CN106563459A - 一种酸碱双功能催化剂及其制备方法和应用 - Google Patents
一种酸碱双功能催化剂及其制备方法和应用 Download PDFInfo
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- CN106563459A CN106563459A CN201610863044.6A CN201610863044A CN106563459A CN 106563459 A CN106563459 A CN 106563459A CN 201610863044 A CN201610863044 A CN 201610863044A CN 106563459 A CN106563459 A CN 106563459A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
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- 238000000034 method Methods 0.000 claims abstract description 27
- 239000011973 solid acid Substances 0.000 claims abstract description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 18
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012752 auxiliary agent Substances 0.000 claims description 15
- 229910000765 intermetallic Inorganic materials 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
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- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
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- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
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- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
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- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
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- 239000012153 distilled water Substances 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
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- 229910002674 PdO Inorganic materials 0.000 claims 1
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- 238000007086 side reaction Methods 0.000 abstract description 4
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910020881 PMo12O40 Inorganic materials 0.000 description 2
- 229910020628 SiW12O40 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910019501 NaVO3 Inorganic materials 0.000 description 1
- UUIRDIWGVMSEBE-UHFFFAOYSA-N acetylene propan-2-one Chemical compound C#C.CC(C)=O UUIRDIWGVMSEBE-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium nitrate Inorganic materials [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical group O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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Classifications
