CN1068104A - 制备乙酸乙烯酯的催化剂和方法 - Google Patents
制备乙酸乙烯酯的催化剂和方法 Download PDFInfo
- Publication number
- CN1068104A CN1068104A CN92104828A CN92104828A CN1068104A CN 1068104 A CN1068104 A CN 1068104A CN 92104828 A CN92104828 A CN 92104828A CN 92104828 A CN92104828 A CN 92104828A CN 1068104 A CN1068104 A CN 1068104A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- compound
- carrier
- catalyst
- acetic ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 title description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 9
- 239000010931 gold Substances 0.000 claims abstract description 9
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052737 gold Inorganic materials 0.000 claims abstract description 8
- 150000001553 barium compounds Chemical class 0.000 claims abstract description 6
- 229910052788 barium Inorganic materials 0.000 claims description 9
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 150000003112 potassium compounds Chemical class 0.000 claims 1
- 150000002941 palladium compounds Chemical class 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 239000013543 active substance Substances 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- -1 silico-aluminate Chemical compound 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 239000011230 binding agent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
- 150000004648 butanoic acid derivatives Chemical class 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 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
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- WHQHAMZACPHHAE-UHFFFAOYSA-K aluminum tetrachlorosilane trichloride Chemical compound [Al+3].[Cl-].[Cl-].[Cl-].Cl[Si](Cl)(Cl)Cl WHQHAMZACPHHAE-UHFFFAOYSA-K 0.000 description 1
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- INIZTEMZWOJCAF-UHFFFAOYSA-J dimagnesium octadecanoate Chemical compound [Mg+2].[Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O INIZTEMZWOJCAF-UHFFFAOYSA-J 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 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 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/12—Acetic acid esters
- C07C69/14—Acetic acid esters of monohydroxylic compounds
