CN113649016A - Hydrogenation catalyst, preparation method and application thereof - Google Patents
Hydrogenation catalyst, preparation method and application thereof Download PDFInfo
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- CN113649016A CN113649016A CN202010397800.7A CN202010397800A CN113649016A CN 113649016 A CN113649016 A CN 113649016A CN 202010397800 A CN202010397800 A CN 202010397800A CN 113649016 A CN113649016 A CN 113649016A
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- Prior art keywords
- acid
- hydrogenation catalyst
- active element
- oxide
- drying
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 108
- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- DCRIQAAPAFMPKP-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Al+3].[Ti+4] DCRIQAAPAFMPKP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000498 ball milling Methods 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 238000000197 pyrolysis Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 8
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 8
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical group [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims 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 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 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
- 229910021586 Nickel(II) chloride Inorganic materials 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
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims 2
- 229940010552 ammonium molybdate Drugs 0.000 claims 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims 2
- 239000011609 ammonium molybdate Substances 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 1
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 239000007864 aqueous solution Substances 0.000 description 21
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 19
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 17
- 238000012512 characterization method Methods 0.000 description 13
- 238000013507 mapping Methods 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 239000002243 precursor Substances 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 8
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 8
- 238000009827 uniform distribution Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 101100386518 Caenorhabditis elegans dbl-1 gene Proteins 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910017313 Mo—Co Inorganic materials 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- -1 and preferably Chemical compound 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/38—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metals, or compounds thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a hydrogenation catalyst, a preparation method and application thereof. The preparation method of the hydrogenation catalyst comprises the following steps: (1) mixing alumina, metatitanic acid and a solvent to obtain a mixture I; (2) carrying out high-energy ball milling on the mixture I to obtain a mixture II with the median particle size of less than 0.1 mu m; (3) performing first drying on the mixture II, mixing the obtained dried product with acid liquor, and sequentially performing molding, second drying and first roasting to obtain a titanium oxide-aluminum oxide composite carrier; (4) and (3) impregnating the titanium oxide-alumina composite carrier with a solution containing a compound containing a first active element and a compound containing a second active element, and carrying out third drying and second roasting, wherein the first active element is a molybdenum element, and the second active element is a cobalt element and a nickel element. The hydrogenation catalyst has the advantages of good low-temperature activity and high hydrogenation activity at high space velocity.
Description
Technical Field
The invention belongs to the field of composite oxides, and particularly relates to a hydrogenation catalyst, and a preparation method and application thereof.
Background
As the pyrolysis gasoline contains impurities such as diolefin, monoolefin, sulfur and the like, all the olefins and sulfur are removed by a hydrogenation method before being subsequently used as an extraction raw material to prepare triphenyl or being used as a gasoline and diesel oil blending component, namely hydrogenation saturation Hydrodesulfurization (HDS). In the process of hydrotreating pyrolysis gasoline, two-stage hydrogenation is generally adopted, and one stage adopts Al loaded with noble metals such as Pd or non-noble metals such as Ni2O3As a selective hydrogenation catalyst, removing diene in the raw material by hydrogenation; two-stage industry generally adopts Al loaded with Co, MO, Ni and other metals2O3And hydrodesulfurizing catalyst to eliminate monoene and sulfide. The manufacturing technology of the cracking gasoline hydrogenation catalyst in foreign countries is developed rapidly, two types of catalysts, namely LD and HR, are adopted in France IFP two-stage hydrogenation, LD-145 is a Mo-Ni type catalyst, and HR-304B is a Mo-Co type catalyst. G-35B developed by Girdler catalyst company and S-12 developed by UOP company in Japan are both Co-Mo/Al2O3A catalyst. However, the hydrogenation catalyst mostly adopts a discontinuous production process in the preparation process, the production efficiency is low, the yield is low, the production cost is high, more anions are generated, the environmental pollution is caused, and the low-temperature activity of the hydrogenation catalyst needs to be improved.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a hydrogenation catalyst aiming at the defects in the prior art, the hydrogenation catalyst obtained by the preparation method has the advantages of good low-temperature activity and high hydrogenation activity at high space velocity, continuous production can be realized, the preparation cost is low, no wastewater or waste gas is generated in the production process, and the preparation method is suitable for large-scale industrial production.
To this end, a first aspect of the present invention provides a method for preparing a hydrogenation catalyst, comprising:
(1) mixing alumina, metatitanic acid and a solvent to obtain a mixture I;
(2) carrying out high-energy ball milling on the mixture I to obtain a mixture II with the median particle size of less than 0.1 mu m;
(3) performing first drying on the mixture II, mixing the obtained dried product with acid liquor, and sequentially performing molding, second drying and first roasting to obtain a titanium oxide-aluminum oxide composite carrier;
(4) and (3) impregnating the titanium oxide-alumina composite carrier with a solution containing a compound containing a first active element and a compound containing a second active element, and carrying out third drying and second roasting, wherein the first active element is a molybdenum element, and the second active element is a cobalt element and a nickel element.
According to some embodiments of the preparation method of the present invention, the mixing order of the alumina, the metatitanic acid, and the solvent is for the purpose of enabling sufficient mixing, and it is preferable that the alumina and the metatitanic acid are mixed, added to the solvent, and mixed.
According to some embodiments of the preparation method of the present invention, the specific surface area of the alumina is 150-300m2(ii) in terms of/g. For example 150m2/g、160m2/g、170m2/g、180m2/g、190m2/g、200m2/g、210m2/g、220m2/g、230m2/g、240m2/g、250m2/g、260m2/g、270m2/g、280m2/g、290m2/g、300m2(iv)/g, and any value between any two of the foregoing values.
According to some embodiments of the preparation method of the present invention, the alumina has a pore volume of 0.6 to 1.2mL/g, preferably 0.8 to 1 mL/g. Such as 0.8mL/g, 0.9mL/g, 1mL/g, and any value therebetween.
According to some embodiments of the method of preparing of the present invention, the alumina is a powder, i.e. alumina powder.
According to some embodiments of the process of the present invention, according to preferred embodiments of the process of the present invention, the weight ratio of alumina to metatitanic acid is (5-10): 1, preferably (5-7): 1.
according to some embodiments of the method of preparing of the present invention, the weight ratio of the total weight of alumina and metatitanic acid to the solvent is 5: (1-5).
According to some embodiments of the preparation method of the present invention, the solvent may be any solvent capable of sufficiently dissolving alumina and metatitanic acid, and preferably, the solvent is one or more of deionized water, ethanol, and methanol.
According to some embodiments of the method of making of the present invention, the conditions of the high energy ball milling comprise: the time is 6-10h, the revolution speed of the ball mill is 30-350r/min, and the rotation speed of the ball mill is 70-670 r/min. The time, revolution speed and rotation speed of the ball mill are used to obtain a mixture II with a median particle size of less than 0.1 μm.
According to some embodiments of the preparation method of the present invention, the high energy ball milling is a stirring ball milling, a vibration ball milling or a planetary ball milling, more preferably a planetary ball milling. The high-energy ball milling apparatus may be a high-energy ball mill, such as a stirred ball mill, a vibratory ball mill or a planetary ball mill, and more preferably a planetary ball mill.
According to some embodiments of the production method of the present invention, the acid solution comprises a solute and a solvent, and the solute in the acid solution is an organic acid and/or an inorganic acid; and/or the solvent in the acid solution is deionized water.
According to some embodiments of the method of the present invention, the weight ratio of the acid solution to the dried product based on the solvent is (1-4): 5, preferably (2-4): 5. the term "acid solution in terms of solvent" refers to the solvent in the acid solution.
According to some embodiments of the method of manufacturing of the present invention, the solute concentration in the acid solution is 0.5 to 4 wt%. Such as 0.5 wt%, 1 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, and any value between any two of the foregoing.
According to some embodiments of the method of manufacturing of the present invention,
the organic acid is one or more of acetic acid, oxalic acid, citric acid and tartaric acid; more preferably, the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid, more preferably nitric acid. For example, the acid solution is an aqueous nitric acid solution or an aqueous hydrochloric acid solution, and more preferably an aqueous nitric acid solution.
According to some embodiments of the method of manufacturing of the present invention, the method of forming is extrusion molding. The extrusion molding equipment can be a screw rod extruder conventional in the field.
According to some embodiments of the preparation method of the present invention, the kind of the compound containing the first active element is selected from a wide range, and may be any substance that is converted into molybdenum oxide in a subsequent process.
According to some embodiments of the preparation method of the present invention, the second active element-containing compound is selected from a wide range of species, and may be any substance that is converted into cobalt oxide and nickel oxide in a subsequent process, and preferably, the second active element-containing compound is one or more of nickel nitrate, nickel sulfate, nickel chloride, cobalt nitrate, cobalt sulfate, cobalt chloride, and cobalt acetate, and preferably, nickel nitrate and cobalt nitrate.
According to some embodiments of the preparation method of the present invention, the amount of the compound containing the first active element and the compound containing the second active element is such that the amount of the first active component is 7.5 to 20 wt%, preferably 10 to 18 wt%, the amount of the second active component is 1 to 15 wt%, preferably 4 to 8 wt%, and the amount of the titania-alumina composite carrier is 65 to 91 wt%, preferably 74 to 86 wt%, based on the total weight of the prepared hydrogenation catalyst, wherein the first active component is molybdenum oxide, and the second active component is cobalt oxide and nickel oxide.
According to a preferred embodiment of the present invention, in the oxide of the second active element, the weight ratio of cobalt oxide to nickel oxide is 1: (0.1-10), preferably 1: (0.2-5). Within this range, the hydrogenation catalyst is more effective.
According to some embodiments of the preparation method of the present invention, the feeding amount of the compound containing the first active element and the compound containing the second active element is such that the weight ratio of the oxide of the first active element to the oxide of the second active element in the prepared hydrogenation catalyst is 1: (0.1-1.8), preferably 1: (0.2-0.8), more preferably 1: (0.4-0.6). When the weight ratio of the first active component to the second active component is within the preferred range of the present invention, the low temperature activity and stability of the hydrogenation catalyst are more excellent.
According to some embodiments of the preparation method of the present invention, the solution of the compound containing the first active element and the compound containing the second active element may be obtained by dissolving the compound containing the first active element and the compound containing the second active element in deionized water. In consideration of the solubility of ammonium molybdate tetrahydrate, ammonia water of a certain concentration may be added to be sufficiently dissolved. For example, 26.68g/100mL of an aqueous solution of ammonium molybdate tetrahydrate (26.68 g of ammonium molybdate tetrahydrate per 100mL of deionized water), 5 to 10mL of 14% strength aqueous ammonia may be added to dissolve the ammonium molybdate tetrahydrate sufficiently.
According to some embodiments of the method of manufacturing of the present invention, the conditions of the first drying, the second drying, and the third drying each independently comprise: the temperature is 110-150 ℃, preferably 110-130 ℃, and the time is 2-16h, preferably 3-12 h. In the present invention, the drying apparatus may be an oven as is conventional in the art.
According to some embodiments of the method of manufacturing of the present invention, the conditions of the first firing and the second firing each independently comprise: the temperature is 500-900 ℃, preferably 550-800 ℃ and the time is 3-16h, preferably 4-12 h. In the present invention, the apparatus for calcination may be a muffle furnace, which is conventional in the art.
According to some embodiments of the method of manufacturing of the present invention, the impregnation conditions include: the temperature is 20-50 deg.C, preferably 25-40 deg.C, and the time is 0.5-24 hr, preferably 8-16 hr.
In a second aspect, the present invention provides a hydrogenation catalyst prepared by the above method.
According to some embodiments of the hydrogenation catalyst of the present invention, the hydrogenation catalyst comprises a titania-alumina composite carrier, a first active component and a second active component, wherein the content of the first active component is 7.5 to 20 wt%, preferably 10 to 18 wt%, the content of the second active component is 1 to 15 wt%, preferably 4 to 8 wt%, and the content of the titania-alumina composite carrier is 65 to 91 wt%, preferably 74 to 86 wt%, based on the total weight of the hydrogenation catalyst, wherein the first active component is molybdenum oxide and the second active component is cobalt oxide and/or nickel oxide.
According to some embodiments of the hydrogenation catalyst of the present invention, in the hydrogenation catalyst, the weight ratio of the oxide of the first active element to the oxide of the second active element in the hydrogenation catalyst is 1: (0.1-1.8), preferably 1: (0.2-0.8), more preferably 1: (0.4-0.6). When the weight ratio of the first active component to the second active component is within the preferred range of the present invention, the low temperature activity and stability of the hydrogenation catalyst are more excellent.
According to a preferred embodiment of the present invention, in the oxide of the second active element, the weight ratio of cobalt oxide to nickel oxide is 1: (0.1-10), preferably 1: (0.2-5). Within this range, the hydrogenation catalyst is more effective.
The hydrogenation catalyst prepared by the method has uniform distribution of titanium atoms, aluminum atoms, cobalt atoms, molybdenum atoms and nickel atoms. Specifically, the carrier can be characterized by SEM-Mapping by using a scanning electron microscope. The specific characterization method can be as follows: and (3) coating the ground sample on a conductive adhesive, spraying gold on the surface of the conductive adhesive by using an ion sputtering instrument, drying, spraying carbon on the sample before characterization, and characterizing the sample by using a QUANTA 200 scanning electron microscope of FEI company. The results of the characterization can be shown in fig. 1a, fig. 1b, fig. 1c, fig. 1d and fig. 1e, and it can be seen from the figure that the titanium atoms, aluminum atoms, cobalt atoms, molybdenum atoms and nickel atoms of the hydrogenation catalyst prepared by the present invention are uniformly distributed (since the original figure is a color figure, the uniform distribution can be clearly seen, and the display effect is affected after the arrangement as a black-and-white figure).
The third aspect of the invention provides the application of the hydrogenation catalyst in the hydrogenation of pyrolysis gasoline.
In the present invention, preferably, the pyrolysis gasoline is C6～C8、C9～C10Cracked gasoline of the distillate.
In the present invention, preferably, the hydrogenation conditions include: the inlet temperature of the reactor is 220-300 ℃, the preferred temperature is 240-250 ℃, and the space velocity is 1-4h-1The volume ratio of hydrogen to oil is 300-800:1, and the pressure is 2.5-3.5 Mpa.
In a preferred embodiment of the invention, the pyrolysis gasoline is C6～C8Fraction pyrolysis gasoline, the hydrogenation conditions include: 220 ℃ and 280 ℃, preferably 240 ℃ and 250 ℃, and the space velocity is 2-4h-1The hydrogen-oil volume ratio is 300-500:1, and the pressure is 2.5-3.5 MPa.
In another preferred embodiment of the invention, the pyrolysis gasoline is C9～C10Fraction pyrolysis gasoline, the hydrogenation conditions include: at 300 ℃ of 220 ℃ and preferably at 250 ℃ of 240 ℃ and at a space velocity of 1-2h-1The volume ratio of hydrogen to oil is 400-800:1, and the pressure is 2.5-3.5 Mpa.
Before the reaction, the hydrogenation catalyst needs to be sulfurized, and the sulfurization method can be a method conventional in the art, for example, at the reactor temperature of 280-350 ℃, the hydrogen-oil volume ratio is 100-200:1, a cyclohexane solution with the DMDS (dimethyl disulfide) content of 1-5 wt% is used, and the volume space velocity is 1-2h-1Vulcanizing for 10-24h, after vulcanizationThe temperature was lowered to room temperature.
Compared with the existing hydrogenation catalyst, the hydrogenation catalyst provided by the invention has the advantages of good low-temperature activity, high hydrogenation activity at high space velocity and good stability in the field of pyrolysis gasoline hydrogenation, can realize continuous production, and has low production cost and no wastewater or waste gas in the production process.
Drawings
FIG. 1a is an SEM-Mapping chart of the distribution of aluminum atoms in a hydrogenation catalyst provided in example 1 of the present invention;
FIG. 1b is an SEM-Mapping chart of the titanium atom distribution in the hydrogenation catalyst provided in example 1 of the present invention;
FIG. 1c is an SEM-Mapping chart of the distribution of cobalt atoms in the hydrogenation catalyst provided in example 1 of the present invention;
FIG. 1d is an SEM-Mapping chart of the distribution of molybdenum atoms in the hydrogenation catalyst provided in example 1 of the present invention;
FIG. 1e is an SEM-Mapping chart of the distribution of nickel atoms in the hydrogenation catalyst provided in example 1 of the present invention.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
The test method of the invention is as follows:
(1) method for measuring median particle size the laser light scattering method for determining the particle size distribution of the catalytic cracking catalyst was referred to standard NB/SH/T0951-2017.
(2) The SEM-Mapping characterization method comprises the following steps: and (3) coating the ground sample on a conductive adhesive, spraying gold on the surface of the conductive adhesive by using an ion sputtering instrument, drying, spraying carbon on the sample before characterization, and characterizing the sample by using a QUANTA 200 scanning electron microscope of FEI company.
[ example 1 ]
This example illustrates the preparation of a hydrogenation catalyst.
Alumina (specific surface area 200 m)2Per g, pore volume of 1mL/g) and metatitanic acid are added into deionized water to be uniformly mixedWherein the weight ratio of the aluminum oxide to the metatitanic acid is 5:1, and the weight ratio of the total weight of the aluminum oxide and the metatitanic acid to the solvent is 5: 4. After mixing well, a mixture I is obtained. Putting the mixture I into a high-energy planetary ball mill for planetary ball milling, wherein the revolution speed of the ball mill is 200r/min, the rotation speed of the ball mill is 500r/min, the high-energy ball mill is 8h, the mixture II with the median particle size of 0.087 mu m is obtained after ball milling, putting the mixture II into an oven for drying overnight at 120 ℃, putting the obtained dried product into a screw rod type extruding machine, adding a nitric acid aqueous solution (the solute is nitric acid, the solvent is deionized water, and the concentration of the solute is 2 wt%), wherein the weight ratio of the deionized water in the acid solution to the dried product is 3:5, extruding and molding, drying for 5h at 110 ℃, then putting into a muffle furnace for roasting for 6h at 550 ℃, and obtaining the titanium oxide-aluminum oxide composite carrier A-1.
Preparing 26.68g/100mL ammonium molybdate tetrahydrate aqueous solution (each 100mL deionized water contains 26.68g of ammonium molybdate tetrahydrate), adding 5mL 14 wt% ammonia water to fully dissolve the ammonium molybdate tetrahydrate, taking 100g of the titanium oxide-alumina composite carrier A-1, soaking at normal temperature for 2h, filtering, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 4h to obtain the precursor. Then, the precursor was impregnated with an aqueous solution of nickel nitrate hexahydrate and cobalt nitrate hexahydrate (23.48 g of nickel nitrate hexahydrate and 11.62g of cobalt nitrate hexahydrate per 100mL of deionized water) at a concentration of 23.48g/100mL, impregnated at normal temperature for 2 hours, filtered, dried at 110 ℃ for 4 hours, and calcined at 550 ℃ for 4 hours to obtain a hydrogenation catalyst. Wherein, based on the total weight of the hydrogenation catalyst, MoO3The content of 15 wt%, the CoO content of 2 wt%, the NiO content of 4 wt%, and the content of the titanium oxide-alumina composite carrier of 79 wt% are MoO3-CoO-NiO/Al2O3-TiO2Hydrogenation catalyst a, denoted hydrogenation catalyst a.
SEM-Mapping characterization was performed on hydrogenation catalyst A, and the characterization results are shown in FIG. 1a, FIG. 1b, FIG. 1c, FIG. 1d and FIG. 1 e. It can be seen from the figure that the hydrogenation catalyst A prepared by the present invention has uniform distribution of aluminum atoms, titanium atoms, cobalt atoms, molybdenum atoms and nickel atoms.
[ example 2 ]
This example illustrates the preparation of a hydrogenation catalyst.
Alumina (specific surface area 150 m)2Per g, pore volume of 0.8mL/g) and metatitanic acid in a weight ratio of 6:1, and a solvent in a weight ratio of 1: 1. After mixing well, a mixture I is obtained. Putting the mixture I into a high-energy planetary ball mill for planetary ball milling, wherein the revolution speed of the ball mill is 300r/min, the rotation speed of the ball mill is 600r/min, the high-energy ball mill is 8h, the mixture II with the median particle size of 0.093 mu m is obtained after ball milling, putting the mixture II into an oven for drying overnight at 120 ℃, putting the obtained dried product into a screw rod type extruding machine, adding a nitric acid aqueous solution (the solute is nitric acid, the solvent is deionized water, and the concentration of the solute is 1.8 wt%), wherein the weight ratio of the deionized water in the acid solution to the dried product is 4:5, extruding and molding, drying for 3h at 130 ℃, and then putting into a muffle furnace for roasting for 4h at 800 ℃ to obtain the titanium oxide-aluminum oxide composite carrier B-1.
Preparing 26.68g/100mL ammonium molybdate tetrahydrate aqueous solution, adding 5mL ammonia water with the concentration of 14 weight percent to fully dissolve the ammonium molybdate tetrahydrate, taking 100g titanium oxide-aluminum oxide composite carrier B-1, soaking at normal temperature for 2h, filtering, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 4 h. Then impregnating the precursor prepared by roasting with an aqueous solution of nickel nitrate hexahydrate and cobalt nitrate hexahydrate, wherein the concentration of the aqueous solution is 17.61g/100mL, and 20.34g/100mL, impregnating at normal temperature for 2 hours, filtering, drying at 110 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours to obtain the hydrogenation catalyst. Wherein, based on the total weight of the hydrogenation catalyst, MoO3The content was 15 wt%, the CoO content was 3.5 wt%, the NiO content was 3 wt%, and the content of the titania-alumina composite carrier was 78.5 wt%, which was MoO3-CoO-NiO/Al2O3-TiO2And the hydrogenation catalyst B is marked as hydrogenation catalyst B.
SEM-Mapping characterization was performed on hydrogenation catalyst B, and the characterization results were similar to those in FIG. 1a, FIG. 1B, FIG. 1c, FIG. 1d and FIG. 1 e. It is shown that the hydrogenation catalyst B prepared by the invention has uniform distribution of aluminum atoms, titanium atoms, cobalt atoms, molybdenum atoms and nickel atoms.
[ example 3 ]
This example illustrates the preparation of a hydrogenation catalyst.
Alumina (specific surface area 300 m)2Per g, pore volume of 1.2mL/g) and metatitanic acid were added to deionized water and mixed uniformly, wherein the weight ratio of alumina to metatitanic acid was 7:1, and the weight ratio of the total weight of alumina and metatitanic acid to the solvent was 5: 3. After mixing well, a mixture I is obtained. Putting the mixture I into a high-energy planetary ball mill for planetary ball milling, wherein the revolution speed of the ball mill is 300r/min, the rotation speed of the ball mill is 300r/min, the high-energy ball mill is 10h, the mixture II with the median particle size of 0.082 mu m is obtained after ball milling, putting the mixture II into an oven for drying overnight at 120 ℃, putting the obtained dried product into a screw rod type extruding machine, adding a hydrochloric acid aqueous solution (the solute is hydrochloric acid, the solvent is deionized water, and the concentration of the solute is 2.5 wt%), wherein the weight ratio of the deionized water in the acid solution to the dried product is 2:5, extruding and molding, drying for 3h at 150 ℃, and then putting into a muffle furnace for roasting for 12h at 550 ℃ to obtain the titanium oxide-aluminum oxide composite carrier C-1.
Preparing 32.56g/100mL ammonium molybdate tetrahydrate aqueous solution, adding 5mL ammonia water with the concentration of 14 weight percent to fully dissolve the ammonium molybdate tetrahydrate, taking 100g titanium oxide-aluminum oxide composite carrier C-1, soaking at normal temperature for 2h, filtering, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 4 h. Then impregnating the precursor prepared by roasting with an aqueous solution of nickel nitrate hexahydrate and cobalt nitrate hexahydrate, wherein the concentration of the aqueous solution is 17.61g/100mL, and 11.62g/100mL, impregnating at normal temperature for 2 hours, filtering, drying at 110 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours to obtain the hydrogenation catalyst. Wherein, based on the total weight of the hydrogenation catalyst, MoO3The content of 18 wt%, the CoO content of 2 wt%, the NiO content of 3 wt%, and the content of the titanium oxide-alumina composite carrier of 77 wt% were MoO3-CoO-NiO/Al2O3-TiO2Hydrogenation catalyst C, the weight ratio of the total weight of nickel oxide and cobalt oxide to molybdenum oxide was 0.28:1, and is designated hydrogenation catalyst C.
SEM-Mapping characterization was performed on hydrogenation catalyst C, and the characterization results were similar to those in FIG. 1a, FIG. 1b, FIG. 1C, FIG. 1d and FIG. 1 e. The hydrogenation catalyst C prepared by the invention has uniform distribution of aluminum atoms, titanium atoms, cobalt atoms, molybdenum atoms and nickel atoms.
[ example 4 ]
A titania-alumina composite carrier C-1 was prepared according to the method of example 3, except that a hydrogenation catalyst was prepared as follows:
preparing ammonium molybdate tetrahydrate aqueous solution with the concentration of 18.28g/100mL, then adding 5mL of ammonia water with the concentration of 14 weight percent to fully dissolve the ammonium molybdate tetrahydrate, then taking 100g of the titanium oxide-alumina composite carrier C-1, dipping for 2h at normal temperature, filtering, drying for 4h at 110 ℃, and roasting for 4h at 550 ℃. Then impregnating the precursor prepared by roasting with aqueous solution of nickel nitrate hexahydrate and cobalt nitrate hexahydrate, the concentrations of which are 11.86g/100mL and 34.94g/100mL, impregnating for 2 hours at normal temperature, filtering, drying for 4 hours at 110 ℃, and roasting for 4 hours at 550 ℃ to obtain the hydrogenation catalyst. Wherein, based on the total weight of the hydrogenation catalyst, MoO3The content of 10 wt%, the CoO content of 6 wt%, the NiO content of 2 wt%, and the content of the titanium oxide-alumina composite carrier of 82 wt% were MoO3-CoO-NiO/Al2O3-TiO2Hydrogenation catalyst D, denoted hydrogenation catalyst D.
The hydrogenation catalyst D was characterized by SEM-Mapping, and the results were similar to those in FIG. 1a, FIG. 1b, FIG. 1c, FIG. 1D and FIG. 1 e. It is shown that the hydrogenation catalyst D prepared by the invention has uniform distribution of aluminum atoms, titanium atoms, cobalt atoms, molybdenum atoms and nickel atoms.
[ example 5 ]
A titania-alumina composite carrier C-1 was prepared according to the method of example 3, except that a hydrogenation catalyst was prepared as follows:
preparing 38.76g/100mL ammonium molybdate tetrahydrate aqueous solution, adding 5mL ammonia water with the concentration of 14 weight percent to fully dissolve the ammonium molybdate tetrahydrate, taking 100g titanium oxide-aluminum oxide composite carrier C-1, soaking at normal temperature for 2h, filtering, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 4 h. The calcined precursor was then impregnated with an aqueous solution of nickel nitrate hexahydrate at a concentration of 17.61g/100mL and cobalt nitrate hexahydrate at a concentration of 6.32g/100mL, oftenSoaking for 2h, filtering, drying at 110 deg.C for 4h, and calcining at 550 deg.C for 4h to obtain the hydrogenation catalyst. Wherein, based on the total weight of the hydrogenation catalyst, MoO3The content of 20 wt%, the CoO content of 1 wt%, the NiO content of 3 wt%, and the content of the titanium oxide-alumina composite carrier of 76 wt% are MoO3-CoO-NiO/Al2O3-TiO2Hydrogenation catalyst E, denoted hydrogenation catalyst E.
SEM-Mapping characterization was performed on hydrogenation catalyst E, and the characterization results were similar to those of FIG. 1a, FIG. 1b, FIG. 1c, FIG. 1d and FIG. 1E. It is shown that the hydrogenation catalyst E prepared by the invention has uniform distribution of aluminum atoms, titanium atoms, cobalt atoms, molybdenum atoms and nickel atoms.
Comparative example 1
Alumina (specific surface area 200 m)2Per g, pore volume of 1mL/g) and metatitanic acid are added into deionized water to be uniformly mixed, wherein the weight ratio of alumina to metatitanic acid is 5:1, and the weight ratio of the total weight of alumina and metatitanic acid to the solvent is 5: 4. After mixing well, a mixture I is obtained. And putting the mixture II into an oven for drying at 120 ℃ overnight, putting the obtained dried product into a screw rod type extruding machine, adding a nitric acid aqueous solution (the solute is nitric acid, the solvent is deionized water, and the concentration of the solute is 2 wt%), wherein the weight ratio of the deionized water to the dried product is 3:5, extruding and molding, drying at 110 ℃ for 5 hours, and then putting into a muffle furnace for roasting at 550 ℃ for 6 hours to obtain the titanium oxide-aluminum oxide composite carrier DBL-1.
Preparing ammonium molybdate tetrahydrate aqueous solution with the concentration of 26.68g/100mL, then adding 5mL of ammonia water with the concentration of 14 wt% to fully dissolve the ammonium molybdate tetrahydrate, then taking 100g of composite carrier DBL-1, soaking at normal temperature for 2h, filtering, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 4h to obtain the precursor. Then, the precursor was impregnated with an aqueous solution of nickel nitrate hexahydrate and cobalt nitrate hexahydrate at a concentration of 23.48g/100mL, and the impregnated solution was immersed at room temperature for 2 hours, filtered, dried at 110 ℃ for 4 hours, and calcined at 550 ℃ for 4 hours to obtain a hydrogenation catalyst designated as hydrogenation catalyst DC-1.
Comparative example 2
A titania-alumina composite carrier DBL-2 was prepared according to the method of example 1 of CN 1184289C.
The specific operation is as follows:
taking the specific surface area of 160 meters290 g of cloverleaf alumina with the pore volume of 0.58 ml/g and the most probable pore diameter of 130 angstrom is soaked by 53 ml of dilute sulphuric acid solution of 0.557 g/ml of titanium sulphate, stirred for 15 minutes, dried at 120 ℃ for 8 hours and then roasted at 900 ℃ for 4 hours to prepare the titanium oxide-alumina composite DB-2. The resulting composite had a titanium oxide content of 10% by weight and a specific surface area of 144 m2A pore volume of 0.56 ml/g, and a pore diameter of 125 angstroms.
Preparing ammonium molybdate tetrahydrate aqueous solution with the concentration of 26.68g/100mL, then adding 5mL of ammonia water with the concentration of 14 wt% to fully dissolve the ammonium molybdate tetrahydrate, then taking 100g of composite carrier DBL-2, dipping for 2h at normal temperature, filtering, drying for 4h at 110 ℃, and roasting for 4h at 550 ℃ to obtain the precursor. The precursor was then impregnated with an aqueous solution of 17.61g/100mL nickel nitrate hexahydrate and 20.34g/100mL cobalt nitrate hexahydrate for 2 hours at ambient temperature, filtered, dried at 110 ℃ for 4 hours, and calcined at 550 ℃ for 4 hours to give the hydrogenation catalyst designated as hydrogenation catalyst DC-2.
Comparative example 3
The procedure is as in example 1, except that mixture II, which after ball milling gave a median particle diameter of 0.087 μm, is replaced by mixture II, which after ball milling gave a median particle diameter of 1.5. mu.m. Obtaining the hydrogenation protective agent DC-3.
[ test example 1 ]
Benzene production apparatus C using China petrochemical Yanshan petrochemical olefin part6～C8The first-stage hydrogenation product of the fraction is used as a hydrofining raw material, the total sulfur content of the raw material is 98ppm, and the bromine number is 19.09 (gBr)2Per 100g of oil). Comparative evaluations were made for hydrogenation catalysts A, B, C, D, E, DC1 to DC3 (all at 100 mL). The evaluation conditions and product analysis are shown in Table 1.
TABLE 1
[ test example 2 ]
Benzene production apparatus C using China petrochemical Yanshan petrochemical olefin part6～C8The first-stage hydrogenation product of the fraction is used as a hydrofining raw material, the total sulfur content of the raw material is 98ppm, and the bromine number is 19.09 (gBr)2Per 100g of oil). Hydrogenation catalyst B and DC2 (both 100mL) were evaluated for comparison. The evaluation conditions and product analysis are shown in Table 2.
TABLE 2
[ test example 3 ]
Chemical engineering plant C from Tianli high New company of Dushan mountain in Xinjiang9～C10Fraction two-stage hydrogenation raw material with total sulfur content of 400ppm and bromine number of 29 (gBr)2Per 100g of oil). Hydrogenation catalyst A and DC1 (both 100mL) were evaluated for comparison. The evaluation conditions and product analysis are shown in Table 3.
TABLE 3
As can be seen from fig. 1a, 1b, 1c, 1d and 1e, the hydrogenation catalyst prepared by the method of the present invention has a uniform distribution of aluminum atoms, titanium atoms, molybdenum atoms, cobalt atoms and nickel atoms.
In addition, it can be seen from test examples 1-3 and tables 1-3 that the hydrogenation catalyst of the present invention has good low temperature activity and hydrogenation activity and stability at high space velocity when applied to the field of hydrogenation of cracked gasoline. And the method can realize continuous production, has low preparation cost and is suitable for large-scale industrial production.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A method of preparing a hydrogenation catalyst comprising:
(1) mixing alumina, metatitanic acid and a solvent to obtain a mixture I;
(2) carrying out high-energy ball milling on the mixture I to obtain a mixture II with the median particle size of less than 0.1 mu m;
(3) performing first drying on the mixture II, mixing the obtained dried product with acid liquor, and sequentially performing molding, second drying and first roasting to obtain a titanium oxide-aluminum oxide composite carrier;
(4) and (3) impregnating the titanium oxide-alumina composite carrier with a solution containing a compound containing a first active element and a compound containing a second active element, and carrying out third drying and second roasting, wherein the first active element is a molybdenum element, and the second active element is a cobalt element and a nickel element.
2. The method as claimed in claim 1, wherein the specific surface area of the alumina is 150-300m2The pore volume is 0.6-1.2mL/g, preferably 0.8-1 mL/g;
preferably, the weight ratio of alumina to metatitanic acid is (5-10): 1, preferably (5-7): 1;
preferably, the weight ratio of the total weight of alumina and metatitanic acid to solvent is 5: (1-5);
more preferably, the solvent is one or more of deionized water, ethanol, and methanol.
3. The method of claim 1 or 2, wherein the conditions of the high energy ball milling comprise: the time is 6-10h, the revolution speed of the ball mill is 30-350r/min, and the rotation speed of the ball mill is 70-670 r/min;
preferably, the high energy ball milling is a stirred ball milling, a vibratory ball milling or a planetary ball milling, more preferably a planetary ball milling.
4. A process according to any one of claims 1 to 3, wherein the solute in the acid solution is an organic acid and/or an inorganic acid; and/or the solvent in the acid solution is deionized water;
preferably, the weight ratio of the acid liquid to the dried product, calculated as the solvent, is (1-4): 5, preferably (2-4): 5;
preferably, the concentration of solute in the acid liquor is 0.5-4 wt%;
more preferably, the organic acid is one or more of acetic acid, oxalic acid, citric acid and tartaric acid;
more preferably, the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid, more preferably nitric acid.
5. The method according to any one of claims 1 to 4, wherein the compound containing the first active element is one or more of ammonium molybdate, molybdenum nitrate and molybdenum chloride, preferably ammonium molybdate;
preferably, the compound containing the second active element is one or more of nickel nitrate, nickel sulfate, nickel chloride, cobalt nitrate, cobalt sulfate, cobalt chloride and cobalt acetate, preferably nickel nitrate and cobalt nitrate;
preferably, the feeding amount of the compound containing the first active element and the compound containing the second active element is such that the content of the first active component is 7.5-20 wt%, preferably 10-18 wt%, the content of the second active component is 1-15 wt%, preferably 4-8 wt%, and the content of the titanium oxide-aluminum oxide composite carrier is 65-91 wt%, preferably 74-86 wt%, based on the total weight of the prepared hydrogenation catalyst, wherein the first active component is molybdenum oxide, and the second active component is cobalt oxide and nickel oxide;
preferably, the weight ratio of cobalt oxide to nickel oxide is 1: (0.1-10), preferably 1: (0.2-5).
6. A process according to any one of claims 1 to 5, wherein the amount of the compound containing the first active element and the compound containing the second active element is such that the weight ratio of the oxide of the first active element to the oxide of the second active element in the hydrogenation catalyst prepared is from 1: (0.1-1.8), preferably 1: (0.2-0.8), more preferably 1: (0.4-0.6).
7. The method according to any one of claims 1 to 6, wherein the conditions of the first drying, the second drying and the third drying each independently comprise: the temperature is 110-150 ℃, preferably 110-130 ℃, and the time is 2-16h, preferably 3-12 h.
8. The method of any one of claims 1-7, wherein the conditions of the first firing and the second firing each independently comprise: the temperature is 500-900 ℃, preferably 550-800 ℃ and the time is 3-16h, preferably 4-12 h.
9. A hydrogenation catalyst prepared by the process of any one of claims 1 to 8.
10. Use of a hydrogenation catalyst according to claim 9 and/or a hydrogenation catalyst prepared according to the process of any one of claims 1-8 in the hydrogenation of pyrolysis gasoline;
preferably, the pyrolysis gasoline is C6～C8、C9～C10Pyrolysis gasoline of the distillate;
preferably, the hydrogenation conditions include: the inlet temperature of the reactor is 220-300 ℃, the preferred temperature is 240-250 ℃, and the space velocity is 1-4h-1Hydrogen ofThe oil volume ratio is 300-800:1, and the pressure is 2.5-3.5 MPa.
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| US5229347A (en) * | 1991-05-08 | 1993-07-20 | Intevep, S.A. | Catalyst for mild hydrocracking of cracked feedstocks and method for its preparation |
| WO1996014152A1 (en) * | 1994-11-04 | 1996-05-17 | Deqing Chemical Industry And Technology Development Company | TITANIA (TiO2) SUPPORT AND PROCESS FOR ITS PREPARATION AND USE THE SAME |
| CN102861593A (en) * | 2011-07-06 | 2013-01-09 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method thereof |
| CN106607043A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Iron-based catalyst and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5229347A (en) * | 1991-05-08 | 1993-07-20 | Intevep, S.A. | Catalyst for mild hydrocracking of cracked feedstocks and method for its preparation |
| WO1996014152A1 (en) * | 1994-11-04 | 1996-05-17 | Deqing Chemical Industry And Technology Development Company | TITANIA (TiO2) SUPPORT AND PROCESS FOR ITS PREPARATION AND USE THE SAME |
| CN102861593A (en) * | 2011-07-06 | 2013-01-09 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method thereof |
| CN106607043A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Iron-based catalyst and preparation method and application thereof |
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