CN101119956B - 使甘油脱水为丙烯醛的方法 - Google Patents
使甘油脱水为丙烯醛的方法 Download PDFInfo
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- CN101119956B CN101119956B CN2006800049026A CN200680004902A CN101119956B CN 101119956 B CN101119956 B CN 101119956B CN 2006800049026 A CN2006800049026 A CN 2006800049026A CN 200680004902 A CN200680004902 A CN 200680004902A CN 101119956 B CN101119956 B CN 101119956B
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- catalyzer
- propenal
- acid
- glycerine
- oxide
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 156
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 45
- 230000008569 process Effects 0.000 title abstract description 9
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 10
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 239000011949 solid catalyst Substances 0.000 claims abstract description 4
- 235000011187 glycerol Nutrition 0.000 claims description 70
- 239000002253 acid Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229930194542 Keto Natural products 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000011964 heteropoly acid Substances 0.000 claims description 3
- 125000000468 ketone group Chemical group 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- OJYBUGUSFDKJEX-UHFFFAOYSA-N tungsten zirconium Chemical compound [Zr].[W].[W] OJYBUGUSFDKJEX-UHFFFAOYSA-N 0.000 claims description 3
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229920002313 fluoropolymer Polymers 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 42
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 18
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 16
- 239000012071 phase Substances 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 11
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 6
- 238000009825 accumulation Methods 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 229930182817 methionine Natural products 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