- C07C69/145—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols
- C07C69/15—Vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种制备乙酸乙烯酯的方法，该方法
为在一种催化剂上，从乙烯、乙酸和氧气或含氧气体
制备乙酸乙烯酯，该催化剂为在一种载体上负载钯和
/或钯化合物和碱金属化合物，而且该催化剂还含至
少一种钡化合物，不含金、镉和其化合物。另外，本发
明还涉及上述催化剂。
Description
已经知道，乙烯在固定床催化剂上以气相形式与乙酸和氧气或含氧气体反应，生成乙酸乙烯酯。一般来说，时空产率大于200g/l×h的催化剂毫无例外地含有钯/镉/钾或钯/金/钾两种组合之一（US-PS3，939，199，US-PS4，668，819，EP-A-O330，853，EP-A-O403，950和EP-A-0431，478）。
令人惊奇的是，已经发现含至少一种钡化合物和至少一种碱金属化合物、且既无镉又无金或其化合物的催化剂，可获得与上述的Pd/Au/K和Pd/Cd/K催化剂体系至少相同的时空产率、相同或更低的乙烯燃烧生成CO2量、相同或较少的乙酸乙酯的生成量。这非常有利，因为镉有害而金的价格高，而钡本身既便宜又无毒，能迅速转化成成硫酸钡，而硫酸钡的溶解度小，完全是惰性的。
因此，本发明涉及一种制备乙酸乙烯酯的方法，该方法为在一催化剂上、以气相形式从乙烯、乙酸和氧气或含氧气体制备乙酸乙烯酯，该催化剂含负载在一种载体上的钯和/或其化合物和碱金属化合物，其中，该催化剂含至少一种钡化合物，而不含金和镉和其化合物。而且，本发明还涉及一种催化剂，该催化剂含负载在一种载体上的钯和/或其化合物和碱金属化合物，其中该催化剂含至少一种钡化合物，而该催化剂中不含金和镉和其化合物。
由于载体催化剂（Supported catalyst）的起始物质不纯，所谓不含这些元素和它们的化合物是指它们不超过痕量，即，基于载体催化剂的总量（载体加上活性组分），镉和金的总含量不大于1ppm。
合适的载体为惰性载体材料，如硅酸、氧化铝、硅铝酸盐、硅酸盐、氧化钛、氧化锆、钛酸盐、碳化硅和碳。比表面为40-350m2/g、平均孔径为50-2000
的硅酸特别合适。
根据US-PS3，939，199，高效载体的总孔体积应为0.4-1.2ml/g，由孔径小于30
（埃）的“微孔”形成的孔体积应小于总孔体积的10%。这类载体可从以玻璃态微珠形式存在的包气的SiO2或包气的SiO2-Al2O3混合物制备，例如该微珠可通过四氯化硅或四氯化硅-三氯化铝混合物在氢氧焰中火焰水解（flame hydrolysis）制得。这些微珠可市购，牌号为（R）Aerosil或（R）Cabosil。
EP-A-O403，950中描述了一种正好为上述类型的载体，该载体含SiO2或SiO2-Al2O3混合物，比表面积为50-250m2/g，孔体积为0.4-1.2ml/g，颗粒大小为4-9mm，5-20%的载体孔体积是由半径为200-3000
的孔形成的，50-90%的孔体积是由半径为70-100
的孔形成的。
根据EP-A-O431，478，成形颗粒，即成型的载体颗粒，例如可采用制片或挤压方式，通过加入一种或多种Li、Mg、Al、Zn、Fe或Mn的羧酸盐作为粘结剂和加入有机填充剂（如糖、尿素、高级脂肪酸、长链链烷烃和纤维素微晶）和润滑剂（如高岭土、石墨和金属皂）从微珠方便地制得，接着该成形颗粒在含氧气体中、约500-900℃下烘烤0.25-5h。
可采用常规的方法将催化活性物质载到载体上，例如，用一种活性物质的溶液浸渍载体，随后进行干燥，如合适的话再进行还原。然而，活性物质也可通过在载体上沉淀或喷涂、气相沉积或浸泡的方法而载上去。
总的来说，催化活性物质的合适溶剂为未取代的、含2-10个碳原子的羧酸，如乙酸、丙酸、正-和异-丁酸和各种戊酸。出于其物理性质和经济方面的考虑，乙酸是优选的溶液，如果活性物质不能在羧酸中充分溶解，加入别的惰性溶剂也是合适的。例如，氯化钯在含水醋酸中比冰醋酸中易溶得多。可能的附加溶剂为那些惰性和能与羧酸互溶的物质如水和醚，（如四氢呋喃或二噁烷）或烃（如苯）。
催化剂载体优选用活性成分的溶液浸渍，即用一层溶液覆盖载体，然后倾掉或滤掉过量的溶液。考虑到载体的损失，合适的是仅采用与催化剂载体的总孔体积相应的溶液，并将各种成分充分混合，以便载体物料颗粒能均匀浸湿。例如这种混合可通过搅拌来实现。合适的是浸渍操作与混合同时进行，例如可在旋转鼓或转筒干燥器中进行，在这种情况下，干燥能立即接着进行。此外，选择用于浸渍催化剂载体的溶液组成以便在单次浸渍中载上所需的活性物质的量是有利的作法。然而，也可采用多次浸渍步骤进行载活。
采用这种溶液浸渍的催化剂载体优选在减压下进行干燥。干燥温度应低于120℃，优选的是低于90℃。而且，通常应在惰性气流中进行干燥，如在氮气或二氧化碳气流中干燥。干燥后，残存的溶剂含量优选应小于8m%，特别是小于6m%。
该催化剂含有作为贵重金属成分的钯和/或其化合物。
合适的钯化合物为易溶（如合适的话为可还原的）且不会在最终催化剂上（如有必要用水洗过的）遗留任何去活物质（如卤素或硫）的所有盐和配合物。特别合适的是羧酸盐，优选的是含2-5个碳原子的脂族单羧酸盐，如乙酸盐、丙酸盐或丁酸盐。而且，例如，硝酸盐、亚硝酸盐、水合氧化物、草酸盐、乙酰丙酮化物和乙酰乙酸盐也适合。因乙酸钯的溶解度和和可得性，它是特别优选的钯化合物。
