CN108554453B - Catalyst for preparing acrolein from glycerol and preparation method and application thereof - Google Patents
Catalyst for preparing acrolein from glycerol and preparation method and application thereof Download PDFInfo
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- CN108554453B CN108554453B CN201810082046.0A CN201810082046A CN108554453B CN 108554453 B CN108554453 B CN 108554453B CN 201810082046 A CN201810082046 A CN 201810082046A CN 108554453 B CN108554453 B CN 108554453B
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- Prior art keywords
- catalyst
- acrolein
- carrier
- glycerol
- temperature
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 347
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 278
- 239000003054 catalyst Substances 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 60
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 32
- 230000018044 dehydration Effects 0.000 claims abstract description 31
- 235000011187 glycerol Nutrition 0.000 claims description 116
- 239000011964 heteropoly acid Substances 0.000 claims description 49
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 42
- 239000000047 product Substances 0.000 claims description 40
- 239000000843 powder Substances 0.000 claims description 37
- 238000001354 calcination Methods 0.000 claims description 31
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 28
- 229910017604 nitric acid Inorganic materials 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 230000010355 oscillation Effects 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 17
- 238000011068 loading method Methods 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 9
- 238000007605 air drying Methods 0.000 claims description 8
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 claims description 7
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical group O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 7
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 1
- 239000010937 tungsten Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000004458 analytical method Methods 0.000 description 17
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 16
- 238000001514 detection method Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000006227 byproduct Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 239000003225 biodiesel Substances 0.000 description 7
- 238000004364 calculation method Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 229910009112 xH2O Inorganic materials 0.000 description 3
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910016523 CuKa Inorganic materials 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
- 206010035148 Plague Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 235000019730 animal feed additive Nutrition 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FFEARJCKVFRZRR-UHFFFAOYSA-N methionine Chemical compound CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 1
- 238000000120 microwave digestion Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- QONMOXAMRUZUCK-UHFFFAOYSA-N niobium;oxotungsten Chemical compound [Nb].[W]=O QONMOXAMRUZUCK-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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- PDDXOPNEMCREGN-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum;hydrate Chemical compound O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O PDDXOPNEMCREGN-UHFFFAOYSA-N 0.000 description 1
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- ACTPFSYIGLFGLY-UHFFFAOYSA-N silicic acid;trioxotungsten;hydrate Chemical compound O.O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 ACTPFSYIGLFGLY-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- 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
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- B01J35/615—
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- B01J35/635—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention relates to a catalyst for preparing acrolein by glycerol, a preparation method and application thereof. The preparation method comprises the steps of carrier preparation, modified metal oxide carrier preparation, catalyst preparation for preparing acrolein by glycerol dehydration and the like. The catalyst for preparing acrolein by glycerol dehydration is simple to prepare, low in cost, high in catalytic activity, good in stability, and high in acrolein selectivity of 90-95%, and the conversion rate of glycerol reaches 100%.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of novel catalysts. More particularly, the present invention relates to a catalyst for preparing acrolein from glycerol, and also relates to a method for preparing the catalyst for preparing acrolein from glycerol, and also relates to a use of the catalyst for preparing acrolein from glycerol.
[ background of the invention ]
Since the energy crisis has become an important problem that plagues the world due to the increasing scarcity of traditional fossil resources, technologists are actively working on developing renewable energy. Among them, biodiesel has been widely used because of its advantages such as environmental protection and renewability. As biodiesel production increases, its main byproduct, glycerol, has also emerged as an over-demand situation. Therefore, finding new utilization routes for the cheap and abundant residual glycerol has become a research focus internationally. The glycerol is used as a raw material, a plurality of chemical products with high added values can be prepared, wherein the preparation of the acrolein is a glycerol value-added route with good prospect.
Acrolein is an important organic chemical product and an important intermediate for preparing fine chemical products, and has wide application in the industries of feed industry, papermaking, water treatment, oil exploitation, medical treatment and the like. Specific applications of acrolein include use as D, L-methionine required for the production of animal feed additives, effective disinfectants as industrial circulating cooling water, effective bactericides for oilfield injection water in the petroleum industry, and the like. Acrolein is the simplest unsaturated aldehyde, and because it has two reactive functional groups, it can be converted into a variety of high value added downstream products.
Acrolein is produced industrially mainly by gas phase oxidation of propylene. In the presence of bismuth molybdate and bismuth phosphomolybdate catalysts, introducing a mixed gas of propylene and air (the molar ratio of propylene to oxygen is 6-8) into a fixed bed or a fluidized bed reactor, and reacting at the reaction temperature of 300-400 ℃ and the pressure of 0.2-0.3 MPa to generate a small amount of acetaldehyde, acetic acid, propionaldehyde, acetone and acrylic acid besides acrolein. The industrial production of acrolein is mainly a propylene oxidation process, whereas propylene is mainly derived from petroleum catalytic cracking. The method takes petroleum as a starting material, does not meet the requirements of low-carbon economy, and has the problem of competing for raw materials with other chemical products. Compared with the acrolein prepared by propylene oxidation, the glycerol is used as a byproduct of biodiesel, has low value, is mainly from the saponification process of animal and vegetable oil and the process of producing biodiesel by ester exchange, and belongs to renewable resources. The acrolein is prepared by sufficiently utilizing the crude glycerol of the biodiesel byproduct, so that the comprehensive utilization rate of resources can be improved, the biodiesel industrial chain can be extended, the overall competitiveness of the biodiesel green industry is improved, and the wide application prospect is realized.
CN 201410496401 discloses a zirconium phosphate catalyst prepared by a coprecipitation method, which is used for preparing acrolein by glycerol dehydration, wherein glycerol can be basically and completely converted, but the selectivity is not high, the yield is only 43.3-81.2%, the yield is obviously reduced after 24 hours, and industrialization is difficult to realize. CN 201180043502 adopts a hydrothermal method to synthesize the niobium or niobium tungsten oxide catalyst, and is used for preparing acrolein by glycerol dehydration, the yield of the acrolein is 16.2-70.4%, and the overall yield is low. CN 201210215811 adopts an immersion method to prepare an immobilized heteropolyacid catalyst, in the application of preparing acrolein by glycerol dehydration, the selectivity of the acrolein can reach 90.2-97.8%, but the conversion rate of the glycerol is only 17.6-25.3%, and the catalyst can run for 100 hours, but the conversion rate of the glycerol is low, and the industrial implementation is difficult. CN 201310735105 discloses that multi-stage pore ZSM-5 is prepared by using a small amount of MFI zeolite seed crystal and part of inorganic salt additive in a general synthesis system (silicon source, aluminum source, alkali source and water) and is applied to the reaction of glycerol dehydration to prepare acrolein, but the preparation method is complicated and the MFI zeolite seed crystal is difficult to store for a long time.
