WO2010078256A1 - Process for producing a methane-rich gas - Google Patents
Process for producing a methane-rich gas Download PDFInfo
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- WO2010078256A1 WO2010078256A1 PCT/US2009/069593 US2009069593W WO2010078256A1 WO 2010078256 A1 WO2010078256 A1 WO 2010078256A1 US 2009069593 W US2009069593 W US 2009069593W WO 2010078256 A1 WO2010078256 A1 WO 2010078256A1
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- WO
- WIPO (PCT)
- Prior art keywords
- gas
- methane
- rich
- carbon dioxide
- produce
- Prior art date
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 421
- 238000000034 method Methods 0.000 title claims abstract description 68
- 239000007789 gas Substances 0.000 claims abstract description 427
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 118
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- 239000000203 mixture Substances 0.000 claims abstract description 62
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 60
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 57
- 229910001868 water Inorganic materials 0.000 claims abstract description 53
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000001257 hydrogen Substances 0.000 claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 8
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004064 recycling Methods 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 60
- 238000003786 synthesis reaction Methods 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 238000002309 gasification Methods 0.000 claims description 24
- 230000001590 oxidative effect Effects 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 8
- 239000002006 petroleum coke Substances 0.000 claims description 5
- 239000011335 coal coke Substances 0.000 claims description 4
- 239000003345 natural gas Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 description 51
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 241000183024 Populus tremula Species 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000004058 oil shale Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000003476 subbituminous coal Substances 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 238000005200 wet scrubbing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/06—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen in the presence of organic compounds, e.g. hydrocarbons
Definitions
- the invention relates to a process for producing a methane-rich gas.
- a methanation reaction is a catalytic reaction of hydrogen with carbon monoxide and/or carbon dioxide to produce a methane -rich gas.
- This methane-rich gas is sometimes also referred to as synthetic natural gas (SNG) and can be used as substitute gas for natural gas.
- SNG synthetic natural gas
- other sources of energy such as coal or petroleum coke, may be partially oxidized in a gasification process to produce a gas comprising hydrogen and carbon monoxide.
- Such a gas comprising hydrogen and carbon monoxide is sometimes also referred to as synthesis gas.
- the synthesis gas can subsequently be used to produce synthetic natural gas (SNG) in a methanation process.
- Reaction (1) is considered the main reaction and reactions (2) and (3) are considered to be side reactions. All the reactions are exothermic.
- the methanation reaction can be carried out in one or more adiabatic reactors.
- a series of adiabatic reactors is used in a methanation process.
- the temperature of a reaction mixture will increase during passage through the adiabatic reactors.
- the methanation reactions are reversible and an increasing temperature will tend to shift the equilibrium towards a lower yield.
- the effluent of an adiabatic reactor is therefore cooled before entering a subsequent adiabatic reactor, for example by using external heat exchangers.
- the temperature increase in a first adiabatic reactor is conventionally limited by diluting a feed gas entering the first adiabatic reactor with a methane-rich gas.
- a considerable portion of methane- rich product gas generated in the first adiabatic reactor is cooled and recycled.
- a feed gas to a first adiabatic reactor may be mixed with recycled methane -rich gas in a volume ratio of recycled methane-rich gas to feed gas as high as about 6:1. Due to this large recycle stream, a large volume of gas needs to be processed through the first adiabatic reactor.
- a first adiabatic reactor conventionally has a large volume that may be as high as about 600 or 700 cubic meters.
- GB2018818 describes a process for preparing a methane-rich gas in at least one adiabatically operating methanation reactor by converting a combination of a preheated synthesis gas stream and a recycle stream from the methanation reactor.
- the combined preheated synthesis gas stream and recycle stream are passed through a layer of shift catalyst directly before passage through a methanation catalyst.
- the process of GB2018818 is illustrated with three experiments.
- GB2018818 states that because of the limitations of the used compressor and in contradistinction with the intended industrial operation the outlet stream of the reactor in these experiments was cooled to below 100°C. According to GB2018818, hereby all the steam was condensed out, whereafter the dry outlet stream was divided into a recycle stream and a product stream.
- the volumetric ratio of the recycle stream to the synthesis gas stream in the experiments was in the range of 2:1 to 3:1.
- the volumetric ratio of the recycle stream to the product stream was in the range from 4: 1 to 5:1.
