EP3265545A1 - Process for producing a substitute natural gas - Google Patents
Process for producing a substitute natural gasInfo
- Publication number
- EP3265545A1 EP3265545A1 EP16707531.6A EP16707531A EP3265545A1 EP 3265545 A1 EP3265545 A1 EP 3265545A1 EP 16707531 A EP16707531 A EP 16707531A EP 3265545 A1 EP3265545 A1 EP 3265545A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bulk
- methanator
- methanation
- feed stream
- methanators
- 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.)
- Granted
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000003345 natural gas Substances 0.000 title claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 129
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 54
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 16
- 230000003134 recirculating effect Effects 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 4
- 239000003245 coal Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 20
- 150000002431 hydrogen Chemical class 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000011144 upstream manufacturing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910002090 carbon oxide Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000002826 coolant Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011335 coal coke Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 238000004939 coking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000003860 storage Methods 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
- 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
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/04—Gasification
-
- 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
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/06—Heat exchange, direct or indirect
-
- 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
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/10—Recycling of a stream within the process or apparatus to reuse elsewhere therein
-
- 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
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/14—Injection, e.g. in a reactor or a fuel stream during fuel production
- C10L2290/148—Injection, e.g. in a reactor or a fuel stream during fuel production of steam
-
- 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
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/46—Compressors or pumps
Definitions
- This invention relates to a process for the production of fuel gases suitable for use as a substitute natural gas (SNG) from a synthesis gas.
- SNG is a clean fuel which can be distributed with existing natural gas pipelines and facilities, and can be used as a substitute for natural gas in a wide range of applications.
- SNG substitute natural gas
- a synthesis gas comprising hydrogen and carbon oxides.
- methane methane
- the synthesis gas may be obtained from coal or petcoke or biomass gasification.
- the reactions are carried out in a methanation section comprising a plurality of adiabatic reactors operated in series with heat recovery and gas recirculation.
- Heat recovery and gas recirculation are used to keep the exothermic reactions under control and avoid an excessive temperature inside reactors, that may damage the reactor itself and/or the catalyst.
- Heat recovery may be provided by heat exchangers cooling the hot gas stream at the outlet of each reactor e.g. by producing high pressure steam.
- Recirculation is a further measure to control the reaction rate and the temperature inside the reactors, by dilution of the fresh synthesis gas fed to the first reactor with a portion of the reacted gas.
- the gas recirculation requires the provision of an appropriate compressor.
- a bulk methanator is one which receives part or all of the synthesis gas feed, i.e. fresh synthesis gas feed to the plant.
- a "bulk methanator” is a reactor in which a reactant gas comprising at least a portion of fresh synthesis gas is catalytically methanated.
- a trim methanator is one that does not receive any fresh synthesis gas feed and carries out trim methanation on a partially methanated gas stream, usually at lower temperature than in the bulk methanator, to produce a SNG product.
- trim methanator is a reactor in which a reactant gas, consisting of a partially methanated gas recovered from either a bulk methanator or a trim methanator, is catalytically methanated.
- a reactant gas consisting of a partially methanated gas recovered from either a bulk methanator or a trim methanator.
- Modern SNG plants typically have two or more bulk methanators in series.
- WO2012001401 discloses providing a feed stream to a first and/or second and/or subsequent bulk methanator; subjecting that feed stream to methanation in the presence of a suitable catalyst; removing an at least partially reacted stream from the first bulk methanator and supplying it to the second and/or subsequent bulk methanator where it is subjected to further methanation; passing a product stream from the final bulk methanator to a trim methanator train where it is subjected to further methanation; removing a recycle stream downstream of the first, second or subsequent bulk methanator, and, in any order, passing it through a compressor, subjecting it to cooling and then supplying to a trim and/or recycle methanator for further methanation before being recycled to the first and/or second and/or subsequent methanator.
- a recycle methanator is one which is contained within the recycle loop returning a methanated gas stream to an upstream methanator and which does not receive any fresh synthesis gas feed.
- a large-scale SNG Plant may be considered to be one with a capacity that requires installation of at-least two bulk methanators in series with one or both of the bulk methanators also having parallel vessels due to the transportation and/or shop floor manufacturing limitations.
- the invention provides a process for producing a substitute natural gas comprising the steps of: feeding a first synthesis gas feed stream comprising hydrogen, methane, carbon monoxide and/or carbon dioxide in parallel to two or more bulk methanators in a first bulk methanation zone comprising a first bulk methanator and a final bulk methanator, feeding a second synthesis gas feed stream comprising hydrogen, carbon monoxide and/or carbon dioxide to one or more bulk methanators in a second bulk methanation zone comprising a first bulk methanator, each methanator containing a methanation catalyst such that the feed streams are at least partially methanated, dividing the methanated gas stream recovered from the final bulk methanator in the first bulk methanation zone into a first portion and a second portion, recirculating the first portion in a recirculation loop to the first bulk methanator of the first bulk methanation zone to dilute the first synthesis gas feed stream fed to said first bulk methanator, and feeding the second portion to the first bulk methanator of
- the invention further comprises a methanation system for converting first and second synthesis gas feed streams into substitute natural gas using the first and second methanation zones, said methanation system being adapted to operate according to the claimed process.
- the invention includes a methanation system comprising a first synthesis gas feed stream supply configured to supply a first synthesis gas feed stream comprising hydrogen, methane, carbon monoxide and/or carbon dioxide at a first feed pressure in parallel to two or more bulk methanators in a first bulk methanation zone comprising a first bulk methanator, and a final bulk methanator, a second synthesis gas feed stream supply configured to supply a second synthesis gas feed stream comprising hydrogen, carbon monoxide and/or carbon dioxide at a feed pressure lower than the first synthesis gas feed pressure by at least the pressure drop through the first methanation zone, to one or more bulk methanators in a second bulk methanation zone comprising a first bulk methanator, each methanator containing a methanation catalyst, wherein dividing means are provided downstream
- the present invention offers lower recycle flow and power consumption and higher capacities can be achieved without installing parallel equipment items. Such a process offers significant capital savings over prior art processes.
- the present invention also process offers a more flexible arrangement and the plant is able to utilise feed streams with different pressures and different methane contents. Simplification of the design also offers lower design and installation costs compared to prior art processes.
- the first and second feed streams are synthesis gases comprising hydrogen, carbon dioxide and carbon monoxide. Other gases such as nitrogen and/or methane and /or higher hydrocarbons may also be present in the feed stream.
- the synthesis gas feed streams have not been subjected to methanation but may contain ⁇ 15mole% methane.
- the feed stream may be formed from the gasification of carbonaceous feedstocks, such as coal or petcoke or biomass using conventional techniques.
- the feed stream mixture may be prepared by mixing a hydrogen-containing gas mixture with a carbon dioxide-containing gas mixture.
- the hydrogen containing gas mixture may be a synthesis gas or may be a gas stream containing hydrogen.
- the first and second feed streams may have the same or different compositions.
- the feed pressure of the second feed stream is lower than the feed pressure of the first feed stream and the difference in pressure between the streams is at least the pressure drop through the first bulk methanation zone, i.e. the second stream pressure is the same as or lower than the pressure of the methanated gas recovered from the final bulk methanator in the first bulk methanation zone.
- the pressure of the methanated gas recovered from the final bulk methanator in the first bulk methanation zone is lower than the feed pressure of the first stream, i.e. there is a pressure drop through the first bulk methanation zone. This is because of the resistance to flow of the first feed gas through the catalyst within the methanators and the pipework connecting them.
- the pressure of the first feed stream may be in the range 5-80 bar abs, preferably 15-80 bar abs.
- the pressure drop through the first bulk methanation zone may be 3 to 10 bar or higher.
- the difference in pressure between the first and send streams may be in the range 3-15 bar, for example 3-10 bar.
- the second stream pressure is the same as the pressure of the methanated gas recovered from the final bulk methanator in the first bulk methanation zone. The pressure of the second feed stream may therefore be adjusted if necessary using conventional means to provide the desired pressure.
- the pressure of the methanated gas recovered from the first methanation zone may be lowered using conventional means before feeding it to the first bulk methanator of the second bulk methanation zone.
- methanators inside the recirculation loop can be operated with a first synthesis gas feed stream having a higher pressure, such as a synthesis gas from a block coal gasifier, and methanators outside the recirculation loop can be operated with a second synthesis gas feed stream having a lower pressure, such as a synthesis gas from a dust coal gasifier.
- a first synthesis gas feed stream having a higher pressure such as a synthesis gas from a block coal gasifier
- methanators outside the recirculation loop can be operated with a second synthesis gas feed stream having a lower pressure, such as a synthesis gas from a dust coal gasifier.
- feed streams may differ in their compositions, e.g. their methane contents.
- the present process is able to cater for these compositional differences as well.
- a feed stream containing carbon monoxide, carbon dioxide and hydrogen for x mols/hr of carbon monoxide and y mols/hr carbon dioxide, and z mols/hr hydrogen; z is about (3x + 4y).
- the upstream adjustment of the feed stream composition may be achieved using known methods, such as by employing one or more water- gas shift stages and/or a stage of acid gas removal (AGR).
- the feed stream mixtures may be passed over separate beds of a particulate zinc oxide desulphurisation material. Suitable inlet temperatures for desulphurisation are in the range 100-300 C.
- a particularly effective zinc oxide desulphurisation material is Puraspec JM TM 2020, available from Johnson Matthey PLC.
- the first and/or second feed stream mixtures may contain unsaturated compounds (e.g. dienes or acetylenes) that might present coking problems on the methanation catalysts, these maybe removed by hydrogenation over a suitable hydrogenation catalyst, such as a copper catalyst. Oxygen and organic sulphur compounds may also be removed using a suitable catalyst or sorbent, such as a copper catalyst, upstream of the first bulk methanator.
- the methanation catalyst used in bulk methanators is desirably a nickel- or ruthenium- methanation catalyst, preferably a particulate nickel-containing methanation catalyst, more preferably a precipitated Ni catalyst with a Ni content in the range 35 to > 50% by weight.
- Particularly suitable methanation catalysts are KatalcoTM CRG-S2R and KatalcoTM CRG-S2CR available from Johnson Matthey PLC.
- the same or different methanation catalyst may be present in the first, second and/or subsequent methanation reactors in each of the first and second bulk methanation zones.
- the methanation catalyst may be in the form of pellets or extrudates, but may also be a foam, monolith or coating on an inert support.
- Particulate methanation catalysts are preferred such that the feed stream is preferably passed over a fixed bed of particulate methanation catalyst disposed within each methanator.
- Suitable particulate catalysts are pellets or extrudates with a diameter or width in the range 2-10 mm and an aspect ratio, i.e. length /diameter or width in the range 0.5 to 4.
- the flow through the catalyst in the first, second and one or more subsequent bulk methanators may be axial-flow, radial flow or axial-radial flow.
- the bulk methanators in the first and/or second bulk methanation zones may contain another type of catalyst in addition to the methanation catalyst.
- a water-gas shift catalyst and/or a methanol synthesis catalyst may be included upstream of the methanation catalyst in one or more of the bulk methanators.
- Suitable water-gas shift catalysts include those based on iron, copper and cobalt/molybdenum.
- Suitable methanol synthesis catalysts include those based on copper/zinc oxide/alumina.
- the methanation catalyst may be operated at an inlet temperature in the range 200-450 C, preferably 200-350 C, more preferably 300-350 C.
- the inlet temperature may be achieved by applying heat exchange to the feed streams with a suitable heating medium.
- the feed stream heating may be done using hot product gas recovered from the final bulk methanator or the final trim methanator using a suitable gas-gas interchanger.
- the exit temperatures may be in the range 450- 750 C, preferably 500-650 C and more preferably 550-650 C.
- the gas hourly space velocity (GHSV) of the feed stream mixtures through the catalyst beds may be in the range 2000 to 20000hr "1 .
- the first bulk methanation zone comprises a first bulk methanator, a final bulk methanator and optionally one or more bulk methanators in between the first and final bulk methanators, hence the first bulk methanation zone may comprise a second bulk methanator and optionally one or more further bulk methanators.
- two, three, four or more bulk methanators may be employed in the first bulk methanation zone, i.e. N may be in the range 2-10, preferably 2-4, where N is the number of bulk methanators in the first bulk methanation zone.
- the second bulk methanation zone comprises a first bulk methanator. This may be the only bulk methanator in the second bulk methanation zone, in which case it may be described as the first and final bulk methanator in the second bulk methanation zone.
- the second bulk methanation zone may comprise one or more additional methanators such that it comprises, a first bulk methanator, a final bulk methanator and optionally one or more bulk methanators in between the first and final bulk methanators, hence the second bulk methanation zone may comprise a second bulk methanator and optionally one or more further bulk methanators.
- N may be in the range 1 -10, preferably 2-4, where N is the number of bulk methanators in the second bulk methanation zone.
- the number, N, of bulk methanators in the first bulk methanation zone is 3 and the number of bulk methanators in the second bulk methanation zone is 2.
- the first feed stream is fed in parallel to the bulk methanators in the first bulk methanation zone. Where two or more bulk methanators are present in the second bulk methanation zone, the second feed stream is desirably fed in parallel to each bulk methanator in the second bulk methanation zone.
- the bulk methanators in the first bulk methanation zone are desirably connected in series. In this way the feed gas to the second and each subsequent bulk methanator, if present, may be diluted with a methanated gas recovered from the previous bulk methanator. Where there are two or more bulk methanators in the second bulk methanation zone, the bulk methanators may also desirably be connected in series. Hence where there are two or more bulk methanators in each bulk methanation zone, preferably in each methanation zone the methanators are connected in series.
- the portions of the feed streams fed to the bulk methanators in each bulk methanation zone may be the same or different. Where there is only one bulk methanator in the second bulk methanation zone, 100% by volume of the second feed stream is fed to that bulk methanator. Where there are two or more bulk methanators in each bulk methanation zone, the portion of the feed streams fed to the first bulk methanators in each bulk methanation zone may be in the range 10vol% to 60vol% of the first or second feed stream, the exact value being adjusted to control the methanator isotherm. However, it will be understood that the split of feed between the methanators will depend on the number of bulk methanators, the operating conditions and the feed composition.
- the hydrogen reacts with carbon dioxide and carbon monoxide to form methane.
- a portion of the hydrogen in the feed stream typically remains unreacted because there is an equilibrium limitation on the extent of conversion.
- cooling may be applied to one or more methanation catalyst beds by passing a coolant, such as a portion of a feed stream, through one or more heat exchange devices disposed within the catalyst.
- the coolant flow may be arranged co-current or counter- current to the flow of reacting gases passing through the methanators.
- the temperature of the partially methanated gas mixture recovered from the first and subsequent bulk methanators may be adjusted by passing the partially methanated gas mixture through one or more heat exchangers, such as a shell and tube heat exchanger fed with water under pressure as the cooling medium.
- a recirculation loop is used to provide a partially methanated gas to the first bulk methanator in the first bulk methanation zone to dilute the portion of the first feed stream fed to it.
- the recirculation loop may be configured using known methods such as using a recycle compressor or by using a steam ejector.
- a steam ejector may also add steam to the process to dilute the feed stream or provide steam for water-gas shift.
- the recycle loop comprises a compressor for the re-circulated gas stream and a pre-heater for heating the diluted gas stream fed to the first bulk methanator.
- This preheater may be a gas-gas interchanger fed with a hot methanated gas stream, e.g. a product gas stream from a final bulk methanator in first methanation zone or from a bulk methanator in second zone methanation zone or a trim methanator.
- the volume ratio between the total diluted gas flow entering the first bulk methanator, and the feed stream fed to the first bulk methanator may be between 1 .5 and 7, with the exact value depending on the feed stream composition and pressure.
- steam may be added at the inlet of at least the first bulk methanator to further dilute the feed stream.
- steam may be added to the feed stream to at least one of the bulk methanators in each bulk methanation zone.
- a methane-containing substitute natural gas product may be recovered from the final bulk methanator of the second bulk methanation zone. If desired, the methane-containing substitute natural gas product may be subjected to further processing including subjecting it to one or more further stages of methanation in a trim methanation zone.
- Trim methanators may be used to produce high-specification substitute natural gases.
- the trim methanator zone may comprise one or more, e.g. 1 to 4, particularly 1 or 2, trim methanators. Where more than one trim methanator is present, they will generally be located in series and be fed with a gas mixture consisting of a methanated gas stream and optionally steam.
- the inlet temperature for trim methanators may be in the range 200-300°C, preferably 230-280°C.
- trim methanator may be operated at the same temperature or the temperature may be lower in the second and any subsequent trim methanator(s) than in the first trim methanator. Otherwise the trim methanation zone may be operated using the same catalysts and catalyst arrangements as the bulk methanation zones.
- a fully methanated substitute natural gas product may be recovered from the final trim methanator, if used.
- the fully methanated gas may be subjected to one or more further SNG preparation stages such as drying to remove water and/or carbon dioxide removal.
- the drying may be performed by cooling the product gas stream to below the dew point and collecting the liquid condensate, optionally with polishing over a suitable desiccant such as molecular sieves or silica gel.
- C0 2 -removal if required, may be accomplished using solvent- or amine-wash techniques known in the art.
- Figure 1 is a depiction of a flow sheet of one embodiment according to the present invention. It will be understood by those skilled in the art that the drawings are diagrammatic and that further items of equipment such as feedstock drums, pumps, vacuum pumps, compressors, gas recycling compressors, temperature sensors, pressure sensors, pressure relief valves, control valves, flow controllers, level controllers, holding tanks, storage tanks and the like may be required in a commercial plant. Provision of such ancillary equipment forms no part of the present invention and is in accordance with conventional chemical engineering practice.
- a first desulphurised synthesis gas feed stream comprising hydrogen, methane, carbon monoxide and/or carbon dioxide is fed in line 1 10 to a first bulk methanation zone which consists of three bulk methanators 1 14, 1 16, & 1 18, each containing a bed of particulate methanation catalyst.
- a second desulphurised synthesis gas feed stream comprising hydrogen, carbon monoxide and/or carbon dioxide and having a lower feed pressure than the first feed stream 1 10 is fed in line 1 12 to a second bulk methanation zone which consists of two bulk methanators 120 and 122, each containing a bed of particulate methanation catalyst.
- the second feed stream 1 12 is at a lower pressure than the first feed stream 1 10.
- the pressure difference between the first feed stream 1 10 and the second feed stream 1 12 is the same as the pressure drop through the first bulk methanation zone.
- the first bulk methanator 1 14, the second bulk methanator 1 16 and third bulk methanator 1 18 are each fed with a portion of the first feed stream 1 10 by lines 124, 126, and 128 respectively.
- the fourth bulk methanator 120 and fifth bulk methanator 122 are each fed with a portion of the second feed stream 1 12 by lines 130, and 132 respectively.
- the feed streams are methanated in the bulk methanatorsl 14, 1 16, 1 18, 120 & 122.
- the methanated gas stream from the first bulk methanator 1 14 in the first bulk methanation zone is passed in line 134 to heat exchanger 136 where it is cooled before being added via line 138 to the feed stream 126 to the second bulk methanator 1 16.
- the methanated gas stream from the second bulk methanator 1 16 is passed in line 140 to a heat exchanger 142 where it is cooled before being added via line 144 to the feed stream 128 to the third bulk methanator 1 18.
- the methanated gas stream from the third bulk methanator 1 18 is passed in line 146 to a heat exchanger 148 where it is cooled.
- a portion of the cooled stream from the heat exchanger 148 is passed in a recycle loop in line 152 to a compressor 154.
- the compressed methanated gas from the compressor 154 is passed via line 156 to dilute the feed stream fed to the first bulk methanator 1 14. If desired the compressed methanated gas may be heated to a suitable methanation inlet temperature in a heat exchanger (not shown).
- the remaining portion of the methanated gas stream from heat exchanger 148 is passed via line 150 to dilute the portion of the second feed stream fed to the second bulk methanation zone first bulk methanator 120.
- the methanated gas stream from the first bulk methanator of the second bulk methanation zone 120 is passed in line 158 to a heat exchanger 160 where it is cooled before being added via line 162 to dilute the feed stream to the second bulk methanator of the second bulk methanation zone 122.
- the product from the second bulk methanator of the second bulk methanation zone 122 is removed in line 164 and passed through heat exchanger 166 where it is cooled. It is then passed in line 168 to one or more subsequent trim methanators (not shown). The product SNG is withdrawn from the trim methanator and then is cooled and dried.
- compositions and operating conditions are compositions and operating conditions.
- This example is based on a production capacity of 1 ,000,000 Nn Vh.
- the process is fed with a first synthesis gas feed stream comprising hydrogen, carbon oxides and methane at a pressure of 3.6 MPa (abs).
- the first desulphurised feed stream composition is as follows; vol%
- the process is fed with a second synthesis gas feed stream comprising hydrogen, carbon oxides at a pressure of 2.8 MPa (abs).
- the second desulphurised feed stream composition is as follows;
- the catalyst volumes are as follows;
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GB201503607A GB201503607D0 (en) | 2015-03-03 | 2015-03-03 | Process |
PCT/GB2016/050480 WO2016139452A1 (en) | 2015-03-03 | 2016-02-25 | Process for producing a substitute natural gas |
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CN (1) | CN107406780B (en) |
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CN109207220B (en) * | 2017-06-29 | 2020-10-30 | 中国石油化工股份有限公司 | Methanation process for preparing synthetic natural gas from coal-based synthetic gas |
DE102018201561A1 (en) * | 2018-02-01 | 2019-08-01 | Friedrich-Alexander-Universität Erlangen-Nürnberg | Tubular reactor and method for operating a tubular reactor |
US20210046441A1 (en) * | 2018-02-09 | 2021-02-18 | Ecole Polytechnique Federale De Lausanne (Epfl) | Methanation reactor and method |
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DE3032123A1 (en) * | 1979-10-22 | 1981-04-30 | Conoco Inc., 74601 Ponca City, Okla. | METHOD FOR PRODUCING A METHANE-REPLACING NATURAL GAS |
EP2110425B2 (en) * | 2008-04-16 | 2022-03-30 | Casale Sa | Process and plant for substitute natural gas |
US9157043B2 (en) * | 2008-07-16 | 2015-10-13 | Kellogg Brown & Root Llc | Systems and methods for producing substitute natural gas |
CN101735009B (en) * | 2009-12-07 | 2013-08-14 | 中国科学院山西煤炭化学研究所 | Sulfur tolerant catalyzing process for preparing low carbon alcohol from synthesis gas and co-producing natural gas |
DE102010032709B4 (en) * | 2010-07-29 | 2016-03-10 | Air Liquide Global E&C Solutions Germany Gmbh | Process for the production of synthetic natural gas |
CN104762115A (en) * | 2011-09-13 | 2015-07-08 | 西南化工研究设计院有限公司 | A methanation process of synthetic natural gas prepared from coal |
CN102344841A (en) * | 2011-09-20 | 2012-02-08 | 中国石油化工集团公司 | Method for preparing substitute natural gas by coal-based syngas |
CN102585949B (en) * | 2012-02-03 | 2013-12-04 | 中国石油化工股份有限公司 | Process for preparing substitute natural gas from synthesis gas |
CN102660339B (en) * | 2012-04-27 | 2014-04-30 | 阳光凯迪新能源集团有限公司 | Gas-steam efficient cogeneration process and system based on biomass gasification and methanation |
CN102827656A (en) * | 2012-08-27 | 2012-12-19 | 东华工程科技股份有限公司 | Methanation method for synthesizing substitute natural gas from industrial hydrocarbon tail gas |
CN103666611B (en) * | 2012-09-19 | 2015-06-10 | 中国石油化工集团公司 | System and method for preparing alternative natural gas |
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GB201603253D0 (en) | 2016-04-13 |
CN107406780B (en) | 2020-06-05 |
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CN107406780A (en) | 2017-11-28 |
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