Although many documents report catalysts for preparing acrolein by selective dehydration of glycerol, no industrial reports exist at present, and the main technical problems are to overcome the problems of easy deactivation of the catalysts, low glycerol conversion rate and poor acrolein selectivity.
Aiming at the defects in the prior art, the inventor finally completes the invention through a large amount of experimental research and exploration.
[ summary of the invention ]
[ problem to be solved ]
The invention aims to provide a catalyst for preparing acrolein by using glycerol.
It is another object of the present invention to provide a method for preparing the catalyst for preparing acrolein from glycerol.
It is another object of the present invention to provide use of the glycerol to prepare an acrolein catalyst.
[ solution ]
The invention is realized by the following technical scheme.
The invention relates to a preparation method of a catalyst for preparing acrolein from glycerol.
The preparation method comprises the following steps:
A. preparation of the support
Adding alumina powder into kneading machine, adding dilute nitric acid solution dropwise into alumina powder to make alumina powder and nitric acid undergo the process of gelatinizing reaction, then making the gelatinizing reaction material pass through the extruder and continuously extruding to obtain Raschig ring blank, naturallyAir-drying, cutting, and calcining and molding in a high-temperature furnace at 380-420 ℃ to obtain a carrier; the pore volume of the carrier is 0.5-0.9 cm3A specific surface area of 100 to 240 m/g2/g；
B. Preparation of modified Metal oxide Supports
Preparing a magnesium, zinc or iron metal nitrate solution with a concentration of 8-12% by weight; adding the carrier prepared in the step A into the metal nitrate solution according to the loading amount of magnesium oxide, zinc oxide or iron oxide being 1-10% of the weight of the carrier, ultrasonically oscillating, dipping, separating, and calcining the carrier loaded with the metal nitrate in a muffle furnace at the temperature of 300-800 ℃ for 4-6 h to obtain the modified metal oxide carrier;
C. preparation of catalyst for preparing acrolein by glycerol dehydration
And B, pouring a tungsten-molybdenum heteropoly acid solution into the modified metal oxide carrier obtained in the step B according to the weight ratio of 1: 1.5-9.0 of the heteropoly acid to the modified metal oxide carrier, carrying the heteropoly acid on the modified metal oxide carrier by ultrasonic oscillation for 1-3 h, drying for 6-8 h at the temperature of 100-120 ℃, and calcining the dried loaded heteropoly acid modified metal oxide carrier for 12-14 h at the temperature of 300-800 ℃ to obtain the catalyst for preparing acrolein by glycerol dehydration.
According to a preferred embodiment of the present invention, in the step a, the concentration of the dilute aqueous nitric acid solution is 4 to 6% by weight.
According to another preferred embodiment of the invention, in the step A, the length of the raschig ring is 6-7 mm.
According to another preferred embodiment of the invention, in the step A, the raschig ring is calcined in a high-temperature furnace for 120-240 min.
According to another preferred embodiment of the invention, in the step B, the carrier prepared in the step A is ultrasonically vibrated in the metal nitrate solution for 2-4 h.
According to another preferred embodiment of the invention, in the step B, the carrier prepared in the step A is continuously immersed in the metal nitrate solution for 10-14 h after ultrasonic oscillation.
According to another preferred embodiment of the present invention, in step C, the tungstomolybdate is phosphotungstic acid, phosphomolybdic acid or silicotungstic acid.
According to another preferred embodiment of the present invention, in the step C, the concentration of the tungsten-molybdenum heteropoly acid solution is 10 to 40% by weight.
The invention also relates to an acrolein catalyst prepared from the glycerol prepared by the preparation method.
The present invention also relates to a method for preparing acrolein by dehydration of glycerol using the catalyst for preparing acrolein with glycerol.
The method comprises the following steps:
A. in the continuous flow fixed bed reactor, a catalyst bed layer is arranged in the middle of the continuous flow fixed bed reactor, and spherical alumina layers are arranged at two ends of the catalyst bed layer;
B. blowing and preheating a catalyst bed layer for 1.2-1.8 h by nitrogen flow under the conditions of the temperature of 260-350 ℃ and the linear velocity of 0.5-1.5 cm/s;
C. sending a glycerol aqueous solution with the concentration of 10-40% by weight to a preheating furnace by using a high-pressure pump, and gasifying for 60-180 min at the temperature of 250-300 ℃;
D. and (C) allowing the gasified glycerol in the step (C) to pass through the preheated catalyst bed in the step (B) at the mass flow rate of 0.4-0.8 kg/kg.h, reacting at the temperature of 260-350 ℃, and allowing a reaction product to flow out of the continuous flow fixed bed reactor and condensing to obtain an acrolein product.
The present invention will be described in more detail below.
The invention relates to a preparation method of a catalyst for preparing acrolein from glycerol.
The preparation method comprises the following steps:
A. preparation of the support
Adding alumina powder into a kneading machine, dropwise adding a dilute nitric acid aqueous solution into the alumina powder to enable the alumina powder and nitric acid to carry out gelling reaction, continuously extruding gelling reaction materials into Raschig annular blanks through an extruder, naturally air-drying, cutting, and calcining and molding in a high-temperature furnace at the temperature of 380-420 ℃ to obtain a carrier; the above-mentionedThe pore volume of the carrier is 0.5-0.9 cm3A specific surface area of 100 to 240 m/g2/g；
The alumina powder used in the present invention is one having a particle size of 300 to 400 mesh, and is currently commercially available, for example, from Shandong England chemical Co., Ltd under the trade name of pseudo-boehmite.
The concentration of the dilute nitric acid aqueous solution used in the invention is 4-6% by weight. The amount of alumina powder used in the present invention is determined by whether the gelling reaction material can be extruded through an extruder. Generally, the weight ratio of the dilute nitric acid aqueous solution to the alumina powder is 1.0-1.2: 1.8 to 2.2.