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- 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
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- 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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/44—Noble metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- 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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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Abstract
本发明公开了一种酸碱双功能催化剂,该催化剂由金属氧化物、助剂、固体酸以及载体组成;固体酸与载体的质量比为0.5‑15:100;金属氧化物与载体的质量比为1‑20:100;助剂与金属氧化物的质量比为0.1‑4:100。本发明还公开了该催化剂的制备方法和应用。本发明所述催化剂利用酸碱协同作用不仅提高了反应的转化率,而且减少了过程中副反应的发生,提高了异戊二烯的收率。另外,本发明提供的酸碱双功能催化剂毒性小,寿命长,适于工业化生产。
Description
技术领域
本发明涉及一种酸碱双功能催化剂及其制备方法和应用。
背景技术
异戊二烯具有典型的共轭双键结构,在常温下是一种无色易挥发、刺激性油状液体,主要用于生产异戊橡胶、苯乙烯-异戊二烯-苯乙烯(SIS)和丁基橡胶等。近年来,异戊二烯还广泛应用于农药、医药、香料、喷雾剂及粘合剂等领域,应用前景十分广阔。工业上主要的异戊二烯的生产方法是分离法,但随着乙烯工业格局的改变和异戊二烯需求量的增长,通过分离法获取异戊二烯已经不能满足市场需求,急需通过化学方法制备异戊二烯。在诸多化学合成法中(异丁烯-甲醛法、乙炔-丙酮法、丙烯共聚法),异丁烯-甲醛法(烯醛法)是最具发展前景的方法。
烯醛法分为两步法和一步法。其中两步法是在液体酸催化作用下首先生成4,4二甲基-1,3二氧六环(DMD),DMD经分离裂解生成异戊二烯。由于用到液体酸催化剂及两步反应,两步法存在设备易腐蚀、副反应多、异戊二烯收率低及环境污染严重等问题。一步法是在催化剂的作用下,气相异丁烯与甲醛直接脱水缩合得到异戊二烯。这种一步法具有流程短、分离简单、产品质量高等特点,一直是国内外研究热点。
烯醛气相一步法的关键是研制一种高效催化剂。 目前国内外对于该反应的催化剂研究体系主要集中三大类:磷酸盐体系,分子筛体系和金属氧化物体系。其中磷酸盐和分子筛体系的催化剂均为固体酸催化剂,具有代表性的磷酸盐为NhP,异戊二烯收率(对甲醛)最高可达57%,且在30 h内可保持活性稳定。CN58102885A 公开了一种以氧化硅和高硅铝比的分子筛为主要成分的催化剂,其中氧化硅为粘结剂组分,主要活性组分为具有三维空间结构的分子筛,该催化剂的优点是具有较高的选择性,对甲醛的选择性为80%以上。金属氧化物体系中也有固体酸催化剂,CN103721729A公开了一种烯醛缩合反应用固体酸催化剂,催化剂组成为金属氧化物,助剂为氧化硼和氧化磷,据称该催化剂的甲醛转化率最高为83.8%, 选择性最高达到86.5%。此外金属氧化物体系也有非固体酸的催化剂,CN86108869A公开了一种以二氧化硅为载体,以铜的氧化物,复合氧化物等为活性组分,以碱金属为助剂组分的催化剂,得到甲醛转化率75~85%,对甲醛的选择性为70~78%。
虽然固体酸催化剂可以催化烯醛缩合反应,但同时也对异丁烯和异戊二烯的芳构、环化、异构、裂解等副反应一样具有催化作用,所以进一步提高催化剂选择性非常困难。并且许多研究表明,该反应的转化和甲醛的活化需要适当的碱性活性位或者氧化还原位,而只有酸性位的催化剂很难提高反应的转化率,因此,制备一种合适的酸碱双功能催化剂,可以使反应同时具有高的选择性和转化率。
发明内容
本发明的目的在于提供一种酸碱双功能催化剂及其制备方法和应用。
一种酸碱双功能催化剂,其特征在于该催化剂由金属氧化物、助剂、固体酸以及载体组成;所述固体酸与载体的质量比为0.5-15:100;所述金属氧化物与载体的质量比为1-20:100;所述助剂与金属氧化物的质量比为0.1-4:100;所述固体酸为HZSM-5分子筛、HY分子筛、USY分子筛、H4SiW12O40、H3PW12O40、H3PMo12O40、AlPO4、BPO4、γ-Al2O3和Nb2O5中的一种或多种;所述金属氧化物为Nd2O3、Cr2O3、CuO、Ag2O、Fe2O3、V2O5、Bi2O3和PdO中的一种或多种;所述助剂为Na、K、Mg、Ca、Ba、Mn、Sb、Ce和Zr元素中的一种或多种;所述载体为SiO2、石墨烯和碳纳米管中的一种或多种。
