CN1318137C - Preparation method of catalyst of sulfur containing transition metal atomic cluster compound for hydrodesulfurizing - Google Patents
Preparation method of catalyst of sulfur containing transition metal atomic cluster compound for hydrodesulfurizing Download PDFInfo
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- CN1318137C CN1318137C CNB2004100099776A CN200410009977A CN1318137C CN 1318137 C CN1318137 C CN 1318137C CN B2004100099776 A CNB2004100099776 A CN B2004100099776A CN 200410009977 A CN200410009977 A CN 200410009977A CN 1318137 C CN1318137 C CN 1318137C
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- transition metal
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- cluster compound
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 150000001875 compounds Chemical class 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 44
- 239000011593 sulfur Substances 0.000 title claims abstract description 44
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 38
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 9
- 229940010552 ammonium molybdate Drugs 0.000 claims description 9
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 9
- 239000011609 ammonium molybdate Substances 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 8
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 8
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 8
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 238000005987 sulfurization reaction Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 22
- 239000011733 molybdenum Substances 0.000 abstract description 22
- 239000010937 tungsten Substances 0.000 abstract description 8
- 238000005470 impregnation Methods 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 235000016768 molybdenum Nutrition 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 238000005303 weighing Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229940126062 Compound A Drugs 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000007096 poisonous effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910000897 Babbitt (metal) Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MRDDPVFURQTAIS-UHFFFAOYSA-N molybdenum;sulfanylidenenickel Chemical compound [Ni].[Mo]=S MRDDPVFURQTAIS-UHFFFAOYSA-N 0.000 description 1
- XOROUWAJDBBCRC-UHFFFAOYSA-N nickel;sulfanylidenetungsten Chemical compound [Ni].[W]=S XOROUWAJDBBCRC-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- -1 phosphonium salt cation Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
Abstract
一种含硫过渡金属原子簇合物的催化剂制备方法，本发明的含二核、三核和四核金属钼或钨的原子簇合物是通过金属氧化物在酸溶液中电解、硫化、氧化、浓缩、分离和化学反应等步骤制备得到。此种原子簇合物具有下列簇芯：[M2OnS2-n]m+，[M3OnS4-n]m+或[M4OnS6-n]m+，(M＝Mo或W，n＝0～6，m＝0～6)。金属Co、Ni、Cu、Fe、Sn等可与此簇芯的阳离子成键，构成多金属物种的过渡金属原子簇合物。此种方法制备得到的含硫过渡金属钼或钨的原子簇合物具有明确的原子或分子结构及很好的稳定性。担载型的含硫钼或钨的原子簇合物比传统的浸渍方法制备的催化剂具有更好的加氢脱硫性能。A catalyst preparation method for sulfur-containing transition metal atom clusters. The atomic clusters containing dinuclear, trinuclear and tetranuclear metal molybdenum or tungsten of the present invention are electrolyzed, vulcanized, and oxidized by metal oxides in acid solution , concentration, separation and chemical reaction steps to prepare. This atomic cluster has the following cluster cores: [M 2 O n S 2-n ] m+ , [M 3 O n S 4-n ] m+ or [M 4 O n S 6-n ] m+ , (M= Mo or W, n=0~6, m=0~6). Metals Co, Ni, Cu, Fe, Sn, etc. can form bonds with the cations of this cluster core to form transition metal atom clusters of multi-metal species. The atomic cluster compound of the sulfur-containing transition metal molybdenum or tungsten prepared by the method has a definite atomic or molecular structure and good stability. The supported sulfur-containing molybdenum or tungsten atomic clusters have better hydrodesulfurization performance than the catalysts prepared by the traditional impregnation method.
Description
Technical field
The present invention relates to the preparation method of a kind of pure phase and loaded sulfur-bearing transition metal cluster compound (comprising molybdenum and tungsten atom cluster compound series).