- 230000009466 transformation Effects 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- -1 propenal compound Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
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- ZKWPMZVVAJSYNI-UHFFFAOYSA-N prop-2-enal Chemical compound C=CC=O.C=CC=O ZKWPMZVVAJSYNI-UHFFFAOYSA-N 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- AKXKFZDCRYJKTF-UHFFFAOYSA-N 3-Hydroxypropionaldehyde Chemical compound OCCC=O AKXKFZDCRYJKTF-UHFFFAOYSA-N 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- 235000019733 Fish meal Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 208000004350 Strabismus Diseases 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
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- 239000003849 aromatic solvent Substances 0.000 description 1
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- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
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- 239000005431 greenhouse gas Substances 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
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- 230000004060 metabolic process Effects 0.000 description 1
- 238000006140 methanolysis reaction Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- FZEFLWKRCHOOCK-UHFFFAOYSA-N propane-1,2,3-triol;prop-2-enal Chemical compound C=CC=O.OCC(O)CO FZEFLWKRCHOOCK-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010223 real-time analysis Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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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
- 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
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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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
- 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
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C47/22—Acryaldehyde; Methacryaldehyde
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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Abstract
本发明涉及一种在Hammett酸度H0为-9~-18且优选-10~-16的强酸性固体催化剂的存在下通过甘油的气相脱水来制备丙烯醛的方法。
Description
本发明涉及通过甘油的气相脱水来制备丙烯醛的方法。
丙烯醛是最简单的不饱和醛。其也公知为2-丙烯醛(2-propenal)、丙烯醛(acrylaldehyde)或丙烯醛(acrylic aldehyde)。由于其结构的原因,丙烯醛由于其两个反应性官能团的存在而具有高反应能力,其能够单独地或者一起地反应。出于该原因,丙烯酸具有多种应用,特别是作为合成中间体。特别是用于合成蛋氨酸的关键中间体,蛋氨酸为用作动物饲料补充物的合成蛋白质,其自身建立了作为鱼粉的代替物。丙烯醛为工业上通过在气相中催化氧化丙烯制备丙烯酸中丙烯酸的未分离的合成中间体。丙烯酸及其衍生物的化学性质的重要性是已知的。借助于与甲基乙烯基醚的反应并随后水解,丙烯醛也获得戊二醛,其在皮革鞣革中具有多种用途,作为油井钻探中和切削油加工期间的杀虫剂,和作为用于医院设备的化学消毒剂和杀菌剂。
丙烯醛经常用作生产场所中合成的衍生物的合成中间体,以使丙烯醛从生产者到客户的运输最小化。主要原因与丙烯醛的毒性相关,其使得产业工人避免该化学品的储存和运输。
最通常用于制备丙烯醛的方法是基于丙烯与空气氧的气相催化氧化反应。随后可以将这样获得的丙烯醛直接引入到丙烯酸制备过程中。当丙烯醛用作用于合成蛋氨酸的合成或者用于精细化学反应的起始材料时,纯化段使得能除去反应副产物,主要为碳氧化物、丙烯酸、乙酸和乙醛。
由此,丙烯醛的制备主要依赖于通过蒸汽裂化或催化裂化石油馏分而获得的丙烯起始材料。该起始材料,化石源的,进一步有助于增加温室效益。由此显得必要的是,可获得不依赖于丙烯作为原料的且使用另一起始材料(其优选地是可再生的)的丙烯醛合成方法。该方法对于蛋氨酸的合成来说是特别有利的,随后可以称其为“由生物量获得的”。特别地,在其在动物饲料中的使用期间,蛋氨酸快速地代谢且排放到大气中的二氧化碳有助于增加温室效益。如果丙烯醛是由可再生的起始材料获得的,例如由植物油获得的,CO2排放不在进入到工艺平衡中,因为它们弥补了生物量生长所使用的二氧化碳;由此不存在温室效益的增加。由此该方法满足了与“绿色化学”的新观点相关联的标准,在持久发展的更大的全球范围之内。
长期已知甘油可以导致丙烯醛的生产。甘油(也公知为丙三醇)源于植物油的醇解,与此同时作为甲基酯,其本身特别地用作柴油或家用燃料油中的燃料或可燃物。天然产物具有“环境友好的”印象,可以大量获得且可以无困难地储存和运输。已投入了许多研究到甘油的经济改良中,依据其纯度,且使甘油脱水为丙烯醛为一种推荐的路线。
用于由甘油获得丙烯醛所涉及的反应为:
CH2OH-CH-OH-CH2OH?CH2=CH-CHO+2H2O
作为一般原理,水合反应有益地在低温下,且脱水反应有益地在高温下。为了获得丙烯醛,由此必须采用有效的温度,和/或部分真空来使反应发生偏移。该反应可以在液相中或在气相中进行。这类反应公知由酸来催化。
依据专利FR 695 9 31,通过将甘油蒸汽在足够高温度下从含有至少三个酸官能团的(例如磷酸盐)酸的盐之上通过,获得丙烯醛。分馏之后所示的产率为大于75%。
在专利US 2 558 520中,脱水反应在气相/液相中进行,在用磷酸盐浸渍的硅藻土的存在下,悬浮于芳族溶剂中。这些条件下获得的甘油转化为丙烯醛的程度为72.3%。
专利申请WO 99/05 085中所述的方法是基于络合的均质催化剂,在CO/H2气氛下,在20/40bar的压力下,和在溶剂的存在下,如环丁砜的水溶液。
中国专利申请CN 1 394 839涉及一种由甘油制备3-羟基丙醛的的方法。通过将蒸发的纯甘油在硫酸钾或硫酸镁类型的催化剂之上通过而获得作为反应中间体制得的丙烯醛。并未给出反应产率。
专利US 5 387 720描述了一种由甘油的脱水来制备丙烯醛的方法,在液相中或在气相中,在由它们的Hammet酸度所定义的酸性固体催化剂之上。该催化剂必须具有小于+2的Hammet酸度,且优选地小于-3。这些催化剂对应于,例如,天然的或合成的硅质材料,例如发光沸石,蒙脱石,酸性沸石;载体,如氧化物或硅质材料,例如氧化铝(Al2O3)、二氧化钛(TiO2),用单-、二-、三-或多酸无机酸涂覆;氧化物或混合的氧化物如γ-氧化铝,混合的氧化物ZnO-Al2O3,或者替换地杂多酸。依据所述专利,使用了包含10%~40%甘油的水溶液,且该方法在180℃~340℃的温度下在液相中、和在250℃~340℃的温度下在气相中进行。依据所述专利的作者,优选气相反应,因为其能使甘油的转化率接近于获得的100%,其导致含有副产物的丙烯醛水溶液。约10%比例的甘油被转化为羟基丙酮,其作为主要的副产物存在于丙烯醛溶液中。将丙烯醛回收并通过分馏浓缩或蒸馏来纯化。对于液相反应,期望转化率限制在15-25%,由此避免过量的选择性损失。在气相反应情形中,最有利地使用的催化剂为酸度H0为+2~-8.2且优选-3~-5.6的催化剂,但是液相反应优选地采用酸度H0为-8.2~-20的催化剂来进行。专利US 5 426 249描述了用于将甘油脱水为丙烯醛的相同气相方法,但是随后将丙烯醛水合和氢化以获得1,2-和1,3-丙二醇。
由此使甘油脱水为丙烯醛的反应通常伴随着导致形成副产物如羟基丙酮、丙醛、乙醛、丙酮、丙烯醛与甘油的加合物、甘油缩聚产物、环状甘油醚等的副反应,而且苯酚和多芳族化合物,其导致催化剂上形成焦炭。这点导致,首先,丙烯醛的产率和选择性的降低,且其次催化剂的钝化。丙烯醛中副产物的存在,如羟基丙酮或丙醛,另外其一些难以分离,使分离和纯化步骤成为必然,其导致对于纯化丙烯醛的高回收成本。另外,必须非常频繁地使催化剂再生,由此再获得令人满意的催化剂活性。
申请人公司已设法解决这些问题且已发现,Hammett酸度H0为-9~-18的一些酸性固体,相对于专利US 5 387 720中所述的更低酸度的固体,对于甘油气相脱水为丙烯醛的反应具有更高催化活性。这些催化剂是更大活性的且钝化速度更慢,这样容许更长的循环和更小的反应器体积。
由此,本发明的一个目的是,通过在Hammett酸度H0为-9~-18的强酸性固体催化剂的存在下甘油的气相脱水来制备丙烯醛的方法。
如专利US 5 387 720中所示,其参考了K.Tanabe等在“Studies in SurfaceScience and Catalysis”,Vol.51,1989第1和2章中的文章,Hammett酸度通过利用指示剂的胺滴定或者通过气相中碱的吸附来测量。满足酸度标准H0为-9~-18的催化剂可以选自天然的或合成的硅质材料或酸性沸石;矿物载体,如氧化物,用单-、二-、三-或多酸无机酸涂覆;氧化物或混合的氧化物,或者替换地杂多酸。
该催化剂有益地选自沸石,Nafion复合材料(基于氟化聚合物的磺酸),氯化氧化铝,磷钨酸和/或硅钨酸和酸盐,和各种金属氧化物类型的固体如氧化钽Ta2O5、氧化铌Nb2O5、氧化铝Al2O3、二氧化钛TiO2、氧化锆ZrO2、氧化锡SnO2、二氧化硅SiO2或硅-铝酸盐SiO2-Al2O3,用酸官能浸渍,如硼酸盐BO3、硫酸盐SO4、钨酸盐WO3、磷酸盐PO4、硅酸盐SiO2或钼酸盐MoO3。
优选的催化剂为硫酸盐氧化锆、磷酸盐氧化锆、钨氧化锆、硅质氧化锆、硫酸钛或氧化锡,和磷酸盐氧化铝或硅石。
该反应可以在分子氧的存在下进行。该分子氧可以为空气形式或者含分子氧的气体的混合物形式。选择氧的量,使得工厂中任意点是在可燃性范围之外。由US专利申请2004/15012的图4来看,丙烯醛/O2/N2混合物中最大含氧量为约7%体积,由此完全在可燃性范围之外。依据本发明的方法中的含氧量将通常进行选择使得相对于进入反应的气体混合物(甘油/H2O/氧/惰性气体的混合物)不超过7%。优选地,含氧量相对于离开反应器的干燥气态混合物(丙烯醛/氧/惰性气体的混合物)来说小于7%。
依据本发明的方法在气相中进行。可以采用本领域技术人员公知的各种工艺技术,即,固定床工艺、流化床工艺或循环的流化床工艺。
依据各种标准来选择最佳的工艺。固定床工艺具有简单的优点。流化床工艺使得能够连续地排出消耗的催化剂和不变地再填充新鲜的催化剂,无需停止生产,具有为等温的的可能性。循环的流化床工艺具有的优点是,通过不变地将新鲜再生的催化剂返回到反应器中来优化反应选择性,同时弥补了反应器与再生器之间的能量交换。催化剂的再生可以采用氧、氢或者采用其它处理如用溶剂洗涤和/或用H2O2处理来进行。