一般来说，催化剂中的钯含量为0.3-3m%，优选的是1.5-2.5m%，特别是2-2.5m%。
该催化剂含有至少一种钡化合物作为活化剂，优选的是羧酸盐，如甲酸盐、乙酸盐、丙酸盐或丁酸盐。还含有至少一种碱金属化合物，优选的是至少一种K、Rb或Cs的化合物，特别是至少一种K化合物。羧酸盐、特别是乙酸盐和丙酸盐尤其适合作为碱金属化合物。
合适的钡和碱金属化合物也为所有那些在反应条件下能转化成乙酸盐的化合物，如氢氧化物、氧化物和碳酸盐。
催化剂中的钡含量通常为0.1-10m%，优选的是0.2-4m%，特别是0.4-3m%。碱金属元素的含量通常为0.3-10m%，优选的是0.5-8m%，特别是1-4m%。上述百分数总量基于催化剂总量，对元素钯、钡和碱金属而言的，计算中不包括任何阴离子。
如果要还原钯化合物（这常常是有益的），可在真空、常压或加压到1MPa下进行。建议采用惰性气体稀释还原剂，压力越高，稀释度越大。一般还原温度为40-260℃，优选的是70-200℃。通常采用惰性气体/还原剂混合物进行还原是有利的，该混合物含0.01-50v%、优选的是0.5-20v%的还原剂。如可用氮气、二氧化碳或稀有气体作为惰性气体。可作为还原剂的例子为氢气、甲醇、甲醛、乙烯、丙烯、异丁烯、丁烯和其它烯烃。还原剂的量取决于钯的量，一般还原当量应至少为氧化当量的1-1.5倍，但更大量的还原剂并没有害处。可在同一设备中在干燥后进行还原。
乙酸乙烯酯常常是这样制备的：在100-200℃下，优选的是120-200℃，0.1-2.5MPa、优选的是0.1-2MPa的压力下，让乙酸、乙烯和氧气或含氧气体通过成品催化剂，使未反应的成分进行循环。氧气含量保持在10v%以下是有利的（基于不含乙酸的气体混合物）。然而在某些情况下，用惰性气体（如N2或CO2）稀释混合物是有益的。在循环过程中，用CO2进行稀释特别合适，因为在反应过程中，会有少量CO2生成。
下面的实施例旨在说明本发明，元素Pd、Ba和K的百分率数据为质量百分率。
对比实施例1
按照EP-A-O 431，478，以硬脂酸镁作为粘结剂，采用挤压、随后进行烘烤的方法，从比表面积为200m2/g的包气的SiO2微珠制备100g的硅酸小片，用一种溶液浸渍并干燥，该溶液为在78.5ml的冰醋酸中含有5.6g乙酸钯、5.1g的乙酸镉和5.5g的乙酸钾。最终的催化剂含2.3%Pd、1.8%的Cd和1.9%的K（基于含盐和载体的体系）。
向内径为8mm、长1.5m的反应管中加入50ml上述催化剂，接着在0.8MPa（反应器入口）的压力、150℃的催化剂温度下通入待反应的气体。该气体（反应器入口）含27v%的乙烯、55v%的N2、12v%的乙酸和6v%的O2，反应结果可从表中看出。
对比实施例2
按对比实施例1的步骤，所不同的是用硬脂酸铝代替硬脂酸镁作为粘结剂，在对比实施例1的条件下进行测试，结果列在表中。
实施例1
100g上述对比实施例1的载体，用一种溶液浸渍并干燥，该溶液为在78.5ml的冰醋酸中含5.6g乙酸钯、5.3g乙酸钡和5.5g乙酸钾。最终的催化剂含2.3%的Pd、2.2%的Ba和1.9%的K（基于含载体和盐的体系）。表中列出的数据是在对比实施例1的条件下得到的。
实施例2
用一种溶液浸渍对比实施例1采用的载体并干燥。该溶液为在78.5ml的冰醋酸中含5.6g乙酸钯、1.1g乙酸钡和5.5g乙酸钾。最终的催化剂含2.3%的Pd、0.5%的Ba和1.9%的K（基于含载体和盐的体系）。在对比实施例1的条件下获得的数据列在表中。
表
对比实施例 实施例
1 2 1 2
STY(g/l xh) 839 790 840 780
燃烧率（％） 5.4 4.6 6 4
乙酸乙酯含量 190 218 20 80
(ppm)
“STY”表示时空产率;“燃烧率（%）”表示反应的乙烯转化为CO2的百分率;“乙酸乙酯的含量”为在反应产物的冷凝部分中乙酸乙酯的含量。
Claims (4)
1、一种制备乙酸乙烯酯的方法，该方法为在一种催化剂上，从乙烯、乙酸和氧气或含氧气体中气相地制备乙酸乙烯酯，该催化剂为在载体上负载钯和/或其化合物和碱金属化合物，其中该催化剂至少含一种钡化合物，并且在该催化剂中不含金和镉和其化合物。
2、权利要求1所述的方法，其中该催化剂至少含一种钾化合物。
3、权利要求1或2所述的方法，其中基于催化剂总量，该催化剂含0.1-10m%的钡。
4、权利要求1-3之一所述的方法，其中基于催化剂总量，该催化剂含0.2-4m%的钡。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4120491 | 1991-06-21 | ||
| DEP4120491.3 | 1991-06-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1068104A true CN1068104A (zh) | 1993-01-20 |
Family
ID=6434436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92104828A Pending CN1068104A (zh) | 1991-06-21 | 1992-06-20 | 制备乙酸乙烯酯的催化剂和方法 |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0519436A1 (zh) |
| JP (1) | JPH05186393A (zh) |
| KR (1) | KR930000463A (zh) |
| CN (1) | CN1068104A (zh) |
| AU (1) | AU1835392A (zh) |
| BG (1) | BG96466A (zh) |
| BR (1) | BR9202324A (zh) |
| CA (1) | CA2071698A1 (zh) |
| CZ (1) | CZ190492A3 (zh) |
| MX (1) | MX9203015A (zh) |
| PL (1) | PL294868A1 (zh) |
| TW (1) | TW213869B (zh) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1090534C (zh) * | 1996-04-04 | 2002-09-11 | 人造丝有限公司 | 用于制备乙酸乙烯酯的方法和催化剂 |
| CN1101728C (zh) * | 1997-12-11 | 2003-02-19 | 人造丝化学欧洲有限公司 | 基于钯、金、碱金属和镧系元素的催化剂以及制备乙酸乙烯酯的方法 |
| CN1104281C (zh) * | 1997-12-12 | 2003-04-02 | 国际人造丝公司 | 含有钯、金、铜和某些第四种金属的醋酸乙烯酯催化剂 |
| CN1104952C (zh) * | 1997-10-30 | 2003-04-09 | 国际人造丝公司 | 用第三种金属掺杂的含钯、金的载体催化剂及生产醋酸乙烯酯的方法 |
| CN1109578C (zh) * | 1999-05-26 | 2003-05-28 | 冯士光 | 一种汽车排气净化催化剂及其净化装置 |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4323980C1 (de) * | 1993-07-16 | 1995-03-30 | Hoechst Ag | Palladium und Kalium sowie Cadmium, Barium oder Gold enthaltender Schalenkatalysator, Verfahren zu dessen Herstellung sowie dessen Verwendung zur Herstellung von Vinylacetat |
| DE4323978C1 (de) * | 1993-07-16 | 1995-02-16 | Hoechst Ag | Palladium und Kalium sowie Cadmium, Barium oder Gold enthaltender Schalenkatalysator, Verfahren zu dessen Herstellung sowie dessen Verwendung zur Herstellung von Vinylacetat |
| DE4323981C1 (de) * | 1993-07-16 | 1995-03-09 | Hoechst Ag | Palladium und Kalium sowie Cadmium, Barium oder Gold enthaltender Schalenkatalysator, Verfahren zu dessen Herstellung sowie dessen Verwendung zur Herstellung von Vinylacetat |
| CA2135021A1 (en) * | 1993-11-19 | 1995-05-20 | David J. Gulliver | Process for the preparation of catalysts for use in the production of vinyl acetate |
| DE69514283T3 (de) * | 1994-06-09 | 2008-01-24 | Institut Français du Pétrole | Verfahren zur katalytischen Hydrierung und in diesem Verfahren zur verwendender Katalysator |
| FR2720957B1 (fr) * | 1994-06-09 | 1996-08-30 | Inst Francais Du Petrole | Catalyseur d'hydrogénation contenant du palladium et au moins un métal alcalin ou alcalino terreux et procédé d'hydrogénation utilisant ce catalyseur. |
