CN116217373A - 一种催化合成甲基丙烯酸的方法 - Google Patents
一种催化合成甲基丙烯酸的方法 Download PDFInfo
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- CN116217373A CN116217373A CN202111477418.8A CN202111477418A CN116217373A CN 116217373 A CN116217373 A CN 116217373A CN 202111477418 A CN202111477418 A CN 202111477418A CN 116217373 A CN116217373 A CN 116217373A
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- Prior art keywords
- catalyst
- propionic acid
- reaction
- acid
- inert gas
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 212
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 106
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 106
- 239000003054 catalyst Substances 0.000 claims abstract description 97
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 49
- 239000001301 oxygen Substances 0.000 claims abstract description 49
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 238000009833 condensation Methods 0.000 claims abstract description 8
- 230000005494 condensation Effects 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 114
- 239000011261 inert gas Substances 0.000 claims description 54
- 239000007789 gas Substances 0.000 claims description 48
- 238000010790 dilution Methods 0.000 claims description 45
- 239000012895 dilution Substances 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910021645 metal ion Inorganic materials 0.000 claims description 13
- 239000011964 heteropoly acid Substances 0.000 claims description 12
- 239000002808 molecular sieve Substances 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 8
- 229940017219 methyl propionate Drugs 0.000 claims description 8
- 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 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound 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 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 4
- 235000011180 diphosphates Nutrition 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 4
- 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 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 15
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 238000004817 gas chromatography Methods 0.000 description 42
- 239000007787 solid Substances 0.000 description 37
- 239000000725 suspension Substances 0.000 description 35
- 238000003756 stirring Methods 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 4
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect 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