In the present invention, a gelling reaction is understood to be a reaction in which alumina is reacted with nitric acid to form a gel. After the gelling reaction, the obtained gelling reaction material can be extruded by an extruder to obtain the Raschig ring-shaped blank after the gelling material meets the viscosity requirement according to the detection of an ultrasonic solid viscometer. The extruder used in the present invention is a product currently on the market, for example, a product sold by Shanghai Zhenlong Hydraulic Equipment complete plant under the trade name JC-50, and the gelling reaction mass is extruded under the conditions described in the product specification.
In the step, the Raschig annular blank is calcined in a high-temperature furnace at 380-420 ℃ for 120-240 min. When the calcination time is 120-240 min, if the calcination temperature is lower than 380 ℃, the blank cannot be formed; if the calcination temperature is higher than 420 ℃, the crystal phase is easily transformed; therefore, the calcination temperature is preferably 380 to 420 ℃. When the calcination temperature is 380-420 ℃, if the calcination time is shorter than 120min, the mechanical strength of the carrier is insufficient; if the calcination time is longer than 240min, the moisture is too little to facilitate the nitrate loading; therefore, the calcination time is preferably 120 to 240 min;
the pore volume of the carrier is 0.5-0.9 cm3A specific surface area of 100 to 240 m/g2(ii) in terms of/g. In the present invention, if the pore volume of the carrier is less than 0.5cm3The heteropoly acid is difficult to enter the pore canal of the carrier; if the pore volume of the carrier is more than 0.9cm3In terms of/g, the heteropoly acid is forced into the poresDeep in the road, the surface of the carrier is rarely loaded by heteropoly acid; therefore, the pore volume of the carrier is 0.5-0.9 cm3The ratio of the specific units in terms of/g is suitable. Likewise, if the specific surface area of the carrier is less than 100m2The supported heteropoly acid is too little and the catalytic activity is low; if the specific surface area of the support is higher than 240m2The acid is strong, and side reaction is easy to cause; therefore, the specific surface area of the carrier is 100-240 m2The/g is feasible; in the invention, the length of the raschig ring is 6-7 mm.
In the present invention, the pore volume and the specific surface area are measured by using a BET specific surface area meter.
B. Preparation of modified Metal oxide Supports
Preparing a magnesium, zinc or iron metal nitrate solution with a concentration of 8-12% by weight; adding the carrier prepared in the step A into the metal nitrate solution according to the loading amount of magnesium oxide, zinc oxide or iron oxide being 1-10% of the weight of the carrier, ultrasonically oscillating, dipping, separating, and calcining the carrier loaded with the metal nitrate in a muffle furnace at the temperature of 300-800 ℃ for 4-6 h to obtain the modified metal oxide carrier;
in the invention, the load capacity of magnesium oxide, zinc oxide or ferric oxide is 1-10% of the weight of the carrier, and if the load capacity is less than 1%, the reaction activity is not obviously increased; if the loading amount is more than 10%, the acidity of the heteropoly acid is reduced, and the reaction activity of the catalyst is reduced; therefore, the loading amount is preferably 1 to 10%, more preferably 2 to 8%, and still more preferably 3 to 6%.
In the present invention, the ultrasonic oscillation is intended to sufficiently load the metal nitrate onto the carrier, and the equipment used for the ultrasonic oscillation is a product currently marketed, for example, by Ningbo Hai Kesheng ultrasonic equipment Co., Ltd., under the trade name of ultrasonic cleaning machine KS-300 EI. And (3) carrying out ultrasonic oscillation on the carrier in a metal nitrate solution for 2-4 h under the condition described in the specification of the ultrasonic oscillation equipment.
After ultrasonic oscillation, the carrier is continuously immersed in the metal nitrate solution for 10-14 h, and the purpose is to enable the metal nitrate load to reach adsorption balance.
And calcining the carrier loaded with the metal nitrate in a muffle furnace at the temperature of 300-800 ℃ for 4-6 h. It is not permissible for the supported metal nitrate carrier to exceed either the temperature range or the time range upon calcination, because the above conditions cause the collapse of the pores of the carrier.
The impregnation equipment and the separation equipment used in this step are those commonly used in the art. These ultrasonic oscillation device, dipping device, and separation device will be used in the following steps, and will not be described in detail.
C. Preparation of catalyst for preparing acrolein by glycerol dehydration
And B, pouring a tungsten-molybdenum heteropoly acid solution into the modified metal oxide carrier obtained in the step B according to the weight ratio of 1: 1.5-9.0 of the heteropoly acid to the modified metal oxide carrier, carrying the heteropoly acid on the modified metal oxide carrier by ultrasonic oscillation for 1-3 h, drying for 6-8 h at the temperature of 100-120 ℃, and calcining the dried loaded heteropoly acid modified metal oxide carrier for 12-14 h at the temperature of 300-800 ℃ to obtain the catalyst for preparing acrolein by glycerol dehydration.
According to the invention, the tungstomolybdenum heteropoly acid is phosphotungstic acid (H)3O40PW12.xH2O), phosphomolybdic acid (H)3Mo12O40P.xH2O) or silicotungstic acid (H)4[Si(W3O10)4]·xH2O), they are all products currently marketed, for example phosphotungstic acid sold under the trade name phosphotungstic acid hydrate by alatin reagent limited, phosphomolybdic acid sold under the trade name phosphomolybdic acid hydrate by the national drug group, silicotungstic acid sold under the trade name silicotungstic acid hydrate by alatin reagent limited.
In the present invention, if the weight ratio of the heteropolyacid to the modified metal oxide support is more than 1: 1.5, the catalyst is too strong in acidity and is liable to cause side reactions; if the weight ratio of the heteropolyacid to the modified metal oxide carrier is less than 1: 9.0, the acidity of the catalyst is too weak, and the conversion rate of glycerol is low; accordingly, a weight ratio of heteropolyacid to modified metal oxide support of 1: 1.5 to 9.0 is suitable, preferably 1: 2.5 to 8.0; more preferably 1: 3.5-6.8.
In the step, the concentration of the tungsten-molybdenum heteropoly acid solution is 10-40% by weight. Concentrations of the tungsten molybdenum heteropolyacid solution outside of the concentration range are not preferable because too low or too high a concentration may result in uneven loading of the solid acid on the support.
The invention also relates to an acrolein catalyst prepared from the glycerol prepared by the preparation method.
