CN101115560B - 耐磨催化剂及其制备方法和应用 - Google Patents
耐磨催化剂及其制备方法和应用 Download PDFInfo
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- CN101115560B CN101115560B CN2005800477664A CN200580047766A CN101115560B CN 101115560 B CN101115560 B CN 101115560B CN 2005800477664 A CN2005800477664 A CN 2005800477664A CN 200580047766 A CN200580047766 A CN 200580047766A CN 101115560 B CN101115560 B CN 101115560B
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- Prior art keywords
- slurry
- catalyst
- zeolite
- boehmite
- clay
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000008569 process Effects 0.000 title abstract description 4
- 239000002002 slurry Substances 0.000 claims abstract description 104
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 43
- 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 43
- 239000010457 zeolite Substances 0.000 claims abstract description 43
- 239000004927 clay Substances 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 34
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 33
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000001935 peptisation Methods 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 10
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- -1 polysiloxane Polymers 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 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
- 239000003245 coal Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 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
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- 239000004115 Sodium 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
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 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 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 50
- 229910052570 clay Inorganic materials 0.000 description 33
- 238000001694 spray drying Methods 0.000 description 26
- 239000000377 silicon dioxide Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- 235000012239 silicon dioxide Nutrition 0.000 description 16
- 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 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 239000005995 Aluminium silicate Substances 0.000 description 11
- 235000012211 aluminium silicate Nutrition 0.000 description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 10
- 235000011130 ammonium sulphate Nutrition 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 229910052723 transition metal Inorganic materials 0.000 description 8
- 150000003624 transition metals Chemical class 0.000 description 8
- 239000003518 caustics Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 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 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910002796 Si–Al Inorganic materials 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
- 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
- 239000012065 filter cake Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 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
- 239000000243 solution Substances 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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 2
- JCCZVLHHCNQSNM-UHFFFAOYSA-N [Na][Si] Chemical compound [Na][Si] JCCZVLHHCNQSNM-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 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
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite 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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 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
- 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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 208000004350 Strabismus Diseases 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JLFVIEQMRKMAIT-UHFFFAOYSA-N ac1l9mnz Chemical compound O.O.O JLFVIEQMRKMAIT-UHFFFAOYSA-N 0.000 description 1
- 238000000184 acid digestion Methods 0.000 description 1
- 239000003463 adsorbent Substances 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
- 238000004873 anchoring 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
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 235000012216 bentonite Nutrition 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
- 239000013590 bulk material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 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
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 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
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003349 gelling agent Substances 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
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 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
- 238000013507 mapping Methods 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product 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
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 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
- 238000009210 therapy by ultrasound 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
本发明提供用于制备催化剂的方法,该方法包括步骤(a)制备含有粘土、沸石和准晶态勃姆石的浆料,条件是,该浆料不包括胶溶的准晶态勃姆石;(b)将单价酸加入该浆料中;(c)将硅源加入该浆料中以及(d)使所述浆料成形以形成颗粒。该方法可以生产高可及性和高耐磨性的催化剂。
Description
本发明涉及用于制备催化剂的方法、由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。
在设计和生产非均相催化剂中的共同挑战是,活性部位的效率和/或可及性与固定基底在给予催化剂颗粒足够物理强度即抗磨损性方面的效率之间找到合适的折中。
在几个现有技术文献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)钠含量小于5wt%的八面沸石与(ii)高岭土、(iii)胶溶的(peptised)假勃姆石和(iv)聚硅酸铵混合来制备。
根据US4,206,085的耐磨催化剂是通过喷雾干燥浆料来制备的,所述浆料通过混合两种酸化的假勃姆石、沸石、氧化铝、粘土以及聚硅酸铵或二氧化硅溶胶来制备。
GB1,315,553公开了耐磨的烃转化催化剂的制备,该催化剂包括沸石、粘土以及氧化铝粘合剂。通过如下方式制备所述催化剂,即首先将沸石与粘土干法混合,接着加入氧化铝溶胶。然后将所得到的混合物混合至塑性稠度,这需要大约20分钟的混合时间。为了形成成形的颗粒,该塑性稠度物可以造粒或者挤出,或者它与水混合,随后喷雾干燥。
在英国专利说明书中所公开的氧化铝溶胶包括摩尔比为4.5到7.0的氢氧化铝和三氯化铝(也称为水合氯化铝(aluminum chlorohydrol))。
US4,458,023涉及类似的制备方法,该方法接着煅烧喷雾干燥的颗粒。在煅烧期间,水合氯化铝组分被转化为氧化铝粘合剂。
WO 96/09890公开了用于制备耐磨的流化催化裂化催化剂的方法。该方法包括将硫酸铝/二氧化硅溶胶、粘土浆料、沸石浆料和氧化铝浆料混合,接着喷雾干燥。在该方法过程中,将耐酸或耐碱的表面活性剂加入二氧化硅溶胶、粘土浆料、沸石浆料、氧化铝浆料和/或喷雾干燥的浆料。
CN 1247885也涉及喷雾干燥的裂化催化剂的制备。该制备使用包括含铝溶胶、假勃姆石、分子筛、粘土和无机酸的浆料。在该方法中,含铝溶胶在粘土和无机酸加入之前被加入到浆料中;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,首先混合假勃姆石与含铝溶胶,接着加入无机酸。在酸化之后,加入分子筛,接着是高岭土。
WO 02/098563公开了用于制备具有高耐磨性和高可及性的FCC催化剂的方法。通过如下方式制备所述催化剂,即使沸石、粘土和勃姆石浆料化,将该浆料送进成形装置,以及使该混合物成形以形成颗粒,其特征在于,刚好在成形步骤之前,该混合物被去稳定。通过例如增加温度、增加pH值、降低pH值或加入凝胶促进剂诸如盐、磷酸盐、硫酸盐以及(部分)凝胶化的二氧化硅等,来完成所述去稳定。在去稳定之前,存在于浆料中的任何可胶溶(peptisable)的化合物必定被很好地胶溶(peptised)。
尽管根据后一文献的催化剂具有相对高的耐磨性和可及性,但现在已经发现,可以进一步改进所述可及性和耐磨性。
通过本发明的方法可以完成这种进一步的改进,该方法包括步骤:
a)制备含有粘土、沸石和准晶态勃姆石的浆料,条件是,该浆料不包含胶溶(peptised)的准晶态勃姆石;
b)将单价酸加入该浆料;
c)将硅源加入该浆料;以及
d)使该浆料成形,形成颗粒。
与其中准晶态勃姆石(如假勃姆石)加入含沸石的浆料之前总是已经被胶溶化的传统方法相比,本发明方法加入非胶溶的准晶态勃姆石(QCB)。酸仅仅在QCB加入之后被加入到,即还包括沸石和粘土的浆料中。
不希望局限于理论,我们认为,在所述传统方法中,带负电的二氧化硅与后加入的、带正电的胶溶勃姆石反应,由此形成Si-Al共凝胶。在其中将酸加入含有沸石、勃姆石和粘土的浆料的本发明方法中,所有这三种化合物的表面可以变成带正电。后加入的二氧化硅将与所有这些带正电的组分(不仅与勃姆石)相互作用,导致形成更少的Si-Al共凝胶。这导致催化剂颗粒具有更高的可及性。
本发明的另外优点是,它能够形成具有足够用于FCC的可及性和耐磨性的、包含微晶和准晶态勃姆石的催化剂。
微晶勃姆石(MCB)是合适的金属钝化剂,特别是用于Ni污染物。但直到目前,含MCB的FCC催化剂颗粒的制备是不成功的,因为MCB很难与传统的FCC型粘合剂结合,导致催化剂颗粒具有无法接受的磨损性。但是,用本发明的方法,现在可能制备出含MCB的、具有满意耐磨性能的催化剂。本发明因此还涉及包括MCB和QCB的FCC催化剂。
勃姆石
术语“勃姆石”在工业中被使用,表示显示出接近于氢氧化氧铝[AlO(OH)]的X射线衍射(XRD)谱图的水合氧化铝。此外,术语勃姆石通常用于表示宽范围的水合氧化铝,它含有不同量的水合作用水,具有不同的表面积、孔体积、比重,且在加热时显示出不同的热特性。尽管它们显示出勃姆石[AlO(OH)]的衍射峰,但是它们的XRD图经常在其衍射峰宽度方面不同,也可能在峰位上偏移。XRD衍射峰的尖锐程度和它们的峰位已经被用来表示结晶度、晶体尺寸和缺陷的量。
大致地,有两类勃姆石氧化铝:准晶态勃姆石(QCB)和微晶态勃姆石(MCB)。
在本技术领域的情况下,准晶态勃姆石还被称为假勃姆石和凝胶状勃姆石。通常这些QCB比MCB具有更高的表面积、更大的孔和孔体积、更低的比重。它们容易分散在水或者酸中,比MCB具有更小的晶体尺寸,含有更大量的水合作用的水分子。QCB的水合作用程度可以具有宽范围的值,例如从每摩尔Al大约1.4到最高大约2摩尔的水,这些水分子通常顺序地插入或以另外的方式插入八面体层间。
DTG(微分热解重量分析法(differential thermographimetry))表明,与从MCB中释放相比,大部分量的水在更低的温度下从QCBs中释放出来。
QCB的XRD图表明,非常宽的衍射峰和它们的半高宽(即在最高强度的一半处的衍射峰宽度)显示出晶体的尺寸和晶体的完整度。
微晶勃姆石与QCB的不同在于它的高结晶度、相对大的晶体尺寸、非常 低的表面积以及高密度。与QCB相反,MCB表现出更高的衍射峰强度和非常窄的半高宽的XRD谱图。这是由于它们相对少量的插层水分子、大的晶体尺寸、体材料(bulk material)的更高结晶度和更少量的晶体缺陷。典型地,所插入的水分子的数量可以在每摩尔Al大约1到最高大约1.4的范围内变化。典型的市售MCB是
MCB和QCB粉末X射线反射来表征。ICDD含有勃姆石的记录条目,确认存在相应于(020)、(021)和(041)面的反射。对于铜射线,这种反射将出现在20为14、28和38度处。该反射的精确位置依赖于结晶度和插层水的量:当插层水的量增加时,(020)反射移向更低的值,这对应于更大的面间距d。然而,接近于上述位置的多条反射线表示存在一种或者多种勃姆石相。
为了本说明书的目的,我们定义准晶态勃姆石为具有半高宽(FWHH)为1.5°或者大于1.5°2θ的(020)反射峰。具有半高宽(FWHH)小于1.5°2θ的(020)反射峰的勃姆石被认为微晶勃姆石。
总之,QCB与MCB之间的基本的、典型的区别包括在以下方面的变化:三维晶格序、晶体尺寸、插入八面体层间的水的量以及晶体缺陷度。
沸石
存在于步骤a)的浆料中的合适沸石包括诸如Y沸石(包括HY、USY、RE-Y、脱铝Y和RE-USY);沸石β;ZSM-5;磷活化的ZSM-5;离子交换型的ZSM-5;MCM-22和MCM-36;金属交换的沸石;ITQ类;SAPO类;ALPO类以及它们的混合物等的沸石。
粘土
合适的粘土包括高岭土、膨润土、滑石粉、海泡石、绿坡缕石、合成粘土(laponite)、锂蒙脱石、英国式粘土(English clay)、阴离子型粘土如水滑石以及热处理或化学处理的粘土如变高岭石(meta-kaolin)。
步骤a)
步骤a)的浆料通过将粘土、沸石和非胶溶的QCB悬浮于水中来制备。任选地,可以加入其它组分,如其它的氧化铝源(像MCB、水合氯化铝、硝酸铝、Al2O3以及Al(OH)3)、阴离子型粘土(如水滑石)、蒙皂石、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、 另外的沸石、镁的氧化物、碱或者盐、和/或者金属的添加剂如含碱土金属(例如Mg、Ca和Ba)、IIIA族过渡金属、IVA族过渡金属(如Ti、Zr)、VA过渡金属(如V、Nb)、VIA过渡金属(如Cr、Mo、W)、VIIA过渡金属(如Mn)、VIIIA过渡金属(如Fe、Co、Ni、Ru、Rh、Pd、Pt)、IB过渡金属(如Cu)、IIB过渡金属(如Zn)、镧系元素(如La、Ce)等的化合物,或者它们的混合物。
尤其优选的组分是MCB,因为它导致制备包含MCB和QCB的催化剂。
粘土、沸石、非胶溶的QCB和可选择的其它组分通过将它们作为干燥固体加入水中来被浆料化。可选择地,将含有各个材料的浆料混合,形成步骤a)的浆料。还可能将有些材料作为浆料或者其它材料作为干燥固体加入。
可以使用任何加入顺序。因此,可能首先加入粘土,然后沸石,接着非胶溶的QCB;或者首先加入沸石,然后粘土,接着非胶溶的QCB;或者首先加入非胶溶的QCB,然后加入沸石,最后是粘土,或者首先加入非胶溶的QCB,然后粘土,最后是沸石;或者首先加入粘土,然后加入非胶溶的QCB,最后加入沸石,或者首先加入沸石,然后非胶溶的QCB,最后是粘土。
还可能将沸石、非胶溶的QCB和粘土同时加入。此外,两种组分如沸石和粘土可以同时加入,而其它组分如非胶溶的QCB随后加入。
可选择的其它组分可以与沸石、粘土和非胶溶的QCB一起加入,或者可以在沸石、粘土和非胶溶的QCB之前或者之后加入。
该浆料优选包括10~70wt%,更优选15~50wt%,最优选15~40wt%的沸石。
该浆料优选包括5~70wt%,更优选10~60wt%,最优选10~50wt%的粘土。
该浆料优选包括1~50wt%,更优选2~40wt%,最优选3~40wt%的非胶溶QCB。
更优选地,该浆料还包括1~25wt%,最优选5~25wt%的MCB。
所有重量百分比都基于干燥固体含量,并且以氧化物计算。
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)
在下一步骤中,将单价酸加入悬浮液中,产生酸消化。可以使用有机和无机的单价酸或者它们的混合物。合适的单价酸的例子是甲酸、乙酸、丙酸、硝酸和盐酸。
将酸以足够获得低于7,更优选在2~5之间,最优选在3~4之间的pH值的量加入浆料中。
在加入酸的过程中,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)
在步骤c)中加入的合适的硅源,包括(聚)硅酸、硅酸钠、无钠硅源以及有机硅源。合适的无钠硅源的例子是硅酸钾、硅酸锂、硅酸钙、硅酸镁、硅酸钡、硅酸锶、硅酸锌、磷硅酸盐以及硼硅酸盐。合适的有机硅源的例子是硅树脂(聚有机硅氧烷如聚甲基苯基硅氧烷和聚二甲基硅氧烷)和含有Si-O-C-O-Si结构的其它化合物;以及它们的先驱体如甲基氯硅烷、二甲基氯硅烷、三甲基氯硅烷;以及它们的混合物。
基于干燥固体的含量并且以SiO2计算,所述硅源优选以1-35wt%的量加入,更优选4-18wt%的量加入。
在本发明优选的实施方式中,硅源不出现在步骤a)的浆料中。这更加防止形成Si-Al共凝胶。
步骤d)
合适的成形方法包括喷雾干燥、脉冲干燥、造粒、挤出(任选地与捏炼组合)、成粒或用于催化剂和吸附剂领域的任何其它传统成形方法、或者它们的组合。优选的成形方法是喷雾干燥。如果该催化剂通过喷雾干燥成形,则喷雾干燥器的入口温度优选为300~600℃范围,出口温度优选为105~200℃范围。
优选在步骤c)中刚好在成形步骤d)之前加入硅源。在加入硅源和成形之间的时限优选为30分钟或者更短,更优选小于5分钟,最优选小于3分钟。
被喷雾干燥的浆料的pH值优选在3以上,更优选在3.5以上,甚至更优选在4以上,最优选在大约4.5或者更高。该浆料的pH值优选不高于7,因为较高pH值的浆料可能难以处理。
该pH值可以通过刚好在喷雾干燥之前将碱(如NaOH或者NH4OH)加 入到浆料中来调节。
所获得的催化剂具有异常优良的耐磨性和可及性。因此,本发明还涉及可通过本发明方法获得的催化剂。
正如上述,本发明进一步涉及包括MCB和QCB的催化剂。优选地,这种催化剂包括1-50wt%,最优选3-40wt%的QCB,优选1-25,最优选5-25wt%的MCB(以氧化物计算)。
该催化剂进一步包括二氧化硅、沸石和粘土。除了QCB和可选择的MCB以外,二氧化硅、沸石和粘土以1-25wt%的二氧化硅、5-50wt%的沸石和其余为粘土的优选量存在。
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、氢生产催化剂和汽车催化剂中的FCC添加剂,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。
本发明因此还涉及本发明方法所获得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、煤转化和氢生产中的催化剂或者添加剂以及用作汽车催化剂的应用。
实施例
可及性测试
通过如下方式测试根据如下实施例制备的催化剂的可及性,即将1g的催化剂加入搅拌容器中,所述搅拌容器含有50g的15g/L科威特减压瓦斯油(KVGO)的甲苯溶液。该溶液在容器与分光光度计之间循环,在该方法中,连续地测试KVGO的浓度。
通过Akzo可及性指数(Akzo Acessibility Index,AAI),来定量催化剂对KVGO的可及性。KVGO在溶液中的相对浓度与时间的平方根作图。AAI被定义为该图的起始斜率:
AAI=-d(Ct/C0)/d(t1/2)*100%
在该等式中,t为时间(以分钟计);C0和Ct分别表示在实验开始时和在时间t时高分子量化合物在溶剂中的浓度。
耐磨性能
通过标准的耐磨测试来测量催化剂的耐磨性能。在该测试中,催化剂床层位于有三喷嘴的耐磨板上。该耐磨板位于耐磨管内,所述耐磨管处于环境温度下。将空气压至喷嘴,所得到的喷射流体产生基本向上输送催化剂颗粒,并产生细颗粒。
在耐磨管的顶部是分离室,在该分离室内,流动消失,大于约16微米的大部分颗粒落回耐磨管。较小的颗粒被收集在集尘袋中。
在600℃下煅烧催化剂样品之后,实施所述测试,首次实验的时间为5小时,基于想像的输入量为50克,测定收集在集尘袋中的细粒的重量百分比。这就是起始耐磨性。然后再实施所述测试15小时,测定在该段时间(5-20小时)内的细粒的重量百分比。这就是固有的耐磨性。磨损指数(AI)是外推的25小时后的细粒的wt%。因此,催化剂的耐磨性越好,AI值越低。
实施例1
通过如下方式制备浆料,即将60.6kg的沸石Y浆料(29.7wt%的固体)与23.3kg的微晶勃姆石浆料(23.2wt%的Al2O3)、16.2kg的高岭土浆料(85.3wt%的固体)、14.2kg含非胶溶的假勃姆石的浆料(71.9wt%的Al2O3)以及48.9kg的水混合。将硝酸加入所得到的浆料中直到pH值为3.3。
通过将稀释的水玻璃(DWG)与H2SO4混合,在管式混合器(5,900rpm)中制备二氧化硅溶胶。重量百分比DWG/H2SO4为2.9。
该二氧化硅溶胶与以上所制备的浆料被泵入到混合容器(1450rpm)中,得到含有21wt%固体的浆料。所述二氧化硅溶胶以0.88kg/min的流速被泵入到混合容器中;所述浆料以2.12kg/min的流速泵入。所得到的浆料具有大约2.5的pH值,然后以3.0kg/min的流速将其送进喷雾干燥器,进口温度为300℃,出口温度为125℃,管嘴压力为40巴。
喷雾干燥的颗粒具有约75微米的d50。
所述颗粒含有30wt%的沸石、17wt%的QCB、9wt%的MCB、21wt%的二氧化硅以及余量为高岭土。
使用该制法,制备本发明的四个样品:
样品A1严格按照上述来制备;
样品B1是通过刚好在喷雾干燥之前将苛性碱加入所述浆料中,由此pH 值达到3.8来制备的;
样品C1是通过刚好在喷雾干燥之前将苛性碱加入所述浆料中,由此pH值达到4.2来制备的;
样品D1是通过刚好在喷雾干燥之前将苛性碱加入所述浆料中,由此pH值达到4.6来制备的;
除了使用胶溶的假勃姆石(用硝酸胶溶)外,通过刚好在喷雾干燥之前增加pH值至4.2(CC1)和4.6(CD1),由相同的方法制备两个比较样品(CC1和CD1)。
为了减少样品的钠含量至低于0.5wt%(以Na2O计算),接下来通过在40升的氨溶液中在5.0的pH值下使12kg的颗粒再浆料化,清洗所述样品。接着,过滤所述颗粒,并用30升的含有420g硫酸铵的氨溶液且在pH值为8.3下清洗;在30升的氨溶液中在7.8的pH值下使该颗粒再次再浆料化,过滤并再次用30升的含有420g硫酸铵的氨溶液在pH值为8.3下再次清洗。最后,用水清洗所述颗粒,随后快速煅烧(出口气体温度为150℃)。
所有的清洗步骤在45℃下进行。
测试所有上述样品的磨损指数(AI)和Akzo可及性指数(AAI):参见表1。该表还显示出AAI/AI的比值。很清楚,本发明方法所制备的催化剂具有较低的磨损性(即较高的耐磨性)和较高的AAI/AI比值。比较样品A1-D1的结果,进一步显示出可及性随着刚好在喷雾干燥之前的pH值的增加而增加。
表1
样品 AI AAI AAI/AI |
A1 1.2 0.9 0.8 B1 2.5 3.3 1.3 C1 2.7 4.4 1.6 D1 4.5 6.6 1.5 |
CC1 6 4.5 0.75 CD1 10.1 6.1 0.6 |
实施例2
通过如下方式制备浆料,即将66.445kg的沸石Y浆料(27.1M%的固体) 与25.851kg的微晶勃姆石浆料(23.2wt%的Al2O3)、24.619kg的高岭土浆料(85.3wt%的固体)、8.054kg含非胶溶的假勃姆石的浆料(74.5wt%的Al2O3)以及48.9kg的水混合。向所得到的浆料,加入5.6kg的HNO3直到pH值为3.3。
通过将稀释的水玻璃(DWG)与H2SO4混合,在管式混合器(5,900rpm)中制备二氧化硅溶胶。重量百分比DWG/H2SO4为2.92。
该二氧化硅溶胶与以上所制备的浆料被泵入到混合容器(1,450rpm)中,得到含有25wt%固体的浆料。所述二氧化硅溶胶以0.75kg/min的流速被泵入到该容器;所述浆料以2.25kg/min的流速泵入。所得到的浆料具有大约2.5的pH值,然后以3.0kg/min的流速将其送进喷雾干燥器,进口温度为300℃,出口温度为125℃,管嘴压力为40巴。
喷雾干燥的颗粒具有约75微米的d50。
所述颗粒含有30wt%的沸石、10wt%的QCB、10wt%的MCB、15wt%的二氧化硅以及余量为高岭土。
使用该制法,制备本发明的四个样品:
样品A2严格按照上述来制备;
样品B2是通过刚好在喷雾干燥之前将苛性碱加入所述浆料中,由此pH值达到3.8来制备的;
样品C2是通过刚好在喷雾干燥之前将苛性碱加入所述浆料中,由此pH值达到4.2来制备的;
样品D2是通过刚好在喷雾干燥之前将苛性碱加入所述浆料中,由此pH值达到4.6来制备的;
除了使用胶溶的假勃姆石外,通过刚好在喷雾干燥之前增加pH值至3.8(CB2)和5(CE2),由相同的方法制备两个比较样品(CB2和CE2)。
为了减少它们的钠含量至低于0.5wt%(以Na2O计),接下来通过在40升的氨溶液中在5.0的pH值下使12kg的颗粒再浆料化,清洗所述样品。接着,过滤所述颗粒,并用30升的含有420g硫酸铵的氨溶液且在pH值为8.3下清洗;在30升的氨溶液中在7.8的pH值下使该颗粒再次再浆料化,过滤并再次用30升的含有420g硫酸铵的氨溶液在pH值为8.3下再次清洗。最后,用水清洗所述颗粒,随后快速煅烧(出口气体温度为150℃)。
所有的清洗步骤在45℃下进行。
测试所有上述样品的磨损指数(AI)和Akzo可及性指数(AAI):参见表2。该表还显示出AAI/AI的比值。本发明催化剂的所述比值比比较催化剂更高。该表再次显示出,可及性随着在喷雾干燥之前的pH值的增加而增加。
表2
实施例3
通过如下方式制备浆料,即将10.4kg的沸石Y浆料(23.1wt%的固体)与5kg的高岭土浆料(86wt%的固体)、16.8kg含非胶溶的假勃姆石的浆料(17.3wt%的Al2O3)以及0.92kg的水混合。向所得到的浆料,加入HNO3直到pH值为3.3。
通过将稀释的水玻璃(DWG)与H2SO4混合,在管式混合器(5,900rpm)中制备二氧化硅溶胶。重量百分比DWG/H2SO4为2.3。
该二氧化硅溶胶与以上所制备的浆料被泵入到混合容器(1,450rpm)中,得到含有25wt%固体的浆料。所述二氧化硅溶胶以0.75kg/min的流速被泵入到该容器;所述浆料以0.93kg/min的流速泵入。所得到的浆料具有大约2.5的pH值,然后以3.0kg/min的流速将其送进喷雾干燥器,进口温度为500℃,出口温度为120℃,喷嘴压力为40巴。
喷雾干燥的颗粒具有约65微米的d50。
所述颗粒含有24wt%的沸石、29wt%的QCB、4wt%的二氧化硅以及余量为高岭土。
使用该制法,制备本发明的五个样品:
样品A3严格按照上述来制备;
样品B3是通过刚好在喷雾干燥之前将氨加入所述浆料中,由此pH值达到3.6来制备的;
样品C3是通过刚好在喷雾干燥之前将氨加入所述浆料中,由此pH值达到3.9来制备的;
样品D3是通过刚好在喷雾干燥之前将氨加入所述浆料中,由此pH值达到4.2来制备的;
样品E3是通过刚好在喷雾干燥之前将氨加入所述浆料中,由此pH值达到5.0来制备的。
除了使用胶溶的假勃姆石外,通过刚好在喷雾干燥之前增加pH值至4.2(CD3)和5.0(CE3),由相同的方法制备两个比较样品(CD3和CE3)。
为了减少它们的钠含量至低于0.5wt%(以Na2O计),随后通过在热水和氨溶液中在5.0的pH值下使2kg的颗粒再浆料化,清洗所述样品。接着,将200g的硫酸铵加入所述浆料中。然后过滤和清洗所述颗粒。在含200g的硫酸铵的热水中再浆料化该滤饼,过滤,清洗,再次在硫酸铵中使该滤饼再浆料化。最后,过滤所述颗粒,用热水和氨在pH值为8.0和8.5之间过滤和清洗所述颗粒。最后过滤之后,在烘箱中盘式干燥所述颗粒。
表3列出了这些催化剂的AI、AAI和AAI/AI的比值。D3和E3的结果与CD3和CE3的结果的比较,说明了本发明方法对催化剂的可及性的积极效果,而没有牺牲耐磨性。此外,可及性随着在喷雾干燥之前的pH值的增加而增加。
表3
实施例4
通过如下方式制备浆料,即将8kg的沸石Y浆料(25wt%的固体)与4.17kg的高岭土浆料(86wt%的固体)、5kg的微晶勃姆石(25wt%的Al2O3)、13.3kg含非胶溶的假勃姆石的浆料(17.3wt%的Al2O3)以及0.92kg的水混合。向所得到的浆料,加入HNO3直到其pH值为3.3。
通过将稀释的水玻璃(DWG)与H2SO4混合,在管式混合器(5,900rpm)中制备二氧化硅溶胶。重量百分比DWG/H2SO4为2.36。
该二氧化硅溶胶与以上所制备的浆料被泵入到混合容器(1450rpm)中,得到含有25wt%固体的浆料。所述二氧化硅溶胶以0.112kg/min的流速被泵入到该容器;所述浆料以0.888kg/min的流速泵入。将氨加入所述浆料中。然后将所述浆料以3.0kg/min的流速送进喷雾干燥器,进口温度为500℃,出口温度为120℃,喷嘴压力为40巴。
喷雾干燥的颗粒具有约65微米的d50。
所述颗粒含有20wt%的沸石、24wt%的QCB、14wt%的MCB、6wt%的二氧化硅以及余量为高岭土。
使用该制法,制备本发明的两个样品:
样品A4是通过刚好在喷雾干燥之前将氨以如下量加入所述浆料,使得pH值达到4.2来制备的;
样品B4是通过刚好在喷雾干燥之前将氨以如下量加入所述浆料,使得pH值达到5.0来制备的;
除了使用胶溶的假勃姆石外,通过刚好在喷雾干燥之前增加pH值至5,由相同的方法制备一个比较样品(CB4)。
为了减少它们的钠含量至低于0.5wt%(以Na2O计算),随后通过在热水和氨溶液中在5.0的pH值下使2kg的颗粒再浆料化,清洗所述样品。接着,将200g的硫酸铵加入所述浆料中。然后过滤和清洗所述颗粒。在含200g的硫酸铵热水中再浆料化该滤饼,过滤,清洗,再次在硫酸铵中使该滤饼浆料化。最后,过滤所述颗粒,用热水和氨在pH值为8.0和8.5之间清洗所述颗粒。最后过滤之后,在烘箱中盘式干燥所述颗粒。
表4列出了这些催化剂的AI、AAI和AAI/AI的比值。清楚地显示出本发明方法对这些催化剂的积极效果。
表4
Claims (8)
1.用于制备催化剂的方法,该方法包括步骤:
a)制备包含粘土、沸石和准晶态勃姆石的浆料,条件是,该浆料不包含胶溶的准晶态勃姆石;
b)将单价酸加入所述浆料;
c)将硅源加入所述浆料;以及
d)使该浆料成形以形成颗粒。
2.如权利要求1的方法,其中,在步骤a)中所获得的浆料不包含硅源。
3.如权利要求1或2的方法,其中,在步骤c)中加入的硅源选自由硅酸钠、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、三甲基氯硅烷以及它们的混合物组成的组。
4.如权利要求1或2的方法,其中,基于干燥固体含量并且以SiO2计算,所述硅源在步骤c)中以1-35wt%的量加入。
5.如权利要求3的方法,其中,基于干燥固体含量并且以SiO2计算,所述硅源在步骤c)中以1-35wt%的量加入。
6.通过前述任一权利要求的方法所获得的催化剂。
7.根据权利要求6所述的催化剂,其中,步骤a)中的浆料进一步包含微晶勃姆石。
8.如权利要求6-7中任一项的催化剂在流化催化裂化、加氢处理、烷基化、重整、气-液转化、煤转化和氢生产中以及作为汽车催化剂的应用。
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