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 229910006367 Si—P Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- FSHNFAOXXJLGJE-UHFFFAOYSA-N [Rh].[P] Chemical compound [Rh].[P] FSHNFAOXXJLGJE-UHFFFAOYSA-N 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical compound [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- OSYUGTCJVMTNTO-UHFFFAOYSA-D oxalate;tantalum(5+) Chemical compound [Ta+5].[Ta+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OSYUGTCJVMTNTO-UHFFFAOYSA-D 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
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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
- B01J27/14—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
- B01J27/18—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 with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1804—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with rare earths or actinides
-
- 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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- 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
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
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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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/143—X-type faujasite
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
- B01J29/68—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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Abstract
本发明涉及一种催化合成甲基丙烯酸的方法,具体涉及一种由丙酸选择氧化催化合成甲基丙烯酸的方法。该过程在固定床反应器中进行,在兼具选择氧化和缩合的催化剂上,丙酸首先与氧发生选择氧化生成甲醛,甲醛再与丙酸缩合生成甲基丙烯酸。
Description
技术领域
本发明涉及一种催化合成甲基丙烯酸的方法,具体涉及由丙酸和氧催化制备甲基丙烯酸的方法。
背景技术
甲基丙烯酸(MAA)是一种重要的有机化工原料,具有碳碳双键和羧酸基官能团,可进行聚合和酯化等反应,可用于制备甲基丙烯酸甲酯(MMA)、涂料、橡胶添加剂、织物处理剂、树脂、高分子材料添加剂和功能高分子材料等。MAA的传统生产方法主要是丙酮氰醇法,但该法原子利用率低,需使用剧毒的HCN和强腐蚀性的硫酸,且会产生固体废弃物硫酸氢铵,该工艺过程的原子利用率只有47%,远不符合绿色化学的要求。因此需要开发新的替代工艺,德国BASF利用乙烯羰基化法通过磷铑催化剂催化乙烯、CO和H2合成丙醛,丙醛通过羟醛缩合反应与甲醛反应生成甲基丙烯醛(MAL),然后MAL氧化成MAA。除上述方法外,MAA还可通过异丁烷直接氧化制得,但目前该方法异丁烷转化率比较低(~30%),MAL和MAA的收率低(<50%);丙烯在HF的催化下进行羰基化反应生成MAA,但该过程操作条件复杂、对设备要求高,MAA收率低;丙烯还可通过羰基化制得异丁醛,异丁醛氧化脱氢制得MAA,或继续氧化为异丁酸,然后再氧化脱氢制MAA,但目前该工艺原料转化率低,产物选择性低。
本申请中以丙酸和氧为原料通过选择氧化-缩合制备MAA,文献中尚无以此为原料的MAA制备技术,仅有类似的过程报道:Wolfgang等以K/Al2O3/SiO2催化剂催化丙酸与甲醛反应,转化率只有33%,选择性为49%。1988年Mamoru Ai报道了P-V催化剂用于丙酸和甲醛的缩合反应,研究发现:丙酸与甲醛的摩尔比为2时,甲基丙烯酸的产率能达到39mol%。使用V-Si-P催化剂,优化反应条件下甲基丙烯酸的收率可达53mol%,选择性为82%。2003年Mamoru Ai又报道了Sn-Si-P催化剂上丙酸与甲醛催化生成甲基丙烯酸的收率可达58%。
反应历程为:
发明内容
本发明要解决的问题在于提供一种甲基丙烯酸的催化合成方法,从廉价、易得、稳定的丙酸和氧出发,通过合适的催化体系,制备甲基丙烯酸。
技术方案为:
一种催化制备甲基丙烯酸的方法,
固定床反应器上,丙酸和O2按一定比例,经气化和惰性气体稀释或不经稀释后,在一定量的兼具选择氧化和缩合功能的催化剂上,于一定温度与压力条件下发生反应生成甲基丙烯酸。
所述丙酸与氧的摩尔比为:3:(1-3);
所述惰性气氛包括:N2、Ar、He;
所述惰性气体占总气体总体积的10-80%;
催化剂上丙酸的质量空速为:0.25-4h-1;
反应温度为:300-460℃;
