EP3265544B1 - Process for producing a substitute natural gas - Google Patents
Process for producing a substitute natural gas Download PDFInfo
- Publication number
- EP3265544B1 EP3265544B1 EP16707530.8A EP16707530A EP3265544B1 EP 3265544 B1 EP3265544 B1 EP 3265544B1 EP 16707530 A EP16707530 A EP 16707530A EP 3265544 B1 EP3265544 B1 EP 3265544B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bulk
- methanator
- gas
- methanators
- methanated
- 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.)
- Active
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 64
- 238000000034 method Methods 0.000 title claims description 60
- 239000003345 natural gas Substances 0.000 title claims description 14
- 239000007789 gas Substances 0.000 claims description 222
- 239000003054 catalyst Substances 0.000 claims description 68
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 39
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 239000001569 carbon dioxide Substances 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002028 Biomass Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000002309 gasification Methods 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 239000000203 mixture Substances 0.000 description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000011144 upstream manufacturing 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
- 238000001816 cooling Methods 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- 229910002090 carbon oxide Inorganic materials 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
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction 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
- 239000000376 reactant Substances 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 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
- 239000011335 coal coke Substances 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
- 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
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009434 installation Methods 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
- 239000002006 petroleum coke Substances 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
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 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
Images
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
- C10L2290/02—Combustion or pyrolysis
-
- 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
- C10L2290/08—Drying or removing water
-
- 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
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 substitute natural 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.
- the process to produce substitute natural gas involves catalytic methanation of a synthesis gas comprising hydrogen and carbon oxides.
- the synthesis gas is converted to a product consisting of 95% or more of methane (CH 4 ) with small amounts of carbon dioxide, hydrogen and inerts.
- the synthesis gas may be obtained from coal 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.
- EP 2 110 425 A1 discloses a process for producing SNG from a fresh syngas feedstock, said process comprising at least the steps of reacting said fresh syngas into a methanation section comprising at least a first adiabatic reactor and further adiabatic reactor(s) connected in series, so that each of said further reactor(s) is fed with a gas stream taken from the previous reactor of the methanation section, and re-circulating at least a portion of the reacted gas as input gas of at least one of said reactors, characterized in that said fresh syngas feedstock is fed in parallel to said reactors.
- Modern SNG plants typically have two or more bulk methanators in series.
- WO2012/001401 discloses providing a feed gas to a first and/or second and/or subsequent bulk methanator; subjecting that feed gas 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.
- having two bulk methanators in series is useful for minimising the pressure drop over the plant, the process requires a higher product gas recycle and places a limitation on capacity due to the maximum size of the methanator vessels that may be fabricated. Therefore, currently for large-scale plants with higher capacities, reactors and equipment items inside the bulk methanation recycle gas loop have to be twinned, i.e. parallel sets of reactors and ancillary equipment have to be used.
- 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 feed gas comprising hydrogen, carbon monoxide and/or carbon dioxide in parallel to a first bulk methanator, a second bulk methanator and one or more subsequent bulk methanators, each bulk methanator containing a methanation catalyst such that the feed gas is at least partially methanated to form a methanated gas stream, wherein the first, second and at least one subsequent methanators are connected in series so that the feed gas to the second and each of the one or more subsequent bulk methanators is diluted with a methanated gas stream recovered from the previous bulk methanator, wherein all of the methanated gas stream recovered from the first bulk methanator is used to dilute the feed gas to the second bulk methanator, a portion of the methanated gas stream recovered from the second or one or more subsequent bulk methanators is recirculated in a recirculation loop to the first bulk methanator and used to dilute the feed gas fed to said first bulk methanator
- the invention further comprises a methanation system for converting a feed gas comprising hydrogen, carbon monoxide and/or carbon dioxide into substitute natural gas, said methanation system being adapted to operate according to the claimed process.
- a methanation system comprising a feed gas supply configured to supply a feed gas in parallel to a first bulk methanator, a second bulk methanator and one or more subsequent bulk methanators, each bulk methanator containing a methanation catalyst, wherein the first, second and at least one subsequent methanators are connected in series so that the feed gas to the second and each of the one or more subsequent bulk methanators may be diluted with a methanated gas stream recovered from the previous bulk methanator, wherein the feed gas supply to the second bulk methanator is configured such that all of the methanated gas stream recovered from the first bulk methanator may be used to dilute the feed gas to the second bulk methanator and a recirculation loop is connected to the second or one or more subsequent bulk methanators so that a portion of
- the methanation system can be a subsection of a plant for producing substitute natural gas, said plant including further subsections like a gasifier, air separation unit (ASU), CO shift converter to provide appropriate ratio between hydrogen and CO content of the syngas, acid gas removal, and so on.
- ASU air separation unit
- CO shift converter to provide appropriate ratio between hydrogen and CO content of the syngas, acid gas removal, and so on.
- US 2009/0264542 discloses a process in which a carbon oxide rich feed is split and fed to a series of bulk methanators wherein the product gas is recycled from the exit of the first bulk methanator back to the inlet of the first bulk methanator.
- the present invention by having at least 2 bulk methanators inside the recycle gas loop provides a saving on recycle flow and shaft power.
- Prior art processes have not used an arrangement of multiple bulk methanators wherein (i) all of the methanated gas stream recovered from the first bulk methanator is used to dilute the feed gas to the second bulk methanator, (ii) a portion of the methanated gas stream recovered from the second or one or more subsequent bulk methanators is recirculated in a recirculation loop to the first bulk methanator and used to dilute the feed gas fed to the first bulk methanator, and (iii) at least one bulk methanator is located outside the recirculation loop.
- the present invention offers lower recycle gas flow and power consumption, an easier plot layout, smaller line sizes and equipment sizes, and higher capacities can be achieved without installing parallel equipment items.
- the feed gas mixture may be a synthesis gas 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 gas.
- the feed gas may be formed from the gasification of carbonaceous feedstocks, such as coal or petcoke or biomass using conventional techniques.
- the feed gas 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.
- a feed gas 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 gas 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 gas mixture may be passed over a bed 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.
- a suitable hydrogenation catalyst such as a copper catalyst, upstream of the first bulk methanator. 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 the first, second and subsequent 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.
- 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 gas 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 first, second or one or more subsequent bulk methanators 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 first bed of methanation catalyst in the first, second or one or more subsequent 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 heat exchange with a suitable heating medium.
- the feed gas 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 process pressure may be in the range 5-80 bar abs.
- the gas hourly space velocity (GHSV) of the feed gas mixtures through the catalyst beds may be in the range 2000 to 20000hr -1 .
- the present invention comprises a first bulk methanator, a second bulk methanator and one or more further bulk methanators in a bulk methanator train.
- three, four or more bulk methanators may be employed, i.e. N may be in the range 3-10, preferably 3-6, where N is the number of bulk methanators.
- the number of bulk methanators in the recycle loop may be N-1, or N-2 when N ⁇ 4.
- four bulk methanators are used, with recycle of the partially methanated gas stream from the second or third bulk methanators to the first bulk methanator such that there are one or two bulk methanators outside the recycle loop.
- six bulk methanators are used, with recycle of the partially methanated gas stream from the fourth bulk methanator to the first bulk methanator such that there are two bulk methanators outside the recycle loop.
- the portion of the feed gas fed to the first bulk methanator and the second and/or subsequent bulk methanator may be the same or different.
- Each of the feed gas streams fed to the first, second and one or more subsequent bulk methanators may be in the range 10vol% to 60vol% of the total feed gas feedstock, the exact value being adjusted to control the methanator isotherm. In one arrangement with three bulk methanators about 15-20vol%, especially about 18vol% of the fresh feed gas is fed to the first bulk methanator, with the remainder being fed to the second and third bulk methanators.
- 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 gas 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 the feed gas mixture, 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, second and subsequent bulk methanators is desirable to adjust the temperature of the partially methanated gas mixture recovered from the first, second and subsequent bulk methanators before mixing it with the feed gas. This may be performed 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.
- one or more heat exchangers such as a shell and tube heat exchanger fed with water under pressure as the cooling medium.
- the re-circulation 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 gas or provide steam for water-gas shift. Where steam is added, a single stage of steam addition is preferred.
- the recycle loop comprises a compressor for the recirculated gas stream and a pre-heater for heating the diluted gas stream before entering 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 or trim methanator.