The catalytic performance of the catalyst for preparing acrolein by using glycerol is determined by adopting a gas chromatography, the glycerol conversion rate of the catalyst is 100%, the acrolein selectivity is 90-95%, and the implementation results of examples 1-6 are specifically shown, so that the catalyst for preparing the acrolein by using the glycerol is a high-efficiency catalyst, and the performance of the catalyst is obviously superior to that of the catalyst used in the prior art.
The chemical composition of the catalyst for preparing acrolein by using glycerol is detected by adopting an ICP method, wherein the ICP detection conditions are as follows:
the measuring instrument is as follows: the inductively coupled plasma emission spectrometer Optima 2100; wavelength range: 160 nm-900 nm; precision: the relative standard deviation RSD is less than or equal to 0.5 percent; resolution 0.003nm (at 200 nm); detection limit: the detection limit of most elements can reach 0.1-1 ppb;
the chemical composition of the detection catalyst is several of P, Si, Mo, W, Fe, Mg and Al elements.
The sample processing method comprises the following steps: microwave digestion;
the phase composition of the catalyst for preparing acrolein by using glycerol is detected by an XRD method, and the detection conditions of the XRD method are as follows:
the measuring instrument is as follows: x-ray powder diffractometer model D8Advance Davinci from Bruker, germany;
measurement conditions were as follows: CuKa ray (lambda is 0.154nm), graphite monochromator, tube voltage of 40kv, tube current of 50mA, scanning speed of 8 deg/min, and scanning range of 10-90 deg;
the phase composition of the detection catalyst is a solid-phase supported mixture of tungsten-molybdenum heteropoly acid and magnesium oxide, aluminum oxide or iron oxide.
The present invention also relates to a method for preparing acrolein by dehydration of glycerol using the catalyst for preparing acrolein with glycerol. The method comprises the following steps:
A. in the continuous flow fixed bed reactor, a catalyst bed layer is arranged in the middle of the continuous flow fixed bed reactor, and spherical alumina layers are arranged at two ends of the catalyst bed layer;
the continuous flow fixed bed reactor used in the present invention is a reactor having a trickle bed structure, which is a product currently marketed, for example, by Beijing Polgming Limited under the trade name of 200mL fixed bed reactor.
B. Blowing and preheating a catalyst bed layer for 1.2-1.8 h by nitrogen flow under the conditions of the temperature of 260-350 ℃ and the linear velocity of 0.5-1.5 cm/s;
in this step, the main function of the nitrogen stream purge is inert gas shielding.
C. Sending a glycerol aqueous solution with the concentration of 10-40% by weight to a preheating furnace by using a high-pressure pump, and gasifying for 60-180 min at the temperature of 250-300 ℃;
the preheating furnace used in the present invention is a heat-insulating apparatus having a heat-insulating structure of asbestos, which is a product currently sold in the market, for example, a product sold under the trade name of a preheating furnace by Beijing Poloming Co.
D. And (C) allowing the gasified glycerol in the step (C) to pass through the preheated catalyst bed in the step (B) at the mass flow rate of 0.4-0.8 kg/kg.h, reacting at the temperature of 260-350 ℃, and allowing a reaction product to flow out of the continuous flow fixed bed reactor and condensing to obtain an acrolein product.
In this step, the reaction product is cooled by circulating cooling water.
In the method for preparing acrolein by dehydrating glycerin to prepare acrolein by using the glycerin-prepared acrolein catalyst, the calculation methods of glycerin conversion rate and acrolein selectivity are as follows:
glycerol conversion rate is converted glycerol amount/glycerol amount in raw material x 100%;
acrolein selectivity ═ amount of actually produced acrolein/amount of theoretically produced acrolein × 100%;
in the catalyst for preparing acrolein by glycerol dehydration, after the catalyst carrier is modified, the passivation speed of the catalyst is reduced, the service life of the catalyst is prolonged, and the activity of the catalyst is improved.
[ advantageous effects ]
The invention has the beneficial effects that: the catalyst for preparing acrolein by glycerol dehydration is simple to prepare, low in cost, high in catalytic activity, good in stability, and high in acrolein selectivity of 90-95%, and the conversion rate of glycerol reaches 100%.
[ description of the drawings ]
FIG. 1 is a schematic diagram of the process for the dehydration of glycerol to acrolein according to the present invention;
in the figure:
1-N2a steel cylinder; 2-a raw material tank; 3-a flow meter; 4-high pressure infusion pump; 5-preheating a furnace; 6-fixed bed reactor; 7-a condenser; 8-a gas-liquid separation tank; 9-collecting tank.
[ detailed description ] embodiments
The invention will be better understood from the following examples.
Example 1: preparation and application of catalyst for preparing acrolein from glycerol
The preparation steps of the catalyst for preparing acrolein by glycerol are as follows:
A. preparation of the support
Adding alumina powder into a kneader, and mixing according to the weight ratio of the dilute nitric acid aqueous solution to the alumina powder of 1.0: 1.8, dropwise adding a dilute nitric acid aqueous solution with the concentration of 4 percent by weight into the alumina powder to enable the alumina powder and nitric acid to carry out gelling reaction, then continuously extruding gelling reaction materials into Raschig annular blanks through an extruder, naturally air-drying, cutting the blanks to be 6mm in length, and then placing the blanks in a high-temperature furnace to calcine for 220min at the temperature of 400 ℃ for forming to obtain a carrier; the pore volume of the carrier was 0.6cm3Per g, specific surface area is 100m2/g；
B. Preparation of modified Metal oxide Supports
Respectively preparing magnesium nitrate, zinc nitrate and ferric nitrate solutions with the concentrations of 8 percent by weight; adding the carrier prepared in the step A into the metal nitrate solution according to the loading amounts of magnesium oxide, zinc oxide and ferric oxide which are respectively 5% of the weight of the carrier, ultrasonically oscillating for 2h, dipping for 10h, separating, and calcining the carrier loaded with the metal nitrate in a muffle furnace at the temperature of 600 ℃ for 5h to obtain three modified metal oxide carriers;
C. preparation of catalyst for preparing acrolein by glycerol dehydration
And (3) according to the weight ratio of the silicotungstic acid to the modified metal oxide carrier of 1: 3.2, pouring a silicotungstic acid heteropoly acid solution with the concentration of 10 percent by weight into the modified metal oxide carrier obtained in the step (B), carrying heteropoly acid on the modified metal oxide carrier by ultrasonic oscillation for 1.6h, drying for 6h at the temperature of 100 ℃, and calcining the dried loaded heteropoly acid modified metal oxide carrier at the temperature of 800 ℃ for 12h to obtain the catalyst for preparing acrolein by glycerol dehydration.
