CN1413170A - 结晶硅铝磷酸盐的合成 - Google Patents
结晶硅铝磷酸盐的合成 Download PDFInfo
- Publication number
- CN1413170A CN1413170A CN00817773A CN00817773A CN1413170A CN 1413170 A CN1413170 A CN 1413170A CN 00817773 A CN00817773 A CN 00817773A CN 00817773 A CN00817773 A CN 00817773A CN 1413170 A CN1413170 A CN 1413170A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- mixture
- aforementioned
- template
- sapo
- 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.)
- Pending
Links
- 230000015572 biosynthetic process Effects 0.000 title claims description 8
- 238000003786 synthesis reaction Methods 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims abstract description 85
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002808 molecular sieve Substances 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 63
- 238000003756 stirring Methods 0.000 claims abstract description 40
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 150000001336 alkenes Chemical class 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 12
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 11
- -1 Ketene dimethyl Chemical compound 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 3
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 3
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 3
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 14
- 238000002425 crystallisation Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 230000008025 crystallization Effects 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 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
- 238000005755 formation reaction Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 235000019587 texture Nutrition 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005216 hydrothermal crystallization Methods 0.000 description 2
- 239000003701 inert diluent Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001344 alkene derivatives Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 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
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000001354 calcination Methods 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
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- HFXKQSZZZPGLKQ-UHFFFAOYSA-N cyclopentamine Chemical compound CNC(C)CC1CCCC1 HFXKQSZZZPGLKQ-UHFFFAOYSA-N 0.000 description 1
- 229960003263 cyclopentamine Drugs 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000012262 fermentative production Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229910052732 germanium 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
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-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
- 230000010512 thermal transition Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/703—Activation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/30—Alpo and sapo
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
- Y10S502/514—Process applicable either to preparing or to regenerating or to rehabilitating catalyst or sorbent
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
本发明涉及一种制备结晶硅铝磷酸盐分子筛的方法。该方法包括向反应器中加入包括含硅组分、含铝组分、含磷组分和模板的混合物,并在足以形成结晶硅铝磷酸盐分子筛的温度和时间内加热的同时连续搅拌该混合物,其中在20-95%的加热时间内施以搅拌。结果可以显著增加结晶分子筛产品。
Description
发明领域
本发明涉及结晶硅铝磷酸盐(SAPO)分子筛的合成。特别是,本发明涉及通过在有效形成结晶硅铝磷酸盐分子筛的温度和时间内施加热的同时对起始原料进行搅拌以增加结晶SAPO分子筛的产率,其中在20-95%的施加热的时间内进行搅拌。
发明背景
分子筛通常具有微孔结构,它由化学上类似于粘土和长石的结晶硅铝酸盐构成,属于一类称为沸石的材料;或者是由包括有机胺或季铵盐的混合物所衍生的结晶铝磷酸盐构成;或者是由包括二氧化硅、氧化铝和磷酸盐的活性源的反应混合物通过水热结晶法制备的结晶硅铝磷酸盐构成。分子筛有多种用途。它们可用于干燥气体和液剂;也可用于基于大小和极性的选择性的分子分离;用作离子交换剂;用作裂解、氢化裂解、歧化、烷基化、异构化、氧化和把含氧物转变为碳氢化合物时的催化剂;用作化学载体;用于气相色谱;和用于石油工业中从蒸馏物中除去正烷烃。
硅铝磷酸盐(SAPO)分子筛近来备受关注。这类分子筛能够把含氧物转化为烯烃、芳香化合物和其它组合物。它们在把如甲醇和二甲醚之类的含氧组合物转化为如乙烯和丙烯之类的烯烃时特别有效。
已经公开了制备SAPO的多种方法。例如,美国专利号4,440,871公开了一种制备SAPO分子筛的方法。该方法通常包括将含磷化合物和含铝化合物相混合直到得到均匀的混合物。向该均匀混合物中加入模板和含二氧化硅的组合物,搅拌该混合物至获得最终的均匀混合物。然后加热该最终的均匀混合物以形成结晶SAPO分子筛。
美国专利号4,943,424和5,087,347公开了一种制备SAPO-11分子筛的方法,据报道该分子筛具有独特和实用的催化和形状选择性能。该分子筛的制备如下:制备含异丙醇铝和磷酸的含水反应混合物,之后将混合物与氧化硅混合,然后将该混合物与有机模板结合以形成反应混合物,接着调节混合物pH并加热以生成结晶分子筛产物。结晶在高压釜中进行,不需搅拌。
美国专利号5,663,471公开了制备SAPO-34的方法。该方法包括将含铝化合物、含磷化合物和酸混合在一起。均化该混合物并加入模板材料。加入模板后的混合物均化,并将全部混合物倾入反应器中。在室温下摇动反应器。然后加热反应器以形成结晶分子筛产物。产物回收并干燥。
美国专利号5,324,493公开了使用1,2-双-(4-吡啶基)-乙烷来结晶具有AEL结构的铝磷酸盐和硅铝磷酸盐的方法。该方法包括将铝、磷,和可有可无的硅的活性源混合在一起,并加入1,2-双-(4-吡啶基)-乙烷。该混合物在封闭体系中在自生压力下加热以形成结晶产品。反应后分离产品,洗涤并干燥。合成既可以静态地进行也可以在搅拌下进行。
遗憾的是,已知的制备结晶硅铝磷酸盐分子筛的方法效率很低。在有些情况下,少于50%重量的反应组分能够反应生成最终的结晶产物。非结晶的反应组分通常不加回收并作为废物处理。因此,希望找到一种反应方法,它不会产生大量的废物。
发明概述
为了克服在生产结晶硅铝磷酸盐分子筛过程中所产生的各种问题,本发明提供了一种新的制备结晶硅铝磷酸盐分子筛的方法。该方法包括向反应器中加入包含以下物质的混合物:含硅组分、含铝组分、模板和含磷组分,并且在有效形成结晶硅铝磷酸盐分子筛的温度和时间下施加热的同时搅拌该混合物,其中在20-95%的施加热的时间内进行搅拌。
理想的加热温度为50℃到250℃。加热持续时间可以为10分钟到240小时。理想的是,在20-90%的加热时间内施以搅拌,更优选地,在30-80%的加热时间内施以连续搅拌。
在另一实施方案中,含硅组分、含铝组分、模板和含磷组分的加入量可以有效地提供具有0.30-0.34SiO2/Al2O3/0.82-0.86P2O5比例的结晶分子筛组成。理想地,所述模板包含氢氧化四乙铵,更理想地,所述模板包含氢氧化四乙铵和二丙基胺。
在另一实施方案中,本发明提供了一种从含氧组合物制备烯烃产品的方法。该方法包括提供通过本发明方法制备的结晶硅铝磷酸盐分子筛,煅烧该分子筛,在有效形成烯烃产物的条件下使煅烧过的分子筛与含氧组合物接触。理想地,含氧组合物包括选自下列物质中的化合物:甲醇;乙醇;正丙醇;异丙醇;C4-C20醇;甲基乙基醚;二甲醚;乙醚;二异丙醚;甲醛;碳酸二甲酯;二甲基酮;乙酸及其混合物。理想地,烯烃产物在有效形成聚烯烃的条件下与生成聚烯烃的催化剂接触。发明详述
硅铝磷酸盐(SAPO)分子筛能够作为将含氧原料转变为烯烃组合物的特别理想的催化剂。它们是从含氧化合物制备烯烃如乙烯和丙烯的特别优良的催化剂。
硅铝磷酸盐分子筛通常被分类为具有8、10或12元环状结构的微孔材料。这些环状结构的平均孔径为约3.5-15埃。优选的小孔SAPO分子筛的平均孔径为约3.5-5埃,更优选为4.0-5.0埃。这些优选的孔径是典型的8元环的分子筛的孔径。
通常硅铝磷酸盐分子筛具有共角(corner-sharing)的[SiO2],[AlO2]和[PO2]四面体单元的分子框架结构。这类框架结构能有效地将各种含氧物转变为烯烃产物。
本发明分子筛框架结构内的[PO2]四面体单元可以由各种组分提供。这些含磷组分的例子包括磷酸,有机磷酸酯如磷酸三乙酯和铝磷酸盐。含磷组分与活性的含硅和铝的组分在合适的条件下混合以形成分子筛。
框架结构内的[AlO2]四面体单元可以由多种组分提供。这些含铝组分的例子包括醇铝如异丙醇铝、磷酸铝、氢氧化铝、铝酸钠和假勃姆石。含铝组分与活性的含硅和磷的组分在合适的条件下混合以生成分子筛。
框架结构内的[SiO2]四面体单元可由多种组分提供。这些含硅组分的例子包括硅溶胶和醇硅,如四乙基原硅酸酯。含硅组分与活性的含铝和磷的组分在合适的条件下混合以生成分子筛。
本发明中也可以使用取代的SAPO。这些化合物通常被称为MeAPSO或含金属的硅铝磷酸盐。金属可以是碱金属离子(IA族),碱土金属离子(IIA族),稀土离子(IIIB族,包括镧系元素:镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱和镥;以及钪或钇),和另外的IVB、VB、VIB、VIIB、VIIIB和IB族的过渡金属阳离子。
优选地,Me代表的原子是例如:Zn、Mg、Mn、Co、Ni、Ga、Fe、Ti、Zr、Ge、Sn和Cr。这些原子可以以[MeO2]四面体单元插入到四面体框架结构中。[MeO2]四面体单元所携带的净电荷取决于金属取代基的价态。当金属组分的价态为+2,+3,+4,+5或+6价时,净电荷为-2到+2。结合金属组分的方法一般是在合成分子筛时添加金属组分。但也可以在合成以后进行离子交换。
合适的硅铝磷酸盐分子筛包括SAPO-5,SAPO-8,SAPO-11,SAPO-16,SAPO-17,SAPO-18,SAPO-20,SAPO-31,SAPO-34,SAPO-35,SAPO-36,SAPO-37,SAPO-40,SAPO-41,SAPO-42,SAPO-44,SAPO-47,SAPO-56,其含金属的形式,及其混合物。优选SAPO-18,SAPO-34,SAPO-35,SAPO-44和SAPO-47,尤其是SAPO-18和SAPO-34,包括其含金属的形式及其混合物。这里术语“混合物”与“组合物”是同义语,是指具有不定的比例的两种或更多种组分的物质组成,而不论其物理状态。
按照本发明,结晶SAPO分子筛是通过水热结晶法合成的。换言之,本发明的产物是通过将起始原料在水热条件下反应以生成结晶产物而得到的结晶分子筛。为了显著增加起始原料转化为结晶分子筛产物的转化率,在结晶或反应过程中要对起始原料进行搅拌。搅拌可以是连续性的或间歇性的,但在反应过程完成之前就要停止。反应过程在结晶的有效终点完成,这时希望停止加热。
为了制备结晶硅铝磷酸盐,通过混合活性的硅、铝和磷组分及至少一种模板形成反应混合物。最终通过煅烧结晶产物而除去模板。煅烧结晶产物意味着模板基本上燃烧干净,在结晶产物中留下多孔通道形状的结构。一旦除去模板,该分子筛就被称为活化的分子筛。也就是说,它可被用于催化应用了。
通常反应混合物被密闭加热,优选在自生压力下被加热至至少50℃。优选在50℃至250℃,更优选在100℃至225℃加热反应混合物。
加热时间应有效地形成结晶产物。无论哪里,形成最终结晶产物所需要的时间为大约30分钟至长达2周。在有些情况下,搅拌或用结晶材料接种会有利于形成产物。加热持续的时间优选为10分钟到2周,更优选为15分钟到240小时,最优选为20分钟至120小时。
搅拌混合物的时间少于各组分反应以有效地形成最终结晶分子筛产品所持续的时间。结晶化有效完成的时间即被认为是反应持续期的完成点。这与加热反应材料的时间长度也应当是一致的。应当在20-95%的加热持续期间内施以搅拌,更优选在20-90%的加热持续时间内施以搅拌,最优选在约30-85%的加热持续时间内施以搅拌。通常搅拌的程度受到结晶温度影响。典型地,结晶温度越高,搅拌所需时间越短。
典型地,结晶分子筛产品在溶液中形成。但是它可以采用标准方法回收,如离心或过滤。产物也可以洗涤、用同样的方法回收并干燥。
作为结晶过程的结果,回收的分子筛在其孔中含有在制备起始反应混合物时所用的至少一部分模板。结晶结构基本上缠绕在模板周围,必须除去该模板以获得催化活性。一旦除去模板,所剩余的结晶结构具有一般被称为晶内孔体系的结晶结构。
SAPO分子筛可以包含一个或多个模板。模板一般是指导结构的试剂,并且一般含有氮、磷、氧、碳、氢或其组合,也可以含有至少一个烷基或芳基,在该烷基或芳基中存在1到8个碳。
代表性的模板包括四乙基铵盐、环戊胺、氨甲基环己烷、哌啶、三乙胺、环己胺、三乙基羟乙基胺、吗啉、二丙胺(DPA)、吡啶、异丙基胺和它们的组合。优选的模板是三乙胺、环己胺、哌啶、吡啶、异丙胺、四乙基铵盐和它们的混合物。四乙基铵盐包括氢氧化四乙铵(TEAOH)、磷酸四乙铵、氟化四乙铵、溴化四乙铵、氯化四乙铵、乙酸四乙铵。优选的四乙基铵盐为氢氧化四乙铵和磷酸四乙铵。优选的模板包括氢氧化四乙铵,优选氢氧化四乙铵和二丙胺。
如本领域中已知的那样,分子筛或包含分子筛的催化剂,在用于催化工艺前必须被活化。活化是以从分子筛中除去模板而留下活性催化位点(分子筛中的微孔通道开放以与原料接触)的方式来完成。活化过程一般通过煅烧完成,或在含氧的气体存在下将模板基本上在200至800℃温度加热完成。在有些情况下,可能希望在低氧浓度的环境中加热。这类过程可用于从晶内孔体系中将模板部分或完全除去。在其它情况下,尤其是模板比较小时,可以使用常规的解吸方法,例如制备标准沸石时使用的那些方法,从分子筛中完全或部分除去模板。
一旦制成分子筛,它可以与其它能为最终的催化剂产品提供附加硬度或催化活性的材料混合。混合后所得的组合物一般被称为硅铝磷酸盐(SAPO)催化剂,该催化剂包含了SAPO分子筛。
能够与分子筛混合的材料可以是各种惰性的或催化活性的材料,或是各种粘合剂材料。这些材料包括如高岭土和其它粘土之类的组分、各种形式的稀土金属、其它非沸石催化剂成份、沸石催化剂成份、氧化铝或氧化铝溶胶、二氧化钛、二氧化锆、石英、二氧化硅或二氧化硅溶胶,及其混合物。这些组分在降低整体催化剂的成本,在再生过程中作为热槽以帮助热屏蔽催化剂,使催化剂致密和增加催化剂的强度方面也是有效的。当与非硅铝磷酸盐分子筛材料混合时,在最终催化剂产品中分子筛的量占整个催化剂的10~90%重量,优选占整个催化剂的30~70%重量。
按照本发明方法合成的分子筛可用于干燥气体和液体;用于基于大小和极性的选择性的分子分离;作为离子交换剂;作为裂解、氢化裂解、歧化、烷基化、异构化、氧化和将含氧物转变为碳氢化合物的催化剂;作为化学载体;用在气相色谱中;和用在石油工业中从蒸馏物中除去正烷烃。它特别适合用作在裂解、氢化裂解、歧化、烷基化、异构化、氧化和将含氧物转变为碳氢化合物中的催化剂。最优选地,该分子筛适合用作将含氧物转变为碳氢化合物的催化剂。
在其最优选的实施方案中,SAPO分子筛被用作将含氧物转化为碳氢化合物的催化剂。在该方法中,包含含氧物的原料与结晶分子筛在反应器的反应区中,在有效生成轻烯烃,特别是乙烯和丙烯的条件下接触。一般地,含氧原料是在含氧物为气相的状态下与催化剂接触。或者,也可以在液相或混合气/液相中完成此过程。当此过程在液相或混合的气/液相中进行时,依催化剂与反应条件的不同,可能导致不同的原料到产品的转化率和选择性。这里所用的术语“反应器”不仅包括工业规模的反应器,而且也包括中试规模的反应器单元和实验室的小型的反应器单元。
通常可在很宽的温度区间内生产烯烃。有效的操作温度范围可以是大约200℃到700℃。在温度范围的较低点,需要的烯烃产物的形成可能会明显变慢。在温度范围的较高点,该过程可能不能生成最佳量的产物。优选操作温度为至少300℃,最高500℃。
该过程可以在动态床系统或使用各种运输床的任何系统中进行,尽管也可以使用固定床系统。特别希望在高空速下操作该反应过程。
将含氧物转化为烯烃产物优选在大规模连续催化反应器中进行。这类反应器包括流化床反应器和并流立管反应器,如在“Free FallReactor”,Fluidization Engineering(D.Kunii和O.Levenspiel,RobertE.Krieger出版公司,NY,1977年)中所述,其整体结合于此作为参考。此外,逆流自由下落反应器也可用于此转化过程。参见,例如,US-A-4,068,136和“Riser Reactor”,Fluidization and Fluid-ParticleSystems(48-59页,F.A.Zenz和D.F.Othmo,Reinhold出版公司,NY 1960年),这里特别结合了其中的描述作为参考。
但是可以使用任何标准工业规模的反应器系统,包括固定床或移动床系统。工业规模的反应器系统可以在重量小时空速(WHSV)为1hr-1到1000hr-1的条件下操作。在工业规模的反应器情况下,WHSV被定义为催化剂中所含每单位重量的硅铝磷酸盐分子筛、每小时的进料中的碳氢化合物的重量。碳氢化合物是含氧物和任选地与含氧物结合的任何碳氢化合物。硅铝磷酸盐分子筛仅指在催化剂中所包含的硅铝磷酸盐分子筛部分。它不包括如粘合剂、稀释剂、惰性物、稀土组分等等成份。
特别希望在至少300℃温度下操作,并且温度校正标准化甲烷灵敏度(TCNMS,Temperature Corrected Normalized Methane Sensitivity)小于约0.016,优选小于约0.012,更优选小于约0.01。特别优选的从含氧物制备烯烃的反应条件包括:WHSV至少约20hr-1产生的烯烃,TCNMS小于约0.016。
在此TCNMS定义为当温度低于400℃时的标准化甲烷灵敏度(NMS)。NMS定义为甲烷产品的产率除以乙烯产品的产率,其中每种产率均以重量%测量,或者是转变为重量%。当温度为400℃或更高时,TCNMS定义为以下等式,其中T是以℃表示的反应器中的平均温度:
压力也可以在很宽的范围内变化,包括自生压力。优选的压力范围为约5kPa到约5MPa,最优选为约50kPa到约0.5MPa。前述的压力排除了任何贫氧稀释剂,因此,是指含氧化合物和/或其与原料的混合物的分压。
在原料中可存在一种或多种惰性稀释剂,其量为例如1至95%摩尔(基于送入反应区(或催化剂)的所有原料和稀释剂组分的总摩尔数)。典型的稀释剂包括,但不局限于氦、氩、氮、一氧化碳、二氧化碳、氢、水、石蜡、烷烃(尤其是甲烷、乙烷和丙烷),烯烃,芳香化合物和它们的混合物。优选的稀释剂是水和氮。水可以以液体或气体的形式注入。
该过程可以以间歇、半连续或连续的方式进行。该过程可以在单个反应区或串联或并联排列的多个反应区内进行。
可以维持含氧物的转化程度以减少不想要的副产物的含量。也可以将转化率保持在足够高的水平以避免工业上不希望水平的未反应原料的再循环。当转化率从100mol%降到约98mol%或更低时,不想要的副产物得到减少。再循环高达约50mol%的原料在工业上是可以接受的。因此,同时实现两个目标的转化率水平为约50mol%到约98mol%,希望为约85mol%到约98mol%。但为了简化再循环过程,转化率为98mol%到100mol%也可以接受。可以采用本领域普通技术人员所熟悉的很多方法将含氧物转化率维持在此水平。实例包括但不局限于调节以下一项或多项内容:反应温度、压力、流速(即WHSV)、催化剂再生的水平和程度、催化剂再循环的数量、特定的反应器结构、进料组成和其它影响转化率的参数。
如果需要再生,分子筛催化剂可以作为移动床连续引入再生区,在那里例如通过除去含碳物质或通过在含氧气氛中氧化进行再生。在一个优选的实施方案中,催化剂经历的再生步骤是将在转化反应中聚集的含碳沉积物烧掉。
含氧原料包括至少一种含有至少一个氧原子的有机化合物,例如脂肪醇、醚、羰基化合物(醛、酮、羧酸、碳酸酯、酯等)。当含氧物是醇时,醇的脂族部分可含有1到10个碳原子,更优选为1到4个碳原子。代表性的醇包括但不局限于低级直链和支链脂肪醇和它们的不饱和对应物。合适的含氧化合物的例子包括,但不局限于:甲醇、乙醇、正丙醇、异丙醇、C4~C20醇、甲乙醚、二甲醚、乙醚、二异丙醚、甲醛、碳酸二甲酯、二甲基酮、乙酸和它们的混合物。优选的含氧化合物是甲醇,二甲醚或它们的混合物。
本发明中制备优选烯烃的方法可以包括从如石油、煤、焦油砂、页岩、生命体和天然气之类的碳氢化合物制备这些组合物的附加步骤。制备这些组合物的方法是本领域已知的。这些方法包括发酵生产醇或醚,制备合成气,然后把合成气转化为醇或醚。合成气可以用已知的方法生产,如蒸汽转化,自热转化和部分氧化。
本领域技术人员也会意识到通过本发明的将含氧物转化为烯烃的反应所制备的烯烃也可以聚合成聚烯烃,特别是聚乙烯和聚丙烯。从烯烃制备聚烯烃的方法是本领域已知的。优选催化过程。特别优选的是金属茂、Ziegler/Natta和酸催化体系。可参见,例如:美国专利号3,258,455;3,305,538;3,364,190;5,892,079;4,659,685;4,076,698;3,645,992;4,302,565和4,243,691,以上各文献中的催化剂和方法被明确地结合在此作为参考。一般地,这些方法包括将烯烃产品与形成聚烯烃的催化剂在有效形成聚烯烃产物的压力和温度下接触。
优选的形成聚烯烃的催化剂是金属茂催化剂。优选的操作温度为50℃到240℃,反应可以在低、中或高压下进行,压力在约1到200巴。对于在溶液中进行的方法,可以使用惰性稀释剂,优选的操作压力范围为10到150巴,优选的温度范围为120到230℃。对于气相方法,优选的温度通常为60℃到160℃,优选操作压力为5到50巴。
除聚烯烃之外,许多其它烯烃衍生物也可以用本发明中回收的烯烃制备。这些包括但不限于:醛、醇、乙酸、线性α-烯烃、乙酸乙烯酯、二氯乙烯和氯乙烯、乙苯、环氧乙烷、异丙基苯、异丙醇、丙烯醛、烯丙基氯、环氧丙烷、丙烯酸、乙丙橡胶和丙烯腈,以及乙烯、丙烯或丁烯的三聚体和二聚体。这些衍生物的制备方法均为本领域所熟知,因此这里不做论述。
参考下面的实施例可以更好地理解本发明,它们是对在所要求的本发明总体范围内的具体实施方案的举例说明。
比较例AA1.无晶种的静态合成
通过混合68.06份的Condea的Alumina Pural SB与110.15份的蒸馏水制备氧化铝浆液,向此混合物中加入含115.74份磷酸(85wt%,ACROS)的溶液,使用24.9份漂洗水,混合均匀。接着加入22.50份Ludox AS40(40wt.%的SiO2),使用10.20份漂洗水,将混合物搅拌均匀。向此均匀混合物中加入183.31份氢氧化四乙铵(TEAOH,EasternChemical)的40wt.%溶液,使用43.17份漂洗水。混合凝胶至均匀,并加入80.79份二丙胺(DPA),使用26.27份漂洗水。当混合物看上去呈均相时,将237.3份转移入不锈钢高压釜,在2小时内加热至175℃,并在此温度保持60小时。A2.加晶种的静态合成
向A1中制备的433.7份混合物中加入2.78份的含6.4wt%的菱沸石结晶的淤浆。将混合物搅拌均匀。接着,将181.5份此凝胶转入不锈钢高压釜,在2小时内加热至175℃,并在此温度保持60小时。A3.加晶种的“转鼓”式合成
将A1中得到的98.9份均匀混合物转移入另一个不锈钢高压釜内。该高压釜装配在一台烘箱内的轴上,并以60rpm速度翻滚,在2小时内加热到175℃,并在该温度保持60小时,在整个加热过程中连续搅拌。
在A1-A3中所描述的合成混合物的摩尔组成如下:
0.3SiO2/Al2O3/P2O5/TEAOH/1.6DPA/52H2O。
经过所指示的结晶时间后,通过离心从母液中定量回收固体。洗涤后的固体在120℃干燥,并记录其XRD图。
A1-A3的结果总结于表1中。
表1
实施例 | 晶种 | 温度(C) | 时间(小时) | 搅动 | 产率(wt.%)* |
A1 | - | 175 | 60 | - | 11.1 |
A2 | + | 175 | 60 | - | 10.7 |
A3 | + | 175 | 60 | + | 7.8 |
*产率是以每100g受热的合成混合物中所回收的干燥产品表示
这些结果表明在整个加热过程中搅拌会降低回收产品的产率,甚至对加晶种的合成混合物也是如此。
比较例BB1.加晶种的搅拌合成
用类似于A2的方法,制备与A1中具有大致相同摩尔组成的加晶种的混合物。在2升的不锈钢Parr高压釜中,经8小时将混合物加热至175℃。然后以144rpm的速度使用组合的Parr锚式和螺旋浆式混合叶片搅拌该混合物。在整个60小时的于175℃的水热处理过程中连续进行混合。经离心从母液中回收固体,洗涤并干燥。干燥产品的产率是7.5wt%的纯SAPO-34。B2.加品种的静态合成
用B1的方法制备加晶种的混合物。混合物静置(无搅拌)下在175℃加热60小时。这种合成方法可以回收到12.5wt%的纯SAPO-34。
实施例1和2
制备与比较例A1和B2中具有大致相同摩尔组成的两种混合物。混合物在具有与比较例B2相同的体积,相同的混合叶片等的高压釜内加热。
(实施例1)第一种混合物在80rpm速度的连续搅拌下,在8小时内加热到165℃,并在165℃维持5小时。然后停止搅拌,但继续再加热19小时。结晶后(即在加热过程的终点),回收到13.4wt%的纯SAPO-34。
(实施例2)第二种混合物在持续搅拌下在8小时内加热到175℃,并在175℃维持5小时。然后停止搅拌,但继续再加热5小时。结晶后回收到12.3wt.%的纯SAPO-34。
实施例1和2说明了半静态合成(即搅拌时间少于整个加热时间)SAPO-34的优越性。
实施例3
制备与比较例A1中具有大致相同摩尔组成的混合物。在工业规模的单元内,持续搅拌下将该混合物在12小时内加热至170℃。在持续搅拌下,在170℃维持该单元54小时,然后停止搅拌。此时的产率为约11wt%的结晶分子筛。搅拌停止后,将该单元在170℃下再保持10小时,这时结晶实际上停止。此时产率为约13wt%。
实施例4
制备与比较例A1中具有大致相同摩尔组成的混合物。在工业单元中,持续搅拌下将该混合物在11小时内加热至170℃。持续搅拌下,该单元在170℃维持30小时,然后停止搅拌。此时的产率为大约11.8wt%的结晶分子筛。搅拌停止后,将该单元在170℃再保持10小时,这时结晶实际上停止。此时产率为约13wt%。
经过对本发明的充分描述,本领域的技术人员可以意识到本发明能够在所要求的宽范围的参数下实施,而不会偏离本发明的精神和范畴。
Claims (11)
1.一种制备结晶硅铝磷酸盐分子筛的方法,包括向反应器内加入包括含硅组分、含铝组分、模板和含磷组分的混合物,并在有效形成结晶硅铝磷酸盐分子筛的温度和时间的条件下施加热的同时搅拌该混合物,其中在20-95%的施加热的时间内进行搅拌。
2.权利要求1的方法,其中加热温度为50℃到250℃。
3.前述权利要求中任意一项的方法,其中加热的持续时间为10分钟到240小时。
4.前述权利要求中任意一项的方法,其中在20-90%的加热持续时间内进行搅拌。
5.前述权利要求中任意一项的方法,其中在30-85%的加热持续时间内进行搅拌。
6.前述权利要求中任意一项的方法,其中含硅组分、含铝组分、模板和含磷组分的加入量有效地提供具有如下比例的分子筛组成:0.30-0.34SiO2/Al2O3/0.82-0.86P2O5。
7.前述权利要求中任意一项的方法,其中所述模板包括氢氧化四乙铵。
8.前述权利要求中任意一项的方法,其中所述模板包括氢氧化四乙铵和二丙胺。
9.一种从含氧组合物制备烯烃产品的方法,包括:
提供用权利要求1-8中任何一项的方法制备的结晶硅铝磷酸盐分子筛,并且
在有效形成烯烃产品的条件下,使煅烧过的分子筛与含氧组合物接触。
10.权利要求9的方法,其中所述含氧组合物包括选自以下的化合物:甲醇、乙醇、正丙醇、异丙醇、C4~C20醇、甲乙醚、二甲醚、乙醚、二异丙醚、甲醛、碳酸二甲酯、二甲酮、乙酸和它们的混合物。
11.权利要求9或10的方法,其中所述烯烃产物在有效形成聚烯烃的条件下与形成聚烯烃的催化剂接触。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17340399P | 1999-12-28 | 1999-12-28 | |
US60/173,403 | 1999-12-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1413170A true CN1413170A (zh) | 2003-04-23 |
Family
ID=22631847
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN00817773A Pending CN1413170A (zh) | 1999-12-28 | 2000-12-28 | 结晶硅铝磷酸盐的合成 |
Country Status (12)
Country | Link |
---|---|
US (1) | US6403855B1 (zh) |
EP (1) | EP1246775B1 (zh) |
CN (1) | CN1413170A (zh) |
AR (1) | AR027119A1 (zh) |
AT (1) | ATE242750T1 (zh) |
AU (1) | AU778142B2 (zh) |
CA (1) | CA2394092A1 (zh) |
DE (1) | DE60003338T2 (zh) |
ES (1) | ES2200986T3 (zh) |
NO (1) | NO20023072D0 (zh) |
TW (1) | TWI222957B (zh) |
WO (1) | WO2001047810A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108473323A (zh) * | 2015-09-28 | 2018-08-31 | 国家科学研究中心 | 制备合成矿物颗粒的方法 |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7014827B2 (en) * | 2001-10-23 | 2006-03-21 | Machteld Maria Mertens | Synthesis of silicoaluminophosphates |
US6685905B2 (en) * | 2001-12-21 | 2004-02-03 | Exxonmobil Chemical Patents Inc. | Silicoaluminophosphate molecular sieves |
US7208442B2 (en) | 2002-02-28 | 2007-04-24 | Exxonmobil Chemical Patents Inc. | Molecular sieve compositions, catalyst thereof, their making and use in conversion processes |
US6906232B2 (en) | 2002-08-09 | 2005-06-14 | Exxonmobil Chemical Patents Inc. | Molecular sieve compositions, catalysts thereof, their making and use in conversion processes |
US6995111B2 (en) | 2002-02-28 | 2006-02-07 | Exxonmobil Chemical Patents Inc. | Molecular sieve compositions, catalysts thereof, their making and use in conversion processes |
US7319178B2 (en) | 2002-02-28 | 2008-01-15 | Exxonmobil Chemical Patents Inc. | Molecular sieve compositions, catalysts thereof, their making and use in conversion processes |
US6844291B2 (en) | 2002-02-28 | 2005-01-18 | Exxonmobil Chemical Patents Inc. | Molecular sieve compositions, catalyst thereof, their making and use in conversion processes |
WO2004046214A2 (en) | 2002-10-15 | 2004-06-03 | Exxonmobil Chemical Patents Inc. | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
US7700707B2 (en) | 2002-10-15 | 2010-04-20 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
US7375050B2 (en) * | 2003-04-28 | 2008-05-20 | Exxonmobil Chemical Patents Inc. | Synthesis and use of aluminophosphates and silicoaluminophosphates |
US7102049B2 (en) * | 2003-06-25 | 2006-09-05 | Exxonmobil Chemical Patens Inc. | Process for operating a quench device in an oxygenate-to-olefin production unit |
US7479468B2 (en) * | 2004-04-15 | 2009-01-20 | Exxonmobil Chemical Patents Inc. | Integrating an air separation unit into an oxygenate-to-olefins reaction system |
US7253331B2 (en) * | 2004-05-12 | 2007-08-07 | Exxonmobil Chemical Patents Inc. | Molecular sieve catalyst composition, its making and use in conversion processes |
US7737316B2 (en) * | 2005-06-24 | 2010-06-15 | Exxonmobil Chemical Patents Inc. | Method of flocculation and formulation of crystalline materials |
HUE030927T2 (en) * | 2009-06-12 | 2017-06-28 | Albemarle Europe Sprl | SAPO molecular filter catalysts and their production and use |
US20140127088A1 (en) * | 2011-08-18 | 2014-05-08 | Ibiden Co., Ltd. | Honeycomb structure and exhaust gas scrubber |
CN112194151B (zh) * | 2020-09-03 | 2021-08-27 | 河南神马催化科技股份有限公司 | 一种sapo-34分子筛的制备方法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
US4673559A (en) * | 1983-12-19 | 1987-06-16 | Mobil Oil Corporation | Silicoaluminophosphate crystallization using hydrolysis |
US4898722A (en) * | 1984-12-19 | 1990-02-06 | Mobil Oil Corp. | Synthesis of crystalline SAPO-37 |
US4803185A (en) | 1987-06-04 | 1989-02-07 | Uop | Octane boosting catalyst |
US4861743A (en) | 1987-11-25 | 1989-08-29 | Uop | Process for the production of molecular sieves |
DE4131268A1 (de) * | 1991-09-20 | 1993-03-25 | Basf Ag | Verfahren zur herstellung von alumo- und silicoalumophosphaten mit ael-struktur unter verwendung von 1,2-bis(4-pyridyl)ethan |
US5294429A (en) * | 1991-10-24 | 1994-03-15 | Shell Oil Company | Crystalline aluminophosphates |
FR2682944B1 (fr) * | 1991-10-25 | 1994-02-04 | Institut Francais Petrole | Nouveau compose aluminophosphate et ses derives. |
US5126308A (en) * | 1991-11-13 | 1992-06-30 | Uop | Metal aluminophosphate catalyst for converting methanol to light olefins |
US5273736A (en) * | 1992-10-09 | 1993-12-28 | Chevron Research And Technology Company | Process for preparing molecular sieves using 9-azabicyclo [3.3.1] nonane templates |
US5879655A (en) | 1992-11-02 | 1999-03-09 | Chevron Research And Technology Company | Method of making microporous non-zeolitic molecular sieves |
ZA979264B (en) * | 1996-10-17 | 1998-12-29 | Exxon Chemical Patents Inc | Synthesis of large crystal zeolites |
-
2000
- 2000-03-07 US US09/519,975 patent/US6403855B1/en not_active Expired - Lifetime
- 2000-12-27 TW TW089128038A patent/TWI222957B/zh active
- 2000-12-27 AR ARP000106956A patent/AR027119A1/es unknown
- 2000-12-28 AT AT00990376T patent/ATE242750T1/de not_active IP Right Cessation
- 2000-12-28 ES ES00990376T patent/ES2200986T3/es not_active Expired - Lifetime
- 2000-12-28 DE DE60003338T patent/DE60003338T2/de not_active Expired - Fee Related
- 2000-12-28 CA CA002394092A patent/CA2394092A1/en not_active Abandoned
- 2000-12-28 WO PCT/US2000/035461 patent/WO2001047810A1/en active IP Right Grant
- 2000-12-28 EP EP00990376A patent/EP1246775B1/en not_active Expired - Lifetime
- 2000-12-28 CN CN00817773A patent/CN1413170A/zh active Pending
- 2000-12-28 AU AU27409/01A patent/AU778142B2/en not_active Ceased
-
2002
- 2002-06-25 NO NO20023072A patent/NO20023072D0/no not_active Application Discontinuation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108473323A (zh) * | 2015-09-28 | 2018-08-31 | 国家科学研究中心 | 制备合成矿物颗粒的方法 |
Also Published As
Publication number | Publication date |
---|---|
DE60003338T2 (de) | 2004-04-29 |
EP1246775A1 (en) | 2002-10-09 |
NO20023072L (no) | 2002-06-25 |
US6403855B1 (en) | 2002-06-11 |
DE60003338D1 (de) | 2003-07-17 |
ES2200986T3 (es) | 2004-03-16 |
AU2740901A (en) | 2001-07-09 |
ATE242750T1 (de) | 2003-06-15 |
TWI222957B (en) | 2004-11-01 |
WO2001047810A1 (en) | 2001-07-05 |
AR027119A1 (es) | 2003-03-12 |
AU778142B2 (en) | 2004-11-18 |
CA2394092A1 (en) | 2001-07-05 |
NO20023072D0 (no) | 2002-06-25 |
EP1246775B1 (en) | 2003-06-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1413170A (zh) | 结晶硅铝磷酸盐的合成 | |
US8450233B2 (en) | Process for obtaining catalyst composites comprising MeAPO and their use in conversion of organics to olefins | |
CN1377325A (zh) | 磷酸硅铝分子筛的合成方法 | |
US7014827B2 (en) | Synthesis of silicoaluminophosphates | |
CN1171678C (zh) | 保持sapo分子筛中的酸催化剂部位 | |
JP5474973B2 (ja) | メタロアルミノホスファート(MeAPO)モレキュラーシーブの製造方法 | |
CN1441701A (zh) | 用于含氧化合物转化的含金属的小孔分子筛催化剂 | |
CN1261354C (zh) | 热处理分子筛和催化剂 | |
WO2009016154A1 (en) | Mixtures of molecular sieves comprising meapo, their use in conversion of organics to olefins. | |
CN1455701A (zh) | 分子筛催化剂的合成 | |
CN1406216A (zh) | 含氧化合物转化法 | |
TW200303238A (en) | Molecular sieve compositions, catalysts thereof, their making and use in conversion processes | |
CN1466488A (zh) | 利用微孔过滤法制备分子筛催化剂 | |
US6812373B2 (en) | Modified metalloaluminophosphate molecular sieves | |
US6436869B1 (en) | Iron, cobalt and/or nickel containing ALPO bound SAPO molecular sieve catalyst for producing olefins | |
WO2001064340A1 (en) | Thorium-containing sapo molecular sieve for producing olefins | |
US20110295050A1 (en) | Method for Preparing Crystalline Metalloaluminophosphate (MeAPO) Molecular Sieve from Amorphous Materials | |
MXPA02006585A (en) | Synthesis of crystalline silicoaluminophosphates |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |