CN102958840A - Uzm-45硅铝酸盐沸石、制备方法和使用uzm-45的方法 - Google Patents
Uzm-45硅铝酸盐沸石、制备方法和使用uzm-45的方法 Download PDFInfo
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- CN102958840A CN102958840A CN2011800292127A CN201180029212A CN102958840A CN 102958840 A CN102958840 A CN 102958840A CN 2011800292127 A CN2011800292127 A CN 2011800292127A CN 201180029212 A CN201180029212 A CN 201180029212A CN 102958840 A CN102958840 A CN 102958840A
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000010457 zeolite Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title claims abstract description 10
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 41
- 229910000323 aluminium silicate Inorganic materials 0.000 title abstract description 11
- 238000002360 preparation method Methods 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 13
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 13
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 8
- 150000001768 cations Chemical class 0.000 claims abstract description 8
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 7
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 4
- 239000011541 reaction mixture Substances 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 229960001231 choline Drugs 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XBMRWQWMMIYMLY-UHFFFAOYSA-N CN(C)C.C(CCC)N Chemical compound CN(C)C.C(CCC)N XBMRWQWMMIYMLY-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 229910052728 basic metal Inorganic materials 0.000 claims description 6
- 150000003818 basic metals Chemical class 0.000 claims description 6
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- YOMFVLRTMZWACQ-UHFFFAOYSA-N ethyltrimethylammonium Chemical compound CC[N+](C)(C)C YOMFVLRTMZWACQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- SDZQEZNDOPDYPP-UHFFFAOYSA-N n,n-dimethylmethanamine;propan-1-amine Chemical compound CCCN.CN(C)C SDZQEZNDOPDYPP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 6
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 claims description 6
- 229910017090 AlO 2 Inorganic materials 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 230000029936 alkylation Effects 0.000 claims description 5
- 238000005804 alkylation reaction Methods 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- -1 DEDMA Chemical compound 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- ZJHQDSMOYNLVLX-UHFFFAOYSA-N diethyl(dimethyl)azanium Chemical compound CC[N+](C)(C)CC ZJHQDSMOYNLVLX-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 238000006317 isomerization reaction Methods 0.000 claims description 2
- 230000000447 dimerizing effect Effects 0.000 claims 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims 1
- 238000002441 X-ray diffraction Methods 0.000 abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- JQDCIBMGKCMHQV-UHFFFAOYSA-M diethyl(dimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)CC JQDCIBMGKCMHQV-UHFFFAOYSA-M 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- KVFVBPYVNUCWJX-UHFFFAOYSA-M ethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)C KVFVBPYVNUCWJX-UHFFFAOYSA-M 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910000373 gallium sulfate Inorganic materials 0.000 description 1
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 238000012988 high-throughput synthesis Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 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
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/56—Addition to acyclic hydrocarbons
- C07C2/58—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
-
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Abstract
已合成了被指定为UZM-45的新的一类结晶硅铝酸盐沸石。所述沸石由下述经验式表示:
Description
优先权声明
本申请要求2010年7月1日提交的美国申请No.61/360,586的优先权,其全文经此引用并入本文。
技术领域
本发明涉及被指定为UZM-45的新的一类硅铝酸盐沸石,它们由下述经验式表示:
Mm n+Rr p+Al1-xExSiyOz
其中M是可交换阳离子,例如钾或锶,R是有机铵阳离子,例如胆碱,且E是骨架元素,例如镓。
背景技术
沸石是结晶硅铝酸盐组合物,它们是微孔的并由共角AlO2和SiO2四面体形成。天然存在的和合成的许多沸石用在各种工业方法中。合成沸石是使用合适的Si、Al源和结构导向剂(例如碱金属、碱土金属、胺或有机铵阳离子)经由水热合成法制备的。结构导向剂留在沸石孔隙中,并且是最终形成的特定结构的主要原因。这些物质平衡了与铝相关的骨架电荷,也可充当空隙填充剂。沸石的特征在于具有尺寸均匀的孔隙开口,具有显著的离子交换容量,并能够可逆解吸散布在晶体内部空隙中的吸附相而不会明显置换构成永久沸石晶体结构的任何原子。沸石可用作烃转化反应的催化剂,该反应可以在外表面上以及在孔隙内的内表面上进行。
Miller在2010年首次公开了被指定为UZM-22的一种特定沸石,见US 7,744,850。此专利描述了使用如US 7,578,993中所述的用于合成沸石的电荷密度失配(CDM)法由胆碱结构导向剂与Li、Sr或这两种阳离子一起合成UZM-22。UZM-22沸石具有如Database of Zeolite Structures,http://www.iza-structure.org/databases定义的MEI结构,其由具有孔径的1维12环孔隙与垂直的7环孔隙系统构成。与组合高吞吐量合成法一起使用CDM法用胆碱结构导向剂以及碱金属和碱土金属阳离子的各种组合进行进一步研究。胆碱-碱金属-碱土金属硅铝酸盐的筛选产生许多已知的沸石结构,包括OFF、ERI、LTL、FAU、FER、LTA、CHA、BPH、MEI等。还生成命名为UZM-45的新沸石结构。
申请人已经成功地制备了被指定为UZM-45的新的一类材料。通过x-射线衍射测定,UZM-45的拓扑是独特的。通过与少量Sr2+和K+一起使用简单的市售结构导向剂,例如氢氧化胆碱[HO(CH2)2NMe3]+OH-,使用用于合成沸石的CDM法制备该材料。
发明概要
如前所述,本发明涉及被指定为UZM-45的新型硅铝酸盐沸石。相应地,本发明的一个实施方案是一种微孔结晶沸石,其具有至少AlO2和SiO2四面体单元的三维骨架,并在合成后未经进一步处理(as synthesized)和无水基础上具有如下述经验式所示的经验组成:
Mm n+Rr p+Al1-xExSiyOz
其中M是选自碱金属、碱土金属和稀土金属的至少一种可交换阳离子,“m”是M与(Al+E)的摩尔比并且为0至4.0,R是选自胆碱、乙基三甲基铵(ETMA+)、二乙基二甲基铵(DEDMA+)、三甲基丙基铵、三甲基丁基铵、二甲基二乙醇铵、四乙基铵(TEA+)、四丙基铵(TPA+)、己烷双胺及其混合物的有机铵阳离子,“r”是R与(Al+E)的摩尔比并具有0.25至4.0的值,“n”是M的加权平均化合价并具有1至3的值,“p”是R的加权平均化合价并具有1至2的值,E是选自镓、铁、硼及其混合物的元素,“x”是E的摩尔分数并具有0至1.0的值,“y”是Si与(Al+E)的摩尔比并且为大于3至20,且“z”是O与(Al+E)的摩尔比并具有通过下述公式确定的值:
z=(m·n+r·p+3+4·y)/2
且其特征在于其具有至少具有表A中所列的d-间距和强度的x射线衍射图:
表A
并且直到高于400℃的温度仍然是热稳定的。
本发明的另一实施方案是制备上述结晶微孔沸石的方法。该方法包括形成含有M、R、Al、Si和任选地E的反应源的反应混合物,并将该反应混合物在60℃至175℃的温度加热达足以形成沸石的时间,该反应混合物具有如下以氧化物摩尔比表示的组成:
aM2/nO:bR2/pO:1-cAl2O3:cE2O3:dSiO2:eH2O
其中“a”具有0.0至8的值,“b”具有1.5至40的值,“c”具有0至1.0的值,“d”具有4至50的值,“e”具有25至4000的值。
本发明的再一实施方案是使用上述沸石的烃转化法。该方法包括使烃与沸石在转化条件下接触以产生转化的烃。
发明详述
申请人制成了已被指定为UZM-45的具有新拓扑结构的硅铝酸盐沸石。本微孔结晶沸石UZM-45在合成后未经进一步处理(as synthesized)的形式和在无水基础上具有如下述经验式所示的经验组成:
Mm n+Rr p+Al1-xExSiyOz
其中M是至少一种可交换阳离子并选自碱金属、碱土金属和稀土金属。M阳离子的具体实例包括但不限于锂、钠、钾、铷、铯、钙、锶、钡、镧、镱及其混合物。R是有机铵阳离子,其实例包括但不限于胆碱阳离子[(CH3)3N(CH2)2OH]+、ETMA+、DEDMA+、三甲基丙基铵、三甲基丁基铵、二甲基二乙醇铵、TEA+、TPA+、己烷双胺及其混合物,且“r”是R与(Al+E)的摩尔比并且为0.25至4.0,而“p”的值是R的加权平均化合价并且为1至2。M的加权平均化合价“n”的值为1至3,而“m”是M与(Al+E)的摩尔比并且为0.0至4。硅与(Al+E)的比率用“y”表示,其为3至20。E是四面体配位的元素,存在于骨架中,并选自镓、铁和硼。E的摩尔分数用“x”表示并具有0至1.0的值,而“z”是O与(Al+E)的摩尔比并通过下述公式给出:
z=(m·n+r·.p+3+4·.y)/2.
如果M是仅一种金属,则加权平均化合价是这一种金属的化合价,即+1或+2。但是,当存在多于一种M金属时,Mm n+为:
Mm n+=Mm1 (n1)++Mm2 (n2)++Mm3 (n3)++…
且加权平均化合价“n”通过下述公式给出:
类似地,如果R是仅一种有机铵阳离子,则加权平均化合价是这种有机铵离子的化合价,即+1或+2。但是,当存在多于一种R有机铵阳离子时,Rr p+为:
Rr p+=Rr1 (p1)++Rr2 (p2)++Rr3 (p3)++…
且加权平均化合价“p”通过下述公式给出:
通过合并M、R、铝、硅和任选地E的反应源而制备反应混合物,通过该反应混合物的水热结晶制备微孔结晶沸石UZM-45。铝的源包括但不限于醇铝、沉淀的氧化铝、铝金属、铝盐和氧化铝溶胶。醇铝的具体实例包括但不限于原仲丁醇铝和原异丙醇铝。二氧化硅的源包括但不限于原硅酸四乙酯、胶态二氧化硅、沉淀的二氧化硅和碱金属硅酸盐。E元素的源包括但不限于碱金属硼酸盐、硼酸、沉淀的羟基氧化镓、硫酸镓、硫酸铁和氯化铁。M金属的源包括各自的碱金属或碱土金属的卤化物盐、硝酸盐、乙酸盐和氢氧化物。R是选自胆碱、ETMA、DEDMA、TEA、TPA、三甲基丙基铵、三甲基丁基铵、二甲基二乙醇铵、己烷双胺及其混合物的有机铵阳离子,且来源包括氢氧化物、氯化物、溴化物、碘化物和氟化物。具体实例包括但不限于氢氧化胆碱和氯化胆碱、乙基三甲基氢氧化铵、二乙基二甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四丙基氯化铵。
含有所需组分的反应源的反应混合物可以通过下式以氧化物摩尔比描述:
aM2/nO:bR2/pO:1-cAl2O3:cE2O3:dSiO2:eH2O
其中“a”为0.0至8.0,“b”为1.5至40,“c”为0至1.0,“d”为4至50,且“e”为25至4000。如果使用醇盐,则优选包括蒸馏或蒸发步骤以除去醇水解产物。现在使该反应混合物在密封反应器中在自压下在60℃至175℃、优选100℃至150℃的温度反应1天至3周,优选3天至14天。在结晶完成后,借助例如过滤或离心从不均匀混合物中分离出固体产物,然后用去离子水洗涤,并在空气中在环境温度至100℃干燥。应该指出,可任选地将UZM-45晶种添加到反应混合物中以加速沸石形成。
用于制造UZM-45的优选合成途径采用如US 7,578,993和Studies inSurface Science and Catalysis,(2004),第154A卷,364-372中公开的电荷密度失配概念。US 7,578,993中公开的方法使用氢氧化季铵以将硅铝酸盐物类溶解,并通常在单独步骤中引入结晶引发剂,例如碱金属和碱土金属,和更高带电的有机铵阳离子。使用市售胆碱制备UZM-45使其合成在经济上有吸引力。
获自上述方法的UZM-45硅铝酸盐沸石以至少具有下表A中所列的d-间距和相对强度的x-射线衍射图为特征。
表A
如实施例中详细显示,该UZM-45材料直到至少400℃的温度仍然是热稳定的。
在合成后未经进一步处理时(as synthesized),UZM-45材料在其孔隙中含有一些可交换的或电荷平衡的阳离子。这些可交换阳离子可以被交换为其它阳离子,或在有机阳离子的情况下,可以通过在受控条件下加热将它们除去。可以以许多方式将该UZM-45沸石改性,以使其适用于特定用途。改性包括煅烧、离子交换、蒸汽加工、各种酸萃取、六氟硅酸铵处理或它们的任何组合,如US 6,776,975B1(其全文经此引用并入本文)中对UZM-4M的情况所概述。被改变的性质包括孔隙率、吸附、Si/Al比、酸度、热稳定性等。
在本文中指定沸石原材料的比例或沸石产品的吸附性质等时,除非另行指明,意指沸石的“无水状态”。术语“无水状态”在本文中用于表示基本不含物理吸附和化学吸附的水的沸石。
