CN106669850B - A kind of preparation method of macropore alumina supporter - Google Patents
A kind of preparation method of macropore alumina supporter Download PDFInfo
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- CN106669850B CN106669850B CN201510761554.8A CN201510761554A CN106669850B CN 106669850 B CN106669850 B CN 106669850B CN 201510761554 A CN201510761554 A CN 201510761554A CN 106669850 B CN106669850 B CN 106669850B
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- ionic liquid
- aqueous solution
- ammonium
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- aging
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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 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002608 ionic liquid Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 35
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical class O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 16
- 238000004898 kneading Methods 0.000 claims abstract description 13
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- 239000005416 organic matter Substances 0.000 claims abstract description 5
- 230000009977 dual effect Effects 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 230000032683 aging Effects 0.000 claims description 31
- -1 alkyl ammonium halide Chemical class 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 238000006386 neutralization reaction Methods 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 10
- 230000026030 halogenation Effects 0.000 claims description 10
- 238000005658 halogenation reaction Methods 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- BKILWHYRLBCASZ-UHFFFAOYSA-M 2-[bis(2-hydroxyethyl)amino]ethanol;2-hydroxypropanoate;phenylmercury(1+) Chemical compound CC(O)C([O-])=O.[Hg+]C1=CC=CC=C1.OCCN(CCO)CCO BKILWHYRLBCASZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- ZRVJNMZHHALBIB-UHFFFAOYSA-N n-butyl-2-methylpentan-2-amine Chemical compound CCCCNC(C)(C)CCC ZRVJNMZHHALBIB-UHFFFAOYSA-N 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 2
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 claims description 2
- ZHQXROVTUTVPGO-UHFFFAOYSA-N [F].[P] Chemical compound [F].[P] ZHQXROVTUTVPGO-UHFFFAOYSA-N 0.000 claims description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 2
- 230000037396 body weight Effects 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 150000001350 alkyl halides Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- 238000009835 boiling Methods 0.000 abstract description 3
- QFIGQGUHYKRFAI-UHFFFAOYSA-K aluminum;trichlorate Chemical compound [Al+3].[O-]Cl(=O)=O.[O-]Cl(=O)=O.[O-]Cl(=O)=O QFIGQGUHYKRFAI-UHFFFAOYSA-K 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 238000005352 clarification Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000002513 implantation Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 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 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 208000012826 adjustment disease Diseases 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 2
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000011959 amorphous silica alumina Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 2
- 229940080818 propionamide Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- MQAYPFVXSPHGJM-UHFFFAOYSA-M trimethyl(phenyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)C1=CC=CC=C1 MQAYPFVXSPHGJM-UHFFFAOYSA-M 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- NRIRRQUXGSWZAG-UHFFFAOYSA-N C(CC)C(CCC)N(CCCC)CCCC Chemical compound C(CC)C(CCC)N(CCCC)CCCC NRIRRQUXGSWZAG-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- HDHICXMXQDZNGS-UHFFFAOYSA-N azanium dimethylazanium dichloride Chemical compound [Cl-].[NH4+].[Cl-].C[NH2+]C HDHICXMXQDZNGS-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- KSFUSYZPOPLNKH-UHFFFAOYSA-N n,n-dibutylpentan-2-amine Chemical class CCCCN(CCCC)C(C)CCC KSFUSYZPOPLNKH-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009736 wetting Methods 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
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B01J35/615—
-
- B01J35/635—
-
- B01J35/638—
-
- B01J35/647—
Abstract
The invention discloses a kind of preparation methods of macropore alumina supporter, including following content: (1) preparation of chloroaluminate ionic liquid I: by organic matter M1With alchlor at 60~150 DEG C, 70 DEG C~100 DEG C are selected, 1~4h of reaction, preferably 1~2h is carried out under stirring condition, then cooled to room temperature, obtains chloroaluminate ionic liquid I；(2) by M2And M3Ionic liquid II is made；(3) modified boehmite is prepared using pH value swing method；(4) boehmite, II aqueous solution of ionic liquid and binder that step (3) obtains are added in kneading machine, through extrusion, molding, drying and roasting after being uniformly mixed, obtain macropore alumina supporter.Needle this method preparation process is simple, green non-pollution.Prepared alumina support specific surface area is high, and aperture and hole appearance are larger, and have dual pore distribution, is well suited for preparing boiling bed residual oil, faulty wax oil hydrotreating carrier and catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of macropore alumina supporter, the alumina support specific surface area is high, aperture and
Hole appearance is larger, and has dual pore distribution, can be used for preparing boiling bed residual oil, faulty wax oil hydrotreating carrier and catalysis
Agent.
Background technique
Currently, the hydrotreating almost all of petroleum refining industry uses alumina support.Due to the irregular contracting of surface hydroxyl
It closes, alumina support all has certain acidity, these acid centres are easy to cause hydro carbons to be condensed and form carbon deposit, causes to be catalyzed
Agent inactivation.Especially for certain mink cell focus hydroprocessing processes for easily leading to carbon deposit, acid strong of catalyst support surface
It is weak directly to determine that catalyst is capable of the length of stable operation cycle.Currently, hydrotreating catalyst is with aluminium oxide or containing one kind
Or the aluminium oxide of various other elements such as Si, Ti, P, B, F etc. are carrier.In catalyst preparation process, can different phase to
Above-mentioned element is introduced in system, its object is to mutual between the acidity of regulating catalyst, and improvement active component and carrier
Effect.
A kind of preparation method of the CN201210462040.9 more particularly to phosphorous, fluorine, the micro-spherical catalyst carrier of titanium.It should
Method is first to be uniformly mixed phosphorous contained amorphous silica-alumina dry glue, fluorine-contained amorphous silica-alumina dry glue with titanium-containing amorphous silicon-aluminum dry gel
Afterwards, then dry glue wetting, extruded moulding will be mixed, and phosphorous, fluorine will be made through granulation, screening, drying, roasting, the microspheroidal of titanium will be catalyzed
Agent carrier.
CN1302848A discloses a kind of hydrogenation catalyst and preparation method thereof, which prepared by coprecipitation
, it is specifically included in aluminum salt solution and fluorine is added, boron, silicon, phosphorus, magnesium, titanium, zirconium or gallium is then added, then be separately added into soluble nickel
Saline solution and soluble tungsten saline solution, are precipitated using ammonium hydroxide.Although this method can be in terms of pore structure or acidity
There is certain adjustment effect, but it is suitable for that acidity is suitable for, but also to make pore structure that the comprehensive performance of carrier, which not only requires pore structure,
It organically cooperates with both acid distributions, the overall performance of catalyst could be improved in this way.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of macropore alumina supporter, this method preparation
Process is simple, green non-pollution.Prepared alumina support specific surface area is high, and aperture and hole appearance are larger, and have double-hole
Road distribution, is well suited for preparing boiling bed residual oil, faulty wax oil hydrotreating carrier and catalyst.
The preparation method of macropore alumina supporter of the invention, including following content:
(1) preparation of chloroaluminate ionic liquid I: by organic matter M1With alchlor at 60~150 DEG C, preferably 70 DEG C~
100 DEG C, 1~4h of reaction, preferably 1~2h are carried out under stirring condition, then cooled to room temperature, obtains chioroaiuminate ionic liquid
Body I；
(2) by M2And M3Ionic liquid II is made；
(3) modified boehmite is prepared using pH value swing method, detailed process is as follows:
I, a certain amount of bottom water is added in plastic reactor and is heated to 45 DEG C~100 DEG C, preferably 50 DEG C~95 DEG C, then
Chloroaluminate ionic liquid I and alkaline precipitating agent aqueous solution are added with certain flow respectively from plastic reactor both ends feed inlet,
Adjusting pH value is 8.6~12.0, preferably 9.0~11.0, neutralization reaction 5min~20min, preferably 10min~15min, then surely
Fixed 5 ~ 20min, preferably 10~15min；
II, it is passed through chloroaluminate ionic liquid I, adjusts pH value to 2~4, preferably 3.0~3.5, stablizes 5 ~ 20min, preferably
10~15min；
III, it is passed through alkaline precipitating agent, adjusting pH value to 8.6~12, preferably 9.0~11.0 stablizes 5 ~ 20min, preferably 10
~15min；
IV, it repeats above step II and III process 1~4 time, preferably 2 ~ 3 times, cemented into bundles carries out aging, filters, washes
It washs and dries, obtain modified boehmite；
(4) preparation of alumina support；
Boehmite, II aqueous solution of ionic liquid and binder that step (3) obtains are added in kneading machine, mixed
Through extrusion, molding, drying and roasting after uniformly, macropore alumina supporter is obtained.
In the method for the present invention, M described in step (1)1One of alkyl ammonium halide for being 1 ~ 4 for carbon atom number is several
Kind, alkyl is preferably one or more of methyl, ethyl, the preferred chlorine of halogen, further preferably dimethy lammonium chloride and/or
Diethyl ammonium halide.
In the method for the present invention, organic matter M as described in step (1)1Molar ratio is reacted to each other with aluminium chloride as 1:1~4:1
Between, preferably 1:1~3:1.
In the method for the present invention, M described in step (2)2For ammonium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate hexafluoro
One or more of ammonium phosphate, sodium hexafluoro phosphate, Potassium Hexafluorophosphate etc., preferably ammonium hexafluorophosphate and/or ammonium tetrafluoroborate.
In the method for the present invention, M described in step (2)3One of alkyl ammonium halide for being 8 ~ 12 for carbon atom number or
Several, preferably halogenated methyl tri-n-butylamine, halogenation dimethyl di-n-butylamine, halogenation propyl tri-n-butylamine, halogenation dipropyl two be just
One or more of butylamine, halogenated methyl puratized agricultural spray, halogenation dimethyl puratized agricultural spray, halogenation trimethyl puratized agricultural spray etc., preferably halogenation first
Base puratized agricultural spray, halogenation dimethyl di-n-butylamine, one or more of, the preferred chlorine of halogen.
In the method for the present invention, alkaline precipitating agent described in step (3) is selected from NaAlO2、KAlO2、NaOH、(NH4)2CO3Or
NH4OH, preferably NaAlO2、(NH4)2CO3Or NH4OH；(NH4)2CO3Or NH4The concentration of OH alkaline precipitating agent aqueous solution be 0.2~
1.0g/ml；NaAlO2Or KAlO2Aqueous solution is with Al2O3Content calculates, and concentration is 0.19~0.30g/ml.The chloro-aluminate
The flow of ionic liquid and alkaline precipitating agent aqueous solution is generally 0.5L/min~1.0 L/min, preferably 0.5 L/min~0.8
L/min。
In the method for the present invention, in step (3), the number of repetition for swinging neutralization is 1 time~4 times, preferably 2 times~3 times.
In the method for the present invention, aging temperature zone described in step (3) is 80~150 DEG C, preferably 90~120 DEG C；Aging
PH value range be 8.0~10.0, preferably 9.0~9.5；The time of aging is 0.5~2h, preferably 0.5~1h.It is preferred that in aging
Temperature be higher than step (3) in 10 DEG C~100 DEG C of neutralization temperature, best 20 DEG C~70 DEG C, aging pH value be higher than neutralization reaction pH
Value 0.5~4.0, preferably 1.5~2.5.
In the method for the present invention, drying condition described in step (3) are as follows: drying temperature be 100 DEG C~300 DEG C, preferably 100
DEG C~220 DEG C, drying time is 1h~5h, preferably 2h~4h.Dry atmosphere can be air or other atmosphere.The roasting
Condition are as follows: maturing temperature is 250 DEG C~500 DEG C, and preferably 300 DEG C~450 DEG C, calcining time is 2h~5h, preferably 3h~5h.Roasting
Burning atmosphere is oxygen-containing gas atmosphere.
In the method for the present invention, drying condition described in step (4) are as follows: drying temperature be 100~300 DEG C, preferably 100~
220 DEG C, drying time is 1~5h, preferably 2~4h.The roasting condition are as follows: maturing temperature be 350~800 DEG C, preferably 400
~550 DEG C, calcining time is 2~5h, preferably 3~5h.
Alumina support prepared by the present invention has the property that 300 ~ 350m of specific surface area2/ g, Kong Rong 0.9 ~
1.2ml/g, has dual pore distribution, and aperture is 10 ~ 15nm and 15 ~ 30nm；Wherein the pore size distribution of 10 ~ 15nm accounts for total pore volume
The pore size distribution of 35% ~ 40%, 15-30nm account for the 30% ~ 35% of total pore volume；On the basis of carrying alumina body weight, auxiliary agent is with amount of element
Meter accounts for 2% ~ 5%, and auxiliary agent is one of I or II form, and wherein I is fluorine and boron, and the molar ratio of fluorine boron is 1:1, II for fluorine and
Phosphorus, the molar ratio of fluorine phosphorus are 1:1.
Compared with prior art, the preparation method of alumina support provided by the invention has the advantage that
1, bialuminate solution is introduced using ionic liquid form, ionic liquid can be improved glue nuclear stability, ion
Liquid can be wrapped in aluminum hydroxide particles surface, play the role of dispersing agent, to prevent the collision between colloidal particle, shape
At micelle it is more complete, size more with, and in xerogel roasting process, the sky that is left after ionic liquid burning
Gap makes alumina grain be difficult to reunite, and obtained product size is tiny, and crystallinity is high.
2, the pore structure and acid distribution of alumina support, i.e. pore size distribution master are adjusted in this method using different ionic liquid
Concentrate on 10 ~ 15nm and 15 ~ 30nm；The auxiliary agents such as auxiliary agent fluorine, boron, phosphorus by the introducing of macromolecular ionic liquid II, to 15 ~
30nm is modified in duct, has the effect of larger space using ionic liquid II, the biggish hole after ionic liquid decomposition
Road will be exposed, and auxiliary agent is dispersed in channel surfaces, be effectively improved the property of channel surfaces, while the duct 15~30nm
Being conducive to the reaction that enters of the impurity such as asphalitine, colloid, the duct 10~15nm is conducive to the small molecule that reaction generates and is spreading, this
Sample makes its mutual cooperation, to improve the comprehensive performance of alumina-based supports, and then improves the comprehensive performance of catalyst.
Specific embodiment
It is described in detail below by preparation method of the specific embodiment to alumina dry glue of the invention.Embodiment
Only to the specific embodiment of the method for the present invention for example, not constituting the limitation of the scope of the present invention.
In the embodiment of the present invention and comparative example: ammonium hydroxide, sodium metaaluminate are that analysis is pure；Urea, propionamide, dimethylammonium chloride
Ammonium, ethyl ammonium chloride, the positive fourth ammonium of Diethylaminoethyl three, trimethylphenyl ammonium chloride, Qingdao Golden Horse Chemical Co., Ltd.；Chlorination 1-
Ethyl-3-methylimidazole, chlorination 1- butyl-pyridinium, Shanghai Bing Qi Chemical Industry Science Co., Ltd.
Embodiment 1
Alkyl dimethyl ammonium chloride 300g, aluminium chloride 190g, pure water 450g are mixed to join in reactor, heat under stiring
To 90 DEG C, after constant temperature 1h, clarification naturally cools to 30 DEG C or so, obtains aluminium chlorate ionic liquid I aqueous solution, ionic liquid I's
Concentration is 5g/L.
Trimethylphenyl ammonium chloride 500g, sodium tetrafluoroborate 260g, pure water 450g, mixing are heated to 90 DEG C under stiring,
After constant temperature 3h, clarification naturally cools to 30 DEG C or so, obtains II aqueous solution of ionic liquid after being diluted with water a certain concentration, from
The mass concentration of sub- liquid aqueous solution is 25%.
5L bottom water is added in reactor, is heated to 60 DEG C.Then respectively from reactor both ends feed inlet I and feed inlet II
It for the sodium aluminate solution of 0.2g/L and with 0.9L/min implantation concentration is the aluminium chlorate of 1.2g/L with 0.5L/min implantation concentration
Ionic liquid I aqueous solution, adjusting pH is neutralization reaction 10min after 10.0；Then stop injection sodium metaaluminate, be passed through aluminium chlorate
Ionic liquid I aqueous solution adjusts pH value to 3.0, after stablizing 10min；Stop injection aluminium chlorate ionic liquid aqueous solution, injection
Sodium metaaluminate aqueous solution adjusts pH value to 9.0, stablizes 15min；Terminate after repeating the above process each 1 time；It is carried out after cemented into bundles
Aging, ageing time 0.5h, aging temperature are 80 DEG C, after aging filtering in 120 DEG C of dry 3h, obtain it is required intend it is thin
Diaspore.
The above-mentioned boehmite of 200g is placed in II aqueous solution of 50g ionic liquid and 60g in kneading machine after being sufficiently mixed
Binder is added in kneading machine, through extrusion, molding, 120 DEG C of dry 3h, 500 DEG C of roasting 3h after being uniformly mixed, finally obtains institute
The alumina support ZT-1 needed.
Embodiment 2
Urea 100g, aluminium chloride 65g, pure water 150g are mixed to join in reactor, are heated to 100 DEG C under stiring, perseverance
After warm 2h, clarification naturally cools to 30 DEG C or so, obtains aluminium chlorate ionic liquid I aqueous solution, and the concentration of ionic liquid I is 9g/
L。
Chlorination 1- ethyl-3-methylimidazole 250g, potassium tetrafluoroborate 130g, pure water 150g, mixing, are heated under stiring
80 DEG C, after constant temperature 2h, clarification naturally cools to 30 DEG C or so, is diluted with water a certain concentration, obtains II aqueous solution of ionic liquid,
Ionic liquid concentration is 30%.
4L bottom water is added in reactor, is heated to 65 DEG C.Then respectively from reactor both ends feed inlet I and feed inlet II
It for the sodium aluminate solution of 0.5g/L and with 1.8L/min implantation concentration is the aluminium chlorate of 1.5g/L with 0.6L/min implantation concentration
Ionic liquid I aqueous solution, adjusting pH is neutralization reaction 15min after 9.0；Then stop injection sodium metaaluminate, be passed through aluminium chlorate
Ionic liquid I aqueous solution adjusts pH value to 3.5, after stablizing 10min；Stop injection aluminium chlorate ionic liquid aqueous solution, injection
Sodium metaaluminate aqueous solution adjusts pH value to 11.0, stablizes 10min；Terminate after repeating the above process each 2 times；Cemented into bundles is laggard
Row aging, ageing time 1.5h, aging temperature are 90 DEG C, and filtering obtains required intend in 130 DEG C of dry 2h after aging
Boehmite.
The above-mentioned boehmite of 250g is placed in II aqueous solution of 70g ionic liquid and 50g in kneading machine after being sufficiently mixed
Binder is added in kneading machine, through extrusion, molding, 110 DEG C of dry 4h, 600 DEG C of roasting 2h after being uniformly mixed, finally obtains institute
The alumina support ZT-2 needed.
Embodiment 3
Propionamide 200g, aluminium chloride 140g, pure water 200g are mixed to join in reactor, are heated to 800 under stiring
DEG C, after constant temperature 1.5h, clarification naturally cools to 30 DEG C or so, obtains aluminium chlorate ionic liquid I aqueous solution, ionic liquid I's is dense
Degree is 10g/L.
Chlorination 1- butyl-pyridinium 500g, potassium tetrafluoroborate 280g, pure water 350g, mixing are heated to 90 DEG C, perseverance under stiring
After warm 3h, clarification naturally cools to 30 DEG C or so, is diluted with water a certain concentration, obtains II aqueous solution of ionic liquid, ionic liquid
The concentration of aqueous solution is 45%.
4L bottom water is added in reactor, is heated to 70 DEG C.Then respectively from reactor both ends feed inlet I and feed inlet II
It for the sodium aluminate solution of 1.0g/L and with 1.8L/min implantation concentration is the aluminium chlorate of 2.6g/L with 1.2L/min implantation concentration
Ionic liquid I aqueous solution, adjusting pH is neutralization reaction 20min after 10.0；Then stop injection sodium metaaluminate, be passed through aluminium chlorate
Ionic liquid I aqueous solution adjusts pH value to 3.0, after stablizing 10min；Stop injection aluminium chlorate ionic liquid I aqueous solution, note
Enter sodium metaaluminate aqueous solution, adjusts pH value to 10.0, stablize 10min；Terminate after repeating the above process each 3 times；After cemented into bundles
Aging, ageing time 1.0h are carried out, aging temperature is 100 DEG C, and filtering obtains institute in 150 DEG C of dry 1.5h after aging
The boehmite needed.
The above-mentioned boehmite of 300g is placed in II aqueous solution of 65g ionic liquid and 70g in kneading machine after being sufficiently mixed
Binder is added in kneading machine, through extrusion, molding, 120 DEG C of dry 3h after being uniformly mixed, finally obtains required carrying alumina
Body ZT-3.
Comparative example 1
In reaction kettle be added 2L distilled water, adjustment reaction temperature be 70 DEG C, by sodium metaaluminate (in terms of aluminium oxide, concentration
Neutralization reaction is carried out for 26g/mL) and aluminum sulfate (in terms of aluminium oxide, concentration 8g/mL) cocurrent, pH value 7.5, after reacting 1h,
Aging is carried out, aging pH is 11, and ageing time 30min, filtration drying obtains required boehmite.By 300g it is above-mentioned intend it is thin
Diaspore is placed in kneading machine be sufficiently mixed after 100g binder is added in kneading machine, be uniformly mixed after through extrusion, molding,
120 DEG C of dry 3h, finally obtain required alumina support ZT-4.
Comparative example 2
It is added in aluminum sulfate aqueous solution (in terms of aluminium oxide, concentration 8g/mL) and tetrafluoro boron is added by the dosage of embodiment 1
Sour ammonium and sodium hexafluoro phosphate obtain the aluminum sulfate solution of fluorine-containing, boron and phosphorus.2L distilled water, adjustment reaction are added in reaction kettle
Temperature is 70 DEG C, by the aluminum sulfate solution of sodium metaaluminate (in terms of aluminium oxide, concentration 26g/mL) and fluorine-containing, boron and phosphorus and is flowed into
Row neutralization reaction, pH value 7.5 after reacting 1h, carry out aging, and aging pH is 11, and ageing time 30min, filtration drying obtains
Required aluminium hydroxide.2L distilled water is added in reaction kettle, adjustment reaction temperature is 70 DEG C, by sodium metaaluminate (with aluminium oxide
Meter, concentration 26g/mL) and the progress neutralization reaction of aluminum sulfate (in terms of aluminium oxide, concentration 8g/mL) cocurrent, pH value 7.5, instead
After answering 1h, aging is carried out, aging pH is 11, and ageing time 30min, filtration drying obtains required boehmite.By 400g
Above-mentioned boehmite is placed in kneading machine be sufficiently mixed after 200g binder is added in kneading machine, be uniformly mixed after through squeeze
Item, molding, 150 DEG C of dry 3h, 700 DEG C of roasting 4h, finally obtain required alumina support ZT-5.
The property of 1 alumina support of table.
Active appraisal experiment:
After catalyst in embodiment 1-3 and comparative example 1-2 is loaded hydrogenation active metal component using conventional method,
Number is CT-1, CT-2, CT-3, CD-1, CD-2 respectively.It is commented using the activity that the miscella of VGO and DAO carries out catalyst as raw material
Valence, catalyst activity evaluation experimental carry out on 50mL small hydrogenation device, carry out presulfurization to catalyst before activity rating.It urges
Agent volume space velocity 1.0h in reaction stagnation pressure 8.0MPa, liquid-1, hydrogen to oil volume ratio 800:1, reaction temperature is 380 DEG C, is as a result seen
Table 2 and 3.
2 raw material oil nature of table.
3 catalyst activity evaluation result of table.
Seen from table 3, the hydrodenitrogeneration, hydrodesulfurization of catalyst prepared by the present invention and metal removal activity be significantly better than than
Compared with example.
Claims (11)
1. a kind of preparation method of macropore alumina supporter, including following content:
(1) preparation of chloroaluminate ionic liquid I: by organic matter M1It is carried out under 60~150 DEG C, stirring condition with alchlor
1~4h is reacted, then cooled to room temperature, obtains chloroaluminate ionic liquid I；The M1It is 1 ~ 4 for carbon atom number
One or more of alkyl ammonium halide；
(2) by M2And M3Ionic liquid II is made；The M2For ammonium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate hexafluoro phosphorus
One or more of sour ammonium, sodium hexafluoro phosphate, Potassium Hexafluorophosphate；The M3The alkyl halide for being 8 ~ 12 for carbon atom number
One or more of ammonium；
(3) modified boehmite is prepared using pH value swing method, detailed process is as follows:
I, a certain amount of bottom water is added in plastic reactor and is heated to 45 DEG C~100 DEG C, then from plastic reactor both ends into
Chloroaluminate ionic liquid I and alkaline precipitating agent aqueous solution is added respectively with certain flow in material mouth, adjust pH value be 8.6~
Then 12.0, neutralization reaction 5min~20min stablize 5 ~ 20min；
II, it is passed through chloroaluminate ionic liquid I, adjusts pH value to 2~4, stablizes 5 ~ 20min；
III, it is passed through alkaline precipitating agent, adjusts pH value to 8.6~12, stablizes 5 ~ 20min；
IV, it repeats above step II and III process 1~4 time, cemented into bundles, carries out aging, is filtered, washed and dried, changed
Property boehmite；
(4) preparation of alumina support；Boehmite, II aqueous solution of ionic liquid and binder that step (3) obtains are added
Enter into kneading machine, through extrusion, molding, drying and roasting after being uniformly mixed, obtains macropore alumina supporter.