Background technology
Recently decades, because the more and more stricter environmental legislation and the demand of low quality feedstock oil, the new technology of the clean fuel oil of developping production has been subjected to World Focusing.The gasoline, diesel oil of exploitation low-sulfur and about heavy crude and coal-based liquid fuel Hydrobon catalyst new preparation technology has become new problem highly visible.At present, the liquid fuel Hydrobon catalyst of industrial widespread usage mostly is interpolation nickel, support type molybdenum sulfide (or tungsten) the class catalyst of auxiliary agents such as cobalt.This type of catalyst is many to be raw material with ammonium molybdate or ammonium tungstate, is auxiliary agent with nickel or cobalt, adopts traditional dipping method to vulcanize and prepare through pyrolytic.The catalyst that this kind preparation method is obtained still exists weak point, and as the degree of scatter of metal at carrier surface, the particle size of active phase metal species etc. all can not reach very desirable state.In order to adapt to more and more stricter environmental demand, exploitation preparation high dispersive, the catalyst new technology that the activity of nanoscale is higher has become scientific worker's main research topic.
United States Patent (USP) 5,872,073 discloses a kind of preparation three constituent element molybdenums and the tungsten sulfide method as Hydrobon catalyst.This kind sulfide is to contain " Mo
6S
8" cluster compound of unit, its concrete molecular formula can be expressed as: M
2x/nMo
6S
8+x(MeOH)
y, (M=Sn, Co, Ni), (n=1,2 or 3; X=0.5～1.5; Y=4～5).Metallic atom cluster compound with this kind structure shows excellent hydrodesulfurization performance, and its HDS activity has surpassed Ni or the Co traditional MoS as auxiliary agent
2Catalyst.But the metallic atom cluster compound of this patent report is non-support type.Its hydrodesulfurization activity will be lower than the sulfide catalyst that the alundum (Al of industrial application supports.
United States Patent (USP) 5,306,683 disclose a kind of transition metal (Mo, Cr or the W) application of sulfide cluster compound in methane conversion.This kind cluster compound has " Mo
3S " bunch core unit, and cluster compound is adsorbed onto on the NaY equimolecular sieve carrier.The catalyst of this kind method preparation under the atmosphere of reduction, only generates C in methane activation transforms
2Alkane has been avoided the generation of the oxide of carbon.And this kind catalyst has certain anti-sulfur poisonous performance.
United States Patent (USP) 4,605,751 disclose a kind of multi-metal cluster compound such as Cp
2Mo
2Fe (μ-S)
2(CO)
8And Cp
2Mo
2Ni
2S
4(CO)
2Deng the synthetic and application in carbon monoxide hydrogenation as high activity and catalysts selective.This multi-metal cluster compound is supported on Al
2O
3On the carrier, show outstanding ethane and generated activity and selectivity, in reaction, be not attended by C
3, C
4Generation with heavy paraffin hydrocarbon.This catalyst is very useful in ethane transforms, and has certain anti-sulphur effect.
United States Patent (USP) 4,430,442 to disclose a kind of molecular formula be B
x[Mo
3S
z]
2-The polysulfide cluster compound.Here [Mo
3S
z]
2-Be negative dianion, B is monovalence or divalence ammonium salt or phosphonium salt cation, x=1 or 2, z=10-46.Cluster compound with this molecular formula supports carrier (as Al
2O
3) on, add Co or Ni as auxiliary agent.This kind catalyst is compared with the CoMoS or the NiMoS catalyst that prepare with conventional method, has higher hydrodesulfurization (HDS) and hydrodenitrogeneration (HDN) performance.
Summary of the invention
The cluster compound that the objective of the invention is at first synthetic a kind of sulfur-bearing transition metal molybdenum or tungsten supports this cluster compound then on the carrier and prepares a kind of high dispersive, nanoscale, highly active Hydrobon catalyst.
The prepared sulfur-bearing transition metal atoms cluster compound of the present invention is the Hydrobon catalyst of presoma, not only have high metal degree of scatter and littler metallic size, and ratio has higher hydrodesulfurization activity with the Hydrobon catalyst with identical component that conventional method prepares, simultaneously, the metal atomic cluster mixture catalyst of this sulfur-bearing has stronger anti-sulfur poisonous performance than the metal cluster compound of the not sulfur-bearing of other method preparation.
The cluster compounds that contain two nuclears, three nuclears and four nuclear sulfur-bearing metal molybdenum or tungsten of the present invention are by metal oxide electrolysis in acid solution, sulfuration, oxidation, concentrate, separate and step such as chemical reaction prepares.This kind cluster compound has following bunch of core: [M
2O
nS
2-n]
M+, [M
3O
nS
4-n]
M+, [M
4O
nS
6-n]
M+, (M=Mo or W, n=0～6, m=0～6).Metal Co, Ni, Cu, Fe, Sn and Hg etc. are the cation Cheng Jian of bunch core therewith, constitutes the transition metal atoms cluster compound of many metals species.The sulfur-bearing transition metal molybdenum that this kind method prepares or the cluster compound of tungsten have clear and definite atom or molecular structure and well stable.The loaded sulfur-bearing molybdenum or the cluster compound of tungsten have better hydrodesulfurization performance than the catalyst of traditional dipping method preparation.
Concrete preparation process of the present invention may further comprise the steps:
(a) molybdenum oxide or tungsten oxide are dissolved in concentrated hydrochloric acid, and are electrolysis in the hydrochloric acid solution of 6-12N, make the hydrochloride solution of molybdenum oxide or tungsten oxide in concentration;
(b) the hydrochloride solution of molybdenum oxide that step a is made or tungsten oxide feeds H
2S gas vulcanizes;
(c) solution that step b sulfuration is finished in 60-120 ℃ under oxygen or air oxidation 24-56 hour;
(d) with the solution decompression distillation of step c, the reactant mixture after obtaining concentrating filters this mixture, and separates with resin column, obtains having following bunch of core: [M
2O
nS
2-n]
M+, [M
3O
nS
4-n]
M+Or [M
4O
nS
6-n]
M+Sulfur-bearing transition metal atoms cluster compound, M=Mo or W in the formula, n=0～6, m=0～6;
(e) the sulfur-bearing transition metal atoms cluster compound that steps d is obtained be lower than in oxygen content under 0.1% the inert atmosphere that method by dipping or ion-exchange supports or grafting to various carriers, obtain the catalyst of loaded sulfur-bearing transition metal atoms cluster compound.
Described preparation method, wherein, sulfur-bearing transition metal atoms cluster compound and another kind of metal M ' reaction as auxiliary agent that steps d is prepared obtain having following bi-component transition metal cluster core: [M ' M
2O
nS
2-n]
M+, [M ' M
3O
nS
4-n]
M+Or [M ' M
4O
nS
6-n]
M+Sulfur-bearing transition metal atoms cluster compound, M=Mo or W in the formula, n=0～6, m=0～6; Metal M as auxiliary agent ' be selected from a kind of in the salt of Co, Ni, Fe, Sn, Bi, Pb, Cu, Ag and metal thereof.
Described preparation method, wherein, molybdenum oxide and tungsten oxide presoma are ammonium molybdate and ammonium tungstate.
Described preparation method, wherein, the electrolysis among the step a is anode with graphite, mercury is negative electrode.
Described preparation method, wherein, catalyst carrier is silica, alundum (Al, activated carbon, H-ZSM5, HY, NaY zeolite, MgO, pharmalyte TiO
2, ZrO
2Or mesopore material.
Described preparation method wherein, is MCM-41, Al-MCM-41, SBA-15, Al-SBA-15 or FSM-16 as the mesopore material of catalyst carrier.
Described preparation method, wherein, the H among the step b
2The flow velocity of S gas is 60～200ml/min.
Described preparation method, wherein, the H among the step b
2S gas replaces carrying out vulcanizing treatment with vulcanized sodium, ammonium sulfide benefit ammonium sulfide.
Described preparation method, wherein, the reactant mixture concentration after will concentrating earlier in the steps d is that the hydrochloric acid of 1-2 N dilutes, and filters, separates.
Described preparation method, wherein, the inert atmosphere among the step e is helium, argon gas or nitrogen atmosphere.
The sulfur-bearing transition metal atoms cluster compound catalyst that the present invention is prepared, its hydrodesulfurization performance not only is better than traditional sulfide catalyst, and this class catalyst can not poisoned by sulphur.
The prepared loaded sulfur-bearing transition metal atoms cluster compound catalyst of the present invention can be used for the fraction oil hydrodesulfurizing process as Hydrobon catalyst.Hydrodesulfurization reaction carries out in fixed bed reactors, and reaction temperature is at 200-400 ℃, pressure 0.2-20MPa.
The loaded sulfur-bearing transition metal atoms cluster compound catalyst of the present invention preparation has good hydrodesulfurization activity, and reaction raw materials is simple and easy to, and cost is lower, and is easy and simple to handle, and most of preparations can be in air, room temperature or low-temperature operation.
Specifically, compared with prior art, the loaded sulfur-bearing transition metal atoms cluster compound catalyst and the desulfurization performance of the present invention's preparation have the following advantages:
1, the preparation method of Fa Ming sulfur-bearing transition metal atoms cluster compound, raw material is simple and easy to, and is cheap, the preparation condition gentleness, operating process is simple.
2, the prepared loaded sulfur-bearing transition metal atoms cluster compound catalyst of the present invention can have the metal similar to traditional catalyst and form, and simultaneously, has better decentralization and less particle size again.This kind catalyst has higher hydrodesulfurization activity than traditional Hydrobon catalyst.
3, the prepared sulfur-bearing transition metal atoms cluster compound of the present invention has very strong anti-sulfur poisonous performance.Therefore, be very potential liquid fuel Hydrobon catalyst.
The specific embodiment
In order to further specify the present invention, enumerate following examples, but it does not limit the defined invention scope of each accessory claim.Such as, the present invention mentions metal M as auxiliary agent ' can be salt of Co, Ni, Fe, Sn, Bi, Pb, Cu, Ag and Hg and metal thereof etc. according to experimental result, and for simplicity's sake, only enumerated the embodiment of nickel, but do not mean that remaining metal can not realize the present invention.
Embodiment 1
Take by weighing MoO
312.0 gram is dissolved in concentrated hydrochloric acid, heating makes MoO
3All dissolvings.This solution is put into electrolytic cell carry out electrolysis.After treating electrolysis fully, this electrolyte is transferred to preservation in the airtight bottle.Get part solution with 1: 10 volume ratio distilled water diluting, get this dilution of part and be transferred in the three-necked bottle, feed H
2S gas carries out vulcanizing treatment, vulcanizes H 12 hours
2The flow velocity of S gas is controlled in the 60-200ml/min scope all can.With the product that vulcanized, add hydrochloric acid solution, at 110 ℃ of bubbling airs, carry out the decompression distillation oxidation, be about 250ml until liquor capacity.With the product after this oxidation, filter.Get the filtrate part, with 1N HCl dilution.Get the product after the dilution, separate with gel chromatographic columns.A bunch core that obtains the present invention's preparation is [Mo
3S
4]
4+Sulfur-bearing transition metal molybdenum cluster compound.This cluster compound is numbered A.
Embodiment 2
With bunch core of preparation is [Mo
3S
4]
4+Sulfur-bearing transition metal molybdenum cluster compound (A) concentrate the back with resin column and excessive metal nickel powder mixes, at room temperature stirred 24 hours, until cluster compound A and nickel powder complete reaction.This mixture is filtered, and filtrate is separated with resin column, with the hydrochloric acid wash-out Ni of 0.5N
2+, separate cluster compound A with 1N salt pickling resin column again.A bunch core that obtains the present invention's preparation is [NiMo
3S
4]
4+Sulfur-bearing transition metal molybdenum cluster compound.This cluster compound is numbered B.
Embodiment 3
Take by weighing 3.0 gram Al
2O
3, measure a certain amount of cluster compound A, the content that makes burning molybdenum in the catalyst is 7.5%.Under nitrogen protection, flood Al
2O
3Carrier, and be lower than 60 ℃ with the solution evaporate to dryness in temperature with Rotary Evaporators.Obtain the Al of the present invention's preparation
2O
3Sulfur-bearing transition metal cluster compound (A) catalyst that supports.This catalyst is numbered C.
Comparative example 1
Take by weighing 3.0 gram Al
2O
3, taking by weighing a certain amount of ammonium molybdate, the content that makes burning molybdenum in the catalyst is 7.5%.With ammonium molybdate solution incipient impregnation Al
2O
3Carrier and water bath method.With the catalyst of preparation 120 ℃ of dryings 6 hours, again 500 ℃ of roastings 4 hours.This catalyst is at 10%H
2S/H
2(v/v) vulcanized 2 hours at 400 ℃ under.Obtain the Al of the present invention's preparation
2O
3The molybdenum sulfide catalyst that supports.This catalyst is numbered D.
Embodiment 4
Take by weighing 3.0 gram Al
2O
3, measure a certain amount of cluster compound B, the content that makes burning molybdenum in the catalyst is 7.5%.Under nitrogen protection, flood Al
2O
3Carrier, and be lower than 60 ℃ with the solution evaporate to dryness in temperature with Rotary Evaporators.Obtain the Al of the present invention's preparation
2O
3Sulfur-bearing transition metal cluster compound (B) catalyst that supports.This catalyst is numbered E.
Comparative example 2
Take by weighing 3.0 gram Al
2O
3, taking by weighing a certain amount of ammonium molybdate and nickel nitrate, the content that makes burning molybdenum in the catalyst is 7.5%, and the mol ratio of Ni/Mo is 1/3.With ammonium molybdate and nickel nitrate solution incipient impregnation Al
2O
3Carrier and water bath method.With the catalyst of preparation 120 ℃ of dryings 6 hours, again 500 ℃ of roastings 4 hours.This catalyst is at 10%H
2S/H
2(v/v) vulcanized 2 hours at 400 ℃ under.Obtain the Al of the present invention's preparation
2O
3The nickel sulfide molybdenum catalyst that supports.This catalyst is numbered F.
Embodiment 5
Take by weighing 3.0 gram NaY, measure a certain amount of cluster compound (A), the content that makes burning molybdenum in the catalyst is 7.5%.Under nitrogen protection, make NaY carrier and cluster compound (A) carry out ion-exchange reactions, reaction was carried out 24 hours, made the metal molybdenum complete reaction in the cluster compound (A), all exchanged on the NaY carrier.The mixture that obtains is filtered with ultra-fine sand core funnel, and with the distilled water washing for several times.Sulfur-bearing transition metal cluster compound (A) catalyst that the NaY that the solid that obtains prepares for the present invention supports.This catalyst is numbered G.
Comparative example 3
Take by weighing 3.0 gram NaY, take by weighing a certain amount of ammonium molybdate, the content that makes burning molybdenum in the catalyst is 7.5%.With ammonium molybdate solution incipient impregnation NaY carrier and water bath method.With the catalyst of preparation 120 ℃ of dryings 6 hours, again 500 ℃ of roastings 4 hours.This catalyst is at 10%H
2S/H
2(v/v) vulcanized 2 hours at 400 ℃ under.Obtain the molybdenum sulfide catalyst that the NaY of the present invention preparation supports.This catalyst is numbered H.
Embodiment 6
Take by weighing 3.0 gram NaY, measure a certain amount of cluster compound (B), the content that makes burning molybdenum in the catalyst is 7.5%.Under nitrogen protection, make NaY carrier and cluster compound (B) carry out ion-exchange reactions, reaction was carried out 24 hours, made the metal molybdenum complete reaction in the cluster compound (B), all exchanged on the NaY carrier.The mixture that obtains is filtered with ultra-fine sand core funnel, and with the distilled water washing for several times.Sulfur-bearing transition metal cluster compound (B) catalyst that the NaY that the solid that obtains prepares for the present invention supports.This catalyst is numbered I.
Comparative example 4
Take by weighing 3.0 gram NaY, take by weighing a certain amount of ammonium tungstate and nickel nitrate, the content that makes burning molybdenum in the catalyst is 7.5%, and the mol ratio of Ni/W is 1/3.With ammonium tungstate and nickel nitrate solution incipient impregnation NaY carrier and water bath method.With the catalyst of preparation 120 ℃ of dryings 6 hours, again 500 ℃ of roastings 4 hours.This catalyst is at 10%H
2S/H
2(v/v) vulcanized 2 hours at 400 ℃ under.The NaY that obtains the present invention's preparation supports the nickel sulfide tungsten catalyst.This catalyst is numbered J.
Embodiment 7
The catalyst hydrogenation desulfurization performance relatively
Decahydronaphthalene solution with the 2wt% thiophene is model compound, and investigating metal cluster compound is the catalyst of presoma preparation and the hydrodesulfurization activity of the sulphided state catalyst that conventional method prepares.The reacting middle catalyst consumption is 0.2 gram.The liquid air speed is 30h
-1Be reflected in the fixed-bed micro-reactor and carry out.Reaction condition is: 280 ℃ of temperature, pressure 3.0MPa, hydrogen flow rate 60ml/min.Product analysis adopts gas-chromatography, hydrogen flame detector.Experimental data sees Table 1 and table 2.
Table 1 Al
2O
3Catalyst hydrogenation desulfurization performance comparison for carrier
| The catalyst numbering | C | D | E | F |
| Thiophene conversion ratio (%) | 40.0 | 35.6 | 71.2 | 62.0 |
Table 2 NaY is that the catalyst hydrogenation desulfurization performance of carrier compares
| The catalyst numbering | G | H | I | J |
| Thiophene conversion ratio (%) | 22.0 | 14.4 | 64.8 | 51.3 |
Table 1 and table 2 result show, the Al of the present invention's preparation
2O
3The sulfur-bearing molybdenum cluster compound that supports with NaY is the presoma catalyst, compares with commercial Hydrobon catalyst, has higher hydrodesulfurization activity, and there is not the problem of sulfur poisoning in the catalyst of this kind method preparation.It is significant to the hydrodesulfurization essence of further exploration catalyst to prepare the cluster compound catalyst with clear and definite structure.
Claims (10)
1, a kind of method for preparing catalyst that is used for the sulfur-bearing transition metal atoms cluster compound of hydrodesulfurization, key step is as follows:
(a) molybdenum oxide or tungsten oxide are dissolved in concentrated hydrochloric acid, and are electrolysis in the hydrochloric acid solution of 6-12N, make the hydrochloride solution of molybdenum oxide or tungsten oxide in concentration;
(b) the hydrochloride solution of molybdenum oxide that step a is made or tungsten oxide feeds H
2S gas vulcanizes;
(c) solution that step b sulfuration is finished in 60-120 ℃ under oxygen or air oxidation 24-56 hour;
(d) with the solution decompression distillation of step c, the reactant mixture after obtaining concentrating filters this mixture, and separates with resin column, obtains having following bunch of core: [M
2O
nS
2-n]
M+, [M
3O
nS
4-n]
M+Or [M
4O
nS
6-n]
M+Sulfur-bearing transition metal atoms cluster compound, M=Mo or W in the formula, n=0～6, m=0～6;
(e) the sulfur-bearing transition metal atoms cluster compound that steps d is obtained be lower than in oxygen content under 0.1% the inert atmosphere that method by dipping or ion-exchange supports or grafting to various carriers, obtain the catalyst of loaded sulfur-bearing transition metal atoms cluster compound.
