CN1011301B - Process for producing manganese-aluminum-phosphorus-silicon-oxide molecular sieve - Google Patents
Process for producing manganese-aluminum-phosphorus-silicon-oxide molecular sieveInfo
- Publication number
- CN1011301B CN1011301B CN 85103260 CN85103260A CN1011301B CN 1011301 B CN1011301 B CN 1011301B CN 85103260 CN85103260 CN 85103260 CN 85103260 A CN85103260 A CN 85103260A CN 1011301 B CN1011301 B CN 1011301B
- Authority
- CN
- China
- Prior art keywords
- mnapso
- phosphorus
- silicon
- molecular sieve
- aluminium
- 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.)
- Expired
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 49
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- -1 manganese-aluminum-phosphorus-silicon-oxide Chemical compound 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims description 38
- 230000008569 process Effects 0.000 title claims description 25
- 239000000203 mixture Substances 0.000 claims abstract description 106
- 239000000126 substance Substances 0.000 claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 36
- 239000011574 phosphorus Substances 0.000 claims abstract description 36
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 34
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000010703 silicon Substances 0.000 claims abstract description 32
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011572 manganese Substances 0.000 claims abstract description 30
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 6
- 238000009415 formwork Methods 0.000 claims description 34
- 239000004411 aluminium Substances 0.000 claims description 33
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- 239000011541 reaction mixture Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 238000010587 phase diagram Methods 0.000 claims description 7
- 229910017090 AlO 2 Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229960001866 silicon dioxide Drugs 0.000 claims description 5
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 4
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 3
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- XDIAMRVROCPPBK-UHFFFAOYSA-N 2,2-dimethylpropan-1-amine Chemical compound CC(C)(C)CN XDIAMRVROCPPBK-UHFFFAOYSA-N 0.000 claims description 2
- JEGMWWXJUXDNJN-UHFFFAOYSA-N 3-methylpiperidine Chemical compound CC1CCCNC1 JEGMWWXJUXDNJN-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- WZELXJBMMZFDDU-UHFFFAOYSA-N Imidazol-2-one Chemical compound O=C1N=CC=N1 WZELXJBMMZFDDU-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 claims description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 2
- 229920000289 Polyquaternium Polymers 0.000 claims description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 2
- 229960001231 choline Drugs 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 150000003053 piperidines Chemical class 0.000 claims description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 1
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 22
- 239000003054 catalyst Substances 0.000 abstract description 14
- 239000003463 adsorbent Substances 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 abstract description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- 239000000047 product Substances 0.000 description 57
- 238000000634 powder X-ray diffraction Methods 0.000 description 46
- 238000004458 analytical method Methods 0.000 description 24
- 238000002441 X-ray diffraction Methods 0.000 description 23
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 19
- 239000002994 raw material Substances 0.000 description 18
- 229930195733 hydrocarbon Natural products 0.000 description 15
- 150000002430 hydrocarbons Chemical class 0.000 description 15
- 239000010457 zeolite Substances 0.000 description 15
- 229910021536 Zeolite Inorganic materials 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 12
- 230000008025 crystallization Effects 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 11
- 238000004517 catalytic hydrocracking Methods 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000002156 adsorbate Substances 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- 238000006317 isomerization reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 6
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 6
- 230000036961 partial effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 150000004645 aluminates Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 4
- 238000006900 dealkylation reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910052728 basic metal Inorganic materials 0.000 description 3
- 150000003818 basic metals Chemical class 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000007233 catalytic pyrolysis Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000020335 dealkylation Effects 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229940071125 manganese acetate Drugs 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 229940001007 aluminium phosphate Drugs 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
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- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 239000000376 reactant Substances 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010555 transalkylation reaction Methods 0.000 description 2
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- ATQUFXWBVZUTKO-UHFFFAOYSA-N 1-methylcyclopentene Chemical compound CC1=CCCC1 ATQUFXWBVZUTKO-UHFFFAOYSA-N 0.000 description 1
- VDWODSPSMJMZQI-UHFFFAOYSA-N 2-methyl-1-azabicyclo[2.2.2]octane Chemical group C1CN2C(C)CC1CC2 VDWODSPSMJMZQI-UHFFFAOYSA-N 0.000 description 1
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- WXJVQQPLIMTRFK-UHFFFAOYSA-N C(CCC)[P](CCCC)(CCCC)CCCC Chemical compound C(CCC)[P](CCCC)(CCCC)CCCC WXJVQQPLIMTRFK-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910018337 Mn(C2 H3 O2)2 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- YWMAPNNZOCSAPF-UHFFFAOYSA-N Nickel(1+) Chemical compound [Ni+] YWMAPNNZOCSAPF-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 238000012952 Resampling Methods 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
- 102000006463 Talin Human genes 0.000 description 1
- 108010083809 Talin Proteins 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 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
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000003705 background correction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229940006444 nickel cation Drugs 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel 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
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
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Abstract
The present invention discloses crystalline molecular sieves in three-dimensional micropore skeleton structure with tetrahedral elements of MnO2, AlO2, SiO2 and PO2. The anhydrous empirical chemical composition of the molecular sieves has the following chemical formula: mR: (Mn<w>Al<x>P<y>Si<z>)O2, wherein R represents at least one organic template agent existing in micropore passages in the crystal; m represents the mol number of R in every mol of mR: (Mn<w>Al<x>P<y>Si<z>)O2 in the formula; w, x, y and z respectively represent the mol fractions of manganese, aluminum, phosphorus and silicon which exist in a tetrahedral oxide. The present invention also discloses related applications of the crystalline molecular sieves used as adsorbents, catalysts, etc.
Description
The present invention is relevant a kind of new crystal class microporosity molecular sieve, its preparation method, and about they purposes as sorbent material and catalyzer.The invention relates to the new manganese-al-p-silicon-oxide molecular sieve that contains tetrahedral oxide skeleton form.These compositions can prepare by the gelinite of hydro-thermal from the active compound that contains manganese, aluminium, phosphorus and the silicon that can form the tetrahedral oxide skeleton, and preferably contain a kind of organic formwork agent (Organic templating agent) at least, this organic formwork agent can play partial action in the process of determining crystallization mechanism and the configuration aspects of crystalline product.
The molecular sieve of crystalline aluminosilicate zeolitic type has been known at process aspect, and the composition of naturally occurring and synthetic, and is existing now more than 150 kinds.Usually, crystalline zeolite is by being total to angle (Corner-Sharing) AlO
2And SiO
2Tetrahedron forms, and its characteristics are to have pore openings of uniform size, has significant loading capacity, and be that reversibly desorb is adsorbed phase (adsorbed phase), this being adsorbed is to be dispersed in the whole internal cavity of crystalline mutually, do not form fixedly any atom of crystalline texture and do not replace.
In addition, known: as not to be other crystalline microporous compositions of zeolite, just not contain AlO as the basic framework component
2The tetrahedral crystal microporous compositions, still, these compositions have the ion-exchange and/or the characterization of adsorption of zeolite.Be considered to have ion-exchange performance, have even hole and reversibly the adsorbed molecules diameter be about 6
Perhaps more micromolecular metal organosilicate.Be presented on March 2nd, 1976 in people's such as Dwyer the United States Patent (USP) 3,941,871 and reported.In addition, be presented on December 6th, 1977 and disclosed a kind of have molecular sieve character and cation not the pure silicon dioxide polymorphic form of the neutral backbone of cation lattice point, silicon zeolite again neither in people's such as R.W.Grose the United States Patent (USP) 4,061,724.
Recently not have the Zn-Al-P-Si-oxide molecular sieve of silicon-dioxide be United States Patent (USP) 4 people such as Wilson to the basic framework of the microporous compositions kind of report and synthetic, 310, the crystalline aluminium phosphate composition that discloses in 440, this United States Patent (USP) are promulgations on January 12 nineteen eighty-two.These materials are by AlO
2And PO
2Tetrahedron forms, and is electricity price neutral skeleton as the silicon-dioxide polymorphic form.Because there are not the positively charged ion of outer structure in SiO 2 molecular sieve, silicon zeolite, are hydrophobic naturies; (Silicalite) is different with SiO 2 molecular sieve, silicon zeolite, and aluminophosphate molecular sieve has moderate wetting ability, and this obviously is because the difference on electronegativity between aluminium and the phosphorus.Their intracrystalline micro pore volumes can be compared with SiO 2 molecular sieve with known zeolite with micro-pore diameter.
File an application in nineteen eighty-two July 26, also in the application number that awaits the reply and made common transfer is 400,438 application documents, described the aluminate or phosphate that a kind of new silicon replaces, this salt be micro porous be again crystalloid.This material is to contain PO
+ 2, AlO
- 2And SiO
2The three-dimensional crystals skeleton of tetrahedral oxide units but do not comprise and can select any basic metal or the calcium that exist.The anhydrous experience chemistry of its synthetic state be combined into
MR: (Si
XAl
YP
Z) O
2Formula
Expression, " R " representative is present at least a organic formwork agent in the microchannel in the crystal in the formula; " m " representative is present in every mole of (Si
XAl
YP
Z) O
2In the mole number of " R ", and its numerical value is from 0 to 0.3; Maximum value separately depends on the molecular size of template and the utilized hole volume of the microchannel that depends on relevant aluminosilicophosphate class; " X ", " Y " and " Z " represent the mole fraction of the silicon, aluminium and the phosphorus that exist as tetrahedral oxide respectively.The minimum value separately of " X ", " Y " and " Z " is 0.01, and preferable is 0.02.The maximum value of " X " is 0.98; The maximum value of " Y " is 0.60; The maximum value of " Z " is 0.52.These aluminosilicophosphates have aluminosilicate zeolites and more peculiar physics of aluminate or phosphate and chemical property.
File an application in nineteen eighty-three March 31, also disclosed a kind of new titaniferous molecular sieve in the U. S. application that awaits the reply and made common transfer number is 480,738 application documents, the chemical constitution of its synthetic state and anhydrous form can be used chemical empirical formula
MR: (Ti
XAl
YP
Z) O
2Expression
" R " representative is present at least a organic formwork agent in the microchannel in the crystal in the formula; " m " representative is present in every mole of (Ti
XAl
YP
Z) O
2In the mole number of " R ", and its numerical value is between 0 and about 5.0; " X ", " Y " and " Z " represent the molar fraction of the titanium, aluminium and the phosphorus that exist as tetrahedral oxide respectively.
File an application in nineteen eighty-three July 15, also in the U. S. application that awaits the reply and made common transfer number is 514,334 application documents, disclosed a kind of new MO with three-dimensional microporous framework structure
2, AlO
2, and PO
2The crystal metal aluminate or phosphate of tetrahedron element, its moisture-free basis experience chemical constitution can be used formula
mR∶（M
XAl
YP
Z）O
2
Expression.
" R " representative is present at least a organic formwork agent in the microchannel in the crystal in the formula; " m " representative is present in every mole of (M
XAl
YP
Z) O
2In the mole number of " R ", and its numerical value is from 0 to 0.3; " M " represents at least a metal in magnesium, manganese, zinc and the cobalt metal group; " X ", " Y " and " Z " represent the molar fraction of the metal " M ", aluminium and the phosphorus that exist as tetrahedral oxide respectively.
File an application in nineteen eighty-three July 15, also in the U. S. application that awaits the reply and made common transfer number is 514,335 application documents, disclosed a kind of new FeO with three-dimensional microporous framework structure
2, AlO
2And PO
2The crystallization iron aluminium phosphate of tetrahedron element, its moisture-free basis experience chemical constitution can be used formula
mR∶（Fe
XAl
YP
Z）O
2
Expression.
" R " representative is present at least a organic formwork agent in the microchannel in this crystal in the formula; " m " representative is present in every mole of (Fe
XAl
YP
Z) O
2In the mole number of " R ".And its numerical value is from 0 to 0.3; " X ", " Y ", " Z " represent the molar fraction of the iron, aluminium and the phosphorus that exist as tetrahedral oxide respectively.
The invention relates to by MnO
-2 2, AlO
- 2, PO
+ 2And SiO
2A kind of recruit's sieve of forming of skeleton tetrahedron element.
Fig. 1 is a ternary phase diagrams, and the variable (parameter) of the relevant present composition is defined as molar fraction among the figure.
Fig. 2 is that the variable (parameter) of the relevant composition of preferentially selecting for use among a ternary phase diagrams, the figure is defined as molar fraction.
Fig. 3 is a ternary phase diagrams, and the relevant variable (parameter) that is used to prepare the reaction batching of the present composition is defined as molar fraction among the figure.
The present invention is relevant a kind of new molecular sieve, and this molecular sieve is to have MnO-2 2、AlO
- 2、PO
+ 2And SiO2A kind of three-dimensional micropore crystallization skeleton structure of tetrahedral oxide units. These new manganese-al-p-silicon-oxide molecular sieves show the performance of ion-exchange, absorption and catalytic action, and have therefore found the extensive use as adsorbent and catalyst. The inscape of this new composition contains MnO-2 2、AlO
- 2、PO
+ 2And SiO2Its moisture-free basis unit empirical formula of tetrahedron oxidation can be used formula
mR∶（Mn
WAl
XP
YSi
Z）O
2
Expression.
" R " representative is present at least a organic formwork agent in the microchannel in the crystal in the formula; " m " represents every mole of (Mn
WAl
XP
YSi
Z) O
2The total moles of " R " that is provided, and its numerical value is from 0 to about 0.3; In addition, " W ", " X ", " Y " and " Z " represent the molar fraction as manganese, aluminium, phosphorus and the silicon of tetrahedral oxide existence respectively.
The present invention to combination of molecular sieve of the present invention and known molecular sieve so far, and comprises that the difference of above-mentioned ternary composition is illustrated aspect several.Molecular sieve characteristics of the present invention are to have improved thermostability and are to have made also undiscovered so far binary and ternary molecular sieve.
Molecular sieve of the present invention generally is abbreviated as: " MnAPSO ", it represents MnO
-2 2, AlO
- 2, PO
+ 2And SiO
2The structural framework of tetrahedron element.
By specifying a numeral for relevant type, can be with actual classification as identification to structure type, so actual classification number discerned by " MnAPSO-i ", wherein i is an integer.Do not plan given typonym is expressed as with any other type by number system name structural similarity is arranged.
That the present invention relates to is a kind of MnO of novel type
-2 2, AlO
- 2, PO
+ 2And SiO
2The molecular sieve of the three-dimensional micropore lattice framework of tetrahedral oxide units.This novel molecular sieve has ion-exchange, absorption and catalysis characteristics, therefore, and widely as sorbent material and catalyzer.
Molecular sieve of the present invention has MnO
-2 2, AlO
- 2, PO
+ 2And SiO
2The tetrahedron element skeleton, express anhydrous matrix with empirical formula and form:
mR∶（Mn
WAl
XP
YSi
Z）O
2
Wherein " R " represents in the crystal and has a kind of organic formwork agent at least in the microchannel; " m " represents every mole of (Mn
WAl
XP
YSi
Z) O
2In the mole number of " R ", its value is about 0 to 0.3; " W " " X " " Y " and " Z " represent the molar fraction of element manganese, aluminium, phosphorus and silicon as tetrahedral oxide respectively.In general, molar fraction " W " " X " " Y " and " Z " are limited at by in A, B, C, D and the determined pentagon composition of E 5 points (Fig. 1 ternary phase diagrams) district, preferably in the tetragonal composition district that a, b, c and d 4 points (Fig. 2 ternary phase diagrams) limit.A, B, C, D and E point have following " W " " X " " Y " and " Z " value among Fig. 1:
The point molar fraction
X Y （W+Z）
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
A, b, c, d point have following " W " " X " " Y " and " Z " value among Fig. 2:
The point molfraction
X Y （W+Z）
a 0.55 0.43 0.02
b 0.43 0.55 0.02
c 0.10 0.55 0.35
d 0.55 0.10 0.35
MnAPSO of the present invention is as sorbent material, catalyzer, ion-exchanger, and very different although its chemistry and physical properties are compared with present used pure aluminium silicate, profile is very similar.
The MnAPSO composition is generally by the reaction source that contains manganese, silicon, aluminium and phosphorus and organic formwork agent (being the structure direction agent) and/or the basic metal of choosing wantonly or the reaction mixture of other metal, and is synthetic through the hydrothermal crystallization method.Wherein organic formwork agent with the compound of VA family element in the periodictable for well.Generally reaction mixture is placed the seal-off pressure container, preferably be lined with inert plastic material (as poly-tetrafluoroethylene) in the container, heating, at 50～250 ℃, preferably in 100～200 ℃ of scopes, be advisable to be under the autogenous pressure, until obtaining the MnAPSO crystal product, the used time be several hours to several weeks.Be 2 hours to 30 days typical working lipe, has been found that 4 hours to 20 days and get final product.With any easy method, as centrifugal or filtered and recycled product.
Synthetic MnAPSO composition of the present invention, with molar ratio expression response constituents of a mixture, as shown in the formula:
aR∶（Mn
WAl
XP
YSi
Z）O
2∶bH
2O
Wherein " R " is a kind of organic formwork agent; " a " is the amount of organic formwork agent " R ", and its value is 0 to about 6 scopes, and best significant quantity is greater than 0 to about 6; " b " value is about 0 to 500, is preferably in about 2～300; " W " " X " " Y " and " Z " value are represented the molar fraction of manganese, aluminium, phosphorus and silicon respectively, and each value all is not less than 0.01.
More particularly, general its molar fraction of selected reaction mixture " W " " X " " Y " and " Z " will be in F, G, H, I and the determined pentagon composition of J 5 points (Fig. 3 ternary phase diagrams) districts, and the F among Fig. 3, G, H, I and J point have following " W " " X " " Y " and " Z " value:
The point molfraction
X Y （W+Z）
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
When utilizing x-ray analysis check reactor product, not that each reaction mixture can both produce crystallization MnAPSO product, its reason is not clear at present.Those reaction mixtures that can obtain crystallization MnAPSO product provide in the embodiment that indicates numeral of back, and those can not identify that with x-ray analysis the reaction mixture of MnASPO product is also come out by report.
In the above-mentioned expression of response composite, with the total value of relevant " W " " X " " Y " and " Z " with reactant normalization method, feasible (W+X+Y+Z)=1.00 mole, in an embodiment, the molar ratio expression response mixture of usefulness oxide compound, but also normalizing to P
2O
5Mole number.Remove the mole number (comprising template and water) of each component with the total mole number of manganese, aluminium, phosphorus and silicon, calculate by such routine, make easily the back plant formal transformation become before the kind form, the molar fraction that so just can obtain based on the normalization method of the total mole number of above-mentioned each component.
For producing in the reaction mixture that molecular sieve of the present invention prepares, it is any that organic formwork agent uses in the time of can being synthetic general at present aluminosilicate zeolite.In general, these compounds contain V A family element in the periodic table of elements, particularly nitrogen, phosphorus, arsenic, antimony, wherein nitrogen or phosphorus are better, best is nitrogen, and these compounds at least also contain a kind of alkyl or aryl of 1～8 carbon atom, and the compound that optimum is done organic formwork agent is amine quaternary phosphonium compound and quaternary ammonium compound, generally uses R for back two kinds
4X
+Formula represents that wherein " X " is nitrogen or phosphorus, and each R is the alkyl or aryl that contains 1～8 carbon atom.Polyquaternium such as X value are not less than 2 [(C
14H
32N
2) (OH)
2]
xAlso be suitable for.It is useful using monoamine, diamine, triamine separately or being used in combination with quaternary ammonium compound or other template.The mixture of two or more template can produce desired MnAPSOs mixture, and the template that perhaps has strong directive action can be controlled the process of reaction, and is mainly established the pH condition of reaction gel by other template.Typical template comprises: the tetramethylammonium ion; The Tetrylammonium ion; The tetrapropylammonium ion; The tetrabutylammonium ion; 4 penta ammonium ions; The 2-Tri N-Propyl Amine; Tripropyl amine; Triethylamine; Trolamine; Piperidines; Hexahydroaniline; The 2-picoline; N, N-diformazan benzylamine; N, N '-dimethylethanolamine; Choline; N, N '-lupetazin; 1, heavy azabicyclic (2,2, the 2) octane of 4-; N methyldiethanol amine; The N-Mono Methyl Ethanol Amine; The N-picoline; The 3-methyl piperidine; N-methylcyclohexylamine; The 3-picoline; The 4-picoline; Rubane; N, N '-dimethyl-1, heavy azabicyclic (2,2,2) the octane ion of 4-; The 2-n-Butyl Amine 99; Neopentyl amine; The 2-n-amylamine; Isopropylamine; TERTIARY BUTYL AMINE; 1, tetramethyleneimine and 2-imidazolone.Not that every kind of template can both orientation produce various MnAPSO; If suitable control reaction conditions, only a kind of template just can orientation produce several MnAPSO compositions, also can produce a kind of desired MnAPSO composition with several different template.
The activated source of silicon can be silicon sol or powdered silica, also can be alkoxide, silicic acid or the alkalimetal silicate etc. of the armorphous deposition of silica of reactive solid, silica gel, silicon.
Active phosphorus source is a phosphoric acid, but that organophosphate can be thought as the triethyl phosphine hydrochlorate is satisfied, therefore also crystal formation or armorphous aluminophosphates such as U.S.P4, the AlPO in 310,440
4Composition.Organo phosphorous compounds clearly can not be as the activated source of phosphorus as bromination tetrabutyl phosphorus, but these compounds can play the effect of template.Conventional microcosmic salt such as sodium-metaphosphate can use, and can be used as part phosphorus source at least, but inadvisable.
Desirable aluminium source is an aluminium alkoxide, as aluminium isopropoxide, or pseudobochmite.Being suitable for crystal formation or the armorphous aluminate or phosphate of doing the phosphorus source also is suitable aluminium source certainly.Be used for other aluminium source such as gibbsite of zeolite synthesis, sodium aluminate and alchlor also can be used, but inadvisable.
The manganese source can be introduced in the reaction system in any form, and this form can be allowed and formed active manganese in position, can form the tetrahedron skeleton unit of manganese.The manganic compound that can adopt comprises oxide compound, alkoxide, acetate, oxyhydroxide, muriate, bromide, iodide, vitriol, nitrate, carboxylate salt etc., and for example, manganese acetate, Manganese dibromide, manganous sulfate etc. here all can adopt.
For synthetic MnAPSO composition, stir or other suitable stirring reaction mixtures, and/or in reaction mixture, introduce on MnAPSO crystal seed to be produced or the topology similarly aluminophosphates, the crystal seed of silico-aluminate or combination of molecular sieve all can promote the crystalline step, but all not necessarily.
After crystallization, the MnAPSO product can separate, and washes with water and at air drying.As the MnAPSO of synthetic state, in its interior microchannel, generally contain at least a template that in it forms, adopts.Usually have the organism of deriving out from organic formwork agent, at least a portion is that the positively charged ion as balancing charge exists, as from containing the situation that the organism reaction system prepares the aluminosilicate zeolite of synthetic state.Yet, might be in specific MnAPSO system, partly or entirely organism is a kind of occlusion molecule.As general rule,, thereby can not pass freely through the micropore of MnAPSO product and must under 200～700 ℃, remove by the organic substance that is sintered into thermal destruction because template and occlusion organic moiety are too big.Under a few cases, the micropore of MnAPSO product is wide enough so that template can move, if template small molecules especially by the desorption step of routine such as the carrier band in the zeolite situation, correspondingly can be removed all or part of template.Should understand, here used predicate " synthetic state " does not comprise the condition of MnAPSO phase, MnAPSO mutually in, the machine that occupies the intercrystalline microchannel that produces as the hydrothermal crystallization process has the amount of part, reduce because of synthetic processing the in back, cause composition mR like this: (Mn
WAl
XP
YSi
Z) O
2Middle m value is less than 0.02.Other symbol such as above-mentioned definition in the formula.Adopt in the preparation of alkoxide as the activated source of manganese, aluminium, phosphorus or silicon at these, corresponding alcohol certainly exists in reaction mixture, and this is because it is the hydrolysate of alkoxide.Whether this alcohol adds building-up process as template also is provided with definite.Yet, for the application's purpose, can from the kind of template, remove this alcohol artificially, even it is present in the MnAPSO material of synthetic state.
Because this MnAPSO composition by band-2 ,-1 respectively ,+the tetrahedron MnO of 1 and 0 net charge
2, AlO
2, PO
2And SiO
2Form, its cation exchange property than the situation complexity of zeolite molecular sieve many, in zeolite molecular sieve, between AlO tetrahedron and charge balance cation, have a stoichiometric relation really.In this composition, AlO
- 2Tetrahedron or with relevant PO
- 2Tetrahedron or simple positively charged ion such as alkali metal cation are present in the mn ion in the reaction mixture, perhaps with by template deutero-organic cation have electrobalance.Similarly, MnO
-2 2Tetrahedron and relevant PO
+ 2Tetrahedron, mn ion, has electrobalance by template deutero-organic cation, simple positively charged ion such as alkali metal cation or extraneous other divalence or the polyvalent cation that comes.Also supposed the AlO of non-vicinity
- 2Tetrahedron is to can be respectively and Na
+And OH
-Reach electrobalance (Flanigen and Grose.Molecular Sieve Zeolites-I, ACS.Washington.DC(1971)).
When MnAPSO composition usefulness of the present invention is analyzed the ion exchange technique that aluminosilicate zeolite adopted up to now, demonstrate cation exchange capacity (CEC).And the inherent micro-pore diameter is arranged in each crystalline network, and its value is at least about 3A.Usually have only and remove from the duct because of behind the synthetic organism that exists, the ion-exchange of MnAPSO composition is only possible.Usually will dewater with the moisture content in the MnAPSO composition of removing synthetic state, will be removed to a certain degree at least, be not remove organicly in common state, can help absorption and desorption process behind the organic substance greatly but remove.The MnAPSO composition has hydro-thermal and thermal stability in various degree, and some highly significants are in this respect arranged, and will be as adsorbent of molecular sieve and hydrocarbon conversion catalyst or catalyst matrix use.
MnAPSO produces with the stainless steel reaction container usually, pollutes for preventing reactant, and the stainless steel reaction container is lined with inert plastic material teflon lined.Usually, therefrom crystallization goes out the final reacting mixture of each MnAPSO composition, is by making the mixture of a part of reagent, then single or add in these mixtures with the intermediate blend of two or more reagent and prepare.Under the certain situation, the reagent of fusion remains unchanged in intermediate blend, and in other cases, partly or entirely reagent generation chemical reaction and generate new reagent.Term " mixture " is applicable to two kinds of situations.Also have, except as otherwise noted, every kind of intermediate blend and final reacting mixture, all to stir up to basic evenly till.
Reaction product is to utilize the x-ray powder diffraction technique of standard to finish x-ray analysis.Source of radiation is a high-intensity copper target X-ray tube with 50 kilovolts and 40 milliamperes controls.By an X-ray spectrum scintillation counter, pulsed height analyzer and chart recorder are suitably noting from the diffraction pattern of copper K-α radiation and graphite monochromator.The powder sample that flattens is with 2 grades of time constants, with 2 ° (2 θ)/minute scan.Can draw spacing (d) from the position of the represented diffraction peak of 2 θ, its unit is
, the θ here is observed Blang's lattice (Bragg) angle from the chart.After background correction, determine intensity by the height of diffraction peak, I
0Be the intensity at the strongest line or peak, I is other each peak intensity.Change kind of a mode, the copper K-α radiation that the X-ray pattern can be obtained by the computer technology of the D-500X-C-ray powder diffraction instrument that utilizes Siemens Company, Siemens K-805X-gamma ray source (purchasing in Siemens Company Cherry Hill.New Jersey) and suitable computer interface and obtaining.
As present technique field professional understood, location parameter 2 θ are subjected to the influence of artificial and two factors of mechanical error, can add ± 0.4 ° of non-quantitative pact on the 2 θ values of whenever measuring.Certainly, this indefinite amount also is with the spacing value representation of measuring, and these values are calculated by 2 θ values.
Tolerance range is general in this technology inadequately, but also can not get rid of the crystallization composition material considered fully each other and the difference between the composition of they and prior art.The report some X-ray diffraction styles in, the relative intensity of spacing respectively with symbol VS, S, m, W and VW represent very strong, strong, in, weak and very weak.
In some cases, the purity of sintetics can be estimated with reference to its X-ray powder diffraction style.For example,, so just only refer to that this sample X-ray pattern does not have to be summed up as the spectral line of crystalline impurity, rather than refer to not have unbodied material to exist if a sample is pure.
Molecular sieve of the present invention is to represent its feature with X-ray powder diffraction style, and to list X-ray pattern data among Table A-K.Wherein said X-ray pattern is applicable to two kinds on synthesis type and roasting type otherwise indicated.
Table A (MnAPSO-5)
2 θ d(
) relative intensity
7.3-7.7 12.11-11.48 is very strong
14.7-15.1 among the 6.03-5.87
19.6-19.9 among the 4.53-4.46
20.8-21.3 among the 4.27-4.17
22.1-22.6 among the 4.02-3.93
29.8-30.2 among the 2.988-2.959
Table B(MnAPSO-11)
2 θ d(
) relative intensity
9.4-9.8 among the 9.41-9.03
16.1-16.2 5.50-5.47 is very strong-in
21.0-21.5 among the 4.23-4.13-very strong
22.1-22.2 among the 4.02-4.00
22.4-22.5 among the 3.97-3.95-strong
23.1-23.5 among the 3.85-3.79
Table C(MnAPSO-16)
2 θ d(
) relative intensity
11.4-11.5 among the 7.76-7.69-very strong
18.6-18.7 among the 4.77-4.75
21.9 in 4.06-very strong
22.9-23.0 a little less than the 3.88-3.87-in
26.5-26.6 among the 3.363-3.351
29.7-29.8 among the 3.008-2.998
Table D(MnAPSO-20)
2 θ d(
) relative intensity
13.904-13.998 among the 6.3692-6.3263-very strong
19.723-19.818 among the 4.5011-4.4918
24.223-24.329 3.6742-3.6584 is very strong
28.039-28.163 a little less than the 3.1822-3.1684
31.434-31.560 a little less than the 2.8458-2.8348
34.527-34.652 a little less than the 2.5976-2.5886
Table E(MnAPSO-31)
2 θ d(
) relative intensity
8.482-9.501 among the 10.4240-9.3084
20.222-20.353 among the 4.3913-4.3632
21.879-21.993 among the 4.0622-4.0415
22.071-22.088 among the 4.0272-4.0242
22.587-22.698 3.9364-3.9174 is very strong
31.724-31.836 among the 2.8546-2.8108
Table F(MnAPSO-34)
2 θ d(
) relative intensity
9.4-9.6 9.41-9.21 is very strong
15.9-16.2 among the 5.57-5.47
20.4-20.8 among the 4.35-4.27-very strong
25.0-25.3 a little less than the 3.562-3.520-in
31.0-31.3 a little less than the 2.885-2.858-in
33.6-33.9 among the 2.667-2.644
Table G(MnAPSO-35)
2 θ d(
) relative intensity
10.8-11.0 among the 8.19-8.04-very strong
13.4-13.7 among the 6.61-6.46-strong
17.2-17.5 among the 5.16-5.07-strong
20.8-21.0 among the 4.27-4.23
21.8-22.3 among the 4.08-3.99-very strong
28.2-28.7 among the 3.164-3.110
Table H(MnAPSO-36)
2 θ d(
) relative intensity
7.596 in 11.6382
7.628-7.981 11.5899-11.0771 is very strong
8.105-8.299 among the 10.9084-10.6537
16.395-16.673 among the 5.4066-5.3172
19.052-19.414 a little less than the 4.6580-4.5721
20.744-20.871 among the 4.2819-4.2560
Table J(MnAPSO-44)
2 θ d(
) relative intensity
9.420-9.498 9.3883-9.3110 is very strong
16.062-16.131 among the 5.5179-5.4944
20.715-20.790 4.2877-4.2725 is strong
24.396-24.424 among the 3.6485-3.6444
26.143-26.184 among the 3.4085-3.4032
30.833-30.853 among the 2.8999-2.8981
Table K(MnAPSO-47)
2 θ d(
) relative intensity
9.434-9.696 9.3746-9.1214 is very strong
15.946-16.276 5.5579-5.4457 is very weak
20.539-20.940 4.3242-4.2423 is very weak-in
24.643 a little less than in the of 3.6125
30.511 a little less than in the of 2.9297
30.820-31.096 2.9011-2.8759 is very weak
Preparation reagent
In following example, the many reagent of preparation composition MnAPSO, agents useful for same and abbreviation title thereof are as follows:
(a), Alipro: aluminum isopropoxide;
(b), the trade mark of the false boehmite of CATAPAL:Condea company hydration;
(c), LUDOX-LS: silicon sol-LS is a 30%(weight) SiO
2With 0.1%(weight) Na
2The trade(brand)name of O aqueous solution Dupont;
(d), H
3PO
4: 85% phosphate aqueous solution;
(e), Mn(AC)
2: manganese acetate, Mn(C
2H
3O
2)
24H
2O;
(f), TEAOH: the tetraethyl ammonium hydroxide 40%(weight) aqueous solution;
(g), TBAOH: the TBAH 40%(weight) aqueous solution;
(h), Pr
2NH: two-Tri N-Propyl Amine;
(i), Pr
3N: tripropyl amine (trimpropylamine) (C
3H
7)
3N;
(j), Quin: rubane, (C
7H
13N);
(k), MQuin: methyl quinuclidine ring oxyhydroxide, (C
7H
13NCH
3OH);
(l), C-hex; Hexahydroaniline;
(m), TMAOH; Tetramethylammonium hydroxide;
(n), TPAOH; TPAOH;
(o), DEEA; The 2-DEAE diethylaminoethanol.
Preparation technology
Following preparation example be through H
3PO
4Be added in 1 half the water and the beginning reaction mixture that generates.After this mixture mixing, again aluminum isopropoxide or CATAPAC are added in this mixture.Till being mixed to evenly.Add silicon sol to this mixture, mix resulting mixture (about 2 minutes) afterwards till evenly.Be second part of mixture of water preparation with manganese acetate all the other (about 50%).Till being mixed to two parts of mixtures evenly.Organic formwork agent is added in the resulting mixture, and with this mixture mixing, promptly 2-4 minute (surveying the pH value and the attemperation of this mixture).Afterwards mixture is put into the stainless steel pressure device of lining,, perhaps put in the container of band screw plug, in 100 ℃ of following hydrolysis in a temperature (150 ℃ or 200 ℃) hydrolysis for some time.Whole hydrolysis is to carry out under the pressure that self produces.
The mole composition of recently representing prepared each batch product with the relative mole of reaction mixture components.The H of reaction mixture
3PO
4And Mn(AC)
2Content is used P respectively
2O
5Represent with MnO.
Following embodiment is for further illustrating the present invention, rather than this is limited:
Example 1-64
According to above-mentioned relevant prepared MnAPSO molecular sieve, and with x-ray analysis product MnAPSO.Below the results are shown in of example 1 to 64 in table I-IV.
The table I
Example
1The template temperature (℃) time (my god) the MnAPSO product
2
1 TEAOH 150 4 MnAPSO-34;MnAPSO-5
2 TEAOH 150 11 MnAPSO-5;MnAPSO-34
3 TEAOH 200 4 MnAPSO-5;MnAPSO-34
4 TEAOH 200 11 MnAPSO-5;MnAPSO-34
5 TEAOH 100 2 -3
6 TEAOH 100 7 MnAPSO-34;
7 TEAOH 150 2 MnAPSO-34;MnAPSO-5
8 TEAOH 150 7 MnAPSO-34;MnAPSO-5
9 TEAOH 200 2 MnAPSO-5;MnAPSO-34
10 TEAOH 200 7 MnAPSO-5;MnAPSO-34
11 TEAOH 100 14 MnAPSO-34;
12 TEAOH 150 14 MnAPSO-34;MnAPSO-5
13 TEAOH 200 14 MnAPSO-5;MnAPSO-34
1, the formation of reaction mixture:
1.OTEAOH: 0.2MnO: 0.9Al
2O
3: 0.9P
2O
5: rSiO
2: 50H
2O wherein " r " is 0.2 for example 1-4; Example 5-13 is 0.6.
2, utilize X-ray powder diffraction style
The main type of fixed output quota product, when identifying two kinds, listed first type is exactly viewed main type.
3, utilize x-ray analysis not observe the MnAPSO product.
The table II
Example
1The template temperature (℃) time (my god) the MnAPSO product
2
14 Quin 150 4 MnAPSO-16;MnAPSO-35
15 Quin 150 11 MnAPSO-16;MnAPSO-35
16 Quin 200 4 MnAPSO-16;MnAPSO-35
17 Quin 200 11 MnAPSO-16;MnAPSO-35
18 Quin 100 4 MnAPSO-35;
19 Quin 100 11 MnAPSO-35;
20 MQuin 150 2 MnAPSO-35;MnAPSO-16
21 MQuin 150 7 MnAPSO-35;
22 MQuin 200 2 MnAPSO-35;
23 MQuin 200 7 MnAPSO-35;
24 Pr
2NH 150 4 MnAPSO-11;
25 Pr
2NH 150 11 MnAPS-11;
26 Pr
2NH 200 4 MnAPS-11;MnAPSO-39
27 Pr
2NH 200 11 MnAPS-11;MnAPSO-39
28 Pr
2NH 100 4 -3
29 Pr
2NH 100 11 -3
1, reaction mixture constitutes:
1.0R: 0.2MnO: 0.9Al
2O
3: 0.9P
2O
5: 0.2SiO
2: 50H
2O wherein " R " is a template, and is consistent with the table II.
2, utilize X-ray powder diffraction style
The main type of fixed output quota product, if identify two kinds, listed first type is exactly viewed main type.
3, utilize x-ray analysis not observe the MnAPSO product.
The table III
Example
1The template temperature (℃) time (my god) the MnAPSO product
2
30 Pr
3N 150 4 MnAPSO-5
31 Pr
3N 150 11 MnAPSO-5
32 Pr
3N 200 4 MnAPSO-5
33 Pr
3N 200 11 MnAPSO-5
34 Pr
3N 100 4 -3
35 Pr
3N 100 11 -3
36 TBAOH 150 4 -3
37 TBAOH 150 10 -3
38 TBAOH 200 4 MnAPSO-5
39 TBAOH 200 10 MnAPSO-5
40 C-hex 150 3 MnAPSO-13
41 C-hex 150 9 MnAPSO-44;MnAPSO-13
42 C-hex 200 3 MnAPSO-5;MnAPSO-44
43 C-hex 200 9 MnAPSO-5;MnAPSO-44
1, reaction mixture constitutes:
A) example 30-35:
1.0Pr
3N∶0.2MnO∶0.9Al
2O
3∶0.9P
2O
5∶0.2SiO
2∶50H
2O
B) example 36-39:
2.0TBAOH∶0.4MnO∶0.8Al
2O
3∶1.0P
2O
5∶0.4SiO
2∶50H
2O
C) example 40-43:
1.0C-hex∶0.2MnO∶0.9Al
2O
3∶0.9P
2O
5∶0.6SiO
2∶50H
2O
2, utilize X-ray powder diffraction style
The main type of fixed output quota product, if identify two kinds, listed first kind is exactly viewed main type.
3, do not observe the MnAPSO product with x-ray analysis.
The table IV
Example
1The template temperature (℃) time (my god) the MnAPSO product
2
44 TPAOH 150 2 MnAPSO-5
45 TPAOH 200 2 MnAPSO-5
46 TMAOH 150 4 MnAPSO-20
47 TMAOH 200 4 MnAPSO-20
48 DEA 150 9 MnAPSO-47
49 DEA 150 18 MnAPSO-47
50
4Pr
2NH 150 4 MnAPSO-31
51
4Pr
2NH 150 10 MnAPSO-31;MnAPSO-46
52
4Pr
2NH 200 4 MnAPSO-31;MnAPSO-11
53
4Pr
2NH 200 10 MnAPSO-31;MnAPSO-11
54
4Pr
2NH 150 2 MnAPSO-31;
55
4Pr
2NH 150 2 MnAPSO-31;
56
4Pr
2NH 200 2 MnAPSO-31;MnAPSO-11
57 Pr
2NH 200 25 MnAPSO-11;MnAPSO-5
MnAPSO-39;MnAPSO-46
58 Quin 225 5 MnAPSO-16;MnAPSO-35
59
5Pr
3N 150 2 MnAPSO-36;
60
5Pr
3N 150 7 MnAPSO-36;MnAPSO-5
61
5Pr
3N 200 2 MnAPSO-36;MnAPSO-5
62
5Pr
3N 200 7 MnAPSO-36;MnAPSO-5
63 C-hex 225 5 MnAPSO-5;MnAPSO-44
64 C-hex 200 4 MnAPSO-44;
1, reaction mixture constitutes:
1.0R∶0.2MnO∶0.9Al
2O
3∶0.9P
2O
5∶0.6SiO
2∶50H
2O
Wherein R is with top consistent, and except example 48,49,57 and 64, the mole number of R is 2.0, example 58, P
2O
5Coefficient be 1.0 rather than 0.9.
2, utilize X-ray powder diffraction style
The main type of fixed output quota product, when identifying two kinds, listed first type is exactly viewed main type.
3, utilize x-ray analysis not observe the MnAPSO product.
4, use the crystal seed AlPO of (United States Patent (USP) 4310440)
4-31.
5, use the crystal seed MnAPSO-36 of the U.S. in the application 514334 that proposes July 15 nineteen eighty-three.
Example 65
(a) sample with the MnAPSO product places air or nitrogen roasting, removes the organic formwork agent in a part of product, has provided the example for preparing given MnAPSO product in the bracket.Utilize the McBain-Bakr weight of standard to adsorb the loading capacity that instrument is measured various sintered samples.Before the mensuration, be placed on activation (less than 0.04 torr) under 350 ℃ the vacuum to sample, hereinafter list the McBain-Bakr data of above-mentioned MnAPSO molecular sieve:
(a) the MnAPSO-5(example 31)
Adsorbate motion diameter
Pressure (torr) temperature (℃) absorption weight %
*
O
23.46 102 -183 8.9
O
23.46 750 -183 10.8
N-butane 4.3 504 23.0 4.4
Hexanaphthene 6.0 65 23.4 5.4
H
2O 2.65 4.6 23.0 8.1
H
2O 2.65 19.5 23.0 17.1
*MnAPSO-5 roasting 4 hours in 600 ℃ air.
The aperture of above digital proof agglomerating MnAPSO-5 product is greater than 6.2
(b) the MnAPSO-11(example 24)
Adsorbate motion diameter
Pressure (torr) temperature (℃) absorption weight %
*
O
23.46 106 -183 7.0
O
23.46 744 -183 11.1
Neopentane 6.2 741 25.3 2.5
Trimethylmethane 5.0 740 24.2 3.5
Hexanaphthene 6.0 82 23.9 10.7
H
2O 2.65 4.6 24.9 5.1
H
2O 2.65 19 24.8 14.9
*MnAPSO roasting 2 hours in 600 ℃ of air.
The aperture of above digital proof agglomerating MnAPSO-11 product is approximately 6.0
(c) the MnAPSO-20(example 46)
Adsorbate motion diameter
Pressure (torr) temperature (℃) absorption weight %
*
O
23.46 102 -183 0.7
O
23.46 744 -183 1.2
H
2O 2.65 4.6 23.3 9.0
H
2O 2.65 19 23.2 13.7
*MnAPSO was 500 ℃ of air roastings 1 hour.
The aperture of above digital proof agglomerating MnAPSO-20 product is greater than 2.65
, less than 3.46
(d) the MnAPSO-31(example 55)
Adsorbate motion diameter
Pressure (torr) temperature (℃) absorption weight %
*
O
23.46 105 -183 5.6
O
23.46 741 -183 9.7
Neopentane 6.2 739 23.5 4.6
H
2O 2.65 4.6 23.8 5.8
H
2O 2.65 20 24.0 15.5
*MnAPSO-31 roasting 1.5 hours in 500 ℃ of air.
The aperture of the MnAPSO-31 product of above digital proof roasting is greater than 6.2
(e) the MnAPSO-34(example 11)
Adsorbate motion diameter
Pressure (torr) temperature (℃) absorption weight %
*
O
23.46 103 -183 11.4
O
23.46 731 -183 15.6
Trimethylmethane 5.0 741 24.5 0.8
N-hexane 4.3 103 24.4 4.6
H
2O 2.65 4.6 24.4 15.2
H
2O 2.65 18.5 23.9 24.4
*MnAPSO-34 calcined two hours in nitrogen in 425 ℃.
Above data show that the aperture of calcining MnAPSO-34 product is about 4.3
(f) MnAPSO-35(embodiment 21)
Adsorbate power diameter (
) pressure (holder) temperature (℃) adsorbate weight %
O
23.46 103 -183 1.8
O
23.46 731 -183 2.6
Normal hexane 4.3 103 24.4 0.8
H
2O 2.65 4.6 24.4 9.9
H
2O 2.65 18.5 23.9 15.9
MnAPSO-35 calcined two hours in nitrogen in 500 ℃.
Above data show that the aperture of calcining MnAPSO-35 product is about 4.3
(g) MnAPSO-44(embodiment 64)
Adsorbate power diameter (
) pressure (holder) temperature (℃) adsorbate weight %
O
23.46 102 -183 18.2
O
23.46 744 -183 20.1
Normal hexane 4.3 95 23.6 1.3
Trimethylmethane 5.0 746 24.1 0.5
H
2O 2.65 4.6 24.8 22.7
H
2O 2.65 19 29.8 27.7
MnAPSO-44 calcined 1 hour in air in 500 ℃.
Above data show that the aperture of calcining MnAPSO-44 product is 4.3
Embodiment 66
Synthetic state sample to some embodiment carries out chemical analysis, indicates in bracket in order to the embodiment of given MnAPSO of preparation, and the chemical analysis results of these MnAPSO is as described below:
(a) chemical analysis of MnAPSO-5 is (embodiment 31)
Form weight percent
Al
2O
331.8
P
2O
546.4
MnO 4.1
SiO
23.0
Carbon 5.2
Loss on ignition 14.5
LOI is a loss on ignition
Above chemical analysis has provided by the represented gross product of oxide mol ratio (butt) and has consisted of: 0.058MnO, 0.312Al
2O
3, 0.327P
2O
5, 0.050SiO
2With chemical formula be (butt)
0.05R（Mn0.04Al0.45P0.47Si0.04）O
2
(b) chemical analysis of MnAPSO-11 is (embodiment 24)
Form weight percent
Al
2O
332.5
P
2O
546.7
MnO 4.3
SiO
22.1
Carbon 4.1
Loss on ignition 14.0
LOI is a loss on ignition
Above chemical analysis has provided by the represented gross product of oxide mol ratio (butt) and has consisted of: 0.061MnO; 0.319Al
2O
3; 0.329P
2O
5; 0.035SiO
2With chemical formula be (butt)
0.06R（Mn
0.04Al
0.46P
0.47Si
0.03）O
2
(c) chemical analysis of MnAPSO-20 is (embodiment 46)
Form weight percent
Al
2O
327.3
P
2O
539.6
MnO 4.6
SiO
28.0
Carbon 8.4
Loss on ignition 19.4
LOI is a loss on ignition
Above chemical analysis has provided by the represented gross product of oxide mol ratio (butt) and has consisted of: 0.065MnO; 0.268Al
2O
3; 0.279P
2O
5; 0.133SiO
2With chemical formula be (butt)
0.18R（Mn
0.05Al
0.41P
0.43Si
0.10）O
2
(d) chemical analysis of MnAPSO-31 is
Form weight percent
Al
2O
331.8
P
2O
543.8
MnO 3.2
SiO
22.6
Carbon 2.9
Loss on ignition 16.7
LOI is a loss on ignition
Above chemical analysis has provided by the represented gross product of oxide mol ratio (butt) and has consisted of: 0.058MnO; 0.312Al
2O
3; 0.309P
2O
5; 0.043SiO
2; And chemical formula (butt is:
0.04R（Mn
0.04Al
0.47P
0.46Si
0.03）O
2
(e) chemical analysis of MnAPSO-34 is (embodiment 6)
Form weight percent
Al
2O
325.0
P
2O
535.8
MnO 7.9
SiO
211.6
Carbon 3.3
Loss on ignition 19.7
LOI is a loss on ignition
Above chemical analysis has provided by the represented gross product of oxide mol ratio (butt) and has consisted of: 0.11MnO; 0.25Al
2O
3; 0.19P
2O
5; 0.19SiO
2And chemical formula (butt) is:
0.04R（Mn
0.09Al
0.38P
0.39Si
0.15）O
2
(f) chemical analysis of MnAPSO-35 is (embodiment 23)
Form weight percent
Al
2O
325.2
P
2O
541.3
MnO 7.1
SiO
24.2
Carbon 12.8
Loss on ignition 21.3
LOI is a loss on ignition
Above chemical analysis has provided by the represented gross product of oxide mol ratio (butt) and has consisted of: 0.100MnO; 0.247Al
2O
3; 0.291P
2O
5; 0.07SiO
2And chemical formula (butt) is:
0.13R（Mn
0.08Al
0.040P
0.47Si
0.06）O
2
(g) chemical analysis of MnAPSO-36 is (embodiment 59)
Form weight percent
Al
2O
327.7
P
2O
537.2
MnO 4.6
SiO
29.5
Carbon 3.0
Loss on ignition 19.6
LOI is a loss on ignition
Above chemical analysis has provided by the represented gross product of oxide mol ratio (butt) and has consisted of: 0.065MnO; 0.272Al
2O
3; 0.262P
2O
5; 0.158SiO
2; And chemical formula (butt) is:
0.03R（Mn
0.05Al
0.42P
0.41Si
0.12）O
2
(h) chemical analysis of MnAPSO-44 is (embodiment 64)
Form weight percent
Al
2O
325.8
P
2O
536.6
MnO 4.4
SiO
29.7
Carbon 2.5
Loss on ignition 23.1
LOI is a loss on ignition
Above chemical analysis has provided by the represented gross product of oxide mol ratio (butt) and has consisted of: 0.062MnO; 0.253Al
2O
3; 0.258P
2O
5; 0.161SiO
2And chemical formula (butt) is:
0.04R（Mn
0.05Al
0.41P
0.41Si
0.13）O
2
(i) chemical analysis of MnAPSO-47 is (embodiment 49)
Form weight percent
Al
2O
327.6
P
2O
536.2
MnO 5.0
SiO
25.7
Carbon 9.9
Loss on ignition 25.1
LOI is a loss on ignition
Above chemical analysis has provided by the represented gross product of oxide mol ratio (butt) and has consisted of: 0.071MnO; 0.271Al
2O
3; 0.255P
2O
5; 0.095SiO
2; And chemical formula (butt) is:
0.17R（Mn
0.06Al
0.44P
0.42Si
0.08）O
2
Embodiment 67
Transparent crystals to some embodiment product carries out the energy-dispersive X-ray analysis with EDAX() analysis that combines of microprobe SEM(scanning electronic microscope, as in the bracket hereinafter determine, crystal analysis with every kind of MnAPSO product of constitutional features provides following data according to the relative height at peak:
A) MnAPSO-5(embodiment 4):
Microcell is surveyed average
Mn 0.5
Al 8.0
P 9.5
Si 0.7
B) MnAPSO-11(embodiment 24):
Microcell is surveyed average
Mn 1.0
Al 8.0
P 9.5
Si 1.5
C) MnAPSO-20(embodiment 46):
Microcell is surveyed average
Mn 0.8
Al 8.2
P 9.4
Si 1.7
D) MnAPSO-34(embodiment 6):
Microcell is surveyed average
Mn 1.3
Al 7.0
P 9.0
Si 1.5
E) MnAPSO-35(embodiment 23):
Microcell is surveyed average
Mn 1.0
Al 7.0
P 10.0
Si 1.2
F) MnAPSO-36(embodiment 59):
Microcell is surveyed average
Mn 0.8
Al 9.3
P 9.9
Si 1.6
G) MnAPSO-44(embodiment 42):
Microcell is surveyed average
Mn 0.7
Al 9.0
P 10.0
Si 1.7
H) MnAPSO-44(embodiment 64):
Microcell is surveyed average
Mn 1.1
Al 8.7
P 10.0
Si 5.6
I) MnAPSO-47(embodiment 49):
Microcell is surveyed average
Mn 1.0
Al 9.0
P 9.5
Si 1.9
Embodiment 68
(a), embodiment 31 prepared MnAPSO-5 are carried out x-ray analysis.MnAPSO-5 is impure, and its principal phase is qualitative by the X-ray powder diffraction style with following data characteristics:
2θ d.（
） I/I
0×100
6.9
＊12.81 13
7.5 11.79 100
8.0
＊11.05 5
9.1
＊9.72 4
9.3
＊9.51 4
13.0 6.81 14
13.7
＊6.46 3
15.0 5.91 27
16.5
＊5.37 3
18.5
＊4.80 7
19.8 4.48 43
21.0 4.23 58
22.3 3.99 75
24.7 3.60 6
25.9 3.440 42
29.0 3.079 18
30.0 2.979 34
33.6 2.667 8
34.5 2.600 21
36.9 2.436 4
37.7 2.386 10
41.5 2.176 5
42.1 2.146 5
42.2 2.141 5
42.6 2.122 5
43.5 2.080 3
44.9 2.019 3
47.5 1.914 7
51.4 1.778 5
51.9 1.762 3
55.5 1.656 5
*The peak that may contain impurity
(b) with the MnAPSO-5 of the synthetic state of part in a) about 2 hours of 500 ℃ of calcinings in air.The feature of calcinate is determined by following X-ray powder diffraction style:
2θ d.（
） I/I
0×100
7.4 11.95 100
＊7.8 11.33 4
12.9 6.86 25
15.0 5.91 21
＊16.5 5.37 3
＊16.7 5.31 3
＊17.5 5.07 5
19.8 4.48 40
21.2 4.19 40
22.5 3.95 43
26.0 3.427 30
29.1 3.069 11
30.1 2.969 35
33.7 2.660 5
34.6 2.592 19
37.1 2.423 4
37.9 2.374 6
42.5 2.127 4
43.1 2.099 3
46.0 1.973 3
47.9 1.899 5
55.8 1.647 4
*May contain impurity peaks
(c) alleged here MnAPSO-5 is one and has MnO
-2 2, AlO
- 2, PO
+ 2And SiO
2The molecular sieve of the three-dimensional micropore crystalline network of tetrahedral oxide units, and an experience chemical constitution is arranged, press the butt chemical formulation:
mR∶（Mn
WAl
XP
YSi
Z）O
2
Wherein " R " representative has an organic formwork agent that is present in microchannel in the lattice at least; " m " represents every mole of (Mn
WAl
XP
YSi
Z) O
2In the mole number of " R ", its value is 0 to 0.3; And " W ", " X ", " Y ", " Z " represent the molar fraction of the manganese, aluminium, phosphorus and the silicon that exist with tetrahedron respectively, this molar fraction is made up of in the district the determined pentagon of an A, B, C, D and E in Fig. 1, more preferable than it is to form in the district with the determined quadrangle of an a, b, c and d in Fig. 2, and this MnAPSO-5 has the X-ray powder diffraction style of the feature of the d-spacing that contains at least shown in the following table V:
The table V
2 θ d.(
) relative intensity
7.3-7.7 12.11-11.48 VS(is very strong)
14.7-15.1 among the 6.03-5.87 m()
19.6-19.9 among the 4.53-4.46 m()
20.8-21.3 among the 4.27-4.17 m()
22.1-22.6 among the 4.02-3.93 m()
29.8-30.2 among the 2.998-2.959 m()
(d) though by present resulting X-ray powder diffraction data be synthetic state all have diffraction pattern in the style scope of being concluded in the following table VI with all MnAPSO-5 compositions of incinerating:
The table VI
2θ d.（
） I/I
0×100
7.3-7.7 12.11-11.48 100
12.7-13.0 6.97-6.81 14-27
14.7-15.1 6.03-5.87 20-60
19.6-19.9 4.53-4.46 36-51
20.8-21.3 4.27-4.17 29-58
22.1-22.6 4.02-3.93 30-75
24.5-24.7 3.63-3.60 4-6
25.7-26.1 3.466-3.414 25-42
28.8-29.2 3.100-3.058 10-30
29.8-30.2 2.998-2.959 34-50
33.4-33.8 2.683-2.652 4-10
34.3-34.7 2.614-2.585 19-44
36.7-37.2 2.449-2.417 3-4
37.5-38.0 2.398-2.368 5-20
41.3-41.5 2.186-2.176 3-5
41.9-42.1 2.156-2.146 4-5
42.0-42.2 2.151-2.141 3-5
42.4-42.6 2.132-2.122 3-5
43.1-43.5 2.099-2.080 3-5
44.7-44.9 2.027-2.019 3-5
46.0-46.1 1.973-1.969 3-4
47.3-47.6 1.922-1.910 5-7
47.9-48.0 1.899-1.895 4-5
51.2-51.4 1.784-1.778 5-7
51.7-51.9 1.768-1.762 3-5
55.3-55.9 1.661-1.645 2-7
Embodiment 69
(a) to carrying out x-ray analysis by embodiment 24 prepared MnAPSO-11.MnAPSO-11 is qualitative by the X-ray powder diffraction style of following characteristic:
2θ d.（
） I/I
0×100
8.1 10.92 36
9.5 9.31 61
13.1 6.76 19
15.7 5.64 36
16.2 5.47 10
19.1 4.65 13
20.5 4.33 45
21.1 4.21 100
22.2 4.00 55
22.5 3.95 52
22.7 3.92 61
23.2 3.83 71
24.5 3.63 13
24.8 3.59 16
25.0 3.562 13
26.4 3.38 26
28.3 3.153 13
28.6 3.121 23
29.5 3.028 13
31.5 2.84 16
32.8 2.730 23
34.2 2.622 16
35.4 2.54 10
35.8 2.508 10
36.3 2.475 10
37.5 2.398 13
37.8 2.370 16
39.4 2.287 10
42.9 2.108 10
44.8 2.023 10
48.8 1.866 3
50.6 1.804 10
54.6 1.681 10
(b) a) MnAPSO-11 of the partial synthesis state of portion calcined about 2 hours 600 ℃ the time in air.This calcined material is a feature with following X-ray powder diffraction style:
2θ d.（
） I/I
0×100
8.1 10.92 33
9.8 9.03 60
11.8 7.50 13
12.8 6.92 27
13.5 6.56 13
14.8 5.99 shades
16.1 5.51 67
19.5 4.55 27
19.9 4.46 40
20.4 4.35 33
21.5 4.13 73
21.8 4.08 100
22.2 4.00 73
22.4 3.97 80
23.5 3.79 73
24.3 3.66 27
25.8 3.453 33
26.7 3.339 27
27.3 3.267 33
27.8 3.209 33
28.5 3.132 27
29.5 3.028 33
29.8 2.998 40
30.4 2.940 27
31.8 2.814 20
32.6 2.747 33
34.0 2.637 20
35.5 2.529 27
37.1 2.423 20
37.4 2.404 20
38.2 2.356 20
38.6 2.332 27
41.0 2.201 20
(c) be called MnAPSO-11 here, be one and have MnO
-2 2, AlO
- 2, PO
+ 2And SiO
2The molecular sieve of the three-dimensional micropore crystalline network of tetrahedral oxide units, and have with following formula
MR: (Mn
WAl
XP
YSi
Z) O
2The experience chemical constitution of represented moisture-free basis:
Wherein the R representative has an organic formwork agent that is present in microchannel in the lattice at least; " m " represents every mole of (Mn
WAl
XP
YSi
Z) O
2In the mole number of " R ", its value is 0 to 0.3; And " W ", " X ", " Y " and " Z " represents the molar fraction of the manganese, aluminium, phosphorus and the silicon that exist with tetrahedron respectively, this molar fraction is made up of in the district the determined pentagon of an A, B, C, D and E in Fig. 1, be more preferably with the determined quadrangle of some a, b, c and d among Fig. 2 and form in the district, this MnAPSO-11 has the X-ray powder diffraction style of the feature of the d-spacing that contains at least shown in the following table VII:
The table VII
2 θ d.(
) relative intensity
9.4-9.8 among the 9.41-9.03
16.1-16.2 5.50-5.47 is very weak-in
21.0-21.5 among the 4.23-4.13-very strong
22.1-22.2 among the 4.02-4.00
22.4-22.5 among the 3.97-3.95-strong
23.1-23.5 among the 3.85-3.79
(d) by present resulting X-ray powder diffraction data,, all have the diffraction pattern in the style scope of in the following table VIII, being concluded no matter be synthetic state and all MnAPSO-11 compositions of incinerating:
The table VIII
2θ d.（
） I/I
0×100
8.0-8.1 11.05-10.92 31-36
9.4-9.8 9.41-9.03 56-61
11.8 7.50 13
12.8-13.1 6.92-6.76 17-27
13.5 6.56 13
14.8 5.99 shades
15.6-15.7 5.68-5.64 33-36
16.1-16.2 5.50-5.47 8-67
19.0-19.5 4.68-4.55 8-27
19.9 4.46 40
20.4-20.5 4.35-4.33 33-45
21.0-21.5 4.23-4.13 73-100
21.8 4.08 100
22.1-22.2 4.02-4.00 55-73
22.4-22.5 3.97-3.95 52-80
22.6-22.7 3.93-3.92 61
23.1-23.5 3.85-3.79 69-73
24.3-24.5 3.66-3.63 11-27
24.7-24.8 3.60-3.59 14-16
24.9-25.0 3.58-3.562 shade-13
25.8 3.453 33
26.3-26.7 3.389-3.339 25-27
27.3 3.267 33
27.8 3.209 33
28.2-28.3 3.164-3.153 11-13
28.5-28.6 3.132-3.121 22-27
29.4-29.5 3.038-3.028 11-33
29.8 2.998 40
30.4 2.940 27
31.4-31.8 2.849-2.814 14-20
32.6-32.8 2.747-2.730 19-33
34.0-34.2 2.637-2.622 14-20
35.3-35.5 2.543-2.529 shade-27
35.7-35.8 2.515-2.508 8-10
36.2-26.3 2.481-2.475 8-10
37.1 2.423 20
37.4-37.5 2.404-2.398 11-20
37.7-37.8 2.386-2.380 16-17
38.2 2.356 20
38.6 2.332 27
39.3-39.4 2.292-2.287 8-10
41.0 2.201 20
42.8-42.9 2.113-2.108 8-10
44.7-44.8 2.027-2.023 8-10
48.7-48.8 1.870-1.866 3-5
50.5-50.6 1.807-1.804 8-10
54.5-54.6 1.684-1.681 8-10
(a) press the prepared MnAPSO-16 of embodiment 14, carry out x-ray analysis.After measured, to have with following data be the X-ray powder diffraction style of feature to MnAPSO-16:
2θ d（
） I/I
0×100
8.6
＊10.28 8
11.0
＊8.04 23
11.4 7.76 48
13.3
＊6.66 11
15.9
＊5.57 5
17.3
＊5.13 24
17.7
＊5.01 8
18.7 4.75 40
21.1
＊4.21 19
21.9
＊＊4.06 100
23.0 3.87 13
23.2
＊3.83 10
23.7
＊3.75 5
25.1 3.548 5
26.6
＊＊3.351 26
26.7
*(3.339 shade)
27.8 3.209 5
28.8
＊3.100 15
29.0 3.079 15
29.8 2.998 24
32.0
＊2.797 16
32.6 2.747 7
34.7
＊＊2.585 10
35.7
＊2.515 5
37.8 2.380 11
39.7 2.270 5
42.0
＊2.151 5
44.2 2.049 5
48.5
＊＊1.877 10
49.4
＊1.845 5
52.4 1.746 5
54.7 1.678 5
* impurity peak value;
*The peak value that may contain impurity.
(b) a) MnAPSO-16 of the partial synthesis state of portion calcined about 2 hours 600 ℃ the time in nitrogen.This calcination product is to be feature with following X-ray powder diffraction style:
2θ d.（
） I/I
0×100
11.5 7.69 100
13.3
＊6.66 9
18.6 4.77 25
20.3
＊4.37 44
20.5
＊4.33 41
21.5
＊4.13 66
21.9
＊＊4.06 72
22.9 3.88 31
23.5
＊3.79 13
26.5
＊＊3.363 31
27.9 3.198 13
29.0 3.079 19
29.7 3.008 34
32.6 2.747 13
34.7
＊＊2.585 13
35.6
＊2.522 16
37.8 2.380 13
48.2
＊＊1.888 9
*The impurity peak value
*The peak value that may contain impurity
(c) being called MnAPSO-16, is a kind ofly to have with MnO
-2 2, AlO
- 2, PO
+ 2And SiO
2The molecular sieve of the three-dimensional micropore crystalline network of tetrahedron element, and have with following formula
MR: (Mn
WAl
XP
YSi
Z) O
2The experience chemical constitution of represented moisture-free basis:
Wherein " R " representative has an organic formwork agent that is present in microchannel in the lattice at least: " m " represents every mole of (Mn
WAl
XP
YSi
Z) O
2The mole number of middle " R " that exists, its value is 0 to 0.3; And " W ", " X ", " Y " and " Z " represent the molar fraction of the manganese, aluminium, phosphorus and the silicon that exist with tetrahedron respectively, this molar fraction is forming in the district with the determined pentagon of A, B, C, D and E point in Fig. 1, be more preferably in by the determined tetragonal compositing area of some a, b, c and d among Fig. 2, this MnAPSO-16 has the X-ray powder diffraction style of the feature of the d-spacing that contains at least shown in the following table IX:
The table IX
2 θ d.(
) relative intensity
11.4-11.5 among the 7.76-7.69-very strong
18.6-18.7 among the 4.77-4.75
21.9 in 4.06-very strong
22.9-23.0 a little less than the 3.88-3.87-in
26.5-26.6 among the 3.363-3.351
29.7-29.8 among the 3.008-2.998
(d) by the X-ray powder diffraction data that obtained at present,, all have the diffraction pattern in the style scope of in the following table X, being concluded no matter be synthetic state and all MnAPSO-16 compositions of incinerating:
The table X
2θ d.（
） I/I
0×100
11.4-11.5 7.76-7.69 48-100
18.6-18.7 4.77-4.75 25-40
21.9
＊4.06 72-80
22.9-23.0 3.88-3.87 13-31
26.5-26.6
＊3.363-3.351 26-31
27.8-27.9 3.209-2.198 5-13
29.0 3.079 15-19
29.7-29.8 3.008-2.998 24-34
32.6 2.747 7-14
34.7
＊2.585 9-14
37.8 2.380 11-15
39.7 2.270 5-6
44.2 2.049 5-6
48.2-48.5
＊1.888-1.877 9-12
49.4 1.845 4-5
52.4 1.746 4-5
54.7 1.678 4-5
*The peak value that may contain impurity
Embodiment 71
(a) carry out x-ray analysis by embodiment 46 prepared MnAPSO-20.After measured, to have with following data be the X-ray powder diffraction style of feature to MnAPSO-20:
2θ d，（
） I/I
0×100
14.0 6.35 49
19.8 4.49 43
22.1 4.02 3
23.7
＊3.75 1
24.3 3.67 100
28.1 3.177 13
31.5 2.842 11
34.6 2.595 16
37.5 2.400 2
40.1 2.247 4
42.7 2.118 4
47.4 1.917 4
51.8 1.764 7
*The peak value that may contain impurity
(b) a) MnAPSO-20 of partial synthesis state of part calcined about 1 hour 500 ℃ the time in air.This incinerating product is a feature with following X-ray powder diffraction style:
2 θ d, (
) relative intensity
7.1 12.51 2
14.0 6.33 100
19.8 4.48 40
22.2 4.00 4
24.3 3.66 99
28.2 3.168 17
31.6 2.835 15
34.7 2.589 17
40.2 2.243 3
42.7 2.116 4
47.5 1.913 4
What (c) be called MnAPSO-20 here is a kind ofly to have with MnO
-2 2, AlO
- 2, PO
+ 2And SiO
2The molecular sieve of the three-dimensional micropore crystalline network of tetrahedral oxide units, and have with following formula
MR: (Mn
WAl
XP
YSi
Z) O
2The experience chemical constitution of represented moisture-free basis:
Wherein " R " representative has an organic formwork agent that is present in microchannel in the lattice at least; " m " represents every mole of (Mn
WAl
XP
YSi
Z) O
2The mole number of middle " R " that exists, its value is 0 to 0.3; And " W ", " X ", " Y " and " Z " represent the molar fraction of the manganese, aluminium, phosphorus and the silicon that exist with tetrahedron respectively, said molar fraction is be made of the district the some A among Fig. 1, B, C, D and the determined pentagon of E in, be more preferably be made of the district the determined quadrangle of some a, b, c and d among Fig. 2 in, this MnAPSO-20 has the X-ray powder diffraction style of the feature of the d-spacing that contains at least shown in the following table XI:
The table XI
2 θ d.(
) relative intensity
13.904-13.998 among the 6.3692-6.3263-very strong
19.723-19.818 among the 4.5011-4.4918
24.223-24.329 3.6742-3.6584 is very strong
28.039-28.163 a little less than the 3.1822-3.1684
31.434-31.560 a little less than the 2.8458-2.8348
34.527-34.652 a little less than the 2.5976-2.5866
(d) by the X-ray powder diffraction data that obtained at present,, all have the figure in the style scope of in the following table XII, being concluded no matter be synthetic state and all MnAPSO-20 compositions of incinerating:
The table XII
2θ d.（
） I/I
0×100
13.904-13.998 6.392-6.3263 49-100
19.723-19.818 4.5011-4.4918 40-43
22.091-22.200 4.0236-4.0041 3-4
24.223-24.329 3.6742-3.6584 99-100
28.039-28.163 3.1822-3.1684 13-17
31.434-31.560 2.8458-2.8348 11-15
34.527-34.652 2.5976-2.5886 15-17
34.413-27.465 2.2501-2.4004 2
40.071-40.207 2.2501-2.2428 3-4
42.627-42.730 2.1209-2.1160 3-4
47.383-47.519 1.9185-1.9134 3-4
51.790-51.840 1.7652-1.7636 7
Embodiment 72
(a) press the prepared MnAPSO-31 of embodiment 54, carry out x-ray analysis.After measured, to have with following data be the X-ray powder diffraction style of feature to MnAPSO-31:
2θ d，（
） I/I
0×100
7.9 11.22 4
8.6 10.27 61
17.2 5.17 5
18.5 4.81 4
20.4 4.36 49
21.2 4.19 4
22.0 4.04 30
22.1 4.02 32
22.7 3.92 100
25.3 3.526 5
25.8 3.459 3
28.1 3.181 12
29.8 2.995 6
31.8 2.812 22
35.2 2.548 9
36.2 2.482 3
37.3 2.411 3
37.8 2.382 3
38.3 2.353 3
38.4 2.346 3
39.4 2.285 3
39.8 2.266 3
40.3 2.241 3
46.8 1.942 3
48.8 1.866 2
51.8 1.766 5
55.6 1.654 2
(b), in air, calcined about 1.5 hours 500 ℃ the time a) MnAPSO-31 of the partial synthesis shape of portion.This calcination product is a feature with following X-ray powder diffraction style:
2θ d（
） I/I
0×100
8.6 10.31 58
14.8 5.98 4
17.1 5.18 9
18.5 4.81 4
20.4 4.36 52
22.1 4.03 44
22.7 3.92 100
25.3 3.526 7
25.8 3.460 8
28.1 3.181 15
29.8 2.998 11
31.1 2.879 3
31.8 2.811 33
35.3 2.546 11
36.3 2.477 6
37.3 2.409 3
37.8 2.383 3
38.3 2.348 3
39.4 2.289 4
40.3 2.236 3
45.4 2.000 3
46.8 1.942 5
47.6 1.909 4
48.9 1.864 3
51.7 1.767 6
That (c) be called MnAPSO-31 here is a kind of MnO of having
2- 2, AlO
-2 2, PO
+ 2And SiO
2The molecular sieve of the three-dimensional micropore crystalline network of tetrahedral oxide units, and have the moisture-free basis experience chemical composition of representing with following formula:
mR∶（Mn
WAl
XP
YSi
Z）O
2
Wherein " R " representative has a kind of organic formwork agent at least in the microchannel in crystal; M represents every mole of (Mn
WAl
XP
YSi
Z) O
2In the mole number of " R ", its value is 0 to about 0.3; And the molar fraction of manganese, aluminium, phosphorus and silicon that each representative of " W ", " X ", " Y " and " Z " exists with tetrahedral oxide, above-mentioned molar fraction is to be ordered by the A among Fig. 1, B, C, D and E in the pentagon Composition Region that is limited.Be more preferably and ordering by a among Fig. 2, b, c and d in the tetragonal Composition Region that is limited.Above-mentioned MnAPSO-31 has the X-ray powder diffraction style that contains listed d-pitch characteristics in as following table X III at least:
Table X III
2 θ d, (
) relative intensity
8.482-9.501 10.4240-9.3084 is medium
20.222-20.353 4.3913-4.3632 is medium
21.879-21.993 4.0622-4.0415 is medium
22.071-22.088 4.0272-4.0242 is medium
22.587-22.698 3.9364-3.9174 is very strong
31.724-31.836 2.8546-2.8108 is medium
(d) according to the X-ray powder diffraction data of gained not long ago, no matter be that diffraction patterns synthetic state or all MnAPSO-31 constituents of agglomerating all are in the broad sense style of the X IV of tabulating down:
Table X IV
2θ d，（
） I/I
0×100
7.694-7.883 11.4904-11.2145 2-4
8.482-9.501 10.4240-9.3084 58-66
14.756-14.822 6.0034-5.9767 2-4
17.016-17.158 5.2105-5.1679 5-9
18.310-18.466 4.8451-4.8046 3-4
20.222-20.353 4.3913-4.3632 45-52
21.032-21.221 4.2238-4.1867 4-5
21.879-21.993 4.0622-4.0415 30-51
22.071-22.088 4.0272-4.0242 32-44
22.587-22.698 3.9364-3.9174 100
23.164-23.190 3.8398-3.8355 2-3
25.115-25.260 3.5457-3.5256 4-7
25.663-25.757 3.4712-3.4588 3-8
27.922-28.050 3.1953-3.1809 12-15
29.701-29.831 3.0078-2.9950 6-11
31.068-31.315 2.8785-2.8564 2-3
31.724-31.836 2.8564-2.8108 21-33
35.117-35.251 2.5553-2.5460 9-11
35.871 2.5033 1
36.070-36.261 2.4900-2.4730 2-6
37.123-37.325 2.4217-2.4091 2-3
37.628-27.763 2.3904-2.3822 2-3
38.163-38.254 2.3581-2.3527 2-3
38.334-38.367 2.3480-2.3461 3
39.285-39.442 2.2933-2.2845 3-4
39.654-39.772 2.2728-2.2663 2-4
40.111-40.337 2.2480-2.2359 2-3
45.179-45.354 2.0069-1.9996 2-3
46.617-46.786 1.9483-1.9416 3-5
47.454-47.631 1.9158-1.9091 2-4
48.610-48.846 1.8729-1.8644 2-3
50.679-50.750 1.8012-1.7989 2
51.588-51.766 1.7716-1.7659 4-6
55.410-55.557 1.6581-1.6541 2
Embodiment 73
(a) to pressing the prepared MnAPSO-34 of embodiment 11, carry out x-ray analysis.After measured, the following column data of X-ray powder diffraction style of MnAPSO-34 is a feature:
2θ d.（
） I/I
0×100
9.6 9.21 100
12.9 6.86 17
14.2 6.24 15
16.1 5.51 33
18.1 4.90 23
20.6 4.31 69
22.3 3.99 10
23.1 3.85 8
25.2 3.534 25
25.8 3.453 19
27.5 3.243 10
28.4 3.143 10
29.5 3.028 10
30.5 2.931 27
31.2 2.867 23
33.8 2.652 8
34.3 2.614 12
36.3 2.475 8
43.0 2.103 6
43.5 2.080 6
47.5 1.914 6
49.9 1.863 8
50.9 1.794 6
53.0 1.728 6
55.7 1.650 6
(b) with the MnAPSO-34 of the partial synthesis state of a portion in nitrogen, in the time of 425 ℃, calcined 2 hours.The incinerating product is that following X-ray powder diffraction style is a feature:
2θ d.（
） I/I
0×100
9.6 9.21 100
13.0 6.86 25
14.1 6.28 5
16.2 5.47 15
17.9 4.96 15
19.1 4.65 5
20.8 4.27 37
22.2 4.00 5
22.4 3.97 5
23.2 3.83 7
25.2 3.534 15
26.0 3.427 12
27.7 3.220 4
28.3 3.153 5
29.7 3.008 4
30.7 2.912 17
31.3 2.849 11
32.4 2.763 3
34.6 2.592 5
36.2 2.481 4
38.8 2.321 3
39.8 2.265 3
43.1 2.099 3
43.6 2.076 3
47.8 1.903 1
49.0 1.859 3
51.0 1.791 3
53.3 1.719 4
54.6 1.681 3
That (c) be called MnAPSO-34 here is a kind of MnO of having
2- 2, AlO
- 2, PO
+ 2And SiO
2The molecular sieve of the three-dimensional micropore crystalline network of tetrahedral oxide units, and have the moisture-free basis experience chemical composition of representing with following formula:
mR∶（Mn
WAl
XP
YSi
Z）O
2
Wherein " R " representative has a kind of organic formwork agent at least in the crystal microchannel; M represents every mole of (Mn
WAl
XP
YSi
Z) O
2In the mole number of " R ", its value is 0 to about 0.3; And the molar fraction of manganese, aluminium, phosphorus and silicon that each representative of " X ", " Y " and " Z " exists with tetrahedral oxide.Above-mentioned molar fraction is to be ordered in the pentagon Composition Region that is limited by the A among Fig. 1, B, C, D and E.Be more preferably and ordered by a among Fig. 2, b, c and d in the tetragonal Composition Region that is limited, above-mentioned MnAPSO-34 has the X-ray powder diffraction style that contains listed d-pitch characteristics in as following table X V at least:
Table X V
2 θ d.(
) relative intensity
9.4-9.6 9.41-9.21 is very strong
15.9-16.2 5.57-5.47 is medium
20.4-20.8 4.35-4.27 is medium-and very strong
25.0-25.3 a little less than the 3.562-3.520-medium
31.0-31.3 a little less than the 2.885-2.858-medium
33.6-33.9 2.667-2.644 is medium
(d) according to the X-ray powder diffraction data of gained not long ago, no matter be that diffraction patterns synthetic state or all MnAPSO-34 compositions of incinerating all are in the broad sense style of the X IV of tabulating down:
Table X IV
2θ d.（
） I/I
0×100
9.4-9.6 9.41-9.21 100
12.7-13.0 6.97-6.86 17-25
14.0-14.2 6.33-6.24 5-17
15.9-16.2 5.57-5.47 15-44
17.9-18.1 4.96-4.90 15-32
19.1 4.65 5
20.4-20.8 4.35-4.27 37-92
22.1-22.3 4.02-3.99 5-16
22.4 3.97 5
22.9-23.2 3.88-3.83 7-16
25.0-25.3 3.562-3.520 15-36
25.8-26.0 3.453-3.427 12-19
27.3-27.7 3.267-3.220 4-28
28.2-28.5 3.164-3.132 5-16
29.3-29.7 3.048-3.008 4-16
30.3-30.7 2.950-2.912 10-17
31.0-31.3 2.885-2.849 11-40
32.4 2.763 3
33.6-33.9 2.667-2.644 23-32
34.3-34.6 2.614-2.592 5-12
36.2-36.4 2.481-2.468 4-16
38.8 2.321 3
39.8 2.265 3
43.0-43.1 2.103-2.099 3-12
43.5-43.6 2.080-2.076 3-12
47.4-47.8 1.918-1.903 1-12
48.8-49.0 1.866-1.859 3-12
50.8-51.0 1.797-1.791 3-12
52.9-53.3 1.731-1.719 4-12
54.6 1.681 3
55.6-55.8 1.653-1.647 6-12
Embodiment 74
(a) to carrying out x-ray analysis by embodiment 22 prepared MnAPSO-35.After measured, the following column data of X-ray powder diffraction style of MnAPSO-35 is a feature:
2θ d.（
） I/I
0×100
8.6 10.28 14
10.9 8.12 45
13.4 6.61 23
15.9 5.57 11
17.4 5.10 80
17.8 4.98 16
20.9 4.25 57
21.9 4.06 100
23.2 3.83 34
24.8 3.59 9
25.7 3.466 7
26.9 3.314 21
28.3 3.153 50
29.1 3.069 11
31.4 2.849 9
32.1 2.788 41
34.3 2.614 14
34.9 2.571 7
35.3 2.543 5
35.8 2.508 7
37.7 2.386 5
39.5 2.281 5
41.9 2.156 7
42.7 2.118 7
44.6 2.032 5
47.6 1.910 7
48.3 1.884 7
49.5 1.841 7
51.0 1.791 9
55.0 1.670 5
55.4 1.658 7
(b) with the part of synthetic MnAPSO-35 in a) part, in nitrogen,, calcined 2 hours in 500 ℃.That calcination product has is following *-feature of ray powder diffraction style:
2θ d，（
） I/I
0×100
8.6 10.28 27
10.9 8.12 96
11.4 7.76 14
13.4 6.61 41
15.8 5.61 14
17.3 5.13 68
17.7 5.01 Sh
20.8 4.27 64
21.9 4.06 100
23.3 3.82 32
24.8 3.59 23
25.7 3.466 18
26.9 3.314 27
28.3 3.153 59
29.1 3.069 23
31.4 2.849 18
32.2 2.780 46
34.2 2.622 18
34.8 2.578 14
35.8 2.508 9
41.9 2.156 9
42.5 2.127 9
44.6 2.032 9
47.4 1.918 9
48.2 1.888 9
49.4 1.845 9
51.0 1.791 14
55.2 1.664 9
55.7 1.650 9
(c) this molecular sieve that is called MnAPSO-35 has MnO
-2 2, AlO
- 2, PO
+ 2And SiO
2The three-dimensional micropore crystalline network of tetrahedral oxide units, its moisture-free basis empirical formula chemical composition molecular formula: mR: (Mn
WAl
XP
YSi
Z) O
2Represent.Wherein: " R " represents in the interior microchannel of crystallization has an organic formwork agent at least; Every mole of (Mn of " m " table table
WAl
XP
YSi
Z) O
2In, the mole number of " R ", its value is 0-0.3; " W ", " X ", " Y ", " Z " represent the molar fraction of the manganese, aluminium, phosphorus and the silicon that exist with tetrahedral oxide respectively.Above-mentioned molar fraction is in the pentagon composition district that is decided by the A among Fig. 1, B, C, D, 5 of E, preferably in the tetragon composition district that is decided by a among Fig. 2, b, 4 of c, d.Above-mentioned MnAPSO-35 has the distinctive X-ray powder diffraction of the spacing style that contains the demonstration of table X VII at least:
Table X VII
2 θ d, (
) relative intensity
10.8-11.0 among the 8.19-8.04-very strong
13.4-13.7 among the 6.61-6.46-strong
17.2-17.5 among the 5.16-5.07-strong
20.8-21.0 among the 4.27-4.23
21.8-22.3 among the 4.08-3.99-very strong
28.2-28.7 among the 3.164-3.110
(d) the present whole MnAPSO-35 composition that has obtained X-ray powder diffraction data, no matter be synthetic or incinerating, their style is all in table X VIII:
Table X VIII
2θ d，（
） I/I
0×100
8.5-8.7 10.40-10.16 13-31
10.8-11.0 8.19-8.04 44-100
11.4-11.5 7.76-7.69 8-14
13.3-13.4 6.66-6.61 22-41
13.4-13.7 6.61-6.46 31-81
15.8-15.9 5.61-5.57 10-14
17.2-17.5 5.16-5.07 38-82
17.7-18.0 5.01-4.93 （Sh）-18
20.8-21.0 4.27-4.23 44-46
21.8-22.3 4.08-3.99 56-100
23.1-23.6 3.85-3.77 31-34
24.7-25.2 3.60-3.534 13-31
25.6-25.8 3.480-3.453 4-25
26.8-27.4 3.326-3.255 19-44
28.2-28.7 3.164-3.110 50-59
29.0-29.6 3.079-3.018 10-31
31.3-31.4 2.858-2.849 9-18
32.0-32.8 2.797-2.730 31-46
34.2-34.3 2.622-2.614 11-18
34.8-34.9 2.578-2.571 4-14
35.2-35.3 2.550-2.543 5-7
35.7-35.8 2.515-2.508 4-9
37.6-37.7 2.392-2.386 4-5
39.4-39.5 2.287-2.281 4-7
41.8-42.0 2.161-2.151 6-9
42.5-42.8 2.127-2.113 5-9
44.5-44.7 2.036-2.027 5-9
47.4-47.7 1.918-1.907 6-9
48.2-48.4 1.888-1.881 6-9
49.4-49.6 1.845-1.838 6-9
50.9-51.1 1.794-1.787 5-14
54.9-55.2 1.672-1.664 5-9
55.3-55.7 1.661-1.650 6-9
Embodiment 75
(a) MnAPSO-36 that will get by the method preparation of embodiment 59 carries out X-ray analysis.After measured, the following column data of its X-ray powder diffraction style is a feature:
2θ d.（
） I/I
O×100
7.4 11.88 15
7.9 11.22 100
8.2 10.82 33
13.5 6.55 5
15.8 5.61 10
16.4 5.41 31
19.1 4.66 14
20.7 4.28 34
21.2 4.19 4
21.7 4.10 16
22.0 4.04 14
22.5 3.96 15
23.0 3.87 5
23.9 3.73 6
27.2 3.276 15
27.9 3.193 3
28.3 3.153 8
29.0 3.079 7
30.2 2.958 4
30.3 2.951 4
32.0 2.798 8
34.8 2.579 7
(b) with the part of synthetic MnAPSO-36 in a) part, in air,, calcined 1 hour in 500 ℃.Calcination product has the feature of following X-ray powder diffraction style:
2θ d，（
） I/I
0×100
7.1 12.39 5
7.6 11.64 21
8.0 11.11 100
8.3 10.65 37
13.6 6.53 17
16.6 5.35 31
19.4 4.57 17
20.8 4.27 19
21.9 4.06 8
22.4 3.97 15
22.7 3.92 11
23.4 3.80 5
23.9 3.73 7
27.3 3.271 16
28.3 3.159 6
28.4 3.141 6
29.1 3.074 7
29.4 3.043 5
32.0 2.798 6
(c) this molecular sieve that is called MnAPSO-36 has MnO
-2 2, AiO
- 2, PO
+ 2And SiO
2The three-dimensional micropore crystalline network of tetrahedral oxide units, its moisture-free basis empirical formula chemical composition molecular formula: mR: (Mn
WAl
XP
YSi
Z) O
2Represent.Wherein: " R " represents in the interior microchannel of crystallization has an organic formwork agent at least; " m " represents every mole of (Mn
WAl
XP
YSi
Z) O
2In, the mole number of " R ", its value is 0-0.3; " W ", " X ", " Y ", " Z " represent the molar fraction of the manganese, aluminium, phosphorus and the silicon that exist with tetrahedral oxide respectively.Above-mentioned molar fraction is in the pentagon composition district that is decided by the A among Fig. 1, B, C, D, 5 of E, preferably in the tetragon composition district that is decided by a among Fig. 2, b, 4 of c, d.Above-mentioned MnAPSO-36 has the distinctive X-ray powder diffraction of the spacing style that contains the demonstration of table X IX at least:
Table X IX
2 θ d.(
) relative intensity
7.596 in 11.6382
7.628-7.981 11.5899-11.0771 is very strong
8.105-8.299 among the 10.9084-10.6537
16.395-16.673 among the 5.4066-5.3172
19.052-19.414 a little less than the 4.6580-4.5721
20.744-20.871 among the 4.2819-4.2560
(d) the present whole MnAPS-36 composition that has obtained X-ray powder diffraction data, no matter be synthetic or incinerating, their style is all in the table XX:
The table XX
2θ d.（
） I/I
0×100
7.132 12.3939 5
7.596 11.6382 21
7.628-7.981 11.5899-11.0771 100
8.105-8.299 10.9084-10.6537 33-37
13.517-13.778 6.5503-6.4270 5-17
15.797-15.928 5.6099-5.5640 10-11
16.395-16.673 5.4066-5.3172 31-32
19.052-19.414 4.6580-4.5721 14-17
20.744-20.871 4.2819-4.2560 20-35
21.230 4.1848 4
21.655 4.1037 16
21.863-21.986 4.0651-4.0427 8-14
22.119-22.470 4.0186-3.9566 15
22.713-23.408 3.9150-3.8001 5-11
23.854-23.965 3.7301-3.7131 5-6
27.219-27.518 3.2761-3.4412 15-16
27.868-27.939 3.2014-3.1934 2-3
28.252 3.1587 6
28.304-28.536 3.1530-3.1279 6-8
29.003-29.268 3.0786-3.0513 6-7
29.347 3.0433 5
30.144-30.230 2.9646-2.9564 4
30.291-30.526 2.9505-2.9284 4
31.983-32.094 2.7982-2.7888 6-9
34.640-34.968 2.5894-2.5659 7
Embodiment 76
(a) MnAPSO-44 that will get by the method preparation of embodiment 64 carries out X-ray analysis.After measured, the following column data of its X-ray powder diffraction style is a feature:
2θ d.（
） I/I
0×100
9.4 9.39 100
13.0 6.83 20
13.7 6.45 4
16.1 5.52 43
17.3 5.12 5
19.0 4.68 7
20.7 4.29 84
21.7 4.09 21
22.6 3.94 8
23.1 3.86 9
24.4 3.65 58
26.1 3.409 22
27.8 3.205 10
29.7 3.012 5
30.1 2.969 16
30.8 2.900 50
32.5 2.753 4
32.9 2.721 6
34.8 2.577 3
35.5 2.528 9
38.5 2.336 2
39.2 2.299 2
40.0 2.255 2
42.2 2.143 3
42.5 2.125 3
43.6 2.076 2
47.3 1.922 2
48.2 1.890 7
48.7 1.870 4
50.3 1.814 7
53.9 1.701 6
(b) with the part of synthetic MnAPSO-44 in a) part, in air,, calcined 1 hour in 500 ℃.Calcination product has the feature of following X-ray powder diffraction style:
2θ d.（
） I/I
0×100
9.6 9.21 100
13.1 6.79 26
14.2 6.26 3
16.2 5.46 12
18.0 4.93 18
19.3 4.60 3
20.9 4.25 28
22.3 3.99 3
23.4 3.80 3
25.3 3.526 13
26.3 3.387 9
28.5 3.137 3
28.6 3.123 4
29.9 2.990 2
30.0 2.976 2
30.6 2.921 3
31.1 2.875 7
31.8 2.811 2
32.1 2.791 2
35.1 2.560 3
(c) this molecular sieve that is called MnAPSO-44 has MnO
-2 2, AlO
- 2, PO
+ 2And SiO
2The three-dimensional micropore crystalline network of tetrahedral oxide units, its moisture-free basis empirical formula chemical composition molecular formula: mR: (Mn
WAl
XP
YSi
Z) O
2Represent.Wherein: " R " represents in the interior microchannel of crystallization has an organic formwork agent at least; " m " represents every mole of (Mn
WAl
XP
YSi
Z) O
2In, the mole number of " R ", its value is 0-0.3; " W ", " X ", " Y ", " Z " represent the molar fraction of the manganese, aluminium, phosphorus and the silicon that exist with tetrahedral oxide respectively.Above-mentioned molar fraction is in the pentagon composition district that is decided by the A among Fig. 1, B, C, D, 5 of E, preferably in the tetragon composition district that is decided by a among Fig. 2, b, 4 of c, d.Above-mentioned MnAPSO-44 has the distinctive X-ray powder diffraction of the spacing style that contains the demonstration of table X XI at least:
Table X XI
2 θ d.(
) relative intensity
9.420-9.498 9.3883-9.3110 is very strong
16.062-16.131 among the 5.5179-5.4944
20.715-20.790 4.2877-4.2725 is strong
24.396-24.424 among the 3.6485-3.6444
26.143-26.184 among the 3.4085-3.4032
30.833-30.853 among the 2.8999-2.8981
(d) the present whole MnAPSO-44 composition that has obtained X-ray powder diffraction data, no matter be synthetic or incinerating, their style is all in table X XII:
Table X XII
2θ d,（
） I/I
0×100
9.420-9.498 9.3883-9.3110 100
12.930-12.958 6.8468-6.8318 20
13.738 6.4458 4
16.062-16.131 5.5179-5.4944 43
17.329-17.396 5.1173-5.0975 5
18.950-18.998 4.6828-4.6713 7
20.715-20.790 4.2877-4.2725 84
21.709-21.743 4.0937-4.0873 21
22.366-22.583 3.9748-3.9372 8
23.061-23.101 3.8566-3.8501 9
24.396-24.424 3.6485-3.6444 58
26.143-26.184 3.4085-3.4032 22
27.837-27.881 3.2049-3.1999 10
29.661 3.0117 5
30.002-30.096 2.9783-2.9692 16
30.833-20.853 2.8999-2.8981 50
32.520-32.562 2.7532-2.7498 4
32.900-32.918 2.7223-2.7208 6
34.812 2.5770 3
35.516-35.534 2.5275-2.5263 9
38.536 2.3361 2
38.185 2.2989 2
39.991 2.2545 2
42.162-42.177 2.1432-2.1425 3
42.533-42.541 2.1254-2.1250 3
43.607-73.621 2.0755-2.0749 2
47.283 1.9224 2
48.157-48.177 1.8895-1.8888 7
48.640-48.697 1.8719-1.8698 4
50.303-50.307 1.8138-1.8137 7
53.885-53.887 1.7014-1.7013 6
Embodiment 77
(a) MnAPSO-47 that will get by the method preparation of embodiment 49 carries out x-ray analysis.After measured, the following column data of its X-ray powder diffraction style is a feature:
2θ d.（
） I/I
0×100
4.8 18.44 1
9.4 9.38 100
12.9 6.89 5
13.9 6.40 3
16.0 5.56 9
17.5 5.06 4
18.9 4.69 3
20.5 4.32 30
21.8 4.08 4
22.4 3.98 1
22.9 3.88 3
24.6 3.61 11
25.9 3.445 7
27.6 3.234 2
27.9 3.199 1
29.5 3.033 2
30.5 2.930 10
30.8 2.901 7
31.5 2.845 1
33.2 2.700 1
34.4 2.604 2
34.8 2.576 1
35.7 2.516 2
38.4 2.343 1
39.2 2.297 1
39.6 2.277 1
42.4 2.132 1
43.3 2.091 1
47.6 1.911 1
48.6 1.874 5
50.3 1.813 2
53.2 1.722 1
54.0 1.698 1
(b) with the part of synthetic MnAPSO-47 in a) part, in air,, calcined 1 hour in 500 ℃.Calcination product has the feature of following X-ray powder diffraction style:
2θ d.（
） I/I
0×100
5.0 17.80 1
9.7 9.12 100
10.0 8.85 1
13.1 6.75 5
14.2 6.23 1
16.3 5.45 2
18.0 4.92 2
19.4 4.58 3
20.9 4.24 7
22.4 3.98 1
23.4 3.80 1
25.3 3.521 2
26.3 3.385 2
28.1 3.176 1
28.6 3.125 1
30.0 2.977 1
31.1 2.876 3
31.5 2.837 2
33.9 2.645 1
35.0 2.562 1
49.6 1.838 1
(c) this molecular sieve that is called MnAPSO-47 has MnO
-2 2, AlO
- 2, PO
+ 2And SiO
2The three-dimensional micropore crystalline network of tetrahedral oxide units, its moisture-free basis empirical formula chemical composition molecular formula: mR: (Mn
WAl
XP
YSi
Z) O
2Represent.Wherein: " R " represents in the interior microchannel of crystallization has an organic formwork agent at least; " m " represents every mole of (Mn
WAl
XP
YSi
Z) O
2In, the mole number of " R ", its value is 0-0.3; " W ", " X ", " Y ", " Z " represent the molar fraction of the manganese, aluminium, phosphorus and the silicon that exist with tetrahedral oxide respectively.Above-mentioned molar fraction is in the pentagon composition district that is decided by the A among Fig. 1, B, C, D, 5 of E, preferably in the tetragon composition district that is decided by a among Fig. 2, b, 4 of c, d.Above-mentioned MnAPSO-47 has the distinctive X-ray powder diffraction style of spacing that contains the demonstration of table XX III at least:
Table XX III
2 θ d.(
) relative intensity
9.434-9.696 9.3746-9.1214 is very strong
15.946-16.276 5.5579-5.4457 is very weak
20.539-20.940 4.3242-4.2423 is very weak-in
24.643 a little less than in the of 3.6125
30.511 a little less than in the of 2.9297
30.820-31.096 2.9011-2.8759 is very weak
(d) the present whole MnAPSO-47 composition that has obtained X-ray powder diffraction data, no matter be synthetic or incinerating, their style is all in table XX IV:
Table XX IV
2θ d.（
） I/I
0×100
4.793-4.964 18.4368-17.8028 1
9.434-9.696 9.3746-9.1214 100
12.847-13.107 6.8907-6.7543 5
13.840-14.211 6.3983-6.2321 1-3
15.946-16.276 5.5579-5.4457 2-9
17.544-18.032 5.0550-4.9191 2-4
18.941-19.365 4.6851-4.5836 3
20.539-20.940 4.3242-4.2423 6-30
21.811 4.0747 4
22.351-22.352 3.9775-3.9774 1
22.936 3.8773 3
23.401 3.8013 1
24.643 3.6125 11
25.294-25.864 3.5210 2-7
26.327-27.577 3.3851-3.2344 2
27.881-28.093 3.1992-3.1762 1
28.560 3.1253 1
29.448-30.019 3.0331-2.9767 1-2
30.511 2.9297 10
30.820-31.096 2.9011-2.8759 3-7
31.448-31.532 2.8446-2.8372 1-2
33.186-33.894 2.6995-2.6447 1
34.444 2.6037 2
34.834-35.026 2.5755-2.5618 1
35.685 2.5159 2
38.412 2.3434 1
39.223 2.2968 1
39.582 2.2768 1
42.403 2.1316 1
43.278 2.0905 1
47.595 1.9105 1
48.584-49.595 1.8739-1.8380 1-5
50.327 1.8130 2
53.205 1.7215 1
54.006 1.6979 1
Embodiment 78
By the catalytic pyrolysis test, measure the catalytic activity of MnAPSO, and check the calcining sample of MnAPSO product among the embodiment 11,21,25,31,49,55,59 and 64.
The mensuration of catalytic activity is to carry out in reactor.Have in the reactor one long be 254 millimeters.Diameter is 10.3 millimeters a garden tubular silica tube.In each test, the granularity of MnAPSO all is a 20-40 order (USS), and add-on is the 0.5-5 gram.The selection of add-on will make under test conditions, has 5% at least, obtains transforming but be no more than 90% normal butane.Most MnAPSO sample will be before mensuration, in air or nitrogen, calcines earlier, and to remove the organic substance in the microchannel, again in reactor, under 500 ℃ of temperature, helium injection air-flow, in-situ activation one hour.Helium-normal butane the mixture material that will contain 2% mole of normal butane then passes through reactor with the flow velocity of 50 ml/min.The conventional gas chromatographic technique analysis of the effluent of raw material and reactor.After reactor effluent will be waited to ventilate 10 minutes, the resampling analysis.
By calculating the constant of speed of flow of pseudo-first-order reaction, to obtain the relative catalytic activity of MnAPSO composition.The K of MnAPSO composition
AValue, list in the following table XX V:
Table XX V
Embodiment constant of speed of flow (the K of MnAPSO preparation
A)
*
MnAPSO-5 31 0.2
MnAPSO-11 25 0.6
MnAPSO-20 46 0.2
MnAPSO-31 55 1.0;0.5
MnAPSO-34 11 3.1
MnAPSO-35 21 0.1
＊＊
MnAPSO-36 59 0.3
MnAPSO-44 64 1.5
MnAPSO-47 49 1.7
*Before the catalytic activity of measuring each specified MnAPSO, calcine as follows:
A) Mn-APSO-5, calcined 2 hours in air at 500 ℃;
B) MnAPSO-11, MnAPSO-34 and MnAPSO-36 calcine in position;
C) MnAPSO-31 in 500 ℃, calcines after 1.5 hours in air, again at 600 ℃, calcines 1 hour;
D) MnAPSO-35, calcined 1 hour in nitrogen at 500 ℃;
E) MnAPSO-20, MnAPSO-44 and MnAPSO-47, calcined 1 hour in air at 500 ℃.
*Less than 0.1
Method is used
In general, MnAPSO composition of the present invention is hydrophilic, and the ability of the energy force rate adsorbed hydrocarbons molecule of planar water is strong.So-called common hydrocarbon molecule for example is: paraffinic hydrocarbons, alkene, aromatic compound and so on, as: benzene, dimethylbenzene, isopropyl benzene etc.So MnAPSO
SIn and splitting gas dry such fractionation by adsorption/purge process dry, can make siccative and use as Sweet natural gas.The ability of its planar water also surpasses the so-called permanent gases of absorption, for example: carbonic acid gas, nitrogen, oxygen and hydrogen.So MnAPSO
SAlso be well suited for being used for oxygen, nitrogen and empty oxygen before dry reforming furnace hydrogen stream and the dry liquefaction.
This MnAPSO composition has also shown special surperficial selectivity characteristic, transforms and oxygen combustion catalyst for reaction or catalyst matrix so can be used as many hydrocarbon.They can be by the method for having known in this technology and the use, saturated or filling catalytically-active metals, as prepare silica-based or aluminium base catalyst composition.Generally be used for catalysis, its micropore is more preferably greater than 4 dusts.
By the catalytic hydrocarbon conversion reaction of MnAPSO composition, comprise cracking, hydrocracking, aromatic hydrocarbon and isoparaffin alkylation, isomerization (comprising the isomerization of dimethylbenzene), polymerization, reformation, hydrogenation, dehydrogenation, transalkylation, take off alkyl, oxidation open loop and deoxidation cyclic action.
The MnAPSO that employing contains just like platinum or palladium hydrogenation promotor is a catalytic composition, can be with heavy oil residual raw materials, cyclic hydrocarbon raw material and other hydrogenatable charging hydrocracking, required condition is: temperature is 400 °F-825 °F, hydrogen is 2-80 to the molar ratio of hydrocarbon, pressure is 10-3500 pound/square inch, liquid hourly space velocity is 0.1-20, is preferably 1.0-10.
This MgAPSO catalyst composition that is used for hydrocracking also is applicable to reforming process, the temperature of hydrocarbon feed contact catalyst is approximately 700 °F to 1000 °F in the reforming process, hydrogen pressure is 100 to 500 pounds/square inch, the liquid hourly space velocity value is 0.1 to 10, hydrogen is 1 to 20 to the mol ratio of hydrocarbon, preferably between 4 to 12.
The same catalyzer that contains hydrogenation promotor also is used for hydroisomerization process, raw material such as positive structure paraffin can be converted into saturated branched chain isomer in this process.The reaction conditions of hydroisomerization is: temperature is about 200 °F to 600 °F, preferably 300 °F to 550 °F; Its liquid hourly space velocity value is about 0.2 to 1.0.Hydrogen is to add reactor with the form with the hydrocarbon feed resulting mixture, and both mol ratios (hydrogen is to hydrocarbon) are between 1 to 5.
When same catalyst composition being used for the positive structure paraffin of hydrogen isomerization, use high slightly temperature, promptly about 650 °F to 1000 °F, in the time of preferred 850 °F to 950 °F, then can use low a little pressure usually, pressure range is greatly between 15-50 pound/square inch.The preferred alkane raw material is for having C
7-C
20The positive structure paraffin of carbon atom.Generally will relatively lack the duration of contact between raw material and the catalyzer, to avoid taking place unwanted pair of reaction, as olefinic polymerization or paraffinic hydrocarbons cracking.The scope of liquid hourly space velocity value between 0.1 to 10, preferably 1.0 to 6.0.
The distinctive crystalline structure of the present invention's MnAPSO catalyzer and do not have the preparation form of basic metal composition fully, help their application in fragrant alkane compound transforms, particularly help the catalytic disproportionation effect of toluene, ethene, trimethylbenzene, durene etc.In the dismutation, also isomerization and transalkylation can take place.Preferablely in the catalyst composition be to contain independent or together with the VI-B family metal such as tungsten, molybdenum, chromium VIII family precious metal auxiliary together, its content should account for the 3-15% weight percent of total component.Keeping temperature is about 400～750 °F, and pressure is that 100～2000 pounds of/square English inch and liquid hourly space velocity are in 0.1～15 the responding layer, may but not necessarily add external hydrogen.
In the catalytic pyrolysis process to raw materials such as gas oil, heavy naphtha, the thick oil residues of diasphaltene, preferably use the catalysis of MnAPSO composition, and resulting primary product is a gasoline.Temperature condition with reaction maintains 850～1100 °F, and the liquid hourly space velocity value is 0.5～10, and pressure condition is advisable at 0～50 pound of/square English inch.
Use paraffinic feed, the normal paraffin of 6 above carbon atoms is preferably arranged, carry out the dehydrocyclization reaction, forming products such as benzene, dimethylbenzene and toluene, the condition that it is used is identical with the used condition of catalytic pyrolysis basically.In these reactions, preferably connect same VIII family base metal, use the MnAPSO catalyzer together as cobalt, nickel cation.
Herein in the said catalytic dealkylationization, alkane side chain on the expectation cracking aromatic proton, and its ring structure of hydrogenation not in fact, must use higher relatively temperature, promptly be approximately 800 °～1000 °F, and the medium degree hydrogen pressure that is approximately 300～1000 pounds of/square English inch, used other condition is then similar to above-mentioned shortening cracking.Preferred catalyzer is with the above-mentioned same type of catalytic dehydrogenation cyclisation that is associated.Dealkylation reaction herein, expectation can comprise methylnaphthalene is converted into naphthalene that toluene and/or dimethylbenzene are converted into benzene.
In the catalytic hydrofinishing, main purpose is to promote organosulfur and/or organic nitrogen compound hydrocracking in the raw material, and does not have influence on hydrocarbon molecule wherein in fact.For this reason, preferably use the used various conditions of above-mentioned shortening cracking, catalyzer then uses and is associated with above-mentioned dehydrocyclization process, the catalyzer with same general aspects.Raw material comprises gasoline fraction, kerosene, jet-propelled starting and fuel fraction, fraction of diesel oil, light and heavy gasoil, deasphalted crude resistates etc., and the sulphur content that it is possible can reach 5% of weight, and nitrogen content reaches 3% of weight.
Can use similar condition, contain unifining processs such as the denitrogenation of hydrocarbon feed of suitable vast scale organosulfur and organic nitrogen compound and desulfurization with influence.People generally recognize, a large amount of existence of this constituents can suppress the activity of hydrocracking catalyst significantly.In addition, when transforming,, must use more extreme condition than containing the less raw material of organic nitrogen compound relatively as the hydrocracking of the more raw material of relative hydrogen content being carried out same degree.Moreover, be necessary the concentration of the feature from raw material, particularly organic nitrogen compound, the condition of determining to make denitrogenation, desulfurization and/or hydrocracking under any given situation, with utmost dispatch, to finish.So, organic nitrogen compound is to the active influence of the hydrocracking of these compositions, be likely because the dehydrogenation that these conditions are suitable for that the most quite high organonitrogen content is arranged and the given raw material of minimum hydrocracking is arranged, the new raw material of per pass less than 20% volume for example, its speed may have low concentration hydrocracking with the hydrocracking another kind, and to suppress the raw material of composition (as organic nitrogen compound) identical.At last, in this technology, be based on primary screening test, come practically to determine condition that some charging is touched special catalyst and raw material.
As use acid higher slightly catalyzer, isomerization reaction is to carry out under the condition similar to above-mentioned conversion reaction.Isomerisation of olefin is preferably under 500 °～900 the temperature and carries out, and the isomerization of paraffinic hydrocarbons, naphthalene class and alkyl aromatics is preferably carried out under 700 °～1000 °F.Here the isomerization reaction of special expectation is nhepene and/or octane can be converted into isoheptane and/or octane-iso; Butane is converted into Trimethylmethane; Methylcyclopentane is converted into hexanaphthene; M-xylene and/or o-Xylol are converted into p-Xylol; 1-butylene is converted into 2-butylene and/or iso-butylene; N-hexylene is converted into dissident's alkene; Tetrahydrobenzene is converted into methyl cyclopentene or the like.Best catalyst mode to be MnAPSO with the polyvalent metal compounds (as thioether) of II-A family, II-B family metal and uncommon earth metals combine form.For alkylation and dealkylation process, expectation MnAPSO composition preferably has at least 5
Micropore.The temperature that the dealkylation of alkyl aromatic hydrocarbon is used, usually be at least 350 °F, produce the substantive cracking of raw material or produce converted product, its temperature range generally will reach about 700 °F, preferably at least 450 °F, but can not be higher than the critical temperature that makes the compound dealkylation.Used pressure condition should can make aromatic raw material remain on liquid state at least.For alkylated reaction, used temperature can be hanged down to 250 °F, but general peaceful choosing is at least 350 °F.In the alkylation process of benzene, toluene and dimethylbenzene, first-selected alkylating agent is an alkene, as ethene and propylene.
Claims (10)
1, a kind of method for preparing crystalline molecular sieve, this molecular sieve has MnO
2, AlO
2, PO
2And SiO
2The three-dimensional micropore network structure of tetrahedral oxide units is that the experience chemistry of basis representation consists of with anhydrous oxide:
mR：(Mn
wAl
xP
ySi
z)O
2
Wherein " R " representative is present at least a organic formwork agent in the intracrystalline micropore system; " m " represents every mole of (Mn
wAl
xP
ySi
z) O
2In the mole number of R, its value is zero to 0.3; And " w ", " x ", " y " and " z " represent to be present in the molar fraction of manganese, aluminium, phosphorus and silicon in the tetrahedral oxide respectively, and this molar fraction is to be in the pentagon Composition Region that is limited by Fig. 1 mid point A, B, C, D and E,
This method comprises descends heating 2 hours to 30 days with containing the reaction source of manganese, aluminium, phosphorus and silicon and the reaction mixture of one or more organic formwork agents composition at 50-250 ℃, to produce this molecular sieve, the composition of this reaction mixture is expressed as with the mol ratio of oxide compound through hydrothermal crystallization:
aR：(Mn
wAl
xP
ySi
z)O
2：bH
2O
Wherein " R " is a kind of organic formwork agent; " a " is the amount of " R ", and its value is greater than 0 to 6; The value of " b " is 2 to 300; " w ", " x ", " y " and " z " represent to be present in (Mn respectively
wAl
xP
ySi
z) O
2In the unit manganese, aluminium, phosphorus and silicon molar fraction, value separately will drop in F, G in Fig. 3 ternary phase diagrams, H, I and 5 determined pentagon compositions of the J district, and the F among Fig. 3, G, H, I and J point have following " w ", " x ", " y " and " z " value:
The point molar fraction
X Y (W+Z)
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.02
I 0.01 0.01 0.98
J 0.60 0.01 0.39
2, the process of claim 1 wherein that the phosphorus source in the reaction mixture is an ortho-phosphoric acid.
3, the process of claim 1 wherein that the phosphorus source in the reaction mixture is an ortho-phosphoric acid, and the aluminium source is a kind of compound that is selected from puppet-boehmite and aluminium alkoxide at least.
4, the method for claim 3, aluminium alkoxide wherein is an aluminium isopropoxide.
5, the silicon source that the process of claim 1 wherein is a silicon-dioxide.
6, the manganese source that the process of claim 1 wherein is to be selected from its vitriol, carboxylate salt, oxide compound, bromide, iodide and their mixture.
7, the process of claim 1 wherein that organic formwork agent is to be selected from quaternary ammonium Huo quaternary phosphonium compound, its chemical formula is as follows:
R
4X
+
X is nitrogen or phosphorus in the formula, and each R is the alkyl or aryl that has 1～8 carbon atom.
8, the organic formwork agent that the process of claim 1 wherein is an amine.
9, the organic formwork agent that the process of claim 1 wherein is to be selected from the tetramethylammonium ion; The Tetrylammonium ion; The tetrapropylammonium ion; The tetrabutylammonium ion; 4 penta ammonium ions; The 2-Tri N-Propyl Amine; Tripropyl amine; Triethylamine; Trolamine; Piperidines; Hexahydroaniline; The 2-picoline; N, N-diformazan benzylamine; N, N '-dimethylethanolamine; Choline; N, N '-lupetazin; 1, heavy azabicyclic (2,2, the 2) octane of 4-; N methyldiethanol amine; The N-Mono Methyl Ethanol Amine; The N-picoline; The 3-methyl piperidine; N-methylcyclohexylamine; 30 methyl piperidines; The 4-picoline; Rubane; N, N '-dimethyl-1, heavy azabicyclic (2,2,2) the octane ion of 4-; The 2-n-Butyl Amine 99; Neopentyl amine; The 2-n-amylamine; Isopropylamine; TERTIARY BUTYL AMINE; 1; Tetramethyleneimine; 2-imidazolone and polyquaternium [(C
14H
32N
2) (OH)
2]
xWherein x is 2 at least.
10, the process of claim 1 wherein molecular sieve 200 °-700 ℃ down calcinings, with remove exist in the system of intracrystalline hole to the small part organic formwork agent.
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|---|---|---|---|
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| US06/600,175 US4686092A (en) | 1984-04-13 | 1984-04-13 | Manganese-aluminum-phosphorus-silicon-oxide molecular sieves |
| CN 85103260 CN1011301B (en) | 1984-04-13 | 1985-04-27 | Process for producing manganese-aluminum-phosphorus-silicon-oxide molecular sieve |
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