| SG101929A1 (en) * | 1999-12-29 | 2004-02-27 | Dairen Chemical Corp | Catalyst for oxacylation and use of the same |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA954875A (en) * | 1963-09-12 | 1974-09-17 | National Distillers And Chemical Corporation | Catalyst activation in process for preparing esters |
| FR1546361A (fr) * | 1967-04-29 | 1968-11-15 | Sir Soc Italiana Resine Spa | Procédé pour la préparation d'esters insaturés |
| ES362221A1 (es) * | 1967-12-28 | 1970-12-01 | Nat Distillers Chem Corp | Procedimiento para la preparacion de acetato de vinilo. |
| JPS4837245B1 (zh) * | 1969-10-02 | 1973-11-09 | ||
| US3939199A (en) * | 1971-01-06 | 1976-02-17 | Hoechst Aktiengesellschaft | Oxacylation of olefins in the gaseous phase |
| JPS5917098B2 (ja) * | 1979-01-17 | 1984-04-19 | ジェイエスアール株式会社 | 共役ジエンモノエステルの製造方法 |
| US4550097A (en) * | 1984-08-20 | 1985-10-29 | Phillips Petroleum Company | Catalyst for the production of allyl acetate |
-
1992
- 1992-06-01 TW TW081104277A patent/TW213869B/zh active
- 1992-06-11 PL PL29486892A patent/PL294868A1/xx unknown
- 1992-06-15 BG BG96466A patent/BG96466A/xx unknown
- 1992-06-17 EP EP92110247A patent/EP0519436A1/de not_active Withdrawn
- 1992-06-19 KR KR1019920010650A patent/KR930000463A/ko not_active Withdrawn
- 1992-06-19 BR BR929202324A patent/BR9202324A/pt not_active Application Discontinuation
- 1992-06-19 AU AU18353/92A patent/AU1835392A/en not_active Abandoned
- 1992-06-19 MX MX9203015A patent/MX9203015A/es unknown
- 1992-06-19 CZ CS921904A patent/CZ190492A3/cs unknown
- 1992-06-19 CA CA002071698A patent/CA2071698A1/en not_active Abandoned
- 1992-06-19 JP JP4161359A patent/JPH05186393A/ja not_active Withdrawn
- 1992-06-20 CN CN92104828A patent/CN1068104A/zh active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1090534C (zh) * | 1996-04-04 | 2002-09-11 | 人造丝有限公司 | 用于制备乙酸乙烯酯的方法和催化剂 |
| CN1104952C (zh) * | 1997-10-30 | 2003-04-09 | 国际人造丝公司 | 用第三种金属掺杂的含钯、金的载体催化剂及生产醋酸乙烯酯的方法 |
| CN1101728C (zh) * | 1997-12-11 | 2003-02-19 | 人造丝化学欧洲有限公司 | 基于钯、金、碱金属和镧系元素的催化剂以及制备乙酸乙烯酯的方法 |
| CN1104281C (zh) * | 1997-12-12 | 2003-04-02 | 国际人造丝公司 | 含有钯、金、铜和某些第四种金属的醋酸乙烯酯催化剂 |
| CN1109578C (zh) * | 1999-05-26 | 2003-05-28 | 冯士光 | 一种汽车排气净化催化剂及其净化装置 |