D. The application of the catalyst for preparing acrolein by glycerol comprises the following steps:
the specific process flow of the catalyst for preparing acrolein by glycerol is shown in figure 1. In the figure 1 is N2A steel cylinder; 2 is a raw material tank; 3 is a flow meter; 4 is a high pressure infusion pump; 5, a preheating furnace; 6 is a fixed bed reactor; 7 is a condenser; 8 is a gas-liquid separation tank; and 9 is a collecting tank.
Arranging a catalyst bed layer in the middle of the continuous flow fixed bed reactor 6, and arranging spherical alumina layers at two ends of the catalyst bed layer; let N be2Nitrogen flow of the steel cylinder 1 is blown by a flowmeter 3 to preheat a catalyst bed layer for 1.2 hours under the conditions of temperature of 280 ℃ and linear velocity of 1.0 cm/s; then, an aqueous solution of glycerin having a concentration of 35% by weight was fed from the stock tank 2 to the preheating furnace 5 using the high-pressure liquid feeding pump 4 to be gasified at a temperature of 250 ℃ for 80 minutes, and then the gasified glycerin was allowed to react at a temperature of 260 ℃ through the preheated catalyst bed at a mass flow rate of 0.4 kg/kg-h, and the reaction product flowed out of the continuous flow fixed bed reactor 6 through the condenser 7, the gas-liquid separator 8 and the collection tank 9 to obtain an acrolein product. The acrolein product was analyzed by conventional gas chromatography with a moisture meter sold under the trade name SF-3 by Tantai instruments, Inc., of Tanzhou, and the results of the measurements are shown in Table 1.
Table 1: analysis of the substance content of acrolein product produced in this example
The acrolein product of example 1 was composed of acrolein, water and other organic by-products, as determined by the analytical method described in this specification, and was a homogeneous mixed solution. The results in Table 1 clearly show that the conversion of glycerol reaches 100% and that the selectivity to acrolein is found to be 90.5%, 93.5% and 90.1%, respectively, by calculation.
Example 2: preparation and application of catalyst for preparing acrolein from glycerol
The preparation steps of the catalyst for preparing acrolein by glycerol are as follows:
1. preparation of the support
Adding alumina powder into a kneader, and mixing according to the weight ratio of the dilute nitric acid aqueous solution to the alumina powder of 1.1: 2.2, dropwise adding a dilute nitric acid aqueous solution with the concentration of 5 percent by weight into the alumina powder to enable the alumina powder and nitric acid to carry out gelling reaction, then continuously extruding gelling reaction materials into Raschig annular blanks through an extruder, naturally air-drying, cutting the blanks to a length of 7mm, and then placing the blanks into a high-temperature furnace to calcine and form for 120min at the temperature of 380 ℃ to obtain a carrier; the pore volume of the carrier was 0.5cm3Per g, the specific surface area is 240m2/g；
B. Preparation of modified Metal oxide Supports
Preparing a magnesium nitrate solution having a concentration of 10% by weight; adding the carrier prepared in the step A into a magnesium nitrate solution according to the loading capacity of magnesium oxide being 1%, 5% and 10% of the weight of the carrier, carrying out ultrasonic oscillation for 3 hours, dipping for 11 hours, separating, and calcining the carrier loaded with metal nitrate in a muffle furnace at the temperature of 400 ℃ for 4 hours to obtain the modified metal oxide carrier;
C. preparation of catalyst for preparing acrolein by glycerol dehydration
And (3) according to the weight ratio of the silicotungstic acid to the modified metal oxide carrier of 1: 1.5, pouring a 18% silicotungstic heteropoly acid solution by weight into the modified metal oxide carrier obtained in the step (B), carrying the heteropoly acid on the modified metal oxide carrier by ultrasonic oscillation for 1.0h, drying for 7h at the temperature of 110 ℃, and calcining the dried loaded heteropoly acid modified metal oxide carrier for 14h at the temperature of 700 ℃ to obtain the catalyst for preparing the acrolein by glycerol dehydration.
D. The application of the catalyst for preparing acrolein by glycerol comprises the following steps:
the specific process flow of the catalyst for preparing acrolein by glycerol is shown in figure 1.
Arranging a catalyst bed layer in the middle of the continuous flow fixed bed reactor, and arranging spherical alumina layers at two ends of the catalyst bed layer; let N be2Nitrogen flow of the steel cylinder 1 is blown by a flowmeter 3 to preheat a catalyst bed layer for 1.8 hours under the conditions of 260 ℃ and 1.2cm/s of linear speed; then, an aqueous glycerin solution having a concentration of 20% by weight is fed from the stock tank 2 to the preheating furnace 5 using the high-pressure pump 4 to be gasified at a temperature of 280 ℃ for 100 min; then, the gasified glycerin was reacted at a temperature of 280 ℃ through the preheated catalyst bed at a mass flow rate of 0.8 kg/kg.h by passing through the preheated catalyst bed, and the reaction product flowed out of the continuous flow fixed bed reactor 6 through the condenser 7, the gas-liquid separator 8 and the collection tank 9 to obtain an acrolein product. The acrolein product was detected by the same analytical method as in example 1, and the detection results are shown in Table 2.
Table 2: analysis of the substance content of acrolein product produced in this example
The acrolein product of example 2 was composed of acrolein, water and other organic by-products, as determined by the analytical method described in this specification, and was a homogeneous mixed solution. The results in Table 2 clearly show that the conversion of glycerol reaches 100% and the selectivity of acrolein is found to be 90.1%, 91.3%, 90.5% by calculation, respectively.
