CN109261153B - Supported nickel-based catalyst and preparation method and application thereof - Google Patents
Supported nickel-based catalyst and preparation method and application thereof Download PDFInfo
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- CN109261153B CN109261153B CN201711441004.3A CN201711441004A CN109261153B CN 109261153 B CN109261153 B CN 109261153B CN 201711441004 A CN201711441004 A CN 201711441004A CN 109261153 B CN109261153 B CN 109261153B
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- nickel
- based catalyst
- supported nickel
- zinc
- magnesium
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 274
- 239000003054 catalyst Substances 0.000 title claims abstract description 147
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 86
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000003921 oil Substances 0.000 claims abstract description 56
- 239000011777 magnesium Substances 0.000 claims abstract description 50
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 45
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 45
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 45
- 239000011701 zinc Substances 0.000 claims abstract description 45
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 38
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 19
- 229910009369 Zn Mg Inorganic materials 0.000 claims abstract description 6
- 229910007573 Zn-Mg Inorganic materials 0.000 claims abstract description 6
- 229910020442 SiO2—TiO2 Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 50
- 238000005984 hydrogenation reaction Methods 0.000 claims description 45
- 239000002243 precursor Substances 0.000 claims description 44
- 239000000843 powder Substances 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000000975 co-precipitation Methods 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 238000007670 refining Methods 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000003570 air Substances 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000002161 passivation Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000011946 reduction process Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 159000000021 acetate salts Chemical class 0.000 claims 3
- 150000003841 chloride salts Chemical class 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 description 24
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 229910000510 noble metal Inorganic materials 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 9
- 239000011268 mixed slurry Substances 0.000 description 9
- 229910052814 silicon oxide Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000010687 lubricating oil Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000011959 amorphous silica alumina Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 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
- B01J23/80—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 zinc, cadmium or mercury
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/61—Surface area
- B01J35/617—500-1000 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
- B01J35/64—Pore diameter
- B01J35/657—Pore diameter larger than 1000 nm
-
- 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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/14—White oil, eating oil
Landscapes
- 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 supported nickel-based catalyst, which comprises an active component and a composite carrier, wherein the active component comprises nickel, zinc and magnesium, the composite carrier consists of silicon dioxide and titanium dioxide, and the active component is supported on the composite carrier to form a structure of Ni-Zn-Mg/SiO2‑TiO2The supported nickel-based catalyst comprises, by mass, 30-80% of nickel, 0.1-15% of zinc, 0.1-15% of magnesium, 10-50% of silica and 1-30% of titanium dioxide. Ni-Zn-Mg/SiO prepared by the invention2‑TiO2The white oil of the supported nickel-based catalyst has obvious hydrofining effect, simple preparation process and equipment, easy industrialization, good application prospect and great economic benefit.
Description
Technical Field
The invention relates to the field of industrial catalysis, in particular to a supported nickel-based catalyst and a preparation method and application thereof.
Technical Field
The white oil is a petroleum product obtained by deeply refining the lubricating oil fraction to remove impurities such as aromatic hydrocarbons, sulfides and the like in the lubricating oil fraction. It is colorless, tasteless, odorless, chemically inert and excellent in light and heat stability, and can be widely applied to the fields of chemical daily necessities, food, medicine, textile, agriculture and the like. White oil can be classified into industrial grade, cosmetic grade, food grade and pharmaceutical grade according to different purposes and refining depths.
The traditional process adopts an acid treatment and clay refining method to produce the white oil, so that the yield of the white oil is low, and the problem of environmental pollution also exists. The hydrogenation process for producing white oil has been developed for a long time due to its advantages of no pollution, high yield of white oil, wide sources of raw materials, complete product types and capability of processing high-viscosity white oil.
The process of producing white oil by a hydrogenation process is essentially a refining process that removes almost all of the sulfur, nitrogen, oxygen and aromatic compounds present in the feedstock. The limit of the white oil product on the content of aromatic hydrocarbon is very strict, and the hydrogenation of the aromatic hydrocarbon is difficult to be carried out at high temperature due to the limitation of thermodynamic equilibrium, so that higher pressure is adopted when the non-noble metal hydrofining catalyst is used for producing the white oil. According to the difference of raw materials and the difference of requirements for products, one-stage hydrogenation or multi-stage hydrogenation is adopted. For the feed with lower aromatic hydrocarbon content, such as hydrocracking tail oil, industrial-grade white oil, even food-grade and medical-grade white oil can be obtained through first-stage hydrogenation. For the raw materials of the base oil of the lubricating oil with higher aromatic hydrocarbon content, such as solvent refined dewaxed oil, two-stage hydrogenation is generally carried out, wherein industrial-grade white oil can be obtained by the first-stage hydrogenation, and food-grade and medical-grade white oil can be obtained by the second-stage hydrogenation.
The conventional metal catalysts are involved in patents CN1769379A, CN1140748A and CN1070215A, the activity is low, and the problem of deep dearomatization of lubricating oil cannot be effectively solved; patents CN1245204A, CN90100187.2 both relate to noble metal hydrogenation catalysts containing bimetallic platinum and palladium, but because of Al in the carriers of these two catalysts2O3The content is low, and is not more than 30%, so that the acidity of the catalyst is weak, and the catalyst is only suitable for hydrogenation processes of light oil products and distillate oil.
The US5393408 patent relates to two catalysts of macroporous amorphous silica-alumina and a medium-pore amorphous silica-alumina carrier loaded with noble metal, and the aim of removing aromatic hydrocarbon can be achieved only by adopting two-stage hydrogenation on hydrogenated lubricating oil base oil. U.S. Pat. No. 5,300,881 describes a noble metal catalyst suitable for dearomatization, desulfurization and denitrification of hydrocarbons with distillation range of 66-371 deg.C, in which the carrier is composed of Y-type zeolite and alumina, the content of Y-type zeolite is 50-80 wt%, the hydrogenation metals are Pt and Pd, the content is 0.1-2.0 wt%, the aromatic content of export oil is 9.9 v%, the conversion rate of aromatic hydrocarbon is 84%, and the sulfur content is 17 mug.g-1. U.S. Pat. No. 5,416,1291 describes a process for hydrogenating aromatics in a feedstock having a boiling range of 125-. The content of Pt and Pd on the carrier is 0.03-3.0%. The arene content of distillate oil treated by the catalyst can be reduced to below 20 wt%.
U.S. Pat. Nos. 4,973,978,804 disclose a process for preparing white oil with ultra-low aromatic hydrocarbon content by hydrogenation, wherein the catalyst is noble metal catalyst, the carrier of the catalyst is alumina, and the auxiliary metal is silicon, zinc or magnesium. CN101745383A discloses a preparation method of a deep hydrogenation dearomatization catalyst, wherein the main active component is Pt, the auxiliary agent is Pd, the carrier is an amorphous silica-alumina carrier, and the content of silica is 40-60% of the weight of the carrier. The catalyst prepared by the method has low carrier acidity, poor metal dispersibility, low catalyst activity and poor dearomatization effect.
Patent CN20140045471 discloses a preparation method of a hydrodearomatization catalyst. According to the method, a NaY type molecular sieve raw material with high silica-alumina ratio, high crystallinity and good stability is adopted, and the small-grain Y type molecular sieve is obtained after ammonium exchange, first hydrothermal treatment, alkali-containing solution treatment, second hydrothermal treatment and treatment by using a mixed solution of acid and ammonium salt in sequence. The small-grain Y-shaped molecular sieve is used as an acidic component, is matched with amorphous silica-alumina, an active component and an auxiliary component, and has higher hydrogenation and dearomatization activity. The catalyst prepared by the method has high activity, but the catalyst is a noble metal catalyst, the production cost is high, and the production process is complex.
Therefore, most of the white oil catalysts currently used in China are noble metal catalysts, which have good hydrogenation reaction characteristics, but are high in cost, and generate small-molecular hydrocarbon compounds along with the occurrence of cracking reaction in the hydrofining process.
Disclosure of Invention
In a first aspect of the invention, the invention provides a supported nickel-based catalyst, wherein the nickel-based catalyst takes nickel, zinc and magnesium as active components and is supported on a composite carrier of silicon oxide and titanium oxide to form Ni-Zn-Mg/SiO2-TiO2The supported catalyst solves the problem of high cost of the noble metal catalyst in the prior art.
In a second aspect of the object of the present invention, a method for preparing a supported nickel-based catalyst is provided.
In a third aspect of the object of the invention, the use of the supported nickel-based catalyst in the hydrofining of white oil is provided.
In a third aspect of the object of the present invention, a method for refining white oil is provided.
The purpose of the invention is realized by the following technical scheme: the invention provides a supported nickel-based catalyst which comprises an active component and a composite carrier, wherein the active component comprises nickel, zinc and magnesium, the composite carrier is composed of silicon dioxide and titanium dioxide, and the active component is supported on the composite carrier to form a structure of Ni-Zn-Mg/SiO2-TiO2The supported nickel-based catalyst comprises, by mass, 30-80% of nickel, 0.1-15% of zinc, 0.1-15% of magnesium, 10-50% of silicon dioxide and 1-30% of titanium dioxide.
Preferably, the mass percent of the nickel is 40-70%, the mass percent of the zinc is 1-12%, the mass percent of the magnesium is 1-12%, the mass percent of the silicon dioxide is 15-45%, and the mass percent of the titanium dioxide is 5-25%.
Further, the silica of the present invention is selected from the group consisting of silica having a specific surface area of 300-800m2The titanium dioxide is selected from titanium dioxide powder with the average aperture of 5-50 nm.
Preferably, the silica of the present invention is selected from silica having a specific surface area of 350-750m2The titanium dioxide is selected from titanium dioxide powder with the average pore diameter of 10-45 nm.
Wherein the average pore size is equal to the result of dividing the corresponding total pore volume by the corresponding specific surface.
Wherein the silicon dioxide powder is silicon dioxide powder with median particle diameter (D50) in the range of 1-20 μm
The titanium dioxide powder is titanium dioxide powder with a median particle diameter (D50) of 1-20 μm.
On the other hand, the invention also provides a preparation method of the supported nickel-based catalyst, which comprises the following steps:
step S1, providing a nickel-containing precursor, a zinc-containing precursor, a magnesium-containing precursor, a composite carrier, an alkaline soluble substance and deionized water, mixing and dissolving the nickel-containing precursor, the zinc-containing precursor and the magnesium-containing precursor in the deionized water to form a precursor solution, and dissolving the alkaline soluble substance in the deionized water to form an alkaline aqueous solution;
step S2, mixing the precursor solution, the alkaline aqueous solution and the composite carrier and carrying out coprecipitation reaction to form slurry;
step S3, filtering the slurry to obtain a filter cake, and then washing, drying and crushing the filter cake in sequence to obtain first catalyst powder;
and step S4, sequentially roasting, reducing and passivating the first catalyst powder to form the supported nickel-based catalyst.
Further, the nickel-containing precursor is any one or more of nickel-containing nitrate, nickel-containing sulfate, nickel-containing chloride or nickel-containing acetate, the zinc-containing precursor is any one or more of zinc-containing nitrate, zinc-containing sulfate, zinc-containing chloride or zinc-containing acetate, the magnesium-containing precursor is any one or more of magnesium-containing nitrate, magnesium-containing sulfate, magnesium-containing chloride or magnesium-containing acetate, the concentration of the nickel-containing precursor in the precursor solution is 0.2-2.0mol/L, the concentration of the zinc-containing precursor is 0.01-0.2mol/L, and the concentration of the magnesium-containing precursor is 0.01-0.2 mol/L.
Further, the alkaline soluble substance is any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, potassium carbonate or potassium bicarbonate, and the concentration of the alkaline soluble substance is 0.2-2.0 mol/L.
Further, the step S2 includes: and mixing the composite carrier and the alkaline aqueous solution to form a first mixed solution, and dropwise adding the precursor solution into the first mixed solution to perform the coprecipitation reaction to form the slurry.
As another preferable embodiment of the present invention, the step S2 includes: and mixing the composite carrier and the precursor solution to form a second mixed solution, and dropwise adding the alkaline aqueous solution to the second mixed solution to perform the coprecipitation reaction to form the slurry.
As another preferable embodiment of the present invention, the step S2 includes: and the composite carrier is mixed with the ionized water to form a third mixed solution, and the precursor solution and the alkaline aqueous solution are simultaneously added into the third mixed solution dropwise to carry out the coprecipitation reaction so as to form the slurry.
Further, the time of the dropping process is 0.25-3.0h, the pH value of the slurry is 7.0-10.0 after the dropping process is finished, and the temperature of the coprecipitation reaction is 30-90 ℃.
Further, in the step S3, in the washing process, the deionized water with the temperature of 10 to 80 ℃ is used to flush the filter cake and generate a filtrate, and the pH value of the filtrate after the washing process is completed is 7.0 to 8.5; the temperature in the drying process is 80-150 ℃, and the drying time is 2-24 h.
Further, in the step S4, the first catalyst powder is subjected to the calcination process in an air atmosphere to form a second catalyst powder, and the calcination temperature is 200-800 ℃ for 1-10 h;
the second catalyst powder is subjected to the reduction process in a hydrogen atmosphere to form third catalyst powder, the temperature of the reduction process is 250-800 ℃, and the reduction time is 1-10 h;
the passivation process treats the third catalyst powder with a mixed gas containing nitrogen to form the supported nickel-based catalyst, wherein the mixed gas further comprises any one of air, oxygen or carbon dioxide, and the temperature of the passivation process is 10-80 ℃.
In another aspect, the invention also includes the use of a supported nickel-based catalyst as described above in the hydrofinishing of white oil.
The invention further comprises a refining method of the white oil, which comprises the step of carrying out hydrogenation reaction on the white oil in a high-pressure reaction device by using the supported nickel-based catalyst, wherein the mass ratio of the supported nickel-based catalyst to the white oil is 0.001:1-0.15:1, the temperature of the hydrogenation reaction is 150-400 ℃, and the pressure of the hydrogenation reaction is 3-25 MPa.
Further, the mass ratio of the supported nickel-based catalyst to the white oil is 0.005:1-0.1:1, the hydrogenation reaction temperature is 200-380 ℃, and the hydrogenation reaction pressure is 12-18 MPa. .
Compared with the prior art, the invention has the following advantages:
(1) compared with noble metal catalysts, the supported nickel catalyst has obvious price advantage.
(2) The silica carrier in the supported nickel-based catalyst has higher specific surface area, and is beneficial to high dispersion of active metal components, so that the hydrogenation reaction activity of the catalyst is improved.
(3) The titanium dioxide in the supported nickel catalyst has larger average pore diameter, and is beneficial to the diffusion of macromolecular white oil on active metal components, thereby accelerating the hydrogenation reaction speed of the white oil.
(4) In the supported nickel catalyst, the active metal comprises nickel, zinc and magnesium, and the three metals are uniformly dispersed on the surface of the silicon oxide carrier and serve as active centers, so that the supported nickel catalyst has better hydrogenation activity compared with the common nickel catalyst.
(5) The titanium dioxide in the supported nickel catalyst can enable active metal to be more uniformly dispersed on the surface of the composite carrier, and can maintain the stability of the micro-morphology of the nickel active site on the composite carrier.
(6) The supported nickel catalyst has white oil hydrogenation reaction activity similar to that of noble metal catalyst, but has higher sulfur poisoning resistance and longer service life.
The preparation process of the supported nickel catalyst is simple, easy to industrialize, and has good application prospect and great economic benefit.
Detailed Description
Unless otherwise defined, technical or scientific terms used in the claims and the specification should have the ordinary meaning as understood by those of ordinary skill in the art to which the invention belongs.
The present invention is described in detail below with reference to specific embodiments, but the present invention is not limited to these embodiments, and structural, methodological, or functional changes made by those skilled in the art according to these embodiments are included in the scope of the present invention.
The embodiment of the invention provides a supported nickel-based catalyst, which comprises an active component and a composite carrier, wherein the active component comprises nickel, zinc and magnesium, the composite carrier consists of silicon dioxide and titanium dioxide, and the active component is loaded on the composite carrier to form a structure of Ni-Zn-Mg/SiO2-TiO2The supported nickel-based catalyst comprises, by mass, 30-80% of nickel, 0.1-15% of zinc, 0.1-15% of magnesium, 10-50% of silicon dioxide and 1-30% of titanium dioxide. The supported nickel-based catalyst provided by the embodiment of the invention solves the problem of high cost of a noble metal catalyst in the prior art, and the dioxygen in the supported nickel-based catalyst provided by the embodiment of the inventionThe silicon oxide has higher specific surface area, which is beneficial to the high dispersion of active metal components, thereby improving the hydrogenation reaction activity of the catalyst.
On the other hand, the embodiment of the invention also provides a preparation method of the supported nickel-based catalyst, which comprises the following steps:
step S1, providing a nickel-containing precursor, a zinc-containing precursor, a magnesium-containing precursor, a composite carrier, an alkaline soluble substance and deionized water, mixing and dissolving the nickel-containing precursor, the zinc-containing precursor and the magnesium-containing precursor in the deionized water to form a precursor solution, and dissolving the alkaline soluble substance in the deionized water to form an alkaline aqueous solution;
step S2, mixing the precursor solution, the alkaline aqueous solution and the composite carrier and carrying out coprecipitation reaction to form slurry;
step S3, filtering the slurry to obtain a filter cake, and then washing, drying and crushing the filter cake in sequence to obtain first catalyst powder;
and step S4, sequentially roasting, reducing and passivating the first catalyst powder to form the supported nickel-based catalyst.
The preparation method of the supported nickel catalyst provided by the embodiment of the invention can enable the active metal to be more uniformly dispersed on the surface of the composite carrier, and can maintain the stability of the micro-morphology of the nickel active site on the composite carrier.
The preparation process of the supported nickel catalyst is simple, easy to industrialize, and has good application prospect and great economic benefit.
On the other hand, the embodiment of the invention also provides the application of the supported nickel catalyst in the hydrofining of the white oil.
Further, the invention also provides a refining method of the white oil, which comprises the step of hydrofining the white oil in a high-pressure reaction device by using the supported nickel-based catalyst, wherein the mass ratio of the supported nickel-based catalyst to the white oil is 0.001:1-0.15:1, the hydrofining reaction temperature is 150-400 ℃, and the reaction pressure is 3-25 MPa. The supported nickel catalyst has white oil hydrogenation reaction activity similar to that of noble metal catalyst, but has higher sulfur poisoning resistance and longer service life.
The present invention is further illustrated by the following examples, which are intended to facilitate the understanding of the present invention and are not intended to limit the scope of the invention as claimed.
Example 1
This example provides a supported nickel-based catalyst having a composition of 60Ni-1Zn-1Mg/30SiO2-8TiO2The supported nickel-based catalyst of this example was prepared by a method comprising: 113.6g of Na were accurately weighed2CO3Placing into a 5L three-neck flask, adding 1.2L deionized water, heating for dissolving, accurately weighing 30.0g of silicon dioxide and 8.0g of titanium dioxide, adding into the three-neck flask, heating and stirring to obtain a mixture containing silicon dioxide, titanium dioxide and Na2CO3When the temperature is raised to 50 ℃, the prepared aqueous solution containing the active components of nickel, zinc and magnesium is dripped into the mixed slurry for precipitation reaction within 0.5 h.
Filtering to remove mother liquor, washing with deionized water at 60 deg.C until the pH of the washed solution is 7.5, and drying the filter cake in a drying oven at 120 deg.C for 5 hr.
Grinding and crushing the dried material, roasting for 5h at the temperature of 250 ℃, reducing for 6h at the temperature of 300 ℃ in a hydrogen atmosphere, cooling to room temperature in a nitrogen atmosphere, and then treating the reduced catalyst powder with air diluted by nitrogen at room temperature to obtain the catalyst powder with the composition of 60Ni-1Zn-1Mg/30SiO prepared by a reverse addition method2-8TiO2The passivated supported nickel-based catalyst of (1).
The specific surface area of the silicon oxide is 380m2Silicon dioxide powder per gram; the titanium oxide is titanium dioxide powder with the average aperture of 15 nm.
Water containing the active Components Nickel, Zinc and magnesium as described in this exampleThe solution was 297g of Ni (NO)3)2·6H2O、5.0g Zn(NO3)2·6H2O and 6.2g Mg (NO)3)2Dissolving in 1L deionized water.
Example 2
This example provides a supported nickel-based catalyst having a composition of 60Ni-1Zn-1Mg/30SiO2-8TiO2The supported nickel-based catalyst of this example was prepared by a method comprising: 113.6g of Na were accurately weighed2CO3Placing into a 5L three-neck flask, adding 1.2L deionized water, heating for dissolving, accurately weighing 30.0g of silicon dioxide and 8.0g of titanium dioxide, adding into the three-neck flask, heating and stirring to obtain a mixture containing silicon dioxide, titanium dioxide and Na2CO3When the temperature of the mixed slurry consisting of the solution is raised to 50 ℃, the aqueous solution which is prepared in advance and contains the active components of nickel, zinc and magnesium is dripped into the mixed slurry for precipitation reaction within 2.0 h.
Filtering to remove the mother liquor, washing with deionized water at room temperature until the pH of the washed solution is 8.5, and drying the filter cake in a drying oven at 120 ℃ for 5 h.
Grinding and crushing the dried material, roasting for 5h at the temperature of 250 ℃, reducing for 6h at the temperature of 300 ℃ in a hydrogen atmosphere, cooling to room temperature in a nitrogen atmosphere, and then treating the reduced catalyst powder with air diluted by nitrogen at room temperature to obtain the catalyst powder with the composition of 60Ni-1Zn-1Mg/30SiO prepared by a reverse addition method2-8TiO2The passivated supported nickel-based catalyst of (1).
The specific surface area of the silicon oxide in this example was 380m2(ii)/g; the average pore diameter of the titanium oxide was 15 nm.
The aqueous solution containing the active components nickel, zinc and magnesium described in this example was prepared by mixing 297g of Ni (NO)3)2·6H2O、5.0g Zn(NO3)2·6H2O and 6.2g Mg (NO)3)2Dissolving in 1L deionized water.
Example 3
This implementationThe example provides a supported nickel-based catalyst, the composition of the supported nickel-based catalyst is 60Ni-1Zn-1Mg/30SiO2-8TiO2The supported nickel-based catalyst of this example was prepared by a method comprising: accurately weighing 56.8g of Na2CO3Placing into a 5L three-neck flask, adding 1.2L deionized water, heating for dissolving, accurately weighing 15.0g of silicon dioxide and 4.0g of titanium dioxide, adding into the three-neck flask, heating and stirring to obtain a mixture containing silicon dioxide, titanium dioxide and Na2CO3When the temperature of the mixed slurry consisting of the solution is raised to 50 ℃, the aqueous solution which is prepared in advance and contains the active components of nickel, zinc and magnesium is dripped into the mixed slurry for precipitation reaction within 2.0 h.
Filtering to remove mother liquor, washing with deionized water at 60 deg.C until the pH of the washed solution is 7.5, and drying the filter cake in a drying oven at 120 deg.C for 5 hr.
Grinding and crushing the dried material, roasting for 5h at the temperature of 250 ℃, reducing for 6h at the temperature of 300 ℃ in a hydrogen atmosphere, cooling to room temperature in a nitrogen atmosphere, and then treating the reduced catalyst powder with air diluted by nitrogen at room temperature to obtain the catalyst powder with the composition of 60Ni-1Zn-1Mg/30SiO prepared by a reverse addition method2-8TiO2The passivated supported nickel-based catalyst of (1).
The specific surface area of the silicon oxide is 380m2Silicon dioxide powder per gram; the titanium oxide is titanium dioxide powder with the average aperture of 15 nm.
The aqueous solution containing the active components nickel, zinc and magnesium described in this example was prepared by mixing 198.5g of Ni (NO)3)2·6H2O、2.5g Zn(NO3)2·6H2O and 3.1g Mg (NO)3)2Dissolving in 1L deionized water.
Example 4
This example provides a supported nickel-based catalyst having the composition 40Ni-1Zn-1Mg/40SiO2-18TiO2The supported nickel-based catalyst of this example was prepared by a method comprising:77.6g of Na were accurately weighed2CO3Placing into a 5L three-neck flask, adding 1.2L deionized water, heating for dissolving, accurately weighing 40.0g of silicon dioxide and 18.0g of titanium dioxide, adding into the three-neck flask, heating and stirring to obtain a mixture containing silicon dioxide, titanium dioxide and Na2CO3When the temperature is raised to 50 ℃, the prepared aqueous solution containing the active components of nickel, zinc and magnesium is dripped into the mixed slurry for precipitation reaction within 0.5 h.
Filtering to remove mother liquor, washing with deionized water at 60 deg.C until the pH of the washed solution is 7.5, and drying the filter cake in a drying oven at 120 deg.C for 5 hr.
Grinding and crushing the dried material, roasting for 2h at the temperature of 600 ℃, reducing for 6h at the temperature of 300 ℃ in a hydrogen atmosphere, cooling to room temperature in a nitrogen atmosphere, and then treating the reduced catalyst powder with air diluted by nitrogen at room temperature to obtain the catalyst powder with the composition of 40Ni-1Zn-1Mg/40SiO prepared by a reverse addition method2-18TiO2The passivated supported nickel-based catalyst of (1).
The specific surface area of the silicon oxide is 380m2Silicon dioxide powder per gram; the titanium oxide is titanium dioxide powder with the average aperture of 15 nm.
The aqueous solution containing the active components nickel, zinc and magnesium described in this example was prepared by mixing 198.3g of Ni (NO)3)2·6H2O、5.0g Zn(NO3)2·6H2O and 6.2g Mg (NO)3)2Dissolved in 1L deionized water.
Example 5
This example provides a supported nickel-based catalyst having the composition 40Ni-10Zn-10Mg/20SiO2-20TiO2The supported nickel-based catalyst of this example was prepared by a method comprising: 77.6g of Na were accurately weighed2CO3Placing into a 5L three-neck flask, adding 1.2L deionized water, heating for dissolving, accurately weighing 20.0g of silicon dioxide and 20.0g of titanium dioxide carrier, adding into the three-neck flask, heating and stirring to obtain a mixture of silicon dioxide and titanium dioxideTitanium oxide and Na2CO3When the temperature is raised to 50 ℃, the prepared aqueous solution containing the active components of nickel, zinc and magnesium is dripped into the mixed slurry for precipitation reaction within 0.5 h.
Filtering to remove mother liquor, washing with deionized water at 60 deg.C until the pH of the washed solution is 7.5, and drying the filter cake in a drying oven at 120 deg.C for 5 hr.
Grinding and crushing the dried material, roasting for 5h at the temperature of 250 ℃, reducing for 2h at the temperature of 600 ℃ in a hydrogen atmosphere, cooling to room temperature in a nitrogen atmosphere, and then treating the reduced catalyst powder with air diluted by nitrogen at room temperature to obtain the catalyst powder with the composition of 40Ni-10Zn-10Mg/20SiO prepared by a reverse addition method2-20TiO2The passivated supported nickel-based catalyst of (1).
The specific surface area of the silicon oxide is 380m2Silicon dioxide powder per gram; the titanium oxide is titanium dioxide powder with the average aperture of 15 nm.
The aqueous solution containing the active components nickel, zinc and magnesium described in this example was prepared with 198.3g of Ni (NO)3)2·6H2O、50.0g Zn(NO3)2·6H2O and 62.0g Mg (NO)3)2Dissolved in 1L deionized water.
Example 6
In this example, the preparation of a supported nickel-based catalyst was carried out in accordance with the method described in example 1, except that the specific surface area of silica was 600m2(ii)/g; the obtained product has the composition of 60Ni-1Zn-1Mg/30SiO2-8TiO2The passivated supported nickel-based catalyst of (1).
Example 7
In this example, the preparation of a supported nickel-based catalyst was carried out in accordance with the method described in example 1, except that the specific surface area of silica was 420m2(ii)/g; the obtained product has the composition of 60Ni-1Zn-1Mg/30SiO2-8TiO2The passivated supported nickel-based catalyst of (1).
Example 8
In this example, a supported nickel-based catalyst was prepared as described in example 6, except that the temperature at precipitation was 70 ℃ to obtain a composition of 60Ni-1Zn-1Mg/30SiO2-8TiO2The passivated supported nickel-based catalyst of (1).
Example 9
In this example, the preparation of a supported nickel-based catalyst was carried out as described in example 6, except that the precipitant Na2CO3Dripping the aqueous solution into mixed slurry formed by aqueous solution containing active components of nickel, zinc and magnesium and the composite carrier to obtain the composite material with the composition of 60Ni-1Zn-1Mg/30SiO through a positive addition method2-8TiO2The passivated supported nickel-based catalyst of (1).
Example 10
In this example, the preparation of a supported nickel-based catalyst was carried out as described in example 9, except that the precipitant Na2CO3The aqueous solution and the aqueous solution containing active components of nickel, zinc and magnesium are simultaneously dripped into the mixed slurry formed by the composite carrier and deionized water (the weight ratio of silicon oxide to the deionized water is 1/10), and the prepared mixture with the composition of 60Ni-1Zn-1Mg/30SiO by addition2-8TiO2The passivated supported nickel-based catalyst of (1).
Example 11
In this example, the preparation of a supported nickel-based catalyst was carried out in accordance with the method described in example 10, except that the active component, nickel Ni (NO), was used3)2·6H2The amount of O added was 312g, and the composition obtained and prepared additively was 63Ni-1Zn-1Mg/30SiO2-8TiO2The passivated supported nickel-based catalyst of (1).
Example 12
In this example, the preparation of a supported nickel-based catalyst was carried out as described in example 10, except that the titania support: the average pore diameter is 28 nm; obtained and additively prepared with a composition of 60Ni-1Zn-1Mg/30SiO2-8TiO2The passivated supported nickel-based catalyst of (1).
Comparative example 1
In comparative example 1, the preparation of a supported nickel-based catalyst was carried out as described in example 1, except that silica was added in an amount of 40.0g, and zinc and magnesium were not added, to obtain a composition prepared by the reverse addition method of 60% Ni/40% SiO2The passivated supported nickel powder catalyst of (1).
Comparative example 2
A supported nickel powder catalyst with 65% nickel content, which is produced by Shanghai Shengbang chemical Co., Ltd, and has the product model of SN-8000P and the batch number of 20151106.
Comparative example 3
A supported nickel powder catalyst with 55% nickel content, which is produced by Shanghai Sheng Pong chemical Co., Ltd, and has the product model of SN-7000P and the batch number of 20151009.
Based on the supported nickel powder catalysts of examples 1 to 12 and comparative examples 1 to 3, the high-pressure reactor white oil was used for hydrofining reaction, and the double bond conversion (hydrogenation rate) in the white oil before and after the hydrodewaxing reaction was measured to reflect the hydrodewaxing performance of the catalyst.
In a specific embodiment, the supported nickel catalyst powder and the white oil raw material are accurately weighed and placed in a high-pressure reaction kettle with the volume of 1L, the reaction kettle is sealed and is subjected to hydrogen replacement, hydrogen with a certain pressure is filled, the reaction kettle is slowly heated to the reaction temperature, a hydrogen valve is adjusted to maintain the system pressure at the reaction pressure, and hydrogenation is maintained under the reaction condition. Cooling to room temperature after the hydrogenation reaction is finished, and filtering to remove catalyst powder to obtain the white oil subjected to hydrogenation and decoloration.
In a specific embodiment, the hydrogenation rate is determined as follows: accurately weighing 0.01-0.02g (accurate to 0.0001g) of white oil, placing the white oil in a 50mL volumetric flask, adding a cyclohexane solution to dissolve and dilute the white oil to a scale, respectively measuring the absorbance of the petroleum resin before and after the hydrogenation reaction by using an ultraviolet spectrophotometer at the wavelength of 275nm, and calculating the hydrogenation rate according to the following formula:
(1-B/A)*100％
a, absorbance of raw white oil
B, absorbance of white oil after hydrogenation and decoloration reaction
The results of the hydrode-chromic reaction of the supported nickel-based catalyst are shown in table 1 below.
TABLE 1 hydrode-color reaction results of supported nickel-based catalysts
As can be seen from table 1, under the same reaction conditions, the hydrogenation rate of the white oil of the catalyst prepared by using the silica carrier with large specific surface area in example 6 is better than that of the catalyst prepared by using the carrier with small specific surface area in example 1, which indicates that the catalyst prepared by using the carrier with large specific surface area has better activity. Meanwhile, by comparing example 12 with comparative example 1, it can be found that the addition of large-pore titanium oxide, zinc and magnesium active metals improves the anti-poison capability of the catalyst and the hydrogenation and decoloration capability of the catalyst. It can also be seen from the table that the catalyst prepared in example 6 still has higher activity at low pressure, low temperature and low addition of catalyst, indicating that the catalyst has stronger hydrogenation activity and is easy for industrial application.
Although the present invention has been described in the above with reference to preferred embodiments, the present invention is not limited thereto, and the present invention is applicable to the field of hydrorefining of petroleum resins, α -olefins, DCPD resins, isoprene resins, and the like, in addition to the hydrogenation of white oil. Various changes and modifications may be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims. It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (15)
1. The supported nickel-based catalyst is characterized by being applied to white oil hydrofining, and comprising an active component and a composite carrier, wherein the active component comprises nickel, zinc and magnesium, the composite carrier consists of silicon dioxide and titanium dioxide, and the active component is supported on the composite carrier to form a structure of Ni-Zn-Mg/SiO2-TiO2Wherein the mass percent of nickel in the supported nickel-based catalyst is 30-80%, the mass percent of zinc is 0.1-15%, the mass percent of magnesium is 0.1-15wt%, the mass percent of silicon dioxide is 10-50%, the mass percent of titanium dioxide is 1-30%, and the silicon dioxide is selected from the group consisting of titanium dioxide with the specific surface area of 300-800m2The titanium dioxide is selected from titanium dioxide powder with the average aperture of 5-50 nm.
2. The supported nickel-based catalyst of claim 1, wherein the nickel is 40 to 70% by mass, the zinc is 1 to 12% by mass, the magnesium is 1 to 12% by mass, the silica is 15 to 45% by mass, and the titania is 5 to 25% by mass.
3. The supported nickel-based catalyst of claim 1, wherein the silica is selected from the group consisting of silica having a specific surface area of 350-750m2The titanium dioxide is selected from titanium dioxide powder with the average pore diameter of 10-45 nm.
4. A process for the preparation of a supported nickel-based catalyst as claimed in any of claims 1 to 3, comprising the steps of:
step S1, providing a nickel-containing precursor, a zinc-containing precursor, a magnesium-containing precursor, a composite carrier, an alkaline soluble substance and deionized water, mixing and dissolving the nickel-containing precursor, the zinc-containing precursor and the magnesium-containing precursor in the deionized water to form a precursor solution, and dissolving the alkaline soluble substance in the deionized water to form an alkaline aqueous solution;
step S2, mixing the precursor solution, the alkaline aqueous solution and the composite carrier and carrying out coprecipitation reaction to form slurry;
step S3, filtering the slurry to obtain a filter cake, and then washing, drying and crushing the filter cake in sequence to obtain first catalyst powder;
and step S4, sequentially roasting, reducing and passivating the first catalyst powder to form the supported nickel-based catalyst.
5. The method for preparing the supported nickel-based catalyst according to claim 4, wherein the nickel-containing precursor is any one or more of nickel-containing nitrate, nickel-containing sulfate, nickel-containing chloride salt or nickel-containing acetate salt, the zinc-containing precursor is any one or more of zinc-containing nitrate, zinc-containing sulfate, zinc-containing chloride salt or zinc-containing acetate salt, the magnesium-containing precursor is any one or more of magnesium-containing nitrate, magnesium-containing sulfate, magnesium-containing chloride salt or magnesium-containing acetate salt, the concentration of the nickel-containing precursor in the precursor solution is 0.2-2.0mol/L, the concentration of the zinc-containing precursor is 0.01-0.2mol/L, and the concentration of the magnesium-containing precursor is 0.01-0.2 mol/L.
6. The method of preparing a supported nickel-based catalyst according to claim 4, wherein the alkali solubles are any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, potassium carbonate or potassium bicarbonate, and the concentration of the alkali solubles in the alkali aqueous solution is 0.2 to 2.0 mol/L.
7. The method of preparing a supported nickel-based catalyst according to claim 4, wherein the step S2 includes: and mixing the composite carrier with the alkaline aqueous solution to form a first mixed solution, and dropwise adding the precursor solution into the first mixed solution to perform a coprecipitation reaction to form the slurry.
8. The method of preparing a supported nickel-based catalyst according to claim 4, wherein the step S2 includes: and mixing the composite carrier and the precursor solution to form a second mixed solution, and dropwise adding the alkaline aqueous solution to the second mixed solution to perform a coprecipitation reaction to form the slurry.
9. The method of preparing a supported nickel-based catalyst according to claim 6, wherein the step S2 includes: and mixing the composite carrier and deionized water to form a third mixed solution, and simultaneously dropwise adding the precursor solution and the alkaline aqueous solution into the third mixed solution for coprecipitation reaction to form the slurry.
10. The method for preparing a supported nickel-based catalyst according to any one of claims 7 to 9, wherein the dropping process is carried out for a time of 0.25 to 3.0 hours, the pH of the slurry after completion of the dropping process is 7.0 to 10.0, and the temperature of the coprecipitation reaction is 30 to 90 ℃.
11. The method of claim 4, wherein in the step S3, the washing process uses deionized water with a temperature of 10-80 ℃ to wash the filter cake and generate a filtrate, and the pH value of the filtrate after the washing process is completed is 7.0-8.5; the temperature in the drying process is 80-150 ℃, and the drying time is 2-24 h.
12. The method of claim 4, wherein in the step S4, the first catalyst powder is subjected to the calcination process under the air atmosphere to form the second catalyst powder, the calcination temperature is 200-800 ℃ and the calcination time is 1-10 h;
the second catalyst powder is subjected to the reduction process in a hydrogen atmosphere to form third catalyst powder, the temperature of the reduction process is 250-800 ℃, and the reduction time is 1-10 h;
the passivation process treats the third catalyst powder with a mixed gas containing nitrogen to form the supported nickel-based catalyst, wherein the mixed gas further comprises any one of air, oxygen or carbon dioxide, and the temperature of the passivation process is 10-80 ℃.
13. Use of a supported nickel-based catalyst according to any one of claims 1 to 3 in the hydrofinishing of white oils.
14. A refining method of white oil, which is characterized in that the refining method comprises the step of carrying out hydrogenation reaction on the white oil in a high-pressure reaction device by using the supported nickel-based catalyst as set forth in any one of claims 1-2, wherein the mass ratio of the supported nickel-based catalyst to the white oil is 0.001:1-0.15:1, the temperature of the hydrogenation reaction is 150-400 ℃, and the pressure of the hydrogenation reaction is 3-25 MPa.
15. The method for refining white oil as defined in claim 14, wherein the mass ratio of the supported nickel-based catalyst to the white oil is 0.005:1-0.1:1, the hydrogenation temperature is 200-380 ℃, and the hydrogenation pressure is 12-18 MPa.
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