CN113649016B - Hydrogenation catalyst and preparation method and application thereof - Google Patents
Hydrogenation catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN113649016B CN113649016B CN202010397800.7A CN202010397800A CN113649016B CN 113649016 B CN113649016 B CN 113649016B CN 202010397800 A CN202010397800 A CN 202010397800A CN 113649016 B CN113649016 B CN 113649016B
- Authority
- CN
- China
- Prior art keywords
- acid
- active element
- oxide
- hydrogenation catalyst
- cobalt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 108
- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 22
- 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 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 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
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 51
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 37
- 238000000498 ball milling Methods 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000197 pyrolysis Methods 0.000 claims description 14
- 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
- 239000011148 porous material Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 9
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 9
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 9
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 9
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 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
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 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
- 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 group 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 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
- 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 description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 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
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 2
- 239000011707 mineral Substances 0.000 claims 2
- 235000010755 mineral Nutrition 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 12
- 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
- 239000007864 aqueous solution Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 15
- 238000013507 mapping Methods 0.000 description 12
- 238000012512 characterization method 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
- 239000002994 raw material Substances 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 4
- 238000012360 testing method 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
- 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
- 238000001125 extrusion Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- 101100386518 Caenorhabditis elegans dbl-1 gene Proteins 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- -1 and more preferably Chemical compound 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004544 sputter deposition Methods 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 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
- 239000007789 gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical group 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
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
Landscapes
- 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 aluminum oxide, meta-titanic acid and a solvent to obtain a mixture I; (2) Performing high-energy ball milling on the mixture I to obtain a mixture II with the median particle diameter smaller than 0.1 mu m; (3) Performing first drying on the mixture II, mixing the obtained dried product with acid liquor, and sequentially performing forming, second drying and first roasting to obtain a titanium oxide-aluminum oxide composite carrier; (4) And impregnating the titanium oxide-aluminum oxide composite carrier with a solution containing a compound of a first active element and a compound of a second active element, and performing third drying and second roasting, wherein the first active element is molybdenum element, and the second active element is cobalt element and nickel element. The hydrogenation catalyst has the advantages of good low-temperature activity and high hydrogenation activity under high space velocity.
Description
Technical Field
The invention belongs to the field of composite oxides, and particularly relates to a hydrogenation catalyst, a preparation method and application thereof.
Background
The pyrolysis gasoline contains the impurities of diolefin, monoolefin, sulfur and the like, and is subsequently usedAll olefins and sulfur are removed by hydrogenation, i.e., hydrodesulphurisation (HDS), prior to extraction of the feedstock to make the triphenyl or as a gasoline and diesel blending component. 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 Ni 2 O 3 As a selective hydrogenation catalyst, the diene in the raw material is removed through hydrogenation; the second-stage industry generally adopts Al loaded with metals such as Co, MO, ni and the like 2 O 3 And (3) removing mono-olefins and sulfides by using the hydrodesulfurization catalyst. The technology for preparing the foreign pyrolysis gasoline hydrogenation catalyst has relatively rapid development, and two types of catalysts, namely LD and HR, are adopted for the second-stage hydrogenation of the French IFP, LD-145 is a Mo-Ni type catalyst, and HR-304B is a Mo-Co type catalyst. G-35B developed by Girdler catalyst Co., ltd. And S-12 catalyst developed by UOP Co., ltd. Are Co-Mo/Al 2 O 3 A catalyst. However, the hydrogenation catalyst is mostly prepared by adopting a discontinuous production process, and has low production efficiency, low yield, high production cost, more anions and environmental pollution, and the low-temperature activity of the hydrogenation catalyst needs to be improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a hydrogenation catalyst, wherein the hydrogenation catalyst prepared by the preparation method has the advantages of good low-temperature activity and high hydrogenation activity at high airspeed, can realize continuous production, has low preparation cost, does not generate waste water and waste gas in the production process, and 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 aluminum oxide, meta-titanic acid and a solvent to obtain a mixture I;
(2) Performing high-energy ball milling on the mixture I to obtain a mixture II with the median particle diameter smaller than 0.1 mu m;
(3) Performing first drying on the mixture II, mixing the obtained dried product with acid liquor, and sequentially performing forming, second drying and first roasting to obtain a titanium oxide-aluminum oxide composite carrier;
(4) And impregnating the titanium oxide-aluminum oxide composite carrier with a solution containing a compound of a first active element and a compound of a second active element, and performing third drying and second roasting, wherein the first active element is molybdenum element, and the second active element is cobalt element and nickel element.
According to some embodiments of the preparation method of the present invention, the mixing sequence of the alumina, the meta-titanic acid and the solvent is preferably added to the solvent and mixed after the alumina and the meta-titanic acid are mixed for the purpose of being able to be sufficiently mixed.