反应压力为:0.3-15atm。
所述丙酸甲酯与水的摩尔比为:1:(1.5-2);
所述惰性气体占总气体总体积的30-70%;
催化剂上丙酸甲酯的质量空速为:0.5-3h-1;
反应温度为:330-430℃;
反应压力为:0.5-10atm。
所述丙酸甲酯与水的摩尔比为:1:(1.5-1.7);
所述惰性气体占总气体总体积的50-60%;
催化剂上丙酸甲酯的质量空速为:0.5-2h-1;
反应温度为:350-400℃;
反应压力为:1-5atm。
所述兼具选择氧化-缩合功能的催化剂为:变价金属离子和(或)酸性金属离子作为助剂修饰的杂多酸类催化剂或其混合物、变价的金属磷酸盐和变价的金属焦磷酸盐或其混合物、变价金属离子和(或)酸性金属离子交换的分子筛类或其混合物。
所述杂多酸类催化剂包括:硅钨酸、磷钨酸和磷钼酸;
所述杂多酸催化剂的载体包括:SiO2、Al2O3、SiC;
所述杂多酸催化剂中杂多酸的担载量为20-40%;
所述变价的金属磷酸盐和变价的金属焦磷酸盐包括:VPO、CePO4、PrPO4、TbPO4、YbPO4;
所述分子筛类催化剂包括:ZSM-5、ZSM-35、Y、β、X、SAPO-34。
所述变价金属离子助剂包括:Ce、V、Bi、Co、Ti、Cr、Mo、Mn、Fe、Cu、Pr、Tb、Yb、Ni的稳定价态离子;
所述酸性金属离子助剂包括:Nb5+、Ta5+。
所述变价金属离子和酸性金属离子助剂的添加量为1-10wt%。
该过程在固定床反应器中进行,在兼具选择氧化和缩合的催化剂上,丙酸首先与氧发生选择氧化生成甲醛,甲醛再与丙酸缩合生成甲基丙烯酸。
有益技术效果
1.本发明中所使用的催化剂原料廉价易得,制备过程可控易操作,可实现丙酸与水为原料制备甲基丙烯酸反应的有效发生;
2.催化剂具有很好的稳定性,反应过程简单可控易操作,其中甲基丙烯酸的产率最高可达78%。
具体实施方式
为了对本发明进行进一步详细说明,下面给出几个具体实施案例,但本发明不限于这些实施例。
实施例1
在分散有SiO2的去离子水形成悬浮液(悬浮液固含量0.1g/mL)中,按Ce占固体总质量5%,硅钨酸占总固体质量20%投入硝酸铈和硅钨酸,室温搅拌6h,120℃蒸干溶剂,所得样品于400℃空气中焙烧充分后(2h),即得5%Ce-20%硅钨酸/SiO2。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为0.5h-1,350℃,1atm条件下进行反应,气相色谱在线监测,反应8h后的产物收率和选择性见表1。
实施例2(使用实施例1中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为0.5h-1,350℃,1atm条件下进行反应,气相色谱在线监测,反应8h后的产物收率和选择性见表1。
实施例3(使用实施例1中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:3,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为0.5h-1,350℃,1atm条件下进行反应,气相色谱在线监测,反应8h后的产物收率和选择性见表1。
实施例4(使用实施例1中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:2,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为0.5h-1,350℃,1atm条件下进行反应,气相色谱在线监测,反应8h后的产物收率和选择性见表1。
实施例5(使用实施例1中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.7,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为0.5h-1,350℃,1atm条件下进行反应,气相色谱在线监测,反应8h后的产物收率和选择性见表1。
实施例6
在分散有Al2O3的乙二醇中形成悬浮液(悬浮液固含量0.5g/mL),按V占总固体质量5%,磷钨酸占总固体质量30%投入偏钒酸铵和磷钨酸,室温搅拌6h,120℃蒸干溶剂,所得样品于400℃空气中焙烧充分后(2h),即得5%V-30%磷钨酸/Al2O3。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为Ar,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为1h-1,360℃,1atm条件下进行反应,气相色谱在线监测,反应6h后的产物收率和选择性见表1。
实施例7(使用实施例6中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为Ar,惰性气体体积占总气体体积的60%,催化剂上丙酸的质量空速为1h-1,360℃,1atm条件下进行反应,气相色谱在线监测,反应6h后的产物收率和选择性见表1。
实施例8(使用实施例6中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为Ar,惰性气体体积占总气体体积的70%,催化剂上丙酸的质量空速为1h-1,360℃,1atm条件下进行反应,气相色谱在线监测,反应6h后的产物收率和选择性见表1。
实施例9(使用实施例6中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为Ar,惰性气体体积占总气体体积的80%,催化剂上丙酸的质量空速为1h-1,360℃,1atm条件下进行反应,气相色谱在线监测,反应6h后的产物收率和选择性见表1。
实施例10(使用实施例6中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为Ar,惰性气体体积占总气体体积的10%,催化剂上丙酸的质量空速为1h-1,360℃,1atm条件下进行反应,气相色谱在线监测,反应6h后的产物收率和选择性见表1。