2. according to the method for claim 1, it is characterised in that: M described in step (1)1For dimethy lammonium chloride and/or two
Ethyl ammonium halide.
3. according to the method for claim 1, it is characterised in that: organic matter M as described in step (1)1It is mutual with alchlor
Reaction molar ratio is 1:1~4:1.
4. according to the method for claim 1, it is characterised in that: M described in step (2)2For ammonium hexafluorophosphate and/or four
Ammonium fluoroborate.
5. according to the method for claim 1, it is characterised in that: M described in step (2)3For halogenation dimethyl di-n-butylamine,
One or more of halogenation dimethyl puratized agricultural spray or halogenation trimethyl puratized agricultural spray.
6. according to the method for claim 1, it is characterised in that: alkaline precipitating agent described in step (3) is selected from NaAlO2、
KAlO2、NaOH、(NH4)2CO3Or NH4OH；(NH4)2CO3Or NH4The concentration of OH alkaline precipitating agent aqueous solution is 0.2~1.0g/
mL；NaAlO2Aqueous solution is with Al2O3Content calculates, and concentration is 0.19~0.30g/mL.
7. according to the method for claim 1, it is characterised in that: step (3) chloroaluminate ionic liquid I and alkalinity are heavy
The flow of shallow lake agent aqueous solution is 0.5~1.0 L/min.
8. according to the method for claim 1, it is characterised in that: aging temperature zone described in step (3) is 80~150
DEG C, the pH value range of aging is 8.0~10.0, and the time of aging is 0.5~2h.
9. according to the method for claim 1, it is characterised in that: drying condition described in step (4) are as follows: drying temperature is
100~300 DEG C, drying time is 1~5h；The roasting condition are as follows: maturing temperature is 350~800 DEG C, calcining time 2
~5h.
10. the alumina support prepared according to method described in claim 1 ~ 9 any claim, it is characterised in that have such as
Lower property: 300 ~ 350m of specific surface area20.9 ~ 1.2ml/g of/g, Kong Rong, has dual pore distribution, and aperture is 10 ~ 15nm and 15
~30nm；Wherein the pore size distribution of 10 ~ 15nm accounts for total pore volume 35% ~ 40%, and the pore size distribution of 15-30nm accounts for the 30% ~ 35% of total pore volume.
11. the alumina support prepared according to method described in claim 1 ~ 9 any claim, it is characterised in that with modification
On the basis of carrying alumina body weight, auxiliary agent accounts for 2% ~ 5% with element meter, and auxiliary agent is one of I or II form, and wherein I is fluorine
And boron, the molar ratio of fluorine boron are 1:1, II is fluorine and phosphorus, and the molar ratio of fluorine phosphorus is 1:1.
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| US4721696A (en) * | 1987-03-11 | 1988-01-26 | Phillips Petroleum Company | Silica-modified alumina and process for its preparation |
| CN1762579A (en) * | 2005-09-09 | 2006-04-26 | 清华大学 | Method for preparing large pore capacity, high specific surface area alumina |
| CN101663239A (en) * | 2007-03-27 | 2010-03-03 | 美铝澳大利亚有限公司 | Method for preparing aluminium oxide |
| CN102167373A (en) * | 2011-03-04 | 2011-08-31 | 南京工业大学 | Method for synthesizing mesoporous aluminum oxide by using dicationic imidazolium ionic liquid |
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2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4721696A (en) * | 1987-03-11 | 1988-01-26 | Phillips Petroleum Company | Silica-modified alumina and process for its preparation |
| CN1762579A (en) * | 2005-09-09 | 2006-04-26 | 清华大学 | Method for preparing large pore capacity, high specific surface area alumina |
| CN101663239A (en) * | 2007-03-27 | 2010-03-03 | 美铝澳大利亚有限公司 | Method for preparing aluminium oxide |
| CN102167373A (en) * | 2011-03-04 | 2011-08-31 | 南京工业大学 | Method for synthesizing mesoporous aluminum oxide by using dicationic imidazolium ionic liquid |
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