CN103191720B - A kind of catalyst for methanation in presence of sulfur of magnesium aluminate spinel load - Google Patents
A kind of catalyst for methanation in presence of sulfur of magnesium aluminate spinel load Download PDFInfo
- Publication number
- CN103191720B CN103191720B CN201310148822.XA CN201310148822A CN103191720B CN 103191720 B CN103191720 B CN 103191720B CN 201310148822 A CN201310148822 A CN 201310148822A CN 103191720 B CN103191720 B CN 103191720B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- methanation
- sulfur
- spinel
- weight
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 214
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 120
- 239000011029 spinel Substances 0.000 title claims abstract description 120
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 81
- 239000011593 sulfur Substances 0.000 title claims abstract description 81
- 239000011777 magnesium Substances 0.000 title claims abstract description 44
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 32
- -1 magnesium aluminate Chemical class 0.000 title claims abstract description 28
- 230000000694 effects Effects 0.000 claims abstract description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 14
- 229910052566 spinel group Inorganic materials 0.000 claims abstract description 14
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 45
- 238000002360 preparation method Methods 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 32
- 239000002131 composite material Substances 0.000 claims description 27
- 239000000969 carrier Substances 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- 238000000975 co-precipitation Methods 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- 238000001802 infusion Methods 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- RBORURQQJIQWBS-QVRNUERCSA-N (4ar,6r,7r,7as)-6-(6-amino-8-bromopurin-9-yl)-2-hydroxy-2-sulfanylidene-4a,6,7,7a-tetrahydro-4h-furo[3,2-d][1,3,2]dioxaphosphinin-7-ol Chemical compound C([C@H]1O2)OP(O)(=S)O[C@H]1[C@@H](O)[C@@H]2N1C(N=CN=C2N)=C2N=C1Br RBORURQQJIQWBS-QVRNUERCSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 150000004675 formic acid derivatives Chemical class 0.000 claims 1
- 150000003891 oxalate salts Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 45
- 230000003197 catalytic effect Effects 0.000 description 37
- 238000005259 measurement Methods 0.000 description 28
- 239000000203 mixture Substances 0.000 description 24
- 238000012360 testing method Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 19
- 239000007789 gas Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 229910052747 lanthanoid Inorganic materials 0.000 description 5
- 150000002602 lanthanoids Chemical class 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 229910052768 actinide Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001093 holography Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000000696 methanogenic effect Effects 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Abstract
A catalyst for methanation in presence of sulfur for magnesium aluminate spinel load, comprising: 0-20 part (weight) catalyst promoter (M
1)
ao
b; 5-90 part (weight) catalyst activity component (M
2)
co
d; 5-90 part (weight) support modification agent (M
3)
eo
fwith 100 parts of (weight) porous carrier-magnesium aluminate spinels, wherein M
1for Co, Ni, La and/or K; M
2for Mo, W and/or V; M
3for Ce, Zr, Ti and/or Si.
Description
Technical field
The present invention relates to a kind of sulfur resistant catalyst for methanation reaction, specifically, relate to a kind of by synthesis gas active principle CO and H containing sour gas such as hydrogen sulfide
2be converted into CH
4methanation reaction catalyst, wherein said catalyst is made up of catalyst promoter, catalyst activity component, support modification agent and porous carrier-magnesium aluminate spinel.The present invention also relates to the preparation method of this catalyst simultaneously.
Background technology
Methanation reaction refers to that in synthesis gas, CO carries out reacting the process generating methane with H2 under the effect of certain temperature, pressure and catalyst.Its reaction equation can be expressed as follows:
CO+3H
2=CH
4+H
2O (1)
CO+H
2O=CO
2+H
2（2）
2CO+2H
2=CH
4+CO
2（3）
It has been generally acknowledged that: the methanation reaction of synthesis gas is one of preferred plan of coal clean utilization, synthesis gas obtains primarily of coal gasification or pyrolysis of coal, under certain temperature and pressure, by synthesis gas with catalyst exposure that effectively catalytic production of methane reacts just can realize the synthesis of methane, methanation not only can reduce the coal greenhouse gas emission that causes and environmental pollution because conventional method burning, also greatly can improve gaseous fuel calorific value simultaneously.
Generally speaking, the oxide carrier of catalyst can increase the contact area of catalyst activity component and reactant, thus the productive rate of product is improved.Conventional catalyst carrier has the oxide carriers such as aluminium oxide, silica, magnesia, titanium oxide, these oxide carriers have the advantages that to significantly improve catalyst activity, but different carriers has Different Effects to differential responses, and the oxide carrier of catalyst is different with different catalyst metal components action modes, has distinct impact by directly causing to catalyst performance.
For methanation reaction, for a long time, the research direction of a lot of scholar attempts to find out not only to have compared with high selectivity to methane, but also carbon monoxide is had to methanation catalyst and the carrier thereof of higher conversion.In existing industrial methanation catalyst, effect is preferably support type NiO catalyst, however NiO catalyst effects on surface carbon distribution and sulfur species very responsive, they can cause catalysqt deactivation and poisoning, when using NiO catalyst, the H comprised in raw material of synthetic gas must be removed
2the acid gas such as S, to make its content lower than 1ppm, this considerably increases the process costs using NiO catalyst undoubtedly.Therefore, find the good catalyst for methanation in presence of sulfur of other effect and just become particularly important.
US4151191 discloses a kind of by containing H
2, CO and sulfide gas admixture of gas produce CH
4or containing CH
4the method of gas, the methanation catalyst wherein used comprises: group of the lanthanides and/or actinide metals oxide and Mo metal oxide, wherein the atomic ratio of group of the lanthanides and/or actinide metals and Mo is 9:1.This catalyst is at H
2/ CO is that 1:1 and sulfide content are up to showing extremely superior methanation catalyst characteristic under the condition of 3%.
US4320030 discloses a kind of catalyst being specially adapted to methanation reaction, and this catalyst comprises: two or more compound mixture in the compound mixture containing Mo, V and/or W or Mo, V and W.The preparation method of this catalyst is as follows: first mixed with solid sulfur or sulfide, then at inert atmosphere or H with component precursors such as stabilizing agents by its active component
2s/H
2under atmosphere, roasting and cooling are carried out to described solid, finally with catalyst described in the oxygen flow passivation of diluting, and carry out pulverizing, grinding and granulation, the catalyst required by final formation.
US4833112 discloses the raw methanogenic method of one sulfur resistant catalyst, and wherein, sulfur resistant catalyst comprises the metal being selected from Mo, V or W and Co and/or Ni, and this catalyst deposit is at CeO
2on carrier, the atomic ratio of Mo and Ce is 1/20-1/7, and the catalyst B ET specific area of described load is 50cm
2/ g, pore volume are 0.15-0.5cm
3/ g, test shows: use CeO
2the Mo of load is catalyst based to be all greatly better than using Al in methanation catalyst activity and methane selectively
2o
3the Mo of load is catalyst based.
US4260553 discloses a kind of three components Catalysts and its preparation method, wherein, three components is respectively the mixture of the oxide of lanthanide series and sulfide, the oxide of Mo metal and the mixture of sulfide and aluminium oxide or silica support, the atomic ratio of described lanthanide series, such as Ce and Mo metal is 9/1, and aluminium oxide or silica support weight account for the 1%-10% of total catalyst weight; This catalyst is added in same container at the nitrate of lanthanide series and other component and ammonium molybdate, then add Al
2o
3carrier, through heating, dry, roasting, thus obtain final catalyst, result shows: described catalyst all obtains certain improvement in CO conversion and methane selectively, and possesses certain resistance to SO_2.
But the catalytic performance high-temperature stability of the methanation in presence of sulfur catalysts disclosed in above-mentioned patent document is poor, after catalyst at high temperature uses shorter a period of time, its catalytic performance is often deteriorated rapidly.
Simultaneously, from the angle selecting industrial catalyst, except to consider the catalytic activity of catalyst and product selective except, also to consider the factor of the aspects such as catalyst reaction stability, Catalyst Production cost and product yield, possess commercial competitiveness in the industrial production to make catalyst.Although the catalyst disclosed in above patent document is in CO conversion and methane selectively, certain improvement is had relative to traditional catalyst, but Shortcomings in reaction stability, along with long applied at elevated temperature, above-mentioned catalyst reaction catalytic activity will obviously decline, this will cause catalyst life to shorten, meanwhile, and raw materials for production, the such as CeO of above-mentioned catalyst
2expensive, so they cannot accomplish well to balance and take into account between serviceability and production cost.
Above-mentioned all documents are introduced with for referencial use in full at this.
In sum, still need at present to develop the methanation reaction catalyst of a kind of cheapness, efficient, resistant to sulfur, it can improve reaction-ure conversion-age and methane selectively, also can improve reaction stability and high-temperature catalytic stability, can also reduce the production cost of catalyst simultaneously.
Summary of the invention
The present inventor is through countless test and attempt finally have found the novel methanation catalyst that can achieve the above object, and experiment proves: the high-temperature catalytic stability of this catalyst is extremely excellent.
According to a first aspect of the invention, provide a kind of catalyst for methanation in presence of sulfur of magnesium aluminate spinel load, it comprises: 0-20 part (weight) catalyst promoter (M
1)
ao
b; 5-90 part (weight) catalyst activity component (M
2)
co
d; 5-90 part (weight) support modification agent (M
3)
eo
fwith 100 parts of (weight) porous carrier-magnesium aluminate spinels, wherein M
1for Co, Ni, La and/or K; M
2for Mo, W and/or V; M
3for Ce, Zr, Ti and/or Si.
Preferably, M
1be Co and/or La further; M
2be Mo and/or W further; M
3be Ce and/or Zr further, more preferably, by weight, described catalyst for methanation in presence of sulfur comprises: 3-10 part CoO; 10-40 part MoO
3; 20-60 part CeO
2; 100 parts of magnesium aluminate spinels, particularly preferably, by weight, described catalyst for methanation in presence of sulfur comprises: 5 parts of CoO; 15 parts of MoO
3; 30-50 part CeO
2; 100 parts of magnesium aluminate spinels, most preferably, by weight, described catalyst for methanation in presence of sulfur comprises: 5 parts of CoO; 15 parts of MoO
3; 33 parts of CeO
2; 100 parts of magnesium aluminate spinels.
According to a second aspect of the invention, provide a kind of catalyst for methanation in presence of sulfur of magnesium aluminate spinel load, it comprises: 0-20 part (weight) catalyst promoter (M
1)
ao
b; 5-90 part (weight) catalyst activity component (M
2)
co
dwith 100 parts of (weight) porous carrier-magnesium aluminate spinels; Wherein M
1for Co, Ni, La and/or K; M
2for Mo, W and/or V.
Preferably, in above-mentioned catalyst for methanation in presence of sulfur, M1 be further Co and or/La; M
2be Mo and/or W further, more preferably, by weight, above-mentioned catalyst for methanation in presence of sulfur comprises: 3-10 part CoO; 10-40 part MoO
3; 100 parts of magnesium aluminate spinels, particularly preferably, by weight, above-mentioned catalyst for methanation in presence of sulfur comprises: 5 parts of CoO; 15 parts of MoO
3; 100 parts of magnesium aluminate spinels.
In in the present invention first and second, component (M in described catalyst for methanation in presence of sulfur
1)
ao
b(M
2)
co
doptionally respectively at least partly or all by M
1sulfide and M
2sulfide replaced.
According to a third aspect of the invention we, provide a kind of preparation method of above-mentioned catalyst for methanation in presence of sulfur, it comprises the following steps successively:
(1) by coprecipitation, deposition-precipitation method, infusion process, kneading method or sol-gal process by support modification agent (M
3)
eo
fand/or the precursor preparation of porous carrier-magnesium aluminate spinel is by (M
3)
eo
fwith the porous carrier of magnesium aluminate spinel compound;
(2) by infusion process or deposition-precipitation method by catalyst promoter (M
1)
ao
bwith catalyst activity component (M
2)
co
dthe load of precursor composite solution on above-mentioned porous carrier;
(3) at above-mentioned (M
1)
ao
b(M
2)
co
dprecursors decompose temperature under or on roasting drying and impregnation or deposition (M
1)
ao
b(M
2)
co
dafter porous carrier, obtain the catalyst for methanation in presence of sulfur of above-mentioned magnesium aluminate spinel load, wherein flood, dry and calcination steps optionally repeatedly.
Preferably, above-mentioned precursor solution is M
1-M
3nitrate solution, chloride solution, oxalate solution, formate solution, acetate solution or their ammonium salt solution.
Preferably, the precursor of above-mentioned magnesium aluminate spinel is that the salting liquid of Mg and Al, oxide are or/and hydroxide.
Usually, by controlling sintering temperature and roasting time and then controlling the specific area of porous carrier and/or final catalyst, aperture structure and aperture size.
Detailed description of the invention
The present invention is further explained in detail by the description below with reference to embodiment, but the description below comprising embodiment, only for enabling general technical staff of the technical field of the invention clearly understand principle of the present invention and marrow, not meaning that and carrying out any type of restriction to the present invention.
The carrier of catalyst for methanation in presence of sulfur of the present invention is the magnalium oxide of spinel structure, and stable oxygen tetrahedron and octahedral structure make it show excellent reactionlessness, relative to magnesium aluminate spinel (MgAl
2o
4), Al
3+be positioned at body space, west, and Mg
2+be positioned at octahedral interstices, the configuration of this structure makes aluminum-spinel have the resistance to water of higher intensity, excellent high-temperature stability and excellence.
As everyone knows, Mo, W and/or V methylmethane catalyst poor high temperature stability of resistant to sulfur, this easily distils mainly due to its Catalytic active phase (metal sulfide) and/or is oxidized when high temperature, thus makes its Catalytic active phase or be lost, or oxidized and become non-catalytic phase.Its process can be represented by following reaction:
(M
1)
ao
b(catalyst aid)+H
2s<=>M
1the active phase of S(catalyst aid)+H
2o (4)
(M
2)
co
d(active component)+H
2s<=>M
2s
2(Catalytic active phase)+H
2o (5)
(M
1)
ao
b(catalyst aid)+CS<=>M
1the active phase of S(catalyst aid)+CO
2(6)
(M
2)
co
d(active component)+CS<=>M
2s
2(Catalytic active phase)+CO
2(7)
Before catalytic reaction, catalyst is once by H
2after S activation, (M
1)
ao
b(catalyst aid) will become M
1the active phase of S(catalyst aid); And (M
2)
co
d(active component) will become M
2s
2(Catalytic active phase), therefore, when catalytic reaction is carried out, that really play catalytic action is M
1the active phase of S(catalyst aid) and M
2s
2(Catalytic active phase), but above-mentioned reaction is reversible reaction, under certain conditions, such as high temperature and there is excessive water and CO
2time, above-mentioned reaction can be carried out towards the direction generating oxide, like this, and M
1the active phase of S(catalyst aid) and M
2s
2(Catalytic active phase) will again become oxide and lose catalytic performance.This is the key factor causing above-mentioned methanation in presence of sulfur catalysts high-temperature stability to be deteriorated.
With above-mentioned methanation in presence of sulfur catalysts unlike non-resistant to sulfur NiO methanation reaction catalyst, its Catalytic active phase is metallic nickel, and activation process can be represented by following reaction:
NiO+H
2<=>Ni(Catalytic active phase)+H
2o (8)
Therefore, before catalytic reaction, NiO catalyst is once by H
2after activation, NiO will become W metal, when containing excessive H in synthesis gas
2time the sour gas such as S (higher than 1ppm), will there is following reaction in Catalytic active phase metallic nickel:
Ni(Catalytic active phase)+H
2s=NiS+H
2(9)
Meanwhile, the surface characteristics of metal of Catalytic active phase Ni makes it produce Carbon deposition very easily from the teeth outwards, thus blocks contacting of catalyst surface and synthesis gas, and like this, NiO catalyst will become inactivation.
At high temperature, the reaction speed of above-mentioned reaction (9) can be accelerated, and the carbon distribution speed of catalyst surface also can be accelerated simultaneously, and this is the major reason that the catalyst based high-temperature stability of NiO is deteriorated.
If the point of penetration solving the catalyst based poor high temperature stability of NiO reduces the H in synthesis gas
2the acidic gas concentration such as S and prevention catalyst surface produce serious Carbon deposition, and the point of penetration of solution resistant to sulfur Mo, W and/or V methylmethane catalyst poor high temperature stability how to prevent above-mentioned M
1the active phase of S(catalyst aid) and M
2s
2(Catalytic active phase) at high temperature distils and oxidized.
The present inventor is surprised to find: when aluminum-spinel be used as above-mentioned resistant to sulfur Mo, W and/or V methylmethane catalyst carrier time, the interaction of the active component Mo in catalyst, the oxide of W and/or V and carrier aluminum magnesia spinel is obviously strengthened, thus the oxidation resistance of whole catalyst components is also obviously strengthened, ultimately increase above-mentioned M
1the active phase of S(catalyst aid) and M
2s
2the high-temperature stability of (Catalytic active phase), makes above-mentioned resistant to sulfur Mo, W and/or V methylmethane catalyst high-temperature stability improves.
In fact, the catalyst for methanation in presence of sulfur of aluminum-spinel load of the present invention is Four composition or three components catalyst, and it can comprise catalyst promoter (M
1)
ao
b, catalyst activity component (M
2)
co
d, support modification agent (M
3)
eo
f, and porous carrier-aluminum-spinel, wherein, catalyst promoter is for improving the performance of catalyst activity component, and support modification agent is for improving the performance of porous carrier, above-mentioned Four composition or three components synergy make final catalyst while production cost declines to a great extent serviceability but be improved significantly.
Catalyst for methanation in presence of sulfur of the present invention can be used for comprising H
2, CO and concentration is not methane higher than the Synthetic holography of the gaseous sulphide of 5 volume %, the operating temperature of above-mentioned methanation reaction is generally 290-650 DEG C, is preferably 450-600 DEG C; H
2/ CO mol ratio is preferably 4/1-0.5/1; Operation pressure is preferably 0.5-8.0MPa, is more preferably 2.0-6.0MPa.
As mentioned above, catalyst for methanation in presence of sulfur of the present invention comprises the composite porous carriers of aluminum-spinel and support modification agent-can prepare with coprecipitation, deposition-precipitation method, infusion process, kneading method or sol-gal process; And prepared by the method that the final catalyst for methanation in presence of sulfur useful catalyst auxiliary agent of aluminum-spinel load and the precursor mixed solution of catalyst activity component flood above-mentioned composite porous carriers.
Exemplarily property and the example of nonrestrictive above-mentioned porous carrier preparation method is as follows:
A: coprecipitation prepares composite porous carriers:
First, by a certain amount of (M
3)
i(NO
3)
j, such as Ce (NO
3)
3solution and aluminum-spinel precursor solution, such as Al (NO
3)
3solution and Mg (NO
3)
2mix in proportion, form mixed solution;
Then slowly drip in this mixed solution ammoniacal liquor to precipitation completely, maybe by this mixed liquor and ammoniacal liquor and stream add in stillpot, and keep pH value between 6-11.5;
Then, by solution left standstill ageing after 2 hours, filter, deionized water is washed, and proceeds in baking oven dry;
Finally, in Muffle furnace at 500-900 DEG C roasting 1-10 hour, obtain (M
3)
eo
f/ aluminum-spinel composite porous carriers.
B: deposition-precipitation method prepares composite porous carriers:
The a certain amount of aluminum-spinel that is purchased is added certain density (M in proportion
3)
i(NO
3)
j, such as Ce (NO
3)
3in solution, in this solution, then slowly drip ammoniacal liquor to (M
3)
i(NO
3)
jprecipitate completely, and keep pH value between 5-10;
Then, by solution left standstill ageing after 2 hours, filter, deionized water is washed, and dries;
Finally, in Muffle furnace at 500-900 DEG C roasting 1-10 hour, obtain (M
3)
eo
f/ aluminum-spinel composite porous carriers.
C: infusion process prepares composite porous carriers:
The a certain amount of aluminum-spinel that is purchased is added appropriate (M in proportion
3)
i(NO
3)
j, such as Ce (NO
3)
3in solution;
Then, by solution left standstill ageing after 2 hours, proceed in baking oven dry;
Finally, in Muffle furnace at 500-900 DEG C roasting 1-10 hour, obtain (M
3)
eo
f/ aluminum-spinel composite porous carriers.
D: kneading method prepares composite porous carriers:
By a certain amount of (M
3)
i(NO
3)
j, such as Ce (NO
3)
3solution and aluminum-spinel precursor, such as boehmite and Mg (NO
3)
2mix in proportion, after fully mediating;
Then, in said mixture, the mixture of acid or acid and the water accounting for said mixture 1-15 % by weight is slowly dripped, to make said mixture completely peptized;
Above-mentioned completely peptized mixture is carried out abundant kneading, kneading or pugging mullering, until mixture presents good plasticity;
Then, carry out extruded with extruder to said mixture, the mixture shape after shaping can be changed into granular, strip, bulk, sheet etc.;
Dry above-mentioned shaping mixture in 70-160 DEG C of drying baker or drying oven;
Finally, in Muffle furnace at 500-900 DEG C roasting 1-10 hour, obtain (M
3)
eo
f/ aluminum-spinel composite porous carriers.
E: sol-gal process prepares composite porous carriers:
(M is purchased by a certain amount of
3)
eo
f, such as CeO
2add in container with MgO, then drip the dilute nitric acid solution of 1.5mol/L in container, simultaneously vigorous stirring, until (M
3)
eo
ffully dissolve with MgO;
At (M
3)
eo
ffully dissolve with MgO, after solution clarification, then drip orthoaluminic acid ester, absolute ethyl alcohol, deionized water successively in proportion in container, and react 4-6 hour in 80-90 ° of C water-bath, thus form colloidal sol;
Colloidal sol is put into drying box dry 5-6 hour under 80 ° of C, thus form xerogel;
Anneal xerogel at 300-900 DEG C 3-15 hour again, obtains (M
3)
eo
f/ aluminum-spinel composite porous carriers.
Exemplarily property and the example of the preparation method of the catalyst for methanation in presence of sulfur of nonrestrictive above-mentioned aluminum-spinel load is as follows:
F: infusion process (I) prepares the catalyst for methanation in presence of sulfur of aluminum-spinel load:
By (the M prepared by above-mentioned A-D method
3)
eo
f/ aluminum-spinel, such as CeO
2/ aluminum-spinel composite porous carriers is immersed in (M
1)
ao
b/ (M
2)
co
d, such as CoO/MoO
3precursor composite solution, in the nitrate of such as Co and the ammonium salt mixed solution of Mo;
Porous carrier after dipping is put into drying baker dry;
At above-mentioned (M
1)
ao
b/ (M
2)
co
dprecursor, at the nitrate of such as Co and the ammonium salt decomposition temperature of Mo or on, such as roasting drying and impregnation (M at 400-800 DEG C
1)
ao
b/ (M
2)
co
dafter porous carrier;
Repeat above-mentioned dipping, drying and calcination steps, until reach (M
1)
ao
b/ (M
2)
co
d/ (M
3)
eo
fpart by weight required by/aluminum-spinel, obtains the catalyst for methanation in presence of sulfur of above-mentioned aluminum-spinel load.
G: infusion process (II) prepares the catalyst for methanation in presence of sulfur of aluminum-spinel load:
By (the M prepared by above-mentioned A-E method
3)
eo
f/ aluminum-spinel, such as CeO
2/ aluminum-spinel composite porous carriers powder joins (M in proportion
1)
ao
b/ (M
2)
co
d, such as CoO/MoO
3precursor composite solution, in the nitrate of such as Co and the ammonium salt mixed solution of Mo, and vigorous stirring, thus form uniform suspension;
By after the suspension evaporating water that formed, then insert in drying baker and carry out drying, thus slough the moisture in suspension;
At above-mentioned (M
1)
ao
b/ (M
2)
co
dprecursor, at the nitrate of such as Co and the ammonium salt decomposition temperature of Mo or on, the such as dry and deposition (M of roasting at 400-800 DEG C
1)
ao
b/ (M
2)
co
dafter porous carrier, obtain the catalyst for methanation in presence of sulfur of above-mentioned aluminum-spinel load.
H: deposition-precipitation method prepares the catalyst for methanation in presence of sulfur of aluminum-spinel load:
By (the M prepared by above-mentioned A-D method
3)
eo
f/ aluminum-spinel, such as CeO
2/ aluminum-spinel composite porous carriers powder joins (M in proportion
1)
ao
b/ (M
2)
co
d, such as CoO/MoO
3precursor composite solution, in the nitrate of such as Co and the ammonium salt mixed solution of Mo, then by adding nitric acid or ammoniacal liquor regulates solution pH value to forming precipitated liquid;
Then, by solution left standstill ageing after 2 hours, filter, deionized water is washed, and dries;
(M is deposited by it
1)
ao
b/ (M
2)
cthe porous carrier of O puts into drying baker drying;
At above-mentioned (M
1)
ao
b/ (M
2)
co
dprecursor, at the nitrate of such as Co and the ammonium salt decomposition temperature of Mo or on, the such as dry and deposition sedimentation (M of roasting at 400-800 DEG C
1)
ao
b/ (M
2)
cthe porous carrier of O, obtains the catalyst for methanation in presence of sulfur of above-mentioned aluminum-spinel load.
Embodiment
Material ratio in following examples without special instruction, is such as all part by weight.
Embodiment 1: preparation 15MoO
3/ 100 aluminum-spinel (0.91Al
2o
3/ 0.09MgO) catalyst
Step (1): prepare 91Al by coprecipitation
2o
3-9MgO aluminum-spinel porous carrier
By 311.4 grams of Al (NO
3)
39H
2o and 32.1 gram of Mg (NO
3)
36H
2o is jointly dissolved in 500 ml deionized water and forms mixed solution, be that the ammoniacal liquor of 3 mol/L is under 70 DEG C of vigorous stirring and stream adds in beaker by this mixed solution and concentration, keep pH value about 11, reaction complete latter still aging 2 hours to precipitation, filtering precipitate, spend deionized water three times, the filter cake obtained is put into 120 DEG C of baking ovens dry 12 hours, obtain dry powder.By the roasting 2 hours in 700 DEG C of Muffle furnaces of above-mentioned dry powder, obtain 91Al
2o
3/ 9MgO aluminum-spinel porous carrier, its BET measurement the specific area is 235m
2/ g.Step (2): preparation 15MoO
3/ 100 aluminum-spinel (0.91Al
2o
3/ 0.09MgO) catalyst
By 5.58 grams of (NH
4)
6mo
7o
244H
2o is dissolved in 50 ml deionized water and forms solution, take 30 grams of above-mentioned aluminum-spinel porous carrier powder and join vigorous stirring in above-mentioned solution, evaporating water, then put into 120 DEG C of drying boxes oven dry 12 hours, last roasting 2 hours in 750 DEG C of Muffle furnaces, obtains 15MoO
3/ 100 aluminum-spinel (0.91Al
2o
3/ 0.09MgO) catalyst for methanation in presence of sulfur, its BET measurement the specific area is 206m
2/ g.
Comparative example 1: preparation 15MoO
3/ 100Al
2o
3methanation catalyst
By 5.58 grams of (NH
4)
6mo
7o
244H
2o is dissolved in 50 ml deionized water and forms solution, and (commercial Sasol product, specific area is 200m to take 30 grams of alumina powders
2/ g), subsequently alumina powder is joined vigorous stirring in above-mentioned solution, evaporating water, then put into 120 DEG C of drying boxes and dry 12 hours, finally roasting 2 hours in 750 DEG C of Muffle furnaces, obtains 15MoO
3/ 100Al
2o
3catalyst for methanation in presence of sulfur, its BET measurement the specific area is 174m
2/ g.
Embodiment 2: preparation 15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
Step (1): prepare 83Al by coprecipitation
2o
3-17MgO aluminum-spinel porous carrier
Except by Mg (NO
3)
36H
2the consumption of O changes into outside 64.2 grams by 32.1 grams, repeats the step (1) in embodiment 1, obtains 83Al
2o
3-17MgO aluminum-spinel porous carrier, its BET measurement the specific area is 213m
2/ g.
Step (2): preparation 15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
Repeat the step (2) in embodiment 1, obtain 15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst for methanation in presence of sulfur, its BET measurement the specific area is 197m
2/ g.
Comparative example 2: preparation 15MoO
3/ 100CeO
2methanation catalyst
Except by Al
2o
3powder changes CeO into
2(specific area is 45m to powder
2/ g) outward, repeat the step in comparative example 1, obtain 15MoO
3/ 100CeO
2catalyst for methanation in presence of sulfur, its BET measurement the specific area is 28m
2/ g.
Implementation column 3: preparation 15MoO
3/ 100 aluminum-spinel (0.8Al
2o
3/ 0.2MgO) catalyst
Except by Mg (NO in embodiment 1
3)
36H
2o weight is increased to outside 80.3 grams by 32.1 grams, repeats the step in embodiment 1, obtains 15MoO
3/ 100 aluminum-spinel (0.8Al
2o
3/ 0.2MgO) catalyst for methanation in presence of sulfur, its BET measurement the specific area is 197m
2/ g.
Implementation column 4: preparation 15MoO
3/ 100 aluminum-spinel (0.74Al
2o
3/ 0.26MgO) catalyst
Except by Mg (NO in embodiment 1
3)
36H
2the weight of O is increased to outside 112.4 grams by 32.1 grams, repeats the step in embodiment 1, obtains 15MoO
3/ 100 aluminum-spinel (0.74Al
2o
3/ 0.26MgO) catalyst for methanation in presence of sulfur, its BET measurement the specific area is 190m
2/ g.
Implementation column 5: preparation 15MoO
3/ 100 aluminum-spinel (0.71Al
2o
3/ 0.29MgO) catalyst
Except by Mg (NO in embodiment 1
3)
36H
2the weight of O is increased to outside 128.4 grams by 32.1g, repeats the step in embodiment 1, obtains 15MoO
3/ 100 aluminum-spinel (0.71Al
2o
3/ 0.29MgO) catalyst for methanation in presence of sulfur, its BET measurement the specific area is 174m
2/ g.
Implementation column 6:15MoO
3/ 100 aluminum-spinel (0.65Al
2o
3/ 0.35MgO) catalyst
Except by Mg (NO in embodiment 1
3)
36H
2the weight of O is increased to outside 173.7 grams by 32.1 grams, repeats the step in embodiment 1, obtains 15MoO
3/ 100 aluminum-spinel (0.65Al
2o
3/ 0.35MgO) catalyst for methanation in presence of sulfur, its BET measurement the specific area is 167m
2/ g.
Test case 1
Test catalytic activity and stability, CO conversion ratio and the CH of the methanation catalyst prepared in embodiment 1-6 and comparative example 1-2
4selective.
Test condition is: react and carry out on fixed bed reactors, raw material of synthetic gas composition (volume %): 45CO; 45H
2; 19.8N
2; 0.2H
2s, raw material of synthetic gas air speed (GHSV): 5000h
-1, reaction pressure: 3.0MPa, reaction temperature: 650 DEG C.
Table 1 gives above-mentioned various catalyst under the above-described reaction conditions respectively at reaction 2 hours and reaction CO conversion ratio and CH after 30 hours below
4optionally result.
Table 1
As can be seen from Table 1: the catalyst for methanation in presence of sulfur (embodiment 1-6) of aluminum-spinel load of the present invention, compared with existing similar catalyst (comparative example 1-2), has active high and high temperature stability performance two distinguishing features.
Embodiment 7: preparation 15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
Step (1): prepare 83Al by infusion process
2o
3-17MgO aluminum-spinel porous carrier
By 53.8 grams of Mg (NO
3)
36H
2o is dissolved in 80 ml deionized water and forms solution.(commercial Sasol product, specific area is 200m to take 42 grams of alumina powders
2/ g), subsequently alumina powder is joined vigorous stirring in above-mentioned solution, evaporating water, then put into 110 DEG C of drying boxes and dry 16 hours, finally roasting 2 hours in 700 DEG C of Muffle furnaces, obtains 83Al
2o
3/ 17MgO aluminum-spinel porous carrier, its BET measurement the specific area is 175m
2/ g.
Step (2): preparation 15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
Repeat the process of step (2) in embodiment 1, obtain 15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst for methanation in presence of sulfur, its BET measurement the specific area is 157m
2/ g.
Embodiment 8: preparation 15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
Step (1): prepare 83Al with kneading method
2o
3-17MgO aluminum-spinel porous carrier
Take 300 grams of boehmite (Al
2o
3: 70 % by weight) put into kneader, then add 269 grams of Mg (NO successively
3)
36H
2o and 90 ml deionized water, to be mixed evenly after, add Aci-Jel solvent, such as nitric acid, hydrochloric acid, glacial acetic acid and/or citric acid, make mixture carry out peptized fully, carries out pugging mullering or kneading subsequently until mixture shows good plasticity, be incorporated with by mixture in the banded extruder of cylindricality orifice plate shaping again, mixture becomes wet bar through extruded.To wet bar after 120 DEG C of dryings, and roasting 5 hours under 700 DEG C of air atmospheres, obtains column aluminum-spinel porous carrier, the composition of porous carrier: 83Al
2o
3/ 17MgO, its BET measurement the specific area is 206m
2/ g.
Step (2): preparation 15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
Repeat the process of step (2) in embodiment 1, obtain 15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst for methanation in presence of sulfur, its BET measurement the specific area is 191m
2/ g.
Embodiment 9: preparation 15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
Step (1): prepare 83Al with sol-gal process
2o
3-17MgO aluminum-spinel porous carrier
By 311.4 grams of Al (NO
3)
39H
2o and 64.2 gram of Mg (NO
3)
36H
2o is jointly dissolved in 350 ml deionized water and forms mixed solution.Take 252.2 grams of citric acid (C
6h
8o
71H
2o) add in above-mentioned solution, put into 80 DEG C of water-baths after dissolved with vigorous agitation, evaporating water obtains clear gel.Gel is put into 120 DEG C of baking ovens dry 20 hours, obtain dry powder.By the roasting 2 hours at 700 DEG C of above-mentioned dry powder, obtain 83Al
2o
3/ 17MgO aluminum-spinel porous carrier, its BET measurement the specific area is 245m
2/ g.。
Step (2): preparation 15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
Repeat the process of step (2) in embodiment 1, obtain 15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst for methanation in presence of sulfur, its BET measurement the specific area is 201m
2/ g.
Test case 2
Test catalytic activity and stability, CO conversion ratio and the CH of the methanation catalyst prepared in embodiment 7-9
4selective.
The test condition of this test case is identical with test case 1.Table with test results is shown in the following Table 2
Table 2
As can be seen from Table 2: the catalyst for methanation in presence of sulfur of aluminum-spinel load of the present invention, no matter how to prepare, final catalytic activity and high-temperature stability are all very good, wherein, aluminum-spinel porous carrier adopts the catalyst for methanation in presence of sulfur performance of the present invention prepared of sol-gal process best.
Embodiment 10: preparation 2CoO/15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
Step (1): prepare 83Al by coprecipitation
2o
3-17MgO aluminum-spinel porous carrier
Repeat the process of step (1) in embodiment 2, obtain 83Al
2o
3-17MgO aluminum-spinel porous carrier, its BET measurement the specific area is 213m
2/ g.
Step (2): preparation 2CoO/15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
By 42.5 grams of (NH
4)
6mo
7o244H
2o and 17.9 gram of Co (NO
3)
26H
2o is dissolved in 250 ml deionized water, forms mixed solution, the 83Al that then will obtain from above-mentioned steps (1)
2o
3228.5 grams ,/17MgO aluminum-spinel porous carrier powder joins vigorous stirring in described mixed solution, after forming unit for uniform suspension, evaporating water, then put into 110 DEG C of drying boxes oven dry 16 hours, last roasting 2 hours in 750 DEG C of Muffle furnaces, obtains 2CoO/15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst for methanation in presence of sulfur, its BET measurement the specific area is 189m
2/ g.
Embodiment 11: preparation 5CoO/15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
Step (1): prepare 83Al by coprecipitation
2o
3-17MgO aluminum-spinel porous carrier
Repeat the process of step (1) in embodiment 2, obtain 83Al
2o
3-17MgO aluminum-spinel porous carrier, its BET measurement the specific area is 213m
2/ g.
Step (2): preparation 5CoO/15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
Except by Co (NO
3)
26H
2o consumption becomes outside 43.8 grams from 17.9 grams, repeats the process of step (2) in embodiment 10, obtains 5CoO/15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst for methanation in presence of sulfur, its BET measurement the specific area is 185m
2/ g.
Embodiment 12: preparation 5NiO/15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
Step (1): prepare 83Al by coprecipitation
2o
3-17MgO aluminum-spinel porous carrier
Repeat the process of step (1) in embodiment 2, obtain 83Al
2o
3-17MgO aluminum-spinel porous carrier, its BET measurement the specific area is 213m
2/ g.
Step (2): preparation 5NiO/15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
Except by 17.9 grams of Co (NO
3)
26H
2o changes 18.0 grams of Ni (NO into
3)
26H
2outside O, repeat the process of step (2) in embodiment 10, obtain 5NiO/15MoO
3/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst for methanation in presence of sulfur, its BET measurement the specific area is 187m
2/ g
Test case 3
Test catalytic activity and stability, CO conversion ratio and the CH of the catalyst for methanation in presence of sulfur of the present invention prepared in above-described embodiment 10-12
4selective.
Test condition: identical with the condition in test case 1.
Table 3 gives above-mentioned catalyst under these conditions respectively at reaction 2 hours and reaction CO conversion ratio and CH after 30 hours below
4optionally result.
Table 3
As can be seen from Table 3: add catalytic activity and high-temperature catalytic stability that catalyst promoter CoO and NiO can significantly improve the catalyst for methanation in presence of sulfur of aluminum-spinel load of the present invention.
Implementation column 13: preparation 15MoO
3/ 9ZrO
2/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst Step (1): prepare 9ZrO by coprecipitation
2/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) composite porous carriers
Except adding 11.8 grams of ZrO (NO again
3)
22H
2outside O, repeat the process of step (1) in embodiment 2, obtain 9ZrO
2/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) composite porous carriers, its BET measurement the specific area is 191m
2/ g.
Step (2): preparation 15MoO
3/ 9ZrO
2/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
Repeat the process of step (2) in embodiment 2, obtain 15MoO
3/ 9ZrO
2/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst, its BET measurement the specific area is 173m
2/ g.
Implementation column 14: preparation 15MoO
3/ 9TiO
2/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
Step (1): prepare 9TiO by coprecipitation
2/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) composite porous carriers
Except with 12.9 grams of TiCl
4replace 11.8 grams of ZrO (NO
3)
22H
2outside O, repeat the process of step (1) in embodiment 13, obtain 9TiO
2/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) composite porous carriers, its BET measurement the specific area is 196m
2/ g.
Step (2): preparation 15MoO
3/ 9TiO
2/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
Repeat the process of step (2) in embodiment 2, obtain 15MoO
3/ 9TiO
2/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst, its BET measurement the specific area is 185m
2/ g.
Implementation column 15: preparation 15MoO
3/ 9CeO
2/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
Step (1): prepare 9CeO by coprecipitation
2/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) composite porous carriers
Except adding 13.7 grams of Ce (NO again
3)
36H
2outside O, repeat the process of step (1) in embodiment 2, obtain 9CeO
2/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) composite porous carriers, its BET measurement the specific area is 186m
2/ g.
Step (2): preparation 15MoO
3/ 9CeO
2/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst
Repeat the process of step (2) in embodiment 2, obtain 15MoO
3/ 9CeO
2/ 100 aluminum-spinel (0.83Al
2o
3/ 0.17MgO) catalyst, its BET measurement the specific area is 170m
2/ g.
Test case 4
Test catalytic activity and stability, CO conversion ratio and the CH of the catalyst for methanation in presence of sulfur of the present invention prepared in above-described embodiment 13-15
4selective.
Test condition: identical with the condition in test case 1.
Table 4 gives above-mentioned catalyst under these conditions respectively at reaction 2 hours and reaction CO conversion ratio and CH after 30 hours below
4optionally result.
Table 4
As can be seen from Table 4: add support modification agent ZrO
2, TiO
2and CeO
2equally also can significantly improve catalytic activity and the high-temperature catalytic stability of the catalyst for methanation in presence of sulfur of aluminum-spinel load of the present invention.
Test case 5 tests the catalytic performance of catalyst for methanation in presence of sulfur under steam atmosphere of aluminum-spinel load of the present invention
The catalytic activity of methanation catalyst under steam atmosphere of test preparation in embodiment 2 and 13 and comparative example 1 and stability, CO conversion ratio and CH
4selective.
Test condition is: react and carry out on fixed bed reactors, raw material of synthetic gas composition (volume %): 40CO; 40H
2; 10H
2o; 19.8N
2; 0.2H
2s, raw material of synthetic gas air speed (GHSV): 5000h
-1, reaction pressure: 3.0MPa, reaction temperature: 650 DEG C.
Table 5 gives above-mentioned various catalyst under the above-described reaction conditions respectively at reaction 2 hours and reaction CO conversion ratio and CH after 30 hours below
4optionally result.
Table 5
As can be seen from Table 5: compared with conventional catalyst for methanation in presence of sulfur (comparative example 1), the catalyst for methanation in presence of sulfur of aluminum-spinel load of the present invention, under high temperature (650 DEG C) and steam (10 volume %) atmosphere, shows extremely excellent stable in catalytic performance.
In sum, the high-temperature catalytic stability of the catalyst for methanation in presence of sulfur of aluminum-spinel load of the present invention is extremely excellent, is suitable for the production of large-scale industrialization synthetic natural gas.
The term that this description is used and form of presentation are only used as descriptive and nonrestrictive term and form of presentation, are not intended to by any equivalents thereof exclude of the feature that represents and describe or its part outside when using these terms and form of presentation.
Although show and described several embodiment of the present invention, the present invention has not been restricted to described embodiment.On the contrary, those of ordinary skill in the art should recognize can carry out any accommodation and improvement to these embodiments when not departing from principle of the present invention and spirit, and protection scope of the present invention determined by appended claim and equivalent thereof.
Claims (14)
1. a catalyst for methanation in presence of sulfur for magnesium aluminate spinel load, is characterized in that: described catalyst comprises: 0-20 part (weight) catalyst promoter (M
1)
ao
b; 5-90 part (weight) catalyst activity component (M
2)
co
d; 5-90 part (weight) support modification agent (M
3)
eo
fwith 100 parts of (weight) porous carriers, wherein, M
1for Co, Ni, La and/or K; M
2for Mo, W and/or V; M
3for Ce, Zr, Ti and/or Si.
2. a catalyst for methanation in presence of sulfur for load, is characterized in that: described catalyst comprises: 0-20 part (weight) catalyst promoter (M
1)
ao
b; 5-90 part (weight) catalyst activity component (M
2)
co
dwith 100 parts of (weight) porous carrier-magnesium aluminate spinels; Wherein, M
1for Co, Ni, La and/or K; M
2for Mo, W and/or V.
3. catalyst for methanation in presence of sulfur according to claim 1, wherein M
1be Co and/or La further; M
2be Mo and/or W further; M
3be Ce and/or Zr further.
4. catalyst for methanation in presence of sulfur according to claim 3, by weight, comprising: 3-10 part CoO; 10-40 part MoO
3; 20-60 part CeO
2; 100 parts of magnesium aluminate spinels.
5. catalyst for methanation in presence of sulfur according to claim 4, by weight, comprising: 5 parts of CoO; 15 parts of MoO
3; 30-50 part CeO
2; 100 parts of magnesium aluminate spinels.
6. catalyst for methanation in presence of sulfur according to claim 5, by weight, comprising: 5 parts of CoO; 15 parts of MoO
3; 33 parts of CeO
2; 100 parts of magnesium aluminate spinels.
7. catalyst for methanation in presence of sulfur according to claim 2, wherein M
1be further Co and or/La; M
2be Mo and/or W further.
8. catalyst for methanation in presence of sulfur according to claim 7, by weight, comprising: 3-10 part CoO; 10-40 part MoO
3; 100 parts of magnesium aluminate spinels.
9. catalyst for methanation in presence of sulfur according to claim 8, by weight, comprising: 5 parts of CoO; 15 parts of MoO
3; 100 parts of magnesium aluminate spinels.
10., according to one of any described catalyst for methanation in presence of sulfur of claim 1-9, it is characterized in that: described component (M
1)
ao
b(M
2)
co
drespectively at least partly or all by M
1sulfide and M
2sulfide replaced.
11. 1 kinds, according to the preparation method of one of any described catalyst for methanation in presence of sulfur of claim 1,3-10, is characterized in that: described preparation method comprises the following steps successively:
(1) by coprecipitation, deposition-precipitation method, infusion process, kneading method or sol-gal process by support modification agent (M
3)
eo
fprepare by (M with the precursor of porous carrier-magnesium aluminate spinel
3)
eo
fwith the porous carrier of magnesium aluminate spinel compound;
(2) by infusion process or deposition-precipitation method by catalyst promoter (M
1)
ao
bwith catalyst activity component (M
2)
co
dthe composite solution load of precursor on above-mentioned porous carrier;
(3) at above-mentioned (M
1)
ao
b(M
2)
co
dprecursors decompose temperature under or on roasting drying and dipping or deposition (M
1)
ao
band/or (M
2)
co
dafter porous carrier, obtain the catalyst for methanation in presence of sulfur of above-mentioned magnesium aluminate spinel load, wherein flood, dry and calcination steps optionally repeatedly.
The preparation method of 12. catalyst for methanation in presence of sulfur according to claim 11, wherein said precursor composite solution is M
1, M
2nitrate, villaumite, oxalates, formates, acetate and/or their ammonium salt solution.
The preparation method of 13. catalyst for methanation in presence of sulfur according to claim 11, wherein the precursor of said magnesium aluminate spinel is that the salting liquid of Mg and Al, oxide are or/and hydroxide.
The preparation method of 14. catalyst for methanation in presence of sulfur according to claim 11, wherein passes through the specific area of control sintering temperature and roasting time control porous carrier and/or final catalyst, aperture structure and aperture size.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310148822.XA CN103191720B (en) | 2013-04-26 | 2013-04-26 | A kind of catalyst for methanation in presence of sulfur of magnesium aluminate spinel load |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310148822.XA CN103191720B (en) | 2013-04-26 | 2013-04-26 | A kind of catalyst for methanation in presence of sulfur of magnesium aluminate spinel load |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103191720A CN103191720A (en) | 2013-07-10 |
| CN103191720B true CN103191720B (en) | 2015-10-21 |
Family
ID=48714640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310148822.XA Active CN103191720B (en) | 2013-04-26 | 2013-04-26 | A kind of catalyst for methanation in presence of sulfur of magnesium aluminate spinel load |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103191720B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103495421B (en) * | 2013-09-05 | 2015-10-14 | 刘博男 | A kind of catalyst for methanation in presence of sulfur and preparation method thereof |
| CN103480362B (en) * | 2013-10-14 | 2016-06-01 | 神华集团有限责任公司 | Preparation method of supported sulfur-tolerant methanation catalyst |
| CN103933994B (en) * | 2014-04-18 | 2015-12-02 | 昌邑凯特新材料有限公司 | A kind of for CO and CO 2the preparation method of the high-temperature methanation catalyst of methane is produced with hydrogen reaction |
| CN105582968B (en) * | 2014-10-24 | 2018-02-13 | 中国石油化工股份有限公司 | Catalyst for methanation in presence of sulfur |
| KR102497673B1 (en) * | 2015-03-18 | 2023-02-09 | 디아이씨 가부시끼가이샤 | Spinel particles, method for producing same, and composition and molding including spinel particles |
| CN107398262B (en) * | 2016-05-19 | 2020-04-07 | 神华集团有限责任公司 | Sulfur-tolerant methanation catalyst and preparation method thereof, and magnesium aluminate spinel composite carrier and preparation method thereof |
| CN107362806B (en) * | 2017-07-12 | 2020-03-10 | 青岛联信催化材料有限公司 | Isothermal sulfur-tolerant shift catalyst and preparation method thereof |
| CN109225241A (en) * | 2018-10-11 | 2019-01-18 | 刘博男 | A kind of methanation catalyst and preparation method thereof |
| CN112354531B (en) * | 2020-10-27 | 2023-04-28 | 中国华能集团清洁能源技术研究院有限公司 | Sulfur-tolerant methanation catalyst with high thermal stability and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85109423A (en) * | 1984-12-28 | 1986-06-10 | 法国气体公司 | With the technology of resisting sulfide Catalyst Production methane and the catalyzer of realizing this technology |
| US5525211A (en) * | 1994-10-06 | 1996-06-11 | Texaco Inc. | Selective hydrodesulfurization of naphtha using selectively poisoned hydroprocessing catalyst |
| US20040152586A1 (en) * | 2003-02-05 | 2004-08-05 | Ou John Di-Yi | Combined cracking and selective hydrogen combustion for catalytic cracking |
| CN102029161A (en) * | 2009-09-28 | 2011-04-27 | 中国科学院大连化学物理研究所 | Method for preparing complete methanation catalyst for hydrothermal chemical process |
| CN102247861A (en) * | 2011-05-11 | 2011-11-23 | 神华集团有限责任公司 | Coal gas high-temperature methanation catalyst and preparation method thereof |
| CN102350375A (en) * | 2011-08-17 | 2012-02-15 | 中国石油化工集团公司 | Preparation method of methane synthetic catalyst carrier |
| CN103055884A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Supported sulfur and heat resistant methanation catalyst and preparation method and application thereof |
-
2013
- 2013-04-26 CN CN201310148822.XA patent/CN103191720B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85109423A (en) * | 1984-12-28 | 1986-06-10 | 法国气体公司 | With the technology of resisting sulfide Catalyst Production methane and the catalyzer of realizing this technology |
| US5525211A (en) * | 1994-10-06 | 1996-06-11 | Texaco Inc. | Selective hydrodesulfurization of naphtha using selectively poisoned hydroprocessing catalyst |
| US20040152586A1 (en) * | 2003-02-05 | 2004-08-05 | Ou John Di-Yi | Combined cracking and selective hydrogen combustion for catalytic cracking |
| CN102029161A (en) * | 2009-09-28 | 2011-04-27 | 中国科学院大连化学物理研究所 | Method for preparing complete methanation catalyst for hydrothermal chemical process |
| CN102247861A (en) * | 2011-05-11 | 2011-11-23 | 神华集团有限责任公司 | Coal gas high-temperature methanation catalyst and preparation method thereof |
| CN102350375A (en) * | 2011-08-17 | 2012-02-15 | 中国石油化工集团公司 | Preparation method of methane synthetic catalyst carrier |
| CN103055884A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Supported sulfur and heat resistant methanation catalyst and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| 甲烷化催化剂及反应机理的研究进展;胡大成 等;《过程工程学报》;20111031;第11卷(第5期);第880-893页 * |
| 硫粉改性Mo基耐硫甲烷化催化剂;尚玉光 等;《石油化工》;20120930;第41卷(第9期);第999-1004页 * |
| 铈铝复合载体对钼基催化剂耐硫甲烷化催化性能的研究;王保伟 等;《燃料化学学报》;20121130;第40卷(第11期);第1390-1306页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103191720A (en) | 2013-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103191720B (en) | A kind of catalyst for methanation in presence of sulfur of magnesium aluminate spinel load | |
| CN103203237B (en) | Aluminum oxide loaded methanation catalyst | |
| KR101286799B1 (en) | Composition including a lanthanum perovskite on an alumina or aluminium oxyhydroxide substrate, preparation method and use in catalysis | |
| US5134109A (en) | Catalyst for reforming hydrocarbon with steam | |
| KR101026536B1 (en) | Fe-based catalyst for the reaction of Fischer-Tropsch synthesis and preparation method thereof | |
| CN103962123A (en) | ZrO2-loaded sulfur-tolerant methanation catalyst and preparation method thereof | |
| EP2237882B1 (en) | Iron-based water gas shift catalyst | |
| CN103908959B (en) | Ce-Zr composite alumina oxide material and preparation method thereof | |
| CN107051439B (en) | Catalyst for combustion of associated tail gas of oil field and preparation method and application thereof | |
| CN102105222A (en) | Catalyst for synthesizing methanol from synthesis gas and preparation method thereof | |
| WO2005079979A1 (en) | Catalyst for producing hydrocarbons, method for preparing the same, and method for producing hydrocarbons using the same | |
| JP5010547B2 (en) | Highly active catalyst and method for producing the same | |
| CN103433026B (en) | ZrO 2Supported high-stability sulfur-tolerant methanation catalyst | |
| CN107970907A (en) | A kind of nano composite oxide catalyst and its preparation method and application | |
| CA2838544A1 (en) | Cobalt- and molybdenum-containing mixed oxide catalyst, and production and use thereof as water gas shift catalyst | |
| KR101359990B1 (en) | Catalyst for Reforming of Methane with the Enhanced Stability for Sulfur components, Preparing Method Thereof and Methane Reforming Method Using The Catalyst | |
| JPS592537B2 (en) | Carbon monoxide conversion catalyst and method for producing the catalyst | |
| CN103801287B (en) | A kind of preparation method of load type sulfur-tolerant methanation catalyst | |
| CN103157485A (en) | Load-type sulfur-tolerant methanation catalyst | |
| JP2010530305A (en) | Process for the preparation of cobalt-zinc oxide Fischer-Tropsch catalyst | |
| CN103846110A (en) | Activation method and application of Fischer-Tropsch synthesis catalyst | |
| CN103933966A (en) | Preparation method of supported sulphur-tolerant methanation catalyst | |
| JP6824168B2 (en) | How to prepare the catalyst | |
| JP4715999B2 (en) | Catalyst for water gas shift reaction and process for producing the same | |
| CN103480362B (en) | Preparation method of supported sulfur-tolerant methanation catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: No. 22, diazepam West Binhe Road, Dongcheng District, Beijing, Beijing Co-patentee after: National Institute of Clean and Low Carbon Energy Patentee after: National energy investment Refco Group Ltd Address before: 100011 Shenhua building 22, West Binhe Road, Dongcheng District, Beijing Co-patentee before: National Institute of Clean and Low Carbon Energy Patentee before: Shenhua Group LLC |
|
| CP03 | Change of name, title or address | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 100011 Beijing Dongcheng District, West Binhe Road, No. 22 Patentee after: CHINA ENERGY INVESTMENT Corp.,Ltd. Patentee after: Beijing low carbon clean energy research institute Address before: 100011 Beijing Dongcheng District, West Binhe Road, No. 22 Patentee before: CHINA ENERGY INVESTMENT Corp.,Ltd. Patentee before: Beijing low carbon clean energy research institute |
|
| CP01 | Change in the name or title of a patent holder |