实施例11(使用实施例6中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为Ar,惰性气体体积占总气体体积的30%,催化剂上丙酸的质量空速为1h-1,360℃,1atm条件下进行反应,气相色谱在线监测,反应6h后的产物收率和选择性见表1。
实施例12
在分散有SiC的去离子水中形成悬浮液(悬浮液固含量1g/mL),按Bi占总固体质量5%,磷钼酸占总固体质量40%投入硝酸铋和磷钼酸,室温搅拌12h,120℃蒸干溶剂,所得样品于350℃空气中焙烧充分后(6h),即得5%Bi-20%硅钨酸/SiC。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为He,惰性气体体积占总气体体积的60%,催化剂上丙酸的质量空速为0.25h-1,350℃,3atm条件下进行反应,气相色谱在线监测,反应12h后的产物收率和选择性见表1。
实施例13(使用实施例12中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为He,惰性气体体积占总气体体积的60%,催化剂上丙酸的质量空速为0.5h-1,350℃,3atm条件下进行反应,气相色谱在线监测,反应12h后的产物收率和选择性见表1。
实施例14(使用实施例12中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为He,惰性气体体积占总气体体积的60%,催化剂上丙酸的质量空速为2h-1,350℃,3atm条件下进行反应,气相色谱在线监测,反应12h后的产物收率和选择性见表1。
实施例15(使用实施例12中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为He,惰性气体体积占总气体体积的60%,催化剂上丙酸的质量空速为3h-1,350℃,3atm条件下进行反应,气相色谱在线监测,反应12h后的产物收率和选择性见表1。
实施例16(使用实施例12中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为He,惰性气体体积占总气体体积的60%,催化剂上丙酸的质量空速为4h-1,350℃,3atm条件下进行反应,气相色谱在线监测,反应12h后的产物收率和选择性见表1。
实施例17
在分散有VPO的去离子水中形成悬浮液(悬浮液固含量0.5g/mL),按Co占总固体质量5%投入硝酸钴,室温搅拌12h,120℃蒸干溶剂,所得样品于450℃空气中焙烧充分后(6h),即得5%Co-VPO。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为0.5h-1,300℃,5atm条件下进行反应,气相色谱在线监测,反应8h后的产物收率和选择性见表1。
实施例18(使用实施例17中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为0.5h-1,330℃,5atm条件下进行反应,气相色谱在线监测,反应8h后的产物收率和选择性见表1。
实施例19(使用实施例17中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为0.5h-1,350℃,5atm条件下进行反应,气相色谱在线监测,反应8h后的产物收率和选择性见表1。
实施例20(使用实施例17中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为0.5h-1,400℃,5atm条件下进行反应,气相色谱在线监测,反应8h后的产物收率和选择性见表1。
实施例21(使用实施例17中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为0.5h-1,430℃,5atm条件下进行反应,气相色谱在线监测,反应8h后的产物收率和选择性见表1。
实施例22(使用实施例17中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为0.5h-1,460℃,5atm条件下进行反应,气相色谱在线监测,反应8h后的产物收率和选择性见表1。
实施例23
在分散有CePO4的去离子水中形成悬浮液(悬浮液固含量0.5g/mL),按Ti占总固体质量10%投入TiCl3,室温搅拌12h,120℃蒸干溶剂,所得样品于450℃空气中焙烧充分后(6h),即得10%Ti-CePO4。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为1h-1,360℃,0.3atm条件下进行反应,气相色谱在线监测,反应8h后的产物收率和选择性见表1。
实施例24(使用实施例23中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为1h-1,360℃,0.5atm条件下进行反应,气相色谱在线监测,反应8h后的产物收率和选择性见表1。
实施例25(使用实施例23中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为1h-1,360℃,1atm条件下进行反应,气相色谱在线监测,反应8h后的产物收率和选择性见表1。
实施例26(使用实施例23中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为1h-1,360℃,5atm条件下进行反应,气相色谱在线监测,反应8h后的产物收率和选择性见表1。
实施例27(使用实施例23中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为1h-1,360℃,10atm条件下进行反应,气相色谱在线监测,反应8h后的产物收率和选择性见表1。
实施例28(使用实施例23中催化剂样品)
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为1h-1,360℃,15atm条件下进行反应,气相色谱在线监测,反应8h后的产物收率和选择性见表1。