本发明的结晶UZM-45沸石可用于分离分子物类的混合物、通过离子交换除去污染物,和催化各种烃转化法。分子物类的分离可以基于分子尺寸(动态直径)或基于分子物类的极性度。
本发明的UZM-45沸石也可用作各种烃转化法中的催化剂或催化剂载体。烃转化法是本领域中公知的,并包括裂化、加氢裂化、芳烃和异链烷烃的烷基化、异构化、聚合、重整、氢化、脱氢、烷基转移、脱烷基化、水合、脱水、加氢处理、加氢脱氮、加氢脱硫、甲烷化和合成气变换法。这些方法中可用的具体反应条件和进料类型列在US 4,310,440和US4,440,871中,它们经此引用并入本文。优选的烃转化法是其中氢是一种组分的那些,例如加氢处理或加氢精制、氢化、加氢裂化、加氢脱氮、加氢脱硫等。
加氢裂化条件通常包括400°至1200°F(204-649℃)、优选600°至950°F(316-510℃)的温度。反应压力为大气压至3,500psig(24,132kPa g),优选200至3000psig(1379–20,685kPa g)。接触时间通常对应于0.1hr-1至15hr-1,优选0.2至3hr-1的液时空速(LHSV)。氢循环速率为1,000至50,000标准立方尺(scf)/每筒装料(178-8,888std.m3/m3),优选2,000至30,000scf/每筒装料(355-5,333std.m3/m3)。合适的加氢处理条件通常在上列加氢裂化条件的宽范围内。
通常从催化剂床中取出反应区流出物,施以部分冷凝和汽液分离,然后分馏以回收其各种组分。将氢和在需要时一些或所有未转化的较重材料再循环至反应器。或者,可以使用两阶段流程,其中将未转化的材料送往第二反应器。本发明的催化剂可用在这种方法的仅一个阶段中或可用在两个反应器阶段中。
优选用该UZM-45组合物使用如瓦斯油、重石脑油、脱沥青原油残渣等原料进行催化裂化法,以汽油为主要的所需产物。850°F至1100°F的温度条件、0.5至10的LHSV值和0至50psig的压力条件是合适的。
芳烃的烷基化通常涉及使芳烃(C2至C12)、尤其苯与单烯烃反应产生直链烷基取代芳烃。该方法在5:1至30:1的芳烃:烯烃(例如苯:烯烃)比率、0.3至6hr-1的LHSV、100℃至250℃的温度和200至1000psig的压力下进行。关于装置的进一步细节可见于US 4,870,222,其经此引用并入本文。
在-30℃至40℃的温度、大气压至6,894kPa(1,000psig)的压力和0.1至120的重时空速(WHSV)下用烯烃将异链烷烃烷基化,以产生适合作为发动机燃料组分的烷基化物。关于链烷烃烷基化的细节可见于US5,157,196和US 5,157,197,它们经此引用并入本文。
下述实施例作为本发明的示例给出,但不是为了不适当地限制如所附权利要求书中阐述的本发明的宽泛范围。
通过x-射线分析法测定本发明的UZM-45沸石的结构。使用标准x-射线粉末衍射技术获得下述实施例中列出的x-射线图。辐射源是在45kV和35ma下运行的高强度x-射线管。通过适当的计算机技术获得来自铜K-α辐射的衍射图。在2°至70°(2θ)连续扫描压平的粉末样品。从表示为θ的衍射峰位置获得以埃为单位的晶面间距(d),其中θ是从数字化数据中观察到的布拉格角。由扣减背景后的衍射峰积分面积测定强度,“Io”是最强线或峰的强度,且“I”是各其它峰的强度。对高吞吐量样品而言,在配有涵盖2Θ=3–38°的面积检测器的Bruker-AXS GADDS衍射计上收集衍射图。
如本领域技术人员理解的那样,参数2θ的测定具有人为和机械误差,这一起在各2θ报道值上产生±0.4°的不确定性。这种不确定性当然也表现在由2θ值计算出的d-间距报道值中。这种不精确性是本领域中普遍的并且不足以排除本结晶材料与彼此和与现有技术的组合物的差异。在一些所报道的x-射线图中,通过符号vs、s、m和w表示d-间距的相对强度,它们分别代表非常强、强、中和弱。就100x I/Io而言,上述符号是指:
w=0-15;m=15-60:s=60-80和vs=80-100
在某些情况下,可以参照其x-射线粉末衍射图评估合成产物的纯度。由此,例如,如果样品被描述为纯净,仅意指该样品的x-射线图不含可归因于结晶杂质的线,而非不存在非晶材料。
为了更充分例证本发明,阐述下述实施例。要理解的是,这些实施例仅作为示例而不是为了不适当地限制如所附权利要求书中阐述的本发明的宽泛范围。
实施例1和2
以下述反应组成为目标,制备两种硅铝酸盐溶液:
2.5胆碱OH:2SiO2:1Al(OH)3:40H2O (溶液1)
8胆碱OH:20SiO2:1Al(OH)3:350H2O (溶液2)
使用高速混合器将Al(OH)3(80重量%,Pfaltz和Bauer)溶解在氢氧化胆碱(50重量%,Sigma-Aldrich)中,同此制备溶液。然后加入适当量的水,然后添加Ludox AS-40(40重量%SiO2)。通过高速搅拌器均化反应混合物,并装入和密封在Teflon瓶中。将反应混合物在95℃消解,直至获得清澈溶液。分析所得溶液以得出下述配方:
Ch2.502Si2.085AlO6.92*40.03H2O (溶液1)
Ch8.15Si20.26AlO46.10*346.79H2O (溶液2)
这些溶液在组合实验中用作实施例1和2的Si和Al源;通过混合适当量的这些溶液,获得中间Si/Al比(5、8和12)。通过添加氢氧化胆碱(50重量%)、KCl*13.78H2O和Sr(NO3)2*40H2O,进一步调节这些实施例中的反应混合物。为了形成反应混合物,通过自动化移液器将这些溶液分配到48孔Teflon块中,将其在试剂添加过程中摇动。一旦移完试剂,密封Teflon块并在油漆摇动器中摇动半小时。在这种均化步骤后,将Teflon块密封在金属壳中并置于100或150℃的炉中。所用各试剂的添加次序和体积列在表1中。
表1
实施例1和2的所得配方为:
实施例1:4ChOH:5SiO2:Al(OH)3:0.5KCl:0.25Sr(NO3)2:111H2O
实施例2:5.24ChOH:8SiO2:1Al(OH)3:0.5KCl:0.25Sr(NO3)2:164H2O
将这两种反应混合物在100℃消解11天。通过离心而洗涤产物,冻干并通过粉末X-射线衍射分析。各产物的衍射线列在表2中。
表2
实施例3
使用高速搅拌器将11.94克Al(OsecBu)3(97重量%)溶解在130.12克氢氧化胆碱(46重量%)中,由此制备硅铝酸盐溶液。然后加入150.0克去离子水。然后经数分钟加入一半的原硅酸四乙酯(TEOS,98重量%),100克,并使该混合物搅拌。在搅拌半小时后,加入100.72克去离子水。在数分钟后,经5分钟加入剩余100克TEOS。在搅拌30分钟后,加入剩余去离子水105.0克,并将反应混合物均化3小时以蒸发乙醇。第二天,将该溶液旋转蒸发以除去剩余乙醇。该溶液的最终重量为498.4克。这种溶液——溶液3,具有20的Si/Al比并含有0.25重量%Al。
使用溶液3制造UZM-45。将150.0克溶液3置于烧杯中并用高速搅拌器搅拌。将18.64克氢氧化胆碱(46重量%)添加到反应混合物中。然后制备溶液,其中2.11克KCl和2.91克Sr(OAc)2一起溶解在15.0克去离子水中。将这种溶液经40分钟缓慢添加到反应混合物中,在此期间该反应混合物从溶液转变成白色溶胶。将反应混合物再均化3小时。将反应混合物装入7个Teflon衬里的高压釜中,使其在自压下在125、150和175℃消解。将产物洗涤,离心分离并干燥。粉末X-射线衍射表明125℃和150℃样品含有UZM-45,但总是伴随着另一相。含有最多UZM-45的样品来自消解8天的150℃反应。这种样品还含有RUT杂质和少量SrCO3。这种产物的x-射线衍射线显示在下表3中,并指出杂质峰。产物的分析表明其含有下述元素比:Si/Al=16.4,K/Al=0.25,Sr/Al=0.57和N/Al=1.95。4.7的C/N比表明胆碱(C/N=5)可能已分解形成四甲基铵(C/N=4),与RUT杂质形成一致。这表明这种样品中UZM-45与RUT的比为2/1。将该样品在空气中在525℃煅烧5小时。煅烧样品的表面积为133平方米/克,由于非微孔RUT和SrCO3杂质而降低。
表3
Claims (10)
1.微孔结晶沸石,其具有至少AlO2和SiO2四面体单元的三维骨架,并在合成后未经进一步处理和无水基础上具有如下述经验式所示的经验组成:
Mm n+Rr p+Al1-xExSiyOz
其中M是选自由碱金属、碱土金属和稀土金属组成的组的至少一种可交换阳离子,“m”是M与(Al+E)的摩尔比并且为0至4.0,R是选自由胆碱、乙基三甲基铵(ETMA)、二乙基二甲基铵(DEDMA)、四乙基铵(TEA)、四丙基铵(TPA)、三甲基丙基铵、三甲基丁基铵、二甲基二乙醇铵、己烷双胺及其混合物组成的组的有机铵阳离子,“r”是R与(Al+E)的摩尔比并具有0.25至4.0的值,“n”是M的加权平均化合价并具有1至3的值,“p”是R的加权平均化合价并具有1至2的值,E是选自由镓、铁、硼及其混合物组成的组的元素,“x”是E的摩尔分数并具有0至1.0的值,“y”是Si与(Al+E)的摩尔比并且为大于3至20,且“z”是O与(Al+E)的摩尔比并具有通过下述公式确定的值:
z=(m·n+r·p+3+4·y)/2
且其特征在于其具有至少具有表A中所列的d-间距和强度的x射线衍射图:
表A
并且直到至少400℃的温度仍是热稳定的。
2.权利要求1的沸石,其中M选自由锂、钠、钾、铷、铯、钙、锶、钡及其混合物组成的组。
3.权利要求1的沸石,其中R是胆碱且M选自由K、Sr及其混合物组成的组。
4.制备微孔结晶沸石的方法,所述沸石具有至少AlO2和SiO2四面体单元的三维骨架,并在合成后未经进一步处理和无水基础上具有如下述经验式所示的经验组成:
Mm n+Rr p+Al1-xExSiyOz
其中M是选自由碱金属、碱土金属和稀土金属组成的组的至少一种可交换阳离子,“m”是M与(Al+E)的摩尔比并且为0至4.0,R是选自由胆碱、乙基三甲基铵(ETMA)、二乙基二甲基铵(DEDMA)、四乙基铵(TEA)、四丙基铵(TPA)、三甲基丙基铵、三甲基丁基铵、二甲基二乙醇铵、己烷双胺阳离子及其混合物组成的组的有机铵阳离子,“r”是R与(Al+E)的摩尔比并具有0.25至4.0的值,“n”是M的加权平均化合价并具有1至3的值,“p”是R的加权平均化合价并具有1至2的值,E是选自由镓、铁、硼及其混合物组成的组的元素,“x”是E的摩尔分数并具有0至1.0的值,“y”是Si与(Al+E)的摩尔比并且为大于3至20,且“z”是O与(Al+E)的摩尔比并具有通过下述公式确定的值:
z=(m·n+r·p+3+4·y)/2
且其特征在于其具有至少具有表A中所列的d-间距和强度的x射线衍射图:
表A
并且直到至少400℃的温度仍是热稳定的;所述方法包括形成含有M、R、Al、Si和任选地E的反应源的反应混合物,并将该反应混合物在60℃至175℃的温度加热达足以形成沸石的时间,所述反应混合物具有如下以氧化物摩尔比表示的组成:
aM2/nO:bR2/pO:1-cAl2O3:cE2O3:dSiO2:eH2O
其中“a”具有0.0至8.0的值,“b”具有1.5至40的值,“c”具有0至1.0的值,“d”具有4至50的值,“e”具有25至4000的值。
5.权利要求4的方法,其中M选自由锂、铯、钠、钾、铷、锶、钡及其混合物组成的组。
6.权利要求4的方法,其中R是胆碱且M选自由K、Sr及其混合物组成的组。
7.权利要求4的方法,进一步包括将UZM-45晶种添加到反应混合物中。
8.烃转化法,包括使烃流与催化剂在烃转化条件下接触以产生转化的产物,所述催化剂包含微孔结晶沸石UZM-45,其中UZM-45具有至少AlO2和SiO2四面体单元的三维骨架,并在合成后未经进一步处理和无水基础上具有如下述经验式所示的经验组成:
Mm n+Rr p+Al1-xExSiyOz
其中M是选自由碱金属和碱土金属组成的组的至少一种可交换阳离子,“m”是M与(Al+E)的摩尔比并且为0至4.0,R是选自由胆碱、ETMA、DEDMA、TEA、TPA、三甲基丙基铵、三甲基丁基铵、二甲基二乙醇铵及其混合物组成的组的有机铵阳离子,“r”是R与(Al+E)的摩尔比并具有0.25至4.0的值,“n”是M的加权平均化合价并具有1至3的值,“p”是R的加权平均化合价并具有1至2的值,E是选自由镓、铁、硼及其混合物组成的组的元素,“x”是E的摩尔分数并具有0至1.0的值,“y”是Si与(Al+E)的摩尔比并且为大于3至20,且“z”是O与(Al+E)的摩尔比并具有通过下述公式确定的值:
z=(m·n+r·p+3+4·y)/2
且其特征在于其具有至少具有表A中所列的d-间距和强度的x射线衍射图:
表A
并且直到至少400℃的温度仍是热稳定的。
9.权利要求8的方法,其中所述烃转化法选自由烷基化、异构化、烯烃二聚和低聚和脱蜡组成的组。
10.权利要求8的方法,其中M是氢离子。
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CN107531587A (zh) * | 2015-06-30 | 2018-01-02 | 环球油品公司 | 使用uzm‑53的烃转化 |
CN107531587B (zh) * | 2015-06-30 | 2020-11-24 | 环球油品公司 | 使用uzm-53的烃转化 |
CN108516565A (zh) * | 2018-05-17 | 2018-09-11 | 中南大学 | 一种利用铝钙粉反应渣制备p型沸石分子筛的方法 |
CN108516565B (zh) * | 2018-05-17 | 2021-06-25 | 中南大学 | 一种利用铝钙粉反应渣制备p型沸石分子筛的方法 |
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RU2521578C1 (ru) | 2014-06-27 |
RU2012151832A (ru) | 2014-06-10 |
CN102958839A (zh) | 2013-03-06 |
WO2012003321A3 (en) | 2012-04-26 |
JP5666701B2 (ja) | 2015-02-12 |
EP2588415A2 (en) | 2013-05-08 |
JP2013537510A (ja) | 2013-10-03 |
US8597611B2 (en) | 2013-12-03 |
WO2012003313A2 (en) | 2012-01-05 |
EP2588414A4 (en) | 2017-04-12 |
US20120004484A1 (en) | 2012-01-05 |
CN102958840B (zh) | 2015-02-04 |
JP5666702B2 (ja) | 2015-02-12 |
JP2013536145A (ja) | 2013-09-19 |
US20120004486A1 (en) | 2012-01-05 |
RU2528259C2 (ru) | 2014-09-10 |
WO2012003313A3 (en) | 2012-04-26 |
EP2588414A2 (en) | 2013-05-08 |
WO2012003321A2 (en) | 2012-01-05 |
US8158104B2 (en) | 2012-04-17 |
RU2012153203A (ru) | 2014-06-20 |
EP2588415A4 (en) | 2017-04-12 |
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