According to some embodiments of the preparation method of the present invention, the specific surface area of the alumina is 150-300m 2 And/g. For example 150m 2 /g、160m 2 /g、170m 2 /g、180m 2 /g、190m 2 /g、200m 2 /g、210m 2 /g、220m 2 /g、230m 2 /g、240m 2 /g、250m 2 /g、260m 2 /g、270m 2 /g、280m 2 /g、290m 2 /g、300m 2 And/g, and any value between any two of the above values.
According to some embodiments of the preparation method of the present invention, the alumina has a pore volume of 0.6-1.2mL/g, preferably 0.8-1mL/g. Such as 0.8mL/g, 0.9mL/g, 1mL/g, and any value between any two of the foregoing.
According to some embodiments of the preparation method of the present invention, the alumina is a powder, i.e., an alumina powder.
According to some embodiments of the preparation method according to the present invention, according to a preferred embodiment of the method according to the present invention, the weight ratio of alumina to meta-titanic acid is (5-10): 1, preferably (5-7): 1.
according to some embodiments of the preparation method of the present invention, the weight ratio of the total weight of alumina and meta-titanic 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 meta-titanic acid, and preferably, the solvent is one or more of deionized water, ethanol, and methanol.
According to some embodiments of the preparation method of the present invention, the conditions of the high energy ball milling include: 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 70-670r/min. The time, revolution speed and rotation speed of the ball mill are aimed at enabling to obtain a mixture II with a median particle diameter smaller than 0.1 μm.
According to some embodiments of the preparation method of the present invention, the high-energy ball milling is stirring ball milling, vibration ball milling or planetary ball milling, more preferably planetary ball milling. The above-mentioned 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 preparation method of the present invention, the acid solution comprises a solute and a solvent, wherein the solute in the acid solution is an organic acid and/or an inorganic acid; and/or the solvent in the acid liquor is deionized water.
According to some embodiments of the preparation method of the present invention, the weight ratio of the acid solution to the dry product in terms of solvent is (1-4): 5, preferably (2-4): 5. wherein, the term "acid solution calculated as solvent" refers to the term of solvent in the acid solution.
According to some embodiments of the method of preparation of the invention, the concentration of solute in the acid solution is 0.5-4 wt%. For example 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 above.
According to some embodiments of the preparation method 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, and 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 preparation of the invention, the method of shaping is extrusion. The extrusion molding apparatus may be a screw extruder as is conventional in the art.
According to some embodiments of the preparation method of the present invention, the type of the compound containing the first active element may be selected from any material that is converted into molybdenum oxide in a subsequent process, preferably, the compound containing the first active element is one or more of ammonium molybdate, molybdenum nitrate and molybdenum chloride, and more preferably, ammonium molybdate.
According to some embodiments of the preparation method of the present invention, the type of the compound containing the second active element may be any material that is converted into cobalt oxide and nickel oxide in a subsequent process, and 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, and preferably, nickel nitrate and cobalt nitrate.
According to some embodiments of the preparation method of the present invention, the amounts of the compound containing the first active element and the compound containing the second active element added are such that 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 support 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 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 has a better catalytic effect.
According to some embodiments of the preparation method of the present invention, the amounts of the compound containing the first active element and the compound containing the second active element fed are 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). The low temperature activity and stability of the hydrogenation catalyst are better when the weight ratio of the first active component to the second active component is within the preferred range of the present invention.
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 view of the solubility of ammonium molybdate tetrahydrate, ammonia water of a certain concentration may be added to make it 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) may be added with 5-10mL of 14% strength aqueous ammonia to dissolve the ammonium molybdate tetrahydrate sufficiently.
According to some embodiments of the method of preparing of the present invention, the conditions of the first drying, the second drying, and the third drying each independently include: the temperature is 110-150deg.C, preferably 110-130deg.C, and the time is 2-16 hr, preferably 3-12 hr. In the present invention, the drying apparatus may be an oven conventional in the art.
According to some embodiments of the method of producing of the present invention, the conditions of the first firing and the second firing each independently include: the temperature is 500-900 ℃, preferably 550-800 ℃, and the time is 3-16h, preferably 4-12h. In the present invention, the roasting apparatus may be a muffle furnace conventional in the art.
According to some embodiments of the method of preparation of the invention, the conditions of the impregnation comprise: the temperature is 20-50deg.C, preferably 25-40deg.C, and the time is 0.5-24 hr, preferably 8-16 hr.
The second aspect of the invention provides a hydrogenation catalyst prepared by the method.
According to some embodiments of the hydrogenation catalyst of the present invention, the hydrogenation catalyst comprises a titanium oxide-alumina composite support, a first active component and a second active component, wherein the first active component is molybdenum oxide and the second active component is cobalt oxide and/or nickel oxide, and the first active component is 7.5 to 20 wt%, preferably 10 to 18 wt%, the second active component is 1 to 15 wt%, preferably 4 to 8 wt%, and the titanium oxide-alumina composite support is 65 to 91 wt%, preferably 74 to 86 wt%, based on the total weight of the hydrogenation catalyst.