实施例29
在分散有PrPO4的去离子水中形成悬浮液(悬浮液固含量0.5g/mL),按Cr占总固体质量5%投入硝酸铬,室温搅拌12h,120℃蒸干溶剂,所得样品于450℃空气中焙烧充分后(6h),即得5%Cr-PrPO4。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.7,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为1h-1,350℃,3atm条件下进行反应,气相色谱在线监测,反应24h后的产物收率和选择性见表1。
实施例30
在分散有TbPO4的去离子水中形成悬浮液(悬浮液固含量0.5g/mL),按Mo占总固体质量5%投入钼酸铵,室温搅拌12h,120℃蒸干溶剂,所得样品于450℃空气中焙烧充分后(6h),即得5%Mo-TbPO4。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.7,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为1h-1,350℃,3atm条件下进行反应,气相色谱在线监测,反应24h后的产物收率和选择性见表1。
实施例31
在分散有YbPO4的去离子水中形成悬浮液(悬浮液固含量0.5g/mL),按Mn占总固体质量5%投入硝酸锰,室温搅拌12h,120℃蒸干溶剂,所得样品于450℃空气中焙烧充分后(6h),即得5%Mn-YbPO4。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.7,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为1h-1,350℃,3atm条件下进行反应,气相色谱在线监测,反应24h后的产物收率和选择性见表1。
实施例32
在分散有铵型ZSM-5的去离子水中形成悬浮液(悬浮液固含量0.5g/mL),按Fe占总固体质量5%投入硝酸铁,室温搅拌12h,抽滤、充分洗涤后干燥,所得样品于500℃空气中焙烧充分后(6h),即得Fe-HZSM-5。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.7,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为1h-1,350℃,3atm条件下进行反应,气相色谱在线监测,反应24h后的产物收率和选择性见表1。
实施例33
在分散有铵型ZSM-35的去离子水中形成悬浮液(悬浮液固含量0.5g/mL),按Cu占总固体质量5%投入硝酸铜,室温搅拌12h,抽滤、充分洗涤后干燥,所得样品于500℃空气中焙烧充分后(6h),即得Cu-HZSM-35。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.7,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为1h-1,350℃,3atm条件下进行反应,气相色谱在线监测,反应24h后的产物收率和选择性见表1。
实施例34
在分散有铵型Y分子筛的去离子水中形成悬浮液(悬浮液固含量0.5g/mL),按Pr占总固体质量5%投入硝酸镨,室温搅拌12h,抽滤、充分洗涤后干燥,所得样品于500℃空气中焙烧充分后(6h),即得Pr-HY。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.7,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为1h-1,350℃,3atm条件下进行反应,气相色谱在线监测,反应24h后的产物收率和选择性见表1。
实施例35
在分散有铵型SAPO-34分子筛的去离子水中形成悬浮液(悬浮液固含量0.5g/mL),按Tb占总固体质量5%投入硝酸铽,室温搅拌12h,抽滤、充分洗涤后干燥,所得样品于500℃空气中焙烧充分后(6h),即得Tb-SAPO-34。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.7,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为1h-1,350℃,3atm条件下进行反应,气相色谱在线监测,反应24h后的产物收率和选择性见表1。
实施例36
在分散有铵型β分子筛的去离子水中形成悬浮液(悬浮液固含量0.5g/mL),按Yb占总固体质量5%投入硝酸镱,室温搅拌12h,抽滤、充分洗涤后干燥,所得样品于500℃空气中焙烧充分后(6h),即得Yb-Hβ。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.7,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为1h-1,350℃,3atm条件下进行反应,气相色谱在线监测,反应24h后的产物收率和选择性见表1。
实施例37
在分散有铵型X分子筛的去离子水中形成悬浮液(悬浮液固含量0.5g/mL),按Ni占总固体质量5%投入硝酸镍,室温搅拌12h,抽滤、充分洗涤后干燥,所得样品于550℃空气中焙烧充分后(6h),即得Ni-HX。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.7,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为1h-1,350℃,3atm条件下进行反应,气相色谱在线监测,反应24h后的产物收率和选择性见表1。
实施例38
在分散有CePO4的去离子水中形成悬浮液(悬浮液固含量0.5g/mL),按Nb占总固体质量1%投入草酸铌铵,室温搅拌12h,120℃蒸干溶剂,所得样品于450℃空气中焙烧充分后(6h),即得Nb-CePO4。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.6,惰性稀释气氛为Ar,惰性气体体积占总气体体积的60%,催化剂上丙酸的质量空速为0.5h-1,360℃,3atm条件下进行反应,气相色谱在线监测,反应12h后的产物收率和选择性见表1。
实施例39
在分散有PrPO4的去离子水中形成悬浮液(悬浮液固含量0.5g/mL),按Ta占总固体质量5%投入草酸钽,室温搅拌12h,120℃蒸干溶剂,所得样品于450℃空气中焙烧充分后(6h),即得Ta-PrPO4。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.6,惰性稀释气氛为Ar,惰性气体体积占总气体体积的60%,催化剂上丙酸的质量空速为0.5h-1,360℃,3atm条件下进行反应,气相色谱在线监测,反应120h后的产物收率和选择性见表1。
对比例1
在分散有SiO2的去离子水中形成悬浮液(悬浮液固含量0.1g/mL),硅钨酸占总固体质量20%投入硅钨酸,室温搅拌6h,120℃蒸干溶剂,所得样品于400℃空气中焙烧充分后(6h),即得20%硅钨酸/SiO2。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.5,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为0.5h-1,350℃,1atm条件下进行反应,气相色谱在线监测,反应8h后的产物收率和选择性见表1。
对比例2
铵型ZSM-5样品于500℃空气中焙烧充分后(6h),即得HZSM-5。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.7,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为1h-1,350℃,3atm条件下进行反应,气相色谱在线监测,反应24h后的产物收率和选择性见表1。
对比例3
将硝酸铁样品于500℃空气中焙烧充分后(6h),即得Fe2O3。
将所得样品压片成型至20-60目,然后加入固定床反应器中,气化后丙酸和氧按摩尔比3:1.7,惰性稀释气氛为N2,惰性气体体积占总气体体积的50%,催化剂上丙酸的质量空速为1h-1,350℃,3atm条件下进行反应,气相色谱在线监测,反应24h后的产物收率和选择性见表1。
表1反应评价结果
从实施例1-5,可见丙酸与氧摩尔比为3:(1.5-1.7),丙酸转化率和目标产物选择性均最佳,其次为3:(1.5-2)。从实施例6-11,可见惰性气体占比越高,转化率越高,选择性也有所提高,惰性气体占比适宜的范围是50-60%。从实施例12-16,可见质量空速越高,转化率越低,选择性也越低,质量空速适宜的范围是0.5~2h-1。从实施例17-22,可见反应温度越高,转化率越高,但甲基丙烯酸选择性降低,反应温度适宜的范围是350~400℃。从实施例23-28,可见反应压力为1-5atm,转化率和选择性均最佳。从对比例1-3,可以看出没有氧化功能的活性组分或没有缩合功能的活性组分,目标产物收率均不理想。
Claims (9)
1.一种催化合成甲基丙烯酸的方法,其特征在于:
固定床反应器上,以丙酸和O2为反应物,丙酸经气化后与O2混合,经惰性气体稀释或不经惰性气体稀释后,在兼具选择氧化和缩合功能的催化剂上,发生反应生成甲基丙烯酸;
所述兼具选择氧化-缩合功能的催化剂为:可变价金属离子和/或酸性金属离子作为助剂修饰的杂多酸类催化剂或其混合物、可变价的金属的磷酸盐和/或可变价的金属的焦磷酸盐或其混合物、可变价金属离子和/或酸性金属离子交换的分子筛类或其混合物中的一种或二种以上。
2.按照权利要求1所述的方法,其特征在于:
所述丙酸与氧的摩尔比为:3:(1-3);
有惰性气体稀释时,所述惰性气氛包括:N2、Ar、He中的一种或二种以上;
有惰性气体稀释时,所述惰性气体占总气体总体积的10-80%;
催化剂上丙酸的质量空速为:0.25-4h-1;
反应温度为:300-460℃;
反应压力为:0.3-15atm。
3.按照权利要求1或2所述的方法,其特征在于:
所述丙酸甲酯与水的摩尔比为:1:(1.5-2);
所述惰性气体占总气体总体积的30-70%;
催化剂上丙酸甲酯的质量空速为:0.5-3h-1;
反应温度为:330-430℃;
反应压力为:0.5-10atm。
4.按照权利要1或2所述的方法,其特征在于:
所述丙酸甲酯与水的摩尔比为:1:(1.5-1.7);
所述惰性气体占总气体总体积的50-60%;
催化剂上丙酸甲酯的质量空速为:0.5-2h-1;
反应温度为:350-400℃;
反应压力为:1-5atm。
5.按照权利要求1所述的方法,其特征在于:所述杂多酸类催化剂至少包括活性组分和载体,杂多酸类催化剂的活性组分包括:硅钨酸、磷钨酸和磷钼酸中的一种或二种以上;
所述杂多酸催化剂的载体包括:SiO2、Al2O3、SiC中的一种或二种以上;
所述杂多酸催化剂中杂多酸的担载量为20-40%(优选20-30%)。
6.按照权利要求1所述的方法,其特征在于:
所述可变价的金属磷酸盐和/或可变价的金属焦磷酸盐包括:VPO、CePO4、PrPO4、TbPO4、YbPO4中的一种或二种以上。
7.按照权利要求1所述的方法,其特征在于:
所述分子筛类催化剂包括:ZSM-5、ZSM-35、Y、β、X、SAPO-34中的一种或二种以上。
8.按照权利要求1、5、6或7所述的方法,其特征在于:
所述可变价金属离子助剂包括:Ce、V、Bi、Co、Ti、Cr、Mo、Mn、Fe、Cu、Pr、Tb、Yb、Ni的稳定价态离子中的一种或二种以上;
所述酸性金属离子助剂包括:Nb5+、Ta5+中的一种或二种。
9.按照权利要求1、5、6、7或8所述的方法,其特征在于:
杂多酸类和分子筛类催化剂上,可变价金属离子和/或酸性金属离子助剂的添加量为1-10wt%(优选5-10wt%)。
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