- US4235044 describes a process for the methanation of a synthesis gas wherein a synthesis gas stream is divided into two separate processing streams. A first stream is reacted with steam in a water gas shift zone to produce a converted gas stream containing carbon dioxide and hydrogen. A first portion of the second unconverted stream is added to the converted gas stream to prepare an adjusted gas stream that is adiabatically reacted in a first adiabatic reaction zone to form an effluent gas stream containing methane.
- the effluent gas stream from the first adiabatic reaction zone is cooled and mixed with the remaining portion of the second unconverted stream to prepare a reaction mixture that is passed to an isothermal methanation zone or to a second adiabatic methanation zone and subsequently to an isothermal methanation zone.
- Carbon dioxide can be removed from the product methane-rich gas or from the methanation feed gas. The process uses no recycle. In between methanation zones no carbon dioxide is removed.
- US3904389 describes a process for the production of a methane-rich gas from a gaseous effluent of a fossil fuel gasification wherein the gaseous effluent is divided into two fractions. The first effluent fraction is subjected to methanation. The second effluent fraction is successively subjected to shift conversion and CO2 removal. Hereafter the resulting effluents are mixed again and subjected to another methanation. The process uses no recycle. In between methanation zones no carbon dioxide is removed.
- the present invention provides a process for producing a methane-rich gas comprising the steps of: a) mixing a feed gas, comprising carbon monoxide and hydrogen, and a recycled methane-rich gas, comprising methane, to produce a gas mixture, comprising carbon monoxide, hydrogen and methane; b) reacting at least part of the carbon monoxide and hydrogen in the gas mixture in the presence of a methanation catalyst to produce a methane-rich product gas comprising methane, carbon dioxide and water; c) treating at least part of the methane-rich product gas to remove carbon dioxide to produce a methane-rich carbon dioxide-lean gas; and d) recycling at least part of the methane-rich carbon dioxide-lean gas to mixing step a) as recycled methane-rich gas.
- FIG. 2 schematically shows the flow scheme for an example of a conventional methanation process.
- the feed gas in step a), comprising carbon monoxide and hydrogen may be any gas comprising carbon monoxide and hydrogen.
- An example of a gas comprising carbon monoxide and hydrogen is synthesis gas.
- synthesis gas is understood to be a gas comprising at least hydrogen and carbon monoxide.
- the synthesis gas may comprise other compounds such as carbon dioxide, water, nitrogen, argon and/or or sulphur containing compounds. Examples of sulphur containing compounds that may be present in synthesis gas include hydrogen sulphide and carbonyl sulphide.
- the synthesis gas may be obtained by reacting a carbonaceous feed and an oxidant in a gasification reaction.
- a carbonaceous feed is understood a feed comprising carbon in some form.
- the carbonaceous feed may be any carbonaceous feed known by the skilled person to be suitable for the generation of synthesis gas.
- the carbonaceous feed may comprise solids, liquids and/or gases. Examples include coal, such as lignite (brown coal), bituminous coal, sub- bituminous coal, anthracite, bitumen, oil shale, oil sands, heavy oils, peat, biomass, petroleum refining residues, such as petroleum coke, asphalt, vacuum residue, or combinations thereof.
- the synthesis gas is used in a methanation process the synthesis gas is preferably obtained by gasification of a solid or liquid carbonaceous feed.
- the synthesis gas is obtained by gasification of a solid carbonaceous feed that comprises coal or petroleum coke.
- an oxidant is understood a compound capable of oxidizing another compound.
- the oxidant may be any compound known by the skilled person to be capable of oxidizing a carbonaceous feed.
- the oxidant may for example comprise oxygen, air, oxygen-enriched air, carbon dioxide (in a reaction to generate carbon monoxide) or mixtures thereof.
- the oxygen-containing gas used may be pure oxygen, mixtures of oxygen and steam, mixtures of oxygen and carbon dioxide, mixtures of oxygen and air or mixtures of pure oxygen, air and steam.
- the oxidant is an oxygen-containing gas containing more than
- substantially pure oxygen is preferred.
- substantially pure oxygen may for example be prepared by an air separation unit (ASU).
- a temperature moderator may also be introduced into the reactor.
- Suitable moderators include steam and carbon dioxide.
- the synthesis gas may be generated by reacting the carbonaceous feed with the oxidant according to any method known in the art. For example it may be generated by a gasification reaction in a gasification process or by a reforming reaction in a steam reforming process. In a preferred embodiment the synthesis gas is generated by a partial oxidation of a carbonaceous feed such as coal or petroleum coke with an oxygen-containing gas in a gasification reactor.
- Synthesis gas leaving a gasification reactor is sometimes also referred to as raw synthesis gas.
- This raw synthesis gas may be cooled and cleaned in a number of downstream cooling and cleaning steps.
- the total of the gasification reactor and the cooling and cleaning steps is sometimes also referred to as gasification unit.
- Suitable gasification processes, reactors for such gasification processes and gasification units are described in "Gasification” by Christopher Higman and Maart van der Burgt, published by Elsevier (2003), especially chapters 4 and 5 respectively. Further examples of suitable gasification processes, reactors and units are described in US2006/0260191, WO2007125047, US20080172941, EP0722999, EP0661373, US20080142408, US20070011945, US20060260191 and US6755980.
- the synthesis gas produced by reacting a carbonaceous feed and an oxidant in a gasification process may be cooled and cleaned before using it as a feed gas in step a).
- Synthesis gas leaving a gasification reactor can for example be cooled by direct quenching with water or steam, direct quenching with recycled synthesis gas, heat exchangers or a combination of such cooling steps, to produce a cooled synthesis gas.
- heat may be recovered. This heat may be used to generate steam or superheated steam.
- Slag and/or other molten solids that may be present in the produced synthesis gas can suitably be discharged from the lower end of a gasification reactor.
- Cooled synthesis gas can be subjected to a dry solids removal, such as a cyclone or a high-pressure high-temperature ceramic filter, and/or a wet scrubbing process, to produce a cleaned synthesis gas.
- the feed gas used in step a) has been desulphurized before mixing it with the recycled methane-rich gas.
- the preferably cooled and cleaned synthesis gas may thus be desulphurized to produce a desulphurized synthesis gas before it is used as feed gas.
- the desulphurization may be carried out in a desulphurizing unit where sulphur containing compounds such as hydrogen sulphide and carbonyl sulphide can be removed from the gas. Desulphurization can for example be carried out by so-called physical absorption and/or by a chemical solvent extraction process.
- the synthesis gas may further be treated to reduce the carbon dioxide content of the synthesis gas.
- the amount of sulphur containing compounds and the amount of carbon dioxide in the feed gas or synthesis gas has been reduced in a combined sulphur/carbon dioxide removal unit before mixing it with the recycled methane-rich gas.
- only part or no carbon dioxide is removed from the feed gas or synthesis gas before mixing it with the recycled methane-rich gas, thereby saving hardware costs.
- most or all the carbon dioxide present in the synthesis gas can be removed from the methane-rich gas produced in the process.
- the feed gas which feed gas comprises carbon monoxide and hydrogen
- a recycled methane-rich gas which recycled methane-rich gas comprises methane
- a methane-rich gas is understood a gas in which the methane content has been increased.
- a methane-rich gas is preferably a gas comprising more than 1 molar percent methane, more preferably a gas comprising more than 5 molar percent methane and most preferably a gas comprising more than 10 molar percent methane.
- a recycled methane-rich gas is understood a methane-rich gas comprising methane that is being recycled.
- methane may be recycled to the methanation reactor in which such methane was produced.
- the mixing may be achieved by simply combining a stream comprising feed gas and a stream comprising recycled methane-rich gas.
- the gas mixture in step a) preferably comprises carbon monoxide and hydrogen in a molar ratio of hydrogen to carbon monoxide in the range from 0.5:1 to 20:1, preferably in the range from 1:1 to 10:1 and more preferably in the range from 1 : 1 to 6: 1.
- the gas mixture comprises carbon monoxide and hydrogen in a molar ratio of hydrogen to carbon monoxide of about 3:1.
- the molar ratio of hydrogen to carbon monoxide in the gas mixture is increased by treating at least part of the feed gas in a water-gas shift unit before mixing it with the recycled methane-rich gas.
- the water-gas shift unit used to treat at least part of the feed gas comprises a high temperature water-gas shift, having a preferred feed temperature in the range from 280°C to 340°C.
- Preferably essentially all feed gas is treated in a water gas shift unit before mixing it with the recycled methane-rich gas.
- water-gas shift unit part of the carbon monoxide present in the feed gas can react with water and/or steam over a water-gas shift catalyst in a water-gas shift reaction.
- the water and/or steam used for the water-gas shift reaction may be water and/or steam already present in the feed gas; water and/or steam added just before or during the water-gas shift reaction; or a combination of both.
- the molar ratio of hydrogen to carbon monoxide in the gas mixture is increased by treating at least part of the gas mixture itself in a water-gas shift unit before reacting at least part of the carbon monoxide and hydrogen in the gas mixture in the presence of a methanation catalyst.
- the water-gas shift unit used to treat the gas mixture comprises a low temperature water-gas shift, having a preferred feed temperature in the range from 250 to 320°C.
- part of the carbon monoxide present in the gas mixture can react with water and/or steam over a water-gas shift catalyst in a water-gas shift reaction.
- the water and/or steam used for the water-gas shift reaction may be water and/or steam already present in the gas mixture; water and/or steam added just before or during the water-gas shift reaction; or a combination of both.
- the water-gas shift reaction is an in- situ water-gas shift reaction of carbon monoxide present in the gas mixture with water and/or steam already present in the gas mixture.
- the water-gas shift unit can include a separate water-gas shift reactor comprising water-gas shift catalyst or can consist merely of a separate layer of water-gas shift catalyst located upstream of a methanation catalyst in a methanation reactor, such as illustrated in
- the molar ratio of hydrogen to carbon monoxide in the gas mixture is increased by first treating at least part of the feed gas in a water-gas shift unit, preferably comprising a separate water-gas shift reactor, to produce a shifted feed gas; then mixing the shifted feed gas with recycled methane -rich gas to produce a gas mixture; and subsequently treating at least part of the gas mixture in a water-gas shift unit, consisting merely of a separate layer of water-gas shift catalyst located upstream of a methanation catalyst in a methanation reactor.
- the water-gas shift catalyst may be any catalyst known to be suitable for such purpose.
- the water-gas shift catalyst may for example contain copper, zinc and/or chromium, optionally in the form of oxides and/or supported by a carrier.
- The, preferably shifted, feed gas is mixed with recycled methane-rich gas to produce a gas mixture, which gas mixture will comprise at least carbon monoxide, hydrogen and methane.
- gas mixture may comprise other compounds such as water, carbon dioxide, nitrogen and argon.
- the molar ratio of feed gas to recycled methane-rich gas in the gas mixture is equal to or less than 2:1, more preferably equal to or less than 1:1 or most preferably equal to or less than 0.5:1. In a further practical embodiment the molar ratio of feed gas to recycled methane-rich gas in the gas mixture is equal to or more than 0.01:1.
- At least part of the carbon monoxide and the hydrogen in the gas mixture are reacted in the presence of a methanation catalyst to produce a methane-rich product gas comprising at least methane, carbon dioxide and water.
- the methane-rich product gas may comprise other compounds such as unreacted carbon monoxide, unreacted hydrogen, nitrogen and argon.
- the reaction of carbon monoxide and hydrogen in the presence of the methanation catalyst may suitably be carried out in a methanation reactor.
- the methanation reactor is an adiabatic methanation reactor.
- an adiabatic methanation reactor is understood to be a methanation reactor, which is not deliberately cooled or heated.
- the adiabatic methanation reactor is a methanation reactor wherein there is substantially no loss or gain of heat with the surroundings of the reactor.
- the methanation reactor may be vertically oriented or horizontally oriented. Preferably the methanation reactor is vertically oriented. In such a vertically oriented methanation reactor the flow of the gas mixture in the methanation reactor may be bottom-up or top-down. Preferably the flow of the gas mixture is top-down.
- the reactor volume of the methanation reactor may conveniently be reduced.
- the process according to the invention causes a reduction in recycle volumes leading to less volume that is to be processed through the reactors.
- the methanation reactor is part of a series of methanation reactors. More preferably the methanation reactor is the first in a series of methanation reactors.
- the gas mixture is fed into a methanation reactor at a temperature in the range from 250°C to 500°C, preferably in the range from 260°C to 400°C, and more preferably in the range from 200 to 300°C and a pressure in the range from 10 to 60 bar, preferably in the range from 20 to 50 bar, more preferably in the range from 25 to 45 bar.
- the flowrate of the gas mixture into the adiabatic methanation reactor is preferably equal to or less than 150 Kmol/sec and preferably at least 10 Kmol/sec.
- the methanation reactor may comprise one or more methanation catalysts and optionally one or more water-gas shift catalysts, as described herein above.
- the methanation catalyst may be any methanation catalyst known to be suitable for this purpose.
- the methanation catalyst may comprise nickel, cobalt, ruthenium or any combination thereof.
- the methanation catalyst comprises nickel.
- the methanation catalyst may comprise nickel, cobalt or ruthenium on a carrier, which carrier may comprise for example alumina, silica, magnesium, zirconia or mixtures thereof.
- the catalyst is a nickel containing catalyst, comprising preferably in the range from 10 wt% to 60 wt% nickel and more preferably in the range from 10 wt% to 30 wt% nickel.
- the nickel containing catalyst may further comprise some molybdenum as promotor.
- suitable methanation catalysts include the catalysts exemplified in GB2018818 and Haldor Topsoe's MCR-2X methanation catalyst.
- the methanation catalyst(s) and/or water-gas shift catalyst(s) may be present in the methanation reactor in any form known to be suitable for catalyzing the methanation reaction respectively water-gas shift reaction.
- the catalyst(s) may be present as a fixed bed, coated on granules packed in a reactor or coated on for example a tubular or spiral structure within the reactor.
- the methanation catalyst is present as a fixed bed of catalyst.
- the water-gas shift catalyst is present as a fixed bed of water-gas shift catalyst upstream of a fixed bed of methanation catalyst, such that the gas mixture first passes the water-gas shift catalyst before coming into contact with the methanation catalyst.
- a layer of water-gas shift catalyst may simply be deposited onto a lower located layer of methanation catalyst.
- the water-gas shift catalyst advantageously allows water and carbon monoxide in the gas mixture to react thereby generating heat, which allows the gas mixture to increase quickly in temperature to a temperature high enough for the methanation reaction to initiate.
- such a water- gas shift reaction may quickly increase the temperature of the gas mixture to a temperature above 300°C but below 400°C.
- At least part of the methane-rich product gas is treated to remove carbon dioxide to produce a methane-rich carbon dioxide-lean gas.
- a carbon dioxide-lean gas is understood a gas from which at least part of the carbon dioxide has been removed.
- essentially all of the carbon dioxide is removed from the gas.
- Carbon dioxide may be removed by any method known to be suitable for that purpose.
- carbon dioxide may be removed by cryogenic cooling, or by physical absorption or in a chemical solvent extraction process.
- At least part of the methane-rich carbon dioxide-lean gas can be recycled as recycled methane-rich gas to step a) for mixing with the feed gas.
- only part of the methane-rich product gas for example in the range from 1 to 99 molar percent, preferably in the range from 10 to 90 molar percent, more preferably in the range from 25 to 75 molar percent, most preferably in the range from 30 to 60 molar percent of the methane-rich product gas produced in step b) is treated to remove carbon dioxide.
- the methane-rich product gas is split into a first part and a second part.
- the first part may be treated to remove carbon dioxide to produce a methane-rich, carbon dioxide- lean gas.
- the second part of the methane-rich product gas may be forwarded to a subsequent methanation reactor, preferable a subsequent adiabatic methanation reactor, or may be used as end product.
- methane-rich carbon dioxide-lean gas is recycled to mixing step a) as recycled methane-rich gas, for example in the range from 1 to 99 molar percent, preferably in the range from 10 to 90 molar percent, more preferably in the range from 25 to 75 molar percent, most preferably in the range from 30 to 60 molar percent of the methane -rich carbon dioxide-lean gas produced in step c) is recycled to step a).
- the methane-rich carbon dioxide-lean gas is preferably split into a first part and a second part.
- the first part may be recycled to step a).
- the second part may be mixed with the methane-rich product gas of step b) and forwarded to a subsequent methanation reactor, preferably a subsequent adiabatic methanation reactor, or may be used as end product.
- from 99 to 100 molar percent, and preferably essentially all, of the methane -rich carbon dioxide-lean gas is recycled to mixing step a) as recycled methane-rich gas.
- the methane-rich product gas produced in step b) is cooled before removing the carbon dioxide to produce a cooled methane -rich product gas.
- Such cooling may be carried out in any manner known in the art.
- the methane-rich product gas is cooled in one or more heat exchanger(s).
- the heat obtained from the methane-rich product gas is used to preheat water, convert water to steam and/or superheat steam in one or more of the heat exchanger(s).
- water is removed from the methane-rich product gas, either before or after carbon dioxide has been removed, to produce a dried methane-rich gas.
- the methane-rich product gas produced in step b) is first cooled to produce a cooled methane-rich product gas and subsequently water is removed from the cooled methane -rich product gas to produce a dried and cooled methane-rich product gas.
- the dried and cooled methane-rich product gas may subsequently be treated to remove carbon dioxide to produce a methane-rich carbon dioxide-lean gas, which can be recycled to step a).
- Water may be removed in any manner known in the art to be suitable for such a purpose. Preferably the water is removed in one or more flashdrum(s).
- the methane-rich carbon dioxide-lean gas that is mixed as recycled methane-rich gas with the feed gas in step a) comprises less than 10 volume percent water, more preferably less than 5 volume percent water and most preferably less than 1 volume percent water; less than 10 volume percent carbon dioxide, more preferably less than 7.5 volume percent carbon dioxide and most perferably less than 5 volume percent carbon dioxide; and/or more than 25 volume percent methane, more preferably more than 30 volume percent methane. More preferably this methane-rich carbon dioxide-lean gas comprises more than 45 volume percent methane and/or more than 30 volume percent hydrogen. In one embodiment part of the methane-rich product gas and/or part of the methane- rich carbon dioxide-lean gas may be used as end-product.
- At least part of the methane-rich product gas and/or at least part of the methane-rich carbon dioxide-lean gas is forwarded to one or more subsequent methanation reactor(s).
- the subsequent methanation reactor(s) may for example be multitubular reactor(s) or adiabatic reactor(s).
- part of the methane -rich product gas and/or part of the methane-rich carbon dioxide-lean gas is forwarded to one or two subsequent adiabatic reactors connected in series.
- the process according to the invention is especially advantageous when converting a carbonaceous feed into a synthetic natural gas.
- the present invention also provides a process for producing a methane- rich gas from a carbonaceous feed comprising the steps of a) reacting a carbonaceous feed and an oxidant in a gasification process to produce a synthesis gas comprising carbon monoxide and hydrogen; which synthesis gas is desulphurized to produce a desulphurized synthesis gas; and of which desulphurized synthesis gas at least part is reacted with water and/or steam in a water-gas shift reaction to produce a shifted synthesis gas; which shifted synthesis gas is mixed with a recycled methane-rich gas, comprising methane, to produce a gas mixture, which gas mixture comprises carbon monoxide, hydrogen and methane; b) reacting at least part of the carbon monoxide and hydrogen in the gas mixture in the presence of a methanation catalyst to produce a methane-rich product gas comprising methane, carbon dioxide and water; c) treating at least part of the methane-rich product gas to remove carbon dioxide to produce
- the process according to the invention produces a methane-rich gas.
- This methane- rich gas may be used in any application known in the art.
- the methane-rich gas may be used for heating, power supply or chemical processes.
- the desulphurized synthesis gas stream (106) is combined with steam provided via a steam stream (108) to provide a water gas shift feed stream (110) that enters a water-gas shift reactor (112).
- steam and the carbon monoxide react to produce a shifted synthesis gas stream (114), comprising carbon dioxide, hydrogen and unreacted carbon monoxide and unreacted water.
- the shifted synthesis gas stream (114) is cooled in heat exchanger (115) and used as feed gas stream (116).
- the feed gas stream (116) is combined with a recycled methane-rich gas stream (117) to produce a gas mixture stream (118) comprising carbon monoxide, carbon dioxide, water, methane and hydrogen.
- Gas mixture stream (118) is forwarded to a first methanation reactor (120).
- the first methanation reactor (120) comprises a first catalyst bed (122) comprising a water-gas shift catalyst on top of a second catalyst bed (124) comprising a methanation catalyst.
- first catalyst bed (122) water and carbon monoxide present in the gas mixture stream (118) are reacted to generate hydrogen and carbon dioxide. As this reaction is exothermic, the temperature of the stream of reactants during this reaction is increased. The stream of increased temperature is subsequently forwarded to the second catalyst bed (124) comprising the methanation catalyst. In the second catalyst bed (124), carbon monoxide and hydrogen are reacted to form methane.
- the first methanation reactor (120) produces a first stream of methane-rich product gas (126) comprising methane, water, hydrogen, carbon monoxide and carbon dioxide. Stream (126) is cooled in heat exchanger (128) and split into a first split methane-rich gas stream (130) and a second split methane-rich gas stream (132).
- the first split methane-rich gas stream (130) is cooled down further in a heat exchanger (134), after which a cooled methane-rich gas stream (136) is forwarded to a flash drum (138) to remove water.
- a cooled methane-rich gas stream (136) is forwarded to a flash drum (138) to remove water.
- water is knocked out and discarded via stream (140) and a stream (142) comprising cooled and dried methane-rich gas is produced.
- Stream (142) is forwarded to a carbon dioxide removal unit (144), where carbon dioxide is removed from the cooled dried methane-rich gas.
- the carbon dioxide removal unit (144) produces a stream (146) comprising cooled and dried methane-rich carbon dioxide-lean gas.
- the cooled and dried methane-rich carbon dioxide-lean gas (146) is compressed in compressor (148) and preheated in heat-exchanger (150) to produce a stream of compressed and dried methane -rich carbon dioxide-lean gas (152).
- This stream of compressed and dried methane-rich carbon dioxide-lean gas (152) can be mixed as recycled methane-rich gas stream (117) with the feed gas stream (116).
- part of the stream of compressed and dried methane- rich carbon dioxide-lean gas (152) may be split off as a stream (154), mixed with second split methane-rich gas stream (132) and forwarded to a second methanation reactor (156).
- the second split methane-rich gas stream (132) is forwarded to a second methanation reactor (156).
- the second methanation reactor (156) comprises a first catalyst bed comprising a water-gas shift catalyst (158) on top of a second catalyst bed (160) comprising a methanation catalyst.
- the second methanation reactor (156) produces a second stream of methane-rich product gas (162).
- the second stream of methane-rich product gas (162) is cooled in a heat exchanger (164) and a stream (166) of cooled methane-rich gas is forwarded to a third methanation reactor (168) comprising a catalyst bed with methanation catalyst (170).
- the third methanation reactor (168) produces a third stream of methane-rich product gas (172).
- the third stream of methane-rich product gas (172) is cooled in a heat exchanger (174) and a stream (176) of cooled methane-rich gas is forwarded to a flash drum (178) to remove water.
- Stream (182) is forwarded to a carbon dioxide removal unit (184), where carbon dioxide is removed from the cooled dried methane-rich gas.
- the carbon dioxide removal unit (184) produces a final product stream (186) comprising cooled dried methane-rich carbon dioxide-lean gas that may be brought to a desired pressure in compressor (188).
- the heat recovered in heat exchangers (115), (128), (134), (164) and (174) is used to convert water into steam.
- a water gas shift feed stream comprising a mixture of desulphurized synthesis gas and water is shifted over a high temperature water-gas shift catalyst in a high temperature water-gas shift reactor to produce a shifted synthesis gas stream.
- the shifted synthesis gas stream is cooled to form a feed gas stream (116) and mixed with recycled methane-rich gas stream (117) to generate a gas mixture stream (118).
- the particulars of a feed gas stream (116), recycled methane-rich gas stream (117) and gas mixture stream (118) are listed in table I.
- Table I Particulars of feed gas stream (116), recycled methane-rich gas stream (117) and gas mixture stream (118).
- the process uses a ratio of recycled methane -rich gas to feed gas of 0.10: 1 to form the mixture that is being fed into the methanation reactor.
- the gas mixture stream (118) is converted over a fixed bed of water-gas shift catalyst and a fixed bed of methanation catalyst in a first methanation reactor into a stream of methane-rich product gas (126).
- Stream (126) was cooled and split into a first split methane-rich gas stream and a second split methane-rich gas stream.
- the first split methane-rich gas stream is recycled as stream (117) after cooling and water and carbon dioxide removal.
- the second split methane- rich gas stream (132) is forwarded to a second methanation reactor and converted into a second stream of methane-rich product gas (162).
- the second stream of methane-rich product gas (162) is cooled to a temperature of 300°C, forwarded to a third methanation reactor and converted into a third stream of methane-rich product gas (172).
- the product stream of the first methanation reactor can be split up in a ratio of gas to be recycled and gas to be forwarded to the second methanation reactor of 9:16.5, i.e. a ratio of less than 1:1.
- Comparative Example 2
- Comparative example 2 As a comparative example 2 a computer calculation was made for methane production according to a conventional process as described in the report titled "Haldor Tops ⁇ e's Recycle Energy-efficient methanation process", with the help of a simulation carried out in Aspen plus 2006.5. Comparative example 2 was calculated for the same feed and product. Both example 1 and comparative example 2 were calculated for a system comprising three methanation reactors. The process of comparative example 2 is illustrated in figure 2.
- synthesis gas comprising carbon monoxide and hydrogen is shifted in a sour shift unit to produce a shifted synthesis gas.
- a sour shift unit is here understood a water-gas shift unit carried out on synthesis gas still containing acid gasses such as carbon dioxide and sulphur hydride).
- acid gasses such as carbon dioxide and hydrogen sulphide are removed in an acid gas removal unit to prepare a feed gas stream (216).
- the feed gas stream (216) is mixed with a recycled methane-rich gas stream (217) to generate a gas mixture stream (218).
- the particulars of a feed gas stream (216), recycled methane-rich gas stream (217) and gas mixture stream (218) for comparative example 2 are listed in table III.
- the gas mixture stream (218) is converted in a first methanation reactor into a stream of methane-rich product gas (226).
- Stream (226) was cooled and split into a first split methane-rich gas stream and a second split methane-rich gas stream.
- the first split methane- rich gas stream is recycled as stream (217).
- the second split methane-rich gas stream (232) is forwarded to a second methanation reactor and converted into a second stream of methane- rich product gas (262).
- the second stream of methane-rich product gas (262) is cooled and forwarded to a third methanation reactor and converted into a third stream of methane-rich product gas (272).
- Table III Particulars of feed gas stream (216), recycled methane -rich gas stream (217) and gas mixture stream (218).
- Table IV Particulars of the stream (226), stream (232), stream(262) and stream (272).
- the product stream of the first methanation reactor is split up in a ratio of gas to be recycled and gas to be forwarded to the second methanation reactor of 39.9:5.7, i.e. a ratio of about 7:1.
- the process according to the invention allows the first adiabatic reactor to be sufficiently cooled with a recycle stream of merely 2.7 Kmol/sec whereas the comparative process requires a recycle stream of 39.9 Kmol/sec.
- the molar ratio of recycled methane-rich gas to feed gas for the process according to the invention is about 0.1:1, whereas the molar ratio of recycled methane-rich gas to feed gas in the comparative process is about 3.8:1.
- the flowrate through the first adiabatic reactor for the process according to the invention i.e. 29.5 Kmol/sec
- the flowrate through the first adiabatic reactor for the comparative process i.e.50.5 Kmol/sec. It is especially advantageous to reduce the volume of the first adiabatic reactor, because the first adiabatic reactor requires expensive metal to withstand the higher temperatures in the reactor.
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AU2009332961A AU2009332961A1 (en) | 2008-12-31 | 2009-12-28 | Process for producing a methane-rich gas |
CN2009801564460A CN102317237A (en) | 2008-12-31 | 2009-12-28 | Process for producing a methane-rich gas |
JP2011544560A JP2012514039A (en) | 2008-12-31 | 2009-12-28 | Generation method of methane rich gas |
EP09796275A EP2376404A1 (en) | 2008-12-31 | 2009-12-28 | Process for producing a methane-rich gas |
ZA2011/04529A ZA201104529B (en) | 2008-12-31 | 2011-06-20 | Process for producing a methane-rich gas |
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EP (1) | EP2376404A1 (en) |
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JP2012514039A (en) | 2012-06-21 |
AU2009332961A1 (en) | 2011-07-14 |
ZA201104529B (en) | 2012-02-29 |
US8470059B2 (en) | 2013-06-25 |
EP2376404A1 (en) | 2011-10-19 |
CN102317237A (en) | 2012-01-11 |
US20100162627A1 (en) | 2010-07-01 |
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