Also Published As
| Publication number | Publication date |
|---|---|
| MX9203015A (es) | 1992-12-01 |
| BG96466A (en) | 1994-03-31 |
| KR930000463A (ko) | 1993-01-15 |
| TW213869B (zh) | 1993-10-01 |
| CZ190492A3 (en) | 1993-01-13 |
| AU1835392A (en) | 1993-03-11 |
| PL294868A1 (en) | 1993-02-22 |
| CA2071698A1 (en) | 1992-12-22 |
| JPH05186393A (ja) | 1993-07-27 |
| EP0519436A1 (de) | 1992-12-23 |
| BR9202324A (pt) | 1993-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100213843B1 (ko) | 캐리어촉매, 이의 제조방법 및 비닐 아세테이트 제조에 있어서의 이의 용도 | |
| EP0004079B1 (de) | Träger-Katalysator für die Herstellung von Vinylacetat aus Ethylen, Essigsäure und Sauerstoff in der Gasphase | |
| US4902823A (en) | Process for the preparation of vinyl acetate | |
| CN1046215C (zh) | 一种含有第ⅲa族和第ⅷ族金属的选择加氢催化剂及用途 | |
| CN1068104A (zh) | 制备乙酸乙烯酯的催化剂和方法 | |
| CZ298441B6 (cs) | Katalyzátor pro výrobu vinylacetátu a zpusob výroby vinylacetátu | |
| RU2202411C2 (ru) | Катализатор синтеза винилацетата, содержащий палладий, золото, медь и определенный четвертый металл | |
| IE42499B1 (en) | Process for the preparation of a palladium catalyst | |
| EP1308442A1 (en) | Catalyst and process for the production of ethylene oxide | |
| SK18242000A3 (sk) | Spôsob prípravy katalyzátora na výrobu vinylacetátu a spôsob výroby vinylacetátu | |
| FR2742679A1 (fr) | Catalyseur d'hydrogenation selective et procede utilisant ce catalyseur | |
| US5225388A (en) | Method for making a catalyst | |
| US6649789B2 (en) | Catalyst based on palladium, gold, alkali metal and lanthanoid and process for preparing vinyl acetate | |
| JP2854143B2 (ja) | 酢酸ビニルの製造方法 | |
| JP2911547B2 (ja) | 酢酸ビニルの製造方法 | |
| JP4069242B2 (ja) | 金属粒子担持体及びカルボン酸エステルの製造方法 | |
| CN1078199C (zh) | 制备醋酸乙烯酯的催化剂和方法 | |
| US6346501B1 (en) | Catalyst based on palladium, cadmium, alkali and lanthanoids and a method for producing vinyl acetate | |
| JP3285655B2 (ja) | タルトロン酸塩の製造方法 | |
| JP3422062B2 (ja) | ジアセトキシブテンの製造方法 | |
| CN1171848C (zh) | 生产醋酸乙烯酯的方法 | |
| JPS59227831A (ja) | 酸素含有炭化水素化合物の製造方法 | |
| CN1340496A (zh) | 采用高活性催化剂的乙烯法制备醋酸乙烯酯的方法 | |
| JP2001163830A (ja) | フェニルエステルの製造方法及び触媒 | |
| JPS6319492B2 (zh) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |