CN101454080A - 制备含铝磷酸盐的催化剂组合物的方法 - Google Patents
制备含铝磷酸盐的催化剂组合物的方法 Download PDFInfo
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- CN101454080A CN101454080A CNA2006800414547A CN200680041454A CN101454080A CN 101454080 A CN101454080 A CN 101454080A CN A2006800414547 A CNA2006800414547 A CN A2006800414547A CN 200680041454 A CN200680041454 A CN 200680041454A CN 101454080 A CN101454080 A CN 101454080A
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- silicate
- phosphate
- alumino
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- 239000000203 mixture Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 10
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title abstract description 7
- 229940001007 aluminium phosphate Drugs 0.000 title abstract description 7
- 239000003054 catalyst Substances 0.000 title description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 70
- 239000002184 metal Substances 0.000 claims abstract description 70
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 55
- 239000004411 aluminium Substances 0.000 claims abstract description 53
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 49
- 239000004927 clay Substances 0.000 claims abstract description 47
- 125000000129 anionic group Chemical group 0.000 claims abstract description 40
- 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 37
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 31
- 239000010703 silicon Substances 0.000 claims abstract description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 25
- 239000011574 phosphorus Substances 0.000 claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 229910019142 PO4 Inorganic materials 0.000 claims description 43
- 150000004645 aluminates Chemical class 0.000 claims description 43
- 239000010452 phosphate Substances 0.000 claims description 43
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 150000002910 rare earth metals Chemical group 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 150000001398 aluminium Chemical class 0.000 claims description 5
- 235000011007 phosphoric acid Nutrition 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 150000003376 silicon Chemical class 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 229910021536 Zeolite Inorganic materials 0.000 description 10
- 239000000654 additive Substances 0.000 description 10
- 239000010457 zeolite Substances 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 8
- 230000032683 aging Effects 0.000 description 8
- -1 phosphorus halides Chemical class 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 7
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 238000004231 fluid catalytic cracking Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000008301 phosphite esters Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910001679 gibbsite Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 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 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 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 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 150000004675 formic acid derivatives Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- RYIOLWQRQXDECZ-UHFFFAOYSA-N phosphinous acid Chemical compound PO RYIOLWQRQXDECZ-UHFFFAOYSA-N 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910020639 Co-Al Inorganic materials 0.000 description 1
- 229910020675 Co—Al Inorganic materials 0.000 description 1
- 229910017767 Cu—Al Inorganic materials 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 229910018657 Mn—Al Inorganic materials 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 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
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate 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
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 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
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- OOSPDKSZPPFOBR-UHFFFAOYSA-N butyl dihydrogen phosphite Chemical compound CCCCOP(O)O OOSPDKSZPPFOBR-UHFFFAOYSA-N 0.000 description 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical group CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052802 copper Inorganic materials 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
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052631 glauconite Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction 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
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229940094522 laponite Drugs 0.000 description 1
- 239000010410 layer Substances 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
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
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Abstract
用于制备含铝磷酸盐的组合物的方法，其中使用含磷化合物将铝源部分地转化成铝磷酸盐，并且(i)使用二价金属(MII)源将该铝源部分地转化成阴离子粘土和/或Al－MII混合金属(氢)氧化物，(ii)使用硅源将该铝源部分地转化成硅铝酸盐，和/或(iii)使用二价金属源和硅源二者将该硅源部分地转化成MII－硅铝酸盐。
Description
本发明涉及用于制备含铝磷酸盐的催化剂组合物的方法。
由现有技术可知含铝磷酸盐的催化剂组合物。例如，EP 0 496 226公开了一种催化剂组合物，该组合物包含沸石、含铝磷酸盐的粘合剂以及可选择的无机氧化物如高岭土。该组合物通过使磷酸与铝盐溶液反应形成铝磷酸盐溶液并将该铝磷酸盐溶液与沸石和可选择的无机氧化物反应制得。将所得混合物喷雾干燥。
US 6,355,591公开了一种流化催化裂化添加剂组合物，该组合物包含4-20重量％铝磷酸盐，1-40重量％选自由发光沸石、ZSM-5、β及它们的混合物所组成的组中的结晶分子筛沸石，以及40-90重量％粘土即高岭土。该组合物通过如此制得：使铝金属粉末与磷酸反应以获得铝磷酸盐，将该铝磷酸盐与粘土混合，将该混合物加入到含沸石的浆料中，接着进行喷雾干燥和煅烧。
因此，这些公开的催化剂组合物通过将铝磷酸盐与其它催化剂组分如沸石和粘土混合制得，导致催化剂颗粒中铝磷酸盐和其它组分分布的相对不均匀。本发明的的目的是提供铝磷酸盐和其它催化剂组分得以更加密切和均匀的混合的含铝磷酸盐的催化剂组合物。
现已发现通过以铝源开始并将该铝源的一部分转化为铝磷酸盐且将其它部分转化为另外的含Al催化剂组分可满足该目的。
本发明因此涉及用于制备含铝磷酸盐的组合物的方法，其中，使用含磷化合物将铝源部分地转化成铝磷酸盐，并且(i)使用二价金属(MII)源将该铝源部分地转化成阴离子粘土和/或Al-MII混合金属(氢)氧化物，(ii)使用硅源将该铝源部分地转化成硅铝酸盐，和/或(iii)使用二价金属源和硅源二者将该硅源部分地转化成MII-硅铝酸盐。
在第一主实施方式中，使部分铝源首先与含磷化合物反应形成铝磷酸盐，其后使未转化的铝源部分与二价金属源或硅源反应以获得包含(a)铝磷酸盐和(b)阴离子粘土、Al-MII混合金属(氢)氧化物、硅铝酸盐和/或MII-硅铝酸盐的组合物。
因此，该第一主实施方式包括如下步骤：
a.使含磷化合物与铝源反应，以获得包含铝磷酸盐和未反应的铝源的组合物，以及
b.使所得组合物与二价金属源和/或硅源反应，以获得包含(a)铝磷酸盐和(b)阴离子粘土、Al-MII混合金属(氢)氧化物、硅铝酸盐和/或MII-硅铝酸盐的组合物。
在第二主实施方式中，使部分铝源首先与二价金属源或硅源反应形成阴离子粘土、Al-MII混合金属氧化物、硅铝酸盐和/或阳离子粘土，其后使未转化的部分铝源与含磷化合物反应，以获得包含(a)铝磷酸盐和(b)阴离子粘土、Al-MII混合金属(氢)氧化物、硅铝酸盐和/或MII-硅铝酸盐的组合物。
因此该第二主实施方式包括如下步骤：
a.使铝源与二价金属源和/或硅源反应，以获得包含(a)未反应的铝源和(b)阴离子粘土、Al-MII混合金属(氢)氧化物、硅铝酸盐和/或MII-硅铝酸盐的组合物，以及
b.使所得组合物与含磷化合物反应，以获得包含(a)铝磷酸盐和(b)阴离子粘土、Al-MII混合金属(氢)氧化物、硅铝酸盐和/或MII-硅铝酸盐的组合物。
根据本发明的方法(包括两个主实施方式)产生铝磷酸盐与硅铝酸盐、阴离子粘土、Al-MII混合金属(氢)氧化物和/或MII-硅铝酸盐的基本均匀的混合物。不希望受理论的束缚，据推测这是由于单一铝源起始颗粒转化成这些不同的相。与公开的组合物相比，这导致这些相的更紧邻近和相互作用，因此改善催化性能。
术语“未反应的铝源”是指未反应形成铝磷酸盐(参照第一主实施方式)或阴离子粘土、Al-MII混合金属(氢)氧化物、硅铝酸盐或MII-硅铝酸盐(参照第二主实施方式)的铝源。然而，术语“未反应的铝源”包括与起始用铝源不同的铝相。例如，如果在该工艺的开始用经快速煅烧的三水合铝作为铝源，并且如果在步骤a)期间该材料转化成勃姆石，术语“未反应的铝源”涵盖该勃姆石。
含磷化合物
合适的含磷化合物包括磷酸及其盐，例如磷酸二氢铵和磷酸氢二铵、连二磷酸铵、正磷酸铵、正磷酸二氢铵、正磷酸氢铵、磷酸三铵、焦磷酸钠、膦和亚磷酸盐。合适的含磷化合物还包括由PX3、RPX2、R2PX、R1P、R3P＝O、RPO2、RPO(OX)2、PO(OX)3、R2P(O)OX、RP(OX)2、ROP(OX)2和(RO)2POP(OR)2表示的多组衍生物，其中R是烷基或苯基，且X是氢、R或卤化物。这些化合物包括伯膦RPH2、仲膦R2PH和叔膦R3P，膦例如丁基膦；叔膦氧化物R3PO例如三丁基膦；伯膦酸RP(O)(OX)2、仲膦酸R2P(O)OX，例如苯膦酸；所述膦酸的酯例如膦酸二乙酯(RO)2P(O)H、膦酸二烷基酯(RO)P(O)R2；三价膦酸R2POX，例如三价膦酸二乙酯，伯亚磷酸酯(RO)P(OX)2、仲亚磷酸酯(RO)2POX和叔亚磷酸酯(RO)3P；及其酯例如单丙酯、次亚膦酸烷基二烷基酯(alkyldialkylphosphinite)(RO)P2和亚膦酸二烷基酯(RO)2PR酯。亚磷酸酯的例子包括亚磷酸酯三甲酯、亚磷酸三乙酯、亚磷酸二异丙基酯、亚磷酸丁酯和焦亚磷酸酯如四焦亚磷酸酯。所提及的化合物中的烷基典型地包含1-4个碳原子。其它合适的含磷化合物包括卤化亚磷(phosphorus halides)例如三氯化亚磷、溴化亚磷和碘化亚磷，二氯代亚磷酸烷基酯(alkyl phosphorodichloridite)(RO)PCl2、氯代亚磷酸二烷基酯(dialkyl phosplzorochloridites)(RO)2PCl、氯代膦酸烷基酯(alkyl phosphonochloridate)(RO)(R)P(O)Cl和氯代膦酸二烷基酯(dialkylphosphinochloridate)R2P(O)Cl。
使用含有机磷酸酯的化合物的优点是，有机基团可以在随后的煅烧之后提高最终产品的孔隙率。
铝源
本文使用的术语“铝源”限定为氧化铝或三水合铝的任何形式及它们的煅烧形式，以及任何可水溶的铝盐或铝酸盐。合适的例子包括氧化铝和氢氧化铝，例如过渡氧化铝、三水合铝-例如铁铝氧石精矿(Bauxite Ore Concentrate，BOC)、三羟铝石、诺三水铝石和水铝矿(gibbsite)-及其热处理形式(包括经快速煅烧的三水合铝)、氧化铝溶胶、氧化铝凝胶、无定形氧化铝和(拟)勃姆石、氯化铝水溶胶、硝酸铝水溶胶、氧化铝盐如硝酸铝、氯化铝、硫酸铝、碱式氯化铝、铝酸钠以及它们的混合物。这些铝的氧化物和氢氧化物相对廉价，并且不趋于在催化剂组合物中留下必须经洗涤除去并且会在加热时放出作为环境中不期望气体的阴离子。
二价金属源
合适的二价金属源是包含Mg2+、Ca2+、Ba2+、Zn2+、Mn2+、Co2+、Mo2+、Ni2+、Fe2+、Sr2+、Cu2+或其混合物的化合物。这些金属的合适化合物是它们的氧化物、氢氧化物、碳酸盐、碱式碳酸盐、甲酸盐、乙酸盐、硝酸盐、氯化物等。所述氧化物、氢氧化物、碳酸盐和碱式碳酸盐相对廉价并且不趋于在产品中留下不期望的金属阴离子。
硅源
合适硅源的例子包括稳定化二氧化硅溶胶、二氧化硅凝胶、(稳定化)聚硅酸、热解法二氧化硅、沉淀二氧化硅、正硅酸四乙酯、水玻璃，以及它们的混合物。
根据第一主实施方式的方法
在根据第一主实施方式的方法中，第一步骤包括磷化合物与铝源的反应。在一个实施方式中，该反应在水溶液或悬浮液中于约25℃-约300℃的温度进行约0.5小时-3小时。在其它实施方式中，该反应在约50℃-约200℃或约70℃-约150℃的温度下进行约0.5小时-约3小时或约1小时-约2小时。根据最终产品的商业应用且因此根据最终组合物的所需铝磷酸盐含量，一个实施方式中反应混合物内的Al/P摩尔比为约1.5-约15。
将步骤a)中所得铝磷酸盐和未反应的铝源的混合物随后与二价金属源和/或硅源反应(步骤b)。该反应通常通过老化铝磷酸盐与二价金属源和/或硅源的水性悬浮液来进行。如果使用二价金属源，则老化产生包含铝磷酸盐和阴离子粘土或Al-MII混合金属(氢)氧化物的组合物；如果使用硅源，则将形成包含铝磷酸盐和硅铝酸盐的组合物，而使用二价金属源和硅源二者则导致形成包含铝磷酸盐和MII-硅铝酸盐的组合物。
所需老化温度取决于所需组合物，但通常范围为约25℃-约375℃、约50℃-约250℃或约80℃-约200℃。压力处于或高于大气压，并且在一个实施方式中是自生压力。老化时间的范围为约20分钟-约12小时或约1小时-约6小时。
对于包含铝磷酸盐和阴离子粘土的组合物的制备，混合物的pH通常范围为约6-约13，更多或为约8-约11，同时以金属计，二价金属与未反应的铝的摩尔比为至少约2，或者约3-约4。
对于包含铝磷酸盐和MII-硅铝酸盐的组合物的制备，混合物的pH范围通常为约6-约13或约8-约11，以金属计，混合物中二价金属:硅:未反应的铝的典型摩尔比为1:1:1和1:1:0.5。
对于包含铝磷酸盐和硅铝酸盐的组合物的制备，硅源与未反应的铝源的重量比强烈取决于所需硅铝酸盐的所需二氧化硅/氧化铝比，其可在宽范围内变化。可添加晶种或模板来提高所需硅铝酸盐的形成。
根据第二主实施方式的方法
在根据第二主实施方式的方法中，第一步骤包括铝源与二价金属源和/或硅源的反应。该反应通常通过老化铝源与二价金属源和/或硅源的水性悬浮液来进行。
如果使用二价金属源，老化产生包含未反应的铝源和阴离子粘土的悬浮液；如果使用硅源，则将形成包含未反应的铝源和硅铝酸盐的悬浮液，而使用二价金属源和硅源二者则产生包含未反应的铝源和MII-硅铝酸盐的组合物。
所需老化温度取决于所需组合物，但通常范围为约25℃-约375℃、约50℃-约250℃或约80℃-约200℃。压力处于或高于大气压，并且在一些实施方式中是自生压力。老化时间范围通常为约20分钟-约12小时，在一个实施方式中为约1小时-约6小时。
对于包含未反应的铝源和阴离子粘土的组合物的制备，混合物的pH范围通常为约6-约13，或为约8-约11，同时以金属计，铝与二价金属的摩尔比为至少约0.25，并且可为约2-约4。
对于包含未反应的铝源和MII-硅铝酸盐的组合物的制备，混合物的pH范围为约8-约12。
对于包含铝磷酸盐和硅铝酸盐的组合物制备，铝与硅的摩尔比强烈取决于所需硅铝酸盐的所需二氧化硅/氧化铝比，其可在宽范围内变化。可添加晶种或模板来提高所需硅铝酸盐的形成。
将所得包含未反应的铝源和阴离子粘土、Al-MII混合金属(氢)氧化物、硅铝酸盐和/或MII-硅铝酸盐的混合物随后与磷源反应(步骤b)。
在本发明的一些实施方式中，该反应在水性悬浮液中于约25℃-约300℃或约50℃-200℃的温度下进行。在本发明的一个实施方式中，该反应在水性悬浮液中于约70℃-约150℃的温度下进行约0.5小时-约3小时或约1小时-约2小时。
根据最终产品的商业应用且因此根据最终组合物的所需铝磷酸盐含量，反应混合物中未反应的铝与磷的摩尔比通常为约1.5-约15。
所得组合物
所得组合物包含(a)铝磷酸盐和(b)阴离子粘土、Al-MII混合金属(氢)氧化物、硅铝酸盐和/或MII-硅铝酸盐。
根据该组合物设想的应用，其铝磷酸盐的量可为少量(例如约5重量％-约25重量％、或约10重量％-约20重量％)、高量(约50重量％-约90重量％、或约60重量％-约80重量％)、或中量(例如约30重量％-约60重量％、或约50重量％)。
阴离子粘土具有晶体结构，该晶体结构由二价和三价金属氢氧化物的特定组合堆积成的带正电荷的层构成，层间存在阴离子和水分子。水滑石是天然产生阴离子粘土的例子，其中三价金属是铝，二价金属是镁，且占主要的阴离子是碳酸根；羟镁铝石是其中三价金属是铝、二价金属是镁、且占主要的阴离子是羟基的阴离子粘土。多种术语被用来描述本说明书称作阴离子粘土的材料。类水滑石和层状双氢氧化物是本领域技术人员可互换使用的术语。在本说明书中将这些材料称作阴离子粘土，其中包括术语类水滑石材料和层状双氢氧化物材料。
在根据本发明的制备过程中可形成的阴离子粘土包括Mg-Al阴离子粘土、Ca-Al阴离子粘土、Ba-Al阴离子粘土、Zn-Al阴离子粘土、Mn-Al阴离子粘土、Co-Al阴离子粘土、Mo-Al阴离子粘土、Ni-Al阴离子粘土、Fe-Al阴离子粘土、Sr-Al阴离子粘土和Cu-Al阴离子粘土。
Al-MII混合金属(氢)氧化物包括无定形混合铝与二价金属氧化物和/或氢氧化物以及铝和二价金属氧化物和/或氢氧化物的共凝胶。所述二价金属可选自上文列举出的二价金属。
术语硅铝酸盐包括分子筛例如β沸石、MCM-41、MCM-22、MCM-36、发光沸石、如X-沸石和Y-沸石的八面沸石、五元环(pentasil)-型沸石如ZSM-5、和非沸石固体酸如二氧化硅-氧化铝。
MII-硅铝酸盐包括(i)掺有典型地选自上文所列举出的二价金属的无定形硅铝酸盐共凝胶和(ii)掺杂的阳离子粘土，该阳离子粘土包含作为四价金属的硅、作为三价金属的铝和典型地选自上文所列举出的二价金属。这些粘土的例子是蒙脱土(包括蒙脱石、锂蒙脱石、皂石、laponiteTM和锌蒙脱石)、膨润土、伊利石、云母、海绿石、蛭石、绿坡缕石和海泡石。
另外的方法的实施方式
本发明的方法可按间歇或连续模式进行，可选地以连续多步骤操作进行。这种连续多步骤操作可在包含两个或更多转化容器的装置内进行，例如按No.US 2003-0003035 A1公开的专利申请中所描述的装置。
例如，在进料制备容器中制备包含铝源和含磷化合物(参照第一主实施方式)或二价金属源和/或硅源(参照第二主实施方式)的浆料。将浆料连续泵送通过两个或多个转化容器。在第一转化容器中，实施步骤a)。在第二实施方式中，将硅源和/或二价金属源(参照第一实施方式)或含磷化合物(参照第二实施方式)加入到所述浆料中并且实施步骤b)。
若需要，可向任何转化容器内的混合物中加入添加剂、酸或碱。各个容器的温度可调节至其自身需要的温度。
可将根据本发明的方法中涉及的反应混合物和/或加入到这些混合物中的组分进行机械处理，例如研磨或捏制，或者单独地或者以混合物进行，以及或者在反应前或者在反应期间。可将该机械处理与热处理组合。在本说明书中，术语“研磨”定义为可致使颗粒尺寸减小的任何方法。这种颗粒尺寸减小可同时导致形成颗粒的活性表面和/或颗粒的发热。可用于研磨的设备包括球磨机、高剪切混合器、胶体磨、微粉机和可将超声波引入到浆料中的电变换器。低剪切混合即进行搅拌使成分基本处于悬浮不被认为是“研磨”。清楚的是，如果金属源不溶解，则只能将其研磨。
若需要，可在任何处理步骤期间向混合物中加入添加剂。可选择地，处理期间使用的多种金属源中的一种可以已经包含(例如掺杂有)一种或多种添加剂。合适的添加剂包括稀土金属(例如Ce、La)、Si、P、B、VI族金属、VIII族金属、碱土金属(例如Mg、Ca和Ba)、贵金属(例如Pd、Pt、Rh)或过渡金属(例如W、V、Mn、Fe、Ti、Zr、Cu、Co、Cr、Ni、Zn、Mo、Sn)的氧化物、氢氧化物、硼酸盐、锆酸盐、铝酸盐、硫化物、碳酸盐、硝酸盐、磷酸盐、硅酸盐、钛酸盐和卤化物盐。
还可以加入有机添加剂，例如孔调节剂(例如糖、表面活性剂、聚合物)、有机酸或碱、以及EDTA。
在本发明的一个实施方式中使用稀土金属(RE)作为添加剂是有效的。更尤其是，该稀土用于形成掺杂RE的铝磷酸盐。
可以在本发明的处理期间或之后将所得催化剂成型。例如，有可能在实施步骤b)之前使步骤a)中制得的混合物成型。
在成型之前，可向混合物中添加另外的催化剂组分，例如粘合剂、粘土(例如高岭土)、沸石(例如ZSM-5、β沸石、发光沸石、REY、USY、RE-USY、脱铝Y)等。
合适的成型方法包括喷雾干燥、造粒、挤出(可选择地与捏制组合)、成珠或任何其它用于催化剂和吸收剂领域的常规成型方法、或其组合。用于成型的浆料中存在的液体的量应适合待进行的特定成型步骤。可能可取的是部分除去浆料中所用的液体和/或添加额外或另外的液体，和/或改变前体混合物的pH以使该浆料可胶凝并因此适于成型。可以将常用于各种成型方法中的各种添加剂例如挤出添加剂加入到用于成型的前体混合物中。
可将所得组合物在成型之前或之后进行离子交换。适用于对含阴离子粘土的组合物进行交换的阴离子包括碳酸盐、碳酸氢盐、硝酸盐、氯化物、硫酸盐、重硫酸盐、钒酸盐、钨酸盐、硼酸盐、磷酸盐、硅酸盐、铝酸盐、柱撑阴离子(pillaring anion)例如HVO4 -、V2O7 4-、HV2O12 4-、V3O9 3-、V10O28 6-、Mo7O24 6-、PW12O40 3-、B(OH)4 -、B4O5(OH)4 2-、[B3O3(OH)4]-、[B3O3(OH)5]2-、HBO4 2-、HGaO3 2-、CrO4 2-和羟基铝离子(Keggin离子)、甲酸盐、乙酸盐、草酸盐及其混合物。
适合于对含蒙脱土粘土和/或硅铝酸盐的组合物进行交换的阳离子包括NH4 +、Na+、K+、Al3+、Ni2+、Cu2+、Fe2+、Co2+、Zn2+、其它过渡金属、碱金属和稀土金属、以及柱撑阳离子例如[Al13]7+Keggin离子。
可选择地将催化剂组合物在约300℃-约1200℃、或约300℃-约800℃、或约300℃-约600℃的温度下煅烧约15分钟-约24小时、或约1小时-约12小时、或约2小时-约6小时。
所得组合物的应用
所得组合物适合用于流化催化裂化(FCC)催化剂或FCC催化剂添加剂。其特别适合在FCC中作为添加剂，用以降低来自FCC再生器的SOx和NOx排放、生产具有低的硫和/或氮含量的燃料、钝化诸如Ni和V的金属以及提高烯烃收率。
Claims (9)
1.用于制备含铝磷酸盐的组合物的方法，其中，使用含磷化合物将铝源部分地转化成铝磷酸盐，并且(i)使用二价金属(MII)源将该铝源部分地转化成阴离子粘土和/或Al-MII混合金属(氢)氧化物，(ii)使用硅源将该铝源部分地转化成硅铝酸盐，和/或(iii)使用二价金属源和硅源二者将该硅源部分地转化成MII-硅铝酸盐。
2.根据权利要求1所述的方法，其包括以下步骤：
a.使含磷化合物与铝源反应，以获得包含铝磷酸盐和未反应的铝源的组合物，以及
b.使所得组合物与二价金属源和/或硅源反应，以获得包含(a)铝磷酸盐和(b)阴离子粘土、Al-MII混合金属(氢)氧化物、硅铝酸盐和/或MII-硅铝酸盐的组合物。
3.根据权利要求1所述的方法，其包括以下步骤：
a.使铝源与二价金属源和/或硅源反应，以获得包含(a)未反应的铝源和(b)阴离子粘土、Al-MII混合金属(氢)氧化物、硅铝酸盐、和/或MII-硅铝酸盐的组合物，以及
b.使所得组合物与含磷化合物反应，以获得包含(a)铝磷酸盐和(b)阴离子粘土、Al-MII混合金属(氢)氧化物、硅铝酸盐、和/或MII-硅铝酸盐的组合物。
4.根据前述权利要求中任一项所述的方法，其中，所述含磷化合物选自由磷酸、磷酸二氢铵、磷酸氢二铵、连二磷酸铵、正磷酸铵、正磷酸二氢铵、正磷酸氢铵、磷酸三铵、焦磷酸钠、膦、亚磷酸化合物和它们的混合物所组成的组中。
5.根据前述权利要求中任一项所述的方法，其中，使用二价金属源，所述二价金属选自由Mg、Zn、Ni、Co、Fe、Mn、Ca和Ba所组成的组中。
6.根据前述权利要求中任一项所述的方法，其中，使用二价金属源，该二价金属源是所述二价金属的氧化物、氢氧化物、碳酸盐或碱式碳酸盐。
7.根据前述权利要求中任一项所述的方法，其中，在至少一个反应步骤期间存在稀土金属。
8.包含(a)铝磷酸盐和(b)阴离子粘土、Al-MII混合金属(氢)氧化物、硅铝酸盐、和/或MII-硅铝酸盐的组合物，该组合物通过权利要求1-7中任一项所述的方法获得。
9.根据权利要求8的组合物，其另外包含稀土金属。
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| CN108025298A (zh) * | 2015-07-23 | 2018-05-11 | 雅宝公司 | Fcc催化剂添加剂和粘合剂 |
| RU2754146C1 (ru) * | 2019-10-04 | 2021-08-30 | Индиан Оил Корпорейшн Лимитед | Композиция присадки флюид-каталитического крекинга для повышения октанового числа бензина и способ её получения |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100010279A1 (en) * | 2004-04-02 | 2010-01-14 | Ranjit Kumar | Catalyst Compositions Comprising Metal Phosphate Bound Zeolite and Methods of Using Same to Catalytically Crack Hydrocarbons |
| US7763359B2 (en) | 2004-08-30 | 2010-07-27 | Bunge Fertilizantes S.A. | Aluminum phosphate, polyphosphate and metaphosphate particles and their use as pigments in paints and method of making same |
| BRPI0403713B1 (pt) | 2004-08-30 | 2021-01-12 | Universidade Estadual De Campinas - Unicamp | processo de fabricação de um pigmento branco baseado na síntese de partículas ocas de ortofosfato ou polifosfato de alumínio |
| CN101195778B (zh) * | 2008-01-02 | 2010-06-02 | 西南石油大学 | 一种天然气精制脱硫剂的制备方法 |
| US9023145B2 (en) | 2008-02-12 | 2015-05-05 | Bunge Amorphic Solutions Llc | Aluminum phosphate or polyphosphate compositions |
| US20120094130A1 (en) * | 2010-10-15 | 2012-04-19 | Universidade Estadual De Campinas | Coating Compositions With Anticorrosion Properties |
| US9005355B2 (en) | 2010-10-15 | 2015-04-14 | Bunge Amorphic Solutions Llc | Coating compositions with anticorrosion properties |
| US9371454B2 (en) | 2010-10-15 | 2016-06-21 | Bunge Amorphic Solutions Llc | Coating compositions with anticorrosion properties |
| US9155311B2 (en) | 2013-03-15 | 2015-10-13 | Bunge Amorphic Solutions Llc | Antimicrobial chemical compositions |
| US9078445B2 (en) | 2012-04-16 | 2015-07-14 | Bunge Amorphic Solutions Llc | Antimicrobial chemical compositions |
| US9611147B2 (en) | 2012-04-16 | 2017-04-04 | Bunge Amorphic Solutions Llc | Aluminum phosphates, compositions comprising aluminum phosphate, and methods for making the same |
| US9944859B2 (en) * | 2013-04-19 | 2018-04-17 | Phillips 66 Company Albermarle Corporation | Deep deoxygenation of biocrudes utilizing fluidized catalytic cracking co-processing with hydrocarbon feedstocks |
| US10894248B2 (en) * | 2018-09-13 | 2021-01-19 | Indian Oil Corporation Limited | Catalyst composition for enhancing yield of olefins in fluid catalytic cracking process (FCC) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4407730A (en) * | 1981-06-22 | 1983-10-04 | Gulf Research & Development Co. | Catalytic supports with controlled pore properties |
| EP0111748B1 (de) * | 1982-11-16 | 1987-03-25 | Hoechst Aktiengesellschaft | Aluminiumsilikate mit Zeolithstruktur und Verfahren zu ihrer Herstellung |
| US5888921A (en) * | 1995-10-25 | 1999-03-30 | Abb Lummus Global Inc. | Binary molecular sieves having a core and shell of different structures and compositions |
| US6355591B1 (en) * | 2000-01-03 | 2002-03-12 | Indian Oil Corporation Limited | Process for the preparation of fluid catalytic cracking catalyst additive composition |
| US20050227853A1 (en) * | 2004-04-02 | 2005-10-13 | Ranjit Kumar | Catalyst compositions comprising metal phosphate bound zeolite and methods of using same to catalytically crack hydrocarbons |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108025298A (zh) * | 2015-07-23 | 2018-05-11 | 雅宝公司 | Fcc催化剂添加剂和粘合剂 |
| US10888852B2 (en) | 2015-07-23 | 2021-01-12 | Albemarle Corporation | FCC catalyst additive and binder |
| RU2754146C1 (ru) * | 2019-10-04 | 2021-08-30 | Индиан Оил Корпорейшн Лимитед | Композиция присадки флюид-каталитического крекинга для повышения октанового числа бензина и способ её получения |
| US11465132B2 (en) | 2019-10-04 | 2022-10-11 | Indian Oil Corporation Limited | Fluid catalytic cracking additive composition for enhancing gasoline octane barrel and a process of preparation thereof |
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|---|---|
| WO2007054488A2 (en) | 2007-05-18 |
| WO2007054488A3 (en) | 2007-07-05 |
| JP2009525936A (ja) | 2009-07-16 |
| US20090149317A1 (en) | 2009-06-11 |
| CA2629359A1 (en) | 2007-05-18 |
| EP1945352A2 (en) | 2008-07-23 |
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