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). The low temperature activity and stability of the hydrogenation catalyst are better when the weight ratio of the first active component to the second active component is within the preferred range of the present invention.
According to a preferred embodiment of the 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 has a better catalytic effect.
The hydrogenation catalyst prepared by the method of the invention has uniform distribution of titanium atoms, aluminum atoms, cobalt atoms, molybdenum atoms and nickel atoms. The carrier can be characterized specifically by SEM-Mapping using a scanning electron microscope. The specific characterization method can be as follows: and (3) coating the ground sample on conductive adhesive, spraying metal on the surface of the sample 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, 1b, 1c, 1d and 1e, and it can be seen from the figures 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 (because the original figure is a color chart, the uniform distribution can be clearly seen, and the display effect is affected after the hydrogenation catalyst is set to a black-and-white chart).
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 C 6 ～C 8 、C 9 ～C 10 Pyrolysis gas of fractionAnd (3) oil.
In the present invention, preferably, the hydrogenation conditions include: the inlet temperature of the reactor is 220-300 ℃, preferably 240-250 ℃ and the space velocity is 1-4h -1 The volume ratio of hydrogen to oil is 300-800:1, and the pressure is 2.5-3.5Mpa.
In a preferred embodiment of the invention, the pyrolysis gasoline is C 6 ～C 8 In the case of cut pyrolysis gasoline, the hydrogenation conditions include: 220-280 deg.c, preferably 240-250 deg.c, and airspeed of 2-4 hr -1 The volume ratio of hydrogen to oil is 300-500:1, and the pressure is 2.5-3.5Mpa.
In another preferred embodiment of the invention, the pyrolysis gasoline is C 9 ～C 10 In the case of cut pyrolysis gasoline, the hydrogenation conditions include: 220-300 ℃, preferably 240-250 ℃ and airspeed of 1-2h -1 The volume ratio of hydrogen to oil is 400-800:1, and the pressure is 2.5-3.5Mpa.
The hydrogenation catalyst may be sulfided prior to reaction, and the sulfiding may be carried out as conventional in the art, for example, by using a cyclohexane solution having a DMDS (dimethyl disulfide) content of 1-5 wt% at a hydrogen oil volume ratio of 100-200:1 at a reactor temperature of 280-350℃and a volume space velocity of 1-2h -1 Vulcanizing for 10-24h, and reducing the temperature to room temperature after vulcanizing.
Compared with the existing hydrogenation catalyst, the hydrogenation catalyst provided by the invention has the advantages of good low-temperature activity, high hydrogenation activity and good stability under high airspeed in the field of pyrolysis gasoline hydrogenation, can realize continuous production, has low production cost, and does not generate waste water and waste gas in the production process.
Drawings
FIG. 1a is an SEM-Mapping graph of the distribution of aluminum atoms in a hydrogenation catalyst according to example 1 of the present invention;
FIG. 1b is an SEM-Mapping graph of the distribution of titanium atoms in a hydrogenation catalyst according to example 1 of the present invention;
FIG. 1c is an SEM-Mapping graph of cobalt atom distribution in a hydrogenation catalyst according to example 1 of the present invention;
FIG. 1d is an SEM-Mapping graph of molybdenum atom distribution in the hydrogenation catalyst according to example 1 of the present invention;
FIG. 1e is an SEM-Mapping graph of nickel atom distribution in a hydrogenation catalyst according to example 1 of the present invention.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
The test method of the invention is as follows:
(1) Measurement of median particle size reference standard NB/SH/T0951-2017, determination of particle size distribution of catalytic cracking catalyst laser scattering method.
(2) SEM-Mapping characterization method: and (3) coating the ground sample on conductive adhesive, spraying metal on the surface of the sample 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 200m 2 Per gram, pore volume of 1 mL/g) and meta-titanic acid are added into deionized water for uniform mixing, wherein the weight ratio of the alumina to the meta-titanic acid is 5:1, and the weight ratio of the total weight of the alumina and the meta-titanic acid to the solvent is 5:4. After mixing uniformly, a mixture I is obtained. Placing the mixture I into a high-energy planetary ball mill for planetary ball milling, wherein the revolution speed of the ball milling is 200r/min, the rotation speed of the ball milling is 500r/min, the high-energy ball milling is carried out for 8 hours, the mixture II with the median particle diameter of 0.087 mu m is obtained after the ball milling, drying the mixture II in an oven at 120 ℃ overnight, placing the obtained dried product into a screw extruder, adding aqueous solution of nitric acid (the solute is nitric acid, the solvent is deionized water, and the concentration of the solute is 2 wt%), wherein the weight ratio of deionized water in the acid solution to the dried product is 3:5, extruding the mixture into strips, drying the strips at 110 ℃ for 5 hours, and then placing the dried product into a muffle furnace for roasting at 550 ℃ for 6 hours, thus obtaining the titanium oxide-aluminum oxide composite carrier A-1.
