CN106540740A - 由合成气高选择性制轻质芳烃的催化剂及其制备方法 - Google Patents
由合成气高选择性制轻质芳烃的催化剂及其制备方法 Download PDFInfo
- Publication number
- CN106540740A CN106540740A CN201610965244.2A CN201610965244A CN106540740A CN 106540740 A CN106540740 A CN 106540740A CN 201610965244 A CN201610965244 A CN 201610965244A CN 106540740 A CN106540740 A CN 106540740A
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- China
- Prior art keywords
- catalyst
- molecular sieve
- synthesis gas
- high selectivity
- zeolite molecular
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 42
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002808 molecular sieve Substances 0.000 claims abstract description 59
- 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 59
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 238000001914 filtration Methods 0.000 claims abstract description 39
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 65
- 238000003756 stirring Methods 0.000 claims description 46
- 239000007789 gas Substances 0.000 claims description 39
- 238000001291 vacuum drying Methods 0.000 claims description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 24
- 229910021536 Zeolite Inorganic materials 0.000 claims description 23
- -1 hydrochlorate Chemical compound 0.000 claims description 23
- 239000010457 zeolite Substances 0.000 claims description 23
- 229910002651 NO3 Inorganic materials 0.000 claims description 15
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000004567 concrete Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical group 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 206010008190 Cerebrovascular accident Diseases 0.000 claims 1
- 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 1
- 208000006011 Stroke Diseases 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 150000003891 oxalate salts Chemical class 0.000 claims 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 235000015424 sodium Nutrition 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 238000010792 warming Methods 0.000 description 33
- 229910008355 Si-Sn Inorganic materials 0.000 description 27
- 229910006453 Si—Sn Inorganic materials 0.000 description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 21
