CN107376887A - A kind of Ludox and silicon-aluminum sol and preparation method and application and catalytic cracking catalyst and preparation method - Google Patents
A kind of Ludox and silicon-aluminum sol and preparation method and application and catalytic cracking catalyst and preparation method Download PDFInfo
- Publication number
- CN107376887A CN107376887A CN201610320487.0A CN201610320487A CN107376887A CN 107376887 A CN107376887 A CN 107376887A CN 201610320487 A CN201610320487 A CN 201610320487A CN 107376887 A CN107376887 A CN 107376887A
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- CN
- China
- Prior art keywords
- weight
- silicon
- alumina gel
- catalyst
- ludox
- Prior art date
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- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 166
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 91
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 41
- 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 227
- -1 chloro ion Chemical class 0.000 claims abstract description 53
- 239000002808 molecular sieve Substances 0.000 claims abstract description 44
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011230 binding agent Substances 0.000 claims abstract description 37
- 230000007797 corrosion Effects 0.000 claims abstract description 18
- 238000005260 corrosion Methods 0.000 claims abstract description 18
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 136
- 238000000034 method Methods 0.000 claims description 69
- 239000004411 aluminium Substances 0.000 claims description 59
- 229910052593 corundum Inorganic materials 0.000 claims description 59
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 59
- 229910052782 aluminium Inorganic materials 0.000 claims description 57
- 239000000126 substance Substances 0.000 claims description 57
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 36
- 239000011159 matrix material Substances 0.000 claims description 27
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 25
- 239000011148 porous material Substances 0.000 claims description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims description 23
- 229910052681 coesite Inorganic materials 0.000 claims description 22
- 229910052906 cristobalite Inorganic materials 0.000 claims description 22
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 22
- 229910052682 stishovite Inorganic materials 0.000 claims description 22
- 229910052905 tridymite Inorganic materials 0.000 claims description 22
- 239000011574 phosphorus Substances 0.000 claims description 21
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 17
- 239000004927 clay Substances 0.000 claims description 16
- 239000000084 colloidal system Substances 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 150000002910 rare earth metals Chemical class 0.000 claims description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 11
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 150000001399 aluminium compounds Chemical class 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000001694 spray drying Methods 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910000147 aluminium phosphate 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000008234 soft water Substances 0.000 claims description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 8
- 238000005457 optimization Methods 0.000 abstract description 6
- 230000000903 blocking effect Effects 0.000 abstract description 4
- 235000010210 aluminium Nutrition 0.000 description 39
- 239000000243 solution Substances 0.000 description 35
- 239000000047 product Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 17
- 238000005336 cracking Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000003292 glue Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000571 coke Substances 0.000 description 9
- 229910052749 magnesium Inorganic materials 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000005995 Aluminium silicate Substances 0.000 description 8
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 8
- 235000012211 aluminium silicate Nutrition 0.000 description 8
- 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 8
- 239000007788 liquid Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000010779 crude oil Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052596 spinel Inorganic materials 0.000 description 6
- 239000011029 spinel Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 241000370738 Chlorion Species 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000010426 asphalt Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910052624 sepiolite Inorganic materials 0.000 description 4
- 235000019355 sepiolite Nutrition 0.000 description 4
- 241000894007 species Species 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000004113 Sepiolite Substances 0.000 description 3
- 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 3
- 239000002585 base Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 229910052621 halloysite Inorganic materials 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910006415 θ-Al2O3 Inorganic materials 0.000 description 2
- 229910019975 (NH4)2SiF6 Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 229910003910 SiCl4 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 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
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229940000406 drug candidate Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003777 experimental drug Substances 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008979 phosphorus utilization Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—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 present invention relates to catalytic cracking catalyst silicon-aluminum sol field, discloses a kind of Ludox and silicon-aluminum sol and preparation method and application and catalytic cracking catalyst and preparation method.SiO in the Ludox2Content be 25~40 weight %, Na2O content is less than 0.15 weight %；The pH value of the Ludox is 2~10, density 1.1g/cm3~1.3g/cm3, viscosity is more than 200mPas.The present invention further provides silicon-aluminum sol contain there is few free chloro ion, structure optimization, the Alumina gel that viscosity is big, rate of corrosion is small, pH value is high, binding agent particle structure can be strengthened, while increasing binding agent adhesive property, reduce blocking of the binding agent to molecules of active components sieve structure in catalyst, reduce influence degree of the binding agent to catalyst activity, the usage amount of molecular sieve in catalyst can be reduced, reduces the cost of catalyst.
Description
Technical field
The present invention relates to catalytic cracking catalyst silicon-aluminum sol field, in particular it relates to a kind of Ludox,
The silicon-aluminum sol and preparation method of Ludox composition, and the silicon-aluminum sol is in catalytic cracking catalyst system
Application in standby, and a kind of catalytic cracking catalyst and preparation method thereof.
Background technology
Fluid catalytic cracking process is the most important means of crude oil secondary operation, with FCC chargings
The intensification of heaviness, in poor quality, the content that molecules of active components is sieved in catalyst is by the 15-20% of early stage
Increase to current 35% or even more than 40%.And with the increase of molecular sieve content, the abrasion of catalyst
Index and sphericity turned into catalyst preparation process one it is particularly significant the problem of.Catalyst must expire
Sufficient some strength requirement catalyst formation simultaneously particle diameter exists in 20-150 microns, catalyst average grain diameter
The microsphere particle of 60-80 microns, it could meet that catalytic cracking catalyst is normal in reaction unit
Flowing operating.
FCC catalyst product in China's is broadly divided into fully synthetic molecular sieve catalyst, semi-synthetic molecule at present
Sieve catalyst and in-situ crystallization method catalyst.The molecule that the preparation flow of fully synthetic molecular sieve catalyst uses
It can be Na types to sieve (X-type or Y types), and Na type molecular sieves can also be used into rare earth ion in advance
Or ammonium ion swaps, then through drying and being calcined, RE types or REH type molecular sieves are obtained, is added to
It is spray-dried that spheric catalyst is made in fully synthetic colloid；And Na type zeolites are added, it is spray-dried
Afterwards, it also can be made into spheric catalyst with redrying through exchanging again.Semi-synthetic molecular sieve catalyst preparation side
Method is more, and main method is first to mix kaolin with colloid, is mixed with kaolinic colloid slurries with surpassing
Slurries that stabilization Y-type molecular sieve is obtained by mixing are spray-dried to be made microspherical catalyst；After spray drying
Catalyst pulp again, is then washed with water the Na formed during except dereaction+, then with soluble rare earth from
Son swaps, and the catalyst after exchange is washed to remove unreacted rare earth exchanged agent and soluble-salt again
Class, semi-synthetic molecular sieve catalyst is made after redrying.And in-situ crystallization rule is using natural high
Ridge soil is used as initial feed, first prepares active component and host material simultaneously using one-step method, then pass through
Kaolin type FCC catalyst is prepared in modification.
With the increase of catalyst activity component molecular sieve content, the preparation method of fully synthetic catalyst is
Requirement of the catalyst to intensity can not be met, and it for matrix, molecular sieve is active component to use kaolin,
Various silicon/aluminium glues are the semi-synthesizing technology of binding agent, and its preparation technology is simple, and preparation cost is low, in molecule
Sieve content has good intensity when high.Semi-synthetic catalyst process is by binding agent, matrix, active group
Matter, which is prepared into well mixed slurries and carries out spray drying again, to be formed, and how to continue to improve catalyst plastic mistake
Journey has become the problem of extremely important in preparation technology：1) productivity ratio is improved, reduces energy consumption, is reduced
Molecular sieve usage amount, reduces cost.2) good sphericity is formed.The purpose of spray drying is one
Moisture unnecessary in slurries is evaporated at fixed temperature, the washiness that needs evaporate when solid content is low, and thing
Material is identical in the residence time of drying tower, thus the evaporation heat needed is more or drying temperature is high, such water
Divide rapidly type particle inner surface effusion at high temperature, form hollow ball or the microballoon with apple stems shape,
On the one hand catalyst strength is made to be deteriorated, on the other hand in FCC reaction-regeneration systems (reaction-regeneration system)
Fluidisation is easily broken.3) preparation method of binding agent is improved, the adhesive property of binding agent is improved, passes through
Improvement to binding agent makes the particle of binding agent more uniform, and more preferable series connection is played in catalyst plastic process
Cementation, while the blocking of molecular sieve pore passage is reduced, improve the activity of catalyst.4) develop more
Suitable matrix, cracking medium of the matrix as macromolecular in catalytic cracking process, the pore passage structure of matrix
Need the sufficiently large cracking process that disclosure satisfy that macromolecular in mink cell focus at this stage, increase catalyst towards heavy oil
Heat endurance in cracking capability and catalyst activity.5) Catalyst Viscosity is reduced, reduces catalyst glue
Body transporting resistance, catalyst spray quality is improved, while reduce catalyst spray tower stopping state.
CN1445167A discloses a kind of new technology for preparing Alumina gel, and preparation method includes：All with
Aluminium chloride and aluminum oxide or/and aluminium hydroxide or/and soft water aluminium are silicon source and hydrochloric acid is according to mol ratio
Al2O3：HCl=1.0-1.4:1 ratio mixing, reacts 3-40 hour at 80-130 DEG C.
CN1743267A discloses a kind of method for preparing colloidal sol containing chloride and aluminium, including is by formula
Al2(OH)1~3Cl3~5Aluminium polychloride the aqueous solution and the abundant haptoreaction of metallic aluminium, aluminium content is made
The Alumina gel for being 0.6~2.0 for 5~13 mass %, Al/Cl mass ratioes.The method is with aluminium polychloride generation
Alumina gel is produced for part metals aluminium, without using hydrochloric acid in production process, the corrosion to equipment is small, discharge
Amounts of hydrogen it is small, operation it is safer.The Alumina gel cost of production is low, suitable for the binding agent of catalyst.
CN1552801A discloses a kind of containing the catalytic cracking catalyst of silica sol binder and its preparation side
Method, it by 20~80m% clay, 5~30m% Ludox (with SiO2Burn base meter), 0~30m%
Boehmite is (with Al2O3Burn base meter), to be selected from lattice constant be 2.432~2.472nm's to 5~40m%
Faujasite, ZSM-5 zeolite, β zeolites and their mixture, 0~5m% (in terms of oxide)
Selected from antimony, mischmetal, titanium, magnesium, zinc, phosphorus, the compound of strontium or their mixture composition.It
The compoiste adhering being combined using silica sol binder matrix or Ludox with part peptization boehmite
Agent matrix, not only enhances the macromolecular cleavage ability of catalyst, while ensures that it has well resistance to again
Performance is ground, its preparation method can use intermittent mode or the side using multiply logistics continuous gel formation
Formula, have the characteristics that technique is simple, production capacity is big.
CN101130162A discloses a kind of Cracking catalyst and preparation method thereof, the catalyst contain with
The weight % of the weight % of butt meter 15~50 clay, 1 weight %~40 weight %'s is derived from Ludox
SiO2, the weight % of 5 weight %~30 Al for being derived from aluminum oxide and/or alumina precursor2O3, with butt
The weight % of 5 weight %~50 molecular sieve is counted, it is prepared by the method comprised the following steps：A is by clay
Be mixed with beating with Ludox, B by step A be beaten gained slurries and aluminum oxide and/or alumina precursor and
Molecular sieve is mixed with beating, and C is split the spray drying of step B mashing gained slurries, washing, re-dry
Change catalyst.Surfactant need not be added in the catalyst preparation process, for RFCC
Gasoline selective is high.
But with crude oil heaviness, (relative oil density is in 0.9~1.0g/cm3(20 DEG C)) degree adds
By force, catalyst property requirement is increased, then the binding agent during catalyst plastic must be improved, increased
While adding additives adhesive property, binding agent can be modified, strengthen binding agent particle structure,
The preventing from heavy metal ability of binding agent is improved, while reduces binding agent to molecules of active components sieve knot in catalyst
The blocking of structure, influence degree of the binding agent to catalyst activity is reduced, while making for molecular sieve can be reduced
Dosage, reduce the cost of catalyst.It is required that prepare the catalyst for adapting to crude oil heaviness processing request.
The content of the invention
It is an object of the invention in order to adapt to crude oil heaviness processing request, there is provided a kind of Ludox and silicon
Alumina gel and preparation method and application and catalytic cracking catalyst and preparation method.
The present inventor, which studies, to be found, improves the preparation method of Ludox, and with free chlorine from
Son less, the sial that is mixed to get of structure optimization, the Alumina gel that viscosity is big, rate of corrosion is small, pH value is high it is molten
Glue, binding agent particle structure can be strengthened when being used as binding agent in preparing catalytic cracking catalyst, increased
While adding additives adhesive property, reduce binding agent and molecules of active components sieve structure in catalyst is blocked up
Plug, influence degree of the binding agent to catalyst activity is reduced, the usage amount of molecular sieve can be reduced, reduced
The cost of catalyst.
To realize object defined above, according to the first aspect of the invention, the invention provides a kind of Ludox,
SiO in the Ludox2Content be 25~40 weight %, Na2O content is less than 0.15 weight %；Institute
The pH value for stating Ludox is 2~10, density 1.1g/cm3~1.3g/cm3, viscosity 200mPas
More than.
According to the second aspect of the invention, the invention provides a kind of silicon-aluminum sol, the silicon-aluminum sol to contain
Alumina gel and Ludox, with SiO in the silicon-aluminum sol2The Ludox of meter with Al2O3The Alumina gel of meter
Weight ratio be (1~4)：1, wherein, the Ludox is Ludox of the invention.
According to the third aspect of the invention we, the invention provides a kind of preparation method of silicon-aluminum sol, the party
Method includes：Will be with Al2O3The Alumina gel of meter with SiO2The Ludox of the invention of meter, according to SiO2：
Al2O3Weight ratio is (1~4)：1 carries out liquid phase at 20~50 DEG C mixes 1~3h, and it is molten to obtain sial
Glue.
According to the fourth aspect of the invention, obtained the invention provides a kind of preparation method by the present invention
Silicon-aluminum sol.
According to the fifth aspect of the invention, split the invention provides the silicon-aluminum sol of the present invention in preparation catalysis
Change the application in catalyst.
According to the sixth aspect of the invention, the invention provides a kind of preparation side of catalytic cracking catalyst
Method, this method include：Binding agent, clay, molecular sieve and optional big pore matrix are beaten to obtain
Catalyst slurry, the catalyst slurry is spray-dried, wherein, the binding agent is the present invention
The silicon-aluminum sol of offer.
According to the seventh aspect of the invention, obtained the invention provides a kind of preparation method by the present invention
Catalytic cracking catalyst.
Provided by the present invention for the silicon-aluminum sol in catalytic cracking catalyst as binding agent, contain this hair
The Ludox of bright offer and with free chloro ion is few, structure optimization, viscosity is big, rate of corrosion is small, pH
It is worth high Alumina gel, when preparing catalytic cracking catalyst, it is possible to increase the catalytic cracking catalyst of preparation
The solid content of slurries reaches more than 40 weight %, the molecular sieve content in obtained catalytic cracking catalyst
It can be reduced to below 30 weight %, for example, 5~30 weight %；The catalyst strength obtained simultaneously and work
The requirement of sexual satisfaction industrial application, and the abrasion index of catalyst substantially reduces.
In the present invention, the preparation method of Ludox is entered using monocrystalline silicon as raw material by substep and sodium hydroxide
Row first reacts and the second reaction, and the method through ion exchange removes sodium ion and is made.Party's legal system
Standby Ludox have it is relatively stable under different pH value (such as 2~6) and temperature (0~50 DEG C),
The advantages that simultaneous oxidation sodium is relatively readily removable.
In addition, in the present invention, the method for preparing the Alumina gel used in silicon-aluminum sol, process is simple and condition
It is easy to control, can prepare Alumina gel at a lower temperature, and the Alumina gel prepared have free chloro ion it is few,
Structure optimization, the advantages that viscosity is big, rate of corrosion is small, pH value is high.
Further, the method provided by the invention for preparing Alumina gel, reduces the usage amount of hydrochloric acid, reduces
The addition of chlorion, reduce destruction of the free acid to Alumina gel property, improve Alumina gel activity and
Reduction avoids the occurrence of salt excessive acid, causes Alumina gel pH value too low, so as to which saboteur sieves, influences to urge
The defects of agent activity.
The method for preparing Alumina gel of the present invention simultaneously, can replace part metals using inorganic aluminium compound
Aluminium, hence it is evident that reduce the production cost of Alumina gel.
, can be by the preferred embodiment of method of Alumina gel is prepared, further making in the present invention
It is modified with phosphorus compound and/or rare earth compound, can both reduces the usage amount of hydrochloric acid, can be obtained again
Alumina gel particle is evenly moderate, specific surface area is bigger, increase Alumina gel and final silicon-aluminum sol
Adhesive property.Phosphorus and/or rare earth modified Alumina gel are used simultaneously, can react to form ultra-fine phosphorus
Acid and/or rare earth glue composite precipitation, the precipitation have certain reactivity and suitable caking property, phase
Than the rare earth and/or phosphorus after shaping of catalyst in catalyst surface depositing dosed quantities, phosphorus compound and/or
Rare earth compound, which is modified Alumina gel, can following advantage：
(1) phosphorus compound and/or rare earth compound can more effectively be utilized, improves rare earth/phosphorus utilization,
Reduce addition and loss of the rare earth/phosphorus in molecular sieve and catalyst preparation process；
(2) improve distribution of the rare earth/phosphorus in catalyst substrates, rare earth/phosphorus is distributed more in matrix
Uniformly, catalyst heavy oil cracking ability is improved；
(3) rare earth ion is modified Alumina gel, and silicon-aluminum sol can be made preferably to be enriched with and be deposited on molecular sieve
Surface and stromal surface, adhesive property is more excellent, strengthens the ability of catalyst preventing from heavy metal；
(4) add phosphorus compound can rugged catalyst structure, and improve certain catalyst activity；
(5) strengthen the adhesive property of silicon-aluminum sol, improve catalyst performance.
The method for preparing catalytic cracking catalyst of the present invention, adds the silicon-aluminum sol of the present invention, and slurries glue
Degree reduces a lot, reduces gelation time and molecular sieve content, simplifies production technology, reduces production
Cost.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing be for providing a further understanding of the present invention, and a part for constitution instruction, with
Following embodiment is used to explain the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is the Alumina gel that embodiment 1 and comparative example 1 are prepared respectively27Al nuclear magnetic spectrograms.
Embodiment
The embodiment of the present invention is described in detail below.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, this
A little scopes or value should be understood to comprising the value close to these scopes or value.For number range, respectively
Between the endpoint value of individual scope, between the endpoint value of each scope and single point value, and single point
Can be combined with each other between value and obtain one or more new number ranges, these number ranges should by regarding
For specific disclosure herein.
According to the first aspect of the invention, the invention provides a kind of Ludox, SiO in the Ludox2
Content be 25~40 weight %, Na2O content is less than 0.15 weight %；The pH of the Ludox
It is worth for 2~10, density 1.1g/cm3~1.3g/cm3, viscosity is more than 200mPas.
In the present invention, SiO in the Ludox2、Na2O content is with the gross weight of the Ludox
On the basis of.
In the present invention, the density and viscosity of the Ludox are the measured value at 20 DEG C.Preferred viscosities are
200~10000mPas；More preferably 200~5000mPas.
According to a kind of preferred embodiment of the present invention, the preparation method of the Ludox includes：(a) by monocrystalline silicon
The first reaction is carried out with sodium hydroxide solution A；First reaction temperature be 50~70 DEG C, first reaction when
Between be 1~3h；(b) first product reacted and sodium hydroxide solution B are subjected to the second reaction,
Second reaction temperature is 70~90 DEG C, and the second reaction time was 1~2h；(c) described second is reacted
Product is cooled down to obtain colloid, and the colloid is carried out into ion exchange reduces sodium ions content, obtains silicon
Colloidal sol；Wherein, the monocrystalline silicon in terms of Si and the sodium hydroxide solution A and sodium hydroxide solution in terms of Na
The weight ratio of B total amount is (0.6~1.4)：1；In terms of Na, sodium hydroxide solution A and hydroxide
Sodium solution B weight ratio is (25~35)：(65-75)；Second reaction temperature is more anti-than described first
Answer temperature high 20~30 DEG C.Cooled down described in step (c), such as be cooled below 40 DEG C, example
Such as it is cooled to 15~40 DEG C
In the preparation method of the Ludox of the present invention, the first reaction is relatively low described in step (a)
At a temperature of carried out using a small amount of alkali so that portion of monocrystalline Si dissolves, and forms a part of effective colloid.
The temperature of second reaction described in step (b) is higher than the temperature of the described first reaction and uses substantial amounts of alkali,
The remaining monocrystalline silicon of reaction of experience first undergoes a high-temperature reaction process with alkali, can cause monocrystalline silicon and
Alkali carries out substantially stabilized secondary response, and the Ludox of acquisition is not easy to be formed condensation, colloidal nature more preferably,
It is more suitable for using for catalytic cracking catalyst binding agent.
In the present invention, the preparation method of the preferable Ludox, it is silicon source to select monocrystalline silicon, and substep adds
Enter sodium hydroxide solution and control the dosage often walked and reaction condition, it is as characterized above to prepare Ludox.
In the present invention, the ion exchange is to be contacted using cationic ion-exchange resin with the colloid,
It is preferred that using strongly acidic cation-exchange, such as it can be Zibo Dong great chemical inc
D101 hydrogen ion exchange resins.
In the case of, according to the invention it is preferred to, the purity of the monocrystalline silicon is 95~99 weight %.
Preferably, sodium hydroxide solution A and sodium hydroxide solution B concentration are 40~70 weight %.
According to the second aspect of the invention, the invention provides a kind of silicon-aluminum sol, the silicon-aluminum sol to contain
Alumina gel and Ludox, with SiO in the silicon-aluminum sol2The Ludox of meter with Al2O3The Alumina gel of meter
Weight ratio be (1~4)：1, wherein, the Ludox is Ludox of the invention.
The present invention silicon-aluminum sol can by by Alumina gel (with Al2O3Meter) with Ludox (with SiO2
Meter) according to (50~80)：The weight ratio of (20~50) is mixed, and is uniformly mixing to obtain.Sial
Colloidal sol is used to prepare catalytic cracking catalyst, can play each different adhesive properties, makes up single viscous
The deficiency of agent is tied, obtained catalyst can have extraordinary wear strength and preferably selectivity.
Ludox and the respective content of Alumina gel can be determined by XRF in the silicon-aluminum sol.
A preferred embodiment of the invention, the Alumina gel of selection have that free chloro ion is few, knot
The advantages that structure optimizes, viscosity is big, rate of corrosion is small, pH value is high.Under preferable case, in the Alumina gel
Aluminium cl molar ratio is (1~1.5)：1, rate of corrosion is not more than 1.5g/m2H, pH value are more than 2.8,
Viscosity is more than 500mPas.
In the present invention, the viscosity of the Alumina gel is the viscosity at 20 DEG C.
, according to the invention it is preferred to the aluminium cl molar ratio of the Alumina gel is (1.35~1.5)：1.
, according to the invention it is preferred to the weight content of aluminium element is 11.5~13% in the Alumina gel.
, according to the invention it is preferred to the density of the Alumina gel is 1.31g/cm3~1.35g/cm3.The aluminium
The density of colloidal sol is the density at 20 DEG C.
, according to the invention it is preferred to the viscosity of the Alumina gel is 500mPas~10000mPas.It is described
The viscosity of Alumina gel is the viscosity at 20 DEG C.
A kind of preferable case, viscosity of the Alumina gel provided by the present invention at 20 DEG C be 500mPas with
On, for example, 500mPas~10000mPas and density is 1.31g/cm3~1.35g/cm3。
, according to the invention it is preferred to the rate of corrosion of the Alumina gel is 1g/m2H~1.5g/m2·h。
, according to the invention it is preferred to the pH value of the Alumina gel is 2.8~3.5.
In the present invention, the Alumina gel can also contain phosphorus pentoxide and/or rare earth oxide.It is a kind of
In preferred embodiment, in the Alumina gel, rare earth oxide is with RE2O3In meter and the Alumina gel
Al2O3Weight ratio=(0.01~1.5)：1；It is preferred that RE2O3：Al2O3Weight ratio=(0.01~0.8)：
1。
In the present invention, when the Alumina gel contains phosphorus pentoxide, in the Alumina gel, P2O5It is molten with aluminium
Al in glue2O3Weight ratio=(0.01~1)：1.
In the present invention, free chloro ion in Alumina gel can be determined by the method for sedimentation, e.g., use ammonia
Water regulation Alumina gel pH value is 5~6, and flocculent deposit occurs in Alumina gel, isolates precipitation, measures upper strata
The content of the chlorion of clear liquid, determine the content of dissociative chlorine ion of the Alumina gel.
In the present invention, the density of the Alumina gel is determined by glass density instrument.
In the present invention, the viscosity of the Alumina gel is determined by rotary viscometer.
In the present invention, the rate of corrosion of the Alumina gel can be determined by the method for coupon test.
In the present invention, constituent content passes through XRF fluorescence spectrometries in the Alumina gel.
In the present invention, Alumina gel can be passed through27Al nuclear magnetic spectrograms observe the structure optimization of Alumina gel.This
The Alumina gel of invention27In Al nuclear magnetic spectrograms, (being labeled as embodiment 1) as shown in Figure 1, chemical potential
The peak height that moves the signal peak to occur at 0~3 is low, peak area is small, shows that the quantity of single poly-aluminium is few；Change
Displacement study is that the peak height of the signal peak occurred at 60~63 is high, peak area is big, illustrates the aluminium of high polymeric form
It is more.27The result of Al nuclear magnetic spectrograms shows that the Alumina gel of the present invention is the structure based on high polymeric form aluminium.
The Alumina gel (CN1445167A embodiment method) that the prior art equally determined obtains is (in Fig. 1
Labeled as comparative example 1), be chemical shift for the signal peak at 0~3 peak height is high, peak area is big,
Chemical shift is that the peak height of the signal peak at peak at 60~63 is low, peak area is small, shows the aluminium of prior art
Colloidal sol is the structure based on single poly-aluminium.
Under preferable case, the Alumina gel27In Al nuclear magnetic spectrograms, chemical shift is to go out at 60~63
The peak area at peak is more than 1 with the peak area ratio that chemical shift is appearance at 0~3；It is preferred that chemical potential
Move peak area for appearance at 60~63 and ratio that chemical shift is the peak area of appearance at 0~3 is
1~1.6, such as this ratio is 1.1,1.2,1.3,1.4 or 1.5.It is possible thereby to the present invention is embodied indirectly
Alumina gel in high polymeric form aluminium and ratio of single poly-aluminium in content more than 1, preferred ratio is 1~
1.5。
When silicon-aluminum sol in the present invention is applied to prepare catalytic cracking catalyst, it is possible to increase preparation is urged
The solid content of fluidized cracking catalysts slurries reaches more than 40 weight %, in obtained catalytic cracking catalyst
Molecular sieve content can be reduced to below 30 weight %；The catalyst strength and activity obtained simultaneously meets
Industrial application requirement, and the abrasion index of catalyst substantially reduces.
According to the third aspect of the invention we, the invention provides a kind of preparation method of silicon-aluminum sol, the party
Method includes：Will be with Al2O3The Alumina gel of meter with SiO2In the claim 1-3 of meter described in any one
Ludox, according to SiO2：Al2O3Weight ratio is (1~4)：1 carries out liquid phase at 20~50 DEG C mixes
1~3h is closed, obtains silicon-aluminum sol.
In the present invention, a kind of preferred embodiment, the preparation process of the Alumina gel includes：(1) by gold
Category aluminium carries out first with hydrochloric acid and contacted；(2) mixture after the first contact is carried out into second with silicon source to contact；
The temperature of first contact is higher than 20~30 DEG C of the temperature of the second contact.
The method for preparing Alumina gel of the present invention, the usage amount of hydrochloric acid can be reduced, reduce adding for chlorion
Enter amount, reduce destruction of the free acid to Alumina gel property, improve the activity of Alumina gel, while can avoid
The defects of salt excessive acid occur causes Alumina gel pH value too low, and saboteur sieves and influences catalyst activity.
In the method for preparing Alumina gel of the present invention, during carrying out first contact and the second contact
With stirring, stop the process that stirring is first contact and the second contact and terminate.As described below first
Contact and the second time of contact are the time under stirring persistently.
According to a kind of preferred embodiment of the present invention, the first Contact Temperature is 50~80 DEG C.
According to a kind of preferred embodiment of the present invention, the second Contact Temperature is 20~50 DEG C.
According to a kind of preferred embodiment of the present invention, in terms of Al, the use of metallic aluminium in step (1)
The mol ratio of amount and the dosage of silicon source described in step (2) is (5~10):1.
A preferred embodiment of the invention, this method also include：Carry out step (2) it
Before, the mixture after the described first contact is stood into 1~30h at normal temperatures, preferably stands 2~6h.Institute
State after standing and referring to that adjoint stirring stops when the described first contact is carried out, after first contact
Mixture is placed under without stirring.
In the present invention, the temperature of first contact is higher than the temperature of the second contact, the first contact knot
It can be cooled after beam, such as by the standing, then be controlled again under the second relatively low Contact Temperature
Carry out second contact.
The method according to the invention, normal temperature are for example generally 0~40 DEG C.
According to a kind of preferred embodiment of the present invention, the condition of the first contact also includes：Relative to
1mol hydrochloric acid, the dosage of metallic aluminium is 0.8mol~1.3mol.
According to a kind of preferred embodiment of the present invention, the condition of the first contact also includes：First contact
Time is 2~5h.
According to a kind of preferred embodiment of the present invention, the condition of the first contact also includes：Hydrochloric acid it is dense
Spend for the weight % of 31 weight %~36.
According to a kind of preferred embodiment of the present invention, the condition of the second contact also includes：Second contact
Time is 3~4h.
According to a kind of preferred embodiment of the present invention, silicon source is preferably metallic aluminium described in the second contact
And/or inorganic aluminium compound.
In the Alumina gel preparation process of the present invention, the optional scope of the species of the inorganic aluminium compound compared with
Width, for the present invention, preferably described inorganic aluminium compound is aluminium chloride, aluminum oxide, aluminium hydroxide and soft
One or more in water aluminium；More preferably described inorganic aluminium compound is Al2O3, more preferably γ-Al2O3
And/or η-Al2O3。
A preferred embodiment of the invention, preparing the method for the Alumina gel also includes, by
The mixture that two contacts obtain, carry out the 3rd with phosphorus compound and/or rare earth compound and contact.
According to the method for preparing the Alumina gel of the present invention, the mixture and rare earth that the second contact is obtained
Optional wider range of the condition of compound contact, for the present invention, is preferably included：3rd Contact Temperature
For 10~50 DEG C, more preferably the 3rd time of contact is more than 10min；It is preferred that the 3rd time of contact be 10~
60min.Phosphorus compound and/or rare earth compound can be fed intake and started as the 3rd contact.
A preferred embodiment of the invention, the optional scope of species of the rare earth compound compared with
Width, rare earth compound species well known in the art is used equally for the present invention, preferably described for the present invention
Rare earth element in rare earth compound includes at least one of La, Ce, Sc, Pr and Nd, such as containing
The mixed rare earth compound of lanthanum and Ce.It is preferred that the rare earth compound be rare earth oxide, rare earth hydrate,
At least one of nitric acid rare earth and rare earth oxalate.
In this present invention, under preferable case, the rare earth compound is with RE2O3Meter contacts with described second
Obtained mixture is with Al2O3Weight ratio=(0.01~1.5) of meter：1；More preferably weight ratio=(0.01~
0.8)：1.
A preferred embodiment of the invention, the phosphorus compound can be those skilled in the art
Well known raw material, for the present invention, the one kind being preferably selected from phosphorus pentoxide, phosphoric acid and phosphate or
A variety of, more preferably described phosphorus compound is with P2O5Meter is with second mixture for contacting to obtain with Al2O3
Weight ratio=(0.01~1) of meter：1.
The method of Alumina gel is prepared in the present invention to be carried out continuously.
According to the fourth aspect of the invention, obtained the invention provides a kind of preparation method by the present invention
Silicon-aluminum sol.
According to the fifth aspect of the invention, present invention also offers the silicon-aluminum sol of the present invention to prepare catalysis
Application in Cracking catalyst.
According to the sixth aspect of the invention, present invention also offers a kind of preparation side of catalytic cracking catalyst
Method, wherein, this method includes：Binding agent, clay, molecular sieve and optional big pore matrix are beaten
Obtained catalyst slurry is starched, the catalyst slurry is spray-dried, the binding agent is this hair
The silicon-aluminum sol of bright offer.
According to the preparation method of the catalytic cracking catalyst of the present invention, it is preferable that washed after spray drying,
It is dried to obtain catalytic cracking catalyst.
Include in the first preferred embodiment of the preparation method of the catalytic cracking catalyst of the present invention：
(1) silicon-aluminum sol, stirring are added；
(2) add molecular sieve dry powder or ground molecular sieve pulp disperses 5-120 minutes, preferably
5-40 minutes；
(3) clay, optional big pore matrix are added, stirs 30-200 minutes, preferably 60-120 minutes；
(4) it is spray-dried；
(5) wash, re-dry produces product.
Include in second of preferred embodiment of the preparation method of the catalytic cracking catalyst of the present invention：
(1) silicon-aluminum sol is added, stirring, clay is added, stirring, adds optional big pore matrix,
Stir 5-200 minutes, preferably 30-90 minutes；
(2) add molecular sieve dry powder or ground molecular sieve pulp disperses 5-120 minutes, preferably
5-50 minutes；
(3) it is spray-dried；
(4) wash, re-dry produces product.
Catalyst according to the invention preparation method, preferably with the dry basis of the catalyst slurry,
The dosage of molecular sieve is 10~50 weight %, and the dosage of clay is 10~50 weight %, and binding agent is with oxygen
The dosage of compound meter is 5~35 weight %, and the dosage of big pore matrix is 0~25 weight %.It is preferred that macropore
The dosage of matrix is 2~25 weight %.Wherein, the binding agent is silicon-aluminum sol, the silicon-aluminum sol
In, with Al2O3The Alumina gel of meter with SiO2The weight ratio of the Ludox of meter is 1：(1~4).
Catalyst according to the invention preparation method, the average pore size of preferably big pore matrix for 100~
200nm。
In the present invention, the matrix with macroporous structure commonly used in the art may be used as the described of the present invention
Big pore matrix.Under preferable case, the big pore matrix be aluminum oxide, silica, complex oxide,
Magnesium aluminate spinel, phosphorus aluminate or modified magnesium aluminate spinel, wherein the complex oxide is metal
Mg, Ca, Sr, Ba, Cu, V, Zn, Ti and nonmetallic B, P oxide and aluminum oxide, oxidation
The compound of silicon.For the present invention, preferably described big pore matrix can be aluminum oxide, such as can be tool
Have a diaspore structure hydrated alumina, with gibbsite structure hydrated alumina, with bayerite knot
The one or more of the hydrated alumina of structure, or χ-Al2O3、δ-Al2O3、η-Al2O3、κ-Al2O3、
θ-Al2O3、ρ-Al2O3、α-Al2O3With γ-Al2O3, wherein κ-Al2O3、δ-Al2O3、θ-Al2O3With α-Al2O3
The high temperature aluminas for the preparation at 900~1000 DEG C that is dehydration temperaturre, χ-Al2O3、η-Al2O3、γ-Al2O3、
ρ-Al2O3The aluminum oxide for being less than 600 DEG C of preparations in dehydration temperaturre, its specific surface area and pore volume it is general all compared with
Greatly, referred to as activated alumina is conventional for γ-Al2O3With η-Al2O3.The big pore matrix can also be
Silica, including sodium metasilicate, silicic acid etc. provide the matrix of silicon source；Can also be metal Mg, Ca,
Sr, Ba, Cu, V, Zn, Ti and nonmetallic B, P oxide and aluminum oxide, the compound of silica；
It can also be magnesium aluminate spinel, phosphorus aluminate, can be preferably magnesium aluminate spinel.
Catalyst according to the invention preparation method, the solid content of preferably described catalyst slurry is in 40 weights
Measure more than %, preferably 40-55 weight %.
The raw clay that clay of the present invention is well known to those skilled in the art, conventional clay kind
Class may be incorporated for the present invention, for the present invention, preferably described clay be kaolin, halloysite,
Montmorillonite, diatomite, galapectite, halloysite, saponite, rectorite, sepiolite, attapulgite,
One or more in hydrotalcite and bentonite.Wherein, sepiolite is that a kind of rich fibrous magnesium silicate glues
Native mineral, in its construction unit, silicon-oxy tetrahedron and magnesia octahedron alternate, have stratiform and
The transitional architectural feature of chain., can be effective by the use of sour modified meerschaum as FCC catalyst matrix
Specific surface area, pore volume and the mesopore volume of catalyst are improved, the preventing from heavy metal that can strengthen catalyst is made
With.And kaolin and halloysite have property relatively, and galapectite then have specific surface area it is big,
Pore volume is big, and pore-size distribution shows the characteristics of macropore is less, mesopore is more, and galapectite also has surface acid
Property the features such as big, micro- index living is high, Pore stability is good.For the present invention, preferably described clay is
It is one or more kinds of in sepiolite, kaolin and galapectite.
In the present invention, Molecular sieve raw material that described molecular sieve is well known in the art, point commonly used in the art
Son sieve species may be incorporated for the present invention, for the preferably molecular sieve of the invention refer to REY, REHY,
REUSY, USY, using gas chemistry method (SiCl4De- Al mends Si methods), liquid chemical method ((NH4)2SiF6
Aluminium-eliminating and silicon-replenishing method) and other methods prepare different silica alumina ratios be modified Y zeolites or their mixture,
And ZSM-5 classes, β classes zeolite or their mixture containing other all kinds of high silica alumina ratios.
The method provided by the present invention for preparing catalytic cracking catalyst, can using the silicon-aluminum sol of the present invention
To reduce the blocking of molecular sieve pore passage, while matrix is preferably wrapped up with binding agent, improve catalyst
The intensity of shaping degree and catalyst.In addition using the silicon-aluminum sol of the present invention, catalytic cracking catalyst is prepared
When, a large amount of acid of addition can not had to and be acidified, molecular sieve is avoided when the colloid for being in low ph value
Destroyed when middle, improve the activity of catalyst.In addition, the preparation method of the catalytic cracking catalyst
It can also reduce the time of catalyst plastic process, increase plastic slurry solid content, reduce slurry viscosity,
Shorten technological process and reduce energy consumption, increase yield.
According to the seventh aspect of the invention, present invention also offers the catalysis that the preparation method of the present invention obtains
Cracking catalyst.
, according to the invention it is preferred in the catalytic cracking catalyst molecular sieve content 30 weight % with
Under.
In the catalytic cracking catalyst that method for preparing catalyst according to the present invention obtains, in terms of dry weight (800
DEG C roasting 1h iglosss content) contain the weight % of molecular sieve 10~50, preferably 25~30 weight %；Clay
10~50 weight %, preferably 35~45 weight %；Silicon-aluminum sol (presses Al2O3And SiO2Summation meter)
15~40 weight %, preferably 18~30 weight %；The big weight % of pore matrix 2~25, preferably 6~16
Weight %.
Catalytic cracking catalyst provided by the invention can reduce the usage amount of binding agent and molecular sieve.
The present invention can also provide the application of the catalytic cracking catalyst progress catalytic cracking reaction of the present invention.
Heaviness crude oil can be handled, there is higher conversion ratio, liquid yield and yield of light oil, and coke
Amount reduces.
The following examples are described further to the features of the present invention, but present disclosure not by
The limitation of embodiment.
The content of dissociative chlorine ion of Alumina gel, is determined by the method for sedimentation, and Alumina gel is adjusted using ammoniacal liquor
PH value is 5~6, and flocculent deposit occurs in Alumina gel, isolates precipitation, measures the chlorion of supernatant liquor
Content.
Ludox, the density of Alumina gel pass through glass density meter (the prosperous preferably limited public affairs of experimental facilities of Shenzhen's ancient cooking vessel
Department) measure.
Ludox, the viscosity of Alumina gel by the flat scientific instrument Co., Ltds of Hai Heng Shang rotary viscometer (,
NDJ-1 types rotary viscosimeter) measure.
Constituent content passes through XRF fluorescence analysis methods (RIPP 117-90 standards in Ludox, Alumina gel
Method (see《Petrochemical Engineering Analysis method》(RIPP test methods) Yang Cui is waited and compiled surely, Science Press,
Nineteen ninety publishes)) measure.
The rate of corrosion of Alumina gel can be determined by the method for coupon test：
Experiment equipment：Use 20# carbon steels test piece (silvery white) as lacing film (size for
50mm × 25mm × 2mm), water bath with thermostatic control, magnetic stirring apparatus, hair-dryer, absorbent cotton；
Experimental drug：Absolute ethyl alcohol, hydrochloric acid (10 weight %), hexamethylenetetramine (0.5 weight %),
5N sodium hydroxide；
Experimental procedure：First by lacing film washes of absolute alcohol sample, the grease of specimen surface is removed；So
5min, further degreasing and dehydration are soaked in absolute ethyl alcohol afterwards.Treat that work above is finished,
Take out sample to be positioned on filter paper, wrapped up after cold wind drying with filter paper, be positioned in drier and preserve, 24h
After weigh, gained scrapes sheet weight, is designated as W1.Lacing film suspension is put into the Alumina gel 1L contained in a reservoir
In 24h is stood at 0~30 DEG C, the container for being contained with lacing film and Alumina gel is then placed in water bath with thermostatic control
In at 80 DEG C of temperature reaction time 6h.First with 10 weight % hydrochloric acid and 0.5 weight % after the completion of reaction
Ammonium mixture (the preparation method of mixture of six methine four：By 10 weight % hydrochloric acid and 0.5 weight % six times
The ammonium of methyl four mixes, and prepares the solution that pH value is 5~7) clean the black corrosion removed on lacing film
Product, until black corrosion product is cleaned out completely, silvery white, the lacing film after cleaning is presented in lacing film
Immerse immediately in 5N sodium hydroxide solution and be passivated 1min；The absolute ethyl alcohol of cleaning is immersed after taking-up
Middle immersion 1min, is dried with filter paper, is wrapped up after cold wind drying with filter paper, is positioned in drier and preserves,
Weighed after 24h, gained weight is designated as W2；Rate of corrosion, rate of corrosion=△ W/ are calculated according to formula below
(T×A)；In formula：△ W=lacing films are weighed after W1- lacing films take out before being linked into and weighed W2；T is lacing film
The time (6h) being linked into；A is the area (0.28dm of lacing film2)。
Alumina gel27Al nuclear-magnetisms determine：Alumina gel addition decationizing water is diluted to 1 weight % (Al2O3
Content) solution sample is made；It is measured by Varian companies INOVA500 type NMR spectrometer with superconducting magnet,
Test condition includes：Resonant frequency 130MHz (27Al), pulse protocol s2pul, spectrum width 90090Hz,
Accumulative frequency 800, time delay 1.0s, sampling time 0.5s, hold agent D2O, outer standard specimen NaAlO2。
The raw material specification used in catalyst preparation example is as follows：
Kaolin：The weight % of solid content 81.2, China Kaolin Clay Co., Ltd. (Suzhou) production；
REY type molecular sieves：Asphalt in Shenli Refinery of Sinopec catalyst Co., Ltd produces, solid content 80
Weight %, rare earth oxide (La or Ce) content are 17~18 weight %；
Magnesium aluminate spinel：Al2O3The weight % of content 43, the weight % of content of MgO 54, Hebei province Xingtai
Ancient cooking vessel magnesium science and technology Chemical Co., Ltd. of city produces, and the weight % of solid content 70.8, average pore size is 120~150nm；
Rare earth oxide solution concentration：328.46g/L, containing La, Ce (La：Ce mol ratios are 1：1),
Asphalt in Shenli Refinery of Sinopec catalyst Co., Ltd produces.
Phosphorus compound：Concentration is 75 weight % phosphoric acid, and Sinopec catalyst Co., Ltd Shandong is divided
Company produces.
Sodium hydroxide：NaOH content is more than 96 weight %, Beijing chemical reagent Co., Ltd.
Each composition is calculated by the inventory of each raw material and determined in the catalyst that catalyst preparation example obtains.
Embodiment 1
This example demonstrates that the preparation method of the Alumina gel of the present invention.
(1) 1mol metallic aluminiums (China Aluminum Co., Ltd) are carried out into first with 1mol (HCl) hydrochloric acid to connect
Touch, control the first contact process temperature as 50 DEG C, the first time of contact was 3h, hydrochloric acid used it is initial
Concentration is 32 weight %；
(2) mixture after the first contact is stood into 6h at 20 DEG C of normal temperature, then with γ-Al2O3(mountain
Eastern aluminium manufacturer) and η-Al2O3(Shandong Aluminum Plant) carries out the second contact, and the second Contact Temperature is 30 DEG C, the
Two times of contact were 4h, the γ-Al in terms of aluminium2O3, η-Al in terms of aluminium2O3With the metal of step (1)
The mol ratio of aluminium is 0.05：0.05：1.The physico-chemical property of Alumina gel is shown in Table 1.
Alumina gel is carried out27Al nuclear-magnetisms determine, and spectrogram is shown in Fig. 1, wherein, chemical shift is at 0~3
Signal peak peak height is low, peak area is small, show that the quantity of single poly-aluminium is few；Chemical shift is 60~63
The peak height of the signal peak at place is high, peak area is big, illustrates that the aluminium of high polymeric form is more.Show the Alumina gel and be with
Structure based on high polymeric form aluminium.Calculate the peak area and chemical potential that chemical shift is appearance at 60~63
It is 1.3 to move as the ratio of the peak area of appearance at 0~3.
Embodiment 2
This example demonstrates that the preparation method of the Alumina gel of the present invention.
(1) 1.1mol metallic aluminiums are carried out into first with 1mol (HCl) hydrochloric acid to contact, control first connects
It is 80 DEG C, time 2h to touch process temperature, and the concentration of hydrochloric acid is 36 weight %；
(2) mixture after the first contact is stood into 2h at 30 DEG C of normal temperature, then with γ-Al2O3With
η-Al2O3The second contact is carried out, the second Contact Temperature is 50 DEG C, and the second time of contact was 3h, in terms of aluminium
γ-Al2O3, η-Al in terms of aluminium2O3Mol ratio with the metallic aluminium of step (1) is 0.1：0.06：1.
The physico-chemical property of Alumina gel is shown in Table 1.
It is the peak area of appearance and the peak that chemical shift is appearance at 0~3 at 60~63 to calculate chemical shift
The ratio of area is 1.1.
Embodiment 3
This example demonstrates that the preparation method of the Alumina gel of the present invention.
(1) 1.1mol metallic aluminiums are carried out into first with 1mol (HCl) hydrochloric acid to contact, control first connects
It is 60 DEG C, time 5h to touch process temperature, and the concentration of hydrochloric acid is 31 weight %；
(2) mixture after the first contact is stood into 4h at 10 DEG C of normal temperature, then with γ-Al2O3、
η-Al2O3The second contact is carried out, the second Contact Temperature is 35 DEG C, and the second time of contact was 3.5h, with aluminium
γ-the Al of meter2O3, η-Al in terms of aluminium2O3Mol ratio with the metallic aluminium of step (1) is 0.12：0.08：
1.The physico-chemical property of Alumina gel is shown in Table 1.
It is the peak area of appearance and the peak that chemical shift is appearance at 0~3 at 60~63 to calculate chemical shift
The ratio of area is 1.2.
Embodiment 4
This example demonstrates that the preparation method of the Alumina gel of the present invention.
Method according to embodiment 3 prepares Alumina gel, unlike, γ-Al are used alone2O3As step
Suddenly the silicon source of (2), the γ-Al in terms of aluminium2O3Mol ratio with metallic aluminium is 0.2：1.
The physico-chemical property of Alumina gel is shown in Table 1.
It is the peak area of appearance and the peak that chemical shift is appearance at 0~3 at 60~63 to calculate chemical shift
The ratio of area is 1.2.
Embodiment 5
This example demonstrates that the preparation method of the Alumina gel of the present invention.
Method according to embodiment 4 prepares Alumina gel, unlike, replace γ-Al using metallic aluminium2O3
As the silicon source of step (2), the Al being introduced into step (2) is with the middle Al's introduced of step (1)
Mol ratio is 0.2：1.
The physico-chemical property of Alumina gel is shown in Table 1.
It is the peak area of appearance and the peak that chemical shift is appearance at 0~3 at 60~63 to calculate chemical shift
The ratio of area is 1.2.
Embodiment 6
This example demonstrates that the preparation method of the Alumina gel of the present invention.
Method according to embodiment 3 prepares Alumina gel, unlike, the temperature of the first contact is 90 DEG C,
The temperature of second contact is 60 DEG C.
The physico-chemical property of Alumina gel is shown in Table 1.
It is the peak area of appearance and the peak that chemical shift is appearance at 0~3 at 60~63 to calculate chemical shift
The ratio of area is 1.2.
Embodiment 7
This example demonstrates that the preparation method of the Alumina gel of the present invention.
The Alumina gel prepared to embodiment 1 is (with Al2O3Meter) in add rare earth oxide solution (with RE2O3
Meter, La and Ce summation), RE2O3：Al2O3=0.8：1,0.5h is stirred, filters, obtains after mixing
To stable Alumina gel product.
The physico-chemical property of Alumina gel is shown in Table 1.
It is the peak area of appearance and the peak that chemical shift is appearance at 0~3 at 60~63 to calculate chemical shift
The ratio of area is 1.5.
Embodiment 8
This example demonstrates that the preparation method of the Alumina gel of the present invention.
The Alumina gel prepared to embodiment 1 is (with Al2O3Meter) in add rare earth oxide solution (with RE2O3
Meter, La and Ce summation), RE2O3：Al2O3=0.8：1, phosphoric acid solution is added (with P2O5Meter),
P2O5：Al2O3=0.8：1,0.5h is stirred, is filtered after mixing, the Alumina gel product stablized.
The physico-chemical property of Alumina gel is shown in Table 1.
It is the peak area of appearance and the peak that chemical shift is appearance at 0~3 at 60~63 to calculate chemical shift
The ratio of area is 1.6.
Preparation example 1
Alumina gel is prepared according to CN1445167A embodiment method.
It is Al in molar ratio by aluminum oxide and hydrochloric acid2O3:HCl=1:3 ratio is put into reactor, control
Reaction temperature processed is 140 DEG C, is kept for 2 hours, prepares liquor alumini chloridi, be continuously added in course of reaction
Dilution heat of sulfuric acid, then the metallic aluminium of supplement point is added to for 4 times by the content of aluminium in the Alumina gel needed for
It is to be reacted 40 hours at 80 DEG C in reactor, to keep 1 atmospheric pressure, control temperature, in course of reaction
Uninterrupted stirring obtains Alumina gel, and the physico-chemical property of Alumina gel is shown in Table 1.
Alumina gel is carried out27Al nuclear-magnetisms determine, and spectrogram is shown in Fig. 1, wherein, chemical shift is at 0~3
Signal peak peak height is high, peak area is big, show that the quantity of single poly-aluminium is few, chemical shift is 60~63
The peak height of the signal peak at place is low, peak area is small, and instruction sheet poly-aluminium is more.It is with single poly-aluminium to show the Alumina gel
Based on structure.
It is the peak area of appearance and the peak that chemical shift is appearance at 0~3 at 60~63 to calculate chemical shift
The ratio of area is 0.6.
Preparation example 2
The Alumina gel prepared to comparative example 1 is (with Al2O3Meter) in add rare earth oxide solution (with RE2O3
Meter, La and Ce summation), RE2O3：Al2O3=0.8：1,0.5h is stirred, filters, obtains after mixing
To stable Alumina gel product, the physico-chemical property of Alumina gel is shown in Table 1.
It is the peak area of appearance and the peak that chemical shift is appearance at 0~3 at 60~63 to calculate chemical shift
The ratio of area is 0.7.
Preparation example 3
Method according to CN1743267A embodiment 1 prepares Alumina gel.
It is Al to take 6.5g formulas2(OH)2.9Cl3.1Aluminium polychloride, wherein the Al containing 29.0 weight %2O3、
31.8 weight % Cl, is dissolved in 10mL water, adds the gold that 1.3g purity is 99.5 weight %
Belong to aluminium, stirring reaction 7.5 hours under 50 DEG C, 0.1MPa, filtering, obtain 16.71g Alumina gel.
The physico-chemical property of Alumina gel is shown in Table 1.
It is the peak area of appearance and the peak that chemical shift is appearance at 0~3 at 60~63 to calculate chemical shift
The ratio of area is 0.4.
Preparation example 4
The Alumina gel prepared to comparative example 3 is (with Al2O3Meter) in add rare earth oxide solution (with RE2O3
Meter, La and Ce summation), RE2O3：Al2O3=0.8：1,0.5h is stirred, filters, obtains after mixing
To stable Alumina gel product, the physico-chemical property of Alumina gel is shown in Table 1.
It is the peak area of appearance and the peak that chemical shift is appearance at 0~3 at 60~63 to calculate chemical shift
The ratio of area is 0.5.
The physico-chemical property of the Alumina gel of table 1
Alumina gel made from embodiment 1-3, preparation example 1 and 3 is subjected to content of dissociative chlorine ion measure,
It was found that less using the Alumina gel free chloro ion prepared by embodiment 1, experimental result is shown in Table 2.
The property of Alumina gel supernatant liquor after table 2 settles
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Preparation example 1 | Preparation example 3 |
| The pH of supernatant liquor | 5.5 | 5.7 | 5.8 | 4.8 | 6.0 |
| Cl-, weight % | 1.23 | 1.59 | 1.78 | 5.63 | 2.63 |
Embodiment 9
This example demonstrates that the preparation method of the Ludox of the present invention.
Monocrystalline silicon (99% purity, from Changzhou YiJing opto-electrical Science Co., Ltd) is molten with sodium hydroxide
Liquid A (NaOH concentration is 46 weight %), the first reaction 2h is carried out at 60 DEG C；
By first product reacted at 80 DEG C with sodium hydroxide solution B (NaOH concentrations 46
Weight %) carry out the second reaction 2h；
Wherein in terms of Na, sodium hydroxide solution A and sodium hydroxide solution B weight ratio is 30：70；
Monocrystalline silicon (Si meters) and the weight of sodium hydroxide solution A and sodium hydroxide solution B total amount (Na meters)
Amount is than being 1：1.
Second product reacted is cooled to 25 DEG C, obtained colloid exchanges tree with D101 hydrogen ions
Fat (Zibo Dong great chemical inc) is contacted, the sodium ion being swapped out in the colloid,
Obtain the Ludox that solid content is 35 weight %.
The SiO of Ludox2Content is 35 weight %, Na2O content is 0.08 weight %, and pH value is
2.81, density 1.162g/cm3, viscosity 540mPas.
Embodiment 10
This example demonstrates that the preparation method of the Ludox of the present invention.
By monocrystalline silicon and sodium hydroxide solution A (NaOH concentration is 70 weight %), carried out at 70 DEG C
First reaction 3h；
By first product reacted at 90 DEG C with sodium hydroxide solution B (NaOH concentrations 40
Weight %) carry out the second reaction 1h；
Wherein in terms of Na, sodium hydroxide solution A and sodium hydroxide solution B weight ratio is 25：75；
Monocrystalline silicon (Si meters) and the weight of sodium hydroxide solution A and sodium hydroxide solution B total amount (Na meters)
Amount is than being 0.6：1.
Second product reacted is cooled to 25 DEG C, obtained colloid exchanges tree with D101 hydrogen ions
Fat is contacted, the sodium ion being swapped out in the colloid, and it is molten to obtain the silicon that solid content is 30 weight %
Glue.
The SiO of Ludox2Content is 30 weight %, Na2O content is 0.10 weight %, and pH value is
7.48, density 1.165g/cm3, viscosity 320mPas.
Embodiment 11
This example demonstrates that the preparation method of the Ludox of the present invention.
By monocrystalline silicon and sodium hydroxide solution A (NaOH concentration is 40 weight %), carried out at 50 DEG C
First reaction 1h；
By first product reacted at 80 DEG C with sodium hydroxide solution B (NaOH concentrations 70
Weight %) carry out the second reaction 1.5h；
Wherein in terms of Na, sodium hydroxide solution A and sodium hydroxide solution B weight ratio is 35：65；
Monocrystalline silicon (Si meters) and the weight of sodium hydroxide solution A and sodium hydroxide solution B total amount (Na meters)
Amount is than being 1.4：1.
Second product reacted is cooled to 25 DEG C, obtained colloid exchanges tree with D101 hydrogen ions
Fat is contacted, the sodium ion being swapped out in the colloid, and it is molten to obtain the silicon that solid content is 40 weight %
Glue.
The SiO of Ludox2Content is 40 weight %, Na2O content is 0.20 weight %, and pH value is
9.55, density 1.241g/cm3, viscosity 4300mPas.
Embodiment 12
This example demonstrates that the preparation method of the silicon-aluminum sol of the present invention.
Will be with Al2O3The Alumina gel of embodiment 8 of meter with SiO2The Ludox of embodiment 9 of meter, according to
SiO2：Al2O3Weight ratio is 4：1 carries out liquid phase mixing 2h at 40 DEG C, obtains silicon-aluminum sol.
Embodiment 13
This example demonstrates that the preparation method of the silicon-aluminum sol of the present invention.
Will be with Al2O3The Alumina gel of embodiment 8 of meter with SiO2The Ludox of embodiment 10 of meter, according to
SiO2：Al2O3Weight ratio is 4：1 carries out liquid phase mixing 2h at 40 DEG C, obtains silicon-aluminum sol.
Embodiment 14
This example demonstrates that the preparation method of the silicon-aluminum sol of the present invention.
Will be with Al2O3The Alumina gel of embodiment 8 of meter with SiO2The Ludox of embodiment 11 of meter, according to
SiO2：Al2O3Weight ratio is 4：1 carries out liquid phase mixing 2h at 40 DEG C, obtains silicon-aluminum sol.
Embodiment 15
This example demonstrates that the preparation method of the silicon-aluminum sol of the present invention.
Will be with Al2O3The Alumina gel of preparation example 1 of meter with SiO2The Ludox of embodiment 9 of meter, according to
SiO2：Al2O3Weight ratio is 4：1 at 40 DEG C in a kettle mix after be stirred 2h, obtain
Silicon-aluminum sol.
Embodiment 16
This example demonstrates that the preparation method of the silicon-aluminum sol of the present invention.
Will be with Al2O3The Alumina gel of preparation example 2 of meter with SiO2The Ludox of embodiment 9 of meter, according to
SiO2：Al2O3Weight ratio is 4：1 carries out mixing 2h in a kettle at 40 DEG C, obtains silicon
Alumina gel.
Catalyst preparation example
(1) 70.72kg silicon-aluminum sols (source is according to listed by table 3) are added into reactor, are stirred,
Kaolin 43.10kg is added, adds magnesium aluminate spinel 21.19kg, stirs 30min；Add ground
REY molecular sieve pulps (asphalt in Shenli Refinery of Sinopec catalyst Co., Ltd produces, and slurries contain admittedly
Measure 31.4 weight %) 95.54kg, stirs 30min, spray drying, by gained catalyst microspheres 500
DEG C roasting 1h；Water is pressed again：The weight ratio of stem-based catalyst is 1：8 wash catalyst with decationized Y sieve
Wash twice, 120 DEG C of freeze-day with constant temperature 2 hours, obtain sample C1~C5, catalyst slurry and properties of product
It is shown in Table 3.
(2) silicon-aluminum sol 70.72kg prepared by embodiment 12 is added in a kettle, stirring, is added high
Ridge soil 61.57kg, stir 30min；Adding ground REY molecular sieve pulps, (Sinopec is catalyzed
Asphalt in Shenli Refinery of agent Co., Ltd produces, the weight % of slurry solid content 31.4) 95.54kg, stirs 30min；
Spray drying, gained catalyst microspheres are calcined 1h at 500 DEG C；Water is pressed again：The weight of stem-based catalyst
Than for 1：8 by catalyst with twice of decationized Y sieve water washing, 120 DEG C of freeze-day with constant temperature 2 hours, obtain sample
Product C6, catalyst slurry and properties of product are shown in Table 3.
Catalyst characterization：
(1) inhaled according to GB/T 5816-1995 methods using Kang Ta companies of U.S. Autosorb-1 nitrogen de-
Attached instrument detects the specific surface area of the Cracking catalyst, and sample needs to deaerate 6 at 300 DEG C before testing
Hour, it the results are shown in Table 3.
(2) according to RIPP 151-90 standard methods (see《Petrochemical Engineering Analysis method》(RIPP is tested
Method), Yang Cui delimits the organizational structure, Science Press, and nineteen ninety publishes) total hole of the detection Cracking catalyst
Volume, it the results are shown in Table 3.
(3) using the multi-functional particle diameter of Camsizer XT Wet-dries and form point of German Lai Chi companies
Analyzer, the sphericity index SPHT of the Cracking catalyst is detected, the results are shown in Table 3.
Sphericity index SPHT refers to and the surface area of the spheroid of object same volume (4 π A) and object
Surface area (P2) ratio, see formula 1.
Table 3
Evaluating catalyst
Evaluate catalyst of the present invention and the cracking reaction performance of comparative catalyst.
Feedstock oil is military mixed three feedstock oils, and physico-chemical property data are shown in Table 4.
Table 5 lists the evaluation result on fixed fluidized bed device.Catalyst pass through 800 DEG C, 17 hours,
The processing of 100% steam aging inactivation, catalyst loading amount 9g, oil ratio 5,500 DEG C of reaction temperature.
Wherein, conversion ratio=yield of gasoline+yield of liquefied gas+dry gas yield+coking yield
Liquid yield=yield of liquefied gas+yield of gasoline+diesel yield
Yield of light oil=yield of gasoline+diesel yield
Coke selectivity=coke yield/conversion ratio
Table 4
Table 5
| Catalyst | 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 | 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 |
| It is total | 100 | 100 | 100 | 100 | 100 | 100 |
| Micro-activity, % | 75 | 77 | 78 | 74 | 72 | 71 |
| Conversion ratio, % | 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, % | 6.94 | 8.20 | 8.78 | 8.35 | 8.57 | 8.38 |
The invention provides silicon-aluminum sol, and Alumina gel therein is can be seen that from embodiment 1-827Al
Nuclear magnetic spectrogram (Fig. 1) shows that the Alumina gel is the structure based on high polymeric form aluminium.And prior art (system
Standby example 1) obtained Alumina gel (Fig. 1) is structure based on single poly-aluminium.The data of table 1 can show
Show, Alumina gel rate of corrosion of the invention is lower, and viscosity is bigger, and pH value is higher.The data of table 2 show,
The Alumina gel that the Alumina gel (embodiment 1-3) that the present invention obtains can obtain than preparation example 1 and 3 has
Lower content of dissociative chlorine ion.Alumina gel provided by the invention have few free chloro ion, structure optimization,
The characteristics of viscosity is big, rate of corrosion is small, pH value is high, therefore be further used for preparing catalytic cracking catalysis
During agent, using the silicon-aluminum sol obtained by above-mentioned Alumina gel, it can obtain that there is urging for more preferable catalytic effect
Agent.
Alumina gel prepared by embodiment 8 adds rare earth element and P elements, can make containing the Alumina gel
The catalyst (embodiment 12, C1) that binding agent is further prepared has more preferable catalytic activity, micro- anti-living
Property, conversion ratio, liquid yield and yield of light oil are higher, and coke selectivity is lower.
The result data of the catalyst obtained from catalyst preparation example can be seen that the sial using the present invention
Catalyst prepared by colloidal sol more adapts to crude oil heaviness processing request.It can be seen that and adopt from the data of table 3
The catalyst (C1~C3) prepared with the Alumina gel (embodiment 12-14) of the present invention, can be with composition
Than prior art Alumina gel prepared by catalyst (C4~C5) reduce molecular sieve and Alumina gel plus
Enter amount, and the solid content of catalyst slurry can be higher, the physical and chemical performance of obtained catalyst：Compare table
Area, total pore volume, SPHT, abrasion index and micro-activity are all significantly better than made from prior art
Catalyst (C4~C5).When can be seen that progress heavy crude processing from the result data of table 5, adopt
The catalyst (C1~C3) made from the Alumina gel of the present invention, makes compared to the Alumina gel of prior art
The catalyst (C4~C5) obtained can obtain higher conversion ratio, liquid yield and yield of light oil,
And amount of coke reduces.
In addition, big pore matrix is not added in catalyst C6, compared to catalyst (C1~C5), active,
Gasoline yield is high and coke selectivity is poor, illustrates to add macropore base in the catalytic cracking catalyst of the present invention
Matter is more beneficial for improving the activity of catalyst, gasoline yield height and coke selectivity.
Lower the addition of molecular sieve in the present invention, advantageously reduce the production cost of catalyst.
Claims (20)
1. a kind of Ludox, SiO in the Ludox2Content be 25~40 weight %, Na2O's contains
Amount is less than 0.15 weight %；The pH value of the Ludox is 2~10, density 1.1g/cm3~1.3
g/cm3, viscosity is more than 200mPas.
2. Ludox according to claim 1, wherein, the preparation method of the Ludox includes：
(a) monocrystalline silicon and sodium hydroxide solution A are subjected to the first reaction；First reaction temperature be 50~
70 DEG C, the first reaction time was 1~3h；
(b) first product reacted and sodium hydroxide solution B are subjected to the second reaction, second is anti-
It is 70~90 DEG C to answer temperature, and the second reaction time was 1~2h；
(c) second product reacted is cooled down to obtain colloid, the colloid is subjected to ion
Exchanging reduces sodium ions content, obtains Ludox；
Wherein, the monocrystalline silicon in terms of Si and the sodium hydroxide solution A and sodium hydroxide solution B in terms of Na
The weight ratio of total amount be (0.6~1.4)：1；
In terms of Na, sodium hydroxide solution A and sodium hydroxide solution B weight ratio is (25~35)：
(65-75)；
Second reaction temperature is higher than first reaction temperature 20~30 DEG C.
3. Ludox according to claim 1 or 2, wherein, the purity of the monocrystalline silicon for 95~
99 weight %；Sodium hydroxide solution A concentration is 40~70 weight %, and sodium hydroxide solution B's is dense
Spend for 40~70 weight %.
4. a kind of silicon-aluminum sol, the silicon-aluminum sol contains Alumina gel and Ludox, in the silicon-aluminum sol
With SiO2The Ludox of meter with Al2O3The weight ratio of the Alumina gel of meter is (1~4)：1, its feature exists
In the Ludox is the Ludox described in any one in claim 1-3.
5. silicon-aluminum sol according to claim 4, wherein, aluminium cl molar ratio in the Alumina gel
For (1~1.5)：1, rate of corrosion is not more than 1.5g/m2H, pH value are more than 2.8, viscosity 500mPas
More than.
6. the silicon-aluminum sol according to claim 4 or 5, wherein, aluminium element in the Alumina gel
Weight content be 11.5%~13%；The rate of corrosion of the Alumina gel is 1g/m2H~1.5g/m2H,
PH value is 2.8~3.5, density 1.31g/cm3~1.35g/cm3, viscosity is 500mPas~10000
mPa·s。
7. according to the silicon-aluminum sol described in any one in claim 4-6, wherein, the Alumina gel
's27In Al nuclear magnetic spectrograms, chemical shift is that the peak area of appearance and chemical shift are 0~3 at 60~63
The peak area ratio for locating appearance is more than 1；It is preferred that chemical shift be 60~63 at appearance peak area with
Chemical shift is that the ratio of the peak area of appearance at 0~3 is 1~1.6.
8. a kind of preparation method of silicon-aluminum sol, this method include：
Will be with Al2O3The Alumina gel of meter with SiO2Silicon in the claim 1-3 of meter described in any one
Colloidal sol, according to SiO2：Al2O3Weight ratio is (1~4)：1 at 20~50 DEG C carry out liquid phase mixing 1~
3h, obtain silicon-aluminum sol.
9. according to the method for claim 8, wherein, the preparation process of the Alumina gel includes：
(1) metallic aluminium is carried out into first with hydrochloric acid to contact；
(2) mixture after the first contact is carried out into second with silicon source to contact；
The temperature of first contact is higher than 20~30 DEG C of the temperature of the second contact.
10. according to the method for claim 9, wherein, the temperature of the first contact is 50~80 DEG C；
The temperature of second contact is 20~50 DEG C.
11. the method according to claim 9 or 10, wherein, in terms of Al, in step (1)
The mol ratio of the dosage of metallic aluminium and the dosage of silicon source described in step (2) is (5~10):1.
12. the method according to claim 9 or 10, wherein, the method for preparing the Alumina gel
Also include：Before step (2) are carried out, the mixture after the described first contact is stood 1 at normal temperatures~
30h, preferably stand 2~6h.
13. the method according to claim 9 or 10, wherein,
The condition of first contact also includes：Relative to the hydrochloric acid of the 1mol in terms of HCl, the use of metallic aluminium
Measure as 0.8mol~1.3mol, the first time of contact was 2~5h, the concentration of hydrochloric acid for 31 weight %~
36 weight %；
The condition of second contact also includes：Second time of contact was 3~4h, source of aluminium be metallic aluminium and/
Or inorganic aluminium compound, the inorganic aluminium compound are aluminium chloride, aluminum oxide, aluminium hydroxide and soft water aluminium
In one or more；It is preferred that the inorganic aluminium compound is Al2O3, more preferably γ-Al2O3And/or
η-Al2O3。
14. the method according to claim 9 or 10, wherein, the method for preparing the Alumina gel
Also include, the mixture that the second contact is obtained, carrying out the 3rd with phosphorus compound and/or rare earth compound connects
Touch；3rd Contact Temperature is 10~50 DEG C, and the 3rd time of contact was more than 10min；
One or more of the phosphorus compound in phosphorus pentoxide, phosphoric acid and phosphate；The phosphorus
Compound is with P2O5Meter is with second mixture for contacting to obtain with Al2O3The weight ratio of meter=(0.01~
1)：1；
The rare earth compound is with RE2O3Meter is with second mixture for contacting to obtain with Al2O3Meter
Weight ratio=(0.01~1.5)：1；More preferably weight ratio=(0.01~0.8)：1；The rare earth compound
In rare earth element include at least one of La, Ce, Sc, Pr and Nd；The rare earth compound is
At least one of rare earth oxide, rare earth hydrate, nitric acid rare earth and rare earth oxalate.
15. the silicon-aluminum sol that the preparation method in a kind of 8-14 as claim described in any one obtains.
16. the silicon-aluminum sol in claim 4-7 and 15 described in any one is urged in preparation catalytic cracking
Application in agent.
17. a kind of preparation method of catalytic cracking catalyst, this method include：By binding agent, clay,
Molecular sieve and optional big pore matrix are beaten obtained catalyst slurry, and the catalyst slurry is entered
Row spray drying, it is characterised in that the binding agent is any one institute in claim 4-7 and 15
The silicon-aluminum sol stated.
18. preparation method according to claim 17, wherein, with the dry of the catalyst slurry
Base weight meter, the dosage of molecular sieve is 10~50 weight %, and the dosage of clay is 10~50 weight %,
For binding agent using the dosage that oxide is counted as 5~40 weight %, the dosage of big pore matrix is 0~25 weight %.
19. the preparation method according to claim 17 or 18, wherein, the catalyst slurry
Solid content is more than 40 weight %, the weight % of preferably 40 weight %~55.
20. the catalytic cracking that the preparation method in a kind of 17-19 as claim described in any one obtains
Catalyst.
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| CN116022794A (en) * | 2022-11-17 | 2023-04-28 | 江西鹏腾实业有限公司 | Preparation method of aluminum-silicon sol |
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