CN113649079A - Titanium oxide-aluminum oxide composite carrier and preparation method and application thereof - Google Patents
Titanium oxide-aluminum oxide composite carrier and preparation method and application thereof Download PDFInfo
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- CN113649079A CN113649079A CN202010398288.8A CN202010398288A CN113649079A CN 113649079 A CN113649079 A CN 113649079A CN 202010398288 A CN202010398288 A CN 202010398288A CN 113649079 A CN113649079 A CN 113649079A
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- alumina
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- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- DCRIQAAPAFMPKP-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Al+3].[Ti+4] DCRIQAAPAFMPKP-UHFFFAOYSA-N 0.000 title abstract description 13
- 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 78
- 239000002253 acid Substances 0.000 claims abstract description 49
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 28
- 239000010936 titanium Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 10
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 98
- 238000000034 method Methods 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000000498 ball milling Methods 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 238000000197 pyrolysis Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 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
- 238000001354 calcination Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 238000001125 extrusion Methods 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
- 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
- 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
- 239000007788 liquid Substances 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 description 54
- 238000012512 characterization method Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 238000013507 mapping Methods 0.000 description 17
- 239000003223 protective agent Substances 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 13
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 13
- 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 13
- 239000002243 precursor Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000009827 uniform distribution Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 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 3
- 230000007547 defect Effects 0.000 description 3
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical group [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 150000001336 alkenes Chemical group 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-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
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 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
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a titanium oxide-aluminum oxide composite carrier and a preparation method and application thereof. The preparation method of the titanium oxide-aluminum oxide composite carrier 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) drying the mixture II, mixing the obtained dried product with acid liquor, and sequentially forming, drying and bakingAnd (6) burning. The titanium source used by the preparation method has low cost and less pollution in the preparation process, and the TiO in the obtained titanium oxide-aluminum oxide composite carrier2The distribution is uniform.
Description
Technical Field
The invention belongs to the field of composite oxides, and particularly relates to a titanium oxide-aluminum oxide composite carrier and a preparation method and application thereof.
Background
TiO2The hydrogenation catalyst developed as the carrier has the characteristics of high activity, good low-temperature activity, strong anti-poisoning property and the like, but TiO2The catalyst support also has some weaknesses, such as relatively small specific surface area, easy conversion of active anatase into inert rutile structure at high temperature, poor mechanical strength and weak acidity, generally through TiO formation2-Al2O3And the composite oxide is used as a carrier to overcome the defects and reach the standard of industrial application. Conventional industrial production of TiO-containing2The method for preparing the composite carrier comprises an impregnation method, a coprecipitation method and a kneading method, wherein the impregnation method mainly adopts organic matters of titanium such as tetraethyl titanate, tetrabutyl titanate and the like as active components to impregnate the formed alumina, the coprecipitation method of the organic matters can adopt titanium chloride or metatitanic acid dissolved by concentrated sulfuric acid as a titanium source, and the methods need to use an expensive organic titanium source or pre-treat the metatitanic acid by concentrated acid and/or concentrated alkali, so that the problems of corrosion of pipelines and containers can occur, and anions influencing subsequent production can be generated, so that the production cost is high, and pollution emission is caused. Preparation of TiO-containing materials by kneading2With a content of metatitanic acidIncrease height and appear TiO in the composite carrier2Uneven distribution, and the surface activity of the carrier is inferior to that of the catalyst prepared by an impregnation method or a coprecipitation method, thereby influencing the hydrogenation activity and stability of the catalyst under the condition of high space velocity.
Therefore, the prior art for preparing the titanium oxide-alumina composite carrier has the defects of expensive titanium source, corrosion of pipelines and containers, pollutant generation and TiO in the titanium oxide-alumina composite carrier2Uneven distribution and thus influence the hydrogenation activity and stability.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a titanium oxide-alumina composite carrier, a preparation method and an application thereof aiming at the defects of the prior art, wherein the titanium source used in the preparation method has low cost, so that the preparation cost is reduced, the pollution in the preparation process is small, the requirement on equipment is low, and the TiO in the obtained titanium oxide-alumina composite carrier2The distribution is uniform, and the hydrogenation catalyst and the hydrogenation protective agent prepared by the titanium oxide-alumina composite carrier have the advantages of high hydrogenation activity and good stability.
To this end, a first aspect of the present invention provides a method for preparing a titania-alumina composite carrier, 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) and drying the mixture II, mixing the obtained dried product with acid liquor, and sequentially forming, drying and roasting.
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 preparation method 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 method of manufacturing of the present invention, the drying conditions comprise: the temperature is 110-150 ℃, preferably 110-130 ℃, and the time is 2-16h, preferably 3-12 h. The drying conditions are such as to evaporate the water present in the mixture II. 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 acid solution comprises a solute and a solvent. Further preferably, 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 solute concentration in the acid solution is 0.5-4 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 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. "acid solution in terms of solvent" means calculated on the solvent in the acid solution.
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, 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 method of manufacturing of the present invention, the drying conditions include: 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 firing include: 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.
In a second aspect, the invention provides a titania-alumina composite carrier prepared by the above method.
The titanium oxide-aluminum oxide composite carrier prepared by the method of the invention, TiO in the carrier2And Al2O3The distribution is uniform, and 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 characterization result can be shown in fig. 1a and 1b, and it can be seen from fig. 1a and 1b that the distribution of aluminum atoms and titanium atoms of the titania-alumina composite carrier prepared by the present invention is uniform (since the original image is a color image, it can be clearly seen that the uniform distribution is observed, and the display effect is affected after the arrangement is a black-and-white image).
In a third aspect, the present invention provides the use of the above titania-alumina composite support and/or the titania-alumina composite support prepared according to the above method in pyrolysis gasoline hydrogenation and DCC pyrolysis naphtha hydrogenation. The application in pyrolysis gasoline hydrogenation and DCC pyrolysis naphtha hydrogenation.
The term "DCC" as used herein refers to catalytic cracking. According to the present invention DCC cracked naphtha refers to cracked naphtha produced by catalytic cracking.
In an embodiment of the present invention, the hydrogenation catalyst is prepared by loading a first active component and a second active component on the above titanium oxide-alumina composite carrier, wherein the first active component is molybdenum oxide, and the second active component is cobalt oxide and nickel oxide. Preferably, the content of the first active component is 12-20 wt% and the content of the second active component is 1-15 wt% based on the total weight of the hydrogenation catalyst. Preferably, the content of cobalt oxide in the second active component is 0.5-14.5 wt%, and the content of nickel oxide in the second active component is 0.5-14.5 wt%And (4) percent of the total amount. The hydrogenation catalyst is applied to C of pyrolysis gasoline6～C8、C9～C10In the distillate hydrogenation process, the method has the characteristics of good low-temperature activity, high hydrogenation activity at high airspeed and good stability.
According to a specific embodiment of the present invention, the preparation method of the hydrogenation catalyst comprises: and (2) impregnating the compound containing the first active component and the compound containing the second active component in the titanium oxide-alumina composite carrier, drying and roasting to obtain the hydrogenation catalyst, wherein the first active component is molybdenum element, and the second active component is cobalt element and nickel element. Preferably, the compound comprising the first active component is ammonium molybdate. Preferably, the compound containing the second active component is nickel nitrate or cobalt nitrate. Preferably, the drying conditions include: the temperature is 110-150 ℃, preferably 110-130 ℃, and the time is 2-16h, preferably 3-12 h. Preferably, the conditions of the calcination include: the temperature is 500-900 ℃, preferably 550-800 ℃ and the time is 3-16h, preferably 4-12 h.
And performing SEM-Mapping on the prepared hydrogenation catalyst for characterization. The results of the characterization can be shown in fig. 2a, 2b, 2c, 2d and 2e, and it can be seen from the figure that the aluminum atoms, titanium atoms, molybdenum atoms, cobalt atoms and nickel atoms of the hydrogenation catalyst prepared by the present invention are uniformly distributed (since the original image is a color image, the uniform distribution can be clearly seen, and the display effect is affected after the arrangement as a black-and-white image).
According to a preferred embodiment of the present invention, the above hydrogenation catalyst is applied to C of pyrolysis gasoline6～C8、C9～C10In the distillate hydrogenation process. Before hydrogenation 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 ℃ and 350 ℃, the hydrogen-oil volume ratio is 100--1And vulcanizing for 10-24h, and reducing the temperature to room temperature after vulcanization.
Preferably, the above hydrogenation catalyst is applied to the cracked steamC of oil6-C8When fraction hydrogenation is carried out, the inlet temperature of the reactor is 220 ℃ and 280 ℃, and the volume space velocity is 2-4h-1The hydrogen-oil volume ratio is 300-500:1, and the pressure is 2.5-3.5 Mp.
Preferably, the hydrogenation catalyst is applied to C of pyrolysis gasoline9～C10When fraction hydrogenation is carried out, the inlet temperature of the reactor is 220 ℃ and 300 ℃, and the volume space velocity is 1-2h-1The volume ratio of hydrogen to oil is 400-800:1, and the pressure is 2.5-3.5 Mpa.
In another embodiment of the invention, the hydrogenation protective agent is obtained by loading molybdenum oxide and nickel oxide on the titanium oxide-alumina composite carrier. Preferably, the molybdenum oxide is present in an amount of 5 to 20 wt% and the nickel oxide is present in an amount of 4 to 15 wt%, based on the total weight of the hydrogenation protection agent. The hydrogenation protective agent is applied to the hydrogenation process of DCC cracked naphtha, and has the characteristics of good low-temperature activity, capability of reducing the inlet temperature of a reactor and improvement on the operation stability of the device.
According to a specific embodiment of the present invention, the preparation method of the hydrogenation protective agent comprises: and (3) impregnating the titanium oxide-alumina composite carrier with a molybdenum-containing compound and a nickel-containing compound, drying and roasting to obtain the hydrogenation protective agent. Preferably, the compound containing molybdenum element is ammonium molybdate. Preferably, the compound containing nickel element is nickel nitrate. Preferably, the drying conditions include: the temperature is 110-150 ℃, preferably 110-130 ℃, and the time is 2-16h, preferably 3-12 h. Preferably, the conditions of the calcination include: the temperature is 500-900 ℃, preferably 550-800 ℃ and the time is 3-16h, preferably 4-12 h.
And performing SEM-Mapping on the prepared hydrogenation protective agent for characterization. The characterization result shows that the aluminum atoms, the titanium atoms, the molybdenum atoms and the nickel atoms of the hydrogenation protective agent prepared by the invention are uniformly distributed.
According to a preferred embodiment of the present invention, the above-described hydrogenation catalyst is applied to a hydrogenation process of DCC cracked naphtha. Before the reaction, the hydrogenation protective agent needs to be vulcanized, and the vulcanization method can be a method conventional in the field, for example, a reaction at 280-350 DEG CAt the reactor temperature, the hydrogen-oil volume ratio is 100-200:1, a cyclohexane solution with the DMDS (dimethyl disulfide) content of 1-5 weight percent is used, and the volume space velocity is 1-2h-1And vulcanizing for 10-24h, and reducing the temperature to room temperature after vulcanization.
Preferably, the conditions of the hydrogenation process of DCC cracked naphtha comprise: the inlet temperature of the reactor is 120-180 ℃, and the volume space velocity is 2-4h-1The hydrogen-oil volume ratio is 300-500:1, and the pressure is 3.5-8 Mpa.
Compared with the existing hydrogenation catalyst and hydrogenation protective agent, the hydrogenation catalyst and hydrogenation protective agent prepared by the titanium oxide-aluminum oxide composite carrier provided by the invention have the advantages of good low-temperature activity, high hydrogenation activity at high space velocity and good stability in the fields of pyrolysis gasoline hydrogenation and DCC naphtha hydrogenation, and the titanium source of the invention is metatitanic acid with relatively low price, so that the problem that the titanium source is expensive in the prior art is solved.
Drawings
FIG. 1a is an SEM-Mapping chart of the distribution of aluminum atoms in a titania-alumina composite carrier provided in example 1 of the present invention;
FIG. 1b is an SEM-Mapping chart of the titanium atom distribution in the titanium oxide-alumina composite carrier provided in example 1 of the present invention;
FIG. 2a is an SEM-Mapping chart of the distribution of aluminum atoms in a hydrogenation catalyst provided in example 4 of the present invention;
FIG. 2b is an SEM-Mapping chart of the distribution of titanium atoms in the hydrogenation catalyst provided in example 4 of the present invention;
FIG. 2c is an SEM-Mapping chart of the distribution of cobalt atoms in the hydrogenation catalyst provided in example 4 of the present invention;
FIG. 2d is an SEM-Mapping chart of the distribution of molybdenum atoms in the hydrogenation catalyst provided in example 4 of the present invention;
FIG. 2e is an SEM-Mapping chart of the distribution of nickel atoms in the hydrogenation catalyst provided in example 4 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 titania-alumina composite support.
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. 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.
SEM-Mapping characterization was performed on the titania-alumina composite carrier A, and the characterization results are shown in FIG. 1a and FIG. 1 b. It can be seen from FIGS. 1a and 1b that the titania-alumina composite carrier A prepared by the present invention has a uniform distribution of aluminum atoms and titanium atoms.
[ example 2 ]
This example illustrates the preparation of a titania-alumina composite support.
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.
And performing SEM-Mapping characterization on the titanium oxide-alumina composite carrier B, wherein the characterization result is similar to that of the figure 1a and the figure 1B. The titanium oxide-aluminum oxide composite carrier B prepared by the invention has uniform distribution of aluminum atoms and titanium atoms.
[ example 3 ]
This example illustrates the preparation of a titania-alumina composite support.
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. Placing the mixture I into a high-energy planetary ball mill for planetary ball milling, wherein the revolution rotating speed of the ball mill is 300r/min, the rotation rotating speed of the ball mill is 300r/min, the high-energy ball mill is 10h, obtaining a mixture II with the median particle size of 0.082 mu m after ball milling, placing the mixture II into an oven for drying overnight at 120 ℃, placing 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 isAnd 2:5, extruding and molding, drying for 3h at 150 ℃, and then roasting for 12h at 550 ℃ in a muffle furnace to obtain the titanium oxide-aluminum oxide composite carrier C.
The titanium oxide-alumina composite carrier C is subjected to SEM-Mapping characterization, and the characterization results are similar to those of FIG. 1a and FIG. 1 b. The titanium oxide-aluminum oxide composite carrier C prepared by the invention has uniform distribution of aluminum atoms and titanium atoms.
[ example 4 ]
This example illustrates the preparation of a hydrogenation catalyst.
Preparing an ammonium molybdate tetrahydrate aqueous solution with the concentration of 26.68g/100mL (26.68 g of ammonium molybdate tetrahydrate is contained in 100mL of deionized water), adding 5mL of ammonia water with the concentration of 14 weight percent to fully dissolve the ammonium molybdate tetrahydrate, taking 100g of the titanium oxide-alumina composite carrier A prepared in the example 1, impregnating for 2h at normal temperature, filtering, drying for 4h at the temperature of 110 ℃, and roasting for 4h at the temperature of 550 ℃ to obtain a precursor. Then the precursor is impregnated with an aqueous solution of nickel nitrate hexahydrate with a concentration of 23.48g/100mL and cobalt nitrate hexahydrate with a concentration of 11.62g/100mL (23.48 g and 11.62g of nickel nitrate hexahydrate per 100mL of deionized water), impregnated at normal temperature for 2h, filtered, dried at 110 ℃ for 4h, and calcined at 550 ℃ for 4h to obtain MoO3Hydrogenation catalyst A (MoO) having a content of 15 wt.%, a CoO content of 2.0 wt.% and a NiO content of 4.0 wt.%3-CoO-NiO/Al2O3-TiO2)。
The hydrogenation catalyst A was subjected to SEM-Mapping characterization, and the results are shown in FIG. 2a, FIG. 2b, FIG. 2c, FIG. 2d and FIG. 2 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, molybdenum atoms, cobalt atoms and nickel atoms.
[ example 5 ]
This example illustrates the preparation of a hydrogenation catalyst.
Preparing an ammonium molybdate tetrahydrate aqueous solution with the concentration of 26.68g/100mL, then adding 5mL of ammonia water with the concentration of 14 weight percent to fully dissolve the ammonium molybdate tetrahydrate, taking 100g of the titanium oxide-alumina composite carrier B prepared in the example 2, dipping for 2h at normal temperature, filtering, drying for 4h at 110 ℃, and roasting for 4h at 550 ℃ to obtain a precursor.Then impregnating the precursor with an aqueous solution of nickel nitrate hexahydrate and cobalt nitrate hexahydrate with the concentration of 17.61g/100mL, impregnating at normal temperature for 2h, filtering, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 4h to obtain MoO3Hydrogenation catalyst B (MoO) having a content of 15 wt.%, a CoO content of 3.5 wt.% and a NiO content of 3.0 wt.%3-CoO-NiO/Al2O3-TiO2)。
SEM-Mapping characterization was performed on hydrogenation catalyst B, and the characterization results were similar to those in FIG. 2a, FIG. 2B, FIG. 2c, FIG. 2d and FIG. 2 e. It can be seen from the figure that the hydrogenation catalyst B prepared by the present invention has a uniform distribution of aluminum atoms, titanium atoms, molybdenum atoms, cobalt atoms and nickel atoms.
[ example 6 ]
This example illustrates the preparation of a hydroprotectant.
Preparing an ammonium molybdate tetrahydrate aqueous solution with the concentration of 15.62g/100mL, then adding 5mL of ammonia water with the concentration of 14 weight percent to fully dissolve the ammonium molybdate tetrahydrate, taking 100g of the titanium oxide-alumina composite carrier C prepared in the example 3, dipping for 2h at normal temperature, filtering, drying for 4h at 110 ℃, and roasting for 4h at 550 ℃ to obtain a precursor. Then impregnating the precursor with aqueous solution of nickel nitrate hexahydrate with the concentration of 55.272g/100mL, impregnating at normal temperature for 2h, filtering, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 4h to obtain MoO3A hydrogenation protective agent C (MoO) with a content of 8.5 wt% and a NiO content of 10.5 wt%3-NiO/Al2O3-TiO2)。
SEM-Mapping characterization was performed on the hydro-protectant C, and the characterization results were similar to those in FIG. 2a, FIG. 2b, FIG. 2d and FIG. 2 e. It can be seen from the figure that the hydrogenation catalyst C prepared by the present invention has uniform distribution of aluminum atoms, titanium atoms, molybdenum atoms and nickel atoms.
[ example 7 ]
A titania-alumina composite carrier was prepared by the method of example 1, except that the specific surface area was set to 200m2The alumina with the pore volume of 1mL/g is replaced by the alumina with the specific surface area of 370m2Alumina with a pore volume of 0.53 mL/g. And a hydrogenation catalyst was prepared as in example 4 and designated hydrogenation catalyst D.
[ example 8 ]
A titania-alumina composite carrier was prepared by the method of example 1, except that the specific surface area was set to 200m2The alumina with the pore volume of 1mL/g is replaced by the alumina with the specific surface area of 350m2Alumina with a pore volume of 1.5 mL/g. And a hydrogenation catalyst was prepared as in example 4 and designated hydrogenation catalyst E.
[ example 9 ]
A titania-alumina composite carrier was prepared according to the method of example 1, except that the weight ratio of alumina to metatitanic acid was 15: 1. and a hydrogenation catalyst was prepared as in example 4 and is designated hydrogenation catalyst F.
[ example 10 ]
A titania-alumina composite carrier was prepared according to the method of example 1, except that the weight ratio of alumina to metatitanic acid was 3: 1. and a hydrogenation catalyst was prepared as in example 4 and designated hydrogenation catalyst G.
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. And (4) uniformly mixing to obtain a mixture. And putting the mixture 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 in the acid solution 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 composite carrier D-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 weight percent to fully dissolve the ammonium molybdate tetrahydrate, taking 100g of the composite carrier D-1, soaking at normal temperature for 2h, filtering, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 4h to obtain the precursor. The precursor was then treated with nickel nitrate hexahydrate at a concentration of 23.48g/100mL and nitric acid hexahydrate at a concentration of 11.62g/100mLSoaking in cobalt water solution at room temperature for 2 hr, filtering, drying at 110 deg.C for 4 hr, and calcining at 550 deg.C for 4 hr to obtain MoO3Hydrogenation catalyst DC-1 (MoO) having a content of 15 wt.%, a CoO content of 2.0 wt.% and a NiO content of 4.0 wt.%3-CoO-NiO/Al2O3-TiO2)。
Comparative example 2
A titania-alumina composite carrier D-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 pore volume of 0.58 ml/g and most probable pore diameter of 130 angstrom is soaked in 53ml of dilute sulfuric acid solution of 0.557 g/ml of titanium sulfate, stirred for 15 min, dried at 120 ℃ for 8h and then roasted at 900 ℃ for 4h to obtain the compound D-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 weight percent to fully dissolve the ammonium molybdate tetrahydrate, taking 100g of the composite carrier D-2, soaking at normal temperature for 2h, filtering, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 4h to obtain the precursor. Then impregnating the precursor with an aqueous solution of nickel nitrate hexahydrate and cobalt nitrate hexahydrate with the concentration of 17.61g/100mL, impregnating at normal temperature for 2h, filtering, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 4h to obtain MoO3Hydrogenation catalyst DC-2 (MoO) having a content of 15 wt.%, a CoO content of 3.5 wt.% and a NiO content of 3.0 wt.%3-CoO-NiO/Al2O3-TiO2)。
Comparative example 3
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. And (4) uniformly mixing to obtain a mixture. Drying the mixture in an oven at 120 deg.C overnight, putting the dried product into a screw rod type extruding machine, and adding nitric acid waterAnd (2) extruding the solution (the solute is nitric acid, the solvent is deionized water, and the concentration of the solute is 2 wt%) at a weight ratio of 3:5, drying at 110 ℃ for 5h, and roasting in a muffle furnace at 550 ℃ for 6h to obtain the composite carrier D-3.
Preparing ammonium molybdate tetrahydrate aqueous solution with the concentration of 26.68g/100mL, then adding 5mL of ammonia water with the concentration of 14 weight percent to fully dissolve the ammonium molybdate tetrahydrate, taking 100g of the composite carrier D-3, soaking at normal temperature for 2h, filtering, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 4h to obtain the precursor. Then impregnating the precursor with aqueous solution of nickel nitrate hexahydrate with the concentration of 55.272g/100mL, impregnating at normal temperature for 2h, filtering, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 4h to obtain MoO3The hydrogenation protective agent DC-3 with the content of 8.5 weight percent and the NiO content of 10.5 weight percent.
Comparative example 4
The procedure is as in example 1, except that, after ball milling, a mixture II having a median particle diameter of 0.15 μm is obtained. A hydrogenation catalyst, designated hydrogenation catalyst DC-4, was prepared according to the procedure of example 4.
[ 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). The hydrogenation catalyst A, B, D, E, F, G and the hydrogenation catalysts DC-1, DC-2 and DC-4 (all having a loading of 100mL) were evaluated in comparison. 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). The comparative evaluation was carried out on the hydrogenation catalyst B and the hydrogenation catalyst DC-2 (both having a loading of 100 mL). 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). The hydrogenation catalyst A, B, D, E, F, G and the hydrogenation catalysts DC-1, DC-2 and DC-4 (all having a loading of 100mL) were evaluated for comparison. The results of the product analysis are shown in Table 3.
TABLE 3
[ test example 4 ]
DCC naphtha hydrogenation raw material of certain chemical plant in Shaanxi is used as raw material, and the diene content of the raw material is 10.5 (gI)2Per 100g of oil) bromine number of 31 (gBr)2Per 100g of oil). Comparative evaluation was carried out on the hydrogenation protective agent C and the hydrogenation protective agent DC-3 (both having a loading of 100 mL). The evaluation conditions and product analysis are shown in Table 4.
TABLE 4
[ test example 5 ]
DCC naphtha hydrogenation raw material of certain chemical plant in Shaanxi is used as raw material, and the diene content of the raw material is 10.5 (gI)2Per 100g of oil) bromine number of 31 (gBr)2Per 100g of oil). 100mL fixed bed reactors are used for series connection, a first-stage reactor is filled with 100mL hydrogenation catalyst B, a first-stage hydrogenation product is used as a raw material at the inlet of a second-stage reactor, and the second-stage reactor is filled with 100mL hydrogenation protective agent C. The results of the evaluation of the hydrogenated product are shown in Table 5.
TABLE 5
As can be seen from FIGS. 1a and 1b, the titanium oxide-alumina composite carrier prepared by the method of the present invention has a uniform distribution of aluminum atoms and titanium atoms, i.e., TiO2The distribution is uniform. And as can be seen from fig. 2a, 2b, 2c, 2d and 2e, the hydrogenation catalyst prepared using the titania-alumina composite carrier 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 to 5 and tables 1 to 5 that the hydrogenation catalyst and the hydrogenation protective agent prepared by using the titanium oxide-alumina composite carrier of the present invention have higher low temperature activity and hydrogenation activity and stability at high space velocity in the fields of pyrolysis gasoline hydrogenation and DCC naphtha hydrogenation, and are suitable for large-scale industrial production due to the use of metatitanic acid as a titanium source, and the preparation cost is low.
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 preparation method of a titanium oxide-alumina composite carrier 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) and drying the mixture II, mixing the obtained dried product with acid liquor, and sequentially forming, drying and roasting.
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.
3. A process according to claim 1 or 2, characterized in that the weight ratio between alumina and 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.
4. The method of any one of claims 1 to 3, wherein the conditions of the high energy ball mill 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.
5. The method according to any one of claims 1 to 4, wherein the drying conditions comprise: the temperature is 110-150 ℃, preferably 110-130 ℃, and the time is 2-16h, preferably 3-12 h.
6. The method according to any one of claims 1 to 5, 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 concentration of solute in the acid liquor is 0.5-4 wt%;
preferably, the weight ratio of the acid liquid to the dried product, calculated as the solvent, is (1-4): 5, preferably (2-4): 5;
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.
7. A method according to any of claims 1-6, characterized in that the method of forming is extrusion.
8. The method according to any one of claims 1 to 7, wherein the drying conditions include: the temperature is 110-150 ℃, preferably 110-130 ℃, and the time is 2-16h, preferably 3-12 h;
preferably, the conditions of the calcination include: the temperature is 500-900 ℃, preferably 550-800 ℃ and the time is 3-16h, preferably 4-12 h.
9. The titania-alumina composite support prepared by the method of any one of claims 1 to 8.
10. Use of the titania-alumina composite support of claim 9 and/or the titania-alumina composite support prepared according to the method of any one of claims 1 to 8 in pyrolysis gasoline hydrogenation and DCC pyrolysis naphtha hydrogenation.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1436594A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Prepn process of waste gas purifying catalyst containing noble metal |
| WO2007114570A1 (en) * | 2006-04-03 | 2007-10-11 | Korea Power Engineering Company, Inc. | Preparation method of vanadium/titania-based catalyst showing excellent nitrogen oxide-removal performance at wide temperature window through introduction of ball milling, and use thereof |
| 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 |
| CN104043442A (en) * | 2014-05-23 | 2014-09-17 | 天津大学 | Titanium aluminum base catalyst synthesis and application thereof to dimethoxy methane production from methanol oxidation |
| CN106745223A (en) * | 2017-03-16 | 2017-05-31 | 东北大学 | Modifying titanium dioxide raw powder's production technology and modifying titanium dioxide powder |
| CN108246302A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of catalytic gasoline faces hydrogen Hydrodearsenic Catalyst and its preparation method and application |
-
2020
- 2020-05-12 CN CN202010398288.8A patent/CN113649079B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1436594A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Prepn process of waste gas purifying catalyst containing noble metal |
| WO2007114570A1 (en) * | 2006-04-03 | 2007-10-11 | Korea Power Engineering Company, Inc. | Preparation method of vanadium/titania-based catalyst showing excellent nitrogen oxide-removal performance at wide temperature window through introduction of ball milling, and use thereof |
| 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 |
| CN104043442A (en) * | 2014-05-23 | 2014-09-17 | 天津大学 | Titanium aluminum base catalyst synthesis and application thereof to dimethoxy methane production from methanol oxidation |
| CN108246302A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of catalytic gasoline faces hydrogen Hydrodearsenic Catalyst and its preparation method and application |
| CN106745223A (en) * | 2017-03-16 | 2017-05-31 | 东北大学 | Modifying titanium dioxide raw powder's production technology and modifying titanium dioxide powder |
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