如上所述酸碱双功能催化剂的制备方法,其特征在于该方法依次步骤为:
a)将固体酸和载体在溶剂中混合后在10-90℃负载1.5-3h,然后在80-120℃干燥至恒重后在300-400℃焙烧0.5-6h即得催化剂前驱体;
b)将金属化合物和助剂原料在溶剂中混合均匀;
c)将步骤a)得到的催化剂前驱体和步骤b)得到的溶液混合在80-100℃负载1-3h,得到催化剂中间体;
d)将步骤c)得到的催化剂中间体在100-140℃干燥至恒重后在450-650℃焙烧1.0-8h即得酸碱双功能催化剂。
所述金属化合物为Nd、Cr、Cu、Ag、Fe、V、Bi、Pd的硝酸盐、硫酸盐或氯化盐中的一种或多种。
所述助剂原料为Na、K、Mg、Ca、Ba、Mn、Sb、Ce、Zr的硝酸盐、硫酸盐或氯化盐中的一种或多种。
所述溶剂为自来水、蒸馏水和去离子水中的一种。
步骤a)中所述负载的温度为10-50℃。
所述负载的方法为等体积浸渍或过量浸渍。
步骤a)所述焙烧的时间为3-4h。
步骤b)中所述金属化合物和助剂原料的总质量与溶剂的质量比为1-3:100。
步骤d)为将步骤c)得到的催化剂中间体在100-140℃干燥至恒重后在80-100℃用氨水处理1-3h,然后经过滤、水洗、在100-140℃干燥至恒重,最后在450-650℃焙烧1.0-8h即得酸碱双功能催化剂。
所述氨水的质量浓度为2-8%。
步骤d)所述焙烧的温度为500-600℃,时间为2-6h。
如上所述酸碱双功能催化剂在烯醛气相一步法合成异戊二烯中的应用:异丁烯和甲醛的摩尔比为5.5-8.0,反应温度250-350℃,接触时间0.4-0.9秒;再生气氛为空气,再生温度为400-600℃,反应时间与再生时间之比为1.0-2.5,反应周期为50-90分钟。
本发明所述催化剂利用酸碱协同作用不仅提高了反应的转化率,而且减少了过程中副反应的发生,提高了异戊二烯的收率。实验结果表明,异丁烯和甲醛在酸碱双功能催化剂的作用下,产物的选择性(以醛计)最高可达90.7%,转化率(以醛计)最高可达85.3%。另外,本发明提供的酸碱双功能催化剂毒性小,寿命长,适于工业化生产。
具体实施方式
实施例1
将6.8g HZSM-5和110mL去离子水置于500mL的圆底烧瓶中,边搅拌边向其中加入100g二氧化硅,然后将圆底烧瓶连接到混浆装置中,在60℃下,使固体酸均匀混入二氧化硅中,负载1h后,将温度提升至120℃,蒸干水分后将干燥的负载有固体酸的载体置于马弗炉中,在300℃下进行第一焙烧3h,使HZSM-5负载到载体上,得到催化剂前驱体;
向催化剂前驱体中加入110mL含2.4g Nd(NO3)3和0.4g KCl的去离子水溶液,继续在90℃的混浆装置中反应2h,得到催化剂中间体;
将温度提升到130℃,蒸干水分,将催化剂中间体置于马弗炉中,在500℃下进行第二焙烧5h, 得到酸碱双功能催化剂。
实施例2
将6.8g HZSM-5和110mL去离子水置于500mL的圆底烧瓶中,边搅拌边向其中加入100g二氧化硅,然后将圆底烧瓶连接到混浆装置中,在20℃下负载4h后,将温度提升至120℃,蒸干水分后将干燥的负载有固体酸的载体置于马弗炉中,在350℃下进行第一焙烧1h,使HZSM-5负载到载体上,得到催化剂前驱体;
向催化剂前驱体中加入110mL含2.4g Nd(NO3)3和0.4g KCl的去离子水溶液,继续在90℃的混浆装置中反应2h,得到催化剂中间体;
将温度提升到130℃,蒸干水分,再向催化剂中间体中加入110mL稀氨水溶液(36%的浓氨水与水体积比为1:5的稀释溶液),在90℃的混浆装置中反应2h,将用氨水溶液处理的催化剂中间体过滤并水洗3次,将温度提升至130℃干燥,最后将干燥后的催化剂中间体置于马弗炉中,在550℃下进行第二焙烧6h, 得到酸碱双功能催化剂。
实施例3
本发明按照实施例2所述的技术方案制备得到双功能催化剂,区别在于,本实施例以4gCuCl2为金属化合物。
实施例4
本发明按照实施例2所述的技术方案制备得到双功能催化剂,区别在于,本实施例以10g Cr(NO3)3为金属化合物。
实施例5
本发明按照实施例2所述的技术方案制备得到双功能催化剂,区别在于,本实施例以18g AgNO3为金属化合物。
实施例6
本发明按照实施例3所述的技术方案制备得到双功能催化剂,区别在于,本实施例以FeCl3为金属化合物。
实施例7
本发明按照实施例2所述的技术方案制备得到双功能催化剂,区别在于,本实施例以Cu(NO3)2为金属化合物。
实施例8
本发明按照实施例2所述的技术方案制备得到双功能催化剂,区别在于,本实施例以Pd(NO3)2为金属化合物。
实施例9
本发明按照实施例2所述的技术方案制备得到双功能催化剂,区别在于,本实施例以NaVO3为金属化合物。
实施例10
本发明按照实施例2所述的技术方案制备得到双功能催化剂,区别在于,本实施例以2gCu(NO3)2和1.2g Nd(NO3)3为金属化合物。
实施例11
本发明按照实施例3所述的技术方案制备得到双功能催化剂,区别在于,本实施例以KCl和MgCl2(比例为1:1)为助剂原料。
实施例12
本发明按照实施例3所述的技术方案制备得到双功能催化剂,区别在于,本实施例以5gH4SiW12O40为固体酸。
实施例13
本发明按照实施例3所述的技术方案制备得到双功能催化剂,区别在于,本实施例以13g H3PW12O40为固体酸。
实施例14
本发明按照实施例3所述的技术方案制备得到双功能催化剂,区别在于,本实施例以H3PMo12O40为固体酸。
实施例15
本发明按照实施例3所述的技术方案制备得到双功能催化剂,区别在于,本实施例以AlPO4为固体酸。
实施例16
本发明按照实施例3所述的技术方案制备得到双功能催化剂,区别在于,本实施例以BPO4为固体酸。
实施例17
本发明按照实施例3所述的技术方案制备得到双功能催化剂,区别在于,本实施例以HY为固体酸。
实施例18
本发明按照实施例3所述的技术方案制备得到双功能催化剂,区别在于,本实施例以1gNb2O5为固体酸。
实施例19
本发明按照实施例3所述的技术方案制备得到双功能催化剂,区别在于,本实施例以H3PW12O40和HY(比例为1:1)为固体酸。
实施例20
本发明按照实施例11所述的技术方案制备得到双功能催化剂,区别在于,本实施例以石墨烯为载体,所述载体在400℃下Ar气氛中焙烧2h后使用。
实施例21
本发明按照实施例11所述的技术方案制备得到双功能催化剂,区别在于,本实施例以碳纳米管为载体,所述载体在400℃下Ar气氛中焙烧2h后使用。
实施例22
本发明按照实施例11所述的技术方案制备得到双功能催化剂,区别在于,本实施例以碳纳米管和石墨烯等重量混合为载体,所述载体在400℃下Ar气氛中焙烧2h后使用。
实施例23
本发明按照实施例2所述的技术方案制备得到双功能催化剂,区别在于,本实施例将催化剂制备工艺等比例放大10倍。
将上述催化剂7mL装于固定床反应器中,进行烯醛气相一步法反应,具体反应条件是:异丁烯和甲醛原料比为6.0(摩尔比);反应温度280℃;接触时间0.7秒,反应80分钟得到产物,具体催化性能数据见表1。
表1
。
Claims (10)
1.一种酸碱双功能催化剂,其特征在于该催化剂由金属氧化物、助剂、固体酸以及载体组成;所述固体酸与载体的质量比为0.5-15:100;所述金属氧化物与载体的质量比为1-20:100;所述助剂与金属氧化物的质量比为0.1-4:100;所述固体酸为HZSM-5分子筛、HY分子筛、USY分子筛、H4SiW12O40、H3PW12O40、H3PMo12O40、AlPO4、BPO4、γ-Al2O3和Nb2O5中的一种或多种;所述金属氧化物为Nd2O3、Cr2O3、CuO、Ag2O、Fe2O3、V2O5、Bi2O3和PdO中的一种或多种;所述助剂为Na、K、Mg、Ca、Ba、Mn、Sb、Ce和Zr元素中的一种或多种;所述载体为SiO2、石墨烯和碳纳米管中的一种或多种。
2.如权利要求1所述的一种酸碱双功能催化剂的制备方法,其特征在于该方法依次步骤为:
a)将固体酸和载体在溶剂中混合后在10-90℃负载1.5-3h,然后在80-120℃干燥至恒重后在300-400℃焙烧0.5-6h即得催化剂前驱体;
b)将金属化合物和助剂原料在溶剂中混合均匀;
c)将步骤a)得到的催化剂前驱体和步骤b)得到的溶液混合在80-100℃负载1-3h,得到催化剂中间体;
d)将步骤c)得到的催化剂中间体在100-140℃干燥至恒重后在450-650℃焙烧1.0-8h即得酸碱双功能催化剂。
3.如权利要求2所述的制备方法,其特征在于所述金属化合物为Nd、Cr、Cu、Ag、Fe、V、Bi、Pd的硝酸盐、硫酸盐或氯化盐中的一种或多种;所述助剂原料为Na、K、Mg、Ca、Ba、Mn、Sb、Ce、Zr的硝酸盐、硫酸盐或氯化盐中的一种或多种;所述溶剂为自来水、蒸馏水和去离子水中的一种。
4.如权利要求2所述的制备方法,其特征在于步骤a)中所述负载的温度为10-50℃;所述焙烧的时间为3-4h。
5.如权利要求2所述的制备方法,其特征在于所述负载的方法为等体积浸渍或过量浸渍。
6.如权利要求2所述的制备方法,其特征在于步骤b)中所述金属化合物和助剂原料的总质量与溶剂的质量比为1-3:100。
7.如权利要求2所述的制备方法,其特征在于步骤d)为将步骤c)得到的催化剂中间体在100-140℃干燥至恒重后在80-100℃用氨水处理1-3h,然后经过滤、水洗、在100-140℃干燥至恒重,最后在450-650℃焙烧1.0-8h即得酸碱双功能催化剂。
8.如权利要求7所述的制备方法,其特征在于所述氨水的质量浓度为2-8%。
9.如权利要求2所述的制备方法,其特征在于步骤d)所述焙烧的温度为500-600℃,时间为2-6h。
10.如权利要求1或2所述酸碱双功能催化剂在烯醛气相一步法合成异戊二烯中的应用:异丁烯和甲醛的摩尔比为5.5-8.0,反应温度250-350℃,接触时间0.4-0.9秒;再生气氛为空气,再生温度为400-600℃,反应时间与再生时间之比为1.0-2.5,反应周期为50-90分钟。
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