CN101119802B - Fcc催化剂及其制备和应用 - Google Patents
Fcc催化剂及其制备和应用 Download PDFInfo
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- CN101119802B CN101119802B CN2005800478224A CN200580047822A CN101119802B CN 101119802 B CN101119802 B CN 101119802B CN 2005800478224 A CN2005800478224 A CN 2005800478224A CN 200580047822 A CN200580047822 A CN 200580047822A CN 101119802 B CN101119802 B CN 101119802B
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- China
- Prior art keywords
- slurry
- catalyst
- boehmite
- zeolite
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 71
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 38
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000010457 zeolite Substances 0.000 claims abstract description 38
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 37
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000004927 clay Substances 0.000 claims abstract description 25
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims description 25
- 229910052708 sodium Inorganic materials 0.000 claims description 25
- 238000001935 peptisation Methods 0.000 claims description 24
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 5
- -1 polysiloxane Polymers 0.000 claims description 5
- 230000029936 alkylation Effects 0.000 claims description 3
- 238000005804 alkylation reaction Methods 0.000 claims description 3
- 235000012241 calcium silicate Nutrition 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000391 magnesium silicate Substances 0.000 claims description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 3
- 235000019792 magnesium silicate Nutrition 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- 239000004110 Zinc silicate Substances 0.000 claims description 2
- 229910052916 barium silicate Inorganic materials 0.000 claims description 2
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 claims description 2
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 claims description 2
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 claims description 2
- ZOIVSVWBENBHNT-UHFFFAOYSA-N dizinc;silicate Chemical compound [Zn+2].[Zn+2].[O-][Si]([O-])([O-])[O-] ZOIVSVWBENBHNT-UHFFFAOYSA-N 0.000 claims description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 229910052917 strontium silicate Inorganic materials 0.000 claims description 2
- QSQXISIULMTHLV-UHFFFAOYSA-N strontium;dioxido(oxo)silane Chemical compound [Sr+2].[O-][Si]([O-])=O QSQXISIULMTHLV-UHFFFAOYSA-N 0.000 claims description 2
- 235000019352 zinc silicate Nutrition 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 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 18
- 239000005995 Aluminium silicate Substances 0.000 description 15
- 235000012211 aluminium silicate Nutrition 0.000 description 15
- 239000000463 material Substances 0.000 description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 238000001694 spray drying Methods 0.000 description 8
- 229910052723 transition metal Inorganic materials 0.000 description 8
- 150000003624 transition metals Chemical class 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052570 clay Inorganic materials 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229960001422 aluminium chlorohydrate Drugs 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 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 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910014571 C—O—Si Inorganic materials 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000013461 design 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
- 230000029087 digestion Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229940094522 laponite Drugs 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
- 235000001055 magnesium Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- CEOCDNVZRAIOQZ-UHFFFAOYSA-N pentachlorobenzene Chemical compound ClC1=CC(Cl)=C(Cl)C(Cl)=C1Cl CEOCDNVZRAIOQZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- 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
-
- 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
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Abstract
本发明涉及催化剂的制备方法,该方法包括步骤(a)制备含有粘土、沸石、无钠的硅石源、准晶勃姆石和微晶勃姆石的浆料,条件是,该浆料不包含胶溶的准晶勃姆石、(b)向该浆料中加入一价酸、(c)调节该浆料的pH值至3以上、以及(d)使该浆料成形以形成颗粒。该方法产生具有良好可及性的耐磨催化剂。
Description
技术领域
本发明涉及用于制备催化剂的方法,通过该方法获得的催化剂以及它们在例如流化催化裂化(FCC)中的应用。
背景技术
在设计和制备非均相催化剂中的共同挑战为,活性位点的效果和/或可及性与固定基质在赋予催化剂颗粒足够物理强度即耐磨性方面的效果之间找到良好的折衷。
在几篇现有技术文件中公开了耐磨催化剂的制备。
US4,086,187公开了通过喷雾干燥含水浆料来制备耐磨催化剂的方法,所述含水浆料通过将(i)钠含量少于5wt%的八面沸石与(ii)高岭土、(iii)胶溶的假勃姆石和(iv)聚硅酸铵混合来制备。
根据US4,206,085,通过喷雾干燥浆料来制备耐磨催化剂,所述浆料通过将两种类型的酸化假勃姆石、沸石、氧化铝、粘土与聚硅酸铵或者硅溶胶混合来制备。
GB 1 315 553公开了含有沸石、粘土和氧化铝粘合剂的烃类转化耐磨催化剂的制备。通过首先干混合沸石和粘土,然后加入氧化铝溶胶,制备该催化剂。然后将所得到的混合物混合至塑性稠度(plasticconsistency),这需要约20分钟的混合时间。为了形成成形颗粒,所述塑性稠度物可以制粒或者挤出,或者与水混合,随后喷雾干燥。
在英国专利说明书中公开的氧化铝溶胶包括摩尔比为4.5至7.0的氢氧化铝和三氯化铝(也称为水合氯化铝(aluminium chlorohydrol))。
US 4,458,023涉及类似的制备过程,该制备过程接着煅烧喷雾干燥颗粒。在煅烧过程中,所述水合氯化铝组分转化为氧化铝粘合剂。
WO 96/09890公开了用于制备耐磨流化催化裂化催化剂的方法。该方法包括混合硫酸铝/硅溶胶、粘土浆料、沸石浆料和氧化铝浆料,然后喷雾干燥。在该方法过程中,向硅溶胶、粘土浆料、沸石浆料、氧化铝浆料和/或喷雾干燥浆料中加入耐酸或耐碱的表面活性剂。
CN 1247885也涉及喷雾干燥的裂化催化剂的制备。所述制备使用包括含铝溶胶、假勃姆石、分子筛、粘土以及无机酸的浆料。在该方法中,在将粘土和无机酸加入之前将含铝溶胶加入浆料,并且在已经加入无机酸之后加入分子筛浆料。根据一个实施方式,假勃姆石和铝溶胶首先混合,然后加入无机酸。酸化之后加入分子筛,然后加入高岭土。
WO 02/098563公开了一种用于制备既具有高耐磨性又具有高可及性的FCC催化剂的方法。通过如下方式制备所述催化剂,即:通过使沸石、粘土和勃姆石浆料化,将所得浆料送入成形设备,使混合物成形以形成颗粒,其特征在于,刚好在成形步骤之前使混合物去稳定。通过如下方式达到所述去稳定,即:通过例如温度升高、pH升高、pH降低或凝胶促进剂如盐、磷酸盐、硫酸盐以及(部分)凝胶化的硅石。在去稳定之前,浆料中存在的任何可胶溶的化合物都必须充分胶溶化。
虽然根据后者的文件所述催化剂具有相对高的耐磨性和可及性,但是现在已经发现,该可及性/耐磨性的比率可以进一步提高。
发明内容
通过本发明的方法实现所述进一步提高,所述方法包括以下步骤:
a)制备含有粘土、沸石、无钠的硅石源(silica source)、准晶勃姆石和微晶勃姆石的浆料,条件是,该浆料不包含胶溶的准晶勃姆石;
b)向该浆料中加入一价酸;
c)调节该浆料的pH值至3以上;以及
d)使该浆料成形以形成颗粒。
与其中准晶勃姆石(如假勃姆石)总是在加入含有沸石的浆料之前已经被胶溶化的传统方法相比,本发明的方法加入非胶溶的准晶勃姆石(QCB)。酸只在QCB加入之后加入到,即还含有沸石和粘土的浆料中。
此外,使用无钠的硅石源。无钠硅石源的例子为(聚)硅酸、无钠的硅溶胶、硅酸钾、硅酸锂、硅酸钙、硅酸镁、硅酸钡、硅酸锶、硅酸锌、磷硅酸盐(phosphorus silicate)和硼硅酸盐(borium silicate)。合适的有机硅酸酯的实例为聚硅氧烷(聚有机硅氧烷例如聚甲基苯基硅氧烷和聚二甲基硅氧烷)和其他含有Si-O-C-O-Si结构的化合物,以及它们的前体例如甲基氯硅烷、二甲基氯硅烷、三甲基氯硅烷以及它们的混合物。
优选的无钠硅石源为(聚)硅酸和无钠的硅溶胶。
此外,本发明的方法导致制备包括微晶勃姆石和准晶勃姆石的催化剂,其具有足够用于FCC中的耐磨性。微晶勃姆石(MCB)是合适的金属钝化剂,特别是对镍污染物的钝化剂。然而直到现在,含有MCB的FCC催化剂颗粒的制备仍然没有获得成功,因为MCB很难与常规FCC-型的粘合剂结合,导致催化剂颗粒具有无法接受的的磨损。使用本发明的方法,得到具有满意耐磨性能的、含有MCB的催化剂。
勃姆石
术语“勃姆石”在工业中用来描述表现出接近于氢氧化氧化铝[AlO(OH)]的X-射线衍射(XRD)图的水合氧化铝。此外,术语勃姆石一般用于描述宽范围的水合氧化铝,它包括不同量的水合作用水,具有不同的表面积、孔体积、比重,并在热处理下表现出不同的热特性。虽然它们展示出特征勃姆石[AlO(OH)]的衍射峰,但是它们的XRD图谱经常在它们的衍射峰宽度方面不同,也可能在它们的峰位上有偏移。XRD峰的尖锐度以及它们的位置已经用来表示结晶度、晶体尺寸以及缺陷的量。
大致地,有两类勃姆石氧化铝:准晶勃姆石(QCB)和微晶勃姆石(MCB)。
在本技术领域的情况中,准晶勃姆石也称为假勃姆石和凝胶勃姆石。通常,这些QCB比MCB具有更大的表面积、更大的孔和孔体积以及更低的比重。它们容易在水或酸中分散,比MCB具有更小的晶体大小,包含更多数量的水合作用的水分子。QCB的水合程度可以具有宽范围的值,例如从每摩尔Al约1.4至约2摩尔水,这些水分子通常顺序***或者以其它方式***八面体层间。
DTG(微分热解重量分析法)表明,与从MCB中释放相比,大部分量的水在更低的温度下从QCB中释放出来。
QCB的XRD谱图显示出非常宽的峰,它们的半峰宽(即在最大强度一半时的峰宽)表示晶体大小和晶体的完整度。
微晶勃姆石与QCB的区别在于它们的高结晶程度、相对大的晶体尺寸、非常低的表面积以及高的密度。与QCB相反,MCB显示出具有更高的峰强度和非常窄的半峰宽的XRD谱图。这是由于它们***相对小数目的水分子、大的晶体尺寸、体材料的较高结晶程度以及较少量的晶体缺陷。通常,***的水分子数目可以在从每摩尔Al约1至约1.4的范围内变化。
MCB和QCB通过粉末X-射线反射表征。国际衍射数据中心ICDD包括勃姆石的条目,并确认存在相应于(020)、(021)和(041)晶面的反射。对铜射线,所述反射将出现在2θ为14、28和38度处。反射的精确位置取决于结晶度以及***的水的量:当***的水的量增加,(020)反射向较低值移动,对应于较大的晶面间距d。然而,接近上述位置的线将表示存在一种或几种类型的勃姆石相。
为了该说明书的目的,我们定义准晶勃姆石为具有总半高宽(FWHH)为1.5°或者大于1.5°(2θ)的(020)反射。具有总半高宽(FWHH)为小于1.5°的(020)反射的勃姆石被认为是微晶勃姆石。
总的说来,QCB和MCB之间的基本、典型差别包括以下方面的变化:三维空间晶格序、晶粒大小、***八面体层间的水的量,以及晶体缺陷程度。
沸石
在本发明的方法中所用的沸石优选具有低钠含量(少于1.5wt%Na2O),或者不含钠。存在于步骤a)的浆料中的合适沸石包括诸如Y型沸石,包括HY、USY、脱铝Y型沸石、RE-Y和RE-USY;沸石β;ZSM-5;磷活化的ZSM-5;离子交换的ZSM-5;MCM-22和MCM-36;金属互换的(metal-exchanged)沸石;ITQ类;SAPO类;ALPO类以及它们的混合物等的沸石。
粘土
粘土也优选具有低钠含量(少于1.5wt%Na2O),或者不含钠。
适合的粘土包括高岭土、膨润土、皂石、海泡石、绿坡缕石、合成粘土(laponite)、锂蒙脱石、英国粘土(English clay)、诸如水滑石的阴离子粘土,以及热或化学处理的粘土例如偏高岭土。
步骤a)
通过在水中悬浮粘土、沸石、无钠的硅石源、非胶溶的准晶勃姆石和微晶勃姆石,来制备步骤a)的浆料。任选地,可以加入其它组分,例如水合氯化铝、硝酸铝、Al2O3、Al(OH)3、阴离子粘土(如水滑石)、蒙脱石、海泡石、钛酸钡、钛酸钙、硅酸钙、硅酸镁、钛酸镁、混合金属氧化物、层状羟基盐(layered hydroxy salts)、另外的沸石、镁的氧化物、碱或盐,和/或者金属添加剂如含有碱土金属(例如Mg、Ca和Ba)、IIIA族过渡金属、IVA族过渡金属(例如Ti和Zr)、VA族过渡金属(例如V和Nb)、VIA族过渡金属(例如Cr、Mo和W)、VIIA族过渡金属(例如锰)、VIIIA族过渡金属(Fe、Co、Ni、Ru、Rh、Pd和Pt)、IB族过渡金属(例如Cu)、IIB族过渡金属(例如Zn)、镧系元素(例如La和Ce)等的化合物,或者它们的混合物。
粘土、沸石、非胶溶的QCB、MCB、无钠硅石源以及可选的其它组分可以通过将它们作为干燥固体添加到水中来调成浆料。任选地,混合含有各个成分的浆料以形成步骤a)的浆料。还可以将作为浆料的有些物质和作为干燥固体的其它物质加入。这些化合物可以使用任何添加顺序。也可以同时混合所有化合物。
该浆料优选含有10-70wt%,更优选15-50wt%,最优选15-35wt%的沸石。
该浆料优选含有5-70wt%,更优选10-60wt%,最优选10-50wt%的粘土。
该浆料优选含有1-50wt%,更优选2-50wt%,最优选5-50wt%的非胶溶QCB。
该浆料优选还含有1-50wt%,更优选1-30wt%,最优选1-20wt%的MCB。
该浆料进一步包括1-35wt%,更优选4-18wt%的无钠硅石源。
所有重量百分比都基于干燥固体含量,并且都以氧化物来计算。
所述浆料的固体含量优选为10-30wt%,更优选为15-30wt%,最优选为15-25wt%。
步骤b)
在接下来的步骤中,将一价酸加入悬浮液,以产生消化。
可以使用有机的和无机的一价酸,或者使用它们的混合物。合适的一价酸的例子是甲酸、乙酸、丙酸、硝酸和盐酸。
加入浆料中的酸的量足以获得低于7,更优选在2至5之间,最优选在3和4之间的pH值。在酸加入过程中,可以搅拌、研磨、磨碎、高剪切混合或者用超声波处理所述浆料。
步骤c)
如果步骤b)的浆料的pH低于3,所述浆料的pH随后被调节至大于3的值,更优选大于3.5,甚至更优选大于4,最优选为约4.5或更高。所述浆料的pH优选不高于7,因为具有更高pH的浆料很难操作。
pH可以通过向浆料中加入碱(例如NaOH或NH4OH)来调节。
然而,如果在步骤b)中加入酸之后pH值为3或者更高,该pH可以但是不必在步骤c)中提高。
pH调节与成形步骤d)之间的时间间隔优选为30分钟或者更小,更优选小于5分钟,最优选小于3分钟。
步骤d)
合适的成形方法包括喷雾干燥、脉冲干燥、造粒、挤出(可选择与捏炼组合)、成球(beading)或者任何其它常见用于催化剂和吸收剂领域的成形方法,或者它们的结合。优选的成形方法是喷雾干燥。如果催化剂通过喷雾干燥成形,喷雾干燥的进口温度优选范围为300-600℃,出口温度优选范围为105-200℃。
如此所得催化剂具有异常优秀的耐磨性和可及性。因此,本发明还涉及根据本发明的方法所得到的催化剂。
本发明还涉及包括MCB、QCB、硅石、沸石和粘土的催化剂。优选地,所述催化剂含有1-50wt%,更优选3-40wt%的QCB;1-25wt%,更优选5-25wt%的MCB;1-25wt%硅石;5-50wt%的沸石;其余量为粘土(以氧化物计算)。
这些催化剂可以用作FCC催化剂;加氢催化剂、烷基化催化剂、重整催化剂、气液转化催化剂、煤转化催化剂、制氢催化剂、汽车催化剂中的FCC添加剂一例如SOx还原添加剂、NOx还原添加剂、CO燃烧添加剂、ZSM-5添加剂或者汽油中的硫还原添加剂。本发明因此还涉及由本发明方法所得到的这些催化剂用作流化催化裂化、加氢处理、烷基化、重整、气液转化、煤转化和制氢中的催化剂或添加剂以及作为汽车催化剂的应用。
实施例
可及性测量
通过如下方式测量根据以下实施例所制备的催化剂的可及性,即将1g催化剂加入搅拌容器,该搅拌容器含有50g的15g/l科威特真空瓦斯油(KVGO)的甲苯溶液。该溶液在该容器和分光光度计之间循环,在该方法中,连续测量KVGO的浓度。
通过Akzo可及性指数(Akzo Accessibility Index,AAI),来定量催化剂对KVGO的可及性。KVGO在溶液中的相对浓度对时间的平方根作图。AAI被定义为该曲线的起始斜率:
AAI=-d(Ct/Co)/d(t1/2)*100%
在该方程中,t为时间(以分钟表示),Co和Ct分别表示在试验开始时和在时间t时高分子量化合物在溶剂中的浓度。
耐磨性测量
通过标准的磨损测试来测量催化剂的耐磨性。在该测试中,催化剂床层位于带有三个喷嘴的耐磨板(attrition plate)上。所述耐磨板位于处在周围环境温度下的耐磨管(attrition tube)内部。将空气压至喷嘴,所产生的喷气流体产生向上输送的催化剂颗粒,并且产生细颗粒。在耐磨管顶部是分离室,其中,颗粒流消失,大于约16微米的大多数颗粒落回耐磨管。较小颗粒被收集在收集袋内。
在600℃下煅烧催化剂样品之后进行该测试,首先进行5小时,并且基于假设的引入量为50克,测定收集袋中收集的细颗粒的重量百分比。这是初始耐磨性。然后该测试又进行了15小时,检测在此时间段(5-20小时)的细颗粒重量百分比。这是固有耐磨性。所述磨损指数(AI)外推25小时后的细尘的wt%。因此,催化剂耐磨性越好,A1值越小。
对比实施例1
将含有可胶溶QCB(13.3kg)的含水浆料与水混合,并且通过用甲酸酸化来胶溶。所得混合物的pH为2。混合物搅拌15分钟。接着,加入MCB(高度结晶的氧化铝5kg)、沸石Y浆料(8kg)、高岭土(4.17kg)、无钠硅石源(2.4kg)和水,与已胶溶的QCB混合。最终浆料的pH为3.2。然后将该浆料送入喷雾干燥机,速度1kg/分钟、进口温度500℃,出口温度120℃。
所得物质包括20wt%沸石、24wt%QCB、14wt%MCB、6%SiO2和其余量为高岭土。粉末具有大约65μm的d50。
磨损指数(AI)、可及性指数(AAI)以及它们的比例如下表所示。
实施例2
将含有非胶溶但是可胶溶的QCB(13.3kg)水浆料、MCB(高度结晶氧化铝5.4kg)、沸石Y浆料(8kg)、高岭土(4.17kg)、无钠硅石源与水一起混合。然后将硝酸加入全部反应混合物中达到pH3.3。然后将该浆料以1kg/分钟的速度送入喷雾干燥机,进口温度500℃,出口温度120℃。
所得物质包括20wt%沸石、24wt%QCB、14wt%MCB、6%SiO2,其余量为高岭土。粉末具有大约65μm的d50。
磨损指数(AI)、可及性指数(AAI)以及它们的比例如下表所示。
对比实施例3
将含有可胶溶的QCB(16.6kg)的水浆料与水混合,并且通过用甲酸酸化来胶溶。所得混合物的pH为2。混合物搅拌15分钟。接着,加入MCB(高度结晶的氧化铝5.4kg)、沸石Y浆料(7.2kg)、高岭土(4.17kg)、无钠的氧化硅源(2.4kg)和水,并且与已胶溶的QCB混合。最终浆料的pH为3.2。然后将该浆料以1kg/分钟的速度送入喷雾干燥机,进口温度500℃,出口温度120℃。
所得物质包括18wt%沸石、30wt%QCB、15wt%MCB、4%SiO2和其余量为高岭土。粉末具有大约65μm的d50。
磨损指数(AI)、可及性指数(AAI)以及它们的比例如下表所示。
实施例4
含有非胶溶但是可胶溶的QCB(16.6kg)水浆料、MCB(高度结晶的氧化铝5.4kg)、沸石Y浆料(8kg)、高岭土(4.17kg)、无钠的硅石源与水一起混合。然后将硝酸加入全部反应混合物中,pH达到3.2。然后将该浆料以1kg/分钟的速度送入喷雾干燥机,进口温度500℃,出口温度120℃。
所得物质包括18wt%沸石、30wt%QCB、15wt%MCB、4%SiO2和其余量为高岭土。粉末具有大约65μm的d50。
磨损指数(AI)、可及性指数(AAI)以及它们的比例如下表所示。
对比实施例5
将含有可胶溶QCB(16.6kg)的水浆料与水混合,并且通过用甲酸酸化来胶溶。所得混合物的pH为2。混合物搅拌15分钟。接着,加入MCB(高度结晶的氧化铝5.4kg)、沸石Y浆料(9.6kg)、高岭土(4.17kg)、无钠的硅石源(2.4kg)和水,并且与已胶溶的QCB混合。最终浆料的pH为3.2。然后将该浆料以1kg/分钟的速度送入喷雾干燥机,进口温度500℃,出口温度120℃。
所得物质包括24wt%沸石、30wt%QCB、15wt%MCB、4%SiO2和其余量为高岭土。粉末具有大约65μm的d50。
磨损指数(AI)、可及性指数(AAI)以及它们的比例如下表所示。
实施例6
含有非胶溶但是可胶溶的QCB(16.6kg)水浆料、MCB(高度结晶的氧化铝5.4kg)、沸石Y浆料(9.6kg)、高岭土(4.17kg)、无钠硅石源与水在一起混合。然后将硝酸加入全部反应混合物中,pH达到3.3。然后将该浆料以1kg/分钟的速度送入喷雾干燥机,进口温度500℃,出口温度120℃。
所得物质包括24wt%沸石、30wt%QCB、15wt%MCB、4%SiO2和其余量为高岭土。粉末具有大约65μm的d50。
磨损指数(AI)、可及性指数(AAI)以及它们的比例如下表所示。
表
实施例 AI AAI AA/AAI |
1(对比) 18 15 0.82 8.1 12 1.5 |
3(对比) 15.8 14 0.94 6.8 11 1.6 |
5(对比) 20.2 18 0.96 9.5 14 1.5 |
与使用预胶溶的勃姆石的方法相比,该表表明本发明的方法获得更强耐磨性能的催化剂(AI减小)以及更高的AAI/AI比值。
Claims (7)
1.用于制备催化剂的方法,该方法包括步骤:
a)制备含有粘土、沸石、无钠的硅石源、准晶勃姆石和微晶勃姆石的浆料,条件是,该浆料不包含胶溶的准晶勃姆石;
b)向该浆料中加入一价酸;
c)调节该浆料的pH值至3以上;以及
d)使该浆料成形以形成颗粒。
2.根据权利要求1所述的方法,其中,所述的无钠硅石源选自无钠的硅溶胶、聚硅酸、硅酸钾、硅酸锂、硅酸钙、硅酸镁、硅酸钡、硅酸锶、硅酸锌、磷硅酸盐、硼硅酸盐、聚有机硅氧烷、甲基氯硅烷、二甲基氯硅烷、三甲基氯硅烷和它们的混合物所组成的组。
3.根据权利要求1或2所述的方法,其中,将步骤c)中的所述pH值调节到4至7之间。
4.催化剂,该催化剂通过前述任意一项权利要求所述的方法获得。
5.根据权利要求4所述的催化剂,该催化剂包括微晶勃姆石、准晶勃姆石、沸石和硅石,并且该催化剂含有1-50wt%的准晶勃姆石;1-25wt%的微晶勃姆石;1-25wt%的硅石;5-50wt%的沸石;其余量为粘土,以氧化物计算。
6.根据权利要求4或5所述的催化剂在流化催化裂化、加氢处理、烷基化、重整、气液转化、煤转化或制氢中的应用。
7.根据权利要求4或5所述的催化剂作为汽车催化剂的应用。
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WO2018027173A1 (en) | 2016-08-04 | 2018-02-08 | Albemarle Corporation | Fcc catalyst with more than one silica, its preparation and use |
CA3087954A1 (en) | 2018-01-12 | 2019-07-18 | Albemarle Corporation | Fcc catalyst prepared by a process involving more than one silica material |
RU2020125402A (ru) * | 2018-01-12 | 2022-02-14 | Альбемарл Корпорейшн | Катализатор fcc с улучшенной мезопористостью, его получение и применение |
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