WO2020082944A1 - 磷铝分子筛scm-18、其制备方法及应用 - Google Patents
磷铝分子筛scm-18、其制备方法及应用 Download PDFInfo
- Publication number
- WO2020082944A1 WO2020082944A1 PCT/CN2019/106628 CN2019106628W WO2020082944A1 WO 2020082944 A1 WO2020082944 A1 WO 2020082944A1 CN 2019106628 W CN2019106628 W CN 2019106628W WO 2020082944 A1 WO2020082944 A1 WO 2020082944A1
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- WO
- WIPO (PCT)
- Prior art keywords
- molecular sieve
- aluminum
- phosphorous
- precursor
- phosphorus
- Prior art date
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 237
- 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 237
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 118
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 115
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 82
- 239000002243 precursor Substances 0.000 claims abstract description 68
- 239000000203 mixture Substances 0.000 claims abstract description 44
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 40
- 239000011574 phosphorus Substances 0.000 claims abstract description 40
- 239000012452 mother liquor Substances 0.000 claims abstract description 33
- 239000000126 substance Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003463 adsorbent Substances 0.000 claims abstract description 13
- RHQQHZQUAMFINJ-GKWSUJDHSA-N 1-[(3s,5s,8s,9s,10s,11s,13s,14s,17s)-3,11-dihydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]-2-hydroxyethanone Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CC[C@H]21 RHQQHZQUAMFINJ-GKWSUJDHSA-N 0.000 claims abstract description 6
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 71
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 55
- 238000002425 crystallisation Methods 0.000 claims description 53
- 230000008025 crystallization Effects 0.000 claims description 53
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- 239000011148 porous material Substances 0.000 claims description 28
- 239000005416 organic matter Substances 0.000 claims description 24
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 claims description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 15
- ATXBDDBELMGWOQ-UHFFFAOYSA-N [OH-].[NH4+].C1(=CC=C(C=C1)CC1N(CCC1)C)CC1N(CCC1)C Chemical compound [OH-].[NH4+].C1(=CC=C(C=C1)CC1N(CCC1)C)CC1N(CCC1)C ATXBDDBELMGWOQ-UHFFFAOYSA-N 0.000 claims description 14
- 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 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical class O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 27
- 238000003756 stirring Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 19
- 229910017119 AlPO Inorganic materials 0.000 description 17
- 238000009616 inductively coupled plasma Methods 0.000 description 13
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 10
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 6
- -1 organic molecules Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 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
- 230000007935 neutral effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- AVUYXHYHTTVPRX-UHFFFAOYSA-N Tris(2-methyl-1-aziridinyl)phosphine oxide Chemical compound CC1CN1P(=O)(N1C(C1)C)N1C(C)C1 AVUYXHYHTTVPRX-UHFFFAOYSA-N 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
- 229910052908 analcime Inorganic materials 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001690 harmotome Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 230000009916 joint effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 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 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 125000003410 quininyl group Chemical group 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 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
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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- B01J29/83—Aluminophosphates [APO compounds]
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/082—Decomposition and pyrolysis
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2006/14—Pore volume
Definitions
- the present application relates to the technical field of molecular sieves, and more particularly to a phosphorous aluminum molecular sieve, its preparation method and application.
- molecular sieves are a type of porous crystalline material. There are more than 250 types of molecular sieves with known structures discovered so far. Most molecular sieves have a large internal specific surface area and open internal space. These internal spaces can be used as a reaction place, and can also be used to accommodate some guest molecules, such as metals, metal oxides, organic molecules, water molecules and so on. Since the molecular sieve has uniform and regular pores, and the pore size is of the same order as the molecule, it is possible to "select" the entry and exit of molecules to obtain the shape selection effect. Because of the above characteristics, molecular sieves are widely used as catalysts, catalyst carriers, adsorbents and detergents. They have been widely used in petrochemical, environmental protection, and adsorption and separation fields.
- Zeolite framework typically by co-vertex (typically an oxygen atom) are connected by a tetrahedral coordination (TO 4) is made to aluminum phosphate molecular sieves, such sieve skeleton by AlO 4 - tetrahedra and PO 4 + tetrahedra connected
- TO 4 tetrahedral coordination
- aluminum or phosphorus in the aluminum phosphate molecular sieve can also be replaced by other elements, the most common of which are silicon (the resulting molecular sieve is called SAPO) and transition metal elements (the resulting molecular sieve is called MAPO)
- SAPO silicon
- MAPO transition metal elements
- US Patent US4310440 uses organic amines or quaternary ammonium compounds as template agents to hydrothermally synthesize a series of aluminum phosphate molecular sieves, including: AlPO 4 -5, AlPO 4 -8, AlPO 4 -9, AlPO 4 -11, AlPO 4 -12, AlPO 4 -14, AlPO 4 -16, AlPO 4 -17, AlPO 4 -18, AlPO 4 -20, AlPO 4 -21, AlPO 4 -22, AlPO 4 -23, AlPO 4 -25, AlPO 4 -26, AlPO 4 -28, AlPO 4 -31, etc.
- the template used includes tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tripropylene Amine, triethylamine, isopropylamine, butylamine, ethylenediamine, piperidine and its derivative
- U.S. Patent No. 4,440,871 gives a synthesis method of silicon-containing phosphoroaluminum molecular sieves, which include SAPO-5, SAPO-11, SAPO-16, SAPO-17, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-37, SAPO-40, SAPO-41, SAPO-42 and SAPO-44 and so on.
- U.S. Patent No. 4,754,651 gives a series of synthetic methods of metal-containing silicoaluminozeolites, including TiAPSO containing titanium, MgAPSO containing magnesium, MnAPSO containing manganese, CoAPSO containing cobalt, ZnAPSO containing zinc and FeAPSO containing iron and many more.
- organic templating agent For the synthesis of phosphoaluminum molecular sieves, the type of organic templating agent is the most important factor in determining its structure. New templating agents tend to be easier to obtain new molecular sieves. So far, organic amines and quaternary ammonium type organic compounds are synthesized by phosphorous aluminum sieve The most widely used template agent.
- the phosphoroaluminum molecular sieve has a unique X-ray diffraction pattern and can be used as an adsorbent, a catalyst, or a catalyst carrier.
- the present application provides a phosphorous-aluminum molecular sieve having a schematic chemical composition of Al 2 O 3 .nP 2 O 5 , where n represents a phosphorus-aluminum molar ratio and is between about 0.8 and about 1.2 Within the range of X, the molecular sieve X-ray diffraction pattern shows the relative intensity characteristics shown in the following table:
- the present application provides a method for preparing phosphorous aluminum molecular sieve, including the following steps:
- the step i) further includes:
- organic substance R is ammonium hydroxide having the following structural formula:
- the groups R1-R12 may be the same or different, and are independently selected from H and C 1-6 alkyl groups, preferably selected from H and C 1-3 alkyl groups, more preferably H; and
- the groups R13 and R14 may be the same or different, and are independently selected from C 1-6 alkyl, preferably C 1-3 alkyl, more preferably methyl.
- the present application provides phosphoroaluminum molecular sieve obtained by the preparation method disclosed herein.
- the present application provides a molecular sieve composition comprising a phosphorous aluminum molecular sieve according to the present application or a phosphorous aluminum molecular sieve prepared according to the method of the present application, and a binder.
- the present application provides the use of the molecular sieve according to the present application, the molecular sieve prepared according to the present application method, or the molecular sieve composition according to the present application as an adsorbent, catalyst, or catalyst carrier.
- the phosphorous aluminum molecular sieve of the present application has an open pore system, so it can accommodate guest molecules, for example, as an adsorbent for small organic molecules and water molecules, or as a catalyst carrier supporting metals or metal oxides, such as copper oxide, etc. Nitrogen oxide tail gas treatment catalyst.
- FIG. 1 is an XRD pattern of the phosphor aluminum molecular sieve precursor obtained in Example 1.
- FIG. 1 is an XRD pattern of the phosphor aluminum molecular sieve precursor obtained in Example 1.
- FIG. 2 is an XRD pattern of the phosphorous aluminum molecular sieve obtained in Example 1.
- phosphorus aluminum ratio or “phosphorus aluminum molar ratio” refers to the molar ratio between phosphorus in terms of P 2 O 5 and aluminum in terms of Al 2 O 3 .
- the term "specific surface area” refers to the total area of the sample per unit mass, including the inner surface area and the outer surface area.
- Non-porous samples only have external surface areas, such as portland cement, some clay mineral powder, etc .; porous and porous samples have external and internal surface areas, such as asbestos fiber, diatomaceous earth, and molecular sieve.
- the surface area of pores with pore diameters of less than 2 nm in porous and porous samples is the internal surface area.
- the surface area after deducting the internal surface area is called the external surface area, and the external surface area per unit mass of the sample is the external specific surface area.
- pore volume refers to the volume of pores per molecular mass sieve.
- total pore volume refers to the volume of all pores (generally only including pores with a pore diameter of less than 50 nm) per unit mass of molecular sieve.
- micropore pore volume refers to the volume of all micropores (generally refers to pores with a channel diameter of less than 2 nm) possessed by a molecular sieve per unit mass.
- the schematic chemical composition of the molecular sieve and molecular sieve precursor refers to the chemical composition of the skeleton of the molecular sieve / molecular sieve precursor, and the chemical composition only schematically represents the phosphorus in the skeleton of the molecular sieve / molecular sieve precursor (In terms of P 2 O 5 ) and aluminum (in terms of Al 2 O 3 ) molar ratio between elements, and does not strictly limit the specific existence of each element, which can usually adopt inductively coupled plasma atomic emission spectroscopy ( ICP) method.
- ICP inductively coupled plasma atomic emission spectroscopy
- XRD X-ray diffraction spectroscopy
- W, M, S, VS, WM, MS, and S-VS, etc. represent the corresponding diffraction peak calculated based on the diffraction peak area relative to the strongest diffraction peak (i.e. area Relative intensity of the largest diffraction peak) I / I 0 , where I represents the peak area of the corresponding diffraction peak and I 0 represents the peak area of the strongest diffraction peak, W represents weak, M represents medium, S represents strong, and VS represents very Strong, WM stands for weak to medium, MS stands for medium to strong, and S-VS stands for strong to very strong, this representation is well known to those skilled in the art. Generally speaking, W represents less than 20; M represents 20-40; S represents 40-60; VS represents greater than 60, WM represents less than 40, MS represents 20-60, and S-VS represents greater than 40.
- the term “after calcination”, “after calcination form” or “post-calcination molecular sieve” refers to the state of the molecular sieve after calcination.
- the post-baking state may be a state in which a synthetic molecular sieve is calcined to further remove organic substances (especially organic template agents) and water that may exist in its pores.
- the present application provides a phosphorous aluminum molecular sieve having a schematic chemical composition of Al 2 O 3: nP 2 O 5 in a mole meter, where n represents a molar ratio of phosphorous to aluminum, and ranges from about 0.8 to Within the range of about 1.2, the X-ray diffraction pattern of the molecular sieve shows the relative intensity characteristics shown in the following table:
- the X-ray diffraction pattern of the molecular sieve shows the relative intensity characteristics shown in the following table:
- the X-ray diffraction pattern of the molecular sieve shows the relative intensity characteristics shown in the following table:
- the X-ray diffraction pattern of the molecular sieve shows the relative intensity characteristics shown in the following table:
- the X-ray diffraction pattern of the molecular sieve shows the relative intensity characteristics shown in the following table:
- the X-ray diffraction pattern of the molecular sieve shows the relative intensity characteristics shown in the following table:
- the specific surface area of the phosphorous aluminum molecular sieve is about 150-500 square meters / gram, preferably about 200-400 square meters / gram; the pore volume of the micropores is about 0.09-0.25 milliliters / gram, preferably about 0.10-0.20 ml / g.
- the present application provides a method for preparing phosphoroaluminum molecular sieve, including the following steps:
- the X-ray diffraction pattern of the molecular sieve precursor shows the relative intensity characteristics shown in the following table:
- the X-ray diffraction pattern of the molecular sieve precursor shows the relative intensity characteristics shown in the following table:
- the X-ray diffraction pattern of the molecular sieve precursor shows the relative intensity characteristics shown in the following table:
- the X-ray diffraction pattern of the molecular sieve precursor shows the relative intensity characteristics shown in the following table:
- the X-ray diffraction pattern of the molecular sieve precursor shows the relative intensity characteristics shown in the following table:
- the framework of the phosphorous-aluminum molecular sieve precursor has a schematic chemical composition of Al 2 O 3 .nP 2 O 5 , where n represents the molar ratio of phosphorous to aluminum, and is between about 0.8 to about Within 1.2.
- step i) further includes:
- organic substance R is ammonium hydroxide having the following structural formula:
- the groups R1-R12 may be the same or different, and are independently selected from H and C 1-6 alkyl groups, preferably selected from H and C 1-3 alkyl groups, more preferably H; and
- the groups R13 and R14 may be the same or different, and are independently selected from C 1-6 alkyl, preferably C 1-3 alkyl, more preferably methyl.
- the aluminum source is not particularly limited, and may be, for example, those conventionally used for preparing aluminum-containing molecular sieves.
- the aluminum source is one or more selected from pseudo-boehmite, aluminum isopropoxide, aluminum sol, aluminum hydroxide, aluminum sulfate, aluminum chloride and aluminum oxide, preferably It is selected from pseudoboehmite and aluminum isopropoxide.
- the phosphorus source in the production method of the present application, there is no particular limitation on the phosphorus source, and for example, it may be those conventionally used for preparing phosphorus-containing molecular sieves.
- the phosphorus source is one or more selected from phosphoric acid, phosphorous acid and phosphorus pentoxide, preferably phosphoric acid.
- the aluminum source, the phosphorus source, the organic matter R and the water are calculated according to the aluminum source (calculated as Al 2 O 3 ): phosphorus source (calculated as P 2 O 5 ): R: H 2
- the molar ratio of O is about 1: (1.0-2.0) :( 2.5-4.8) :( 100-300).
- the organic substance R is N, N '-(1,4-phenylene bis (methylene)) bis (N-methylpyrrolidine) ammonium hydroxide, and its chemical structural formula is as follows :
- step ib) is performed under the following conditions: a closed reaction vessel, a crystallization temperature of about 130-200 ° C, and a crystallization time of about 24-150 hours. Further preferably, the crystallization temperature is about 145-185 ° C and the crystallization time is about 48-120 hours.
- the step ib) further includes washing and drying the obtained phosphorous aluminum molecular sieve precursor.
- the present application does not particularly limit the washing and drying steps, and can be performed in a conventional manner.
- the washing may be performed with deionized water, and methods such as suction filtration or centrifugal separation may be used until the washing solution is near neutral; and the drying may be, for example, in an oven at about 100-250 Dry for about 1-48 hours at °C.
- the molar ratio of phosphorus in P 2 O 5 and aluminum in Al 2 O 3 (P 2 O 5 / Al 2 O 3 ) in the molecular sieve precursor obtained in step ib) is about It is in the range of 0.8 to about 1.2, and the weight content of organic matter is in the range of about 8% to about 40% by weight of the molecular sieve precursor.
- the phosphorous aluminum molecular sieve precursor prepared in step ib) of the present application has a stable crystal structure, and can be calcined according to a conventional calcination method, which is not particularly limited in this application.
- the baking treatment may be performed at about 500-750 ° C in an air atmosphere, and the baking time may be, for example, about 1-10 hours.
- the roasting may be roasting in an air atmosphere at about 550 ° C for about 6 hours.
- there may be a certain amount of carbonaceous material remaining in the resulting phosphorous aluminum molecular sieve but such residual carbonaceous material is not counted in the chemical composition of the molecular sieve.
- the X-ray diffraction pattern of the phosphoroaluminum molecular sieve obtained in step ii) shows the relative intensity characteristics shown in the following table:
- the X-ray diffraction pattern of the phosphorus aluminum molecular sieve obtained in step ii) shows the relative intensity characteristics shown in the following table:
- the X-ray diffraction pattern of the phosphorous aluminum molecular sieve obtained in step ii) shows the relative intensity characteristics shown in the following table:
- the X-ray diffraction pattern of the phosphorus aluminum molecular sieve obtained in step ii) shows the relative intensity characteristics shown in the following table:
- the X-ray diffraction pattern of the phosphorus aluminum molecular sieve obtained in step ii) shows the relative intensity characteristics shown in the following table:
- the X-ray diffraction pattern of the phosphorous aluminum molecular sieve obtained in step ii) shows the relative intensity characteristics shown in the following table:
- the phosphorous aluminum molecular sieve with a specific X-ray diffraction pattern of the present application can be prepared in a directional manner.
- the present application provides phosphoroaluminum molecular sieves prepared by the method of the present application.
- the present application provides a molecular sieve composition comprising the phosphorous aluminum molecular sieve according to the present application or the phosphorous aluminum molecular sieve prepared according to the method of the present application, and a binder.
- the molecular sieve composition can be in any physical form, such as powder, granules, or molded products (such as strips, clover, etc.). These physical forms can be obtained in any manner conventionally known in the art, and are not particularly limited.
- the binder is not particularly limited, for example, those conventionally used for preparing adsorbents or catalysts can be used, including but not limited to clay, clay, silica, silica gel, alumina, zinc oxide or Its mixture.
- the present application provides the use of the phosphoroaluminum molecular sieve according to the present application, the phosphoroaluminum molecular sieve prepared according to the present application method, or the molecular sieve composition according to the present application as an adsorbent, catalyst or catalyst support.
- adsorbent examples include the removal of a small amount of water in organic solvents such as isopropanol, isobutanol, and isobutanone, and for the adsorption and removal of a small amount of water in natural gas.
- the catalyst it may be mentioned, for example, that Cu is supported on an SCM-18 molecular sieve so that it can be used for catalytic decomposition of nitrogen-containing oxides in automobile exhaust.
- the present application provides the following technical solutions:
- Item 1 An SCM-18 molecular sieve, which has a chemical composition of the following molar ratio without calculating moisture: Al 2 O 3: nP 2 O 5 , n is 1.0-3.0, X-ray of the molecular sieve The diffraction pattern shows the relative intensity characteristics shown in the following table:
- step ib) After washing and drying the product obtained in step ib) above, a precursor of SCM-18 molecular sieve is obtained;
- SCM-18 molecular sieve can be obtained by roasting the precursor of the above SCM-18 molecular sieve.
- Item 3 The preparation method of SCM-18 molecular sieve according to item 2, characterized in that the aluminum source, the phosphorus source, the organic matter R and the water are in accordance with Al 2 O 3 : (1.0-2.0) P 2 O 5 : (2.5- 4.8) The ratio of R: (100-300) H 2 O is uniformly mixed to obtain a synthetic mother liquor.
- Item 4 The preparation method of SCM-18 molecular sieve according to item 2, characterized in that the organic matter R is N, N '-(1,4-phenylene bis (methylene)) bis (N-methylpyrrole Alkane) ammonium hydroxide.
- Item 5 The preparation method of the SCM-18 molecular sieve according to item 2, characterized in that the crystallization temperature is 130 ° C-200 ° C and the crystallization time is 24-150 hours.
- Item 6 The preparation method of SCM-18 molecular sieve according to item 2, characterized in that the aluminum source is at least one of pseudo-boehmite, aluminum isopropoxide, aluminum sol, and alumina; the phosphorus source is selected One or more of autophosphoric acid, phosphorous acid, or phosphorus pentoxide.
- the aluminum source is at least one of pseudo-boehmite, aluminum isopropoxide, aluminum sol, and alumina
- the phosphorus source is selected One or more of autophosphoric acid, phosphorous acid, or phosphorus pentoxide.
- Item 7 The preparation method of SCM-18 molecular sieve according to item 2, characterized in that the precursor of SCM-18 molecular sieve has the following X-ray diffraction pattern:
- Item 8 The preparation method of the SCM-18 molecular sieve according to item 2, characterized in that the precursor of the SCM-18 molecular sieve has the following composition, excluding moisture: m Organic composition: Al2O 3 : P 2 O 5 , where 0.03 ⁇ m ⁇ 0.3.
- a molecular sieve composition comprising the molecular sieve described in item 1 or the molecular sieve prepared according to the preparation method of any one of items 2-8, and a binder.
- Item 10 Application of the molecular sieve described in Item 1, the molecular sieve prepared according to the preparation method of any one of Items 2-8, or the molecular sieve composition described in Item 9 as an adsorbent or a catalyst.
- the raw materials used for N, N '-(1,4-phenylene bis (methylene)) bis (N-methylpyrrolidine) ammonium hydroxide are produced by Sankai Chemical Co., Ltd.
- the concentration is 20.75% (aqueous solution) chemically pure; pseudoboehmite is produced by Shandong Yinglang Chemical Co., Ltd., with a weight content of 72% based on Al 2 O 3 , chemically pure; phosphoric acid is purchased from Sinopharm Group Chemical Reagent Co., Ltd., quality
- the concentration is 85% (aqueous solution), analytically pure; aluminum isopropoxide is purchased from Sinopharm Group Chemical Reagent Co., Ltd., and the weight content in terms of Al 2 O 3 is 24.7%, chemically pure.
- the chemical composition of the molecular sieve was determined by inductively coupled plasma atomic emission spectrometry (ICP) method.
- the instrument used was Kontron Model S-35.
- the solid molecular sieve sample was dissolved in HF to make a solution before the test.
- the specific surface area and pore volume of the molecular sieve are determined by the N 2 physical adsorption and desorption method.
- the instrument used is the Quadrasorb evo gas adsorption specific surface area and pore volume tester of Kangta Company. The temperature is measured at 77K. Before the test, the sample is placed at 573K Vacuum pretreatment for 6h.
- the specific surface area is calculated from the BET equation, and the pore volume is calculated using the t-plot method.
- the content of organic matter in the molecular sieve precursor is determined by thermogravimetric analysis.
- the instrument used is a NETZSCH STA449F3 thermogravimetric analyzer with an air flow rate of 30 ml / min and a heating rate of 10 ° C / min.
- the weight loss percentage is taken as the weight percentage content of organic matter.
- the above synthetic mother liquor is placed in a closed reaction vessel for crystallization.
- the crystallization temperature is 175 ° C and the crystallization time is 84 hours.
- a precursor of the phosphorous aluminum molecular sieve is obtained.
- the molar ratio of phosphorus in terms of P 2 O 5 and aluminum in terms of Al 2 O 3 was 1.0, and the weight content of organic matter was 15.3%. It has the XRD pattern shown in Figure 1 and the XRD pattern data shown in Table 1A.
- the precursor of the phosphorous aluminum molecular sieve is calcined at 550 ° C for 5 hours to obtain the phosphorous aluminum molecular sieve.
- the schematic chemical composition of the product molecular sieve measured by inductively coupled plasma atomic emission spectrometry is Al 2 O 3 ⁇ 1.0P 2 O 5
- the specific surface area of the molecular sieve of the product obtained is 394 square meters / gram
- the pore volume of the micropores is 0.17 milliliters / gram
- the XRD pattern is shown in FIG. 2
- the corresponding XRD pattern data is shown in Table 1B.
- the above synthetic mother liquor is placed in a closed reaction vessel for crystallization.
- the crystallization temperature is 175 ° C and the crystallization time is 84 hours.
- a precursor of the phosphorous aluminum molecular sieve is obtained.
- the molar ratio of phosphorus in P 2 O 5 to aluminum in Al 2 O 3 (P 2 O 5 / Al 2 O 3 ) is 1.0, and the weight content of organic matter is 17.9%.
- the XRD pattern data is shown in Table 2A .
- the schematic chemical composition of the product molecular sieve measured by inductively coupled plasma atomic emission spectrometry (ICP) is Al 2 O 3 ⁇ 1.0P 2 O 5.
- the specific surface area of the product molecular sieve obtained is 363 square meters / gram, and the pore volume is 0.16 Ml / g
- XRD pattern data is shown in Table 2B.
- the above synthetic mother liquor is placed in a closed reaction vessel for crystallization.
- the crystallization temperature is 175 ° C and the crystallization time is 84 hours.
- a precursor of the phosphorous aluminum molecular sieve is obtained.
- the molar ratio of phosphorus in P 2 O 5 to aluminum in Al 2 O 3 (P 2 O 5 / Al 2 O 3 ) is 0.98, and the weight content of organic matter is 14.4%.
- the XRD pattern data is shown in Table 3A .
- the precursor of the phosphorous aluminum molecular sieve is calcined at 550 ° C for 5 hours to obtain a phosphorous aluminum molecular sieve.
- the schematic chemical composition of the product molecular sieve measured by inductively coupled plasma atomic emission spectrometry (ICP) is Al 2 O 3 ⁇ 0.98P 2 O 5
- the specific surface area of the molecular sieve of the product obtained is 410 square meters / gram
- the pore volume of the micropore is 0.18 milliliters / gram
- the XRD pattern data is shown in Table 3B.
- the above synthetic mother liquor is placed in a closed reaction vessel for crystallization.
- the crystallization temperature is 190 ° C and the crystallization time is 60 hours.
- a precursor of the phosphorous aluminum molecular sieve is obtained.
- the molar ratio of phosphorus in P 2 O 5 to aluminum in Al 2 O 3 (P 2 O 5 / Al 2 O 3 ) is 1.0, and the weight content of organic matter is 20.2%.
- the XRD pattern data is shown in Table 4A .
- the precursor of the phosphorous aluminum molecular sieve is calcined at 550 ° C for 5 hours to obtain the phosphorous aluminum molecular sieve.
- the schematic chemical composition of the product molecular sieve measured by inductively coupled plasma atomic emission spectrometry (ICP) is Al 2 O 3 ⁇ 1.0P 2 O 5
- the specific surface area of the molecular sieve of the product obtained is 357 square meters / gram
- the micropore pore volume is 0.15 milliliters / gram
- the XRD pattern data is shown in Table 4B.
- the above synthetic mother liquor is placed in a closed reaction vessel for crystallization.
- the crystallization temperature is 150 ° C. and the crystallization time is 120 hours.
- a precursor of a phosphorus aluminum molecular sieve is obtained.
- the molar ratio of phosphorus in P 2 O 5 to aluminum in Al 2 O 3 (P 2 O 5 / Al 2 O 3 ) is 0.95, the weight content of organic matter is 19.0%, and the XRD pattern data is shown in Table 5A .
- the precursor of the phosphorous aluminum molecular sieve is calcined at 550 °C for 5 hours to obtain the phosphorous aluminum molecular sieve.
- the schematic chemical composition of the product molecular sieve measured by inductively coupled plasma atomic emission spectrometry (ICP) is Al 2 O 3 ⁇ 0.95P 2 O 5
- the specific surface area of the molecular sieve of the product obtained is 330 m 2 / g
- the pore volume of the micropores is 0.15 ml / g.
- the corresponding XRD pattern data is shown in Table 5B.
- the above synthetic mother liquor is placed in a closed reaction vessel for crystallization.
- the crystallization temperature is 175 ° C and the crystallization time is 84 hours.
- a precursor of the phosphorous aluminum molecular sieve is obtained.
- the molar ratio of phosphorus in P 2 O 5 to aluminum in Al 2 O 3 (P 2 O 5 / Al 2 O 3 ) is 1.0, and the weight content of organic matter is 15.6%.
- the XRD pattern data is shown in Table 6A .
- the precursor of the phosphorous aluminum molecular sieve is calcined at 550 ° C for 5 hours to obtain the phosphorous aluminum molecular sieve.
- the schematic chemical composition of the product molecular sieve measured by inductively coupled plasma atomic emission spectrometry is Al 2 O 3 ⁇ 1.0P 2 O 5
- the specific surface area of the molecular sieve of the product obtained is 408 square meters / gram
- the pore volume of the micropores is 0.19 milliliters / gram
- the XRD pattern data is shown in Table 6B.
- the above synthetic mother liquor is placed in a closed reaction vessel for crystallization.
- the crystallization temperature is 175 ° C and the crystallization time is 84 hours.
- a precursor of the phosphorous aluminum molecular sieve is obtained.
- the molar ratio of phosphorus in P 2 O 5 to aluminum in Al 2 O 3 (P 2 O 5 / Al 2 O 3 ) is 1.03, the weight content of organic matter is 17.8%, and the XRD pattern data is shown in Table 7A .
- the precursor of the phosphorous aluminum molecular sieve is calcined at 550 ° C for 5 hours to obtain the phosphorous aluminum molecular sieve.
- the schematic chemical composition of the product molecular sieve measured by inductively coupled plasma atomic emission spectrometry (ICP) is Al 2 O 3 ⁇ 1.03P 2 O 5
- the specific surface area of the molecular sieve of the obtained product is 390 square meters / gram
- the micropore pore volume is 0.17 milliliters / gram
- the XRD pattern data is shown in Table 7B.
- the above synthetic mother liquor is placed in a closed reaction vessel for crystallization.
- the crystallization temperature is 175 ° C and the crystallization time is 84 hours.
- a precursor of the phosphorous aluminum molecular sieve is obtained.
- the molar ratio of phosphorus in P 2 O 5 to aluminum in Al 2 O 3 (P 2 O 5 / Al 2 O 3 ) is 1.0, and the weight content of organic matter is 16.4%.
- the XRD pattern data is shown in Table 8A
- the phosphorous aluminum molecular sieve can be obtained by roasting the precursor of the phosphorous aluminum molecular sieve at 550 ° C for 5 hours.
- the schematic chemical composition of the product molecular sieve measured by inductively coupled plasma atomic emission spectrometry (ICP) is Al 2 O 3 ⁇ 1.0P 2 O 5.
- the specific surface area of the product molecular sieve obtained is 392 square meters / gram, and the micropore volume is 0.19 Ml / g.
- the corresponding XRD pattern data is shown in Table 8B.
- the above synthetic mother liquor is placed in a closed reaction vessel for crystallization.
- the crystallization temperature is 190 ° C and the crystallization time is 60 hours.
- a precursor of the phosphorous aluminum molecular sieve is obtained.
- the molar ratio of phosphorus in P 2 O 5 to aluminum in Al 2 O 3 (P 2 O 5 / Al 2 O 3 ) is 0.99, the weight content of organic matter is 16.3%, and the XRD pattern data is shown in Table 9A .
- the phosphorous aluminum molecular sieve can be obtained by roasting the precursor of the phosphorous aluminum molecular sieve at 550 ° C for 5 hours.
- the schematic chemical composition of the product molecular sieve measured by inductively coupled plasma atomic emission spectrometry (ICP) is Al 2 O 3 ⁇ 0.99P 2 O 5.
- the specific surface area of the product molecular sieve obtained is 310 square meters / gram, and the pore volume is 0.15 Ml / g.
- the corresponding XRD pattern data is shown in Table 9B.
- the above synthetic mother liquor is placed in a closed reaction vessel for crystallization.
- the crystallization temperature is 190 ° C and the crystallization time is 60 hours.
- a precursor of the phosphorous aluminum molecular sieve is obtained.
- the molar ratio of phosphorus in P 2 O 5 to aluminum in Al 2 O 3 (P 2 O 5 / Al 2 O 3 ) is 1.0, the weight content of organic matter is 20.1%, and the XRD pattern data is shown in Table 10A .
- the phosphorous aluminum molecular sieve can be obtained by roasting the precursor of the phosphorous aluminum molecular sieve at 550 ° C for 5 hours.
- the schematic chemical composition of the product molecular sieve measured by inductively coupled plasma atomic emission spectrometry (ICP) was Al 2 O 3 ⁇ 1.0P 2 O 5.
- the specific surface area of the product molecular sieve obtained was 345 square meters / gram, and the micropore volume was 0.17. Ml / g.
- the corresponding XRD pattern data is shown in Table 10B.
- the above synthetic mother liquor is placed in a closed reaction vessel for crystallization.
- the crystallization temperature is 150 ° C. and the crystallization time is 120 hours.
- a precursor of a phosphorus aluminum molecular sieve is obtained.
- the molar ratio of phosphorus in P 2 O 5 to aluminum in Al 2 O 3 (P 2 O 5 / Al 2 O 3 ) is 1.01, and the weight content of organic matter is 14.7%.
- the XRD pattern data is shown in Table 11A .
- the phosphorous aluminum molecular sieve can be obtained by roasting the precursor of the phosphorous aluminum molecular sieve at 550 ° C for 5 hours.
- the schematic chemical composition of the product molecular sieve measured by inductively coupled plasma atomic emission spectrometry (ICP) is Al 2 O 3 ⁇ 1.01P 2 O 5.
- the specific surface area of the product molecular sieve obtained is 372 square meters / gram, and the micropore volume is 0.16 Ml / g.
- the corresponding XRD pattern data is shown in Table 11B.
- the molecular sieve composition can be used as an adsorbent or catalyst.
- Adsorption amount (weight of sample after adsorption-initial weight of sample) ⁇ initial weight of sample.
- the dried AlPO-5, AlPO-11, ZSM-5 molecular sieve and 3A molecular sieve were made into compositions according to the method given in Example 12, and 2 grams were taken out for the adsorption performance test. The results are listed in Table 12. in. In addition, 2 grams of silica gel was also tested for adsorption performance, and the results are also listed in Table 12.
- Table 12 The adsorption capacity of different adsorbents for different adsorbates
- the molecular sieve / molecular sieve composition of the present invention can be used as an adsorbent for many small organic molecules and water, and particularly has good adsorption performance for H 2 O.
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Abstract
Description
Claims (15)
- 根据权利要求1-3中任一项所述的磷铝分子筛,其中所述分子筛的比表面积为约150-500平方米/克,优选约200-400平方米/克;微孔孔容为约0.9-0.25毫升/克,优选约0.10-0.20毫升/克。
- 根据权利要求7所述的制备方法,其中在步骤ia)中将铝源、磷源、有机物R和水按照铝源(以Al 2O 3计)∶磷源(以P 2O 5计)∶R∶H 2O的摩尔比为大约1∶(1.0-2.0)∶(2.5-4.8)∶(100-300)的比例混合。
- 根据权利要求7或8所述的制备方法,其中所述有机物R为N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵。
- 根据权利要求7-9中任一项所述的制备方法,其中步骤ib)在如下条件下进行:密闭反应容器,晶化温度为约130-200℃、优选约145-185℃,晶化时间为约24-150小时、优选约48-120小时;以及优选地,所述步骤ib)还包括对所得磷铝分子筛前驱体进行洗涤和干燥。
- 根据权利要求7-10中任一项所述的制备方法,其中所述铝源为选自拟薄水铝石,异丙醇铝,铝溶胶,氢氧化铝,硫酸铝,氯化铝和氧化铝中的一种或多种,优选选自拟薄水铝石和异丙醇铝;和/或所述磷源为选自磷酸,亚磷酸和五氧化二磷中的一种或多种,优选磷酸。
- 根据权利要求5-11中任一项所述的制备方法,其中,所述磷铝分子筛前驱体中以P 2O 5计的磷和以Al 2O 3计的铝的摩尔比例(P 2O 5/Al 2O 3)在约0.8至约1.2的范围内,以及任选地,以所述磷铝分子筛前驱体的重量计,所述磷铝分子筛前驱体包含约8重量%至约40重量%的有机物。
- 通过权利要求5-12中任一项所述的制备方法得到的磷铝分子筛。
- 一种分子筛组合物,包含权利要求1-4和13中任一项所述的磷铝分子筛,以及粘结剂。
- 权利要求1-4和13中任一项所述的磷铝分子筛、或权利要求14所述的分子筛组合物作为吸附剂、催化剂或者催化剂载体的应用。
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JP2021523060A JP7373561B2 (ja) | 2018-10-25 | 2019-09-19 | アルミノリン酸塩分子篩scm-18、その調製、およびその用途 |
EP19876975.4A EP3872032A4 (en) | 2018-10-25 | 2019-09-19 | MOLECULAR SIEVE OF ALUMINOPHOSPHATE SCM-18, METHOD FOR PREPARATION AND USE |
US17/288,891 US11819834B2 (en) | 2018-10-25 | 2019-09-19 | Aluminophosphate molecular sieve SCM-18, its preparation and application thereof |
CA3117388A CA3117388C (en) | 2018-10-25 | 2019-09-19 | Aluminophosphate molecular sieve scm-18, its preparation and application thereof |
SG11202104152VA SG11202104152VA (en) | 2018-10-25 | 2019-09-19 | Aluminophosphate molecular sieve SCM-18, its preparation and application thereof |
BR112021007662-0A BR112021007662A2 (pt) | 2018-10-25 | 2019-09-19 | peneira molecular de aluminofosfato scm-18, método para preparação da mesma e uso da mesma |
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CN114180597B (zh) * | 2020-09-14 | 2023-06-06 | 中国石油化工股份有限公司 | Scm-34分子筛及其制备方法和应用 |
CN115504485B (zh) * | 2021-06-23 | 2023-08-29 | 中国石油化工股份有限公司 | 一种sapo-17分子筛的制备方法 |
CN116618002A (zh) * | 2023-05-04 | 2023-08-22 | 鲁西催化剂有限公司 | 一种氧化铝基吸附剂及其制备方法 |
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CN111099603B (zh) | 2022-12-09 |
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