An aqueous ammonium molybdate tetrahydrate solution (per 100 mL) was prepared at a concentration of 26.68g/100mLThe deionized water contains 26.68g of ammonium molybdate tetrahydrate), then 5mL of ammonia water with the concentration of 14 wt% is added to enable the ammonium molybdate tetrahydrate to be fully dissolved, then 100g of titanium oxide-aluminum oxide composite carrier A-1 is taken, immersed for 2 hours at normal temperature, filtered, dried for 4 hours at 110 ℃, and baked for 4 hours at 550 ℃ to obtain the precursor. The precursor was then impregnated with an aqueous solution of nickel nitrate hexahydrate at a concentration of 23.48g/100mL and cobalt nitrate hexahydrate at a concentration of 11.62g/100mL (each 100mL of deionized water containing 23.48g of nickel nitrate hexahydrate and 11.62g of cobalt nitrate hexahydrate), 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. Wherein, based on the total weight of the hydrogenation catalyst, moO 3 15 wt%, coO 2 wt%, niO 4 wt%, and composite titania-alumina carrier 79 wt%, which is MoO 3 -CoO-NiO/Al 2 O 3 -TiO 2 The hydrogenation catalyst A is denoted as hydrogenation catalyst A.
SEM-Mapping characterization of hydrogenation catalyst A was performed, and the characterization results are shown in FIG. 1a, FIG. 1b, FIG. 1c, FIG. 1d and FIG. 1e. From the figure, it can be seen that the aluminum atoms, titanium atoms, cobalt atoms, molybdenum atoms and nickel atoms of the hydrogenation catalyst A prepared by the present invention are uniformly distributed.
[ example 2 ]
This example illustrates the preparation of a hydrogenation catalyst.
Alumina (specific surface area 150m 2 Per gram, pore volume of 0.8 mL/g) and meta-titanic acid are added into deionized water for uniform mixing, wherein the weight ratio of the alumina to the meta-titanic acid is 6:1, and the weight ratio of the total weight of the alumina and the meta-titanic acid to the solvent is 1:1. After mixing uniformly, a mixture I is obtained. Placing the mixture I into a high-energy planetary ball mill for planetary ball milling, wherein the revolution speed of the ball milling is 300r/min, the rotation speed of the ball milling is 600r/min, the high-energy ball milling is carried out for 8 hours, the mixture II with the median particle diameter of 0.093 mu m is obtained after the ball milling, the mixture II is placed into an oven for drying at 120 ℃ overnight, the obtained dried product is placed into a screw extruder, nitric acid aqueous solution (the solute is nitric acid, the solvent is deionized water, the concentration of the solute is 1.8 wt%) is added, wherein the weight ratio of deionized water in the acid liquid to the dried product is 4:5, and the extrusion is carried outShaping, drying at 130 ℃ for 3 hours, and then placing the shaped product into a muffle furnace for roasting at 800 ℃ for 4 hours to obtain the titanium oxide-aluminum oxide composite carrier B-1.
Preparing 26.68g/100mL of ammonium molybdate tetrahydrate aqueous solution, adding 5mL of ammonia water with the concentration of 14 wt% to fully dissolve the ammonium molybdate tetrahydrate, soaking 100g of titanium oxide-aluminum oxide composite carrier B-1 at normal temperature for 2h, filtering, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 4h. Then, the precursor prepared by roasting is impregnated with an aqueous solution of nickel nitrate hexahydrate with the concentration of 17.61g/100mL and cobalt nitrate hexahydrate with the concentration of 20.34g/100mL, impregnated for 2 hours at normal temperature, filtered, dried for 4 hours at 110 ℃ and roasted for 4 hours at 550 ℃ to obtain the hydrogenation catalyst. Wherein, based on the total weight of the hydrogenation catalyst, moO 3 15 wt%, coO 3.5 wt%, niO 3 wt%, and titania-alumina composite carrier 78.5 wt%, which is MoO 3 -CoO-NiO/Al 2 O 3 -TiO 2 The hydrogenation catalyst B is denoted as hydrogenation catalyst B.
SEM-Mapping characterization of hydrogenation catalyst B was performed with similar results as in FIGS. 1a, 1B, 1c, 1d and 1e. The aluminum atoms, titanium atoms, cobalt atoms, molybdenum atoms and nickel atoms of the hydrogenation catalyst B prepared by the method are uniformly distributed.
[ example 3 ]
This example illustrates the preparation of a hydrogenation catalyst.
Alumina (specific surface area 300m 2 Per gram, pore volume of 1.2 mL/g) and meta-titanic acid are added into deionized water for uniform mixing, wherein the weight ratio of the alumina to the meta-titanic acid is 7:1, and the weight ratio of the total weight of the alumina and the meta-titanic acid to the solvent is 5:3. After mixing uniformly, a mixture I is obtained. Placing the mixture I into a high-energy planetary ball mill for planetary ball milling, wherein the revolution speed of the ball milling is 300r/min, the rotation speed of the ball milling is 300r/min, the high-energy ball milling is carried out for 10 hours, the mixture II with the median particle diameter of 0.082 mu m is obtained after the ball milling, the mixture II is placed into an oven for drying at 120 ℃ overnight, the obtained dried product is placed into a screw extruder, and hydrochloric acid aqueous solution (the solute is hydrochloric acid, the solvent is deionized water, and the concentration of the solute is 2.5 wt%) is added, wherein the acidThe weight ratio of deionized water to the dried product in the solution is 2:5, the mixture is extruded and molded, dried for 3 hours at 150 ℃, and then put into a muffle furnace for roasting for 12 hours at 550 ℃ to obtain the titanium oxide-aluminum oxide composite carrier C-1.
Preparing an aqueous solution of ammonium molybdate tetrahydrate with the concentration of 32.56g/100mL, adding 5mL of ammonia water with the concentration of 14 wt% to enable the ammonium molybdate tetrahydrate to be fully dissolved, soaking 100g of titanium oxide-aluminum oxide composite carrier C-1 at normal temperature for 2h, filtering, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 4h. Then, the precursor prepared by roasting is impregnated with an aqueous solution of nickel nitrate hexahydrate with the concentration of 17.61g/100mL and cobalt nitrate hexahydrate with the concentration of 11.62g/100mL, impregnated for 2 hours at normal temperature, filtered, dried for 4 hours at 110 ℃ and roasted for 4 hours at 550 ℃ to obtain the hydrogenation catalyst. Wherein, based on the total weight of the hydrogenation catalyst, moO 3 18 wt%, coO 2 wt%, niO 3 wt%, and composite titania-alumina carrier 77 wt%, which is MoO 3 -CoO-NiO/Al 2 O 3 -TiO 2 The weight ratio of the total weight of the nickel oxide and the cobalt oxide to the molybdenum oxide of the hydrogenation catalyst C is 0.28:1, which is marked as the hydrogenation catalyst C.
SEM-Mapping characterization of hydrogenation catalyst C was performed with similar results as in FIGS. 1a, 1b, 1C, 1d and 1e. The aluminum atoms, titanium atoms, cobalt atoms, molybdenum atoms and nickel atoms of the hydrogenation catalyst C prepared by the method are uniformly distributed.
[ example 4 ]
A titanium oxide-alumina composite support C-1 was prepared as in example 3, except that the hydrogenation catalyst was prepared as follows:
preparing an ammonium molybdate tetrahydrate aqueous solution with the concentration of 18.28g/100mL, adding 5mL of ammonia water with the concentration of 14 wt% to enable the ammonium molybdate tetrahydrate to be fully dissolved, soaking 100g of titanium oxide-aluminum oxide composite carrier C-1 at normal temperature for 2h, filtering, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 4h. Then, the precursor prepared by roasting is impregnated with aqueous solution of nickel nitrate hexahydrate with the concentration of 11.86g/100mL and cobalt nitrate hexahydrate with the concentration of 34.94g/100mL, impregnated for 2 hours at normal temperature, filtered, dried for 4 hours at 110 ℃ and roasted for 4 hours at 550 ℃ to obtain the hydrogenation catalyst.Wherein, based on the total weight of the hydrogenation catalyst, moO 3 The content of the composite carrier is 10 weight percent, the content of CoO is 6 weight percent, the content of NiO is 2 weight percent, and the content of the titanium oxide-aluminum oxide composite carrier is 82 weight percent, namely MoO 3 -CoO-NiO/Al 2 O 3 -TiO 2 The hydrogenation catalyst D is denoted as hydrogenation catalyst D.
SEM-Mapping characterization of hydrogenation catalyst D was performed with similar results as in FIGS. 1a, 1b, 1c, 1D and 1e. The aluminum atoms, titanium atoms, cobalt atoms, molybdenum atoms and nickel atoms of the hydrogenation catalyst D prepared by the method are uniformly distributed.
[ example 5 ]
A titanium oxide-alumina composite support C-1 was prepared as in example 3, except that the hydrogenation catalyst was prepared as follows:
preparing an ammonium molybdate tetrahydrate aqueous solution with the concentration of 38.76g/100mL, adding 5mL of ammonia water with the concentration of 14 wt% to enable the ammonium molybdate tetrahydrate to be fully dissolved, soaking 100g of titanium oxide-aluminum oxide composite carrier C-1 at normal temperature for 2h, filtering, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 4h. Then, the precursor prepared by roasting is impregnated with an aqueous solution of nickel nitrate hexahydrate with the concentration of 17.61g/100mL and cobalt nitrate hexahydrate with the concentration of 6.32g/100mL, impregnated for 2 hours at normal temperature, filtered, dried for 4 hours at 110 ℃ and roasted for 4 hours at 550 ℃ to obtain the hydrogenation catalyst. Wherein, based on the total weight of the hydrogenation catalyst, moO 3 The content of the titanium oxide-aluminum oxide composite carrier is 20 weight percent, the CoO content is 1 weight percent, the NiO content is 3 weight percent, and the content of the titanium oxide-aluminum oxide composite carrier is 76 weight percent, namely MoO 3 -CoO-NiO/Al 2 O 3 -TiO 2 The hydrogenation catalyst E is denoted as hydrogenation catalyst E.
SEM-Mapping characterization of hydrogenation catalyst E was performed with similar results as in FIGS. 1a, 1b, 1c, 1d and 1E. The aluminum atoms, titanium atoms, cobalt atoms, molybdenum atoms and nickel atoms of the hydrogenation catalyst E prepared by the method are uniformly distributed.
Comparative example 1
Alumina (specific surface area 200m 2 Per gram, pore volume of 1 mL/g) and meta-titanic acid are added into deionized water for uniform mixingAnd 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 uniformly, a mixture I is obtained. And then putting the mixture II into an oven for drying overnight at 120 ℃, putting the obtained dried product into a screw extruder, adding aqueous solution of nitric acid (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 the mixture into strips, drying the strips at 110 ℃ for 5 hours, and then putting the strips into a muffle furnace for roasting at 550 ℃ for 6 hours to obtain the titanium oxide-aluminum oxide composite carrier DBL-1.
Preparing 26.68g/100mL of ammonium molybdate tetrahydrate aqueous solution, adding 5mL of ammonia water with the concentration of 14 wt% to enable the ammonium molybdate tetrahydrate to be fully dissolved, taking 100g of composite carrier DBL-1, soaking for 2h at normal temperature, filtering, drying for 4h at 110 ℃, and roasting for 4h at 550 ℃ to obtain a precursor. Then, the precursor was impregnated with an aqueous solution of nickel nitrate hexahydrate at a concentration of 23.48g/100mL and cobalt nitrate hexahydrate at a concentration of 11.62g/100mL, immersed 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, which was designated as hydrogenation catalyst DC-1.
Comparative example 2
Titanium oxide-alumina composite support DBL-2 was prepared as in example 1 of CN 1184289C.
The specific operation is as follows:
taking a specific surface area of 160 meters 2 Per gram, 90 g of clover-shaped alumina with a pore volume of 0.58 ml/g and a most probable pore diameter of 130 angstrom, is immersed in 0.557 g/ml of dilute sulfuric acid solution of 53 ml of titanium sulfate, stirred for 15 minutes, dried at 120 ℃ for 8 hours and then calcined 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 m 2 Per gram, pore volume is 0.56 ml/gram, and the most probable pore diameter is 125 angstroms.
Preparing 26.68g/100mL of ammonium molybdate tetrahydrate aqueous solution, adding 5mL of ammonia water with the concentration of 14 wt% to enable the ammonium molybdate tetrahydrate to be fully dissolved, taking 100g of composite carrier DBL-2, soaking for 2h at normal temperature, filtering, drying for 4h at 110 ℃, and roasting for 4h at 550 ℃ to obtain a precursor. Then, the precursor was impregnated with an aqueous solution of nickel nitrate hexahydrate at a concentration of 17.61g/100mL and cobalt nitrate hexahydrate at a concentration of 20.34g/100mL, immersed 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, which was designated as hydrogenation catalyst DC-2.
[ comparative example 3 ]
The procedure of example 1 was followed except that the mixture II having a median particle diameter of 0.087 μm after ball milling was replaced with the mixture II having a median particle diameter of 1.5 μm after ball milling. Obtaining the hydrogenation protective agent DC-3.
Test example 1
Benzene making device C using China petrochemical, yanshan petrochemical and olefin part 6 ～C 8 The 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) 2 100g of oil). Hydrogenation catalysts A, B, C, D, E, DC to DC3 (loading was 100 mL) were each subjected to comparative evaluation. The evaluation conditions and product analysis are shown in Table 1.
TABLE 1
Test example 2
Benzene making device C using China petrochemical, yanshan petrochemical and olefin part 6 ～C 8 The 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) 2 100g of oil). Comparative evaluations were conducted on hydrogenation catalyst B and DC2 (loading of 100mL each). The evaluation conditions and product analysis are shown in Table 2.
TABLE 2
Test example 3
Chemical industry factory C of Dushantian Li Gao New company from Xinjiang 9 ～C 10 Fraction two-stage hydrogenation raw material, total sulfur content of raw material is 400ppm, bromine number is 29 (gBr) 2 100g of oil). Hydrogenation catalysts A and DC1 (loading was 100 mL) were evaluated for comparison. The evaluation conditions and product analysis are shown in Table 3.
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 cracked gasoline hydrogenation. And can realize continuous production, has low preparation cost and is suitable for large-scale industrial production.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (35)
1. A method of preparing a hydrogenation catalyst comprising:
(1) Mixing aluminum oxide, meta-titanic acid and a solvent to obtain a mixture I;
(2) Performing high-energy ball milling on the mixture I to obtain a mixture II with the median particle diameter smaller than 0.1 mu m;
(3) Performing first drying on the mixture II, mixing the obtained dried product with acid liquor, and sequentially performing forming, second drying and first roasting to obtain a titanium oxide-aluminum oxide composite carrier;
(4) Impregnating the titanium oxide-aluminum oxide composite carrier with a solution containing a compound of a first active element and a compound of a second active element, and performing third drying and second roasting, wherein the first active element is molybdenum element, and the second active element is cobalt element and nickel element;
the specific surface area of the alumina is 150-300m 2 Per gram, the pore volume is 0.6-1.2mL/g;
the weight ratio of the alumina to the meta-titanic acid is (5-10): 1.
2. the method of claim 1, wherein the alumina has a pore volume of 0.8-1mL/g.
3. The method according to claim 1, wherein the weight ratio of alumina to meta-titanic acid is (5-7): 1.
4. the method according to claim 1, wherein the weight ratio of the total weight of alumina and meta-titanic acid to the solvent is 5: (1-5).
5. The method of claim 1, wherein the solvent is one or more of deionized water, ethanol, and methanol.
6. The method of any one of claims 1-5, wherein the conditions of 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 70-670r/min.
7. The method of claim 6, wherein the high energy ball milling is stirred ball milling, vibratory ball milling or planetary ball milling.
8. The method of claim 7, wherein the high energy ball milling is planetary ball milling.
9. The method according to any one of claims 1-5, 7-8, wherein the solute in the acid liquor is an organic acid and/or an inorganic acid; and/or the solvent in the acid liquor is deionized water.
10. The method according to claim 9, wherein the weight ratio of acid solution to dry product in terms of solvent is (1-4): 5.
11. the method of claim 10, wherein the weight ratio of acid solution to dry product, calculated as solvent, is (2-4): 5.
12. the method of claim 9, wherein the concentration of solute in the acid solution is 0.5-4 wt%.
13. The method of claim 9, wherein the organic acid is one or more of acetic acid, oxalic acid, citric acid, and tartaric acid.
14. The method of claim 9, wherein the mineral acid is one or more of hydrochloric acid, sulfuric acid, and nitric acid.
15. The method of claim 9, wherein the mineral acid is nitric acid.
16. The method according to any one of claims 1 to 5, 7 to 8, 10 to 15, wherein the compound containing the first active element is one or more of ammonium molybdate, molybdenum nitrate and molybdenum chloride.
17. The method of claim 16, wherein the compound containing the first active element is ammonium molybdate.
18. The method according to any one of claims 1 to 5, 7 to 8, 10 to 15, 17, wherein 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.
19. The method of claim 18, wherein the compound containing the second active element is nickel nitrate and cobalt nitrate.
20. The method according to any one of claims 1 to 5, 7 to 8, 10 to 15, 17, 19, wherein the amounts of the compound containing the first active element and the compound containing the second active element are such that the content of the first active component is 7.5 to 20% by weight, the content of the second active component is 1 to 15% by weight, and the content of the titania-alumina composite support is 65 to 91% by weight, 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.
21. The method of claim 20, wherein the first active component is present in an amount of 10 to 18 wt%, the second active component is present in an amount of 4 to 8 wt%, and the titania-alumina composite support is present in an amount of 74 to 86 wt%.
22. The method of claim 21, wherein the weight ratio of cobalt oxide to nickel oxide is 1: (0.1-10).
23. The method of claim 22, wherein the weight ratio of cobalt oxide to nickel oxide is 1: (0.2-5).
24. The method according to any one of claims 1 to 5, 7 to 8, 10 to 15, 17, 19, 21 to 23, wherein the compound containing a first active element and the compound containing a second active element are fed in amounts 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).
25. The method of claim 24, wherein the weight ratio of the oxide of the first active element to the oxide of the second active element is 1: (0.2-0.8).
26. The method of claim 25, wherein the weight ratio of the oxide of the first active element to the oxide of the second active element is 1: (0.4-0.6).
27. The method of any one of claims 1-5, 7-8, 10-15, 17, 19, 21-23, 25-26, wherein the conditions of the first, second, and third drying each independently comprise: the temperature is 110-150 ℃ and the time is 2-16h.
28. The method of claim 27, wherein the temperature is 110-130 ℃ for a period of 3-12 hours.
29. The method of any one of claims 1-5, 7-8, 10-15, 17, 19, 21-23, 25-26, 28, wherein the conditions of the first firing and the second firing each independently comprise: the temperature is 500-900 ℃ and the time is 3-16h.
30. The method of claim 29, wherein the temperature is 550-800 ℃ for a period of 4-12 hours.
31. A hydrogenation catalyst prepared by the process of any one of claims 1-30.
32. Use of a hydrogenation catalyst according to claim 31 and/or a hydrogenation catalyst prepared according to the method of any one of claims 1 to 30 in the hydrogenation of pyrolysis gasoline.
33. The use according to claim 32, characterized in that the pyrolysis gasoline is C 6 ～C 8 、C 9 ～C 10 Pyrolysis gasoline of fraction.
34. The use according to claim 32 or 33, characterized in that the hydrogenation conditions comprise: the inlet temperature of the reactor is 220-300 ℃ and the airspeed is 1-4h -1 The volume ratio of hydrogen to oil is 300-800:1, and the pressure is 2.5-3.5Mpa.
35. The use according to claim 34, characterized in that the reactor inlet temperature is 240-250 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010397800.7A CN113649016B (en) | 2020-05-12 | 2020-05-12 | Hydrogenation catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010397800.7A CN113649016B (en) | 2020-05-12 | 2020-05-12 | Hydrogenation catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113649016A CN113649016A (en) | 2021-11-16 |
| CN113649016B true CN113649016B (en) | 2023-11-10 |
Family
ID=78488704
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010397800.7A Active CN113649016B (en) | 2020-05-12 | 2020-05-12 | Hydrogenation catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113649016B (en) |
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 |
-
2020
- 2020-05-12 CN CN202010397800.7A patent/CN113649016B/en active Active
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113649016A (en) | 2021-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101618326B (en) | Heavy oil hydrogenation processing catalyst and method for preparing same | |
| JP5501483B2 (en) | Method for producing hydrotreating catalyst | |
| CN104540585B (en) | Improvement Residual oil hydrotreating catalyst comprising titanium dioxide | |
| JP2011502050A (en) | Selective nickel-based hydrogenation catalyst and its production | |
| WO2011103698A1 (en) | Hydro refining catalyst | |
| CN109304183B (en) | Hydrotreating catalyst for treating inferior oil and its prepn and application | |
| CN110773209A (en) | Heavy oil hydrogenation deasphaltened catalyst and preparation and application thereof | |
| CN104437578B (en) | Hydrodesulfurization catalyst, preparation method and applications thereof | |
| CN113649016B (en) | Hydrogenation catalyst and preparation method and application thereof | |
| CN110773183A (en) | Heavy oil hydrogenation deasphaltened catalyst and preparation and application thereof | |
| CN112547034A (en) | Residual oil hydrotreating catalyst and preparation method thereof | |
| CN112275310A (en) | Heavy aromatic hydrocarbon lightening catalyst based on VIB and VIII group composite metal elements and preparation method and application thereof | |
| CN113649080B (en) | Hydrogenation protective agent and preparation method and application thereof | |
| CN103801333B (en) | The preparation method of a kind of year sulfur type hydrogenation catalyst | |
| CN110773187A (en) | Heavy oil hydrogenation deasphaltened catalyst and preparation and application thereof | |
| CN113649079B (en) | Titanium oxide-aluminum oxide composite carrier and preparation method and application thereof | |
| CN105473225A (en) | Production of mixed alcohols from synthesis gas | |
| CN111097500B (en) | Supported catalyst, preparation method and application thereof, and method for hydrotreating diesel fraction | |
| CN104437571B (en) | A kind of Hydrobon catalyst, preparation method and applications | |
| CN112934209A (en) | High-desulfurization-activity hydrotreating catalyst carrier and preparation method of catalyst | |
| CN102861601A (en) | Hydrogenation catalyst containing fluorine and preparation method thereof | |
| CN113856694A (en) | Sulfurized hydrogenation catalyst, and preparation method and application thereof | |
| CN112742404A (en) | Gasoline selective hydrodesulfurization catalyst, preparation method and application thereof, and gasoline selective hydrodesulfurization method | |
| CN111097436A (en) | Heavy oil hydrotreating catalyst and preparation method and application thereof | |
| CN115990487B (en) | Hydrogenation catalyst and heavy oil hydrotreating method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |