CN102463118A - A sulfur-resistant methanation catalyst and its preparation method - Google Patents
A sulfur-resistant methanation catalyst and its preparation method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 111
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 29
- 239000011593 sulfur Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000011733 molybdenum Substances 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002808 molecular sieve Substances 0.000 claims abstract description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000654 additive Substances 0.000 claims abstract 4
- 230000000996 additive effect Effects 0.000 claims abstract 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract 2
- 239000002243 precursor Substances 0.000 claims description 37
- 239000007789 gas Substances 0.000 claims description 30
- 238000007598 dipping method Methods 0.000 claims description 24
- 229910017052 cobalt Inorganic materials 0.000 claims description 22
- 239000010941 cobalt Substances 0.000 claims description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 22
- 229910052746 lanthanum Inorganic materials 0.000 claims description 20
- 229910052726 zirconium Inorganic materials 0.000 claims description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 18
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 18
- 239000003381 stabilizer Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052684 Cerium Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 230000000536 complexating effect Effects 0.000 claims description 11
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012695 Ce precursor Substances 0.000 claims description 8
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 6
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000000703 Cerium Chemical class 0.000 claims description 3
- -1 alcohol amine Chemical class 0.000 claims description 3
- 150000002603 lanthanum Chemical class 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000005486 sulfidation Methods 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229910000428 cobalt oxide Inorganic materials 0.000 claims 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims 1
- 150000003754 zirconium Chemical class 0.000 claims 1
- 150000001869 cobalt compounds Chemical class 0.000 abstract 1
- 238000011156 evaluation Methods 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 24
- 230000000694 effects Effects 0.000 description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- 235000016768 molybdenum Nutrition 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000012498 ultrapure water Substances 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000003245 coal Substances 0.000 description 8
- 239000012752 auxiliary agent Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229940043237 diethanolamine Drugs 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 238000002803 maceration Methods 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000005987 sulfurization reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical class [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- 229910020641 Co Zr Inorganic materials 0.000 description 1
- 229910020520 Co—Zr Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910015234 MoCo Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical group [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种耐硫甲烷化催化剂及其制备方法，尤其涉及一种适用于宽操作条件特别是能在高温下使用的耐硫甲烷化催化剂及其制备方法，其包含载体和负载在该载体上的活性组分，其中所述载体选自三氧化二铝、二氧化硅、二氧化锆、活性炭或分子筛，所述活性组分包括：钼的氧化物，作为主活性组分；钴的氧化物，作为第一助剂；和，锆的氧化物、铈的氧化物或镧的氧化物，或它们中至少两种的混合物，作为第二助剂。本发明还公开了，包括浸渍步骤、干燥步骤和煅烧步骤的耐硫甲烷化催化剂的制备方法。The invention relates to a sulfur-resistant methanation catalyst and a preparation method thereof, in particular to a sulfur-resistant methanation catalyst suitable for wide operating conditions, especially at high temperatures, and a preparation method thereof, which comprises a carrier and is loaded on the carrier The active component on, wherein the carrier is selected from aluminum oxide, silicon dioxide, zirconium dioxide, activated carbon or molecular sieve, the active component includes: the oxide of molybdenum, as the main active component; the oxide of cobalt compound, as the first additive; and, zirconium oxide, cerium oxide or lanthanum oxide, or a mixture of at least two of them, as the second additive. The invention also discloses a preparation method of the sulfur-resistant methanation catalyst comprising impregnating steps, drying steps and calcining steps.
Description
Technical field
The present invention relates to a kind of methanation catalyst and preparation method thereof, relate in particular to a kind of catalyst for methanation in presence of sulfur that wide operating condition particularly can at high temperature be used and preparation method thereof that is applicable to.
Background technology
Natural gas is as low-carbon (LC), efficient, safe clean energy resource, and the consumption proportion that accounts for the disposable energy is with increasing.The natural gas allowable exploitation is very limited, and the source of the gas crisis causes the rise of nationwide Gas Prices.Therefore, lot of domestic and international company and research and development institution utilize coal or heavy oil and other fossil feedstock to prepare natural gas, and China has also carried out the project of a lot of coal preparing natural gas.The simple process flow of coal preparing natural gas is: coal gasification makes synthesis gas (CO, H
2), carry out desulfurization and decarburization and Water gas shift/WGS then, obtain CH through methanation workshop section at last
4
Catalytic coal gasifaction is the coal gasifying process of a kind of efficiency height and environmental protection, and the synthesis gas that the steam coal gasification produces generally contains H
2, CO, CO
2, CH
4, H
2S and unreacted H
2O.Wherein, H
2/ CO mol ratio is 1.5-2.5, CH
4Content is about about 20%, H
2, CO wants further methanation to generate CH
4
Ni is catalyst based to have very high methanation activity, but Ni is very responsive to S, and the sulfide that is easy to be synthesized in the gas poisons.For Ni was catalyst based, it was fatal and lasting that S poisons, because Ni is very strong to the absorption of S, and the H of low concentration in absorption S and the reaction system
2S can reach balance.Therefore, S content should be lower than 0.1～0.01ppm (volume content) in the Ni catalyst requirement unstripped gas.Contain a large amount of sulphur in the synthesis gas that catalytic coal gasifaction produces, thereby before carrying out methanation reaction, carry out desulfurization purification process expensive and consuming time synthesis gas.In addition, the easy carbon distribution inactivation of Ni will carry out Water gas shift/WGS in advance and regulate H
2/ CO ratio is greater than 3.
Mo methylmethane catalyst has many good qualities, and like anti-sulphur, is difficult for carbon distribution, and has shift activity, and shortcoming is that methanation activity is not high.If Mo base sulfur resistant catalyst has enough methanation activity, it will have great commercial significance.If dust burdening is less, then can save gas cleanup step in the synthesis gas that catalytic coal gasifaction makes.Unreacted steam does not need condensation to remove yet, because the Mo catalyst has the Water gas shift/WGS activity, can a part of CO in the synthesis gas be transformed to H
2Synthesis gas need not cooling can directly feed the catalyst for methanation in presence of sulfur bed, the energy consumption of having avoided gas to lower the temperature and afterwards heat up and cause earlier like this, and saved desulfurizing and purifying workshop section, save the cost of investment of production process greatly and reduced energy consumption.
The CO methanation is the reaction of strong heat release, and too high temperature can make catalysqt deactivation, and reduces methane production, and this will reduce temperature through inner or outside heat exchange.For example, catalyst for methanation in presence of sulfur can carry out the multistage filling, controls temperature through heat exchange between the bed, and produces high-grade steam simultaneously.Another kind method is to adopt fluidized-bed process, and fluid bed can be accelerated the heat transmission, prevents hot-spot.
It is active high that desirable methanation catalyst is not only wanted, and the life-span is long, and hear resistance will be got well.Can not cause that bed temperature sharply increases because the methanation reaction liberated heat is in time led away, cause the sintering of catalyst inactivation easily.
Generally speaking, traditional Mo base catalyst for methanation in presence of sulfur initial reaction temperature is 350 ℃, and the optimum response warm area is 450-550 ℃, and reaction pressure is 1.5-2.2MPa.In addition, the methane selectively of catalyst is lower, the highest 70-80% that is merely.
The method that improves catalyst activity and high-temperature stability has a lot, such as adding auxiliary agent or improving catalyst carrier.Zr, La, Ce or other rare-earth oxide usually use as carrier and auxiliary agent; For example; A kind of catalyst for methanation in presence of sulfur that is used for by preparing methane by synthetic gas is disclosed among patent CN1033580A1 and the CN85109423; Its main active component is vanadium, molybdenum or tungsten, and promoter is nickel and/or cobalt, and carrier is porous C eO
2Or ZrO
2, but do not provide the existence of each active component in this patent, the existence that does not yet have detailed preparation embodiment can infer each active component.Though this catalyst is at 500 ℃ of CO conversion ratios that can reach 80-88% down, its methane selectively is merely 30-50%, and is obviously on the low side.Another shortcoming of this catalyst is CeO
2Very big as the carrier consumption, this is unfavorable for reducing the catalyst cost, and CeO
2The specific area and the pore volume of carrier are all very little, thereby synthetic specific surface area of catalyst and pore volume are all less.Catalyst is after 20h is aging, and active and selectivity has obvious reduction, explains that catalyst stability is relatively poor.
Patent US4540714 is disclosed in the V base catalyst for methanation in presence of sulfur and adds auxiliary agent CeO
2Help improving catalyst performance.Patent US4491639 mentions that Zr, Ce etc. add in the sulfide catalyst of V, Mo or W, can strengthen the stability of catalyst, and this patent spells out does not use porous mass as carrier; But the sulfide of directly using above-mentioned metal is as catalyst, but do not mention the use of La in this patent, and the CO conversion ratio that is obtained in this patent is still lower; Under 530 ℃, be merely 50-78%; And the methane ratio from its product gas, its methane selectively is not high, is merely 70-80%.
Patent CN101745401 and CN101733115 also disclose catalyst for methanation in presence of sulfur; Wherein carrier is porous masses such as aluminium oxide or silica; Main reactive metal is one or more among Mo, W and the V in the active component; Second metal is one or more among Fe, Co, Ni, Cr, Mn, La, Y or the Ce, and the various metals in its active component all exist with the form of metal carbides.
Summary of the invention
First aspect; The invention provides a kind of catalyst for methanation in presence of sulfur; It comprises carrier and loads on the active component on this carrier, and wherein said carrier is selected from alundum (Al, silica, zirconium dioxide, active carbon or molecular sieve, and said active component comprises:
The oxide of molybdenum is as main active component;
The oxide of cobalt is as first auxiliary agent;
The oxide of the oxide of zirconium, the oxide of cerium, lanthanum or at least two kinds mixture in them are as second auxiliary agent.
Second aspect the invention provides a kind of preparation method of catalyst for methanation in presence of sulfur, and it comprises following sequential steps:
A prepares dipping solution, and said solution contains:
Molybdenum precursor and cobalt precursors; And,
At least a in zirconium precursors, cerium precursor or the lanthanum precursor;
B. use this dipping solution impregnated carrier;
C. the product to step b carries out drying;
D. the product of step c is calcined.
The third aspect, the present invention also provides the preparation method of another kind of catalyst for methanation in presence of sulfur, may further comprise the steps:
A. with the dipping solution impregnated carrier that comprises the molybdenum precursor, carry out drying and calcining then;
B. with the dipping solution impregnated carrier that comprises cobalt precursors, carry out drying and calcining then;
C. with comprising at least a dipping solution impregnated carrier in zirconium precursors, cerium precursor or the lanthanum precursor, carry out drying and calcining then;
Wherein the order of step a-c is not limit, and the carrier among the step a-c is an identical carrier.
Fourth aspect, the present invention also provides the catalyst for methanation in presence of sulfur that makes first aspect of the present invention to be contained H
2Product after the gas temperature programming vulcanizing treatment of S.
Detailed Description Of The Invention
In the first aspect of the present invention; Said catalyst for methanation in presence of sulfur comprises carrier and loads on the active component on this carrier; Wherein said carrier is selected from alundum (Al, silica, zirconium dioxide, active carbon or molecular sieve; These carriers are porous mass, and which kind of carrier those skilled in the art can select specifically to use according to the character of desired finished catalyst and according to their indexs such as specific area, surface acidity, pore volume, particle diameter and breaking strength, repeat no more at this.
In the said active component, the oxide of molybdenum is as main active component; The oxide of cobalt is as first auxiliary agent; And the oxide of the oxide of the oxide of zirconium, cerium, lanthanum or in them at least two kinds mixture as second auxiliary agent.Among the present invention, the oxide of the oxide of the oxide of said molybdenum, the oxide of cobalt, zirconium, the oxide of cerium or lanthanum refers to oxide or the hopcalite of various valence states of the various valence states of each metal respectively.For example, the oxide of molybdenum can be molybdenum trioxide, molybdenum dioxide or their mixture etc., and the oxide of cobalt can be cobalt protoxide, cobalt sesquioxide or their mixture, by that analogy.
The amount of active component is following: with the catalyst gross mass is benchmark, with MoO
3The oxide of molybdenum of meter accounts for 2%-20%, accounts for 0.5-10% in the oxide of the cobalt of CoO, respectively with ZrO
2, CeO
2Or La
2O
3The oxide of oxide, the cerium of the zirconium of meter, the oxide of lanthanum or in them at least two kinds mixture account for 0.2%-5%.In preferred embodiments, be benchmark with the catalyst gross mass, with MoO
3The oxide of molybdenum of meter accounts for 4%-15%, accounts for 1-5% in the oxide of the cobalt of CoO, respectively with ZrO
2, CeO
2Or La
2O
3The oxide of oxide, the cerium of the zirconium of meter, the oxide of lanthanum or in them at least two kinds mixture account for 0.4%-3%.This paper alleged with MoO
3Meter is meant that the quality with the oxide of various molybdenums all is converted to MoO
3Quality, then with the conversion after MoO
3Gross mass is represented the total quality of the oxide of molybdenums all in the catalyst.This conversion is well known to a person skilled in the art.
Second aspect of the present invention is the preparation method of the said catalyst for methanation in presence of sulfur of first aspect of the present invention, summarizes, and comprises common impregnation steps, drying steps and calcining step.Specifically, step a is the preparation dipping solution, and this solution contains molybdenum precursor and cobalt precursors, and comprises at least a in zirconium precursors, cerium precursor or the lanthanum precursor.Because this solution is used for impregnated carrier, so be referred to as dipping solution.Wherein, solvent is a water, and said molybdenum precursor is water-soluble molybdate, and said cobalt precursors is a water soluble cobaltous salt, and said zirconium precursors is water-soluble zirconates or water-soluble zirconates or zirconate, and said cerium precursor is water-soluble cerium salt, and said lanthanum precursor is water-soluble lanthanum salt.
Wherein said water-soluble molybdate is selected from sodium molybdate, potassium molybdate or ammonium molybdate, not hoping to introduce under the situation of foreign metal ion, preferably uses ammonium molybdate.
Said water soluble cobaltous salt can be selected from the cobalt salt of inorganic acid, and for example cobalt chloride, cobalt nitrate or cobaltous sulfate etc., or organic acid cobalt salt like cobalt acetate, cobalt oxalate etc., preferably use the cobalt salt of inorganic acid; Perhaps said water soluble cobaltous salt can be selected from the inferior cobalt salt of inorganic acid, and the for example inferior cobalt of cobalt chloride, colbaltous nitrate or sulfuric acid etc., or the inferior cobalt salt of organic acid like the inferior cobalt of acetate, the inferior cobalt of oxalic acid etc., preferably uses the inferior cobalt salt of inorganic acid.
Said water-soluble zirconates can selected among zirconium various inorganic acid salts or acylate, ZrCl for example
4, Zr (SO
4)
2, ZrOSO
4Deng, perhaps can selected among zirconium hydrochlorate or zirconic acid Ester, as long as its water soluble.
Said water-soluble cerium salt can be selected from the salt of various acid of the cerium of various valence states, and as long as the for example sulfate of cerium, nitrate, acetate or the like are its water soluble.
Said water-soluble lanthanum salt can be selected from the salt of various acid of the lanthanum of various valence states, and as long as the for example sulfate of lanthanum, nitrate, acetate or the like are its water soluble.
The concentration of each precursor in dipping solution can be calculated according to target content and the dipping efficient of active component in catalyst, and these are well known to a person skilled in the art.
In a preferred embodiment of the invention, before with the dipping solution impregnated carrier, can regulate the pH value of said dipping solution, so that each precursor more stably exists in solution.The step of target pH value and such adjust pH all is those skilled in the art's a conventional knowledge.For example, target pH value can scope can be 8-11.
In another preferred embodiment of the present invention, also comprise the complexing stabilizing agent in the said dipping solution, this complexing stabilizing agent is selected from hydramine, tartaric acid, ethylenediamine, one or more in urea or the ammoniacal liquor.The amount of complexing stabilizing agent accounts for the 1.0-1.5% of carrier quality.
In the second aspect of the present invention, step b is with said dipping solution impregnated carrier.Dipping method is well known to a person skilled in the art.Behind dipping, various active components are dispersed in the carrier hole.In a preferred embodiment of the invention, adopt equi-volume impregnating, the volume of promptly controlling dipping solution approximates the saturated adsorption volume of carrier.The benefit of doing like this is to make active component be dispersed on the carrier quantitatively.
In the second aspect of the present invention, step c is that the product to step b carries out drying.Can adopt any suitable drying means, for example, dry or dry or the two combination.In one embodiment, the product with step b dries under environmental condition.In another embodiment, with the oven dry of the product of step b, for example carried out preferred 8-12 hour 6-14 hour at 90-140 ℃, preferred 100-120 ℃ of following drying.In preferred embodiments, the product with step b dries earlier, and then oven dry under these conditions.
In second aspect of the present invention, steps d is that the product of step c is calcined.Calcining was carried out under 300-600 ℃ 2-10 hour under the condition that has oxygen to exist.Do not receive the restriction of any theory, think such calcining meeting with the precursors decompose of various active components and/or be oxidized to metal oxide, the metal oxide here is meant oxide or the hopcalite of various valence states of the various valence states of each metal.These metal oxides still are dispersed on the surfaces externally and internally of carrier and/or in the hole.
The third aspect of the invention is the another kind of preparation method of the said catalyst for methanation in presence of sulfur of first aspect of the present invention, summarizes, and comprises carrying out repeatedly with next group step: impregnation steps-drying steps-calcining step.Specifically,
A. with the dipping solution impregnated carrier that comprises the molybdenum precursor, carry out drying and calcining then;
B. with the dipping solution impregnated carrier that comprises cobalt precursors, carry out drying and calcining then;
C. with comprising at least a dipping solution impregnated carrier in zirconium precursors, cerium precursor or the lanthanum precursor, carry out drying and calcining then;
Wherein the order of step a-c is not limit, and the carrier among the step a-c is an identical carrier.
Wherein each dipping solution all only contains a kind of precursor of active component, and each dipping solution also can preferably be conditioned the pH value, and also can preferably contain the complexing stabilizing agent.Each precursor, complexing selection of stabilizers are as second aspect of the present invention.The condition of drying and calcining repeats no more also as second aspect of the present invention.
Fourth aspect of the present invention then provides the catalyst for methanation in presence of sulfur of first aspect of the present invention to be contained H
2Product after the gas temperature programming vulcanizing treatment of S.The wherein said H that contains
2The gas of S is H
2And H
2The mist of S.Wherein said temperature programming sulfuration is meant according to time dependent temperature carries out vulcanizing treatment to product.In one embodiment, said temperature programming vulcanizing treatment process is following: after being loaded into the catalyst of first aspect of the present invention in the reaction tube, feeding and contain 5 volume %H
2The H of S
2With H
2The S gaseous mixture.With the heating rate of 10 ℃/min the temperature of catalyst is heated to 400 ℃ from room temperature,, slowly is cooled to reaction temperature again at 400 ℃ of constant temperature sulfuration 4h.Do not receive any one theory, think after such temperature programming sulfidation is accomplished, have the sulfide that at least a portion, the preferred overwhelming majority change into the various valence states of each metal in the oxide of the various valence states of each metal.Carrier then has basically no variation.After the catalyst process temperature programming vulcanizing treatment of first aspect of the present invention, can be used for the methanation reaction of catalysis synthesis gas.
Embodiment
Through embodiment the present invention is detailed below, the embodiment that provides has been merely elaboration the present invention, and limits scope of the present invention never in any form.For example, although the carrier that uses in following examples is alundum (Al, in fact other listed carrier of this paper can use too.
Embodiment 1
Take by weighing 18.42g (NH respectively
4)
6Mo
7O
244H
2O, 9.67g Co (NO
3)
26H
2O, 5.06gCe (NO
3)
36H
2O is dissolved in the 60mL high purity water, and adds N-diethanol amine complexing stabilizing agent.With 100g Al
2O
3(this Al
2O
3Be γ-Al
2O
3, its physical property is following: specific area>=200m2/g, pore volume>=0.40mL/g, water absorption rate>=52%; Apparent density is 0.65-0.72g/mL, breaking strength>=80N/ grain, and particle diameter is 3-5mm; Drop in the mixed impregnant liquor for preparing down together), placement is spent the night, and dries naturally; Dry 8h under 120 ℃ calcines 3h at last under 450 ℃ then, obtains the MoCoCe-a catalyst.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Embodiment 2
Take by weighing 18.42g (NH respectively
4)
6Mo
7O
244H
2O, 9.67g Co (NO
3)
26H
2O, 5.26g ZrOCl
28H
2O is dissolved in the 60mL high purity water, and adds the citric acid complex stabilizing agent.With 100gAl
2O
3In the mixed impregnant liquor that input prepares, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h at last under 450 ℃ then, obtains the MoCoZr-a catalyst.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Embodiment 3
Take by weighing 18.42g (NH respectively
4)
6Mo
7O
244H
2O, 9.67g Co (NO
3)
26H
2O, 5.07g La (NO
3)
36H
2O is dissolved in the 60mL high purity water, and adds the citric acid complex stabilizing agent.With 100g Al
2O
3In the mixed impregnant liquor that input prepares, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h at last under 450 ℃ then, obtains the MoCoLa catalyst.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Embodiment 4
Take by weighing 18.42g (NH
4)
6Mo
7O
244H
2O is dissolved in the 60mL high purity water, and adds the citric acid complex stabilizing agent.With 100g Al
2O
3Drop in the Mo maceration extract, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h down at 450 ℃ at last then.Flood 9.67g Co (NO then successively
3)
26H
2O, 5.06g Ce (NO
3)
36H
2The salting liquid of O preparation, per step dipping is dry 8h under 120 ℃ all, calcines 3h down at 450 ℃ at last, obtains the Mo-Co-Ce catalyst.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Embodiment 5
Take by weighing 18.42g (NH
4)
6Mo
7O
244H
2O is dissolved in the 60mL high purity water, and adds the citric acid complex stabilizing agent.With 100g Al
2O
3Drop in the Mo maceration extract, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h down at 450 ℃ at last then.Flood 9.67g Co (NO then successively
3)
26H
2O, 5.26g ZrOCl
28H
2The salting liquid of O preparation, per step dipping is dry 8h under 120 ℃ all, calcines 3h down at 450 ℃ at last, obtains the Mo-Co-Zr catalyst.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Embodiment 6
Take by weighing 2.53g Ce (NO respectively
3)
36H
2O, 18.42g (NH
4)
6Mo
7O
244H
2O, 9.67g Co (NO
3)
26H
2O is dissolved in the 60mL high purity water, and adds N-diethanol amine complexing stabilizing agent.With 100g Al
2O
3In the mixed impregnant liquor that input prepares, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h at last under 450 ℃ then, obtains the MoCoCe-b catalyst.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Embodiment 7
Take by weighing 2.53g Ce (NO respectively
3)
36H
2O, 18.42g (NH
4)
6Mo
7O
244H
2O, 6.45g Co (NO
3)
26H
2O is dissolved in the 60mL high purity water, and adds N-diethanol amine complexing stabilizing agent.With 100g Al
2O
3In the mixed impregnant liquor that input prepares, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h at last under 450 ℃ then, obtains the MoCoCe-c catalyst.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Comparative example 1
Take by weighing 18.42g (NH
4)
6Mo
7O
244H
2O is dissolved in the 60mL high purity water, and adds the citric acid complex stabilizing agent.With 100g Al
2O
3Drop in the Mo maceration extract, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h down at 450 ℃ at last and obtains the Mo catalyst then.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Comparative example 2
Take by weighing 18.42g (NH respectively
4)
6Mo
7O
244H
2O, 9.67g Co (NO
3)
26H
2O is dissolved in the 60mL high purity water, and adds N-diethanol amine complexing stabilizing agent.With 100g Al
2O
3In the mixed impregnant liquor that input prepares, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h at last under 450 ℃ then, obtains the MoCo catalyst.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Comparative example 3
Take by weighing 5.06g Ce (NO
3)
36H
2O is dissolved in the 60mL high purity water, and adds the citric acid complex stabilizing agent.With 100g Al
2O
3Drop in the Ce maceration extract, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h down at 450 ℃ at last and obtains the Ce catalyst then.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Comparative example 4
Take by weighing 2.53g Ce (NO respectively
3)
36H
2O, 18.42g (NH
4)
6Mo
7O
244H
2O is dissolved in the 60mL high purity water, and adds N-diethanol amine complexing stabilizing agent.With 100g Al
2O
3In the mixed impregnant liquor that input prepares, placement is spent the night, and dries naturally, and dry 8h under 120 ℃ calcines 3h at last under 450 ℃ then, obtains the MoCe catalyst.Get the 5mL catalyst and carry out evaluation test, the result of catalyst activity evaluation and hear resistance evaluation experimental sees table 1.
Activity rating:
Adopt fixed bed reactors to estimate the activity of the catalyst for methanation in presence of sulfur in each embodiment and the comparative example.The loadings of catalyst for methanation in presence of sulfur is 5mL, at first makes the catalyst of each embodiment preparation carry out the temperature programming sulfuration under the same conditions, begins to feed synthesis gas then and carries out the synthesis gas methanation reaction.Reaction condition is: reaction pressure (absolute pressure, down together) is 3.5MPa, and 500 ℃ of reaction temperatures, gas space velocity are 800h
-1, synthesis gas (percent by volume) CO/H
2Ratio is 2, with CO conversion ratio and CH
4Selectivity is represented catalyst activity and selectivity.
Hear resistance is estimated:
In order to estimate the hear resistance of catalyst of the present invention, also carried out following experiment.To pass through each catalyst behind the above-mentioned active appraisal experiment under reaction atmosphere behind 700 ℃ of following heat treatment 12h, estimate activity according to above-mentioned active appraisal experiment program again, but condition changes slightly, see Table 1 table and annotate.Observe CO conversion ratio and CH
4Whether selectivity has remarkable decline.If remarkable decline is arranged, explain that this catalyst is heat labile.
Table 1 has been listed with aforementioned various catalyst, through H
2/ H
2After S gaseous mixture temperature programming presulfurization is handled, the active testing result before heat-resisting and behind 700 ℃ of heat-resisting 12h respectively.
The various activity of such catalysts evaluation result of table 1 *
* appreciation condition: loaded catalyst: 5.0mL, temperature: 500 ℃, pressure: 3.5Mpa, air speed: 1000h
-1, H in the unstripped gas
2/ CO is 2.
The heat-resisting back of *: catalyst is reduced to 500 ℃ of results that survey behind 700 ℃ of reaction 12h behind 500 ℃ of active testings.
Interpretation of result: the catalyst in the embodiments of the invention has all been realized high relatively CO conversion ratio and CH
4Selectivity.And after 700 ℃ of following heat treatments, find the CO conversion ratio and the CH of the catalyst in the embodiments of the invention
4Selectivity only has a spot of decline, explains that catalyst tolerates of the present invention is hot good.By contrast, the catalyst of comparative example then shows CO conversion ratio and CH
4Optionally significantly descend, explain that they are thermo-labile.
Advantage of the present invention is following:
The invention provides a kind of catalyst for methanation in presence of sulfur, this catalyst is not only high to the selectivity of methane, and maximum characteristics are good heat resistances, can be 500 ℃ of following stable operations.It is worthy of note that catalyst of the present invention still can keep active preferably after experience under 700 ℃ the high temperature reaches 12 hours.In a word, this catalyst has the low temperature active height, the advantage that high-temperature stability is good.
Claims (13)
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| CN109912372A (en) * | 2017-12-13 | 2019-06-21 | 中国石油化工股份有限公司 | Synthesis gas methanation catalyst and its preparation method |
| CN109912372B (en) * | 2017-12-13 | 2022-03-08 | 中国石油化工股份有限公司 | Synthetic gas methanation catalyst and preparation method thereof |
| CN111468132A (en) * | 2020-05-22 | 2020-07-31 | 成都中科凯特科技有限公司 | Supported multi-metal oxide catalyst and preparation method thereof |
| CN114797884A (en) * | 2022-05-19 | 2022-07-29 | 四川鸿鹏新材料有限公司 | Catalyst for vinylene carbonate production, preparation method and application |
| CN114797884B (en) * | 2022-05-19 | 2023-05-09 | 四川鸿鹏新材料有限公司 | Catalyst for producing vinylene carbonate, preparation method and application |
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