2. the preparation method of claim 1 is characterized in that, sulfur-bearing transition metal atoms cluster compound and another kind of metal M ' reaction as auxiliary agent that steps d is prepared obtain having following bi-component transition metal cluster core: [M ' M
2O
nS
2-n]
M+, [M ' M
3O
nS
4-n]
M+Or [M ' M
4O
nS
6-n]
M+Sulfur-bearing transition metal atoms cluster compound, M=Mo or W in the formula, n=0～6, m=0～6; Metal M as auxiliary agent ' be selected from a kind of in the salt of Co, Ni, Fe, Sn, Bi, Pb, Cu, Ag and metal thereof.
3. the preparation method of claim 1 is characterized in that, molybdenum oxide and tungsten oxide presoma are ammonium molybdate and ammonium tungstate.
4. the preparation method of claim 1 is characterized in that, the electrolysis among the step a is anode with graphite, and mercury is negative electrode.
5. by the preparation method of claim 1, it is characterized in that catalyst carrier is silica, alundum (Al, activated carbon, H-ZSM5, HY, NaY zeolite, MgO, pharmalyte TiO
2, ZrO
2Or mesopore material.
6. the preparation method of claim 5 is characterized in that, is MCM-41, Al-MCM-41, SBA-15, Al-SBA-15 or FSM-16 as the mesopore material of catalyst carrier.
7. the preparation method of claim 1 is characterized in that, the H among the step b
2The flow velocity of S gas is 60～200ml/min.
8. claim 1 or 7 preparation method is characterized in that the H among the step b
2S gas replaces carrying out vulcanizing treatment with vulcanized sodium, ammonium sulfide and ammonium polysulfide.
9. the preparation method of claim 1 is characterized in that, the reactant mixture concentration after will concentrating earlier in the steps d is that the hydrochloric acid of 1-2N dilutes, and filters, separates.
10. the preparation method of claim 1 is characterized in that, the inert atmosphere among the step e is helium, argon gas or nitrogen atmosphere.
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| CN100422395C (en) * | 2006-07-17 | 2008-10-01 | 南京理工大学 | Preparation method of functional molecular crystal of pentanuclear planar square chalcogenide metal clusters |
| CN100387513C (en) * | 2006-07-17 | 2008-05-14 | 南京理工大学 | Preparation method of cationic bird's nest metal cluster molecular functional material |
| FR2913691B1 (en) * | 2007-03-16 | 2010-10-22 | Inst Francais Du Petrole | PROCESS FOR HYDROCONVERSION OF HYDROCARBON LOADS HEAVY IN SLURRY REACTOR IN THE PRESENCE OF A CATALYST BASED ON HETEROPOLYANION |
| CN104275202B (en) * | 2014-10-09 | 2017-02-15 | 山东华星石油化工集团有限公司 | Load type diesel hydrotreating catalyst and application thereof |
| US11033883B2 (en) * | 2018-06-26 | 2021-06-15 | Uop Llc | Transition metal molybdotungstate material |
| CN110465305B (en) * | 2019-08-28 | 2022-10-04 | 辽宁科技大学 | A kind of preparation method of acidic supported hydrodesulfurization catalyst |
| CN113209992B (en) * | 2021-04-30 | 2023-12-15 | 北京化工大学 | A sulfur-containing Ni-based atom cluster catalyst for selective hydrogenation of carbon-carbon triple bonds and its preparation method |
| CN116351441B (en) * | 2023-03-21 | 2024-07-02 | 北京化工大学 | Supported selective hydrogenation catalyst with synergistic sites and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5306683A (en) * | 1992-05-01 | 1994-04-26 | Arch Development Corporation | Transition metal sulfide loaded catalyst |
| US5872073A (en) * | 1995-10-08 | 1999-02-16 | The United States Of America As Represented By The United States Department Of Energy | Reduced ternary molybdenum and tungsten sulfides and hydroprocessing catalysis therewith |
-
2004
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5306683A (en) * | 1992-05-01 | 1994-04-26 | Arch Development Corporation | Transition metal sulfide loaded catalyst |
| US5872073A (en) * | 1995-10-08 | 1999-02-16 | The United States Of America As Represented By The United States Department Of Energy | Reduced ternary molybdenum and tungsten sulfides and hydroprocessing catalysis therewith |
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