Example 3: preparation and application of catalyst for preparing acrolein from glycerol
The preparation steps of the catalyst for preparing acrolein by glycerol are as follows:
1. preparation of the support
Adding alumina powder into a kneader, and mixing according to the weight ratio of the dilute nitric acid aqueous solution to the alumina powder of 1.2: 2.0, dropwise adding a dilute nitric acid aqueous solution with the concentration of 6 percent by weight into the alumina powder to enable the alumina powder and nitric acid to carry out gelling reaction, then continuously extruding gelling reaction materials into Raschig annular blanks through an extruder, naturally air-drying, cutting the blanks to be 6mm in length, and then placing the blanks into a high-temperature furnace to calcine and form for 240min at the temperature of 390 ℃ to obtain a carrier; the pore volume of the carrier was 0.8cm3A specific surface area of 200 m/g2/g；
B. Preparation of modified Metal oxide Supports
Preparing a magnesium nitrate solution having a concentration of 9% by weight; adding the carrier prepared in the step A into a magnesium nitrate solution according to the magnesium oxide loading amount of 1% of the weight of the carrier, ultrasonically oscillating for 4h, soaking for 14h, separating, and calcining the carrier loaded with metal nitrate in a muffle furnace at the temperature of 300 ℃ for 6h to obtain the modified metal oxide carrier;
C. preparation of catalyst for preparing acrolein by glycerol dehydration
And B, according to the weight ratio of 1: 9.0 of the heteropoly acid to the modified metal oxide carrier, respectively pouring 26% by weight of heteropoly acid solutions of phosphotungstic acid, phosphomolybdic acid and silicotungstic acid into the modified metal oxide carrier obtained in the step B, carrying the heteropoly acid on the modified metal oxide carrier by ultrasonic oscillation for 2.0h, drying the heteropoly acid on the modified metal oxide carrier at the temperature of 120 ℃ for 8h, and calcining the dried loaded heteropoly acid modified metal oxide carrier at the temperature of 600 ℃ for 13h to obtain the catalyst for preparing the acrolein by glycerol dehydration.
D. The application of the catalyst for preparing acrolein by glycerol comprises the following steps:
the specific process flow of the catalyst for preparing acrolein by glycerol is shown in figure 1.
Arranging a catalyst bed layer in the middle of the continuous flow fixed bed reactor, and arranging spherical alumina layers at two ends of the catalyst bed layer; by N2The steel cylinder 1 and the flow meter 3 allow nitrogen flow to purge and preheat at the temperature of 300 ℃ and the linear velocity of 0.5cm/sThe catalyst bed layer is 1.4 h; then, an aqueous solution of glycerin having a concentration of 10% by weight was fed from the stock tank 2 to the preheating furnace 5 using the high-pressure pump 4 to be gasified at a temperature of 300 ℃ for 60 minutes, and then the gasified glycerin was allowed to react at a temperature of 300 ℃ through the preheating catalyst bed by passing it through the preheating catalyst bed at a mass flow rate of 0.6 kg/kg-h, and the reaction product flowed out of the continuous flow fixed bed reactor 6 through the condenser 7, the gas-liquid separator 8 and the collection tank 9 to obtain an acrolein product. The acrolein product was detected by the same analytical method as in example 1, and the detection results are shown in Table 3.
Table 3: analysis of the substance content of acrolein product produced in this example
The acrolein product of example 3 was composed of acrolein, water and other organic by-products, as determined by the analytical method described in this specification, and was a homogeneous mixed solution. The results in Table 3 clearly show that the conversion of glycerol reaches 100% and that the selectivity to acrolein is found to be 90.6%, 91.7%, 92.5%, respectively, by calculation.
Example 4: preparation and application of catalyst for preparing acrolein from glycerol
The preparation steps of the catalyst for preparing acrolein by glycerol are as follows:
1. preparation of the support
Adding alumina powder into a kneader, and mixing according to the weight ratio of the dilute nitric acid aqueous solution to the alumina powder of 1.0: 2.1, dropwise adding a dilute nitric acid aqueous solution with the concentration of 6 percent by weight into the alumina powder to enable the alumina powder and nitric acid to carry out gelling reaction, then continuously extruding gelling reaction materials into Raschig annular blanks through an extruder, naturally air-drying the blanks, cutting the blanks to be 7mm in length, and then placing the blanks into a high-temperature furnace to be calcined and molded for 140min at the temperature of 420 ℃ to obtain a carrier; the pore volume of the carrier was 0.9cm3Per g, specific surface area 140m2/g；
B. Preparation of modified Metal oxide Supports
Preparing a 12% by weight magnesium nitrate solution; adding the carrier prepared in the step A into a magnesium nitrate solution according to the magnesium oxide loading amount of 10% of the weight of the carrier, carrying out ultrasonic oscillation for 2 hours, dipping for 12 hours, separating, and calcining the carrier loaded with metal magnesium nitrate in a muffle furnace at the temperature of 500 ℃ for 5 hours to obtain the modified metal oxide carrier;
C. preparation of catalyst for preparing acrolein by glycerol dehydration
According to the weight ratio of silicotungstic acid to the modified metal oxide carrier of 1: 2 and 1: 2.3, 1: and 3, pouring a silicotungstic acid heteropoly acid solution with the concentration of 34 percent by weight into the modified metal oxide carrier obtained in the step B, carrying out ultrasonic oscillation for 3.0h to load heteropoly acid on the modified metal oxide carrier, then drying the heteropoly acid on the modified metal oxide carrier at the temperature of 105 ℃ for 6h, and calcining the dried loaded heteropoly acid modified metal oxide carrier at the temperature of 400 ℃ for 12h to obtain the catalyst for preparing acrolein by glycerol dehydration.
D. The application of the catalyst for preparing acrolein by glycerol comprises the following steps:
the specific process flow of the catalyst for preparing acrolein by glycerol is shown in figure 1.
Arranging a catalyst bed layer in the middle of the continuous flow fixed bed reactor, and arranging spherical alumina layers at two ends of the catalyst bed layer; by N2The steel cylinder 1 and the flow meter 3 allow nitrogen flow to blow and preheat the catalyst bed for 1.6h under the conditions of 320 ℃ and 0.8cm/s of linear speed; then, an aqueous solution of glycerin having a concentration of 25% by weight was fed from the stock tank 2 to the preheating furnace 5 using the high-pressure pump 4 to be gasified at a temperature of 250 ℃ for 180min, and then the gasified glycerin was allowed to react at a temperature of 320 ℃ through the preheating catalyst bed at a mass flow rate of 0.4 kg/kg-h, and the reaction product flowed out of the continuous flow fixed bed reactor 6 through the condenser 7, the gas-liquid separator 8 and the collection tank 9 to obtain an acrolein product. The acrolein product was detected by the same analytical method as in example 1, and the detection results are shown in Table 4.
