of carbon oxides will be present in the final product gas as carbon dioxide which can be easily removed afterwards.
The methanation reactions are catalysed by various metals supported on suitable catalyst supports.
Among such metals are cobalt, rhodium, palladium9 platinum, ruthenium, and preferably nickel. A suitable methanation catalyst consists essentially of reduced nickel (i.e.
metallic nickel) on a support material. Such a catalyst ' 1(1i75906 may be prepared by impre~nating ~ ~ecomposa~le nickel compound on the support or by precipi~ating a decomposable nickel compound together with the support. The nickel compound is then ~irst converted ~o nickel oxide by ~ calcination and thereafter reduced to metallic nickel prior to or during the methanation process.
A pre~erred methanation catalyst suitable ~or the methanation process in accordanc~ with the present invention comprises nickel or nickel oxide together with an alumina-containing support. A particularly suitable catalyst consists essentially of nickel oxide together with an alumina/zirconia support material. Such a catalyst, in which nickel oxide may be present partly in chemical combination with alumina, may be prepared by the process described in our co-pending British Patent 1.505.254. However, the process o~ this invention is not limited to the use of such a catalyst. Any nickel catalyst having a good activity at temperatures o~ about 300C and having good resistance up to temperatures o~
about 600C can be used.
The catalyst is arranged in a reactor having a ~ixed catalyst bed. The reactor may be a cylindrical vessel having a large diameter and the gas may pass upwards or preferably downwards through the catalyst bed in the axial direction. However, if pressure drop across the catalyst bed is a limiting ~actor, it may be pre~erable to arrange the catalyst in an annular bed through which the gas will pass inwards or outwards in the radial direction.
In many known processes it has been necessary to provide ~or cooling in the methanation reactor. Several means ~or such cooling have been suggested in the past.
~?,,,',...
..
~07550~i One suggestion was to subdivide the catalyst bed into several sections and provide cooling either by introducing cold synthesis gas between the sections or to withdraw the product from one section for cooling before passing it to a subsequent section. Another suggestion was to insert into the catalyst bed a number of tubes and to pass a fluid cooling medium through these tubes. It will be understood that a methanation reactor based on such principles is more complicated in construction as well as in operation than the methanation reactor used in the process of this invention.
Therefore, the process of this invention has an overall improved economy compared to hitherto known processes.
It will be known and understood from the reaction schemes (1) and (2) that increasing pressure will tend to displace the equilibrium towards higher methane concentrations.
Operation of the methanation process at high pressure is, ! therefore, an advantage. However, other considerations may also be applicable in the selection of the operating pressure.
Normally, the process will be operated either at the pressure at which the methane synthesis gas is available or at the pressure at which the final product is required. If the product gas is intended for use as synthetic substitute for natural gas, it will preferably be produced at the pressure under which natural gas lines are operated, i.e.
at about 50-90 atmospheres. If, however, the methane synthesis gas is available at a lower pressure, the methanation process may be operated at such lower pressure, for instance at about 20-40 atmospheres.
At the inlet to the methanation reactor the synthesis gas stream is combined with a recycle stream of hot product gas. The temperature of the combined streams _ 9 _ ';
` 10~590~;
should be as low as possible but high enough for the methanation reactions to initiate when the catalyst is contacted by the combined streams. A suitable inlet temperature will be between 250 and 350C.
The ratio of recycle stream to synthesis gas inlet stream should be selected in accordance with the composition of the latter to give an outlet temperature between 500 and 700C.
In selecting the recycle ratio, the risk of carbon formation will have to be considered. Although such a consideration will involve rather complicated calculations, sufficient thermodynamic data are available for a fairly good assessment of whether or not carbon formation will occur at the selected operating conditions. In this connection, it is an important advantage of the process of the present invention that it can be operated with added steam as well as without added steam in the methane synthesis gas, since addition of a certain amount of steam is an efficient means of avoiding carbon deposition in cases where there would otherwise be a risk of such carbon deposition.
In cases where a product gas having a high methane content is desired~ two or more methanation reactors in series may be required. The product gas from the first reactor will be cooled to the inlet temperature used for the second reactor in which the gas is subjected to further methanation. Also in the second and any subsequent reactor product gas may be recycled; however, this is normally not necessary since the temperature increase will only be moderate in the second and possible subsequent reactors.
Consequently, the process of the present invention is - 10 _ .
107S90~;
preferably used in connection with the first methanation reactor and further treatment of the product gas from the first reactor in subsequent reactors or other subsequent equipment does not form an essential part of the present invention.
An essential feature of the process of the present invention is that hot product gas is recycled to the methanation reactor by means of an ejector. Recycling of a gas stream which has been cooled to temperatures high enough to avoid condensation of steam is an advantage because of the better energy economy compared to processes where the recycle gas has to be cooled to temperatures below the condensation temperature. There may be several means for recycling such a hot gas stream. It has, however, been found that it is a considerable advantage to use an ejector for this purpose. The design of an ejector operating at high temperatures and pressures and at varying capacities is rather simple and such an ejector is relatively cheap.
Consequently, in addition to an increase of the energy economy, the use of an ejector also contributes to an improvement of the overall economy of the methanation process.
It is a particular advantage that in the process of this invention the ejector can either be driven by the methane synthesis gas or, when added steam is required, by high pressure steam. Either of these two embodiments presents considerable advantages and they will both be described with reference to the accompanying drawings, figs. 1 and 2, showing flow sheets of preferred embodiments of the invention.
The flow sheet given in fig. 1 relates to an embodiment in which the ejector is driven by the synthesis gas, while the flow sheet of 1075~0~
fig. 2 relates to an embocliment in which the ejector is driven by added high pressure steam generated in the methanation process itself or obtained from other sources.
Both figures show simplified process flow sheets in which a number of details have been omitted, such as gas blowers, compressors, details of coolers, heaters, and boilers, auxiliaries for controlling temperatures, pressure, flow, etc. Only the principal features essentially related to the invention have been included in these flow sheets, since once such features have been disclosed, it will be obvious to those skilled in the art how to work out detailed flow sheets and designs for processes incorporating such features. Particularly, it is known in the art or obvious how to integrate heating and cooling systems in the form of heat exchangers, boilers, etc. to give an optimum energy economy of the process. ;~
In fig. 1 a methane synthesis gas stream 1 available at elevated pressure is heated to the desired temperature in heat exchangers 2 and 3 by the product gas streams from a first methanation reactor 6 and a second methanation reactor 10, respectively. In ejector 4 the synthesis gas stream is combined with a recycle gas stream
, 107590~;
dew point of the outlet stream (i.e. the condensation temperature of the steam present in the outlet stream) at the actual pressure and composition thereof, the recycle stream being withdrawn after this cooling from the outlet stream and combined without further treatment with the inlet stream.
In effect this means that the improved process according to the invention for producing a methane rich gas in at least one adiabatically operated methanation reactor containing a bed of a methanation catalyst comprises, in combination, the steps of ta) supplying to the methanation reactor an inlet stream of a preheated methanation synthesis gas containing hydrogen and carbon monoxide (and often also carbon dioxide), the inlet stream being combined with a stream of a recycle gas and being passed through the catalyst bed, (b) operating the methanation reactor so as to provide an outlet stream having a temperature between 500C and 700C~ (c) cooling the outlet stream to a temperature between 250C and 350C and being at least 50C
above the dew point of the outlet stream at the actual pressure and composition of that stream, (d) after the cooling withdrawing said recycle stream from the outlet stream and combining it without further treatment with the inlet stream and (e) passing the outlet stream on for further processing or for cooling and use as a desired ultimate product.
According to the invention it is very convenient to withdraw the recycle stream from the outlet stream by means of an ejector.
'~' _ 5 -.. . - .. . . ~
107590~j This may be carried out in various ways. Firstly, it is possible according to the invention to withdraw the recycle stream from the outlet stream by means of an ejector driven by the inlet stream. Secondly, it is possible according to the invention to withdraw the recycle stream from the outlet stream by means of an ejector driven by steam. In any of these situations, it is advantageous according to the invention to preheat the inlet stream to a temperature approximately the same as the temperature to which the outlet stream is cooled before the withdrawal of the recycle stream therefrom.
A methane synthesis gas suitable for methanation in a process according to this invention may have a dry gas composition within the following ranges, expressed in percent by volume: 10-50% carbon monoxide, 0-35% carbon dioxide, 40-80% hydrogen, and vsrying concentrations of methane depending upon the source of the synthesis gas.
Gases containing hydrogen and carbon monoxide are manufactured in large quantities by gasification of coal and by gasification of fuel oils. In such processes, the coal and fuel oil, respectively, is reacted at high temperatures with oxidizing gases containing oxygen, air, and/or steam. Depending upon its composition, the crude gas obtained from such processes must be subjected to various treatments before it is suitable for use as a methane synthesis gas. It will, normally, have to be purified for dust, tar products, solids, sulphur compounds, etc.
Furthermore, if the composition of the crude gas is far from being stoichiometric with respect to methane formation, it has been necessary in hitherto known processes ~;
~)75~Q6 to adjust the gas composition, for instance by converting part of its carbon monoxide with water to carbon dioxide and hydrogen according to reaction scheme (3) and by complete or partial removal of its carbon dioxide and steam, etc. However, it is an advantage of the process of this invention that it is rather flexible with respect to composition of the methane synthesis gas. This flexibility is in particular achieved because the process can be operated in such a way that the carbon monoxide conversion can take place in the methanation reactor simultaneously with the methanation reactions, and because a hot recycle is used.
In this way, it is possible to compensate for deviations from stoichiometry by varying the concentration of steam present in the methane synthesis gas. Accordingly, a much wider range of synthesis gas composition can be used in the ; process of this invention than hitherto known processes.
This means an improved economy of the process.
In cases where a product gas is desired which is equivalent to natural gas~ i.e. rich in methane, the process of this invention should preferably be operated ! on a methane synthesis gas having a slight excess of carbon oxides. If appropriate operating conditions are selected, this excess of carbon oxides will be present in the final product gas as carbon dioxide which can be easily removed afterwards.
The methanation reactions are catalysed by various metals supported on suitable catalyst supports.
Among such metals are cobalt, rhodium, palladium9 platinum, ruthenium, and preferably nickel. A suitable methanation catalyst consists essentially of reduced nickel (i.e.
metallic nickel) on a support material. Such a catalyst ' 1(1i75906 may be prepared by impre~nating ~ ~ecomposa~le nickel compound on the support or by precipi~ating a decomposable nickel compound together with the support. The nickel compound is then ~irst converted ~o nickel oxide by ~ calcination and thereafter reduced to metallic nickel prior to or during the methanation process.
A pre~erred methanation catalyst suitable ~or the methanation process in accordanc~ with the present invention comprises nickel or nickel oxide together with an alumina-containing support. A particularly suitable catalyst consists essentially of nickel oxide together with an alumina/zirconia support material. Such a catalyst, in which nickel oxide may be present partly in chemical combination with alumina, may be prepared by the process described in our co-pending British Patent 1.505.254. However, the process o~ this invention is not limited to the use of such a catalyst. Any nickel catalyst having a good activity at temperatures o~ about 300C and having good resistance up to temperatures o~
about 600C can be used.
The catalyst is arranged in a reactor having a ~ixed catalyst bed. The reactor may be a cylindrical vessel having a large diameter and the gas may pass upwards or preferably downwards through the catalyst bed in the axial direction. However, if pressure drop across the catalyst bed is a limiting ~actor, it may be pre~erable to arrange the catalyst in an annular bed through which the gas will pass inwards or outwards in the radial direction.
In many known processes it has been necessary to provide ~or cooling in the methanation reactor. Several means ~or such cooling have been suggested in the past.
~?,,,',...
..
~07550~i One suggestion was to subdivide the catalyst bed into several sections and provide cooling either by introducing cold synthesis gas between the sections or to withdraw the product from one section for cooling before passing it to a subsequent section. Another suggestion was to insert into the catalyst bed a number of tubes and to pass a fluid cooling medium through these tubes. It will be understood that a methanation reactor based on such principles is more complicated in construction as well as in operation than the methanation reactor used in the process of this invention.
Therefore, the process of this invention has an overall improved economy compared to hitherto known processes.
It will be known and understood from the reaction schemes (1) and (2) that increasing pressure will tend to displace the equilibrium towards higher methane concentrations.
Operation of the methanation process at high pressure is, ! therefore, an advantage. However, other considerations may also be applicable in the selection of the operating pressure.
Normally, the process will be operated either at the pressure at which the methane synthesis gas is available or at the pressure at which the final product is required. If the product gas is intended for use as synthetic substitute for natural gas, it will preferably be produced at the pressure under which natural gas lines are operated, i.e.
at about 50-90 atmospheres. If, however, the methane synthesis gas is available at a lower pressure, the methanation process may be operated at such lower pressure, for instance at about 20-40 atmospheres.
At the inlet to the methanation reactor the synthesis gas stream is combined with a recycle stream of hot product gas. The temperature of the combined streams _ 9 _ ';
` 10~590~;
should be as low as possible but high enough for the methanation reactions to initiate when the catalyst is contacted by the combined streams. A suitable inlet temperature will be between 250 and 350C.
The ratio of recycle stream to synthesis gas inlet stream should be selected in accordance with the composition of the latter to give an outlet temperature between 500 and 700C.
In selecting the recycle ratio, the risk of carbon formation will have to be considered. Although such a consideration will involve rather complicated calculations, sufficient thermodynamic data are available for a fairly good assessment of whether or not carbon formation will occur at the selected operating conditions. In this connection, it is an important advantage of the process of the present invention that it can be operated with added steam as well as without added steam in the methane synthesis gas, since addition of a certain amount of steam is an efficient means of avoiding carbon deposition in cases where there would otherwise be a risk of such carbon deposition.
In cases where a product gas having a high methane content is desired~ two or more methanation reactors in series may be required. The product gas from the first reactor will be cooled to the inlet temperature used for the second reactor in which the gas is subjected to further methanation. Also in the second and any subsequent reactor product gas may be recycled; however, this is normally not necessary since the temperature increase will only be moderate in the second and possible subsequent reactors.
Consequently, the process of the present invention is - 10 _ .
107S90~;
preferably used in connection with the first methanation reactor and further treatment of the product gas from the first reactor in subsequent reactors or other subsequent equipment does not form an essential part of the present invention.
An essential feature of the process of the present invention is that hot product gas is recycled to the methanation reactor by means of an ejector. Recycling of a gas stream which has been cooled to temperatures high enough to avoid condensation of steam is an advantage because of the better energy economy compared to processes where the recycle gas has to be cooled to temperatures below the condensation temperature. There may be several means for recycling such a hot gas stream. It has, however, been found that it is a considerable advantage to use an ejector for this purpose. The design of an ejector operating at high temperatures and pressures and at varying capacities is rather simple and such an ejector is relatively cheap.
Consequently, in addition to an increase of the energy economy, the use of an ejector also contributes to an improvement of the overall economy of the methanation process.
It is a particular advantage that in the process of this invention the ejector can either be driven by the methane synthesis gas or, when added steam is required, by high pressure steam. Either of these two embodiments presents considerable advantages and they will both be described with reference to the accompanying drawings, figs. 1 and 2, showing flow sheets of preferred embodiments of the invention.
The flow sheet given in fig. 1 relates to an embodiment in which the ejector is driven by the synthesis gas, while the flow sheet of 1075~0~
fig. 2 relates to an embocliment in which the ejector is driven by added high pressure steam generated in the methanation process itself or obtained from other sources.
Both figures show simplified process flow sheets in which a number of details have been omitted, such as gas blowers, compressors, details of coolers, heaters, and boilers, auxiliaries for controlling temperatures, pressure, flow, etc. Only the principal features essentially related to the invention have been included in these flow sheets, since once such features have been disclosed, it will be obvious to those skilled in the art how to work out detailed flow sheets and designs for processes incorporating such features. Particularly, it is known in the art or obvious how to integrate heating and cooling systems in the form of heat exchangers, boilers, etc. to give an optimum energy economy of the process. ;~
In fig. 1 a methane synthesis gas stream 1 available at elevated pressure is heated to the desired temperature in heat exchangers 2 and 3 by the product gas streams from a first methanation reactor 6 and a second methanation reactor 10, respectively. In ejector 4 the synthesis gas stream is combined with a recycle gas stream
5 drawn from the outlet stream from the first methanation reactor 6. In order to create the necessary driving force for the ejector to withdraw the recycle gas stream 5, the synthesis gas stream 1 must be available at a pressure slightly higher than the pressure required at the inlet to the methanation reactor.
The combined streams of synthesis gas 1 and recycle gas 5 enter the first methanation reactor 6 through 10759n~
line 16 and pass through the catalyst bed 7 situated in reactor 6. The outlet stream 8 from the first methanation reactor 6, now heated to a higher temperature by the exothermic reactions~ is cooled in heat exchanger 9 which is operated as a high pressure steam generator. After withdrawal of the recycle gas stream 5, the product gas stream from the first reactor may be further cooled in heat exchanger 2 and passed to the second methanation reactor 10 and through catalyst bed 11 contained therein.
The outlet stream or product gas stream from the second methanation reactor 10 is cooled in heat exchangers 3 and 13. Steam is removed in separator 14 and the final product gas stream 15 is obtained.
In fig. 2 most of the flow sheet is unchanged from ; 15 fig. 1 ~nd same numerals are used to designate identicalgas streams and pieces of equipment. Therefore, only the differences resulting from driving the ejector 4 by high , pressure steam will be described here. The added steam for driving the ejector ~s high pressure steam generated in heat exchanger 9 from where it is passed to the ejector through line 17. In this case the methane synthesis gas stream 1 is passed directly to the first methanation reactor through line 16 and no excess of pressure is required as in the case illustrated in fig. 1 .
~75906 Examples ________ , Eight examples of operating data are given in Table I for further illustration of the operation of the process of the present invention on various methane synthesis gases and with the ejector driven by high pressure steam (Examples 4, 5, 7, a.nd 8) or with methane synthesis gas (Examples 1, 2, 3, and 6).
The final product gas obtained in some of the Examples (particularly Examples 2, 3, and 4) still contains some hydrogen and carbon dioxide. Therefore, if a methane concentration above 90 vol.% is desired, the outlet stream 12 from the second methanation reactor could, a~ter cooling to 250-300C, be subjected to further methanation in a third methanation reactor. However, since this does not form an essential part of this invention, it has not been shown on the flow sheets. In the remaining examples (Examples 1, 5, ~, 7, and 8) the methane concentration is either above 90 vol % or it can be increased to more than 90 vol % by a simple removal of carbon dioxide. This is particularly the case in Examples 5 and 8 where removal of the carbon dioxide would give gases containing 97.5% and 94.5% methane, respectively.
'''' . '.~
~ . A `
? 1~75906 o o o o o o o o o o o ~r ~r co u~ ~ ~ ~ ~ ~ ~ c~
~ o o o o o oo ~ o ,~ Ln o o n ~ ~ o~ OD ~ CO O ~n ~ ~ ~r u~ o ~ o ~r ~ ~ ~ o ~ ~ ~ o o o o o o ~
O 1--~ O O O O ~COOD ~ O O ~ ~ o o O O O C~ ~D O n o o o o o ~ OD ~ ~ U~ O ~g ~ 00 ~ ~ ~r ~ o ~n o ~ o ~r ~ ~ ~ ~ o ~ ~ ~ o~ o ~ In ~ a ~1 ~ ~ ~ ~1 ~D Q
o o o o ~) o o o `--tQ O r~ ~ ~ ~ o o o ~D ~D ~ ~ ~ O O O ~ D 1` O
O O O CO ~90~ O O O ~D O ~ ~1--~ O t~l O ~ O~ 0 o ~ o ~r ~J ~ o ~ o ~ u~ ~ r` ~) ~1 ~ ~1 o o o o o o o co co ~ ~ o o o~ r o ~ o n ~1 ~1 ~ 1` C~ O
o o o ~ a~ o o o o ~9 o o ~ OD ~ r~ ~ O ~ ) ~ ~ 00 ~ U~ O
U~ o ~ o ~ ~ ~ ~ o ~ ~ ~ ~ ~ ~1 O ~D O
o C~) o o o~ ~r t~ ~ o o ~D ~ cn o ln ~ o ~ ~ ~ o ~ ~ o ~ O O O ~D ~ ~ ~ O O ~ O O ~ o c~ o ~ u~ Ln 1~ o U~ o ~ o ~ ~ ~ ~ ~ o ~ ~ ~ I~ o o o o o o ~
- u~ o co ~r ~ ~ o o o co ~ O ~ 1~ ~ ~ 0~ ~ O
. ~ o o o ~ ~ o o o ~ o ~ ~r~ 1~ o ~ 1~ D O
o ~ o ~ ~ ~ o ~ o ~ ~ ~J ~ ~ ~ ~ ~
a) ~ o o o .~ o o 1 u~ o ~ ~ ~ o o r-- o ~ o~ n o ~ ~ In o o ~ o In ~oo o o o ~ o ~ ~D~ ~ O ~ ~ O ~roo ~r o ~ o 1` ~ o ~ o ~ ~ ~ n o .;
- o o ~
. o o 1`
U~ O ~--~ ~ ~ O O O CS~ ~ ~ ~ ~ O ~D 00 LO ~ I` ~ O
o ~r o o~ DOU~ O O O ~J O 10 ~I-n O O ~1 ~D O Ot~ O
O [` O ~r ~-1 ~ Lr) 1-- O N 11 ) ~I N ~ ~1 ~ ~1 a) U~ ~ U~
~1 ~ ~1 ~\
. ~rO ~ ~ O S~ o ~ ~ro a) O U~ NOOX ~ ~U~ ~OOX N~ t~ ~IOO~
rq ~ X O C,) O ~ rl O ..,~ t~ ~ 1~ 0 ~
a) ~, ~ 0~O 0~o 0~o 0~o 0~o 0~o ~ ~ ~ 0~o 0~o 0~o 0~o 0~o 0~o ¢~ ~ oP 0~o 0~o 0~o 0~o 0~o r ~ E~ ~1 ~1~1~1 ~1 ~1 ~ ~ E~ ~1 ~1 ~i ~1 ~1 ~1 ~ ~1 ~1~1~1 ~1 ~1 e z ~ o~ g g g g g g ~ ~ ~o~ g g g g g g ~ :~0'~ g g g g g g .
. ~ U~ ~ ~ ~ ~ CO
~ Ul h O 51 0 ~ 5-1 0 rl (~~ ~ J --1 ~ a) ~ ~ ~ a~ ~ ~ Q) o a) ~ 1 ~ ~ rl S-l t~ rl Z ~ U~ ~ ~ ) ~ ~ u~ a) o ~ ~ u~ a) o u~ ~ ~D O
O~ a~ ~ u~ ~ ~ Q~
a~ ~ a) ~ ~ ~ ~ a) ~ ~ ~ ~ ~ ~
~1 ~ ~ o ~ ~ ~ a) o ~ ~ a) o ~> ~t~ l O Q ~ ~ P~
~1 , X ~ ~ O
. ~ a u~ c~ o ~7s~a~
o o o o o o vl U~ ~ ~ ~D O ~ O U~ ~ C~ O ~ ~ C~ O
o a~ o o~ o ~ ~ oo ~ ~ o ~ o oo~c\~oc~
o o o o O ~ o O u~ O C~ > ~ O ~ U~ ~ ~ ~ O C~J O
O O~ O ~ O O ~ ~D O ~ C~i ~ O ~ 00 0 a~ o c~i ) o o o C\l o c~ O a~
o o o o o o ~ o o ~ o oU~ O t~ U~ ~ O ~ O a~ J o ~D ^ ^ _. . . . . . _ . .. . . . .
o u~ o c~ o a~ o ~oo~c\Jo ~ ~ o ~oo~oo O C~ O C-- O ~D 0~ ~ C\l U~
o o o o O o r~ O
O C~l ~ O C~ C`~ O ~ U~ C\l O C~ l O
~ o~ o o~ o U~ ~ oo~,lo~o ~ ~ o ~ot~oo O ~ O ) U~ ~C\J C~ ~ ~ U~ ~ ~ ~ U~
.
o ~ ~ ,1 o o o u~ c~ ~ ~ o c~ ~ o o a~ ~ C\l ~ ~ C\~ c~ o O ~ O ~ O C~ D O C~ O r-- o~ O C~l O ~ ~ O O
aJ O O C~J
o a~
O U~ ~ ~ O ~ L~ O ~ U~ O ~1 0 t~ C\l O
O 1-~ 0 d- O 00 d- t~ O C~i (Y) ~ O ~ ~ O l-i O ~ ~ O O
O C~ O ~ ~ U~ ~ U\
O C~
U
O O O O
H O ~ O 00 O 1~ J O C~l ~ O ~' O OC) O ~ O C~J ~ OC) O ~1 11~ ~ t~ O ~ O ~) O O ~U
C~J O 11-~ 0 (~ (~ ~') C~
E~ ' `
0 00 ~ U~ :
O ~ t~ U~ :
O Ir~ ~ 0 d- ~--~1 0 U~ ~ O U~ H ~I O
O O O ~ O CO t~ ~i O O ~ ~) O C~l ~ O C~J O O L--O O
. .
O O
h h O O
a) K
h .~ c~ ~Q a) ~ ~ ~0 0 ~n G) ~ cUOOXC~J~ u~ c~100XC~
,~ ~ ~ ) X r~ ~ ~ m ~
\ a) ~ \ ~ s~ ~ s~
.. ~ ~ ~ C\~ ~ r~ I rl ~1 ~ h c~
Lr\ E~ ~ t) OD ~ C) ~ ~ C~ O O O O O O ~ ~ ~ U O O O O O O
Z~o Zo Z~ Z~o ~ ~ ~ Ul a~ a ~ ~ h â~ ~ O $~ ~) ~
U~ ^ .~ ~ U~ ~ ~ O
. ln ~ ~ u O ~ h 1~ ~ t~5 ~ d ~rl ~ h t~S ~
Z C!) ~ h ~ h C~ ~ ul O ~ h ul u~ a) - a~ (U o ~ cr ~ o ~n ~ JJ a~ ~ ~ a~ ~ ~4 ~ a) u~
~1 ~ ~ Q) ~ V ~ ~U ~ ~ ~ ~ ~ ~ ~
h a) ~5 t~ 5 ~ a) O ~ ~ h . ~) O
~ :~ K ~ E~ ~ ~ E~ ~ K E~ K P~
,a u o o ~:
X K ~4 1~ i:~
`, o U~ o L~
;. :
....
The combined streams of synthesis gas 1 and recycle gas 5 enter the first methanation reactor 6 through 10759n~
line 16 and pass through the catalyst bed 7 situated in reactor 6. The outlet stream 8 from the first methanation reactor 6, now heated to a higher temperature by the exothermic reactions~ is cooled in heat exchanger 9 which is operated as a high pressure steam generator. After withdrawal of the recycle gas stream 5, the product gas stream from the first reactor may be further cooled in heat exchanger 2 and passed to the second methanation reactor 10 and through catalyst bed 11 contained therein.
The outlet stream or product gas stream from the second methanation reactor 10 is cooled in heat exchangers 3 and 13. Steam is removed in separator 14 and the final product gas stream 15 is obtained.
In fig. 2 most of the flow sheet is unchanged from ; 15 fig. 1 ~nd same numerals are used to designate identicalgas streams and pieces of equipment. Therefore, only the differences resulting from driving the ejector 4 by high , pressure steam will be described here. The added steam for driving the ejector ~s high pressure steam generated in heat exchanger 9 from where it is passed to the ejector through line 17. In this case the methane synthesis gas stream 1 is passed directly to the first methanation reactor through line 16 and no excess of pressure is required as in the case illustrated in fig. 1 .
~75906 Examples ________ , Eight examples of operating data are given in Table I for further illustration of the operation of the process of the present invention on various methane synthesis gases and with the ejector driven by high pressure steam (Examples 4, 5, 7, a.nd 8) or with methane synthesis gas (Examples 1, 2, 3, and 6).
The final product gas obtained in some of the Examples (particularly Examples 2, 3, and 4) still contains some hydrogen and carbon dioxide. Therefore, if a methane concentration above 90 vol.% is desired, the outlet stream 12 from the second methanation reactor could, a~ter cooling to 250-300C, be subjected to further methanation in a third methanation reactor. However, since this does not form an essential part of this invention, it has not been shown on the flow sheets. In the remaining examples (Examples 1, 5, ~, 7, and 8) the methane concentration is either above 90 vol % or it can be increased to more than 90 vol % by a simple removal of carbon dioxide. This is particularly the case in Examples 5 and 8 where removal of the carbon dioxide would give gases containing 97.5% and 94.5% methane, respectively.
'''' . '.~
~ . A `
? 1~75906 o o o o o o o o o o o ~r ~r co u~ ~ ~ ~ ~ ~ ~ c~
~ o o o o o oo ~ o ,~ Ln o o n ~ ~ o~ OD ~ CO O ~n ~ ~ ~r u~ o ~ o ~r ~ ~ ~ o ~ ~ ~ o o o o o o ~
O 1--~ O O O O ~COOD ~ O O ~ ~ o o O O O C~ ~D O n o o o o o ~ OD ~ ~ U~ O ~g ~ 00 ~ ~ ~r ~ o ~n o ~ o ~r ~ ~ ~ ~ o ~ ~ ~ o~ o ~ In ~ a ~1 ~ ~ ~ ~1 ~D Q
o o o o ~) o o o `--tQ O r~ ~ ~ ~ o o o ~D ~D ~ ~ ~ O O O ~ D 1` O
O O O CO ~90~ O O O ~D O ~ ~1--~ O t~l O ~ O~ 0 o ~ o ~r ~J ~ o ~ o ~ u~ ~ r` ~) ~1 ~ ~1 o o o o o o o co co ~ ~ o o o~ r o ~ o n ~1 ~1 ~ 1` C~ O
o o o ~ a~ o o o o ~9 o o ~ OD ~ r~ ~ O ~ ) ~ ~ 00 ~ U~ O
U~ o ~ o ~ ~ ~ ~ o ~ ~ ~ ~ ~ ~1 O ~D O
o C~) o o o~ ~r t~ ~ o o ~D ~ cn o ln ~ o ~ ~ ~ o ~ ~ o ~ O O O ~D ~ ~ ~ O O ~ O O ~ o c~ o ~ u~ Ln 1~ o U~ o ~ o ~ ~ ~ ~ ~ o ~ ~ ~ I~ o o o o o o ~
- u~ o co ~r ~ ~ o o o co ~ O ~ 1~ ~ ~ 0~ ~ O
. ~ o o o ~ ~ o o o ~ o ~ ~r~ 1~ o ~ 1~ D O
o ~ o ~ ~ ~ o ~ o ~ ~ ~J ~ ~ ~ ~ ~
a) ~ o o o .~ o o 1 u~ o ~ ~ ~ o o r-- o ~ o~ n o ~ ~ In o o ~ o In ~oo o o o ~ o ~ ~D~ ~ O ~ ~ O ~roo ~r o ~ o 1` ~ o ~ o ~ ~ ~ n o .;
- o o ~
. o o 1`
U~ O ~--~ ~ ~ O O O CS~ ~ ~ ~ ~ O ~D 00 LO ~ I` ~ O
o ~r o o~ DOU~ O O O ~J O 10 ~I-n O O ~1 ~D O Ot~ O
O [` O ~r ~-1 ~ Lr) 1-- O N 11 ) ~I N ~ ~1 ~ ~1 a) U~ ~ U~
~1 ~ ~1 ~\
. ~rO ~ ~ O S~ o ~ ~ro a) O U~ NOOX ~ ~U~ ~OOX N~ t~ ~IOO~
rq ~ X O C,) O ~ rl O ..,~ t~ ~ 1~ 0 ~
a) ~, ~ 0~O 0~o 0~o 0~o 0~o 0~o ~ ~ ~ 0~o 0~o 0~o 0~o 0~o 0~o ¢~ ~ oP 0~o 0~o 0~o 0~o 0~o r ~ E~ ~1 ~1~1~1 ~1 ~1 ~ ~ E~ ~1 ~1 ~i ~1 ~1 ~1 ~ ~1 ~1~1~1 ~1 ~1 e z ~ o~ g g g g g g ~ ~ ~o~ g g g g g g ~ :~0'~ g g g g g g .
. ~ U~ ~ ~ ~ ~ CO
~ Ul h O 51 0 ~ 5-1 0 rl (~~ ~ J --1 ~ a) ~ ~ ~ a~ ~ ~ Q) o a) ~ 1 ~ ~ rl S-l t~ rl Z ~ U~ ~ ~ ) ~ ~ u~ a) o ~ ~ u~ a) o u~ ~ ~D O
O~ a~ ~ u~ ~ ~ Q~
a~ ~ a) ~ ~ ~ ~ a) ~ ~ ~ ~ ~ ~
~1 ~ ~ o ~ ~ ~ a) o ~ ~ a) o ~> ~t~ l O Q ~ ~ P~
~1 , X ~ ~ O
. ~ a u~ c~ o ~7s~a~
o o o o o o vl U~ ~ ~ ~D O ~ O U~ ~ C~ O ~ ~ C~ O
o a~ o o~ o ~ ~ oo ~ ~ o ~ o oo~c\~oc~
o o o o O ~ o O u~ O C~ > ~ O ~ U~ ~ ~ ~ O C~J O
O O~ O ~ O O ~ ~D O ~ C~i ~ O ~ 00 0 a~ o c~i ) o o o C\l o c~ O a~
o o o o o o ~ o o ~ o oU~ O t~ U~ ~ O ~ O a~ J o ~D ^ ^ _. . . . . . _ . .. . . . .
o u~ o c~ o a~ o ~oo~c\Jo ~ ~ o ~oo~oo O C~ O C-- O ~D 0~ ~ C\l U~
o o o o O o r~ O
O C~l ~ O C~ C`~ O ~ U~ C\l O C~ l O
~ o~ o o~ o U~ ~ oo~,lo~o ~ ~ o ~ot~oo O ~ O ) U~ ~C\J C~ ~ ~ U~ ~ ~ ~ U~
.
o ~ ~ ,1 o o o u~ c~ ~ ~ o c~ ~ o o a~ ~ C\l ~ ~ C\~ c~ o O ~ O ~ O C~ D O C~ O r-- o~ O C~l O ~ ~ O O
aJ O O C~J
o a~
O U~ ~ ~ O ~ L~ O ~ U~ O ~1 0 t~ C\l O
O 1-~ 0 d- O 00 d- t~ O C~i (Y) ~ O ~ ~ O l-i O ~ ~ O O
O C~ O ~ ~ U~ ~ U\
O C~
U
O O O O
H O ~ O 00 O 1~ J O C~l ~ O ~' O OC) O ~ O C~J ~ OC) O ~1 11~ ~ t~ O ~ O ~) O O ~U
C~J O 11-~ 0 (~ (~ ~') C~
E~ ' `
0 00 ~ U~ :
O ~ t~ U~ :
O Ir~ ~ 0 d- ~--~1 0 U~ ~ O U~ H ~I O
O O O ~ O CO t~ ~i O O ~ ~) O C~l ~ O C~J O O L--O O
. .
O O
h h O O
a) K
h .~ c~ ~Q a) ~ ~ ~0 0 ~n G) ~ cUOOXC~J~ u~ c~100XC~
,~ ~ ~ ) X r~ ~ ~ m ~
\ a) ~ \ ~ s~ ~ s~
.. ~ ~ ~ C\~ ~ r~ I rl ~1 ~ h c~
Lr\ E~ ~ t) OD ~ C) ~ ~ C~ O O O O O O ~ ~ ~ U O O O O O O
Z~o Zo Z~ Z~o ~ ~ ~ Ul a~ a ~ ~ h â~ ~ O $~ ~) ~
U~ ^ .~ ~ U~ ~ ~ O
. ln ~ ~ u O ~ h 1~ ~ t~5 ~ d ~rl ~ h t~S ~
Z C!) ~ h ~ h C~ ~ ul O ~ h ul u~ a) - a~ (U o ~ cr ~ o ~n ~ JJ a~ ~ ~ a~ ~ ~4 ~ a) u~
~1 ~ ~ Q) ~ V ~ ~U ~ ~ ~ ~ ~ ~ ~
h a) ~5 t~ 5 ~ a) O ~ ~ h . ~) O
~ :~ K ~ E~ ~ ~ E~ ~ K E~ K P~
,a u o o ~:
X K ~4 1~ i:~
`, o U~ o L~
;. :
....
Claims (5)
1. In a process for producing a methane rich gas in at least one adiabatically operated methanation reactor in which process an inlet stream of a preheated methane synthesis gas containing 10-50% (v/v) of carbon monoxide, 0.35% (v/v) of carbon dioxide, 40-50% (v/v) of hydrogen and optionally some methane, is combined with a recycle stream of product gas from the methanation reactor and the combined streams are passed through a bed of a methanation catalyst contained in the methanation reactor, the outlet stream from the methanation reactor being divided into the recycle stream and a stream of product gas to be passed on, the improvement which comprises the steps of (a) operating the methanation reactor so as to provide the outlet stream at a temperature of between 500°C and 700°C, (b) cooling the outlet stream from the temperature of between 500°C and 700°C to a temperature of between 250°C and 350°C and being at least 50°C
above the dew point of the outlet stream at its actual pressure and composition, and (c) withdrawing the recycle stream from the outlet stream after the cooling and without further treatment combining it with the inlet stream.
above the dew point of the outlet stream at its actual pressure and composition, and (c) withdrawing the recycle stream from the outlet stream after the cooling and without further treatment combining it with the inlet stream.
2. The process of Claim 1, wherein the recycle stream is withdrawn from the outlet stream by means of an ejector driven by the inlet stream.
3. The process of Claim 2, wherein the inlet stream is preheated to a temperature approximately the same as that to which the outlet stream is cooled before the withdrawal of the recycle stream therefrom.
4. The process of Claim 1, wherein the recycle stream is withdrawn from the outlet stream by means of an ejector driven by steam.
5. The process of Claim 4, wherein the inlet stream is preheated to a temperature approximately the same as that to which the outlet stream is cooled before the withdrawal of the recycle stream therefrom.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB47924/74A GB1516319A (en) | 1974-11-06 | 1974-11-06 | Process for preparing methane-rich gases |
GB1664175 | 1975-04-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1075906A true CA1075906A (en) | 1980-04-22 |
Family
ID=26252155
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA237,997A Expired CA1075906A (en) | 1974-11-06 | 1975-10-20 | Process for preparing methane rich gases |
Country Status (11)
Country | Link |
---|---|
US (1) | US4130575A (en) |
JP (1) | JPS5953245B2 (en) |
AR (1) | AR205595A1 (en) |
BR (1) | BR7507253A (en) |
CA (1) | CA1075906A (en) |
DD (1) | DD122066A5 (en) |
DE (1) | DE2549439A1 (en) |
DK (1) | DK142501B (en) |
FR (1) | FR2290410A1 (en) |
IN (1) | IN142700B (en) |
SU (1) | SU1215617A3 (en) |
Families Citing this family (62)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2729921C3 (en) * | 1977-07-02 | 1985-01-03 | Metallgesellschaft Ag, 6000 Frankfurt | Process for generating a gas that is exchangeable with natural gas |
DK142624B (en) * | 1978-04-13 | 1980-12-01 | Topsoe Haldor As | Process for producing a methane-rich gas. |
DK143162C (en) * | 1978-12-12 | 1981-12-14 | Topsoee H A S | PROCEDURE AND PLANT FOR THE MANUFACTURING OF A METAN rich gas |
JPS59100190A (en) * | 1982-11-30 | 1984-06-09 | Ishii Tekkosho:Kk | Combustible gas producing equipment |
JPS62146992A (en) * | 1985-12-21 | 1987-06-30 | Kansai Coke & Chem Co Ltd | Production of highly calorific gas |
US5366708A (en) * | 1992-12-28 | 1994-11-22 | Monsanto Eviro-Chem Systems, Inc. | Process for catalytic reaction of gases |
TW410170B (en) * | 1996-07-08 | 2000-11-01 | Boc Group Inc | Removal of nitrogen oxides from gas streams |
US6588504B2 (en) | 2000-04-24 | 2003-07-08 | Shell Oil Company | In situ thermal processing of a coal formation to produce nitrogen and/or sulfur containing formation fluids |
US6715548B2 (en) | 2000-04-24 | 2004-04-06 | Shell Oil Company | In situ thermal processing of a hydrocarbon containing formation to produce nitrogen containing formation fluids |
US6715546B2 (en) | 2000-04-24 | 2004-04-06 | Shell Oil Company | In situ production of synthesis gas from a hydrocarbon containing formation through a heat source wellbore |
NZ522139A (en) | 2000-04-24 | 2004-12-24 | Shell Int Research | In situ recovery from a hydrocarbon containing formation |
US6698515B2 (en) | 2000-04-24 | 2004-03-02 | Shell Oil Company | In situ thermal processing of a coal formation using a relatively slow heating rate |
US6685754B2 (en) | 2001-03-06 | 2004-02-03 | Alchemix Corporation | Method for the production of hydrogen-containing gaseous mixtures |
US6929067B2 (en) | 2001-04-24 | 2005-08-16 | Shell Oil Company | Heat sources with conductive material for in situ thermal processing of an oil shale formation |
CA2463110C (en) | 2001-10-24 | 2010-11-30 | Shell Canada Limited | In situ recovery from a hydrocarbon containing formation using barriers |
WO2004002927A1 (en) * | 2002-06-26 | 2004-01-08 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of hydrocarbons |
AU2003285008B2 (en) | 2002-10-24 | 2007-12-13 | Shell Internationale Research Maatschappij B.V. | Inhibiting wellbore deformation during in situ thermal processing of a hydrocarbon containing formation |
AU2004235350B8 (en) | 2003-04-24 | 2013-03-07 | Shell Internationale Research Maatschappij B.V. | Thermal processes for subsurface formations |
CN1957158B (en) | 2004-04-23 | 2010-12-29 | 国际壳牌研究有限公司 | Temperature limited heaters used to heat subsurface formations |
ES2341776T3 (en) * | 2004-06-04 | 2010-06-28 | Haldor Topsoe A/S | METHOD AND SYSTEM FOR FUEL PROCESSING. |
US7435037B2 (en) | 2005-04-22 | 2008-10-14 | Shell Oil Company | Low temperature barriers with heat interceptor wells for in situ processes |
NZ567415A (en) | 2005-10-24 | 2010-12-24 | Shell Int Research | Solution mining systems and methods for treating hyrdocarbon containing formations |
FR2893627B1 (en) * | 2005-11-18 | 2007-12-28 | Total Sa | PROCESS FOR ADJUSTING THE HIGHER CALORIFIC POWER OF GAS IN THE LNG CHAIN |
US7793722B2 (en) | 2006-04-21 | 2010-09-14 | Shell Oil Company | Non-ferromagnetic overburden casing |
US7608129B2 (en) * | 2006-04-24 | 2009-10-27 | Hyl Technologies S.A. De C.V. | Method and apparatus for producing direct reduced iron |
WO2008051822A2 (en) | 2006-10-20 | 2008-05-02 | Shell Oil Company | Heating tar sands formations to visbreaking temperatures |
AU2008242797B2 (en) | 2007-04-20 | 2011-07-14 | Shell Internationale Research Maatschappij B.V. | In situ recovery from residually heated sections in a hydrocarbon containing formation |
RU2496067C2 (en) | 2007-10-19 | 2013-10-20 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Cryogenic treatment of gas |
AU2009233786B2 (en) * | 2008-04-09 | 2014-04-24 | Velocys Inc. | Process for converting a carbonaceous material to methane, methanol and/or dimethyl ether using microchannel process technology |
US8100996B2 (en) * | 2008-04-09 | 2012-01-24 | Velocys, Inc. | Process for upgrading a carbonaceous material using microchannel process technology |
EP2110425B2 (en) * | 2008-04-16 | 2022-03-30 | Casale Sa | Process and plant for substitute natural gas |
US8177305B2 (en) | 2008-04-18 | 2012-05-15 | Shell Oil Company | Heater connections in mines and tunnels for use in treating subsurface hydrocarbon containing formations |
JP5715568B2 (en) | 2008-10-10 | 2015-05-07 | ヴェロシス,インク. | Processes and equipment using microchannel process technology |
AU2009303610A1 (en) * | 2008-10-13 | 2010-04-22 | Shell Internationale Research Maatschappij B.V. | Systems and methods for treating a subsurface formation with electrical conductors |
US8327932B2 (en) | 2009-04-10 | 2012-12-11 | Shell Oil Company | Recovering energy from a subsurface formation |
CN101649233B (en) * | 2009-07-14 | 2012-12-19 | 上海国际化建工程咨询公司 | Isothermal methanation process and device for the preparation of synthetic natural gas |
CN101985574B (en) * | 2009-07-29 | 2015-12-02 | 华东理工大学 | A kind of processing method utilizing synthetic gas to prepare Sweet natural gas |
US20110083997A1 (en) * | 2009-10-09 | 2011-04-14 | Silva Laura J | Process for treating heavy oil |
US9033042B2 (en) | 2010-04-09 | 2015-05-19 | Shell Oil Company | Forming bitumen barriers in subsurface hydrocarbon formations |
US8631866B2 (en) | 2010-04-09 | 2014-01-21 | Shell Oil Company | Leak detection in circulated fluid systems for heating subsurface formations |
US8701769B2 (en) | 2010-04-09 | 2014-04-22 | Shell Oil Company | Methods for treating hydrocarbon formations based on geology |
US8820406B2 (en) | 2010-04-09 | 2014-09-02 | Shell Oil Company | Electrodes for electrical current flow heating of subsurface formations with conductive material in wellbore |
DE102010014992A1 (en) * | 2010-04-14 | 2011-10-20 | Uhde Gmbh | Method for heating or keeping warm the flow paths of a process plant |
DE102010032528A1 (en) * | 2010-07-28 | 2012-02-02 | Uhde Gmbh | Process for the preparation of a methane-containing gas from synthesis gas and methane extraction plant for carrying out the process |
DE102010040757A1 (en) | 2010-09-14 | 2012-03-15 | Man Diesel & Turbo Se | Tube reactor |
DE102010037980A1 (en) * | 2010-10-05 | 2012-04-05 | Thyssenkrupp Uhde Gmbh | Process and apparatus for producing a methane-rich gas from synthesis gas |
US8420031B2 (en) * | 2010-10-19 | 2013-04-16 | General Electric Company | System and method of substitute natural gas production |
EA023934B1 (en) * | 2010-12-20 | 2016-07-29 | Хальдор Топсёэ А/С | Process and reactor system for production of methane rich product gas |
US9016370B2 (en) | 2011-04-08 | 2015-04-28 | Shell Oil Company | Partial solution mining of hydrocarbon containing layers prior to in situ heat treatment |
RU2478078C1 (en) * | 2011-09-14 | 2013-03-27 | Открытое акционерное общество "Газпром" | Method of producing methane and hydrogen mixture |
CA2850741A1 (en) | 2011-10-07 | 2013-04-11 | Manuel Alberto GONZALEZ | Thermal expansion accommodation for circulated fluid systems used to heat subsurface formations |
CA2862463A1 (en) | 2012-01-23 | 2013-08-01 | Genie Ip B.V. | Heater pattern for in situ thermal processing of a subsurface hydrocarbon containing formation |
DE102013002583A1 (en) * | 2013-02-14 | 2014-08-14 | Etogas Gmbh | Converting hydrocarbon compound, preferably methane containing starting gas in carbon containing solid and hydrogen containing residual gas, comprises methanizing carbon dioxide and hydrogen-containing reactant gas to product gas |
US9676623B2 (en) | 2013-03-14 | 2017-06-13 | Velocys, Inc. | Process and apparatus for conducting simultaneous endothermic and exothermic reactions |
JP2014198789A (en) * | 2013-03-29 | 2014-10-23 | 大阪瓦斯株式会社 | Methane-rich gas production system |
EP2910523A1 (en) | 2014-02-21 | 2015-08-26 | Haldor Topsoe A/S | Methanation process with a passive heat exchange medium |
US10093996B2 (en) * | 2014-12-14 | 2018-10-09 | Synthesis Energy Systems, Inc. | Method and apparatus for recycling top gas for shaft furnace |
US10927424B2 (en) | 2015-12-28 | 2021-02-23 | Hyl Technologies, S. A. De C.V. | Method and system for producing high-carbon DRI using syngas |
US20180172322A1 (en) * | 2016-12-19 | 2018-06-21 | William J. Scharmach | Method for controlling a recycle gas stream utilizing an ejector for the cooling of a unit operation |
US10870810B2 (en) | 2017-07-20 | 2020-12-22 | Proteum Energy, Llc | Method and system for converting associated gas |
DE102018113737A1 (en) | 2018-06-08 | 2019-12-12 | Man Energy Solutions Se | Process and reactor system for carrying out catalytic gas phase reactions |
DE102018113735A1 (en) | 2018-06-08 | 2019-12-12 | Man Energy Solutions Se | Process, tube bundle reactor and reactor system for carrying out catalytic gas phase reactions |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2345957A (en) * | 1939-09-05 | 1944-04-04 | Wirth Gustav | Process for the production of hydrocarbons |
US2711419A (en) * | 1951-03-30 | 1955-06-21 | Surface Combustion Corp | Process and apparatus for making fuel gas |
US2937077A (en) * | 1954-05-05 | 1960-05-17 | Foster Wheeler Corp | Process for chemical reaction of fluids |
DE2212700C2 (en) * | 1972-03-16 | 1982-07-08 | Metallgesellschaft Ag, 6000 Frankfurt | Process for producing a methane-rich gas that is exchangeable with natural gas |
US3890113A (en) * | 1973-06-25 | 1975-06-17 | Texaco Inc | Production of methane |
US3927997A (en) * | 1973-12-28 | 1975-12-23 | Texaco Inc | Methane-rich gas process |
US3927999A (en) * | 1973-12-28 | 1975-12-23 | Texaco Inc | Methane-rich gas process |
US3922148A (en) * | 1974-05-16 | 1975-11-25 | Texaco Development Corp | Production of methane-rich gas |
US3904389A (en) * | 1974-08-13 | 1975-09-09 | David L Banquy | Process for the production of high BTU methane-containing gas |
US3967936A (en) * | 1975-01-02 | 1976-07-06 | The United States Of America As Represented By The United States Energy Research And Development Administration | Methanation process utilizing split cold gas recycle |
US4002658A (en) * | 1975-05-01 | 1977-01-11 | Ford Motor Company | Methanation catalyst and process of using the same |
US4005996A (en) * | 1975-09-04 | 1977-02-01 | El Paso Natural Gas Company | Methanation process for the production of an alternate fuel for natural gas |
-
1975
- 1975-01-01 AR AR261065A patent/AR205595A1/en active
- 1975-10-20 CA CA237,997A patent/CA1075906A/en not_active Expired
- 1975-10-22 US US05/624,818 patent/US4130575A/en not_active Expired - Lifetime
- 1975-11-04 JP JP50131542A patent/JPS5953245B2/en not_active Expired
- 1975-11-04 DE DE19752549439 patent/DE2549439A1/en active Granted
- 1975-11-04 DK DK495675AA patent/DK142501B/en not_active IP Right Cessation
- 1975-11-04 BR BR7507253*A patent/BR7507253A/en unknown
- 1975-11-04 SU SU752185807A patent/SU1215617A3/en active
- 1975-11-04 IN IN2109/CAL/75A patent/IN142700B/en unknown
- 1975-11-04 FR FR7533634A patent/FR2290410A1/en active Granted
- 1975-11-05 DD DD189262A patent/DD122066A5/xx unknown
Also Published As
Publication number | Publication date |
---|---|
JPS5168502A (en) | 1976-06-14 |
US4130575A (en) | 1978-12-19 |
DE2549439C2 (en) | 1988-02-25 |
FR2290410A1 (en) | 1976-06-04 |
SU1215617A3 (en) | 1986-02-28 |
DD122066A5 (en) | 1976-09-12 |
DK142501B (en) | 1980-11-10 |
FR2290410B1 (en) | 1980-05-09 |
IN142700B (en) | 1977-08-13 |
DK142501C (en) | 1981-06-29 |
AR205595A1 (en) | 1976-05-14 |
DK495675A (en) | 1976-05-07 |
BR7507253A (en) | 1976-08-03 |
DE2549439A1 (en) | 1976-05-13 |
JPS5953245B2 (en) | 1984-12-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1075906A (en) | Process for preparing methane rich gases | |
CA1065347A (en) | Methanol | |
CA1144099A (en) | Catalytic steam reforming of hydrocarbons | |
US4910228A (en) | Methanol | |
EP0011404B1 (en) | Integrated process for synthesis of methanol and of ammonia | |
EP0601956B1 (en) | Process for the preparation of carbon monoxide rich gas | |
US4618451A (en) | Synthesis gas | |
CA2507922C (en) | Autothermal reformer-reforming exchanger arrangement for hydrogen production | |
AU742314B2 (en) | Steam reforming | |
AU607059B2 (en) | Hydrogen | |
US5512599A (en) | Process for the production of methanol | |
US4383982A (en) | Ammonia production process | |
GB2215345A (en) | Production of heavier hydrocarbons from gaseous hydrocarbons | |
CA1119621A (en) | Process and a plant for preparing a gas rich in methane | |
GB1006745A (en) | Process for forming a hydrogen rich synthesis gas | |
GB2213496A (en) | Production of hydrogen-containing gas streams | |
US4134907A (en) | Process for enhancing the fuel value of low BTU gas | |
US4124628A (en) | Serial adiabatic methanation and steam reforming | |
GB2179366A (en) | Process for the production of synthesis gas | |
US4028067A (en) | Process for producing combustible gases | |
GB2139644A (en) | Synthesis gas | |
CA1116640A (en) | Production of methanol synthesis gas | |
US3595619A (en) | Shift conversion process for production of hydrogen | |
JPH0257134B2 (en) | ||
US4257781A (en) | Process for enhancing the fuel value of low BTU gas |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MKEX | Expiry |