依据本发明的一种特定实施方式,该方法在板式换热器类型的反应器中进行。这种反应器由在它们自身循环通到之间形成的板组成,该通道可以含有催化剂。这种技术在热交换方面具有许多优点,其与高热量交换能力相关。由此,这类反应器特别适用于在放热反应情形中容易地除去热量,或者用于在反应的开始阶段中或者在吸热反应情形中供给热量。更特别地,这种反应器使得能够加热或者冷却催化剂。热交换对于该系统中热交换的流体的循环是特别有效的。可以将板组装在模块中,其获得更大灵活性,无论是关于反应器的尺寸、其维护或是催化剂的更换。可以适用于本发明方法的系统为,例如,文献EP 995 491或者EP1 147 807中所述的反应器,将其内容引入作为参考。这些反应器特别适用于反应介质的催化转化,特别地其它反应介质,如本发明中所使用的那些。用于借助于C3或C4前体的催化氧化来制备(甲基)丙烯醛或(甲基)丙烯酸的板式换热器,描述于文献US 2005/0020851,也可以适用于借助于甘油的脱水来制备丙烯醛,其为本发明的目的。
优选地,该反应的实验条件为250℃~350℃的温度和1~5bar的压力。已发现,更低温度导致甘油转化率的降低,但是,同时,丙烯醛选择性增加。为了避免连续的反应和不需要的产物的形成,重要的是限制反应器中的停留时间;另外,通过增加停留时间,也能够具有更高转化率。当采用更低温度时,特别期望增加催化剂区域中反应物的接触时间(停留时间),由此弥补转化率的降低。
甘油可廉价地以水溶液形式获得。有益地,反应器中使用浓度为10%~50%且优选15%~30%重量的甘油水溶液。浓度应当不能过高,由此避免假反应如甘油醚的形成或生成的丙烯醛与甘油之间的反应。另外,考虑到甘油水溶液的蒸发中涉及的能量成本,甘油水溶液应当不能太稀释。任意情形中,可以通过反应制得的水循环来调节甘油溶液的浓度。为了降低甘油运输和储存成本,可以给反应器进料40%~100%重量的浓缩溶液,通过循环一些反应生成的蒸汽和稀释水来进行稀释到最佳含量。类似地,反应器出口处热量的回收也可以使进料反应器的甘油溶液被蒸发。
源于碱性介质中植物油的甲醇分解的甘油可能含有一些杂质,如氯化钠或硫酸钠、非甘油的有机物、和甲醇。钠盐的存在对于催化脱水反应来说特别有害,因为这些盐能够使酸性位点中毒。可以建议通过离子交换来预处理该甘油。
与通过选择性氧化丙烯来制备丙烯酸的传统方法相比,依据本发明方法制得的丙烯醛可以含有不同类型或不同量的杂质。依据推荐的使用,丙烯酸的合成、蛋氨酸的合成或精细化学反应,可以建议浓据本领域技术人员已知的技术来纯化丙烯醛。更特别地,可以将副产物回收和焚烧,由此提供蒸汽或能量。甘油脱水的副产物的有效升级进一步使得能够大大降低该方法的温室气体排放,相对于传统方法,对此生成的CO2在副产物的焚烧期间由化石碳获得。
下列实施例阐述了本发明,但是并非限定其范围。
实施例
实施例中,采用由85cm长且内径为6mm的管组成的管式反应器,在大气压下在气相中进行甘油脱水反应。将该反应器置于保持在反应温度下加热室中,温度为300℃,除非另外指出。将使用的催化剂磨碎和/或造粒以获得0.5~1.0mm的颗粒。将10mL催化剂装填到反应器中以形成35cm长的催化剂床。将该床保持在反应温度下5~10分钟,在引入反应物之前。给反应器以12mL/h的平均进料速度进料含有20wt%的甘油的水溶液。将甘油水溶液在加热室中蒸发,并随后在催化剂之上通过。预计的接触时间为约2.9sec。催化剂试验的持续时间为约7小时,其对应于约80mL的甘油水溶液在催化剂之上通过。反应之后,将产物在用碎冰冷冻的收集器中冷凝。
定期收集流出物的样品。低于每个样品收集,将流动打断且将轻度的氮气流从反应器中通过以将其净化。随后替换反应器出口处的收集器,将氮气流停止且在反应物的流动下再次打开反应器。继续试验,直到察觉到可感知的催化剂钝化。
对于每个试验,测量进入和离开的产物的总质量,其能使得测量物料平衡。类似地,通过色谱分析形成的产物。进行两种类型的分析:
-在填充柱(FFAP柱2m*1/8”)上在装有TCD检测器的Carlo Erba色谱仪上通过色谱来分析。采用外部标转(2-丁酮)来浸析定量分析;
-在毛细管柱(FFAP柱50m*0.25mm)在装有FID检测器的HP6890色谱仪通过色谱来分析,采用在-15℃下储存的相同样品。
第一种方法特别适用于快速分析产物,且特别是丙烯醛的产率。第二种方法用于更精确地分析所有的反应副产物。另外,进行硅烷化之后通过GC-MS或者通过色谱的分析以证实这些结果。
由此定量的产物为未反应的甘油、形成的丙烯醛、和副产物如羟基丙酮、乙醛、丙醛、丙酮和苯酚。
在下列实施例中,甘油转化率、丙烯醛选择性和各种产物的转化率定义如下:
甘油转化率(%)=100-剩余的甘油的摩尔数/引入的甘油的摩尔数;
丙烯醛产率(%)=制得的丙烯醛的摩尔数/引入的甘油的摩尔数;
丙烯醛选择性(%)=100*制得的丙烯醛的摩尔数/反应的甘油的摩尔数
至于丙烯醛产率,计算丙酮或羟基产率:
乙醛产率(%)=2/3*制得的乙酸的摩尔数/引入的甘油的摩尔数。
苯酚产率(%)=2*制得的苯酚的摩尔数/引入的甘油的摩尔数。
所有结果均表示为相对于引入的甘油的摩尔百分比。
实施例1和1a(现有技术的对比)
将10mL专利US 5 387 720所述制得的、Hammett酸度H0为-3~-5.6的H3PO4/α-氧化铝催化剂(代表10g的质量)装填到反应器中。以下列方式来制备该催化剂:将15.9g来自Ceramtec的α-氧化铝(索引EO-19-比表面积0.7m2/g-平均粒径2.5μm-表观孔隙率65%-以环状形式提供并磨碎以仅保留直径1-1.4mm的颗粒)用4g 20wt%磷酸溶液(通过加入16.25mL水和5g 85wt%的磷酸来制得)浸渍。随后将固体在80℃下在旋转蒸发器上干燥,并且对于实施例1就直接使用。对于实施例1a,该固体在300℃下在空气中进行另外的活化3小时,由此使磷酸固定于载体上。结果在下面表1中进行比较。
表1
观察到催化剂的快速钝化。
实施例2
使用Daiichi Kigenso的硫酸盐氧化锆(90%ZrO2-10%SO4)(供应商索引H1416)作为催化剂。该催化剂在1000℃下点燃时具有8.81%的损失且比表面积为54.3m2/g(BET,1点)。依据酸基催化剂的出版物的第71页中给出的表,(C.Marcilly)Vol.1,Technip出版(ISBN No.2-7108-0841-2),酸度H0等于-16。将10mL(代表16.5g的质量)催化剂装填到反应器中。结果在下面表2中给出:
表2
引入的累积甘油,(g) | 9 17 27 36 44 53 |
甘油转化率,丙烯醛产率,丙烯醛选择性, | 100 99 96 91 89 8434.0 43.3 40.6 36.0 33.8 35.434 44 42 39 38 42 |
羟基丙酮产率,乙醛产率,丙醛产率,丙酮产率,苯酚产率, | 8.5 13.8 13.7 14.6 15.1 14.35.6 4.2 3.4 2.9 2.9 3.412.4 9.7 7.2 6.5 6.7 7.80.0 0.0 0.3 0.0 0.0 0.01.9 0.4 0.4 0.3 0.3 0.3 |
材料平衡(收集的质量/引入的质量),定量的产物平衡(检定的产物/引入的甘油) | 96.5 99.0 98.4 99.3 98.6 99.562.5 72.8 70.0 69.0 69.6 77.2 |
这类催化剂相对于实施例1的催化剂钝化速度更慢。
实施例3和3a
将10mL依据and Harmer,Green Chemistry 2000,2,第7-14页的出版物中所述的工序制得的40%Nafion/SiO2复合材料(代表4.77g的质量),装填到反应器中。这类催化剂的酸度H0为约-12,依据商品说明。
结果在下面表3中给出。
表3
引入的累积甘油,(g) | 8 16 24 33 41 50 58 67 |
甘油转化率,丙烯醛产率,丙烯醛选择性, | 100 100 100 97 92 87 80 7363.6 76.0 72.5 68.3 64.0 58.6 52.6 47.264 76 73 70 69 68 66 65 |
羟基丙酮产率,乙醛产率,丙醛产率,丙酮产率,苯酚产率, | 5.0 9.5 9.3 9.4 9.0 8.0 7.0 6.41.3 0.5 0.4 0.3 0.2 0.2 0.2 0.15.1 2.1 1.4 1.1 0.9 0.7 0.6 0.50.0 0.0 0.0 0.1 0.0 0.0 0.0 0.02.5 1.5 1.6 0.0 1.2 1.1 1.0 0.9 |
材料平衡(收集的质量/引入的质量),定量的产物平衡(检定的产物/引入的甘油) | 97.5 98.8 98.8 99.5 99.0 99.5 99.0 99.077.5 89.7 85.5 81.7 83.3 82.1 81.6 82.0 |
试验相同的催化剂,此时反应温度为280℃,代替300℃。结果在下面表3a中给出。
表3a
引入的累积甘油,(g) | 8 16 24 32 40 56 72 80 |
甘油转化率,丙烯醛产率,丙烯醛选择性, | 100 100 100 100 97 93 85 8062.3 73.2 72.5 70.8 67.3 62.1 55.0 50.462 73 72 71 69 67 65 63 |
羟基丙酮产率,乙醛产率,丙醛产率,丙酮产率,苯酚产率, | 4.4 8.8 9.5 9.5 9.5 9.2 9.1 8.31.0 0.4 0.3 0.3 0.2 0.2 0.1 0.14.9 2.2 1.7 1.4 1.0 0.9 0.6 0.60.0 0.0 0.0 0.0 0.0 0.0 0.0 0.02.5 1.7 1.4 1.2 1.0 1.0 1.0 0.9 |
材料平衡(收集的质量/引入的质量),定量的产物平衡(检定的产物/引入的甘油) | 97.2 98.5 98.7 98.6 99.0 98.5 98.5 99.275.2 86.4 85.4 83.1 81.6 80.3 80.8 80.0 |
这类催化剂是活性的和选择性的,且相对于实施例1的催化剂钝化速度更慢。
实施例4
使用了Daiichi Kigenso的磷酸盐氧化锆(91.5%ZrO2-8.5%PO4)(索引H1418)。该催化剂在1000℃下点燃时具有4.23%的损失且比表面积为128.7m2/g。将10mL该催化剂(代表12.7g的质量)装填到该反应器中。
结果在下面表4中给出。
表4
引入的累积甘油,(g) | 8 16 24 32 41 49 57 65 |
甘油转化率,丙烯醛产率,丙烯醛选择性, | 100 100 100 100 99 97 96 9516.6 40.4 46.7 45.2 46.2 46.5 45.3 46.917 40 47 45 46 48 47 49 |
羟基丙酮产率,乙醛产率,丙醛产率,丙酮产率,苯酚产率, | 0.0 9.4 13.0 13.5 14.7 15.0 15.2 16.76.9 6.3 5.0 4.7 4.3 4.0 3.5 3.715.0 14.2 11.7 11.1 9.8 9.0 8.0 8.20.0 0.0 0.0 0.0 0.0 0.0 0.0 0.04.2 4.4 2.9 2.5 1.8 2.2 1.7 1.8 |
材料平衡 | 95.0 98.2 95.2 97.7 97.6 98.4 97.9 97.9 |
(收集的质量/引入的质量),定量的产物平衡(检定的产物/引入的甘油) | 42.7 74.6 79.3 77.0 77.4 79.4 77.3 82.3 |
实施例5
使用Daiichi Kigenso的钨氧化锆(90.7%ZrO2-9.3%WO3)(供应商索引H1417)。该催化剂在1000℃下点燃时具有1.75%的损失且比表面积为47.4m2/g(BET,1点)。依据酸基催化剂的出版物的第71页中给出的表,(C.Marcilly)Vol.1,Technip出版(ISBN No.2-7108-0841-2),酸度H0等于-14.5。
将10mL(代表17g的质量)催化剂装填到反应器中。
结果在下面表5中给出:
表5
引入的累积甘油,(g) | 8 16 25 32 39 48 61 78 |
甘油转化率,丙烯醛产率,丙烯醛选择性, | 100 100 100 100 100 100 100 10046.9 69.2 71.6 72.1 71.4 72.7 73.5 73.147 69 72 72 71 73 74 73 |
羟基丙酮产率,乙醛产率,丙醛产率,丙酮产率,苯酚产率, | 0.3 4.5 7.4 8.6 6.7 9.7 10.8 12.94.7 4.4 4.0 3.8 3.7 3.4 2.7 1.78.7 7.4 7.0 6.7 6.6 5.4 5.6 3.62.3 3.0 2.5 2.4 2.4 2.3 1.7 1.12.1 1.5 1.3 1.2 0.1 1.0 0.2 0.0 |
材料平衡(收集的质量/引入的质量),定量的产物平衡(检定的产物/引入的甘油) | 96.8 98.2 98.4 99.0 97.0 99.0 99.0 98.665.0 89.9 93.9 94.7 90.9 94.5 94.6 92.3 |
该催化剂保持了高产率,大大优于实施例1的催化剂的性能。
实施例6
将10mL实施例1中所述的(H1416)、Daiichi Kigenso的磷酸盐氧化锆(代表16.5g的质量)装填到反应器中。此时在流速为0.8L/h的分子氧的存在下进行反应。结果在下面表6中给出。
表6
引入的累积甘油, (g) | 9 18 27 |
甘油转化率,丙烯醛产率,丙烯醛选择性, | 10 0 100 10042.3 53.8 52.542 54 52 |
羟基丙酮产率,乙醛产率,丙醛产率,丙酮产率,苯酚产率, | 0.0 0.0 0.010.3 9.1 8.24.9 3.7 4.00.0 0.4 0.00.0 0.0 0.3 |
材料平衡(收集的质量/引入的质量),定量的产物平衡(检定的产物/引入的甘油) | 96.5 98.0 98.057.5 66.9 65.0 |
氧的加入使得能够通过抑制副产物的形成而获得更高产率。
Claims (15)
1.一种制备丙烯醛的方法,通过在Hammett酸度H0为-9~-18的强酸性固体催化剂的存在下甘油的气相脱水来制备。
2.权利要求1的方法,其特征在于,该催化剂的Hammett酸度H0为-10~-16。
3.权利要求1或2的方法,其特征在于,该催化剂选自天然的或合成的硅质材料或酸性沸石;矿物载体,用单-或多酸无机酸涂覆;氧化物或混合的氧化物,或者杂多酸。
4.权利要求3的方法,其特征在于,所述矿物载体为氧化物。
5.权利要求3的方法,其特征在于,所述多酸无机酸是二-或三-酸无机酸。
7.权利要求6的方法,其特征在于,所述金属氧化物类型的各种固体为氧化钽Ta2O5、氧化铌Nb2O5、氧化铝Al2O3、二氧化钛TiO2、氧化锆ZrO2、氧化锡SnO2、二氧化硅SiO2或硅-铝酸盐SiO2-Al2O3,其用酸官能硼酸盐BO3、硫酸盐SO4或磷酸盐PO4浸渍。
8.权利要求1或2的方法,其特征在于,该催化剂选自硫酸盐氧化锆、磷酸盐氧化锆、钨氧化锆、硅质氧化锆、和硫酸钛或氧化锡。
9.权利要求1或2的方法,其特征在于,该甘油为反应器中浓度为10%~50%重量的水溶液形式。
10.权利要求9的方法,其特征在于,该甘油为反应器中浓度为15%~30%重量的水溶液形式。
11.权利要求1或2的方法,其特征在于,该反应在分子氧的存在下进行,选择分子氧的量,使得工厂中任意点是在可燃性范围之外。
12.权利要求11的方法,其特征在于,该分子氧为含分子氧的气体的混合物形式。
13.权利要求12的方法,其特征在于,该含分子氧的气体的混合物为空气。
14.权利要求1或2的方法,其特征在于,该反应在固定床反应器、流化床反应器中或者在板式换热器中进行。
15.权利要求14的方法,其特征在于,所述流化床反应器是循环的流化床反应器。
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EP1848681A2 (en) | 2007-10-31 |
JP5107060B2 (ja) | 2012-12-26 |
PT1848681E (pt) | 2008-09-09 |
CN101119956A (zh) | 2008-02-06 |
ES2308717T3 (es) | 2008-12-01 |
PL1848681T3 (pl) | 2009-03-31 |
EP1848681B1 (en) | 2008-07-02 |
WO2006087084A2 (en) | 2006-08-24 |
KR101249632B1 (ko) | 2013-04-02 |
ATE399751T1 (de) | 2008-07-15 |
BRPI0607726B1 (pt) | 2015-06-09 |
DE602006001638D1 (de) | 2008-08-14 |
KR20070104413A (ko) | 2007-10-25 |
FR2882053B1 (fr) | 2007-03-23 |
US7655818B2 (en) | 2010-02-02 |
FR2882053A1 (fr) | 2006-08-18 |
JP2008530151A (ja) | 2008-08-07 |
WO2006087084A3 (en) | 2007-01-18 |
US20080214880A1 (en) | 2008-09-04 |
BRPI0607726A2 (pt) | 2009-10-06 |
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