Table 4: analysis of the substance content of acrolein product produced in this example
The acrolein product of example 4 was composed of acrolein, water and other organic by-products, as determined by the analytical method described in this specification, and was a homogeneous mixed solution. The results in Table 4 clearly show that the conversion of glycerol reaches 100%, and the selectivity of acrolein reaches 92.8%, 94.8% and 91.9% by calculation.
Example 5: preparation and application of catalyst for preparing acrolein from glycerol
The preparation steps of the catalyst for preparing acrolein by glycerol are as follows:
1. preparation of the support
Adding alumina powder into a kneader, and mixing according to the weight ratio of the dilute nitric acid aqueous solution to the alumina powder of 1.1: 1.9, dropwise adding a dilute nitric acid aqueous solution with the concentration of 4 percent by weight into the alumina powder to enable the alumina powder and nitric acid to carry out gelling reaction, then continuously extruding gelling reaction materials into Raschig annular blanks through an extruder, naturally air-drying, cutting the blanks to be 6mm in length, and then placing the blanks into a high-temperature furnace to calcine and form for 180min at the temperature of 410 ℃ to obtain a carrier; the pore volume of the carrier was 0.6cm3A specific surface area of 180 m/g2/g；
B. Preparation of modified Metal oxide Supports
Preparing a zinc nitrate solution having a concentration of 11% by weight; adding the carrier prepared in the step A into a zinc nitrate solution according to the zinc oxide loading capacity of 4% of the weight of the carrier, carrying out ultrasonic oscillation for 3h, dipping for 13h, separating, and calcining the carrier loaded with metal nitrate in a muffle furnace at the temperature of 800 ℃ for 4h to obtain the modified metal oxide carrier;
C. preparation of catalyst for preparing acrolein by glycerol dehydration
And (3) according to the weight ratio of the phosphotungstic acid to the modified metal oxide carrier of 1: 6.4, pouring a phosphotungstic acid heteropoly acid solution with the concentration of 40% by weight into the modified metal oxide carrier obtained in the step (B), carrying out ultrasonic oscillation for 2.2 hours to load the heteropoly acid on the modified metal oxide carrier, drying for 7 hours at the temperature of 115 ℃, and calcining the dried loaded heteropoly acid modified metal oxide carrier for 14 hours at the temperature of 300 ℃ to obtain the catalyst for preparing the acrolein by glycerol dehydration.
D. The application of the catalyst for preparing acrolein by glycerol comprises the following steps:
the specific process flow of the catalyst for preparing acrolein by glycerol is shown in figure 1.
Arranging a catalyst bed layer in the middle of the continuous flow fixed bed reactor, and arranging spherical alumina layers at two ends of the catalyst bed layer; by N2The steel cylinder 1 and the flowmeter 3 respectively purge and preheat a catalyst bed layer for 1.5h under the conditions of the temperature of 260 ℃, 280 ℃, 350 ℃ and the linear velocity of 1.5cm/s by nitrogen flow; then, an aqueous solution of glycerin having a concentration of 30% by weight was fed from the stock tank 2 to the preheating furnace 5 using the high-pressure pump 4 to be gasified at a temperature of 260 deg.C, 280 deg.C, 300 deg.C for 120min, and then the gasified glycerin was passed through the preheating catalyst bed at a mass flow rate of 0.8 kg/kg-h to be reacted at a temperature of 260 deg.C, 280 deg.C, 350 deg.C, respectively, and the reaction product was discharged from the continuous flow fixed-bed reactor 6 through the condenser 7, the gas-liquid separator 8, and the collection tank 9 to obtain an acrolein product. The acrolein product was detected by the same analytical method as in example 1, and the detection results are shown in Table 5.
Table 5: analysis of the substance content of acrolein product produced in this example
The acrolein product of example 5 was composed of acrolein, water and other organic by-products, as determined by the analytical method described in this specification, and was a homogeneous mixed solution. The results in Table 5 clearly show that the conversion of glycerol reaches 100% and that the selectivity to acrolein is found to be 91.0%, 92.5% and 90.5%, respectively, by calculation.
Example 6: preparation and application of catalyst for preparing acrolein from glycerol
The preparation steps of the catalyst for preparing acrolein by glycerol are as follows:
1. preparation of the support
Adding alumina powder into kneader, and dilutingWeight ratio of aqueous nitric acid solution to alumina powder 1.2: 2.0, dropwise adding a dilute nitric acid aqueous solution with the concentration of 5 percent by weight into the alumina powder to enable the alumina powder and nitric acid to carry out gelling reaction, then continuously extruding gelling reaction materials into Raschig annular blanks through an extruder, naturally air-drying, cutting the blanks to a length of 7mm, and then placing the blanks into a high-temperature furnace to calcine and form for 200min at the temperature of 400 ℃ to obtain a carrier; the pore volume of the carrier was 0.8cm3Per g, specific surface area 120m2/g；
B. Preparation of modified Metal oxide Supports
Preparing a ferric nitrate solution having a concentration of 10% by weight; adding the carrier prepared in the step A into the metal nitrate solution according to the loading capacity of ferric oxide being 2% of the weight of the carrier, carrying out ultrasonic oscillation for 4h, dipping for 12h, separating, and calcining the carrier loaded with the metal nitrate in a muffle furnace at the temperature of 700 ℃ for 6h to obtain the modified metal oxide carrier;
C. preparation of catalyst for preparing acrolein by glycerol dehydration
And (3) according to the weight ratio of 1: 8.0 of the heteropoly acid to the modified metal oxide carrier, pouring 30% of phosphomolybdic acid heteropoly acid solution by weight into the modified metal oxide carrier obtained in the step (B), carrying the heteropoly acid on the modified metal oxide carrier by ultrasonic oscillation for 2.6h, drying for 8h at the temperature of 110 ℃, and calcining the dried loaded heteropoly acid modified metal oxide carrier for 13h at the temperature of 500 ℃ to obtain the catalyst for preparing the acrolein by glycerol dehydration.
D. The application of the catalyst for preparing acrolein by glycerol comprises the following steps:
the specific process flow of the catalyst for preparing acrolein by glycerol is shown in figure 1.