- the temperature of the recycled portion is adjusted, to a temperature in the range 100-200°C, preferably 120-180°C.
- the proportion of the methanated gas stream recycled to the first bulk methanator may be 40-60% vol, preferably 45-55% vol of the methanated gas recovered from the second or one or more subsequent bulk methanators.
- the volume ratio between the total diluted gas flow entering the first bulk methanator, and the feed gas stream fed to said first bulk methanator may be between 1.5 and 7, with the exact value depending on the feed gas composition and pressure.
- Steam may be added at the inlet of at least the first bulk methanator to further dilute the inlet gas. Hence, if desired steam may be used to further dilute the feed gas to the first, second, and one or more further bulk methanators.
- a methane-containing substitute natural gas product may be recovered from the final bulk methanator. 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 methanator train.
- Trim methanators may be used to produce high-specification substitute natural gases.
- the trim methanator train 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 train may be operated using the same catalysts and catalyst arrangements as the bulk methanation train.
- 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.
- CO 2 -removal if required, may be accomplished using solvent- or amine-wash techniques known in the art.
- FIG. 1 One embodiment of the present invention is illustrated in Figure 1 .
- Desulphurised feed gas rich in carbon monoxide is fed in line 110 to the bulk methanation section which consists of four bulk methanators 112, 114, 116, 118, each containing a bed of particulate methanation catalyst.
- the first bulk methanator 112, the second bulk methanator 114, third bulk methanator 116 and fourth bulk methanator 118 are each fed with a diluted portion of the feed gas 110 by lines 120, 122, 124 and 126 respectively.
- the feed gas is methanated in the bulk methanators 112, 114, 116, 118.
- the methanated gas stream from the first bulk methanator 112 is passed in line 128 to heat exchanger 130 where it is cooled before being added via line 132 to the feed stream to the second bulk methanator 114.
- the methanated gas stream from the second bulk methanator 114 is passed in line 134 to a heat exchanger 136 where it is cooled.
- a portion of the stream from the heat exchanger 136 is passed in a recycle loop in line 138 to a compressor 140.
- the compressed methanated gas from the compressor 140 is passed via line 142 to dilute the inlet feed gas fed to the first bulk methanator 112. 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 stream from heat exchanger 136 is passed via line 144 to dilute the inlet feed gas to the third bulk methanator 116.
- the methanated gas stream from the third bulk methanator 116 is passed in line 146 to a heat exchanger 148 where it is cooled.
- the methanated gas stream from heat exchanger 148 is passed via line 150 to dilute the inlet feed gas to the fourth bulk methanator 118.
- the product from the fourth bulk methanator 118 is removed in line 152 and passed through heat exchanger 154 where it is cooled. It is then passed in line 156 to one or more subsequent trim methanators (not shown).
- the product SNG is withdrawn from the trim methanator and then is cooled and dried.
- first 212, second 214, third 216 and fourth 218 bulk methanators is the same as depicted in Figure 1 except that the recycle loop of methanated gas 242 feed to the first bulk methanator 212 is recovered from the cooled methanated gas stream obtained from the third bulk methanator 216, rather than the second bulk methanator.
- desulphurised feed gas rich in carbon monoxide is fed in line 210 to the bulk methanation section which consists of four bulk methanators 212, 214, 216, 218, each containing a bed of particulate methanation catalyst.
- the first bulk methanator 212, the second bulk methanator 214, third bulk methanator 216 and fourth bulk methanator 218 are each fed with a diluted portion of the feed gas 210 by lines 220, 222, 224 and 226 respectively.
- the feed gas is methanated in the bulk methanators 212, 214, 216, 218.
- the methanated gas stream from the first bulk methanator 212 is passed in line 228 to heat exchanger 230 where it is cooled before being added via line 232 to the feed stream to the second bulk methanator 214.
- the methanated gas stream from the second bulk methanator 214 is passed in line 234 to a heat exchanger 236 where it is cooled before being added via line 244 to the feed stream to the third bulk methanator 216.
- the methanated gas stream from the third bulk methanator 216 is passed in line 246 to a heat exchanger 248 where it is cooled.
- a portion of the stream from the heat exchanger 248 is passed in a recycle loop in line 238 to a compressor 240.
- the compressed methanated gas from the compressor 240 is passed via line 242 to dilute the inlet feed gas fed to the first bulk methanator 212. 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 stream from heat exchanger 248 is passed via line 250 to dilute the inlet feed gas to the fourth bulk methanator 218.
- a product stream 252 is recovered from the fourth bulk methanator and cooled in heat exchanger 254. It is then passed in line 256 to one or more subsequent trim methanators (not shown). The product SNG is withdrawn from the trim methanator and then is cooled and dried.
- FIG. 3 a comparative flow sheet is depicted in which the four bulk methanators are arranged as twinned pairs.
- a desulphurised feed gas 310 is divided and fed in parallel via lines 312 & 313 to paired bulk methanators 316 & 318, and via lines 314 and 315 to paired bulk methanators 320 & 322, each containing a bed of a particulate methanation catalyst.
- fresh feed gas in line 312 is combined with a recycle methanated gas stream 354.
- the resulting mixed gas feed stream 313 is divided and fed via a line 324 to bulk methanator 316 and line 326 to bulk methanator 318.
- the methanated gas stream 317 recovered from bulk methanator 316 is cooled in heat exchanger 332 to produce a cooled methanated gas stream 340.
- the methanated gas stream 319 recovered from bulk methanator 318 is cooled in heat exchanger 334 to produce a cooled methanated gas stream 342.
- the cooled methanated gas streams 340 and 342 are combined and fed via line 343 to be mixed with the feed stream 314.
- the resulting mixed gas feed stream 315 is divided and fed via a line 328 to bulk methanator 320 and line 330 to bulk methanator 322.
- the methanated gas stream 321 recovered from bulk methanator 320 is cooled in heat exchanger 336 to produce a cooled methanated gas stream 344.
- the methanated gas stream 323 recovered from bulk methanator 322 is cooled in heat exchanger 338 to produce a cooled methanated gas stream 346.
- the cooled methanated gas streams 344 and 346 are combined to form a cooled product gas stream 347.
- a portion of the product gas stream 347 is taken as a recycle loop via line 350 to a compressor 352, where it is compressed and provided via line 354 to be mixed with fresh feed in line 312.
- the remaining portion of the cooled product gas stream 348 is passed in to one or more subsequent trim methanators (not shown).
- the product SNG is withdrawn from the trim methanator and then is cooled and dried.
- FIG 4 a comparative flow sheet is depicted in which the arrangement of first 412, second 414, third 416 and fourth 418 bulk methanators is the same as depicted in Figure 1 except that the recycle loop of methanated gas 442 feed to the first bulk methanator 412 is recovered from the cooled methanated gas stream obtained from the first bulk methanator 412, rather than the second bulk methanator.
- desulphurised feed gas rich in carbon monoxide is fed in line 410 to the bulk methanation section which consists of four bulk methanators 412, 414, 416, 418, each containing a bed of particulate methanation catalyst.
- the first bulk methanator 412, the second bulk methanator 414, third bulk methanator 416 and fourth bulk methanator 418 are each fed with a diluted portion of the feed gas 410 by lines 420, 422, 424 and 426 respectively.
- the feed gas is methanated in the bulk methanators 412, 414, 416, 418.
- the methanated gas stream from the first bulk methanator 412 is passed in line 428 to heat exchanger 430 where it is cooled.
- a portion of the methanated gas stream from the heat exchanger 430 is passed in a recycle loop in line 438 to a compressor 440.
- the compressed methanated gas from the compressor 440 is passed via line 442 to dilute the inlet feed gas fed to the first bulk methanator 412.
- the remaining portion of the stream from heat exchanger 430 is passed via line 432 to dilute the inlet feed gas to the second bulk methanator 414.
- the methanated gas stream from the second bulk methanator 414 is passed in line 434 to a heat exchanger 436 where it is cooled before being passed by line 444 to the inlet of the third bulk methanator 416.
- the methanated gas stream from the third bulk methanator 416 is passed in line 446 to a heat exchanger 448 where it is cooled before being passed by line 450 to the inlet of the fourth bulk methanator 418.
- a product stream 452 is recovered from the fourth bulk methanator and cooled in heat exchanger 454. It is then passed in line 456 to one or more subsequent trim methanators (not shown).
- the product SNG is withdrawn from the trim methanator and then is cooled and dried.
- a desulphurised feed gas rich in carbon monoxide is fed in line 510 to the bulk methanation section which consists of six bulk methanators 512, 514, 516, 518, 520 and 522 each containing a bed of particulate methanation catalyst.
- the first bulk methanator 512, the second bulk methanator 514, third bulk methanator 516, fourth bulk methanator 518, fifth bulk methanator 520 and sixth bulk methanator 522 are each fed with a diluted portion of the feed gas 510 by lines 524, 526, 528, 530, 532 and 534 respectively.
- the feed gas is methanated in the bulk methanators.
- the methanated gas stream from the first bulk methanator 512 is passed in line 536 to heat exchanger 538 where it is cooled before being added via line 540 to dilute the feed to the second bulk methanator 514.
- the methanated gas stream from the second bulk methanator 514 is passed in line 542 to a heat exchanger 544 where it is cooled before being added via line 546 to dilute the feed to the third bulk methanator 516.
- the methanated gas stream from the third bulk methanator 516 is passed in line 548 to a heat exchanger 550 where it is cooled before being added via line 552 to dilute the feed to the fourth bulk methanator 518.
- the methanated gas stream from the fourth bulk methanator 518 is passed in line 554 to a heat exchanger 556 where it is cooled.
- a portion of the stream from the heat exchanger 556 is passed in a recycle loop in line 558 to a compressor 560.
- the compressed methanated gas from the compressor 560 is passed via line 562 to dilute the inlet feed gas fed to the first bulk methanator 512. 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 stream from heat exchanger 556 is passed via line 564 to dilute the inlet feed gas to the fifth bulk methanator 520.
- the methanated gas stream from the fifth bulk methanator 520 is passed in line 566 to a heat exchanger 568 where it is cooled before being passed via line 570 to dilute the inlet feed gas to the sixth bulk methanator 522.
- the product from the sixth bulk methanator 522 is removed in line 572 and passed through heat exchanger 574 where it is cooled. It is then passed in line 576 to one or more subsequent trim methanators (not shown).
- the product SNG is withdrawn from the trim methanator and then is cooled and dried.
- a first example considers the case where the feed gas comprises hydrogen, carbon oxides and some methane, and is based on a SNG production capacity of 250,000 Nm3/h.
- the desulphurised feed gas composition is as follows; vol% Water 0.10 Hydrogen 63.74 Carbon Monoxide 20.00 Carbon Dioxide 1.00 Methane 14.93 Nitrogen & Argon 0.21 Ethane 0.030
- the catalyst volumes are as follows; Bulk Methanator 112 114 116 118 Catalyst Bed Diameter (mm) 4755 5500 4055 4630 Catalyst volume (m 3 ) 41 54 28 37
- the equipment count and required catalyst volumes remains the same as the comparative process depicted in Figure 3 , however, the equipment items related to the recycle are smaller by 40 % due to reduced flow.
- the required recycle gas flow is approximately 16,000 kmol/h and recycle compressor shaft power is approximately 1,860 kW.
- the shaft power has been calculated using a 75% polytropic efficiency and 4% losses.
- the catalyst volumes are as follows; Bulk Methanator 212 214 216 218 Catalyst Bed Diameter (mm) 4030 4800 5485 4660 Catalyst volume (m 3 ) 30 40 53 37
- the equipment count and required catalyst volumes remains the same as the comparative process depicted in Figure 3 , however, the equipment items related to the recycle are smaller by 55 % due to reduced flow.
- the required recycle gas flow is approximately 11,900 kmol/h and recycle compressor shaft power is approximately 1,750 kW.
- Figure 3 which represents current practice for large scale SNG plants, uses 2 bulk methanators in series and the reactors/equipment items inside the bulk methanation recycle loop are twinned due to manufacturing and transportation limitations.
- the required recycle gas flow is approximately 27,100 kmol/h and recycle compressor shaft power is approximately 3,800 kW.
- the following Table sets out the operation of this flow sheet using KatalcoTM CRG-S2R, and KatalcoTM CRG-S2CR.
- the catalyst volumes are as follows; Bulk Methanator 316 318 320 322 Catalyst Bed Diameter (mm) 4380 4380 5180 5180 Catalyst volume (m 3 ) 34.5 34.5 45.5 45.5
- Figure 4 which represents an alternative comparative process, has 1 bulk methanator inside the recirculation loop and 3 bulk methanators outside the recirculation loop.
- the equipment items related to the recycle are larger by 78% and 139%.
- the required recycle gas flow for process in Figure 4 is approximately 28,400 kmol/h and recycle compressor shaft power is approximately 2,380 kW.
- the following Table sets out the operation of this flow sheet using KatalcoTM CRG-S2R, and KatalcoTM CRG-S2CR.
- the catalyst volumes are as follows; Bulk Methanator 412 414 416 418 Catalyst Bed Diameter (mm) 6415 3495 4025 4660 Catalyst volume (m 3 ) 74 21 28 37
- a second example considers the case where the feed gas comprises hydrogen, carbon oxides and no methane, and is based on a SNG production capacity of 250,000 Nm3/h.
- the desulphurised feed gas composition is as follows; vol% Water 0.10 Hydrogen 74.44 Carbon Monoxide 24.16 Carbon Dioxide 0.57 Methane 0.00 Nitrogen & Argon 0.74
- the catalyst volumes are as follows; Bulk Methanator 512 514 516 518 520 522 Catalyst Bed Diameter (mm) 4440 4980 5490 5895 4470 4935 Catalyst volume (m 3 ) 37 45 55 67 36 43
- the catalyst volumes are as follows; Bulk Methanator 316 318 320 322 Catalyst Bed Diameter (mm) 4125 4125 4635 4635 Catalyst volume (m 3 ) 2 x 32 2 x 32 2 x 39 2 x 39
- a process as depicted in Figure 4 the process would need 4 bulk methanators in series, with 1 methanator placed inside the recycle gas loop and 3 methanators placed outside the recycle gas loop.
- the equipment items related to the recycle would be larger by 37% due to increased recycle flow when compared with the flowsheet depicted in Figure 3 .
- the equipment items related to the recycle are larger by 174%.
- the required recycle gas flow is approximately 77,000 kmol/h and recycle compressor shaft power is approximately 12,200 kW.
- the catalyst volumes are as follows; Bulk Methanator 412 414 416 418 Catalyst Bed Diameter (mm) 9685 3895 4295 4730 Catalyst volume (m 3 ) 180 28 34 41
Description
- 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.
- The process to produce substitute natural gas (SNG) involves catalytic methanation of a synthesis gas comprising hydrogen and carbon oxides. By the reaction of methanation, the synthesis gas is converted to a product consisting of 95% or more of methane (CH4) with small amounts of carbon dioxide, hydrogen and inerts. The synthesis gas may be obtained from coal or biomass gasification. The methanation of the syngas involves the following, highly exothermic reactions:
CO + 3H2 → CH4 + H2O ΔH = minus 206 kJ/mol
CO2 + 4H2 → CH4 + 2H2O ΔH = minus165 kJ/mol
- Typically 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.
- Various processes are known for producing SNG. One such process is described in
US 4016189 . Here the feed gas is treated in a single high temperature bulk methanator followed by treatment in a single low temperature trim methanator. In this process all of the fresh feed is fed to the bulk methanator where a large proportion of the carbon oxides are methanated to methane. Since the reaction is highly exothermic, a thermal mass is required to limit the temperature rise across the bulk methanator to an acceptable level. This thermal mass is supplied in the form of a recycle gas which is taken from downstream of the bulk methanator but prior to the trim methanator. The recycle stream is compressed prior to being fed upstream of the bulk methanator. The single stage of trim methanation described inUS 4016189 is adequate to produce a low calorific gas with a methane content of 60%. This is below the required methane level for current SNG product specifications. - In general it should be noted that a bulk methanator is one which receives part or all of the synthesis gas feed, i.e. fresh synthesis gas feed to the plant. Thus 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. Thus a "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.
