EP2870125A1 - Procédé pour la méthanation de gaz de gazogène issu de gazéification sur des catalyseurs métalliques en présence de soufre - Google Patents
Procédé pour la méthanation de gaz de gazogène issu de gazéification sur des catalyseurs métalliques en présence de soufreInfo
- Publication number
- EP2870125A1 EP2870125A1 EP13734007.1A EP13734007A EP2870125A1 EP 2870125 A1 EP2870125 A1 EP 2870125A1 EP 13734007 A EP13734007 A EP 13734007A EP 2870125 A1 EP2870125 A1 EP 2870125A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- methanation
- catalyst
- sulfur
- reactor
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 52
- 239000011593 sulfur Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 title claims abstract description 22
- 238000002309 gasification Methods 0.000 title claims description 11
- 238000011069 regeneration method Methods 0.000 claims abstract description 51
- 230000008929 regeneration Effects 0.000 claims abstract description 50
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 40
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 150000002739 metals Chemical class 0.000 claims abstract description 9
- 150000001722 carbon compounds Chemical class 0.000 claims abstract description 7
- 150000004767 nitrides Chemical class 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 6
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 150000001247 metal acetylides Chemical class 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 52
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 12
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- 229930192474 thiophene Natural products 0.000 claims description 6
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 5
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 239000003546 flue gas Substances 0.000 claims description 2
- 238000003780 insertion Methods 0.000 claims description 2
- 230000037431 insertion Effects 0.000 claims description 2
- 125000001806 thionaphthenyl group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 230000001590 oxidative effect Effects 0.000 abstract description 9
- 150000001336 alkenes Chemical class 0.000 abstract description 6
- 239000011269 tar Substances 0.000 abstract description 5
- 150000003464 sulfur compounds Chemical class 0.000 abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 239000002028 Biomass Substances 0.000 description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 238000005201 scrubbing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- -1 mercaptanes ) Chemical class 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RFSDQDHHBKYQOD-UHFFFAOYSA-N 6-cyclohexylmethyloxy-2-(4'-hydroxyanilino)purine Chemical compound C1=CC(O)=CC=C1NC1=NC(OCC2CCCCC2)=C(N=CN2)C2=N1 RFSDQDHHBKYQOD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KSECJOPEZIAKMU-UHFFFAOYSA-N [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] Chemical compound [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] KSECJOPEZIAKMU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000005574 cross-species transmission Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- 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
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
-
- 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
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/104—Carbon dioxide
Definitions
- Catalytic conversion of producer gases from gasification of solid feedstocks usually requires desulfurization in order to protect catalysts in downstream processes such as state-of the-art Fischer-Tropsch synthesis or methanation for production of Synthetic Natural Gas
- Rabou & Bos describe the use of a commercial molybdenum based hydrodesulphurization (HDS) catalyst to convert thiophenes etc. to hydrogen sulfide (H 2 S) which is followed by H 2 S removal by means of a metal oxide bed (ZnO) and subsequent methanation over a nickel catalyst.
- HDS molybdenum based hydrodesulphurization
- ZnO metal oxide bed
- Catalysts for sulfur tolerant methanation are for instance molybdenum sulfide or vanadium sulfide [2b, 2c] .
- Li et al . [4] describe the regenerative desulfurization of producer gas from coal or biomass gasification over metal based absorber materials.
- Carr et al. [8] describe a method of regeneration of sulfur poisoned hydrocarbon cracking catalysts consisting of several cycles of oxidation and subsequent reduction.
- the catalyst used is based on Co, Ni, W, Cu, Mo, Cr, Mn, V or their oxides while the temperature for oxidation is between 900 - 1100 ° F.
- Aguinaga & Montes [9] describe the regeneration of nickel catalysts by a sequence of oxidation- and reduction steps at constant temperature between 200°C and 500°C.
- the catalysts were poisoned by thiophene and the regeneration procedure with very low O 2 concentration (0.05 vol-%) removed up to 80% of the sulfur in 26 minutes.
- Li et al [10] describe the regeneration of sulfur-poisoned nickel steam reforming catalysts with an oxidation- and a reduction step.
- the proposed temperatures are > 750°C for the oxidation in diluted oxygen, and > 850 °C for the regeneration in inert gas and subsequent reduction in diluted hydrogen which is far above the temperature limit for a typical methanation catalyst.
- the methanation catalyst is a metal, a metal oxide, a metal sulfide or a mixture of metals, metal oxides or metal sulfide/nitride/phosphide on a support;
- said metal or metals are selected from a group
- the metal or metals can be promoted by one or more of the following elements: K, P, Na, Ba, Ni, Ru, Rh, Co,
- This method provides for the methanation of a producer gas proposing a simplified process as compared to the prior art.
- the method achieves a nearly complete methanation of CO in the presence of both organic and inorganic sulfur compounds, as well as olefins, tars etc., combined with an at least partial uptake of sulfur followed by a relatively fast oxidative regeneration of the methanation catalyst (bed material) and sulfur release, preferably at a temperature level near the methanation temperature.
- sulfur species present in the synthesis gas mixture include, but are not limited to, one or more of the following compounds: hydrogen sulfide (H 2 S) , carbonyl sulfide (COS) , carbon disulfide (CS 2 ) , thiophene (C 4 H 4 S) , Benzothiophene (CsH 6 S) , Dibenzothiophene (Ci 2 H 8 S) and their derivates.
- H 2 S hydrogen sulfide
- COS carbonyl sulfide
- CS 2 carbon disulfide
- thiophene C 4 H 4 S
- Benzothiophene CsH 6 S
- Dibenzothiophene Dibenzothiophene
- a fast regeneration of the methanation catalyst is achieved when the regeneration of the methanation catalyst is performed by oxidation of the methanation catalyst in the presence of an oxidizing agent, preferably when the regeneration of the methanation catalyst is performed by oxidation of the catalyst with a gaseous oxidizing agent.
- said gaseous oxidizing agent may be air, air diluted with inert gas or air diluted with product gas after the methanation step. From the energetic point of view, suitable reaction
- conditions can be achieved when the methanation and the regeneration are performed at different temperatures between 300°C and 1100°C, thereby preferring for the methanation step a range between 300°C and 450°C.
- the methanation and the regeneration may be performed at the same temperature between 300°C and 700°C, preferably in the range from 300°C and 450°C.
- a further preferred embodiment of the present invention can be achieved when a resulting product of the catalyst
- the catalytic methanation can be performed in a fluidized bed reactor or an entrained flow reactor, from which a part of the catalyst can be conveyed to another fluidized bed reactor or another entrained flow reactor, in which the methanation catalyst can be oxidized and subsequently conveyed back to said methanation reactor.
- the catalytic methanation can be performed in a fluidized bed reactor or an entrained flow reactor, from which a part of the catalyst can be conveyed to another fluidized bed reactor or another entrained flow reactor, in which the methanation catalyst can be oxidized and
- Another alternative can provide for the catalytic reaction
- methanation being performed in one or more fixed bed
- reactors of which at least one is temporarily disconnected from a feed of the synthesis gas mixture thereby being subject to an exposure to a gaseous oxidizing agent.
- another advantageous feature of a preferred embodiment of the present invention provides for controlling the temperature in the catalytic methanation by means of internal heat exchangers or external heat exchange in a recycle stream or in a transfer line between methanation part and regeneration part.
- the temperature control for the catalytic methanation can be supported or achieved by controllable insertion of the reactant gases and/or by several feeding points and/or by cross flow and/or flow reversal .
- the catalyst support can be modified to minimize the adsorption of sulfur or carbon species.
- Fig. 1 a biomass methanation method as described by
- Fig. 2 a simplified biomass methanation process
- Fig. 3 a simplified scheme of the combined sulfur removal and methanation process
- Fig. 4 measured signal at the outlet of the methanation reactor at constant temperature of 430°C versus time for diverse reactants .
- the present invention for the process of the methanation of producer gas proposes a simplified process (see Fig. 2) with nearly complete methanation of CO in the presence of both organic and inorganic sulfur compounds, olefins, tars etc. combined with an at least partial uptake of sulfur followed by a relatively fast oxidative regeneration of the bed material and sulfur release at a temperature level near the methanation temperature.
- the present invention comprises continuous methanation, catalyst regeneration and sulfur removal and therefore leads to less unit operations.
- the catalyst regeneration can be performed at relatively high oxygen partial pressures, which allows performing the regeneration much faster.
- the catalyst reduction can be performed in the methanation reactor and does not require, but may have a specific reduction reactor.
- the product gas, coming from a low temperature gasifier is sent into a catalytic reactor, where H 2 and CO form CH 4 and H 2 0. (see Fig. 2) .
- the catalytic reactor comprises a
- the sulfur species e.g. H 2 S, COS, C 4 H 4 S, thiophene-derivates , benzothiophenes , dibenzothiophenes
- carbon species e.g. C 2 H 4 , aromatics and other unsaturated hydrocarbons
- the catalyst looses its activity for the synthesis, while sulfur and/or some carbon adsorb or deposit on the catalyst, thereby removing the sulfur and/or carbon species from the gas stream.
- the inactive catalyst is regenerated in the
- the regeneration part of the reactor in presence of an oxidant such as diluted oxygen (e.g. air mixed with oxygen-depleted flue gas, but also peroxides, N20 or metal oxides) .
- diluted oxygen e.g. air mixed with oxygen-depleted flue gas, but also peroxides, N20 or metal oxides
- This oxidizes the adsorbed or deposited carbon and sulfur species on the catalyst surface and removes them in the form of S0 2 and C0 2 to the exhaust.
- the regenerated catalyst is fed back to the synthesis part where it catalyses the desired reactions (methanation etc.) until the catalyst is deactivated again.
- Both parts of the reactor can be operated at different temperatures, where the synthesis part is operated at preferentially around 300 °C, and the temperature in the regeneration part is > 300°C (see Fig. 3) .
- Both parts of the reactor can be operated at the same temperature, especially in the range of 400 - 450°C.
- the reactor can be designed
- the reactor can be designed as a swing reactor, where the fuel gas and the oxygen-containing gas are switched between two or more packed bed reactors, e.g. when the catalyst activity drops below a certain limit.
- the catalyst can be mechanically transported in a moving bed design between the synthesis reactor and the regeneration reactor.
- the regeneration of the catalyst may take place in a certain zone of a combined reactor .
- the poisoned catalyst can be transported from a first methanation reactor where it is exposed to sulfur- laden synthesis gas to the regeneration reactor, and from said regeneration reactor to a second methanation reactor which is placed downstream of said first methanation reactor, where the catalyst is exposed to a sulfur-depleted synthesis gas which had been at least partially converted to methane. From said second methanation reactor, the catalyst can be then transported to said first methanation reactor or to said oxidation reactor. Further, it is possible to introduce a solid adsorber bed such as ZnO between the first and the second methanation reactor to further deplete the gas in sulfur before it enters the second methanation reactor downstream.
- a solid adsorber bed such as ZnO
- the catalyst can be deposited on a solid substrate, such as a monolith, where one or more monoliths are exposed to sulfur-laden synthesis gas while one or more monoliths are exposed to oxidizing conditions, and the gas feeds (e.g. reducing/methanation/sulfur
- the catalyst may be suspended in a liquid (e.g. ionic liquid), which may have additional useful absorption capacity for sulfur species, nitrogen species, ions, salts, tars, olefins and/or C02.
- a liquid e.g. ionic liquid
- the reactions are then carried out in three phase flow such as a bubble column.
- the change of atmosphere around the catalyst material may then be achieved either by change of the gas composition fed, by addition of liquid or solid oxidants or by transporting the liquid phase with the suspended catalyst between one or more reactors fed with differing gas
- the catalyst may be connected to a moving part (similar to a recuperator, e.g. in form of a spinning monolith) which is moved or turned between reactors or reactor parts with the differing gas atmosphere.
- a moving part similar to a recuperator, e.g. in form of a spinning monolith
- the addition of the oxidant to the regeneration step may take place by addition of (diluted) air or oxygen containing (flue) gas, by addition of gaseous or liquid peroxides or other oxidizing species (e.g. hydrogen peroxide, N20) , by addition of solid oxidizing species (e.g. metal oxides), by transport of oxygen (e.g as ion or carbonate) through a membrane or by a combination of them.
- oxygen containing gases or species that may split off oxygen are fed on the retention side of the membrane.
- gas and/or liquid and/or solids may be taken out and cooled externally, followed by recycle to the methanation/reducing steps.
- cooling may be achieved by evaporation of a liquid in the reducing/methanation step or in the transfer lines, by latent heat uptake in a solid or liquid or by coupling with an endothermic reaction.
- temperature control may be achieved or supported by suitable addition of the reactant gases, e.g. several feeding points, cross flow, flow reversal etc.
- the catalyst is preferably a supported Ru catalyst or Ru containing catalyst, which may contain species supporting the sulfur uptake and/or the methanation reaction. Further, a combination or common transport of species or materials supporting the sulfur uptake and/or the methanation reaction may be applied. It is advantageous to choose the support and the regeneration conditions such that adsorption of sulfur species (e.g. H2S, S02) on the support and subsequent release and spill-over on the catalyst in any further step is minimized. Besides the choice of non-acidic supports (e.g. carbides, nitrides or phosphides), this may be accomplished or supported by modification of the (surface) properties of the support.
- sulfur species e.g. H2S, S02
- Fig. 4 shows the measured signal at the outlet of the reactor at constant temperature of 430°C versus time.
- H 2 (m/z 2) starts flowing through the reactor at time tl.
- CO is added at time t2, which is reflected by the increasing methane signal (m/z 15) .
- H 2 S/COS/C 4 H 4 S/Ar are added at time t3.
- COS m/z 60
- C 4 H 4 S (m/z 84) are
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Abstract
Priority Applications (1)
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EP13734007.1A EP2870125B1 (fr) | 2012-07-09 | 2013-06-25 | Procédé destiné à produire un mélange gazeux riche en méthane à partir de gaz de synthèse contenant du soufre provenant d'une gazéification |
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EP12175567.2A EP2684856A1 (fr) | 2012-07-09 | 2012-07-09 | Procédé destiné à produire un mélange gazeux riche en méthane à partir de gaz de synthèse contenant du soufre provenant d'une gazéification |
EP13734007.1A EP2870125B1 (fr) | 2012-07-09 | 2013-06-25 | Procédé destiné à produire un mélange gazeux riche en méthane à partir de gaz de synthèse contenant du soufre provenant d'une gazéification |
PCT/EP2013/063288 WO2014009146A1 (fr) | 2012-07-09 | 2013-06-25 | Procédé pour la méthanation de gaz de gazogène issu de gazéification sur des catalyseurs métalliques en présence de soufre |
Publications (2)
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EP2870125A1 true EP2870125A1 (fr) | 2015-05-13 |
EP2870125B1 EP2870125B1 (fr) | 2018-11-07 |
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EP12175567.2A Withdrawn EP2684856A1 (fr) | 2012-07-09 | 2012-07-09 | Procédé destiné à produire un mélange gazeux riche en méthane à partir de gaz de synthèse contenant du soufre provenant d'une gazéification |
EP13734007.1A Active EP2870125B1 (fr) | 2012-07-09 | 2013-06-25 | Procédé destiné à produire un mélange gazeux riche en méthane à partir de gaz de synthèse contenant du soufre provenant d'une gazéification |
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EP12175567.2A Withdrawn EP2684856A1 (fr) | 2012-07-09 | 2012-07-09 | Procédé destiné à produire un mélange gazeux riche en méthane à partir de gaz de synthèse contenant du soufre provenant d'une gazéification |
Country Status (3)
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EP (2) | EP2684856A1 (fr) |
DK (1) | DK2870125T3 (fr) |
WO (1) | WO2014009146A1 (fr) |
Families Citing this family (9)
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GB201406890D0 (en) * | 2014-04-16 | 2014-05-28 | Johnson Matthey Plc | Process |
EP2977103A1 (fr) * | 2014-07-22 | 2016-01-27 | Paul Scherrer Institut | Production de gaz naturel de synthèse à l'aide d'un catalyseur résistant au carbone, promoté et supporté |
CN105688919B (zh) * | 2016-01-29 | 2018-04-03 | 太原理工大学 | 一种沉淀燃烧法制备的浆态床镍基甲烷化催化剂及其应用 |
CN107029726B (zh) * | 2017-05-04 | 2019-09-13 | 太原理工大学 | 一种纳米镍基co甲烷化催化剂的制备方法及应用 |
EP3762350A1 (fr) * | 2018-03-09 | 2021-01-13 | Clariant International Ltd | Catalyseurs de méthanisation à base de nickel dopés au manganèse présentant une meilleure résistance au soufre |
CN108855230A (zh) * | 2018-06-20 | 2018-11-23 | 杭州同久净颢科技有限责任公司 | 一种涂覆型脱硝催化剂及其制备方法 |
CN110152651A (zh) * | 2019-05-17 | 2019-08-23 | 太原理工大学 | 应用于合成气甲烷化的耐硫催化剂及其制法和应用 |
CN115216347A (zh) * | 2022-06-24 | 2022-10-21 | 沈阳航空航天大学 | 一种流化床气化与固定床甲烷化耦合系统及方法 |
CN116059811A (zh) * | 2022-11-30 | 2023-05-05 | 中国船舶集团有限公司第七一一研究所 | 一种甲烷逃逸治理方法及处理系统 |
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US2455419A (en) | 1944-10-11 | 1948-12-07 | Standard Oil Co | Synthesis of hydrocarbons and regeneration of synthesis catalyst |
US2987486A (en) | 1957-12-11 | 1961-06-06 | Pure Oil Co | Process for regenerating sulfurdegenerated catalysts |
DE2759049C3 (de) | 1977-01-05 | 1987-01-22 | Hitachi, Ltd., Tokio/Tokyo | Verfahren zur Entfernung und Gewinnung von H↓2↓S aus Kohlengas |
US4177202A (en) | 1977-03-07 | 1979-12-04 | Mobil Oil Corporation | Methanation of synthesis gas |
US4260518A (en) | 1979-05-15 | 1981-04-07 | University Of Delaware | Process for the regeneration of metallic catalysts |
DK144530C (da) | 1979-12-18 | 1982-09-06 | Topsoee H A S | Fremgangsmaade til fremstilling af en gasblanding med hoejt indhold af metan |
US4728672A (en) * | 1984-10-08 | 1988-03-01 | Research Association For Petroleum Alternatives Development | Process for producing hydrocarbons |
US8158545B2 (en) | 2007-06-18 | 2012-04-17 | Battelle Memorial Institute | Methods, systems, and devices for deep desulfurization of fuel gases |
CA2693459A1 (fr) | 2007-07-10 | 2009-01-15 | Paul Scherrer Institut | Procede destine a produire un melange gazeux riche en methane a partir de gaz de synthese contenant du soufre provenant d'une gazeification |
US20110039686A1 (en) | 2009-08-14 | 2011-02-17 | Battelle Memorial Institute | Fast regeneration of sulfur deactivated Ni-based hot biomass syngas cleaning catalysts |
-
2012
- 2012-07-09 EP EP12175567.2A patent/EP2684856A1/fr not_active Withdrawn
-
2013
- 2013-06-25 EP EP13734007.1A patent/EP2870125B1/fr active Active
- 2013-06-25 DK DK13734007.1T patent/DK2870125T3/en active
- 2013-06-25 WO PCT/EP2013/063288 patent/WO2014009146A1/fr active Application Filing
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See references of WO2014009146A1 * |
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Publication number | Publication date |
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DK2870125T3 (en) | 2019-02-11 |
EP2870125B1 (fr) | 2018-11-07 |
WO2014009146A1 (fr) | 2014-01-16 |
EP2684856A1 (fr) | 2014-01-15 |
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