CN106669647A - 一种含钛氧化铝干胶粉及其制备方法 - Google Patents
一种含钛氧化铝干胶粉及其制备方法 Download PDFInfo
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- CN106669647A CN106669647A CN201510751277.2A CN201510751277A CN106669647A CN 106669647 A CN106669647 A CN 106669647A CN 201510751277 A CN201510751277 A CN 201510751277A CN 106669647 A CN106669647 A CN 106669647A
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- oxide
- nano titanium
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000000843 powder Substances 0.000 title claims abstract description 21
- 239000010936 titanium Substances 0.000 title abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title abstract description 10
- 229910052719 titanium Inorganic materials 0.000 title abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 59
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 30
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 29
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000975 co-precipitation Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 210000002966 serum Anatomy 0.000 claims description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 28
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 26
- 239000003292 glue Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 9
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 9
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 8
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 159000000013 aluminium salts Chemical class 0.000 claims description 5
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 15
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 5
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 239000011268 mixed slurry Substances 0.000 abstract 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 10
- 238000006386 neutralization reaction Methods 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- PJVCMJFYKHBNOG-UHFFFAOYSA-M [N+](=O)([O-])[O-].[Al+3].[OH-].[Al+3] Chemical compound [N+](=O)([O-])[O-].[Al+3].[OH-].[Al+3] PJVCMJFYKHBNOG-UHFFFAOYSA-M 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010010 raising Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- -1 zirconia compound Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
-
- 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
-
- 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
- B01J35/647—2-50 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
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
本发明公开一种含钛氧化铝干胶粉及其制备方法。所述含钛氧化铝干胶粉制备过程包括如下步骤:(1)配制纳米二氧化钛和柠檬酸铵的混合浆液,混合浆液中纳米二氧化钛的质量含量为5%-30%,柠檬酸铵的质量含量为0.25%-5%,所述纳米二氧化钛的粒径为10~100nm;(2)配制铝盐和沉淀剂,并进行共沉淀反应得到含有氢氧化铝溶胶的溶液,老化后加入步骤(1)制备的混合溶液继续进行老化,步骤(1)制备的混合溶液的加入量以最终催化剂中纳米二氧化钛的质量含量为1%-10%;(3)老化后的物料经过滤、洗涤、干燥后得到含钛氧化铝。该方法有利于钛富集在氧化铝载体表面且高度分散、改善氧化铝干胶粉的物化性质。
Description
技术领域
本发明涉及一种含钛氧化铝干胶粉及其制备方法,具体地说涉及一种适用于加氢处理催化剂载体的含钛氧化铝干胶粉及其制备方法。
背景技术
随着原油重质化劣质化日益加剧和环保法规的日益严格要求,对油品轻质化的要求不断提高。为了达到环保法规的要求,加氢是降低燃料油中的硫化物、氮化物的主要方法之一。在加氢过程中,催化剂起到重要的作用。当前,所使用的催化剂大多数是以氧化铝为载体,以第Ⅷ族和/或第ⅥB族金属为活性组分。单一氧化铝表面性质不能满足催化剂的使用要求,例如,氧化铝表面上活性金属与载体间的相互作用力较强,容易形成没有活性的尖晶石物种,使金属活性组分不易硫化,活性降低。降低活性组分与载体之间的作用力,成为制备高活性加氢处理催化剂的关键技术。
为了制备高活性、高稳定性的加氢处理催化剂,许多研究者对载体氧化铝进行化学改性处理,以达到所需要的物化性质。如添加镁、钛、硼、氟、硅、锌、锆、钒、磷等助剂,主要是改变氧化铝与活性组分间的相互作用和氧化铝表面的酸性,提高氧化铝稳定性等。
EP0339640公布了一种共沉淀法制备含有钛的氧化铝制备方法,能够得到分散性好的含钛氧化铝,但共沉淀法存在体相滞留问题,二氧化钛的主要作用不能够充分的发挥。而共沉条件不可能同时满足多种物质的共沉,影响了载体的物化性能。
CN 00123133.2公开了一种含有氧化锆载体的制备方法,主要是在载体成型过程中加入氧化锆化合物制得含有氧化锆的载体。CN
99112940.7公开了一种烃类加氢处理催化剂的制备方法,载体主要是用含有氯化钛和磷酸的混合溶液与氧化铝干胶混捏后,挤条成型,经干燥、焙烧后得到含有钛、磷的氧化铝载体。CN
200410050777.5公开了一种大孔氧化铝载体的制备方法。将含有硼酸的助剂溶液加入到氧化铝前身物和含有扩孔剂的混合物料中,经混捏、成型、干燥、焙烧后得到最终的载体,其助剂溶液中也可含有硅、磷、镁、锌、钛等助剂。上述方法均采用混捏的方式引入助剂钛,钛在氧化铝载体表面分布不均匀,影响了载体的物化性能。
CN
200610013758.4公开了一种负载型氧化锆催化剂载体的制备方法。该载体是氧化锆、氧化铝、氧化硅、氧化态、氧化镁、活性炭或分子筛,用含有氧化锆或硝酸锆配制成的溶液对载体进行等体积浸渍或者过量浸渍,经过干燥、焙烧得到负载氧化锆的催化剂载体。该方法制备的催化剂活性上没有较大的变化。
CN 1289636A公布了一种在氢氧化铝浆液中沉淀钛盐制备含钛的氢氧化铝的方法,由于钛盐溶液中含有氯离子和硫酸根离子,容易对设备造成腐蚀,并且在焙烧过程中会产生污染环境的气体,限制了工业上的应用。
发明内容
针对现有技术中的不足,本发明提供了一种含钛氧化铝干胶粉及其制备方法。该方法有利于钛富集在氧化铝载体表面且高度分散、改善氧化铝干胶粉的物化性质。
本发明含钛氧化铝干胶粉的制备方法,包括如下步骤:
(1)配制纳米二氧化钛和柠檬酸铵的混合浆液,混合浆液中纳米二氧化钛的质量含量为5%-
30%,优选10%-20%,柠檬酸铵的质量含量为0.25%-5%,优选0.5%-3%,所述纳米二氧化钛的粒径为10~100nm,最好为10~60nm;
(2)配制铝盐和沉淀剂,并进行共沉淀反应得到含有氢氧化铝溶胶的溶液,老化10-30min后加入步骤(1)制备的混合溶液继续进行老化,步骤(1)制备的混合溶液的加入量以最终催化剂中纳米二氧化钛的质量含量为 1%-10%,优选 2%-6%计;
(3)老化后的物料经过滤、洗涤、干燥后得到含钛氧化铝。
本发明方法中,铝盐包括但不限于硫酸铝、氯化铝、硝酸铝中的一种或几种,沉淀剂包括但不限于氢氧化钠、氢氧化铵、铝酸钾、铝酸钠中的一种或几种。
本发明方法中,共沉淀反应为并流共沉淀,共沉淀反应的温度为 58℃-62℃,pH为7.5-8.5,优选8.0-8.2,共沉淀反应时间为35-65min,得到含有氢氧化铝溶胶的溶液中氢氧化铝质量浓度以氧化铝计为1~30g/100mL,较适为5~10 g/100mL。
本发明方法中,加入混合浆液前老化温度为58℃-62℃,老化pH为 8.0-8.5 ,加入混合浆液后继续进行老化15min-30min,老化温度相比加入混合溶液前提高 2℃ - 4℃,老化pH提高0.2-1.0。
本发明方法中,干燥温度为80℃-150℃,优选 100℃-130℃干燥时间为 1-10h,优选4-8h。
一种采用上述方法制备的含钛氧化铝干胶粉,所述含钛氧化铝干胶粉二氧化钛的含量为1%~20%,优选2%~10%,比表面积为350~520m2/g,优选380~490m2/g,孔容为0.6~1.5mL/g,优选0.8~1.2mL/g,平均孔直径为7nm~12nm,优选 8~10nm,分散度为 0.3~0.5 ,优选 0.35~0.4。
本发明方法在氢氧化铝溶胶老化阶段加入纳米二氧化钛和柠檬酸铵的混合水溶液抑制了纳米二氧化钛在氢氧化铝溶胶上的聚集,提高了二氧化钛与氢氧化铝溶胶的相互作用力,含钛氧化铝中形成了稳定的Al-O-Ti键,氧化钛和氧化铝呈均匀的分布,提高了含钛氧化铝中二氧化钛与氧化铝的协同作用及含钛氧化铝干胶粉比表面积、孔容、孔径等物化性质,采用该含钛氧化铝干胶粉能够制备出性质优异的加氢处理催化剂,提高催化剂的反应活性。
具体实施方式
下面结合实施例进一步说明本发明的作用和效果,但以下实施例不构成对本发明方法的限制。
本发明米二氧化钛和柠檬酸铵的混合浆液具体制备过程如下:将适量的柠檬酸铵加入到高速搅拌的二氧化钛浆液中,搅拌时间为5-30min,最优选取10-25 min。
本发明氢氧化铝溶胶的具体制备过程如下:在成胶装置中加入适量的去离子水,用氢氧化钠或者氢氧化铵或者碱金属铝盐水溶液如铝酸钾或铝酸钠等碱性沉淀剂去中和酸性铝盐溶液如硫酸铝、氯化铝、硝酸铝等形成氢氧化铝浆液。若采用铝酸钠或铝酸钾等碱金属铝盐溶液也可以采用盐酸、硝酸、二氧化碳等酸沉淀剂制备氢氧化铝浆液。
本发明方法中分散度的测定采用XPS,具体过程如下:1.将焙烧后的样品送样进行XPS( X 射线光电子能谱)分析;2.对分析后的数据进行整理计算;3.分散度(表面原子摩尔浓度比值)=Ti At.%/Al At.%。
实施例 1
(1)配制纳米二氧化钛和柠檬酸铵的混合浆液,混合浆液中纳米二氧化钛的质量含量为10%,柠檬酸铵的质量含量为0.8%,所述纳米二氧化钛的粒径为10nm;
(2)配制浓度为30g
/L的铝酸钠溶液和浓度为40g/L的硫酸铝溶液,在搅拌条件下同时并流加入到中和反应装置中,控制pH值为8.2,温度为58℃,中和时间为55min得到含有氢氧化铝溶胶的溶液,含有氢氧化铝溶胶的溶液中氢氧化铝质量浓度以氧化铝计为5
g/100mL,老化10min后加入步骤(1)制备的混合溶液继续进行老化,步骤(1)制备的混合溶液的加入量以最终催化剂中纳米二氧化钛的质量含量为2%;控制加入混合浆液前老化温度为60℃,老化pH为8.0 ,加入混合浆液后继续进行老化20min,老化温度相比加入混合溶液前提高2℃,老化pH提高0.5;
(3)老化后的物料经过滤、洗涤、干燥得到含钛氧化铝A,物化性质见表1,干燥温度为110℃,干燥时间为 6h。
实施例 2
(1)配制纳米二氧化钛和柠檬酸铵的混合浆液,混合浆液中纳米二氧化钛的质量含量为15%,柠檬酸铵的质量含量为1.5% ,所述纳米二氧化钛的粒径为60nm;
(2)配制浓度为30g
/L的铝酸钠溶液和浓度为40g/L的硫酸铝溶液,在搅拌条件下同时并流加入到中和反应装置中,控制pH值为8.0,温度为62℃ ,中和时间为35min得到含有氢氧化铝溶胶的溶液,含有氢氧化铝溶胶的溶液中氢氧化铝质量浓度以氧化铝计为10
g/100mL,老化30min后加入步骤(1)制备的混合溶液继续进行老化,步骤(1)制备的混合溶液的加入量以最终催化剂中纳米二氧化钛的质量含量为3%;控制加入混合浆液前老化温度为62℃,老化pH为8.0,加入混合浆液后继续进行老化20min,老化温度相比加入混合溶液前提高3℃,老化pH提高 0.6个单位;
(3)老化后的物料经过滤、洗涤、干燥、焙烧后得到含钛氧化铝B,物化性质见表1,干燥温度为120℃ ,干燥时间为6h 。
实施例 3
(1)配制纳米二氧化钛和柠檬酸铵的混合浆液,混合浆液中纳米二氧化钛的质量含量为20%,柠檬酸铵的质量含量为2%,所述纳米二氧化钛的粒径为60nm;
(2)配制浓度为30g
/L的铝酸钠溶液和浓度为40g/L的硫酸铝溶液,在搅拌条件下同时并流加入到中和反应装置中,控制pH值为8.0,温度为60℃,中和时间为55min得到含有氢氧化铝溶胶的溶液,含有氢氧化铝溶胶的溶液中氢氧化铝质量浓度以氧化铝计为10
g/100mL,老化30min后加入步骤(1)制备的混合溶液继续进行老化,步骤(1)制备的混合溶液的加入量以最终催化剂中纳米二氧化钛的质量含量为4% ;控制加入混合浆液前老化温度为58℃,老化pH为8.2,加入混合浆液后继续进行老化25 min,老化温度相比加入混合溶液前提高2℃ ,老化pH提高0.3个单位 ;
(3)老化后的物料经过滤、洗涤、干燥、焙烧后得到含钛氧化铝C,物化性质见表1,干燥温度为120℃,干燥时间为 8h。
实施例 4
(1)配制纳米二氧化钛和柠檬酸铵的混合浆液,混合浆液中纳米二氧化钛的质量含量为25%,柠檬酸铵的质量含量为1%,所述纳米二氧化钛的粒径为60nm;
(2)配制浓度为30g
/L的铝酸钠溶液和浓度为40g/L的硫酸铝溶液,在搅拌条件下同时并流加入到中和反应装置中,控制pH值为8.0,温度为60℃,中和时间为55min得到含有氢氧化铝溶胶的溶液,含有氢氧化铝溶胶的溶液中氢氧化铝质量浓度以氧化铝计为10
g/100mL,老化30min后加入步骤(1)制备的混合溶液继续进行老化,步骤(1)制备的混合溶液的加入量以最终催化剂中纳米二氧化钛的质量含量为5% ;控制加入混合浆液前老化温度为60℃,老化pH为8.2 ,加入混合浆液后继续进行老化25 min,老化温度相比加入混合溶液前提高2℃,老化pH提高 0.2个单位;
(3)老化后的物料经过滤、洗涤、干燥、焙烧后得到含钛氧化铝D,物化性质见表1,干燥温度为110 ,干燥时间为 6h。
实施例5
(1)配制纳米二氧化钛和柠檬酸铵的混合浆液,混合浆液中纳米二氧化钛的质量含量为30% ,柠檬酸铵的质量含量为2.0%,所述纳米二氧化钛的粒径为60nm;
(2)配制浓度为30g
/L的铝酸钠溶液和浓度为40g/L的硫酸铝溶液,在搅拌条件下同时并流加入到中和反应装置中,控制pH值为8.0,温度为 62℃ ,中和时间为55min得到含有氢氧化铝溶胶的溶液,含有氢氧化铝溶胶的溶液中氢氧化铝质量浓度以氧化铝计为10
g/100mL,老化30min后加入步骤(1)制备的混合溶液继续进行老化,步骤(1)制备的混合溶液的加入量以最终催化剂中纳米二氧化钛的质量含量为 6%;控制加入混合浆液前老化温度为60℃,老化pH为8.0 ,加入混合浆液后继续进行老化30 min,老化温度相比加入混合溶液前提高2℃
,老化pH提高0.2个单位 。
(3)老化后的物料经过滤、洗涤、干燥、焙烧后得到含钛氧化铝E,物化性质见表1,干燥温度为120℃ ,干燥时间为 8h。
比较例1
同实施例1,不同之处在于浆液中无柠檬酸铵,得到含钛氧化铝F,物化性质见表1。
比较例2
同实施例1,不同之处在于纳米二氧化钛在共沉淀过程中加入,得到含钛氧化铝G,物化性质见表1。
表1含钛氧化铝干胶粉的物化性质
称取上述实施例及比较例的干胶粉200克,加入SB粉100克、田菁粉和柠檬酸各4克,混匀后加入酸性溶液,酸性溶液中硝酸的浓度为2wt%,其余为蒸馏水。碾压15~25分钟,用直径为1.7mm的三叶草孔板进行挤条,经120℃干燥12小时,550℃焙烧3小时,得到催化剂载体。采用含有Mo、Ni的浸渍液浸渍载体,得到催化剂C-1至C7,催化剂中氧化钼的质量含量均为24% ,氧化镍的质量含量均为4% 。对上述催化剂进行活性评价,原料油为常三线柴油,氮含量为280
ng/ul,硫含量1.2% ,评价条件:反应压力4.0MPa,反应温度340℃,空速2.0h-1 ,氢油比600:1,评价结果见表2。
表2催化剂活性评价结果
催化剂编号 | C-1 | C-2 | C-3 | C-4 | C-5 | C-6 | C-7 |
相对脱氮活性,% | 148 | 152 | 146 | 145 | 138 | 125 | 128 |
相对脱硫活性,% | 135 | 146 | 129 | 128 | 121 | 112 | 118 |
通过表2可知,采用本发明方法制备的催化剂活性明显高于比较例制备的催化剂。
Claims (11)
1.一种含钛氧化铝干胶粉的制备方法,其特征在于:包括如下步骤:
(1)配制纳米二氧化钛和柠檬酸铵的混合浆液,混合浆液中纳米二氧化钛的质量含量为5%- 30%,柠檬酸铵的质量含量为0.25%-5%,所述纳米二氧化钛的粒径为10~100nm;
(2)配制铝盐和沉淀剂,并进行共沉淀反应得到含有氢氧化铝溶胶的溶液,老化10-30min后加入步骤(1)制备的混合溶液继续进行老化,步骤(1)制备的混合溶液的加入量以最终催化剂中纳米二氧化钛的质量含量为
1%-10%计;
(3)老化后的物料经过滤、洗涤、干燥后得到含钛氧化铝。
2.根据权利要求1所述的方法,其特征在于:混合浆液中纳米二氧化钛的质量含量为10%-20%,柠檬酸铵的质量含量为0.5%-3%,所述纳米二氧化钛的粒径为10~60nm。
3.根据权利要求1所述的方法,其特征在于:铝盐包括但不限于硫酸铝、氯化铝、硝酸铝中的一种或几种,沉淀剂包括但不限于氢氧化钠、氢氧化铵、铝酸钾、铝酸钠中的一种或几种。
4.根据权利要求1所述的方法,其特征在于:共沉淀反应为并流共沉淀,共沉淀反应的温度为55℃-65℃,pH为7.5-8.5,共沉淀反应时间为35-65min,得到含有氢氧化铝溶胶的溶液中氢氧化铝质量浓度以氧化铝计为1~30g/100mL。
5.根据权利要求1所述的方法,其特征在于:加入混合浆液前老化温度为58℃-62℃,老化pH为8.0-8.5。
6.根据权利要求1所述的方法,其特征在于:加入混合浆液后继续进行老化15min-30min
,老化温度相比加入混合溶液前提高 2℃- 4℃,老化pH提高0.2-1.0。
7.根据权利要求1所述的方法,其特征在于:步骤(1)制备的混合溶液的加入量以最终催化剂中纳米二氧化钛的质量含量为2%-6%计。
8.根据权利要求1所述的方法,其特征在于:干燥温度为80℃-150℃ ,干燥时间为 1-10h。
9.根据权利要求1所述的方法,其特征在于:干燥温度为100℃-130℃,干燥时间为1-10h。
10.权利要求1至9任一所述方法制备的催化剂,其特征在于:所述含钛氧化铝干胶粉二氧化钛的含量为1%~20%,比表面积为350~520m2/g,孔容为0.6~1.5mL/g,平均孔直径为7nm~12nm,分散度为 0.3~0.5。
11. 根据权利要求10所述的方法,其特征在于:所述含钛氧化铝干胶粉二氧化钛的含量为2%~10%,比表面积为380~490m2/g,孔容为0.8~1.2mL/g,平均孔直径为8~10nm,分散度为0.35~0.4。
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