CN107376887B - Silica sol, silicon-aluminum sol, preparation method and application thereof, catalytic cracking catalyst and preparation method - Google Patents
Silica sol, silicon-aluminum sol, preparation method and application thereof, catalytic cracking catalyst and preparation method Download PDFInfo
- Publication number
- CN107376887B CN107376887B CN201610320487.0A CN201610320487A CN107376887B CN 107376887 B CN107376887 B CN 107376887B CN 201610320487 A CN201610320487 A CN 201610320487A CN 107376887 B CN107376887 B CN 107376887B
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- Prior art keywords
- sol
- aluminum
- silica
- catalyst
- alumina
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- 239000003054 catalyst Substances 0.000 title claims abstract description 180
- 238000002360 preparation method Methods 0.000 title claims abstract description 79
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 50
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 175
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 168
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 151
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 90
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 52
- 239000002808 molecular sieve Substances 0.000 claims abstract description 51
- 239000011230 binding agent Substances 0.000 claims abstract description 32
- 238000005260 corrosion Methods 0.000 claims abstract description 17
- 230000007797 corrosion Effects 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 135
- 238000000034 method Methods 0.000 claims description 75
- 238000006243 chemical reaction Methods 0.000 claims description 61
- -1 aluminum compound Chemical class 0.000 claims description 54
- 229910052593 corundum Inorganic materials 0.000 claims description 52
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 43
- 239000000126 substance Substances 0.000 claims description 43
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 38
- 239000002002 slurry Substances 0.000 claims description 27
- 239000011159 matrix material Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 23
- 229910052681 coesite Inorganic materials 0.000 claims description 21
- 229910052906 cristobalite Inorganic materials 0.000 claims description 21
- 229910052682 stishovite Inorganic materials 0.000 claims description 21
- 229910052905 tridymite Inorganic materials 0.000 claims description 21
- 239000011574 phosphorus Substances 0.000 claims description 20
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 239000000084 colloidal system Substances 0.000 claims description 17
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 17
- 239000004927 clay Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 238000001694 spray drying Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910052596 spinel Inorganic materials 0.000 claims description 11
- 239000011029 spinel Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- 238000004537 pulping Methods 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 18
- 239000002245 particle Substances 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 38
- 239000000047 product Substances 0.000 description 20
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 12
- 239000004411 aluminium Substances 0.000 description 11
- 239000005995 Aluminium silicate Substances 0.000 description 10
- 235000012211 aluminium silicate Nutrition 0.000 description 10
- 239000000571 coke Substances 0.000 description 10
- 238000005336 cracking Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000010779 crude oil Substances 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- 150000002910 rare earth metals Chemical class 0.000 description 9
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 8
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 229910052621 halloysite Inorganic materials 0.000 description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- 238000012545 processing Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000004113 Sepiolite Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
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- 235000019355 sepiolite Nutrition 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
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- 238000005299 abrasion Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 3
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- 239000010936 titanium Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 2
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- 235000012239 silicon dioxide Nutrition 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
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- 229910006415 θ-Al2O3 Inorganic materials 0.000 description 2
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- 241001391944 Commicarpus scandens Species 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ILXDAXZQNSOSAE-UHFFFAOYSA-N [AlH3].[Cl] Chemical compound [AlH3].[Cl] ILXDAXZQNSOSAE-UHFFFAOYSA-N 0.000 description 1
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- 150000001399 aluminium compounds Chemical class 0.000 description 1
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- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
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Images
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
- B01J21/08—Silica
-
- 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
- B01J21/12—Silica and alumina
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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Abstract
The invention relates to the field of silica-alumina sol for catalytic cracking catalysts, and discloses silica sol, silica-alumina sol, a preparation method and application of the silica sol and the silica-alumina sol, a catalytic cracking catalyst and a preparation method of the catalytic cracking catalyst. SiO in the silica sol2Is 25 to 40 wt% of Na2The content of O is less than 0.15 wt%; the silica sol has a pH value of 2-10 and a density of 1.1g/cm3～1.3g/cm3The viscosity is 200 mPas or more. The silicon-aluminum sol further provided by the invention contains the aluminum sol with the advantages of less free chloride ions, optimized structure, large viscosity, small corrosion rate, high pH value and the like, can strengthen the particle structure of the binder, increase the binding performance of the binder, reduce the blockage of the binder on the molecular sieve structure of the active component in the catalyst, reduce the influence degree of the binder on the activity of the catalyst, reduce the usage amount of the molecular sieve in the catalyst and reduce the cost of the catalyst.
Description
Technical Field
The invention relates to the field of silicon-aluminum sol for a catalytic cracking catalyst, in particular to silicon sol, silicon-aluminum sol consisting of the silicon sol, a preparation method of the silicon-aluminum sol, application of the silicon-aluminum sol in preparation of the catalytic cracking catalyst, the catalytic cracking catalyst and a preparation method of the catalytic cracking catalyst.
Background
The fluidized catalytic cracking process is the most important means for the secondary processing of crude oil, and the content of the active component molecular sieve in the catalyst is increased from 15-20% in the early stage to 35% or even more than 40% in the current stage as the heavy and the poor FCC feed is increased. With the increase of the content of the molecular sieve, the attrition index and the sphericity of the catalyst become very important problems in the catalyst preparation process. The catalyst must meet certain strength requirements and form microsphere particles with the particle size of 20-150 microns and the average particle size of 60-80 microns, so that the normal flowing operation of the catalytic cracking catalyst in a reaction device can be met.
At present, FCC catalyst products in China are mainly divided into fully synthetic molecular sieve catalysts, semi-synthetic molecular sieve catalysts and in-situ crystallization catalysts. The molecular sieve (X type or Y type) adopted in the preparation process of the fully-synthesized molecular sieve catalyst can be Na type, or the Na type molecular sieve can be exchanged by rare earth ions or ammonium ions in advance, and then the RE type or REH type molecular sieve is obtained by drying and roasting, added into the fully-synthesized colloid and spray-dried to prepare the spherical catalyst; adding Na-type zeolite, spray drying, exchanging again, and secondary drying to obtain spherical catalyst. The preparation method of the semi-synthetic molecular sieve catalyst is more, and the main method is that kaolin is firstly mixed with colloid, and slurry obtained by mixing the colloid slurry mixed with the kaolin and the ultra-stable Y-shaped molecular sieve is prepared into the microsphere catalyst by spray drying; the spray-dried catalyst was reslurried and washed with water to remove Na formed during the reaction+Then using soluble rare earth ion to make exchange, washing the exchanged catalyst to remove unreacted rare earth exchanger and soluble salt, secondary dryingAfter drying, the semi-synthetic molecular sieve catalyst is prepared. The in-situ crystallization method is to use natural kaolin as an initial raw material, prepare an active component and a matrix material simultaneously by a one-step method, and then prepare the kaolin type FCC catalyst by modification treatment.
With the increase of the content of the molecular sieve which is the active component of the catalyst, the preparation method of the fully synthetic catalyst can not meet the requirement of the catalyst on the strength, but adopts the semi-synthesis process of taking kaolin as a substrate, taking the molecular sieve as the active component and taking various silicon/aluminum glues as binders, the preparation process is simple, the preparation cost is low, and the catalyst has good strength when the content of the molecular sieve is high. The semisynthetic catalyst process is prepared by preparing a binder, a matrix and an active matrix into uniformly mixed slurry and then performing spray drying, and how to continuously improve the catalyst gelling process becomes a very important problem in the preparation process: 1) the productivity is improved, the energy consumption is reduced, the usage amount of the molecular sieve is reduced, and the cost is reduced. 2) Forming a good sphericity. The aim of spray drying is to evaporate excessive moisture in slurry at a certain temperature, the moisture which needs to be evaporated when the solid content is low is large, the retention time of materials in a drying tower is the same, the evaporation heat which needs to be increased or the drying temperature is high, so that the moisture rapidly escapes from the inner surface of particles at high temperature to form hollow spheres or microspheres with apple base shapes, on one hand, the strength of the catalyst is reduced, and on the other hand, the catalyst is easy to break when fluidized in an FCC reaction-regeneration system (reverse regeneration system). 3) The preparation method of the adhesive is improved, the adhesive property of the adhesive is improved, the particles of the adhesive are more uniform through the improvement of the adhesive, a better series adhesive effect is achieved in the gelling process of the catalyst, the blockage of molecular sieve pore channels is reduced, and the activity of the catalyst is improved. 4) A more suitable matrix is developed, the matrix is used as a cracking medium of macromolecules in the catalytic cracking process, the pore structure of the matrix needs to be large enough to meet the cracking process of the macromolecules in the heavy oil at the present stage, and the thermal stability of the catalyst to the heavy oil cracking capability and the catalyst activity is improved. 5) The viscosity of the catalyst is reduced, the conveying resistance of the catalyst colloid is reduced, the spraying quality of the catalyst is improved, and the blocking condition of a catalyst spraying tower is reduced.
CN1445167A discloses a new process for preparing aluminum sol, the preparation method comprises: all taking aluminum chloride and aluminum oxide or/and aluminum hydroxide or/and soft aluminum as aluminum sources and hydrochloric acid as Al according to a molar ratio2O3: mixing HCl 1.0-1.4:1, and reacting at 80-130 deg.C for 3-40 hr.
CN1743267A discloses a method for preparing a chlorine-containing aluminum sol, which comprises the following steps of mixing Al2(OH)1～3Cl3～5The aqueous solution of polyaluminum chloride is brought into full contact with metallic aluminum to react to prepare an aluminum sol containing 5 to 13 mass% of aluminum and having an Al/Cl mass ratio of 0.6 to 2.0. The method uses the polyaluminium chloride to replace part of metal aluminium to produce the aluminium sol, does not use hydrochloric acid in the production process, has small corrosion to equipment, discharges small amount of hydrogen and is safer to operate. The produced alumina sol has low cost and is suitable for the adhesive of the catalyst.
CN1552801A discloses a catalytic cracking catalyst containing a silica sol binder and a preparation method thereof, wherein the catalyst comprises 20-80 m% of clay and 5-30 m% of silica sol (SiO2Calculated as pyroxylin), 0-30 m% of pseudo-boehmite (calculated as Al)2O3calculated by pyroxylin), 5-40 m% of faujasite, ZSM-5 zeolite, β zeolite and their mixture with unit cell constant of 2.432-2.472 nm, 0-5 m% (calculated by oxide) of compound selected from antimony, mixed rare earth, titanium, magnesium, zinc, phosphorus, strontium or their mixture.
CN101130162A discloses a cracking catalyst and a preparation method thereof, the catalyst contains 15-50 wt% of clay and 1-40 wt% of SiO from silica sol on a dry basis25 to 30% by weight of Al originating from alumina and/or alumina precursors2O35 to 50 wt.% on a dry basis of a molecular sievePrepared by a method comprising the following steps: mixing and pulping clay and silica sol, mixing and pulping the pulp obtained by the pulping in the step A, alumina and/or an alumina precursor and a molecular sieve, and spray-drying, washing and drying the pulp obtained by the pulping in the step B to obtain the cracking catalyst. The catalyst does not need to add a surfactant in the preparation process, and is high in selectivity when used for heavy oil catalytic cracking gasoline.
But the crude oil is changed into heavy crude oil (the relative density of the crude oil is 0.9-1.0 g/cm)3(20 ℃) and the requirement on the property of the catalyst is increased, so that the binder in the gelling process of the catalyst needs to be improved, the binding performance of the binder is increased, the binder can be modified, the particle structure of the binder is strengthened, the heavy metal resistance of the binder is improved, the blockage of the binder on the structure of an active component molecular sieve in the catalyst is reduced, the influence degree of the binder on the activity of the catalyst is reduced, the use amount of the molecular sieve is reduced, and the cost of the catalyst is reduced. It is desirable to prepare catalysts that meet the processing requirements of crude oil upgrading.
Disclosure of Invention
The invention aims to meet the requirements of crude oil heavy processing, and provides a silica sol, a silica-alumina sol, a preparation method and application of the silica sol and the silica-alumina sol, a catalytic cracking catalyst and a preparation method of the catalytic cracking catalyst.
The inventor of the invention researches and discovers that the preparation method of the silica sol is improved, and the silica-alumina sol obtained by mixing the silica sol with the alumina sol with less free chlorine ions, optimized structure, high viscosity, low corrosion rate and high pH value can be used as a binder in the preparation of a catalytic cracking catalyst, so that the particle structure of the binder is strengthened, the binding performance of the binder is improved, the blockage of the binder on the molecular sieve structure of an active component in the catalyst is reduced, the influence degree of the binder on the activity of the catalyst is reduced, the use amount of the molecular sieve is reduced, and the cost of the catalyst is reduced.
In order to achieve the foregoing object, according to a first aspect of the present invention, there is provided a silica sol in which SiO is contained2Is 25 to 40 wt% of Na2The content of O is less than 0.15 wt%; the pH value of the silica sol is 2-10, and the silica sol is denseThe degree is 1.1g/cm3～1.3g/cm3The viscosity is 200 mPas or more.
According to a second aspect of the present invention, there is provided a silica-alumina sol comprising an alumina sol and a silica sol, wherein the silica-alumina sol is formed of SiO2Calculated as silica sol and Al2O3The weight ratio of the aluminum sol is (1-4): 1, wherein the silica sol is the silica sol of the present invention.
According to a third aspect of the present invention, there is provided a process for the preparation of a silica alumina sol comprising: will be mixed with Al2O3Calculated as alumina sol and SiO2Calculated as SiO for the silica sols according to the invention2：Al2O3The weight ratio is (1-4): 1, carrying out liquid phase mixing for 1-3 h at the temperature of 20-50 ℃ to obtain the silicon-aluminum sol.
According to a fourth aspect of the present invention, there is provided a silica-alumina sol obtainable by the process of the invention.
According to a fifth aspect of the present invention there is provided the use of the silica alumina sol of the present invention in the preparation of a catalytic cracking catalyst.
According to a sixth aspect of the present invention, there is provided a process for preparing a catalytic cracking catalyst, the process comprising: the preparation method comprises the steps of pulping a binder, clay, a molecular sieve and an optional macroporous matrix to obtain catalyst slurry, and carrying out spray drying on the catalyst slurry, wherein the binder is the silicon-aluminum sol provided by the invention.
According to a seventh aspect of the present invention, there is provided a catalytic cracking catalyst obtained by the production method of the present invention.
The silicon-aluminum sol used as the binder in the catalytic cracking catalyst provided by the invention contains the silicon sol and the aluminum sol with less free chloride ions, optimized structure, large viscosity, small corrosion rate and high pH value, when the catalytic cracking catalyst is prepared, the solid content of the prepared catalytic cracking catalyst slurry can be improved to be more than 40 wt%, and the molecular sieve content in the prepared catalytic cracking catalyst can be reduced to be less than 30 wt%, for example, 5-30 wt%; meanwhile, the strength and the activity of the obtained catalyst meet the industrial use requirements, and the abrasion index of the catalyst is obviously reduced.
The preparation method of the silica sol takes monocrystalline silicon as a raw material, and is prepared by carrying out a first reaction and a second reaction with sodium hydroxide step by step and removing sodium ions by an ion exchange method. The silica sol prepared by the method has the advantages of stability under different pH values (such as 2-6) and temperatures (0-50 ℃), easy removal of sodium oxide and the like.
In addition, the method for preparing the aluminum sol used for the silicon-aluminum sol has the advantages of simple process, easily controlled conditions, capability of preparing the aluminum sol at a lower temperature, less free chloride ions, optimized structure, high viscosity, low corrosion rate, high pH value and the like.
Furthermore, the method for preparing the aluminum sol reduces the usage amount of hydrochloric acid, reduces the addition amount of chloride ions, reduces the damage of free acid to the properties of the aluminum sol, improves the activity of the aluminum sol, and avoids the defects that the pH value of the aluminum sol is too low, so that a molecular sieve is damaged, and the activity of a catalyst is influenced due to excessive hydrochloric acid.
Meanwhile, the method for preparing the aluminum sol can use the inorganic aluminum compound to replace part of metallic aluminum, thereby obviously reducing the production cost of the aluminum sol.
In the invention, the phosphorus compound and/or the rare earth compound are further used for modification in the preferred embodiment of the method for preparing the aluminum sol, so that the use amount of hydrochloric acid can be reduced, the obtained aluminum sol particles are more uniform and moderate, the specific surface area is larger, and the bonding performance of the aluminum sol and the final silicon-aluminum sol is improved. The phosphorus and/or rare earth modified alumina sol is used simultaneously, the reaction can be carried out to form ultrafine phosphoric acid and/or rare earth colloidal composite precipitate, the precipitate has certain reaction activity and equivalent cohesiveness, and compared with the method that a certain amount of rare earth and/or phosphorus is deposited on the surface of the catalyst after the catalyst is molded, the phosphorus compound and/or rare earth compound modified alumina sol has the following advantages:
(1) the phosphorus compound and/or the rare earth compound can be more effectively utilized, the utilization rate of the rare earth/phosphorus is improved, and the adding amount and the loss of the rare earth/phosphorus in the preparation process of the molecular sieve and the catalyst are reduced;
(2) the distribution of the rare earth/phosphorus in the catalyst matrix is improved, so that the rare earth/phosphorus is more uniformly distributed in the matrix, and the heavy oil cracking capability of the catalyst is improved;
(3) the rare earth ion modified aluminum sol can better enrich and deposit the silicon-aluminum sol on the surface of a molecular sieve and the surface of a matrix, has better bonding property and enhances the heavy metal resistance of the catalyst;
(4) the addition of the phosphorus compound can stabilize the catalyst structure and improve certain catalyst activity;
(5) the adhesive property of the silicon-aluminum sol is enhanced, and the catalyst performance is improved.
The method for preparing the catalytic cracking catalyst has the advantages that the silicon-aluminum sol is added, the viscosity of the slurry is greatly reduced, the gelling time and the content of the molecular sieve are reduced, the production process is simplified, and the production cost is reduced.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 shows the preparation of aluminum sols prepared in example 1 and comparative example 127Nuclear magnetic spectrum of Al.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, there is provided a silica sol in which SiO is present2Is 25 to 40 wt% of Na2The content of O is less than 0.15 wt%; the silica sol has a pH value of 2-10 and a density of 1.1g/cm3～1.3g/cm3The viscosity is 200 mPas or more.
In the present invention, SiO in the silica sol2、Na2The content of O is based on the total weight of the silica sol.
In the present invention, the density and viscosity of the silica sol were measured at 20 ℃. Preferably, the viscosity is 200-10000 mPa & s; more preferably 200 to 5000 mPas.
According to a preferred embodiment of the present invention, the method for preparing the silica sol comprises: (a) carrying out a first reaction on monocrystalline silicon and a sodium hydroxide solution A; the first reaction temperature is 50-70 ℃, and the first reaction time is 1-3 h; (b) carrying out a second reaction on the product of the first reaction and a sodium hydroxide solution B, wherein the second reaction temperature is 70-90 ℃, and the second reaction time is 1-2 h; (c) cooling the product of the second reaction to obtain colloid, and performing ion exchange on the colloid to reduce the content of sodium ions to obtain silica sol; wherein the weight ratio of the monocrystalline silicon calculated by Si to the total amount of the sodium hydroxide solution A and the sodium hydroxide solution B calculated by Na is (0.6-1.4): 1; and (3) the weight ratio of the sodium hydroxide solution A to the sodium hydroxide solution B is (25-35) calculated by Na: (65-75); the second reaction temperature is 20-30 ℃ higher than the first reaction temperature. Cooling in step (c), for example to a temperature below 40 ℃, for example to a temperature of 15 to 40 ℃
In the method for preparing the silica sol of the present invention, the first reaction in the step (a) is performed at a lower temperature using a small amount of alkali, so that a part of single crystal Si is dissolved to form a part of effective colloid. The temperature of the second reaction in the step (b) is higher than that of the first reaction, a large amount of alkali is used, and the monocrystalline silicon and the alkali which are left after the first reaction undergo a high-temperature reaction process, so that the monocrystalline silicon and the alkali can perform sufficiently and stably secondary reaction, the obtained silica sol is not easy to form condensation, and the colloidal property is better, and the catalyst is more suitable for being used as a catalytic cracking catalyst binder.
In the preferred preparation method of the silica sol, monocrystalline silicon is selected as a silicon source, sodium hydroxide solution is added step by step, and the dosage and the reaction condition of each step are controlled, so that the silica sol prepared has the characteristics.
In the present invention, the ion exchange is carried out using a cation exchange resin in contact with the colloid, preferably a cation exchange resin of the strong acid type, such as a D101 hydrogen ion exchange resin which can be from Zimbodong David, Inc.
According to the present invention, the purity of the single crystal silicon is preferably 95 to 99% by weight.
Preferably, the concentration of the sodium hydroxide solution A and the sodium hydroxide solution B is 40-70 wt%.
According to a second aspect of the present invention, there is provided a silica-alumina sol comprising an alumina sol and a silica sol, wherein the silica-alumina sol is formed of SiO2Calculated as silica sol and Al2O3The weight ratio of the aluminum sol is (1-4): 1, wherein the silica sol is the silica sol of the present invention.
The silica-alumina sol of the present invention can be prepared by mixing alumina sol (as Al)2O3Calculated as SiO) and silica sol2Calculated) according to (50-80): (20-50) and uniformly stirring. The silicon-aluminum sol is used for preparing the catalytic cracking catalyst, can exert different adhesive properties, makes up the defect of a single adhesive, and the obtained catalyst has very good abrasion resistance and better selectivity. The respective contents of silica sol and alumina sol in the silica-alumina sol can be determined by a fluorescence analysis method.
According to a preferred embodiment of the invention, the selected aluminum sol has the advantages of less free chloride ions, optimized structure, high viscosity, low corrosion rate, high pH value and the like. Preferably, the aluminum is dissolvedThe molar ratio of aluminum to chlorine in the adhesive is (1-1.5): 1, corrosion rate is not more than 1.5g/m2H, a pH of 2.8 or more and a viscosity of 500 mPas or more.
In the present invention, the viscosity of the aluminum sol is 20 ℃.
According to the invention, the aluminum-chlorine molar ratio of the aluminum sol is preferably (1.35-1.5): 1.
according to the invention, the aluminum sol preferably contains 11.5-13% of aluminum element by weight.
According to the invention, the aluminium sol preferably has a density of 1.31g/cm3～1.35g/cm3. The density of the aluminum sol is at 20 ℃.
According to the invention, the viscosity of the aluminium sol is preferably between 500 and 10000 mPas. The viscosity of the aluminum sol was 20 ℃.
Preferably, the alumina sol of the present invention has a viscosity of 500 mPas or more, for example, 500 to 10000 mPas and a density of 1.31g/cm at 20 ℃3～1.35g/cm3。
According to the invention, the corrosion rate of the aluminium sol is preferably 1g/m2·h～1.5g/m2·h。
According to the present invention, the pH of the alumina sol is preferably 2.8 to 3.5.
In the present invention, the aluminum sol may further contain phosphorus pentoxide and/or a rare earth oxide. In a preferred embodiment, in the aluminum sol, the rare earth oxide is RE2O3Calculating Al in the aluminum sol2O3(0.01-1.5): 1; preferably RE2O3：Al2O3(0.01-0.8): 1.
in the present invention, when the aluminum sol contains phosphorus pentoxide, P is present in the aluminum sol2O5With Al in the aluminium sol2O3(0.01-1): 1.
in the invention, free chloride ions in the aluminum sol can be measured by a sedimentation method, for example, ammonia water is used for adjusting the pH value of the aluminum sol to be 5-6, the aluminum sol is flocculent and precipitated, the precipitate is separated, the content of chloride ions in supernatant liquid is measured, and the content of free chloride ions in the aluminum sol is determined.
In the present invention, the density of the aluminum sol is measured by a glass densitometer.
In the present invention, the viscosity of the aluminum sol is measured by a rotational viscometer.
In the invention, the corrosion rate of the aluminum sol can be measured by a method of a hanging piece experiment.
In the invention, the element content in the aluminum sol is measured by an XRF fluorescence method.
In the present invention, the reaction can be carried out by using an aluminum sol27And (4) observing the structure optimization of the aluminum sol by using an Al nuclear magnetic spectrum. Of the aluminum sols of the invention27In the Al nuclear magnetic spectrum, as shown in FIG. 1 (labeled as example 1), the peak height and peak area of a signal peak appearing at a chemical shift of 0-3 are small, which indicates that the quantity of the monomeric aluminum is small; the peak height and the peak area of a signal peak appearing at the chemical shift of 60-63 are large, which indicates that the high polymeric aluminum is much.27The result of Al nuclear magnetic spectrum shows that the aluminum sol of the invention is a structure mainly comprising high-polymerization aluminum. The same measurement of the alumina sol obtained in the prior art (example method of CN 1445167A) (marked as comparative example 1 in fig. 1) showed that the alumina sol of the prior art is mainly composed of monomeric aluminum, but has a high peak height and a large peak area of the signal peak with a chemical shift of 0 to 3, and a low peak height and a small peak area of the signal peak with a chemical shift of 60 to 63.
Preferably, the aluminum sol is prepared by27In the Al nuclear magnetic spectrogram, the ratio of the peak area with chemical shift of 60-63 to the peak area with chemical shift of 0-3 is more than 1; preferably, the ratio of the peak area with a chemical shift of 60 to 63 to the peak area with a chemical shift of 0 to 3 is 1 to 1.6, for example 1.1, 1.2, 1.3, 1.4 or 1.5. Therefore, the content ratio of the high polymeric aluminum to the mono-polyaluminium in the alumina sol indirectly embodies the invention is more than 1, and the preferable ratio is 1-1.5.
When the silicon-aluminum sol is applied to the preparation of the catalytic cracking catalyst, the solid content of the prepared catalytic cracking catalyst slurry can be improved to be more than 40 weight percent, and the content of the molecular sieve in the prepared catalytic cracking catalyst can be reduced to be less than 30 weight percent; meanwhile, the strength and the activity of the obtained catalyst meet the industrial use requirements, and the abrasion index of the catalyst is obviously reduced.
According to a third aspect of the present invention, there is provided a process for the preparation of a silica alumina sol comprising: will be mixed with Al2O3Calculated as alumina sol and SiO2Silica sol according to any one of claims 1 to 3 in terms of SiO2：Al2O3The weight ratio is (1-4): 1, carrying out liquid phase mixing for 1-3 h at the temperature of 20-50 ℃ to obtain the silicon-aluminum sol.
In a preferred embodiment of the present invention, the preparation of the aluminum sol comprises: (1) first contacting metallic aluminum with hydrochloric acid; (2) carrying out second contact on the mixture after the first contact and an aluminum source; the temperature of the first contact is 20-30 ℃ higher than that of the second contact.
The method for preparing the aluminum sol can reduce the usage amount of hydrochloric acid, reduce the addition amount of chloride ions, reduce the damage of free acid to the properties of the aluminum sol, improve the activity of the aluminum sol, and simultaneously avoid the defects that the pH value of the aluminum sol is too low due to excessive hydrochloric acid, and the molecular sieve is damaged to influence the activity of a catalyst.
In the method for producing an aluminum sol of the present invention, stirring is carried out while the first contact and the second contact are carried out, and the stirring is stopped, that is, the first contact and the second contact are completed. The first contact and the second contact time are described below as the time when stirring is continued.
According to a preferred embodiment of the present invention, the first contact temperature is 50 to 80 ℃.
According to a preferred embodiment of the present invention, the second contact temperature is 20 to 50 ℃.
According to a preferred embodiment of the invention, the molar ratio of the amount of the aluminum metal in the step (1) to the amount of the aluminum source in the step (2) is (5-10): 1 calculated as Al.
According to a preferred embodiment of the invention, the method further comprises: and (3) before the step (2), standing the mixture after the first contact at normal temperature for 1-30 h, preferably standing for 2-6 h. The standing means that the mixture after the first contact is left without stirring after the stirring accompanying the first contact is stopped.
In the invention, the temperature of the first contact is higher than that of the second contact, and the temperature can be reduced after the first contact is finished, for example, the first contact is kept still, and then the second contact is carried out under the lower second contact temperature.
According to the method of the present invention, the normal temperature is, for example, generally 0 to 40 ℃.
According to a preferred embodiment of the present invention, the conditions of the first contacting further comprise: the amount of the metallic aluminum is 0.8mol to 1.3mol relative to 1mol of hydrochloric acid.
According to a preferred embodiment of the present invention, the conditions of the first contacting further comprise: the first contact time is 2-5 h.
According to a preferred embodiment of the present invention, the conditions of the first contacting further comprise: the concentration of hydrochloric acid is 31 to 36 wt%.
According to a preferred embodiment of the present invention, the conditions of the second contacting further comprise: the second contact time is 3-4 h.
According to a preferred embodiment of the present invention, said aluminium source in the second contacting is preferably metallic aluminium and/or an inorganic aluminium compound.
In the preparation process of the alumina sol of the present invention, the optional range of the kind of the inorganic aluminum compound is wide, and for the present invention, it is preferable that the inorganic aluminum compound is one or more of aluminum chloride, aluminum oxide, aluminum hydroxide and soft aluminum; more preferably, the inorganic aluminum compound is Al2O3More preferably gamma-Al2O3and/or η -Al2O3。
According to a preferred embodiment of the present invention, the method for preparing the aluminum sol further comprises a third contacting of the mixture obtained by the second contacting with a phosphorus compound and/or a rare earth compound.
According to the method for producing the aluminum sol of the present invention, the conditions for contacting the mixture obtained by the second contacting with the rare earth compound can be selected within a wide range, and for the present invention, it is preferable to include: the third contact temperature is 10-50 ℃, and the third contact time is more than 10min preferably; preferably, the third contact time is 10 to 60 min. The phosphorus compound and/or rare earth compound feed can be initiated as the third contact.
According to a preferred embodiment of the present invention, the rare earth compound has a wide variety of types, and any rare earth compound known in the art can be used in the present invention, and for the present invention, the rare earth element in the rare earth compound preferably includes at least one of La, Ce, Sc, Pr and Nd, for example, a mixed rare earth compound containing lanthanum and Ce. Preferably, the rare earth compound is at least one of rare earth oxide, rare earth hydroxide, rare earth nitrate and rare earth oxalate.
In the present invention, it is preferable that the rare earth compound is RE2O3The mixture obtained by the second contact is counted as Al2O3The weight ratio is (0.01-1.5): 1; more preferably, the weight ratio is (0.01 to 0.8): 1.
according to a preferred embodiment of the invention, the phosphorus compound may be a starting material well known to the person skilled in the art, and for the purposes of the present invention, it is preferably selected from one or more of phosphorus pentoxide, phosphoric acid and a phosphate salt, more preferably the phosphorus compound is present as P2O5The mixture obtained by the second contact is counted as Al2O3The weight ratio is (0.01-1): 1.
the method for preparing the aluminum sol in the present invention can be continuously performed.
According to a fourth aspect of the present invention, there is provided a silica-alumina sol obtainable by the process of the invention.
According to a fifth aspect of the invention, there is also provided the use of the silica alumina sol of the invention in the preparation of a catalytic cracking catalyst.
According to a sixth aspect of the present invention, there is also provided a process for preparing a catalytic cracking catalyst, wherein the process comprises: the preparation method comprises the steps of pulping a binder, clay, a molecular sieve and an optional macroporous matrix to obtain catalyst slurry, and carrying out spray drying on the catalyst slurry, wherein the binder is the silicon-aluminum sol provided by the invention.
According to the preparation method of the catalytic cracking catalyst, the catalytic cracking catalyst is preferably obtained by spraying, drying, washing and drying.
In a first preferred embodiment of the method for preparing a catalytic cracking catalyst of the present invention comprises:
(1) adding silicon-aluminum sol and stirring;
(2) adding molecular sieve dry powder or ground molecular sieve slurry to disperse for 5-120 min, preferably 5-40 min;
(3) adding clay and optional macroporous matrix, and stirring for 30-200 min, preferably 60-120 min;
(4) spray drying;
(5) washing and drying to obtain the product.
In a second preferred embodiment of the method for preparing a catalytic cracking catalyst of the present invention comprises:
(1) adding silica-alumina sol, stirring, adding clay, stirring, adding optional macroporous matrix, stirring for 5-200 min, preferably 30-90 min;
(2) adding molecular sieve dry powder or ground molecular sieve slurry to disperse for 5-120 min, preferably 5-50 min;
(3) spray drying;
(4) washing and drying to obtain the product.
According to the catalyst preparation method, preferably, the amount of the molecular sieve is 10-50 wt%, the amount of the clay is 10-50 wt%, the amount of the binder is 5-35 wt% and the amount of the macroporous matrix is 0-25 wt% based on the dry weight of the catalyst slurry. Preferably, the amount of the macroporous matrix is 2 to 25 wt%. Wherein the binder is silicon-aluminum sol, and Al is used in the silicon-aluminum sol2O3Calculated as alumina sol and SiO2Calculated weight of silica solThe ratio is 1: (1-4).
According to the preparation method of the catalyst, the average pore diameter of the macroporous matrix is preferably 100-200 nm.
In the present invention, a substrate having a macroporous structure commonly used in the art may be used as the macroporous substrate of the present invention. Preferably, the macroporous matrix is alumina, silica, an oxide composite, magnesium aluminate spinel, phosphoaluminate spinel, or modified magnesium aluminate spinel, wherein the oxide composite is a composite of metal Mg, Ca, Sr, Ba, Cu, V, Zn, Ti, and non-metal B, P oxides with alumina and silica. For the present invention, it is preferable that the macroporous matrix may be alumina, and for example, may be one or more of hydrated alumina having a monohydrate alumina structure, hydrated alumina having a gibbsite structure, hydrated alumina having a bayer structure, and also may be chi-Al2O3、δ-Al2O3、η-Al2O3、κ-Al2O3、θ-Al2O3、ρ-Al2O3、α-Al2O3And gamma-Al2O3In which κ -Al2O3、δ-Al2O3、θ-Al2O3and α -Al2O3Is high-temperature alumina, chi-Al, prepared at the dehydration temperature of 900-1000 DEG C2O3、η-Al2O3、γ-Al2O3、ρ-Al2O3Is alumina prepared at a dehydration temperature of less than 600 ℃, has a large specific surface area and a large pore volume, is called activated alumina, and is commonly used as gamma-Al2O3and η -Al2O3. The macroporous matrix can also be silicon dioxide, including sodium silicate, silicic acid and the like which provide silicon sources; or the compound of metal Mg, Ca, Sr, Ba, Cu, V, Zn, Ti and nonmetal B, P oxide with aluminum oxide and silicon oxide; it may also be a magnesium aluminate spinel, a phosphoaluminate spinel, and may preferably be a magnesium aluminate spinel.
According to the catalyst preparation method of the present invention, the solid content of the catalyst slurry is preferably 40% by weight or more, preferably 40 to 55% by weight.
The clay of the present invention is a clay raw material well known to those skilled in the art, and any kind of commonly used clay can be used in the present invention, and for the present invention, the clay is preferably one or more of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, pseudohalloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite. Wherein, the sepiolite is a magnesium-rich fibrous silicate clay mineral, and in the structural unit, silicon-oxygen tetrahedron and magnesium-oxygen octahedron are mutually alternated, and have the transitional structural characteristics of layer shape and chain shape. The acid modified sepiolite is used as the FCC catalyst substrate, so that the specific surface area, the pore volume and the mesopore pore volume of the catalyst can be effectively improved, and the heavy metal resistant effect of the catalyst can be enhanced. The kaolinite and the quasi-halloysite have the properties which are relatively similar to each other, the halloysite has the characteristics of large specific surface area, large pore volume, small pore size distribution, few macropores and more mesopores, and the halloysite also has the characteristics of large surface acidity, high micro-activity index, good pore structure stability and the like. For the present invention, preferably the clay is one or more of sepiolite, kaolin and halloysite.
In the invention, the molecular sieve is a well-known molecular sieve raw material in the field, the molecular sieves commonly used in the field can be used in the invention, and the molecular sieves are preferably REY, REHY, REUSY and USY in the invention, and the gas phase chemical method (SiCl) is adopted4Al removal and Si supplement method), liquid phase chemical method ((NH)4)2SiF6aluminum extraction and silicon supplement) and other methods, and ZSM-5 type and β type zeolites with other high silicon-aluminum ratios or the mixture thereof.
The method for preparing the catalytic cracking catalyst provided by the invention has the advantages that the silicon-aluminum sol can reduce the blockage of molecular sieve pore channels, simultaneously, the substrate is better wrapped by the binder, and the forming degree of the catalyst and the strength of the catalyst are improved. In addition, when the silicon-aluminum sol is used for preparing a catalytic cracking catalyst, a large amount of acid is not required to be added for acidification, so that the molecular sieve is prevented from being damaged when being in colloid with too low pH value, and the activity of the catalyst is improved. In addition, the preparation method of the catalytic cracking catalyst can also reduce the gelling process time of the catalyst, increase the solid content of gelling slurry, reduce the viscosity of the slurry, shorten the process flow, reduce the energy consumption and increase the yield.
According to the seventh aspect of the present invention, the present invention also provides a catalytic cracking catalyst obtained by the preparation method of the present invention.
According to the present invention, it is preferable that the content of the molecular sieve in the catalytic cracking catalyst is 30% by weight or less.
The catalytic cracking catalyst obtained by the catalyst preparation method of the invention contains 10-50 wt%, preferably 25-30 wt% of molecular sieve based on dry weight (calcined at 800 ℃ for 1h ignition loss); 10-50 wt% of clay, preferably 35-45 wt%; silica-alumina sol (Al)2O3And SiO2In total) 15 to 40 wt.%, preferably 18 to 30 wt.%; 2-25 wt%, preferably 6-16 wt% of macroporous matrix.
The catalytic cracking catalyst provided by the invention can reduce the usage amount of the adhesive and the molecular sieve.
The invention also provides the application of the catalytic cracking catalyst in catalytic cracking reaction. Can process heavy crude oil, and has higher conversion rate, liquid yield and light oil yield, and the coke amount is reduced.
The following examples further illustrate the features of the present invention, but the present invention is not limited to the examples.
And (3) measuring the content of free chloride ions in the aluminum sol by a sedimentation method, adjusting the pH value of the aluminum sol to 5-6 by using ammonia water, separating out precipitates when the aluminum sol is flocculent, and measuring the content of the chloride ions in the supernatant.
The densities of the silica sol and the alumina sol were measured by a glass densitometer (Shenzhen Shenxin Yiwei Experimental facility, Ltd.).
The viscosity of silica sol and alumina sol was measured by a rotational viscometer (Shanghai Proc. balance scientific instruments Co., Ltd., model NDJ-1 rotational viscometer).
The contents of elements in silica sol and alumina sol were measured by XRF fluorescence analysis (RIPP 117-90 standard method (compiled by "analytical methods in petrochemical industry" (RIPP test method) Yangcui et al, published by scientific Press, 1990)).
The corrosion rate of the aluminum sol can be measured by a method of a hanging piece experiment:
experimental equipment: adopting a 20# carbon steel test piece (silver white) as a hanging piece (the size is 50mm multiplied by 25mm multiplied by 2mm), a constant-temperature water bath, a magnetic stirrer, a blower and absorbent cotton;
experimental drugs: anhydrous ethanol, hydrochloric acid (10 wt%), hexamethylenetetramine (0.5 wt%), 5N sodium hydroxide;
the method comprises the following experimental steps of firstly cleaning a hanging piece with absolute ethyl alcohol, removing grease on the surface of a sample, then soaking the hanging piece in absolute ethyl alcohol for 5min, further degreasing and dewatering, taking out the sample, placing the sample on a filter paper, drying the sample with cold air, wrapping the sample with the filter paper, placing the sample in a dryer for storage, weighing the sample after 24h, marking the weight of the obtained scraping piece as W1, hanging the hanging piece in an aluminum sol 1L in a container, standing the sample for 24h at 0-30 ℃, placing the container containing the hanging piece and the aluminum sol in a constant-temperature water bath, reacting for 6h at 80 ℃, cleaning and removing black corrosion products on the hanging piece by using 10 wt% hydrochloric acid and 0.5 wt% hexamethylenetetramine after the reaction is finished (a mixture preparation method, mixing 10 wt% hydrochloric acid and 0.5 wt% hexamethylenetetramine to prepare a solution with a pH value of 5-7, cleaning the black corrosion products until the black corrosion products are completely cleaned, the hanging piece is in a white color, immediately storing the cleaned hanging piece with N5 times, immersing the hanging piece in a passivating solution after drying, marking the hanging piece as W2-6 h, weighing the hanging piece with the weight of the drying time of the hanging piece, marking the hanging piece as W2-6 h, and drying the hanging piece after the drying time of the hanging piece, marking the hanging piece as W2-6 h, and drying the hanging piece, and weighing the hanging piece, and drying the hanging piece, and weighing the hanging piece in the hanging piece, and drying time of the hanging piece after the hanging piece, and drying time of the hanging piece, wherein the hanging piece is marked as W22)。
Aluminium sol27Nuclear magnetic measurement of Al: adding decationized water to dilute the aluminum sol to 1 wt% (Al)2O3Content) to prepare a solution sample; measured by means of a superconducting nuclear magnetic resonance apparatus of the type INOVA500, manufactured by Varian corporation, under test conditions comprising: resonance frequency 130 MHz: (27Al), pulse program s2pul, spectral width 90090Hz, number of accumulations 800, delay time 1.0s, sampling time 0.5s, solvent D2O, external standard NaAlO2。
The specifications of the raw materials used in the catalyst preparation examples are as follows:
kaolin: a solid content of 81.2% by weight, produced by Kaolin corporation of China (Suzhou);
REY type molecular sieve: the catalyst is produced by Qilu division of China petrochemical catalyst, and has the solid content of 80 weight percent and the content of rare earth oxide (La or Ce) of 17 to 18 weight percent;
magnesium aluminate spinel: al (Al)2O343 wt% of MgO, 54 wt% of MgO, 70.8 wt% of solid content and 120-150 nm of average pore diameter, produced by a magnesium technology and chemical company Limited, from the company Shichentai, Hebei;
concentration of the rare earth oxide solution: 328.46g/L, containing La and Ce (La: Ce molar ratio 1: 1), produced by Qilu division of China petrochemical catalyst, Inc.
Phosphorus compound: phosphoric acid having a concentration of 75% by weight, produced by Qilu division, petrochemical catalyst, Inc., China.
Sodium hydroxide: NaOH content greater than 96 wt%, Beijing chemical Co., Ltd.
The composition of the catalyst obtained in the catalyst preparation example was determined by calculation based on the charge amount of each raw material.
Example 1
This example illustrates the preparation of an aluminum sol according to the present invention.
(1) Carrying out first contact on 1mol of metal aluminum (China aluminum industry Co.) and 1mol of (HCl) hydrochloric acid, controlling the temperature of the first contact process to be 50 ℃, controlling the first contact time to be 3h, and controlling the initial concentration of the used hydrochloric acid to be 32 wt%;
(2) standing the mixture after the first contact at the normal temperature of 20 ℃ for 6h, and then reacting with gamma-Al2O3(Shandong aluminum works) and η -Al2O3(Shandong aluminum works) intoCarrying out second contact at 30 ℃ for 4h, wherein the second contact time is gamma-Al calculated by aluminum2O3eta-Al calculated as aluminum2O3The molar ratio of the aluminum metal to the metal aluminum in the step (1) is 0.05: 0.05: 1. the physicochemical properties of the aluminum sol are shown in Table 1.
Subjecting the aluminium sol to27Performing Al nuclear magnetic measurement, wherein a spectrogram is shown in figure 1, wherein the peak height and the peak area of a signal peak with chemical shift of 0-3 are small, and the number of the monomeric aluminum is small; the signal peak with the chemical shift of 60-63 has high peak height and large peak area, which indicates that the high polymeric aluminum is much. The result shows that the aluminum sol is a structure mainly containing high-polymerization aluminum. And calculating the ratio of the peak area with the chemical shift of 60-63 to the peak area with the chemical shift of 0-3 to be 1.3.
Example 2
This example illustrates the preparation of an aluminum sol according to the present invention.
(1) Carrying out first contact on 1.1mol of metal aluminum and 1mol of (HCl) hydrochloric acid, controlling the temperature of the first contact process to be 80 ℃ and the time to be 2h, wherein the concentration of the hydrochloric acid is 36 weight percent;
(2) standing the mixture after the first contact at the normal temperature of 30 ℃ for 2h, and then reacting with gamma-Al2O3and η -Al2O3Carrying out second contact at 50 deg.C for 3 hr of gamma-Al2O3eta-Al calculated as aluminum2O3The molar ratio of the aluminum metal to the metal aluminum in the step (1) is 0.1: 0.06: 1. the physicochemical properties of the aluminum sol are shown in Table 1.
And calculating the ratio of the peak area with the chemical shift of 60-63 to the peak area with the chemical shift of 0-3 to be 1.1.
Example 3
This example illustrates the preparation of an aluminum sol according to the present invention.
(1) Carrying out first contact on 1.1mol of metal aluminum and 1mol of (HCl) hydrochloric acid, controlling the temperature of the first contact process to be 60 ℃ and the time to be 5h, wherein the concentration of the hydrochloric acid is 31 wt%;
(2) standing the mixture after the first contact at normal temperature of 10 ℃ for 4h, and then reacting with gamma-Al2O3、η-Al2O3Carrying out second contact at 35 deg.C for 3.5h, calculated as Al, of gamma-Al2O3eta-Al calculated as aluminum2O3The molar ratio of the aluminum metal to the metal aluminum in the step (1) is 0.12: 0.08: 1. the physicochemical properties of the aluminum sol are shown in Table 1.
And calculating the ratio of the peak area with the chemical shift of 60-63 to the peak area with the chemical shift of 0-3 to be 1.2.
Example 4
This example illustrates the preparation of an aluminum sol according to the present invention.
An alumina sol was prepared according to the method of example 3, except that gamma-Al was used alone2O3As the aluminum source in the step (2), gamma-Al in terms of aluminum2O3The molar ratio to metallic aluminum was 0.2: 1.
the physicochemical properties of the aluminum sol are shown in Table 1.
And calculating the ratio of the peak area with the chemical shift of 60-63 to the peak area with the chemical shift of 0-3 to be 1.2.
Example 5
This example illustrates the preparation of an aluminum sol according to the present invention.
An alumina sol was prepared as in example 4, except that metallic aluminum was used instead of γ -Al2O3As the aluminum source of step (2), the molar ratio of Al introduced in step (2) to Al introduced in step (1) was 0.2: 1.
the physicochemical properties of the aluminum sol are shown in Table 1.
And calculating the ratio of the peak area with the chemical shift of 60-63 to the peak area with the chemical shift of 0-3 to be 1.2.
Example 6
This example illustrates the preparation of an aluminum sol according to the present invention.
An alumina sol was prepared as in example 3, except that the temperature of the first contact was 90 ℃ and the temperature of the second contact was 60 ℃.
The physicochemical properties of the aluminum sol are shown in Table 1.
And calculating the ratio of the peak area with the chemical shift of 60-63 to the peak area with the chemical shift of 0-3 to be 1.2.
Example 7
This example illustrates the preparation of an aluminum sol according to the present invention.
To the alumina sol prepared in example 1 (as Al)2O3Calculated by RE) is added into the rare earth oxide solution2O3Sum of La and Ce), RE2O3：Al2O30.8: 1, stirring for 0.5h, mixing and filtering to obtain a stable alumina sol product.
The physicochemical properties of the aluminum sol are shown in Table 1.
And calculating the ratio of the peak area with the chemical shift of 60-63 to the peak area with the chemical shift of 0-3 to be 1.5.
Example 8
This example illustrates the preparation of an aluminum sol according to the present invention.
To the alumina sol prepared in example 1 (as Al)2O3Calculated by RE) is added into the rare earth oxide solution2O3Sum of La and Ce), RE2O3：Al2O30.8: 1, adding phosphoric acid solution (with P)2O5Meter), P)2O5：Al2O30.8: 1, stirring for 0.5h, mixing and filtering to obtain a stable alumina sol product.
The physicochemical properties of the aluminum sol are shown in Table 1.
And calculating the ratio of the peak area with the chemical shift of 60-63 to the peak area with the chemical shift of 0-3 to be 1.6.
Preparation example 1
The alumina sol was prepared according to the example method of CN 1445167A.
Aluminum oxide and hydrochloric acid are mixed according to the molar ratio of Al2O3Putting HCl into a reaction kettle in a ratio of 1:3, controlling the reaction temperature to be 140 ℃, keeping the reaction temperature for 2 hours, preparing aluminum chloride solution, continuously adding dilute sulfuric acid solution in the reaction process, and supplementing gold according to the content of aluminum in the required aluminum solAdding aluminum into a reaction kettle for 4 times, keeping 1 atmosphere pressure, controlling the temperature to be 80 ℃, reacting for 40 hours, and continuously stirring in the reaction process to obtain aluminum sol, wherein the physicochemical properties of the aluminum sol are shown in Table 1.
Subjecting the aluminium sol to27And (3) performing Al nuclear magnetic measurement, wherein a spectrogram is shown in a figure 1, wherein the peak height and the peak area of a signal peak with a chemical shift of 0-3 are large, which indicates that the quantity of the monomeric aluminum is small, and the peak height and the peak area of a signal peak with a chemical shift of 60-63 are small, which indicates that the amount of the monomeric aluminum is large. The result shows that the aluminum sol is mainly of single poly aluminum.
And calculating the ratio of the peak area with the chemical shift of 60-63 to the peak area with the chemical shift of 0-3 to be 0.6.
Preparation example 2
To the alumina sol prepared in comparative example 1 (in Al)2O3Calculated by RE) is added into the rare earth oxide solution2O3Sum of La and Ce), RE2O3：Al2O30.8: 1, stirring for 0.5h, mixing and filtering to obtain a stable aluminum sol product, wherein the physicochemical properties of the aluminum sol are shown in table 1.
And calculating the ratio of the peak area with the chemical shift of 60-63 to the peak area with the chemical shift of 0-3 to be 0.7.
Preparation example 3
An aluminum sol was prepared according to CN1743267A, example 1.
Taking 6.5g of Al2(OH)2.9Cl3.1The polyaluminum chloride of (1), which contains 29.0% by weight of Al2O331.8% by weight of Cl was dissolved in 10mL of water, 1.3g of metallic aluminum having a purity of 99.5% by weight was added, and the mixture was reacted at 50 ℃ under 0.1MPa with stirring for 7.5 hours and then filtered to obtain 16.71g of an alumina sol.
The physicochemical properties of the aluminum sol are shown in Table 1.
And calculating the ratio of the peak area with the chemical shift of 60-63 to the peak area with the chemical shift of 0-3 to be 0.4.
Preparation example 4
To the alumina sol prepared in comparative example 3 (in Al)2O3Calculated by RE) is added into the rare earth oxide solution2O3Sum of La and Ce), RE2O3：Al2O30.8: 1, stirring for 0.5h, mixing and filtering to obtain a stable aluminum sol product, wherein the physicochemical properties of the aluminum sol are shown in table 1.
And calculating the ratio of the peak area with the chemical shift of 60-63 to the peak area with the chemical shift of 0-3 to be 0.5.
TABLE 1 physicochemical Properties of the aluminum Sol
When the free chloride ion contents of the aluminum sols obtained in examples 1 to 3 and preparation examples 1 and 3 were measured, it was found that the aluminum sol prepared in example 1 had less free chloride ions, and the experimental results are shown in Table 2.
TABLE 2 Properties of the supernatant of the settled Aluminosol
| Item | Example 1 | Example 2 | Example 3 | Preparation example 1 | Preparation example 3 |
| pH of the supernatant | 5.5 | 5.7 | 5.8 | 4.8 | 6.0 |
| Cl-To weight percent | 1.23 | 1.59 | 1.78 | 5.63 | 2.63 |
Example 9
This example illustrates the preparation of a silica sol according to the invention.
First reacting monocrystalline silicon (99% purity, from billion crystal photoelectric technology limited, Changzhou) with a sodium hydroxide solution A (NaOH concentration of 46 wt%) at 60 ℃ for 2 hours;
carrying out a second reaction on the product of the first reaction and sodium hydroxide solution B (NaOH concentration is 46 weight percent) at 80 ℃ for 2 h;
wherein the weight ratio of the sodium hydroxide solution A to the sodium hydroxide solution B is 30: 70; the weight ratio of single crystal silicon (Si) to the total amount (Na basis) of the sodium hydroxide solution A and the sodium hydroxide solution B was 1: 1.
and cooling the product of the second reaction to 25 ℃, and contacting the obtained colloid with D101 hydrogen ion exchange resin (Zibodong Daichi chemical Co., Ltd.) to exchange sodium ions in the colloid to obtain silica sol with the solid content of 35 wt%.
SiO of silica sol235% by weight of Na2O content of 0.08 wt%, pH 2.81, and density 1.162g/cm3The viscosity was 540 mPas.
Example 10
This example illustrates the preparation of a silica sol according to the invention.
Carrying out first reaction on monocrystalline silicon and a sodium hydroxide solution A (the concentration of NaOH is 70 weight percent) at 70 ℃ for 3 h;
carrying out a second reaction on the product of the first reaction and sodium hydroxide solution B (NaOH concentration is 40 weight percent) at 90 ℃ for 1 h;
wherein the weight ratio of the sodium hydroxide solution A to the sodium hydroxide solution B is 25: 75; the weight ratio of single crystal silicon (in terms of Si) to the total amount (in terms of Na) of sodium hydroxide solution a and sodium hydroxide solution B was 0.6: 1.
and cooling the product of the second reaction to 25 ℃, and contacting the obtained colloid with D101 hydrogen ion exchange resin to exchange sodium ions in the colloid to obtain silica sol with the solid content of 30 weight percent.
SiO of silica sol2The content of Na was 30% by weight2O content of 0.10 wt%, pH 7.48, and density 1.165g/cm3The viscosity was 320 mPas.
Example 11
This example illustrates the preparation of a silica sol according to the invention.
Carrying out first reaction on monocrystalline silicon and a sodium hydroxide solution A (the concentration of NaOH is 40 weight percent) at 50 ℃ for 1 h;
carrying out a second reaction on the product of the first reaction and sodium hydroxide solution B (NaOH concentration is 70 weight percent) at 80 ℃ for 1.5 h;
wherein the weight ratio of the sodium hydroxide solution A to the sodium hydroxide solution B is 35: 65; the weight ratio of single crystal silicon (in terms of Si) to the total amount (in terms of Na) of sodium hydroxide solution a and sodium hydroxide solution B was 1.4: 1.
and cooling the product of the second reaction to 25 ℃, and contacting the obtained colloid with D101 hydrogen ion exchange resin to exchange sodium ions in the colloid to obtain silica sol with the solid content of 40 weight percent.
SiO of silica sol2The content of Na is 40 wt%2O content of 0.20 wt%, pH 9.55, and density 1.241g/cm3The viscosity was 4300 mPas.
Example 12
This example illustrates the preparation of a silica alumina sol according to the invention.
Will be mixed with Al2O3Example 8 aluminum Sol with SiO2Example 9 silica Sol according to SiO2：Al2O3The weight ratio is 4:1, carrying out liquid phase mixing for 2h at the temperature of 40 ℃ to obtain the silicon-aluminum sol.
Example 13
This example illustrates the preparation of a silica alumina sol according to the invention.
Will be mixed with Al2O3Example 8 aluminum Sol with SiO2Example 10 silica Sol according to SiO2：Al2O3The weight ratio is 4:1, carrying out liquid phase mixing for 2h at the temperature of 40 ℃ to obtain the silicon-aluminum sol.
Example 14
This example illustrates the preparation of a silica alumina sol according to the invention.
Will be mixed with Al2O3Example 8 aluminum Sol with SiO2Example 11 silica Sol according to SiO2：Al2O3The weight ratio is 4:1, carrying out liquid phase mixing for 2h at the temperature of 40 ℃ to obtain the silicon-aluminum sol.
Example 15
This example illustrates the preparation of a silica alumina sol according to the invention.
Will be mixed with Al2O3Preparation example 1 aluminum sol and SiO2Example 9 silica Sol according to SiO2：Al2O3The weight ratio is 4:1 at 40 ℃ in a reaction kettle, and stirring for 2 hours to obtain the silicon-aluminum sol.
Example 16
This example illustrates the preparation of a silica alumina sol according to the invention.
Will be mixed with Al2O3Preparation example 2 aluminum sol and SiO2Example 9 silica Sol according to SiO2：Al2O3The weight ratio is 4:1 at 40 ℃ in a reaction kettle for 2 hours to obtain the silica-alumina sol.
Examples of preparation of catalysts
(1) 70.72kg of silica-alumina sol (the source is listed in the table 3) is added into the reaction kettle, stirred, 43.10kg of kaolin is added, 21.19kg of magnesia-alumina spinel is added, and stirred for 30 min; adding 95.54kg of ground REY molecular sieve slurry (produced by Qilu division of petrochemical catalyst Co., Ltd., China, the slurry has a solid content of 31.4 wt%), stirring for 30min, spray drying, and calcining the obtained catalyst microspheres at 500 deg.C for 1 h; then adding water: the weight ratio of the dry-based catalyst is 1: 8 the catalyst was washed twice with decationized water and dried at 120 ℃ for 2 hours to obtain samples C1-C5, the catalyst slurry and the product properties are shown in Table 3.
(2) 70.72kg of the silica-alumina sol prepared in the example 12 is added into a reaction kettle and stirred, 61.57kg of kaolin is added and stirred for 30 min; adding 95.54kg of ground REY molecular sieve slurry (produced by Qilu division of petrochemical catalyst, China) with solid content of 31.4 wt%, and stirring for 30 min; spray drying, and roasting the obtained catalyst microspheres for 1h at 500 ℃; then adding water: the weight ratio of the dry-based catalyst is 1: 8 the catalyst was washed twice with decationized water and dried at 120C for 2 hours to obtain sample C6, the catalyst slurry and the product properties are shown in table 3.
Catalyst characterization:
(1) the specific surface area of the cracking catalyst was measured according to GB/T5816-1995 using an Autosorb-1 nitrogen desorption apparatus from Congta, USA, and the sample was degassed at 300 ℃ for 6 hours before the test, and the results are shown in Table 3.
(2) The total pore volume of the cracking catalyst was measured according to the RIPP 151-90 standard method (see "analytical methods for petrochemical industry" (RIPP test method), eds. Yang Cui, science publishers, 1990), and the results are shown in Table 3.
(3) The sphericity index SPHT of the cracking catalyst was measured using a Camsizer XT dry-wet multifunctional particle size and morphology analyzer from leysh, germany, and the results are shown in table 3.
The sphericity index SPHT refers to the surface area of a sphere (4 π A) and the surface area of an object (P) that are the same volume as the object2) See equation 1.
TABLE 3
Catalyst evaluation
The cracking reaction performance of the catalyst of the present invention and the comparative catalyst was evaluated.
The raw oil is Wu-MI-Sanyuan oil, and the physicochemical property data are shown in Table 4.
Table 5 lists the results of the evaluations on the fixed fluidized bed apparatus. The catalyst is aged and deactivated by 100 percent of water vapor at 800 ℃ for 17 hours, the loading of the catalyst is 9g, the catalyst-oil ratio is 5, and the reaction temperature is 500 ℃.
Wherein, the conversion rate is gasoline yield, liquefied gas yield, dry gas yield and coke yield
Liquid yield is liquefied gas yield, gasoline yield and diesel oil yield
Yield of light oil is gasoline yield and diesel oil yield
Coke selectivity-coke yield/conversion
TABLE 4
TABLE 5
| Catalyst and process for preparing same | C1 | C2 | C3 | C4 | C5 | C6 |
| Dry gas | 1.31 | 1.36 | 1.38 | 1.42 | 1.51 | 1.55 |
| Liquefied gas | 17.11 | 17.19 | 17.95 | 17.84 | 16.96 | 15.96 |
| Gasoline (gasoline) | 52.21 | 50.99 | 50.11 | 50.23 | 48.19 | 49.06 |
| Diesel oil | 18.21 | 18.58 | 18.12 | 18.32 | 20.11 | 20.33 |
| Heavy oil | 5.89 | 5.67 | 5.76 | 5.86 | 6.98 | 7.01 |
| Coke | 5.27 | 6.21 | 6.68 | 6.33 | 6.25 | 6.09 |
| Total up to | 100 | 100 | 100 | 100 | 100 | 100 |
| Slightly counteractive activity, is | 75 | 77 | 78 | 74 | 72 | 71 |
| Conversion rate% | 75.9 | 75.75 | 76.12 | 75.82 | 72.91 | 72.66 |
| Liquid yield% | 87.53 | 86.76 | 86.18 | 86.39 | 85.26 | 85.35 |
| Yield of light oil,% | 70.42 | 69.57 | 68.23 | 68.55 | 68.3 | 69.39 |
| Coke selectivity,% of | 6.94 | 8.20 | 8.78 | 8.35 | 8.57 | 8.38 |
The present invention provides silica alumina sols, as seen in examples 1-8, of which27The nuclear magnetic spectrum of Al (FIG. 1) shows that the aluminum sol is mainly of high-polymerization aluminum. The alumina sol (fig. 1) obtained in the prior art (preparation example 1) had a structure mainly composed of monoaluminum. The data in Table 1 show that the inventive aluminum sols have lower corrosion rates, higher viscosities, and higher pH values. The data in Table 2 show that the aluminum sols obtained according to the invention (examples 1 to 3) can have a lower free chloride ion content than the aluminum sols obtained in preparation examples 1 and 3. The invention provides an aluminum meltThe gel has the characteristics of less free chloride ions, optimized structure, high viscosity, low corrosion rate and high pH value, so that when the gel is further used for preparing a catalytic cracking catalyst, the catalyst with better catalytic effect can be obtained by using the silicon-aluminum sol obtained from the aluminum sol.
The addition of rare earth elements and phosphorus elements to the alumina sol prepared in example 8 can make the catalyst (example 12, C1) prepared by the binder containing the alumina sol have better catalytic activity, higher micro-reverse activity, conversion rate, liquid yield and light oil yield, and lower coke selectivity.
It can be seen from the result data of the catalyst obtained in the catalyst preparation example that the catalyst prepared by using the silica-alumina sol of the invention is more suitable for the heavy processing requirements of crude oil. As can be seen from the data in Table 3, the catalysts (C1-C3) prepared by using the alumina sol (examples 12-14) of the present invention have the advantages that the addition amount of the molecular sieve and the alumina sol can be reduced compared with the catalysts (C4-C5) prepared by using the prior art alumina sol, the solid content of the catalyst slurry can be higher, and the physicochemical properties of the prepared catalysts are as follows: the specific surface area, the total pore volume, the SPHT, the attrition index and the micro-reaction activity are all obviously better than the catalysts (C4-C5) prepared by the prior art. As can be seen from the results data in Table 5, the catalysts (C1-C3) prepared by using the alumina sol of the present invention can achieve higher conversion, liquid yield and light oil yield and reduced coke amount compared to the catalysts (C4-C5) prepared by using the prior art alumina sol when heavy crude oil processing is carried out.
In addition, the catalyst C6 is not added with a macroporous matrix, compared with the catalyst (C1-C5), the activity, the gasoline yield and the coke selectivity are poor, which shows that the addition of the macroporous matrix in the catalytic cracking catalyst is more favorable for improving the activity, the gasoline yield and the coke selectivity of the catalyst.
The invention reduces the addition of the molecular sieve, and is beneficial to reducing the production cost of the catalyst.
Claims (25)
1. A silica sol containing SiO2Is 25 to 40 wt% of Na2Containing of OIn an amount less than 0.15 wt%; the silica sol has a pH value of 2-10 and a density of 1.1g/cm3～1.3 g/cm3A viscosity of 200 mPas or more;
wherein the preparation method of the silica sol comprises the following steps:
(a) carrying out a first reaction on monocrystalline silicon and a sodium hydroxide solution A; the first reaction temperature is 50-70 ℃, and the first reaction time is 1-3 h;
(b) carrying out a second reaction on the product of the first reaction and a sodium hydroxide solution B, wherein the second reaction temperature is 70-90 ℃, and the second reaction time is 1-2 h;
(c) cooling the product of the second reaction to obtain colloid, and performing ion exchange on the colloid to reduce the content of sodium ions to obtain silica sol;
wherein the weight ratio of the monocrystalline silicon calculated by Si to the total amount of the sodium hydroxide solution A and the sodium hydroxide solution B calculated by Na is (0.6-1.4): 1;
and (3) the weight ratio of the sodium hydroxide solution A to the sodium hydroxide solution B is (25-35) calculated by Na: (65-75);
the second reaction temperature is 20-30 ℃ higher than the first reaction temperature.
2. The silica sol according to claim 1, wherein the purity of the single-crystal silicon is 95 to 99 wt%; the concentration of the sodium hydroxide solution A is 40-70 wt%, and the concentration of the sodium hydroxide solution B is 40-70 wt%.
3. The silicon-aluminum sol contains silicon sol and aluminum sol, wherein SiO is used in the silicon-aluminum sol2Calculated as silica sol and Al2O3The weight ratio of the aluminum sol is (1-4): 1, wherein the silica sol is the silica sol according to claim 1 or 2.
4. The silicon-aluminum sol according to claim 3, wherein the molar ratio of aluminum to chlorine in the aluminum sol is (1-1.5): 1, corrosion rate is not more than 1.5g/m2H, pH of 2.8 or more, viscosity of 500 mPas or moreThe above.
5. The silica alumina sol according to claim 3 or 4, wherein the aluminum sol has an aluminum element content of 11.5 to 13% by weight based on the total amount of the alumina sol; the corrosion rate of the aluminum sol is 1g/m2·h～1.5 g/m2H, pH value of 2.8-3.5, density of 1.31g/cm3～1.35 g/cm3The viscosity is 500 to 10000 mPas.
6. The silica-alumina sol according to claim 3 or 4, wherein the alumina sol is27In the Al nuclear magnetic spectrogram, the ratio of the peak area with chemical shift of 60-63 to the peak area with chemical shift of 0-3 is more than 1.
7. The silica alumina sol of claim 6, wherein the alumina sol is27In the Al nuclear magnetic spectrogram, the ratio of the peak area with the chemical shift of 60-63 to the peak area with the chemical shift of 0-3 is 1-1.6.
8. A method for preparing a silica alumina sol, the method comprising:
will be mixed with Al2O3Calculated as alumina sol and SiO2Silica sol according to claim 1 or 2, in terms of SiO2：Al2O3The weight ratio is (1-4): 1, carrying out liquid phase mixing for 1-3 h at the temperature of 20-50 ℃ to obtain the silicon-aluminum sol.
9. The method of claim 8, wherein the preparing of the aluminum sol comprises:
(1) first contacting metallic aluminum with hydrochloric acid;
(2) carrying out second contact on the mixture after the first contact and an aluminum source;
the temperature of the first contact is 20-30 ℃ higher than that of the second contact.
10. The method of claim 9, wherein the temperature of the first contacting is 50 to 80 ℃; the temperature of the second contact is 20-50 ℃.
11. The method of claim 9 or 10, wherein the molar ratio of the amount of aluminum metal used in step (1) to the amount of aluminum source used in step (2) is (5-10): 1, calculated as Al.
12. The method of claim 9 or 10, wherein the method of preparing the aluminum sol further comprises: and (3) before the step (2), standing the mixture after the first contact at normal temperature for 1-30 h.
13. The method of claim 12, wherein the method of preparing the aluminum sol further comprises: and (3) before the step (2), standing the mixture after the first contact at normal temperature for 2-6 h.
14. The method of claim 9 or 10,
the conditions of the first contacting further comprise: the dosage of the metal aluminum is 0.8-1.3 mol relative to 1mol of hydrochloric acid calculated by HCl, the first contact time is 2-5 h, and the concentration of the hydrochloric acid is 31-36 wt%;
the conditions of the second contacting further comprise: the second contact time is 3-4 h, the aluminum source is metallic aluminum and/or an inorganic aluminum compound, and the inorganic aluminum compound is one or more of aluminum chloride, aluminum oxide and aluminum hydroxide.
15. The method of claim 14, wherein the inorganic aluminum compound is Al2O3。
16. The method of claim 15, wherein the inorganic aluminum compound is γ -Al2O3and/or η -Al2O3。
17. The method according to claim 9 or 10, wherein the method for preparing the aluminum sol further comprises a third contacting of the mixture obtained by the second contacting with a phosphorus compound and/or a rare earth compound; the third contact temperature is 10-50 ℃, and the third contact time is more than 10 min;
the phosphorus compound is selected from one or more of phosphorus pentoxide, phosphoric acid and phosphate; the phosphorus compound is represented by P2O5The mixture obtained by the second contact is counted as Al2O3The weight ratio = (0.01-1): 1;
the rare earth compound is represented by RE2O3The mixture obtained by the second contact is counted as Al2O3The weight ratio = (0.01-1.5): 1; the rare earth elements in the rare earth compound comprise at least one of La, Ce, Sc, Pr and Nd; the rare earth compound is at least one of rare earth oxide, rare earth hydroxide, rare earth nitrate and rare earth oxalate.
18. The method of claim 17, wherein the rare earth compound is provided as RE2O3The mixture obtained by the second contact is counted as Al2O3Calculated weight ratio = (0.01-0.8): 1.
19. a silica alumina sol obtainable by the process of any one of claims 8 to 18.
20. Use of the silica alumina sol according to any one of claims 3 to 7 and 19 for the preparation of a catalytic cracking catalyst.
21. A process for preparing a catalytic cracking catalyst, the process comprising: a catalyst slurry obtained by pulping a binder, clay, a molecular sieve and optionally a macroporous matrix, and spray-drying the catalyst slurry, wherein the macroporous matrix is alumina, silica, an oxide composite, magnesia alumina spinel, phosphoaluminate spinel or modified magnesia alumina spinel, wherein the oxide composite is a composite of metal Mg, Ca, Sr, Ba, Cu, V, Zn, Ti and non-metal B, P oxides with alumina and silica, characterized in that the binder is the silica alumina sol according to any one of claims 3 to 7 and 19.
22. The method of claim 21, wherein the molecular sieve is present in an amount of 10 to 50 wt%, the clay is present in an amount of 10 to 50 wt%, the binder is present in an amount of 5 to 40 wt%, and the macroporous matrix is present in an amount of 0 to 25 wt%, based on the dry weight of the catalyst slurry.
23. The production method according to claim 21 or 22, wherein the solid content of the catalyst slurry is 40% by weight or more.
24. The production method according to claim 23, wherein the solid content of the catalyst slurry is 40 to 55% by weight.
25. A catalytic cracking catalyst obtained by the production method according to any one of claims 21 to 24.
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| CN101857236A (en) * | 2010-06-04 | 2010-10-13 | 西南科技大学 | Method for preparing high-concentration silica sol by using superfine silica powder |
| CN102974386A (en) * | 2012-11-27 | 2013-03-20 | 山东迅达化工集团有限公司 | Catalytic cracking catalyst and preparation method thereof |
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| CN1445167A (en) * | 2003-03-20 | 2003-10-01 | 淄博市临淄正华助剂有限公司 | Technique for preparing aluminium sol |
| CN1727443A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Cracking catalyst and its application |
| CN101857236A (en) * | 2010-06-04 | 2010-10-13 | 西南科技大学 | Method for preparing high-concentration silica sol by using superfine silica powder |
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