Arranging a catalyst bed layer in the middle of the continuous flow fixed bed reactor, and arranging spherical alumina layers at two ends of the catalyst bed layer; by N2The steel cylinder 1 and the flowmeter 3 allow nitrogen flow to blow and preheat the catalyst bed for 1.5h under the conditions of 300 ℃ and 1.0cm/s of linear speed; then, an aqueous solution of glycerin having a concentration of 40% by weight was fed from the stock tank 2 to the preheating furnace 5 using the high-pressure pump 4 to be gasified at a temperature of 300 ℃ for 150min, and then the gasified glycerin was allowed to evaporateThe oil is reacted at a mass flow rate of 0.6 kg/kg-h through a preheated catalyst bed at a temperature of 300 ℃, and the reaction product flows out of the continuous flow fixed bed reactor 6 through a condenser 7, a gas-liquid separator 8 and a collection tank 9 to obtain an acrolein product. The acrolein products obtained after the catalyst was operated for 24 hours, 100 hours and 500 hours were measured by the same analytical method as in example 1, and the measurement results are shown in Table 6.
Table 6: analysis of the substance content of acrolein product produced in this example
The acrolein product of example 6 was composed of acrolein, water and other organic by-products, as determined by the analytical method described in this specification, and was a homogeneous mixed solution. The results in Table 6 clearly show that the catalyst has 100% glycerol conversion after 24h, 100h and 500h of operation, and the acrolein selectivity is up to 90.2% by calculation. The catalyst for preparing acrolein by using glycerol prepared by the invention has good stability, and after the catalyst is stably operated for 500 hours, the catalyst still has high conversion rate and selectivity in glycerol dehydration reaction, and has very good application value in industrial production.
Claims (8)
1. A method for preparing a catalyst for preparing acrolein by glycerol is characterized by comprising the following steps:
A. preparation of the support
Adding alumina powder into a kneader, dropwise adding a dilute nitric acid aqueous solution with the concentration of 4-6% by weight into the alumina powder to enable the alumina powder and nitric acid to carry out gelling reaction, continuously extruding gelling reaction materials into Raschig annular blanks through an extruder, naturally air-drying, cutting, and calcining and molding for 120-240 min at the temperature of 380-420 ℃ in a high-temperature furnace to obtain a carrier; the pore volume of the carrier is 0.5-0.9 cm3A specific surface area of 100 to 240 m/g2/g；
B. Preparation of modified Metal oxide Supports
Preparing a magnesium, zinc or iron metal nitrate solution with a concentration of 8-12% by weight; adding the carrier prepared in the step A into the metal nitrate solution according to the loading amount of magnesium oxide, zinc oxide or iron oxide being 1-10% of the weight of the carrier, ultrasonically oscillating, dipping, separating, and calcining the carrier loaded with the metal nitrate in a muffle furnace at the temperature of 300-800 ℃ for 4-6 h to obtain the modified metal oxide carrier;
C. preparation of catalyst for preparing acrolein by glycerol dehydration
And B, pouring a tungsten-molybdenum heteropoly acid solution into the modified metal oxide carrier obtained in the step B according to the weight ratio of 1: 1.5-9.0 of the heteropoly acid to the modified metal oxide carrier, carrying the heteropoly acid on the modified metal oxide carrier by ultrasonic oscillation for 1-3 h, drying for 6-8 h at the temperature of 100-120 ℃, and calcining the dried loaded heteropoly acid modified metal oxide carrier for 12-14 h at the temperature of 300-800 ℃ to obtain the catalyst for preparing acrolein by glycerol dehydration.
2. The preparation method according to claim 1, wherein in the step A, the raschig rings have a length of 6 to 7 mm.
3. The preparation method according to claim 1, wherein in the step B, the carrier prepared in the step A is ultrasonically oscillated in the metal nitrate solution for 2-4 h.
4. The preparation method according to claim 1, wherein in the step B, the carrier prepared in the step A is continuously immersed in the metal nitrate solution for 10-14 hours after ultrasonic oscillation.
5. The process according to claim 1, wherein in the step C, the heteropoly tungstomolybdate is phosphotungstic acid, phosphomolybdic acid or silicotungstic acid.
6. The method according to claim 1, wherein in the step C, the concentration of the heteropoly acid solution of tungsten and molybdenum is 10-40% by weight.
7. The catalyst for producing acrolein from glycerin produced by the production method according to any one of claims 1 to 6.
8. A method for producing acrolein by dehydration of glycerin using the catalyst for producing acrolein according to claim 7, characterized by comprising the steps of:
A. in the continuous flow fixed bed reactor, a catalyst bed layer is arranged in the middle of the continuous flow fixed bed reactor, and spherical alumina layers are arranged at two ends of the catalyst bed layer;
B. blowing and preheating a catalyst bed layer for 1.2-1.8 h by nitrogen flow under the conditions of the temperature of 260-350 ℃ and the linear velocity of 0.5-1.5 cm/s;
C. sending a glycerol aqueous solution with the concentration of 10-40% by weight to a preheating furnace by using a high-pressure pump, and gasifying for 60-180 min at the temperature of 250-300 ℃;
D. and (C) allowing the gasified glycerol in the step (C) to pass through the preheated catalyst bed in the step (B) at the mass flow rate of 0.4-0.8 kg/kg.h, reacting at the temperature of 260-350 ℃, and allowing a reaction product to flow out of the continuous flow fixed bed reactor and condensing to obtain an acrolein product.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417928A (en) * | 2008-12-09 | 2009-04-29 | 江苏工业学院 | Method for preparing acrylic aldehyde by biological glycerol dehydration |
| CN101786020A (en) * | 2010-02-05 | 2010-07-28 | 江苏工业学院 | Phosphotungstic acid modified catalyst, preparation method and application in acrolein preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417928A (en) * | 2008-12-09 | 2009-04-29 | 江苏工业学院 | Method for preparing acrylic aldehyde by biological glycerol dehydration |
| CN101786020A (en) * | 2010-02-05 | 2010-07-28 | 江苏工业学院 | Phosphotungstic acid modified catalyst, preparation method and application in acrolein preparation thereof |
Non-Patent Citations (2)
| Title |
|---|
| Coke-tolerant SiW20-Al/Zr10 catalyst for glycerol dehydration to acrolein;Amin Talebian-Kiakalaieh等;《Chinese Journal of Catalysis》;20171005;第38卷(第10期);全文 * |
| Production of acrolein from glycerol in liquid phase on heterogeneous catalysts;R. Estevez等;《Chemical Engineering Journal》;20150316(第282期);全文 * |
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