-
EP 2 110 425 A1 discloses a process for producing SNG from a fresh syngas feedstock, said process comprising at least the steps of reacting said fresh syngas into a methanation section comprising at least a first adiabatic reactor and further adiabatic reactor(s) connected in series, so that each of said further reactor(s) is fed with a gas stream taken from the previous reactor of the methanation section, and re-circulating at least a portion of the reacted gas as input gas of at least one of said reactors, characterized in that said fresh syngas feedstock is fed in parallel to said reactors. Modern SNG plants typically have two or more bulk methanators in series. For example, an alternative process is described inWO2012/001401 (A1 ), which discloses providing a feed gas to a first and/or second and/or subsequent bulk methanator; subjecting that feed gas 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.
Whereas having two bulk methanators in series is useful for minimising the pressure drop over the plant, the process requires a higher product gas recycle and places a limitation on capacity due to the maximum size of the methanator vessels that may be fabricated. Therefore, currently for large-scale plants with higher capacities, reactors and equipment items inside the bulk methanation recycle gas loop have to be twinned, i.e. parallel sets of reactors and ancillary equipment have to be used. 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.
We have now surprisingly found that by increasing the number of bulk methanators both inside and outside the recycle gas loop, higher capacities can be achieved without the need for parallel reactors and ancillary equipment items.
Accordingly, the invention provides a process for producing a substitute natural gas comprising the steps of: feeding a feed gas comprising hydrogen, carbon monoxide and/or carbon dioxide in parallel to a first bulk methanator, a second bulk methanator and one or more subsequent bulk methanators, each bulk methanator containing a methanation catalyst such that the feed gas is at least partially methanated to form a methanated gas stream, wherein the first, second and at least one subsequent methanators are connected in series so that the feed gas to the second and each of the one or more subsequent bulk methanators is diluted with a methanated gas stream recovered from the previous bulk methanator, wherein all of the methanated gas stream recovered from the first bulk methanator is used to dilute the feed gas to the second bulk methanator, a portion of the methanated gas stream recovered from the second or one or more subsequent bulk methanators is recirculated in a recirculation loop to the first bulk methanator and used to dilute the feed gas fed to said first bulk methanator, and wherein at least one bulk methanator is located outside the recirculation loop. - The invention further comprises a methanation system for converting a feed gas comprising hydrogen, carbon monoxide and/or carbon dioxide into substitute natural gas, said methanation system being adapted to operate according to the claimed process. Accordingly the invention includes a methanation system comprising a feed gas supply configured to supply a feed gas in parallel to a first bulk methanator, a second bulk methanator and one or more subsequent bulk methanators, each bulk methanator containing a methanation catalyst, wherein the first, second and at least one subsequent methanators are connected in series so that the feed gas to the second and each of the one or more subsequent bulk methanators may be diluted with a methanated gas stream recovered from the previous bulk methanator, wherein the feed gas supply to the second bulk methanator is configured such that all of the methanated gas stream recovered from the first bulk methanator may be used to dilute the feed gas to the second bulk methanator and a recirculation loop is connected to the second or one or more subsequent bulk methanators so that a portion of a methanated gas stream may be recovered from the second or one or more subsequent bulk methanators and recirculated in the recirculation loop to the first bulk methanator and used to dilute the feed gas fed to said first bulk methanator and wherein at least one bulk methanator is located outside the recirculation loop.
- The methanation system can be a subsection of a plant for producing substitute natural gas, said plant including further subsections like a gasifier, air separation unit (ASU), CO shift converter to provide appropriate ratio between hydrogen and CO content of the syngas, acid gas removal, and so on.
-
US 2009/0264542 discloses a process in which a carbon oxide rich feed is split and fed to a series of bulk methanators wherein the product gas is recycled from the exit of the first bulk methanator back to the inlet of the first bulk methanator. Unlike the aforesaidUS 2009/0264542 in which only one methanator is placed inside the recycle gas loop and second, third and subsequent trim methanators are placed outside the recycle gas loop, the present invention by having at least 2 bulk methanators inside the recycle gas loop provides a saving on recycle flow and shaft power. - Similar methanation processes are disclosed in
US2013/0165535 ,US2013/0047509 ,US2013/0055637 ,WO2013/159662 ,GB2060686 CA1088311 ,CN103865600 ,CN102329671 andCN101649233 . - Prior art processes have not used an arrangement of multiple bulk methanators wherein (i) all of the methanated gas stream recovered from the first bulk methanator is used to dilute the feed gas to the second bulk methanator, (ii) a portion of the methanated gas stream recovered from the second or one or more subsequent bulk methanators is recirculated in a recirculation loop to the first bulk methanator and used to dilute the feed gas fed to the first bulk methanator, and (iii) at least one bulk methanator is located outside the recirculation loop.
- Accordingly, compared to prior art processes, the present invention offers lower recycle gas flow and power consumption, an easier plot layout, smaller line sizes and equipment sizes, and higher capacities can be achieved without installing parallel equipment items.
- The feed gas mixture may be a synthesis gas 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 gas. The feed gas may be formed from the gasification of carbonaceous feedstocks, such as coal or petcoke or biomass using conventional techniques. Alternatively, the feed gas 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.
- In the methanation process it is desirable that for a feed gas 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 gas 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).
- It may be desirable, in order to prevent catalyst poisoning, to subject the feed gas mixture to a desulphurisation step prior to the methanation process. For example the feed gas mixture may be passed over a bed 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 PuraspecJM™ 2020, available from Johnson Matthey PLC. In addition, should the feed gas mixture contain unsaturated compounds (e.g. dienes or acetylenes) that might present coking problems on the methanation catalyst, these maybe removed by hydrogenation over a suitable hydrogenation catalyst, such as a copper catalyst, upstream of the first bulk methanator. 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 the first, second and subsequent 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 Katalco™ CRG-S2R, and Katalco™ 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. 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 gas 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 first, second or one or more subsequent bulk methanators may contain another type of catalyst in addition to the methanation catalyst. For example, a water-gas shift catalyst and/or a methanol synthesis catalyst may be included upstream of the first bed of methanation catalyst in the first, second or one or more subsequent 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 heat exchange with a suitable heating medium. In one embodiment the feed gas 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. Where the methanators are operated adiabatically, the exit temperatures may be in the range 450-750°C, preferably 500-650°C and more preferably 550-650°C. The process pressure may be in the range 5-80 bar abs. The gas hourly space velocity (GHSV) of the feed gas mixtures through the catalyst beds may be in the range 2000 to 20000hr-1.
- The present invention comprises a first bulk methanator, a second bulk methanator and one or more further bulk methanators in a bulk methanator train. Hence three, four or more bulk methanators may be employed, i.e. N may be in the range 3-10, preferably 3-6, where N is the number of bulk methanators. The number of bulk methanators in the recycle loop may be N-1, or N-2 when N≥4. In one preferred arrangement four bulk methanators are used, with recycle of the partially methanated gas stream from the second or third bulk methanators to the first bulk methanator such that there are one or two bulk methanators outside the recycle loop. In an alternative preferred arrangement, six bulk methanators are used, with recycle of the partially methanated gas stream from the fourth bulk methanator to the first bulk methanator such that there are two bulk methanators outside the recycle loop.
- The portion of the feed gas fed to the first bulk methanator and the second and/or subsequent bulk methanator may be the same or different. Each of the feed gas streams fed to the first, second and one or more subsequent bulk methanators may be in the range 10vol% to 60vol% of the total feed gas feedstock, the exact value being adjusted to control the methanator isotherm. In one arrangement with three bulk methanators about 15-20vol%, especially about 18vol% of the fresh feed gas is fed to the first bulk methanator, with the remainder being fed to the second and third bulk methanators. 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.
- In each bulk methanator, the hydrogen reacts with carbon dioxide and carbon monoxide to form methane. A portion of the hydrogen in the feed gas typically remains unreacted because there is an equilibrium limitation on the extent of conversion
- Whereas the present process is particularly suited for adiabatic operation of the bulk methanators, if desired cooling may be applied to one or more methanation catalyst beds by passing a coolant, such as a portion of the feed gas mixture, 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.
- In order to prevent overheating of the catalyst and unwanted side reactions in the second and subsequent bulk methanators it is desirable to adjust the temperature of the partially methanated gas mixture recovered from the first, second and subsequent bulk methanators before mixing it with the feed gas. This may be performed 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.
- The re-circulation 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 gas or provide steam for water-gas shift. Where steam is added, a single stage of steam addition is preferred. Preferably the recycle loop comprises a compressor for the recirculated gas stream and a pre-heater for heating the diluted gas stream before entering 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 or trim methanator. Preferably the temperature of the recycled portion is adjusted, to a temperature in the range 100-200°C, preferably 120-180°C.
- The proportion of the methanated gas stream recycled to the first bulk methanator may be 40-60% vol, preferably 45-55% vol of the methanated gas recovered from the second or one or more subsequent bulk methanators.
The volume ratio between the total diluted gas flow entering the first bulk methanator, and the feed gas stream fed to said first bulk methanator may be between 1.5 and 7, with the exact value depending on the feed gas composition and pressure. - Steam may be added at the inlet of at least the first bulk methanator to further dilute the inlet gas. Hence, if desired steam may be used to further dilute the feed gas to the first, second, and one or more further bulk methanators.
- A methane-containing substitute natural gas product may be recovered from the final bulk methanator. 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 methanator train. Trim methanators may be used to produce high-specification substitute natural gases. The trim methanator train 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. Where more than one trim methanator is used, they 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 train may be operated using the same catalysts and catalyst arrangements as the bulk methanation train.
- 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. CO2-removal, if required, may be accomplished using solvent- or amine-wash techniques known in the art.
- The invention is further illustrated by reference to the accompanying drawings in which;
-
Figure 1 is a depiction of a flow sheet of one embodiment according to the present invention, -
Figure 2 is a depiction of a flow sheet of a further embodiment according to the present invention, -
Figure 3 is a depiction of a comparative process with twinned pairs of bulk methanators, -
Figure 4 is a depiction of a comparative process as described inUS 2009/0264542 , and -
Figure 5 is a depiction of a flow sheet of a further 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.
- One embodiment of the present invention is illustrated in
Figure 1 . Desulphurised feed gas rich in carbon monoxide is fed inline 110 to the bulk methanation section which consists of fourbulk methanators first bulk methanator 112, thesecond bulk methanator 114,third bulk methanator 116 andfourth bulk methanator 118 are each fed with a diluted portion of thefeed gas 110 bylines bulk methanators first bulk methanator 112 is passed inline 128 toheat exchanger 130 where it is cooled before being added vialine 132 to the feed stream to thesecond bulk methanator 114. The methanated gas stream from thesecond bulk methanator 114 is passed inline 134 to aheat exchanger 136 where it is cooled. A portion of the stream from theheat exchanger 136 is passed in a recycle loop inline 138 to acompressor 140. The compressed methanated gas from thecompressor 140 is passed vialine 142 to dilute the inlet feed gas fed to thefirst bulk methanator 112. 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 stream fromheat exchanger 136 is passed vialine 144 to dilute the inlet feed gas to thethird bulk methanator 116. The methanated gas stream from thethird bulk methanator 116 is passed inline 146 to aheat exchanger 148 where it is cooled. The methanated gas stream fromheat exchanger 148 is passed vialine 150 to dilute the inlet feed gas to thefourth bulk methanator 118. The product from thefourth bulk methanator 118 is removed inline 152 and passed throughheat exchanger 154 where it is cooled. It is then passed inline 156 to one or more subsequent trim methanators (not shown). The product SNG is withdrawn from the trim methanator and then is cooled and dried. - Depending on the feed composition and the operating conditions, it may be necessary or desirable to remove water from the methanated gas recovered from the
second bulk methanator 114. This can be conveniently done before the compressor inline 138. - Steam may be added in
line 120. This will only be required with some feed compositions and operating conditions. - In
Figure 2 , the arrangement of first 212, second 214, third 216 and fourth 218 bulk methanators is the same as depicted inFigure 1 except that the recycle loop ofmethanated gas 242 feed to thefirst bulk methanator 212 is recovered from the cooled methanated gas stream obtained from thethird bulk methanator 216, rather than the second bulk methanator. Hence desulphurised feed gas rich in carbon monoxide is fed inline 210 to the bulk methanation section which consists of fourbulk methanators first bulk methanator 212, thesecond bulk methanator 214,third bulk methanator 216 andfourth bulk methanator 218 are each fed with a diluted portion of thefeed gas 210 bylines bulk methanators first bulk methanator 212 is passed inline 228 toheat exchanger 230 where it is cooled before being added vialine 232 to the feed stream to thesecond bulk methanator 214. The methanated gas stream from thesecond bulk methanator 214 is passed inline 234 to aheat exchanger 236 where it is cooled before being added vialine 244 to the feed stream to thethird bulk methanator 216. The methanated gas stream from thethird bulk methanator 216 is passed inline 246 to aheat exchanger 248 where it is cooled. A portion of the stream from theheat exchanger 248 is passed in a recycle loop inline 238 to acompressor 240. The compressed methanated gas from thecompressor 240 is passed vialine 242 to dilute the inlet feed gas fed to thefirst bulk methanator 212. 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 stream fromheat exchanger 248 is passed vialine 250 to dilute the inlet feed gas to thefourth bulk methanator 218. Aproduct stream 252 is recovered from the fourth bulk methanator and cooled inheat exchanger 254. It is then passed inline 256 to one or more subsequent trim methanators (not shown). The product SNG is withdrawn from the trim methanator and then is cooled and dried. - In
Figure 3 a comparative flow sheet is depicted in which the four bulk methanators are arranged as twinned pairs. Hence a desulphurisedfeed gas 310 is divided and fed in parallel vialines 312 & 313 to paired bulk methanators 316 & 318, and vialines methanators line 312 is combined with a recyclemethanated gas stream 354. The resulting mixedgas feed stream 313 is divided and fed via aline 324 tobulk methanator 316 andline 326 tobulk methanator 318. Themethanated gas stream 317 recovered frombulk methanator 316 is cooled inheat exchanger 332 to produce a cooledmethanated gas stream 340. Themethanated gas stream 319 recovered frombulk methanator 318 is cooled inheat exchanger 334 to produce a cooledmethanated gas stream 342. The cooledmethanated gas streams line 343 to be mixed with thefeed stream 314. The resulting mixedgas feed stream 315 is divided and fed via aline 328 tobulk methanator 320 andline 330 tobulk methanator 322. Themethanated gas stream 321 recovered frombulk methanator 320 is cooled inheat exchanger 336 to produce a cooledmethanated gas stream 344. Themethanated gas stream 323 recovered frombulk methanator 322 is cooled inheat exchanger 338 to produce a cooledmethanated gas stream 346. The cooledmethanated gas streams product gas stream 347. A portion of theproduct gas stream 347 is taken as a recycle loop vialine 350 to acompressor 352, where it is compressed and provided vialine 354 to be mixed with fresh feed inline 312. The remaining portion of the cooledproduct gas stream 348 is passed in to one or more subsequent trim methanators (not shown). The product SNG is withdrawn from the trim methanator and then is cooled and dried. - In
Figure 4 a comparative flow sheet is depicted in which the arrangement of first 412, second 414, third 416 and fourth 418 bulk methanators is the same as depicted inFigure 1 except that the recycle loop ofmethanated gas 442 feed to thefirst bulk methanator 412 is recovered from the cooled methanated gas stream obtained from thefirst bulk methanator 412, rather than the second bulk methanator. Hence, desulphurised feed gas rich in carbon monoxide is fed inline 410 to the bulk methanation section which consists of fourbulk methanators first bulk methanator 412, thesecond bulk methanator 414,third bulk methanator 416 andfourth bulk methanator 418 are each fed with a diluted portion of thefeed gas 410 bylines bulk methanators first bulk methanator 412 is passed inline 428 to heat exchanger 430 where it is cooled. A portion of the methanated gas stream from the heat exchanger 430 is passed in a recycle loop inline 438 to acompressor 440. The compressed methanated gas from thecompressor 440 is passed vialine 442 to dilute the inlet feed gas fed to thefirst bulk methanator 412. The remaining portion of the stream from heat exchanger 430 is passed vialine 432 to dilute the inlet feed gas to thesecond bulk methanator 414. The methanated gas stream from thesecond bulk methanator 414 is passed inline 434 to aheat exchanger 436 where it is cooled before being passed byline 444 to the inlet of thethird bulk methanator 416. The methanated gas stream from thethird bulk methanator 416 is passed inline 446 to aheat exchanger 448 where it is cooled before being passed byline 450 to the inlet of thefourth bulk methanator 418. Aproduct stream 452 is recovered from the fourth bulk methanator and cooled inheat exchanger 454. It is then passed inline 456 to one or more subsequent trim methanators (not shown). The product SNG is withdrawn from the trim methanator and then is cooled and dried. - In
Figure 5 a desulphurised feed gas rich in carbon monoxide is fed inline 510 to the bulk methanation section which consists of sixbulk methanators first bulk methanator 512, thesecond bulk methanator 514,third bulk methanator 516,fourth bulk methanator 518,fifth bulk methanator 520 andsixth bulk methanator 522 are each fed with a diluted portion of thefeed gas 510 bylines first bulk methanator 512 is passed inline 536 toheat exchanger 538 where it is cooled before being added vialine 540 to dilute the feed to thesecond bulk methanator 514. The methanated gas stream from thesecond bulk methanator 514 is passed inline 542 to aheat exchanger 544 where it is cooled before being added vialine 546 to dilute the feed to thethird bulk methanator 516. The methanated gas stream from thethird bulk methanator 516 is passed inline 548 to aheat exchanger 550 where it is cooled before being added vialine 552 to dilute the feed to thefourth bulk methanator 518. The methanated gas stream from thefourth bulk methanator 518 is passed inline 554 to aheat exchanger 556 where it is cooled. A portion of the stream from theheat exchanger 556 is passed in a recycle loop inline 558 to acompressor 560. The compressed methanated gas from thecompressor 560 is passed vialine 562 to dilute the inlet feed gas fed to thefirst bulk methanator 512. 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 stream fromheat exchanger 556 is passed vialine 564 to dilute the inlet feed gas to thefifth bulk methanator 520. The methanated gas stream from thefifth bulk methanator 520 is passed inline 566 to aheat exchanger 568 where it is cooled before being passed vialine 570 to dilute the inlet feed gas to thesixth bulk methanator 522. The product from thesixth bulk methanator 522 is removed inline 572 and passed throughheat exchanger 574 where it is cooled. It is then passed inline 576 to one or more subsequent trim methanators (not shown). The product SNG is withdrawn from the trim methanator and then is cooled and dried. - The invention is further illustrated by reference to the following Examples.
- A first example considers the case where the feed gas comprises hydrogen, carbon oxides and some methane, and is based on a SNG production capacity of 250,000 Nm3/h.
- The desulphurised feed gas composition is as follows;
vol% Water 0.10 Hydrogen 63.74 Carbon Monoxide 20.00 Carbon Dioxide 1.00 Methane 14.93 Nitrogen & Argon 0.21 Ethane 0.030 - The product specification is as follows;
vol% Hydrogen < 2% Carbon Dioxide < 1% Methane > 95% - In a process according to the flow sheet depicted in
Figure 1 , there are 4 bulk methanators in series, with 2 methanators placed inside the recycle loop and the 2 methanators placed outside the recycle loop. The following Table sets out the operation of this flow sheet using Katalco™ CRG-S2R, and Katalco™ CRG-S2CR.Stream Number 110 120 128 122 134 124 146 126 152 142 Temperature (°C) 225 320 620 320 620 320 620 320 620 353 Pressure (MPa abs) 4.57 4.02 3.97 3.93 3.88 3.80 3.75 3.80 3.75 4.02 Vapour Flow (kNm3/h) 684.1 527.2 464.2 698.6 616.4 363.1 320.7 479.6 423.7 358.1 Composition (mol%) H2O 0.10 11.98 20.15 13.43 21.28 14.18 22.06 14.78 22.75 17.58 H2 63.74 33.42 17.82 33.22 18.24 33.49 18.67 33.60 18.82 19.10 CO 20.00 7.39 1.37 7.62 1.37 7.61 1.39 7.55 1.37 1.43 CO2 1.00 2.92 3.55 2.69 3.65 2.76 3.75 2.84 3.79 3.83 N2 0.21 0.32 0.36 0.31 0.35 0.30 0.34 0.30 0.34 0.37 CH4 14.93 43.97 56.75 42.72 55.10 41.64 53.79 40.91 52.93 57.69 C2H6 0.03 0.01 - 0.01 - 0.01 - 0.01 - - - The catalyst volumes are as follows;
Bulk Methanator 112 114 116 118 Catalyst Bed Diameter (mm) 4755 5500 4055 4630 Catalyst volume (m3) 41 54 28 37 - The equipment count and required catalyst volumes remains the same as the comparative process depicted in
Figure 3 , however, the equipment items related to the recycle are smaller by 40 % due to reduced flow. The required recycle gas flow is approximately 16,000 kmol/h and recycle compressor shaft power is approximately 1,860 kW. The shaft power has been calculated using a 75% polytropic efficiency and 4% losses. - In a process according to the flow sheet depicted in
Figure 2 , there are 4 bulk methanators in series, with 3 placed inside the recycle loop and the 4th place outside the recycle loop. The following Table sets out the operation of this flow sheet using Katalco™ CRG-S2R, and Katalco™ CRG-S2CR.Stream Number 210 220 228 222 234 224 246 226 252 242 Temperature (°C) 225 320 620 320 620 320 620 320 620 352 Pressure (MPa abs) 4.57 4.02 3.97 3.93 3.88 3.85 3.79 3.71 3.66 4.02 Vapour Flow (kNm3/h) 684.1 389.4 342.7 515.7 455.0 383.3 603.4 480.0 424.1 267.0 Composition (mol%) H2O 0.10 11.83 20.15 13.43 21.28 14.20 22.11 14.75 22.66 17.20 H2 63.74 33.58 17.81 33.21 18.23 33.44 18.59 33.68 18.97 19.76 CO 20.00 7.29 1.37 7.62 1.37 7.59 1.37 7.60 1.40 1.46 CO2 1.00 3.04 3.55 2.69 3.65 2.77 3.74 2.82 3.81 3.97 N2 0.21 0.32 0.36 0.31 0.35 0.30 0.34 0.30 0.34 0.37 CH4 14.93 43.94 56.76 42.73 55.11 41.69 53.85 40.84 52.83 57.24 C2H6 0.03 0.01 - 0.01 - 0.01 - 0.01 - - - The catalyst volumes are as follows;
Bulk Methanator 212 214 216 218 Catalyst Bed Diameter (mm) 4030 4800 5485 4660 Catalyst volume (m3) 30 40 53 37 - The equipment count and required catalyst volumes remains the same as the comparative process depicted in
Figure 3 , however, the equipment items related to the recycle are smaller by 55 % due to reduced flow. The required recycle gas flow is approximately 11,900 kmol/h and recycle compressor shaft power is approximately 1,750 kW. - Whereas each additional bulk reactor in series adds 0.8 - 1 bar pressure drop across the plant, the lower product pressure has a small impact on product quality.
- In comparison,
Figure 3 , which represents current practice for large scale SNG plants, uses 2 bulk methanators in series and the reactors/equipment items inside the bulk methanation recycle loop are twinned due to manufacturing and transportation limitations. The required recycle gas flow is approximately 27,100 kmol/h and recycle compressor shaft power is approximately 3,800 kW. The following Table sets out the operation of this flow sheet using Katalco™ CRG-S2R, and Katalco™ CRG-S2CR.Stream Number 310 313 317+319 315 321+323 354 Temperature (°C) 273 320 620 320 320 337 Pressure (MPa abs) 3.97 3.96 3.91 3.87 3.82 3.97 Vapour Flow (kNm3/h) 684.8 894.2 787.4 1185.7 1046.3 607.6 Composition (mol%) H2O 0.10 12.00 20.17 13.43 21.27 17.62 H2 63.74 33.48 17.91 33.30 18.36 19.21 CO 20.00 7.40 1.38 7.64 1.39 1.45 CO2 1.00 2.93 3.56 2.70 3.67 3.84 N2 0.21 0.32 0.36 0.31 0.35 0.37 CH4 14.93 43.86 56.61 42.61 54.97 57.51 C2H6 0.03 0.01 - 0.01 - - - The catalyst volumes are as follows;
Bulk Methanator 316 318 320 322 Catalyst Bed Diameter (mm) 4380 4380 5180 5180 Catalyst volume (m3) 34.5 34.5 45.5 45.5 - In comparison,
Figure 4 , which represents an alternative comparative process, has 1 bulk methanator inside the recirculation loop and 3 bulk methanators outside the recirculation loop. In comparison to process depicted inFigure 1 and Figure 2 , the equipment items related to the recycle are larger by 78% and 139%. The required recycle gas flow for process inFigure 4 is approximately 28,400 kmol/h and recycle compressor shaft power is approximately 2,380 kW. - Furthermore for process in
Figure 4 , the first bulk methanator and downstream effluent cooling system may require parallel items due to large reactor diameter required for a single vessel. (estimated catalyst bed diameter = 6400 mm). The following Table sets out the operation of this flow sheet using Katalco™ CRG-S2R, and Katalco™ CRG-S2CR.Stream Number 410 420 428 422 434 424 446 426 452 442 Temperature (°C) 225 320 620 320 620 320 620 320 320 354 Pressure (MPa abs) 4.03 4.02 3.97 3.89 3.84 3.80 3.75 3.72 3.67 4.02 Vapour Flow (kNm3/h) 684.1 947.6 834.8 273.4 241.3 362.4 320.0 480.0 424.1 636.5 Composition (mol%) H2O 0.10 12.15 20.15 13.41 21.24 14.17 22.07 14.74 22.67 18.04 H2 63.74 33.20 17.81 33.25 18.31 33.49 18.66 33.68 18.96 18.28 CO 20.00 7.51 1.37 7.64 1.38 7.60 1.38 7.59 1.39 1.41 CO2 1.00 2.77 3.55 2.69 3.66 2.77 3.74 2.83 3.81 3.64 N2 0.21 0.32 0.36 0.31 0.35 0.30 0.34 0.30 0.34 0.37 CH4 14.93 44.03 56.76 42.69 55.06 41.65 53.80 40.85 52.84 58.26 C2H6 0.03 0.01 - 0.01 - 0.01 - 0.01 - - - The catalyst volumes are as follows;
Bulk Methanator 412 414 416 418 Catalyst Bed Diameter (mm) 6415 3495 4025 4660 Catalyst volume (m3) 74 21 28 37 - A second example considers the case where the feed gas comprises hydrogen, carbon oxides and no methane, and is based on a SNG production capacity of 250,000 Nm3/h. The desulphurised feed gas composition is as follows;
vol% Water 0.10 Hydrogen 74.44 Carbon Monoxide 24.16 Carbon Dioxide 0.57 Methane 0.00 Nitrogen & Argon 0.74 - The product specification is as follows;
vol% Hydrogen < 2% Carbon Dioxide < 1% Methane > 95% - In a process according to the flow sheet depicted in
Figure 5 , there are 6 bulk methanators in series, with 4 methanators placed inside the recycle loop and 2 methanators placed outside the recycle loop. The equipment count is reduced when compared to the process depicted inFigure 3 because the production capacity in this example can be achieved via a single train using process depicted inFigure 5 , but two trains are necessary for the process depicted inFigure 3 . The required catalyst volumes remain the same as the comparative process depicted inFigure 3 ; however equipment items related to the recycle forFigure 5 are smaller by 70 % due to reduced flow via a single train versus the combined flow of two trains forFigure 3 . The required recycle gas flow is approximately 16,800 kmol/h and recycle compressor shaft power is approximately 4,850 kW. - The following Table sets out the operation of this flow sheet using Katalco™ CRG-S2R, and Katalco™ CRG-S2CR.
Stream Number 510 524 536 526 542 528 548 530 554 532 566 534 572 562 Temperature (°C) 195 320 620 320 620 320 620 320 320 320 620 320 320 352 Pressure (MPa abs) 2.95 2.90 2.85 2.82 2.77 2.73 2.68 2.65 2.59 2.48 2.43 2.39 2.34 2.91 Vapour Flow (kNm3/h) 964.3 484.6 426.8 586.8 520.0 712.5 632.3 864.5 768.0 459.9 409.1 557.3 496.1 377.1 Composition (mol%) H2O 0.10 11.36 20.35 14.83 22.43 16.40 24.10 17.66 25.43 18.61 26.37 19.38 27.22 14.57 H2 74.44 36.23 20.14 34.94 20.90 35.36 21.53 35.74 22.11 36.21 22.83 36.56 23.29 25.33 CO 24.16 6.86 1.70 7.83 1.68 7.75 1.68 7.71 1.68 7.74 1.73 7.69 1.74 1.93 CO2 0.57 4.07 3.94 3.02 4.13 3.17 4.29 3.29 4.43 3.39 4.57 3.50 4.66 5.07 N2 0.74 1.52 1.73 1.46 1.65 1.40 1.58 1.35 1.52 1.31 1.47 1.28 1.44 1.74 CH4 - 39.96 52.14 37.92 49.21 35.92 46.82 34.24 44.82 32.75 43.03 31.58 41.65 51.35 - The catalyst volumes are as follows;
Bulk Methanator 512 514 516 518 520 522 Catalyst Bed Diameter (mm) 4440 4980 5490 5895 4470 4935 Catalyst volume (m3) 37 45 55 67 36 43 - In comparison, a process as depicted in
Figure 3 , where the reactors/equipment items inside the bulk methanation recycle loop would be twinned due to manufacturing and transportation limitations, and for the same reason two trains would be required, the number of bulk methanator reactor vessels increases to eight. The required recycle gas flow would be approximately 2 x 28,100 kmol/h and recycle compressor shaft power approximately 2 x 5,470 kW. The following Table sets out the operation of this flow sheet using Katalco™ CRG-S2R, and Katalco™ CRG-S2CR.Stream Number 310 313 317+319 315 321+323 354 Temperature (°C) 262 320 620 320 320 333 Pressure (MPa abs) 2.87 2.86 2.81 2.77 2.72 2.87 Vapour Flow (kNm3/h) 483.3 836.0 737.9 1015.3 899.9 330.1 Composition (mol%) H2O 0.10 12.06 20.36 14.82 22.40 15.97 H2 74.44 35.51 20.24 35.05 21.04 22.79 CO 24.16 7.34 1.72 7.85 1.71 1.85 CO2 0.57 3.53 3.95 3.03 4.15 4.50 N2 0.74 1.52 1.72 1.46 1.64 1.78 CH4 - 40.04 52.01 37.80 49.06 53.12 - The catalyst volumes are as follows;
Bulk Methanator 316 318 320 322 Catalyst Bed Diameter (mm) 4125 4125 4635 4635 Catalyst volume (m3) 2 x 32 2 x 32 2 x 39 2 x 39 - In comparison, a process as depicted in
Figure 4 , the process would need 4 bulk methanators in series, with 1 methanator placed inside the recycle gas loop and 3 methanators placed outside the recycle gas loop. The equipment items related to the recycle would be larger by 37% due to increased recycle flow when compared with the flowsheet depicted inFigure 3 . In comparison to process depicted inFigure 5 , the equipment items related to the recycle are larger by 174%. The required recycle gas flow is approximately 77,000 kmol/h and recycle compressor shaft power is approximately 12,200 kW. Furthermore, the first bulk methanator and downstream effluent cooling system may require to be twinned / tripled due to significantly large reactor diameter required for a single reactor (catalyst bed diameter = 9700 mm). The following Table sets out the operation of this flow sheet using Katalco™ CRG-S2R, and Katalco™ CRG-S2CR.Stream Number 410 420 428 422 434 424 446 426 452 442 Temperature (°C) 225 320 620 320 320 320 620 320 320 343 Pressure (MPa abs) 2.93 2.92 2.87 2.77 2.72 2.68 2.63 2.60 2.55 2.92 Vapour Flow (kNm3/h) 966.7 2334.8 2063.0 358.7 318.0 435.7 386.7 528.4 469.5 1725.9 Composition (mol%) H2O 0.10 12.46 20.36 14.81 22.37 16.35 24.03 17.61 25.37 16.82 H2 74.44 34.93 20.10 34.98 21.00 35.44 21.64 35.80 22.20 20.99 CO 24.16 7.61 1.70 7.85 1.70 7.77 1.69 7.72 1.70 1.77 CO2 0.57 3.18 3.93 3.01 4.15 3.18 4.31 3.30 4.44 4.11 N2 0.74 1.53 1.73 1.46 1.64 1.40 1.58 1.35 1.52 1.81 CH4 - 40.29 52.18 37.89 49.15 35.87 46.75 34.21 44.77 54.50 - The catalyst volumes are as follows;
Bulk Methanator 412 414 416 418 Catalyst Bed Diameter (mm) 9685 3895 4295 4730 Catalyst volume (m3) 180 28 34 41
Claims (15)
- A process for producing a substitute natural gas comprising the steps of: feeding a feed gas comprising hydrogen, carbon monoxide and/or carbon dioxide in parallel to a first bulk methanator, a second bulk methanator and one or more subsequent bulk methanators, each bulk methanator containing a methanation catalyst such that the feed gas is at least partially methanated to form a methanated gas stream, wherein the first, second and at least one subsequent methanators are connected in series so that the feed gas to the second and each of the one or more subsequent bulk methanators is diluted with a methanated gas stream recovered from the previous bulk methanator, wherein all of the methanated gas stream recovered from the first bulk methanator is used to dilute the feed gas to the second bulk methanator, a portion of the methanated gas stream recovered from the second or one or more subsequent bulk methanators is recirculated in a recirculation loop to the first bulk methanator and used to dilute the feed gas fed to said first bulk methanator, and wherein at least one bulk methanator is located outside the recirculation loop.
- A process according to claim 1 wherein the feed gas is a desulphurised synthesis gas obtained from the gasification of coal or biomass.
- A process according to claim 1 or claim 2 wherein the methanation catalyst is operated at an inlet temperature in the range 200-450°C, preferably 200-350°C, more preferably 300-350°C.
- A process according to any one of claims 1 to 3 operated at a pressure in the range 5-80 bar abs.
- A process according to any one of claims 1 to 4 wherein the process is operated with N bulk methanators, N is in the range 3-10, preferably 3-6,
- A process according to claim 5 wherein the number of bulk methanators in the recycle loop is N-1, or N-2 when N≥4.
- A process according to any one of claims 1 to 6 comprising four bulk methanators, with recycle of the partially methanated gas stream from the second or third bulk methanators to the first bulk methanator such that there are one or two bulk methanators outside the recycle loop.
- A process according to any one of claims 1 to 6 comprising six bulk methanators, with recycle of the partially methanated gas stream from the fourth bulk methanator to the first bulk methanator such that there are two bulk methanators outside the recycle loop.
- A process according to any one of claims 1 to 8, wherein the feed gas streams fed to the first, second and one or more subsequent bulk methanators is in the range 10vol% to 60vol% of the total feed gas feedstock.
- A process according to any one of claims 1 to 9, wherein the re-circulation loop comprises a compressor for the re-circulated gas stream and a pre-heater for heating said diluted gas stream before entering the first bulk methanator.
- A process according to any one of claims 1 to 10 wherein the proportion of the methanated gas stream recycled to the first bulk methanator is 40-60% vol, preferably 45-55% vol, of the methanated gas recovered from the second or one or more subsequent bulk methanators.
- A process according to any one of claims 1 to 11 wherein the temperature of the recirculated portion of the methanated gas stream is adjusted to a temperature in the range 100-200°C, preferably 120-180°C.
- A process according to any one of claims 1 to 12, wherein steam is added at the inlet of at least the first bulk methanator to further dilute the inlet gas.
- A process according to any one of claims 1 to 13 further comprising subjecting a product gas from the final bulk methanator to further methanation in one or more trim methanators and subjecting a product gas from the final trim methanator to a drying step.
- A methanation system for converting a feed gas containing hydrogen, carbon monoxide and/or carbon dioxide into substitute natural gas, said methanation train being adapted to operate according to the process of any one of claims 1 to 14.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB201503606A GB201503606D0 (en) | 2015-03-03 | 2015-03-03 | Process |
PCT/GB2016/050478 WO2016139451A1 (en) | 2015-03-03 | 2016-02-25 | Process for producing a substitute natural gas |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3265544A1 EP3265544A1 (en) | 2018-01-10 |
EP3265544B1 true EP3265544B1 (en) | 2018-10-31 |
Family
ID=52876451
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16707530.8A Active EP3265544B1 (en) | 2015-03-03 | 2016-02-25 | Process for producing a substitute natural gas |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP3265544B1 (en) |
CN (1) | CN107087415B (en) |
GB (2) | GB201503606D0 (en) |
WO (1) | WO2016139451A1 (en) |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US264542A (en) * | 1882-09-19 | Snow-plow | ||
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 |
GB201011063D0 (en) * | 2010-07-01 | 2010-08-18 | Davy Process Techn Ltd | Process |
DE102010032709B4 (en) * | 2010-07-29 | 2016-03-10 | Air Liquide Global E&C Solutions Germany Gmbh | Process for the production of synthetic natural gas |
CN102010767A (en) * | 2010-11-30 | 2011-04-13 | 新奥新能(北京)科技有限公司 | Natural gas synthesizing process |
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 |
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 |
CN103740425B (en) * | 2012-10-17 | 2016-08-17 | 中国石油化工股份有限公司 | Synthesis gas produces the method substituting natural gas |
CN103773527A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing substitutive natural gas by synthesis gas methanation |
CN102952598A (en) * | 2012-11-05 | 2013-03-06 | 中国五环工程有限公司 | Methanation process for producing natural gas based on underground coal gasification |
CN103865600B (en) * | 2012-12-12 | 2016-06-08 | 中国石油化工股份有限公司 | A kind of methanation process |
EP3018190A1 (en) * | 2014-11-04 | 2016-05-11 | Haldor Topsøe A/S | Process for production of methane rich gas |
-
2015
- 2015-03-03 GB GB201503606A patent/GB201503606D0/en not_active Ceased
-
2016
- 2016-02-25 WO PCT/GB2016/050478 patent/WO2016139451A1/en active Application Filing
- 2016-02-25 EP EP16707530.8A patent/EP3265544B1/en active Active
- 2016-02-25 CN CN201680003017.XA patent/CN107087415B/en active Active
- 2016-02-25 GB GB1603252.6A patent/GB2537219B/en active Active
Also Published As
Publication number | Publication date |
---|---|
GB201603252D0 (en) | 2016-04-13 |
GB2537219B (en) | 2017-04-26 |
EP3265544A1 (en) | 2018-01-10 |
CN107087415B (en) | 2020-06-30 |
GB201503606D0 (en) | 2015-04-15 |
CN107087415A (en) | 2017-08-22 |
WO2016139451A1 (en) | 2016-09-09 |
GB2537219A (en) | 2016-10-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3402773B1 (en) | Methanol process | |
EP3402772B1 (en) | Methanol process | |
CN108368037B (en) | Integrated process for producing formaldehyde-stabilized urea | |
EP3132009B1 (en) | Process | |
CN110177772B (en) | Combined production of methanol, ammonia and urea | |
AU2019269094B2 (en) | Process for synthesising methanol | |
EP3265545B1 (en) | Process for producing a substitute natural gas | |
EP3265544B1 (en) | Process for producing a substitute natural gas | |
US11261086B2 (en) | Process for producing methanol and ammonia | |
EA041436B1 (en) | TECHNOLOGICAL SCHEME OF METHANOL SYNTHESIS FOR LARGE-SCALE PRODUCTION |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20170727 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20180704 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1059366 Country of ref document: AT Kind code of ref document: T Effective date: 20181115 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602016006816 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1059366 Country of ref document: AT Kind code of ref document: T Effective date: 20181031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190228 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190131 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190131 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20190204 Year of fee payment: 10 Ref country code: CH Payment date: 20190125 Year of fee payment: 4 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190201 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190301 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20190128 Year of fee payment: 4 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602016006816 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 602016006816 Country of ref document: DE Representative=s name: BARDEHLE PAGENBERG PARTNERSCHAFT MBB PATENTANW, DE |
|
26N | No opposition filed |
Effective date: 20190801 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190225 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20190228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190225 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: EUG |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200226 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200229 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200229 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200225 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20160225 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181031 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20230119 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20230119 Year of fee payment: 8 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230526 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20240123 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240123 Year of fee payment: 9 |