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 20
- 238000006555 catalytic reaction Methods 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 11
- 239000005456 alcohol based solvent Substances 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 11
- 239000004570 mortar (masonry) Substances 0.000 description 11
- 229920000573 polyethylene Polymers 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 229910052593 corundum Inorganic materials 0.000 description 9
- 239000012467 final product Substances 0.000 description 9
- 235000011150 stannous chloride Nutrition 0.000 description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000008096 xylene Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241001120493 Arene Species 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 241000894007 species Species 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002249 LaCl3 Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- 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
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
由合成气高选择性制轻质芳烃的催化剂及其制备方法,属于催化剂领域。所述催化剂由改性沸石分子筛和含锆复合氧化物组成;按质量百分比含锆复合氧化物的含量为20%~60%,改性沸石分子筛的含量为40%~80%。制备方法:将含锆复合氧化物加入到溶剂中超声分散得溶液A;将改性沸石分子筛加入到溶液A中;将超声分散后的混合物抽滤,洗涤后将所得滤饼干燥;将干燥后所得样品磨成粉末;将所得粉末样品焙烧,所得样品即为由合成气高选择性制轻质芳烃的催化剂。可高选择性制得轻质芳烃,且稳定性良好;所述由合成气高选择性制轻质芳烃的催化剂的制备方法简单,成本较低,具有较好的工业应用前景。
Description
技术领域
本发明属于催化剂领域,具体涉及一种由合成气高选择性制轻质芳烃的催化剂及其制备方法。
背景技术
由于石油资源的不断匮乏,近年来开发各类非油基资源(如煤、天然气、页岩气和生物质等)经由费托合成(CO加氢)制清洁液体燃料和化学品(如低碳烯烃和芳烃等)的研究重新引起了广泛的兴趣。CO加氢反应的主要挑战在于选择性的调控,如难以高选择性一步获得各类中间馏分油如汽油、柴油、航煤等。目前基于煤或天然气制燃料油的工业化(如南非Sasol公司、英荷Shell公司、中科合成油、兖矿集团等)均采用两步或多步法工艺,成本较高。针对合成气一步法制芳烃如苯、甲苯、二甲苯的过程,已有相关的研究报道,但该技术尚未实现产业化,主要存在问题是产物选择性的调控难以取得突破。此外,催化剂易于失活,催化性能的稳定性难以保持。
提高合成气一步制芳烃的选择性关键在于高性能催化剂的研制,这也是当前研究的主攻方向。使用甲醇合成催化剂与分子筛耦合组成的复合催化剂具有较好的催化性能。如Lasa等早期报道了Cr-Zn/ZSM-5催化剂上合成气制芳烃的性能(Ind.Eng.Chem.Res.,1991,30,1448),芳烃在碳氢化合物中选择性可达到70.8%,但该催化剂上的芳烃分布未提及;后续又报道了Cr-Zn/ZSM-5复合催化剂上的合成气制芳烃性能(Appl.Catal.A,1995,125,81),在629~683K、3.6~4.5MPa的反应条件下,CO2选择性约70%,碳氢化合物中芳烃选择性达到75%,但轻质芳烃苯、甲苯、二甲苯(BTX)的选择性不超过27%,约30%的三甲苯产物。Fujimoto等报道了甲醇合成Pd/SiO2催化剂与ZSM-5物理混合,在反应条件为2.06MPa、630K下,芳烃选择性约50%,但产物中以重质芳烃为主,BTX选择性仅1%(J.Catal.,1984,87,136)。将费托合成催化剂如Fe-Mn与Ga-HZSM-5或Zn-HZSM-5组成的复合催化剂(Catal.Today,1996,30,207;催化学报,2002,23,333)也具有一定的催化效果。尽管上述催化剂上均可从合成气一步得到芳烃,但芳烃选择性往往不超过45%,且难以维持较好的寿命。此外,反应产物中轻质芳烃苯、甲苯、二甲苯的选择性低。因此,提高芳烃特别是轻质芳烃的选择性,降低工艺复杂性和成本,是合成气一步法制芳烃急需解决的技术难点。
发明内容
本发明旨在提供一种由合成气高选择性制轻质芳烃的催化剂及其制备方法。
所述由合成气高选择性制轻质芳烃的催化剂由改性沸石分子筛和含锆复合氧化物组成;按质量百分比含锆复合氧化物的含量为20%~60%,改性沸石分子筛的含量为40%~80%。
所述含锆复合氧化物可采用ZrO2-MOx,其中M为碱金属元素、碱土金属元素、稀土元素、IVB族元素、VIIB族元素、IB族元素、IIB族元素、IIIA族元素等中的至少一种;Zr与M的摩尔比可为1︰(0.001~10)。
所述改性沸石分子筛可采用经硅和锡、镓、钛、锌等中的至少一种元素改性后的沸石分子筛,沸石分子筛种类包括ZSM-34、Beta、MCM-22、SAPO-34、ZSM-5、ZSM-18、SSZ-13、Y、MOR、ALPO-11等中的至少一种。
所述碱金属元素、碱土金属元素、稀土元素、IVB族元素、VIIB族元素、IB族元素、IIB族元素、IIIA族元素包括K、Rb、Cs、Ca、Mg、Ce、Pr、Nd、Ti、Hf、Mn、Cu、Zn、Al、Ga、In等中的至少一种。
所述含锆复合氧化物的具体制备步骤如下:
(1)按所述含锆复合氧化物的组分配比称取锆盐,加入醇类溶剂中配成质量百分浓度为0.1%~20%的溶液,于25~60℃下搅拌0.5~5h,得溶液A;所述锆盐为硝酸锆、氯化锆、硝酸氧锆、乙酸锆、氯氧化锆等中的至少一种,所述醇类溶剂为C1~C6的醇类等中的至少一种;
(2)向溶液A中加入计量的表面活性剂,继续搅拌0.5~5h,得溶液B;所述表面活性剂为聚乙二醇、聚乙烯醇、烷基溴化铵、吐温等中的至少一种,表面活性剂与Zr的摩尔比为(0.005~0.1):1;
(3)按照所述含锆复合氧化物的组分配比向步骤(2)所得溶液B中加入计量的含M元素的盐类,于25~60℃下继续搅拌0.5~5h,得溶液C;所述盐类包括硝酸盐、盐酸盐、醋酸盐、溴酸盐、乙酰丙酮盐等中的至少一种;
(4)向溶液C中加入质量百分浓度为1%~20%的碱溶液,调节体系pH值为7~13,调节温度至50~120℃,回流搅拌1~10h,得固液混合物;所述碱溶液为碳酸氢铵、氨水、氢氧化钠、碳酸氢钠、碳酸钠、碳酸铵等中的至少一种;
(5)将获得的固液混合物经抽滤、洗涤后,移至真空干燥箱内于70~120℃下干燥,时间为1~24h;
(6)将干燥后的样品移至马弗炉内焙烧,温度为250~600℃,时间为1~10h,所得产物即为含锆复合氧化物,记为ZrO2-MOx(m/n),其中m/n为Zr与M元素的摩尔比。
所述改性沸石分子筛的具体制备步骤如下:
(1)称取计量的沸石分子筛,加入到500mL的圆底烧瓶中,加入有机溶剂C5~C12烷烃,升温至50~100℃,搅拌0.5~5h,得混合物A;所述C5~C12烷烃为直链烷烃,其中沸石分子筛与C5~C12烷烃的固液质量比为1:(0.5~100);
(2)向混合物A中加入计量的有机硅分子,所述有机硅包括但不限于正硅酸乙酯、正硅酸丁酯、四甲氧基硅烷、丙基三甲氧基硅烷等中的至少一种,搅拌回流0.5~10h,得混合物B;有机硅分子用量按质量百分比为沸石分子筛的5%~30%;
(3)将混合物B转移至旋转蒸发仪内,于50~120℃下真空加热2~10h;将真空加热干燥后的样品移至马弗炉内以2℃/min的速率升温至300~600℃焙烧,时间为1~20h;
(4)称取计量的含锡、钛、镓、锌等中的至少一种元素的盐类,溶解于丙酮溶剂中,配制成质量百分浓度为2%~20%的溶液,将步骤(3)焙烧后的样品加入丙酮溶液中,于40~80℃下搅拌0.5~5h,得固液混合物;所述盐类为乙酰丙酮盐、醋酸盐、盐酸盐、硝酸盐、草酸盐等中的至少一种,盐类的用量按质量百分比为沸石分子筛的0.1%~10%;
(5)将步骤(4)获得的固液混合物经抽滤、洗涤后,移至真空干燥箱内于70~110℃下干燥,时间为1~20h;后移至马弗炉内以2℃/min的速率升温至400~650℃焙烧,时间为0.5~10h。所得样品即为改性沸石分子筛。
所述由合成气高选择性制轻质芳烃的催化剂的制备方法,包括以下步骤:
(1)按照所述催化剂的组分,称取计量的含锆复合氧化物,加入到溶剂中超声分散,时间为0.5~10h,得溶液A;
在步骤(1)中,所述溶剂可选自甲醇、乙醇、丙酮、乙二醇等中的一种;所述含锆复合氧化物与溶剂的固液质量比可为1︰(1~50);
(2)按照所述催化剂配比,称取计量的改性沸石分子筛,加入到溶液A中,继续超声分散0.5~5h;
(3)将超声分散后的混合物抽滤,用乙醇进行洗涤,后将所得滤饼移至真空干燥箱内于40~90℃下干燥1~48h;
(4)将干燥后所得样品磨成粉末;
在步骤(4)中,所述将干燥后所得样品磨成粉末可采用研磨或球磨,所述研磨或球磨的时间可为0.5~3h;
(5)将所得粉末样品移至管式炉内采用流动空气进行焙烧,升温速率为0.5~2℃/min,温度为300~600℃,焙烧时间为1~24h,所得样品即为由合成气高选择性制轻质芳烃的催化剂。
本发明所提供的由合成气高选择性制轻质芳烃的催化剂可用于固定床,也可用于流化床或浆态床。一般情况下,本发明所提供的由合成气高选择性制轻质芳烃的催化剂用于合成气转化的条件为:合成气中H2与CO的体积比为0.5-4,反应压力为0.5-8MPa,合成气空速为500-20000h-1,反应温度为180-600℃,反应时间50h以上。
与现有技术相比,本发明的有益效果主要体现在以下方面:
(1)本发明所提供的由合成气高选择性制轻质芳烃的催化剂具有优异的催化性能,芳烃选择性达90%,且其中轻质芳烃(苯、甲苯、二甲苯)占芳烃比例达70%以上,CO转化率高于20%。
(2)由合成气高选择性制轻质芳烃的催化剂为双功能催化剂,其中含锆复合氧化物主要活化CO加氢生成含氧中间体,改性沸石分子筛则负责催化该中间物种的进一步转化生成芳烃。
(3)相比于常规沸石分子筛,改性沸石分子筛的表面酸浓度减弱,因而抑制了含氧中间物种在分子筛表面的聚合等副反应,使得大部分中间体进入分子筛孔道内并进一步催化转化为芳烃,因此提高了选择性;且由于孔道的择型作用,产物中以轻质芳烃(苯、甲苯、二甲苯)为主。
(4)由合成气高选择性制轻质芳烃的催化剂上两种组分的耦合方法可控,易于发挥双组分的协同作用。
综上,使用本发明所提供的由合成气高选择性制轻质芳烃的催化剂可高选择性制得轻质芳烃,且稳定性良好;所述由合成气高选择性制轻质芳烃的催化剂的制备方法简单,成本较低,具有较好的工业应用前景。
具体实施方式
下面进一步详细说明本发明所提供的由合成气高选择性制轻质芳烃的催化剂及其制备方法。
实施例1
称取12.5g Zr(NO3)4·5H2O加入100ml乙醇中,于50℃下搅拌2h;加入0.2g聚乙烯醇(平均分子量300),继续搅拌3h;加入0.055g MgCl2,于50℃下继续搅拌2h;继续加入10wt%的氢氧化钠溶液,调节体系pH值为9.5,升温至70℃下回流搅拌5h;经抽滤、洗涤后,所得样品移至真空干燥箱内于100℃下干燥12h;将干燥后的样品移至马弗炉内于500℃下焙烧6h,所得产物即为ZrO2-MgO(1/0.02)。
称取5.0g沸石分子筛Hbeta加入到含50ml正庚烷的圆底烧瓶中,升温至80℃下搅拌2h;加入0.5g正硅酸丁酯,继续搅拌回流4h;后将混合物转移至旋转蒸发仪内,于70℃下真空加热3h;将真空加热干燥后的样品移至马弗炉内以2℃/min的速率升温至450℃焙烧5h;称取0.25g氯化亚锡溶解于5.0g丙酮中,后将焙烧后的样品加入含锡溶液中,于50℃下搅拌2h,并经抽滤、洗涤,后移至真空干燥箱内于90℃下干燥5h;移至马弗炉内以2℃/min的速率升温至500℃下焙烧6h,即得改性的沸石分子筛,记为Hbeta-Si-Sn。
称取1.0g含锆复合氧化物ZrO2-MgO(1/0.02)加入到30g乙醇溶剂中超声分散4h;后加入1.5g改性沸石分子筛Hbeta-Si-Sn并继续超声分散1h;将混合物抽滤,用乙醇进行洗涤,后将所得滤饼移至真空干燥箱内于70℃下干燥12h;所得样品放入研钵中研磨1h,后移至管式炉内于流动空气气氛下升温至520℃下焙烧12h,所得样品即为催化剂,记为ZrO2-MgO/Hbeta-Si-Sn。
催化反应在固定床高压微型反应器中进行,合成气中H2与CO的体积比为2.5,反应压力为2.5MPa,合成气空速为5000h-1,反应温度为420℃,反应时间50h。反应产物和原料气用气相色谱在线分析。具体反应性能列于表1中。
实施例2
称取12.5g Zr(NO3)4·5H2O加入100ml乙醇中,于50℃下搅拌2h;加入0.2g聚乙烯醇(平均分子量300),继续搅拌3h;加入0.14g LaCl3,于50℃下继续搅拌2h;加入10wt%的氢氧化钠溶液,调节体系pH值为9.5,升温至70℃下回流搅拌5h;经抽滤、洗涤后,所得样品移至真空干燥箱内于100℃下干燥12h;将干燥后的样品移至马弗炉内于500℃下焙烧6h,所得产物即为ZrO2-La2O3(1/0.02)。
称取5.0g沸石分子筛HZSM-5加入到含50ml正庚烷的圆底烧瓶中,升温至80℃下搅拌2h;加入0.35g正硅酸丁酯,继续搅拌回流4h;后将混合物转移至旋转蒸发仪内,于70℃下真空加热3h;将真空加热干燥后的样品移至马弗炉内以2℃/min的速率升温至450℃焙烧5h;称取0.25g氯化亚锡溶解于5.0g丙酮中,后将焙烧后的样品加入含锡溶液中,于50℃下搅拌2h,并经抽滤、洗涤,后移至真空干燥箱内于90℃下干燥5h;移至马弗炉内以2℃/min的速率升温至500℃下焙烧6h,即得改性的沸石分子筛,记为HZSM-5-Si-Sn。
称取1.0g含锆复合氧化物ZrO2-La2O3(1/0.02)加入到30g乙醇溶剂中超声分散4h;后加入1.5g改性沸石分子筛HZSM-5-Si-Sn并继续超声分散1h;将混合物抽滤,用乙醇进行洗涤,后将所得滤饼移至真空干燥箱内于70℃下干燥12h;所得样品放入研钵中研磨1h,后移至管式炉内于流动空气气氛下升温至550℃下焙烧12h,所得样品即为催化剂,记为ZrO2-La2O3/HZSM-5-Si-Sn。
催化反应在固定床高压微型反应器中进行,反应条件及产物分析同实施例1,反应性能见表1。
实施例3
称取12.5g Zr(NO3)4·5H2O加入100ml乙醇中,于50℃下搅拌2h;加入0.2g聚乙烯醇(平均分子量300),继续搅拌3h;加入0.073g MnCl2,于50℃下继续搅拌2h;加入10wt%的氢氧化钠溶液,调节体系pH值为9.5,升温至70℃下回流搅拌5h;经抽滤、洗涤后,所得样品移至真空干燥箱内于100℃下干燥12h;将干燥后的样品移至马弗炉内于500℃下焙烧6h,所得产物即为ZrO2-MnO(1/0.02)。
称取5.0g沸石分子筛HZSM-34加入到含50ml正庚烷的圆底烧瓶中,升温至80℃下搅拌2h;加入0.35g正硅酸丁酯,继续搅拌回流4h;后将混合物转移至旋转蒸发仪内,于70℃下真空加热3h;将真空加热干燥后的样品移至马弗炉内以2℃/min的速率升温至450℃焙烧5h;称取0.25g氯化亚锡溶解于5.0g丙酮中,后将焙烧后的样品加入含锡溶液中,于50℃下搅拌2h,并经抽滤、洗涤,后移至真空干燥箱内于90℃下干燥5h;移至马弗炉内以2℃/min的速率升温至500℃下焙烧6h,即得改性的沸石分子筛,记为HZSM-34-Si-Sn。
称取1.0g含锆复合氧化物ZrO2-MnO(1/0.02)加入到30g乙醇溶剂中超声分散4h;后加入1.5g改性沸石分子筛HZSM-34-Si-Sn并继续超声分散1h;将混合物抽滤,用乙醇进行洗涤,后将所得滤饼移至真空干燥箱内于70℃下干燥12h;所得样品放入研钵中研磨1h,后移至管式炉内于流动空气气氛下升温至550℃下焙烧12h,所得样品即为催化剂,记为ZrO2-MnO/HZSM-34-Si-Sn。
催化反应在固定床高压微型反应器中进行,反应条件及产物分析同实施例1,反应性能见表1。
实施例4
称取12.5g Zr(NO3)4·5H2O加入100ml乙醇中,于50℃下搅拌2h;加入0.2g聚乙烯醇(平均分子量300),继续搅拌3h;加入0.079g ZnCl2,于50℃下继续搅拌2h;加入10wt%的氢氧化钠溶液,调节体系pH值为9.5,升温至70℃下回流搅拌5h;经抽滤、洗涤后,所得样品移至真空干燥箱内于100℃下干燥12h;将干燥后的样品移至马弗炉内于500℃下焙烧6h,所得产物即为ZrO2-ZnO(1/0.02)。
称取5.0g沸石分子筛HY加入到含50ml正庚烷的圆底烧瓶中,升温至80℃下搅拌2h;加入0.42g正硅酸丁酯,继续搅拌回流4h;后将混合物转移至旋转蒸发仪内,于70℃下真空加热3h;将真空加热干燥后的样品移至马弗炉内以2℃/min的速率升温至450℃焙烧5h;称取0.35g氯化亚锡溶解于5.0g丙酮中,后将焙烧后的样品加入含锡溶液中,于50℃下搅拌2h,并经抽滤、洗涤,后移至真空干燥箱内于90℃下干燥5h;移至马弗炉内以2℃/min的速率升温至500℃下焙烧6h,即得改性的沸石分子筛,记为HY-Si-Sn。
称取1.0g含锆复合氧化物ZrO2-ZnO(1/0.02)加入到30g乙醇溶剂中超声分散4h;后加入1.5g改性沸石分子筛HY-Si-Sn并继续超声分散1h;将混合物抽滤,用乙醇进行洗涤,后将所得滤饼移至真空干燥箱内于70℃下干燥12h;所得样品放入研钵中研磨1h,后移至管式炉内于流动空气气氛下升温至550℃下焙烧12h,所得样品即为催化剂,记为ZrO2-ZnO/HY-Si-Sn。
催化反应在固定床高压微型反应器中进行,反应条件及产物分析同实施例1,反应性能见表1。
实施例5
称取12.5g Zr(NO3)4·5H2O加入100ml乙醇中,于50℃下搅拌2h;加入0.2g聚乙烯醇(平均分子量300),继续搅拌3h;加入0.077g AlCl3,于50℃下继续搅拌2h;加入10wt%的氢氧化钠溶液,调节体系pH值为9.5,升温至70℃下回流搅拌5h;经抽滤、洗涤后,所得样品移至真空干燥箱内于100℃下干燥12h;将干燥后的样品移至马弗炉内于400℃下焙烧6h,所得产物即为ZrO2-Al2O3(1/0.02)。
称取5.0g沸石分子筛HMOR加入到含50ml正庚烷的圆底烧瓶中,升温至80℃下搅拌2h;加入0.35g正硅酸丁酯,继续搅拌回流4h;后将混合物转移至旋转蒸发仪内,于70℃下真空加热3h;将真空加热干燥后的样品移至马弗炉内以2℃/min的速率升温至450℃焙烧5h;称取0.35g氯化亚锡溶解于5.0g丙酮中,后将焙烧后的样品加入含锡溶液中,于50℃下搅拌2h,并经抽滤、洗涤,后移至真空干燥箱内于90℃下干燥5h;移至马弗炉内以2℃/min的速率升温至500℃下焙烧6h,即得改性的沸石分子筛,记为HMOR-Si-Sn。
称取1.0g含锆复合氧化物ZrO2-Al2O3(1/0.02)加入到30g乙醇溶剂中超声分散4h;后加入1.5g改性沸石分子筛HMOR-Si-Sn并继续超声分散1h;将混合物抽滤,用乙醇进行洗涤,后将所得滤饼移至真空干燥箱内于70℃下干燥12h;所得样品放入研钵中研磨1h,后移至管式炉内于流动空气气氛下升温至550℃下焙烧12h,所得样品即为催化剂,记为ZrO2-Al2O3/HMOR-Si-Sn。
催化反应在固定床高压微型反应器中进行,反应条件及产物分析同实施例1,反应性能见表1。
实施例6
称取12.5g Zr(NO3)4·5H2O加入100ml乙醇中,于50℃下搅拌2h;加入0.2g聚乙烯醇(平均分子量300),继续搅拌3h;加入0.203g SnCl4·5H2O,于50℃下继续搅拌2h;加入10wt%的氢氧化钠溶液,调节体系pH值为9.5,升温至70℃下回流搅拌5h;经抽滤、洗涤后,所得样品移至真空干燥箱内于100℃下干燥12h;将干燥后的样品移至马弗炉内于400℃下焙烧6h,所得产物即为ZrO2-SnO2(1/0.02)。
称取5.0g沸石分子筛H-MCM-22加入到含50ml正庚烷的圆底烧瓶中,升温至80℃下搅拌2h;加入0.35g正硅酸丁酯,继续搅拌回流4h;后将混合物转移至旋转蒸发仪内,于70℃下真空加热3h;将真空加热干燥后的样品移至马弗炉内以2℃/min的速率升温至450℃焙烧5h;称取0.35g氯化亚锡溶解于5.0g丙酮中,后将焙烧后的样品加入含锡溶液中,于50℃下搅拌2h,并经抽滤、洗涤,后移至真空干燥箱内于90℃下干燥5h;移至马弗炉内以2℃/min的速率升温至500℃下焙烧6h,即得改性的沸石分子筛,记为H-MCM-22-Si-Sn。
称取1.0g含锆复合氧化物ZrO2-SnO2(1/0.02)加入到30g乙醇溶剂中超声分散4h;后加入1.5g改性沸石分子筛H-MCM-22-Si-Sn并继续超声分散1h;将混合物抽滤,用乙醇进行洗涤,后将所得滤饼移至真空干燥箱内于70℃下干燥12h;所得样品放入研钵中研磨1h,后移至管式炉内于流动空气气氛下升温至550℃下焙烧12h,所得样品即为催化剂,记为ZrO2-SnO2/H-MCM-22-Si-Sn。
催化反应在固定床高压微型反应器中进行,反应条件及产物分析同实施例1,反应性能见表1。
实施例7
称取12.5g Zr(NO3)4·5H2O加入100ml乙醇中,于50℃下搅拌2h;加入0.2g聚乙烯醇(平均分子量300),继续搅拌3h;加入0.078g CuCl2,于50℃下继续搅拌2h;加入10wt%的氢氧化钠溶液,调节体系pH值为9.5,升温至70℃下回流搅拌5h;经抽滤、洗涤后,所得样品移至真空干燥箱内于100℃下干燥12h;将干燥后的样品移至马弗炉内于400℃下焙烧6h,所得产物即为ZrO2-CuO(1/0.02)。
称取5.0g沸石分子筛SAPO-34加入到含50ml正庚烷的圆底烧瓶中,升温至80℃下搅拌2h;加入0.35g正硅酸丁酯,继续搅拌回流4h;后将混合物转移至旋转蒸发仪内,于70℃下真空加热3h;将真空加热干燥后的样品移至马弗炉内以2℃/min的速率升温至450℃焙烧5h;称取0.35g氯化亚锡溶解于5.0g丙酮中,后将焙烧后的样品加入含锡溶液中,于50℃下搅拌2h,并经抽滤、洗涤,后移至真空干燥箱内于90℃下干燥5h;移至马弗炉内以2℃/min的速率升温至500℃下焙烧6h,即得改性的沸石分子筛,记为SAPO-34-Si-Sn。
称取1.0g含锆复合氧化物ZrO2-CuO(1/0.02)加入到30g乙醇溶剂中超声分散4h;后加入1.5g改性沸石分子筛SAPO-34-Si-Sn并继续超声分散1h;将混合物抽滤,用乙醇进行洗涤,后将所得滤饼移至真空干燥箱内于70℃下干燥12h;所得样品放入研钵中研磨1h,后移至管式炉内于流动空气气氛下升温至550℃下焙烧12h,所得样品即为催化剂,记为ZrO2-CuO/SAPO-34-Si-Sn。
催化反应在固定床高压微型反应器中进行,反应条件及产物分析同实施例1,反应性能见表1。
实施例8
称取12.5g Zr(NO3)4·5H2O加入100ml乙醇中,于50℃下搅拌2h;加入0.2g聚乙烯醇(平均分子量300),继续搅拌3h;加入0.385g AlCl3,于50℃下继续搅拌2h;加入10wt%的氢氧化钠溶液,调节体系pH值为9.5,升温至70℃下回流搅拌5h;经抽滤、洗涤后,所得样品移至真空干燥箱内于100℃下干燥12h;将干燥后的样品移至马弗炉内于400℃下焙烧6h,所得产物即为ZrO2-Al2O3(1/0.1)。
称取5.0g沸石分子筛SSZ-13加入到含50ml正庚烷的圆底烧瓶中,升温至80℃下搅拌2h;加入0.35g正硅酸丁酯,继续搅拌回流4h;后将混合物转移至旋转蒸发仪内,于70℃下真空加热3h;将真空加热干燥后的样品移至马弗炉内以2℃/min的速率升温至450℃焙烧5h;称取0.35g氯化亚锡溶解于5.0g丙酮中,后将焙烧后的样品加入含锡溶液中,于50℃下搅拌2h,并经抽滤、洗涤,后移至真空干燥箱内于90℃下干燥5h;移至马弗炉内以2℃/min的速率升温至500℃下焙烧6h,即得改性的沸石分子筛,记为SSZ-13-Si-Sn。
称取1.0g含锆复合氧化物ZrO2-Al2O3(1/0.1)加入到30g乙醇溶剂中超声分散4h;后加入1.5g改性沸石分子SSZ-13-Si-Sn并继续超声分散1h;将混合物抽滤,用乙醇进行洗涤,后将所得滤饼移至真空干燥箱内于70℃下干燥12h;所得样品放入研钵中研磨1h,后移至管式炉内于流动空气气氛下升温至550℃下焙烧12h,所得样品即为催化剂,记为ZrO2-Al2O3/SSZ-13-Si-Sn。
催化反应在固定床高压微型反应器中进行,反应条件及产物分析同实施例1,反应性能见表1。
实施例9
催化剂组成及制备过程同实施例5。催化反应在固定床高压微型反应器中进行,除合成气中H2与CO的体积比为4外,反应条件及产物分析同实施例1,反应性能见表1。
实施例10
催化剂组成及制备过程同实施例5。催化反应在固定床高压微型反应器中进行,除合成气中H2与CO的体积比为0.5外,反应条件及产物分析同实施例1,反应性能见表1。
对比例1
称取12.5g Zr(NO3)4·5H2O加入100ml乙醇中,于50℃下搅拌2h;加入0.2g聚乙烯醇(平均分子量300),继续搅拌3h;加入10wt%的氢氧化钠溶液,调节体系pH值为9.5,升温至70℃下回流搅拌5h;经抽滤、洗涤后,所得样品移至真空干燥箱内于100℃下干燥12h;将干燥后的样品移至马弗炉内于400℃下焙烧6h,所得产物即为ZrO2。
称取5.0g沸石分子筛HMOR加入到含50ml正庚烷的圆底烧瓶中,升温至80℃下搅拌2h;加入0.35g正硅酸丁酯,继续搅拌回流4h;后将混合物转移至旋转蒸发仪内,于70℃下真空加热3h;将真空加热干燥后的样品移至马弗炉内以2℃/min的速率升温至450℃焙烧5h;称取0.35g氯化亚锡溶解于5.0g丙酮中,后将焙烧后的样品加入含锡溶液中,于50℃下搅拌2h,并经抽滤、洗涤,后移至真空干燥箱内于90℃下干燥5h;移至马弗炉内以2℃/min的速率升温至500℃下焙烧6h,即得改性的沸石分子筛,记为HMOR-Si-Sn。
称取1.0g ZrO2加入到30g乙醇溶剂中超声分散4h;后加入1.5g改性沸石分子筛HMOR-Si-Sn并继续超声分散1h;将混合物抽滤,用乙醇进行洗涤,后将所得滤饼移至真空干燥箱内于70℃下干燥12h;所得样品放入研钵中研磨1h,后移至管式炉内于流动空气气氛下升温至550℃下焙烧12h,所得样品即为催化剂,记为ZrO2/HMOR-Si-Sn。
催化反应在固定床高压微型反应器中进行,反应条件及产物分析同实施例1,反应性能见表1。
对比例2
称取12.5g Zr(NO3)4·5H2O加入100ml乙醇中,于50℃下搅拌2h;加入0.2g聚乙烯醇(平均分子量300),继续搅拌3h;加入0.077g AlCl3,于50℃下继续搅拌2h;加入10wt%的氢氧化钠溶液,调节体系pH值为9.5,升温至70℃下回流搅拌5h;经抽滤、洗涤后,所得样品移至真空干燥箱内于100℃下干燥12h;将干燥后的样品移至马弗炉内于400℃下焙烧6h,所得产物即为ZrO2-Al2O3(1/0.02)。
称取1.0g含锆复合氧化物ZrO2-Al2O3(1/0.02)加入到30g乙醇溶剂中超声分散4h;后加入1.5g沸石分子筛HMOR并继续超声分散1h;将混合物抽滤,用乙醇进行洗涤,后将所得滤饼移至真空干燥箱内于70℃下干燥12h;所得样品放入研钵中研磨1h,后移至管式炉内于流动空气气氛下升温至550℃下焙烧12h,所得样品即为催化剂,记为ZrO2-Al2O3/HMOR。
催化反应在固定床高压微型反应器中进行,反应条件及产物分析同实施例1,反应性能见表1。
对比例3
称取12.5g Zr(NO3)4·5H2O加入100ml乙醇中,于50℃下搅拌2h;加入0.2g聚乙烯醇(平均分子量300),继续搅拌3h;加入10wt%的氢氧化钠溶液,调节体系pH值为9.5,升温至70℃下回流搅拌5h;经抽滤、洗涤后,所得样品移至真空干燥箱内于100℃下干燥12h;将干燥后的样品移至马弗炉内于400℃下焙烧6h,所得产物即为ZrO2。
称取1.0g ZrO2加入到30g乙醇溶剂中超声分散4h;后加入1.5g沸石分子筛HMOR并继续超声分散1h;将混合物抽滤,用乙醇进行洗涤,后将所得滤饼移至真空干燥箱内于70℃下干燥12h;所得样品放入研钵中研磨1h,后移至管式炉内于流动空气气氛下升温至550℃下焙烧12h,所得样品即为催化剂,记为ZrO2/HMOR。
催化反应在固定床高压微型反应器中进行,反应条件及产物分析同实施例1,实施例和对比例中催化剂性能数据见表1。
表1
注:C2-4为C2-C4烃,Aromatics为芳烃(苯、甲苯、二甲苯及多甲基苯),Other C5+为碳数≥5的烷烃和烯烃,BTX fraction in aromatics为芳烃中轻质芳烃(苯、甲苯和二甲苯)所占的比重。
Claims (10)
1.由合成气高选择性制轻质芳烃的催化剂,其特征在于由改性沸石分子筛和含锆复合氧化物组成;按质量百分比含锆复合氧化物的含量为20%~60%,改性沸石分子筛的含量为40%~80%。
2.如权利要求1所述由合成气高选择性制轻质芳烃的催化剂,其特征在于所述含锆复合氧化物采用ZrO2-MOx,其中M为碱金属元素、碱土金属元素、稀土元素、IVB族元素、VIIB族元素、IB族元素、IIB族元素、IIIA族元素中的至少一种;Zr与M的摩尔比可为1︰(0.001~10)。
3.如权利要求1所述由合成气高选择性制轻质芳烃的催化剂,其特征在于所述改性沸石分子筛采用经硅和锡、镓、钛、锌中的至少一种元素改性后的沸石分子筛,沸石分子筛种类包括ZSM-34、Beta、MCM-22、SAPO-34、ZSM-5、ZSM-18、SSZ-13、Y、MOR、ALPO-11中的至少一种。
4.如权利要求1所述由合成气高选择性制轻质芳烃的催化剂,其特征在于所述碱金属元素、碱土金属元素、稀土元素、IVB族元素、VIIB族元素、IB族元素、IIB族元素、IIIA族元素包括K、Rb、Cs、Ca、Mg、Ce、Pr、Nd、Ti、Hf、Mn、Cu、Zn、Al、Ga、In中的至少一种。
5.如权利要求1所述由合成气高选择性制轻质芳烃的催化剂,其特征在于所述含锆复合氧化物的具体制备步骤如下:
(1)按所述含锆复合氧化物的组分配比称取锆盐,加入醇类溶剂中配成质量百分浓度为0.1%~20%的溶液,于25~60℃下搅拌0.5~5h,得溶液A;所述锆盐为硝酸锆、氯化锆、硝酸氧锆、乙酸锆、氯氧化锆中的至少一种,所述醇类溶剂为C1~C6的醇类中的至少一种;
(2)向溶液A中加入计量的表面活性剂,继续搅拌0.5~5h,得溶液B;所述表面活性剂为聚乙二醇、聚乙烯醇、烷基溴化铵、吐温中的至少一种,表面活性剂与Zr的摩尔比为(0.005~0.1):1;
(3)按照所述含锆复合氧化物的组分配比向步骤(2)所得溶液B中加入计量的含M元素的盐类,于25~60℃下继续搅拌0.5~5h,得溶液C;所述盐类包括硝酸盐、盐酸盐、醋酸盐、溴酸盐、乙酰丙酮盐中的至少一种;
(4)向溶液C中加入质量百分浓度为1%~20%的碱溶液,调节体系pH值为7~13,调节温度至50~120℃,回流搅拌1~10h,得固液混合物;所述碱溶液为碳酸氢铵、氨水、氢氧化钠、碳酸氢钠、碳酸钠、碳酸铵中的至少一种;
(5)将获得的固液混合物经抽滤、洗涤后,移至真空干燥箱内于70~120℃下干燥,时间为1~24h;
(6)将干燥后的样品移至马弗炉内焙烧,温度为250~600℃,时间为1~10h,所得产物即为含锆复合氧化物,记为ZrO2-MOx(m/n),其中m/n为Zr与M元素的摩尔比。
6.如权利要求1所述由合成气高选择性制轻质芳烃的催化剂,其特征在于所述改性沸石分子筛的具体制备步骤如下:
(1)称取计量的沸石分子筛,加入到500mL的圆底烧瓶中,加入有机溶剂C5~C12烷烃,升温至50~100℃,搅拌0.5~5h,得混合物A;所述C5~C12烷烃为直链烷烃,其中沸石分子筛与C5~C12烷烃的固液质量比为1:(0.5~100);
(2)向混合物A中加入计量的有机硅分子,所述有机硅包括但不限于正硅酸乙酯、正硅酸丁酯、四甲氧基硅烷、丙基三甲氧基硅烷中的至少一种,搅拌回流0.5~10h,得混合物B;有机硅分子用量按质量百分比为沸石分子筛的5%~30%;
(3)将混合物B转移至旋转蒸发仪内,于50~120℃下真空加热2~10h;将真空加热干燥后的样品移至马弗炉内以2℃/min的速率升温至300~600℃焙烧,时间为1~20h;
(4)称取计量的含锡、钛、镓、锌中的至少一种元素的盐类,溶解于丙酮溶剂中,配制成质量百分浓度为2%~20%的溶液,将步骤(3)焙烧后的样品加入丙酮溶液中,于40~80℃下搅拌0.5~5h,得固液混合物;所述盐类为乙酰丙酮盐、醋酸盐、盐酸盐、硝酸盐、草酸盐中的至少一种,盐类的用量按质量百分比为沸石分子筛的0.1%~10%;
(5)将步骤(4)获得的固液混合物经抽滤、洗涤后,移至真空干燥箱内于70~110℃下干燥,时间为1~20h;后移至马弗炉内以2℃/min的速率升温至400~650℃焙烧,时间为0.5~10h。所得样品即为改性沸石分子筛。
7.如权利要求1所述由合成气高选择性制轻质芳烃的催化剂的制备方法,其特征在于包括以下步骤:
(1)按照所述催化剂的组分,称取计量的含锆复合氧化物,加入到溶剂中超声分散,时间为0.5~10h,得溶液A;
(2)按照所述催化剂配比,称取计量的改性沸石分子筛,加入到溶液A中,继续超声分散0.5~5h;
(3)将超声分散后的混合物抽滤,用乙醇进行洗涤,后将所得滤饼移至真空干燥箱内于40~90℃下干燥1~48h;
(4)将干燥后所得样品磨成粉末;
(5)将所得粉末样品移至管式炉内采用流动空气进行焙烧,升温速率为0.5~2℃/min,温度为300~600℃,焙烧时间为1~24h,所得样品即为由合成气高选择性制轻质芳烃的催化剂。
8.如权利要求7所述由合成气高选择性制轻质芳烃的催化剂的制备方法,其特征在于在步骤(1)中,所述溶剂选自甲醇、乙醇、丙酮、乙二醇中的一种。
9.如权利要求7所述由合成气高选择性制轻质芳烃的催化剂的制备方法,其特征在于所述含锆复合氧化物与溶剂的固液质量比为1︰(1~50)。
10.如权利要求7所述由合成气高选择性制轻质芳烃的催化剂的制备方法,其特征在于在步骤(4)中,所述将干燥后所得样品磨成粉末采用研磨或球磨,所述研磨或球磨的时间可为0.5~3h。
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