CN1829674A - 氢化分解含有多元醇的反应混合物中的甲酸铵的方法 - Google Patents
氢化分解含有多元醇的反应混合物中的甲酸铵的方法 Download PDFInfo
- Publication number
- CN1829674A CN1829674A CNA2004800220241A CN200480022024A CN1829674A CN 1829674 A CN1829674 A CN 1829674A CN A2004800220241 A CNA2004800220241 A CN A2004800220241A CN 200480022024 A CN200480022024 A CN 200480022024A CN 1829674 A CN1829674 A CN 1829674A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- weight
- catalyzer
- ruthenium
- tmp
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 69
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical group [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 title description 4
- 239000011541 reaction mixture Substances 0.000 title description 4
- 229920005862 polyol Polymers 0.000 title 1
- 150000003077 polyols Chemical class 0.000 title 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 47
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 125000005208 trialkylammonium group Chemical group 0.000 claims abstract description 26
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 21
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 37
- 238000005984 hydrogenation reaction Methods 0.000 claims description 22
- -1 methylol alkane Chemical class 0.000 claims description 20
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000010306 acid treatment Methods 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000007789 gas Substances 0.000 abstract description 5
- 230000036571 hydration Effects 0.000 abstract 1
- 238000006703 hydration reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000009835 boiling Methods 0.000 description 10
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 8
- MCXYTDHHOJAPGI-UHFFFAOYSA-N 2-(dihydroxymethyl)butanal Chemical compound CCC(C=O)C(O)O MCXYTDHHOJAPGI-UHFFFAOYSA-N 0.000 description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 125000005270 trialkylamine group Chemical group 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000004255 ion exchange chromatography Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229940059574 pentaerithrityl Drugs 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- UBUYAZUEYAXMBU-UHFFFAOYSA-N azane;n,n-dimethylmethanamine Chemical compound N.CN(C)C UBUYAZUEYAXMBU-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- YYKMQUOJKCKTSD-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanal Chemical compound CCC(CO)(CO)C=O YYKMQUOJKCKTSD-UHFFFAOYSA-N 0.000 description 1
- XIKVGYYSAJEFFR-UHFFFAOYSA-N 2-(hydroxymethyl)butanal Chemical compound CCC(CO)C=O XIKVGYYSAJEFFR-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-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
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QIPLUHUCBWAFNS-UHFFFAOYSA-N C(C)C(=O)C(=O)C.[Ru] Chemical compound C(C)C(=O)C(=O)C.[Ru] QIPLUHUCBWAFNS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000005705 Cannizzaro reaction Methods 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 239000012045 crude solution Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002912 waste gas Substances 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
- 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
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/392—Metal surface area
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J37/06—Washing
-
- 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
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
-
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种从通过甲醛与高级醛缩合获得的羟甲基烷中除去三烷基甲酸铵的方法。本发明方法的特征在于在升高的温度下、在含氢气气体存在下、在担载于二氧化钛上的含有钌的催化剂上分解三烷基甲酸铵。该方法可以从通过有机Cannizzaro方法和通过所述氢化方法制得的羟甲基烷中分离三烷基甲酸铵。
Description
本发明涉及有机化学工业领域。更特别地,本发明提供了一种有效氢化分解三烷基甲酸铵的方法,该三烷基甲酸铵存在于羟甲基烷中,并且是由在制备羟甲基烷醛中用作催化剂的三烷基胺和作为副产物形成的甲酸形成的。
甲醛与CH-酸高级链烷醛缩合形成羟甲基烷醛(一般为二羟甲基烷醛和三羟甲基烷醛)以及将所得化合物转化为多元醇是化学工业中广泛使用的方法。以此方式得到的重要三元醇的实例是三羟甲基丙烷、三羟甲基乙烷和三羟甲基丁烷,它们广泛用于生产表面涂料、聚氨酯和聚酯。其他重要化合物是通过甲醛和乙醛缩合可获得的季戊四醇以及从异丁醛与甲醛得到的新戊二醇。四元醇季戊四醇也经常用在表面涂料工业中,但是在生产炸药中也很重要。
上述多元醇可以通过多种方法制备。一种方法是Cannizzaro方法,进一步分为无机Cannizzaro方法和有机Cannizzaro方法。在无机方案中,过量甲醛与相应链烷醛在化学计量量的无机碱例如NaOH或Ca(OH)2存在下反应。第一步中形成的羟甲基烷醛在第二步中与过量甲醛在歧化反应中反应,以形成相应的多元醇和相应碱的甲酸盐,即例如甲酸钠或甲酸钙。
在有机Cannizzaro方法中,使用叔胺(一般为三烷基胺)代替所述无机碱。如上所述进行反应,形成相应胺的1当量甲酸铵。可以通过合适的方法进一步处理,以使得至少所述胺可以被回收并返回该反应中。所得的粗制多元醇可以用多种方法处理以得到纯净的多元醇。
一种进一步的改进是其中合适的链烷醛与甲醛不是在至少化学计量量而是在催化量(一般为约5~10mol%)的叔胺存在下相互反应的氢化方法。该方法中,反应在2,2-二羟甲基烷醛阶段停止,随后通过氢化将其转化为三羟甲基烷。对有效方法的描述可以在本申请人的WO 98/28253中找到。
尤其在专利申请DE-A-2507461、DE-A-2702582、DE-A-2813201和DE-A-3340791中对该氢化方法的许多变换方案作了描述。
虽然所述氢化方法有利地不象在有机Cannizzaro方法中那样形成化学计量量的甲酸盐,但是三烷基甲酸铵会作为微小程度上作为副反应发生的交叉Cannizzaro反应的产物而形成。
三烷基甲酸铵在特定条件下反应(例如对所得的三羟甲基烷溶液脱水或加热)以形成三烷基胺和三羟甲基丙烷甲酸酯。这些会降低三羟甲基烷的产率,并难以在不发生不希望的降解反应的情况下分离。因此除去三烷基甲酸铵特别值得关注。
DE 19848569公开了一种分解作为副产物存在于通过有机Cannizzaro方法制备的三羟甲基烷溶液中的叔胺甲酸盐的方法。这些甲酸盐通过加热、优选在改性的贵金属催化剂存在和超大气压下分解为氢气和二氧化碳和/或水和一氧化碳以及叔胺。该方法中甲酸盐的转化率不能令人满意,而且还观察到形成另外的副产物。
DE 10152525公开了在多相催化剂上分解三烷基甲酸铵,该多相催化剂含有元素周期表8~12族中的至少一种金属,特别优选的是担载的含有铜、镍和/或钴的催化剂。
此外,上述方法只有限地适用于对通过以下氢化方法获得的三羟甲基烷混合物的有效处理:其中仅使用催化量的三烷基胺,并因此所述产物混合物也仅仅含有少量的三烷基甲酸铵。
本发明的目的在于提供了一种适于处理通过氢化方法获得的反应混合物以及通过有机Cannizzaro方法获得的反应混合物的方法。此外,该方法使得可以以比使用现有技术的已知方法更高的转化率分解三烷基甲酸铵。此外,该分解可以产生以工业规模易于处理的并且不会引起副反应的分解产物,从而提供更经济的制备高纯度三羟甲基丙烷的方法。
我们发现,该目的可以通过一种从甲醛与高级醛缩合获得的羟甲基烷中除去三烷基甲酸铵的方法而实现,该方法包括在升高的温度下、在含氢气气体存在下、在含有担载于二氧化钛上的钌的催化剂上分解三烷基甲酸铵。
可以通过本发明方法处理的羟甲基烷例如是新戊二醇、季戊四醇、三羟甲基丙烷、三羟甲基丁烷、三羟甲基乙烷、2-乙基-1,3-丙二醇、2-甲基-1,3-丙烷-二醇、甘油、二羟甲基丙烷、二季戊四醇和1,1-、1,2-、1,3-和1,4-环己烷二甲醇。
在本发明方法中,优选在氢化条件下从通过所述有机Cannizzaro方法或所述氢化方法制得的三羟甲基烷中除去三烷基甲酸铵。优选纯化通过所述氢化方法制备的三羟甲基烷,特别优选三羟甲基丙烷,以下简称为TMP。
通过Cannizzaro方法制备含有三烷基甲酸铵的粗制TMP例如在DE 19848569中作了公开。
在所述氢化方法中,TMP是通过正丁醛与甲醛在催化量的叔胺存在下缩合以及随后催化氢化所形成的二羟甲基丁醛混合物而获得的。该粗制TMP不含有任何碱金属或碱土金属的甲酸盐或其他在无机Cannizzaro方法中形成的杂质。同样,粗制TMP只含有少量约5~10mol%的三烷基甲酸铵或游离的三烷基胺,这不同于从有机Cannizzaro方法得到的产物。
来自所述氢化作用并对其进行本发明的纯化方法的粗制TMP含有三羟甲基丙烷和水,一起的有甲醇、三烷基胺、三烷基甲酸铵、长链的线型和支化醇以及二元醇(例如,甲基丁醇或乙基丙二醇)、甲醛和甲醇向三羟甲基丙烷上的加成产物、缩醛例如二羟甲基丁醛TMP缩醛和二-TMP。
使用含有10~40重量%三羟甲基丙烷、0~10重量%2,2-二羟甲基丁醛、0.5~5重量%甲醇、0~6重量%甲基丁醇、1~10重量%三烷基甲酸铵、0~5重量%2-乙基丙二醇、0.1~10重量%高沸点化合物(例如二-TMP或其他加成产物)和5~80重量%水的粗制氢化产物可以获得良好的结果。具有这种组成的粗制氢化产物可以例如通过WO 98/28253中描述的方法获得。在进行本发明的纯化以分解所述三烷基甲酸铵之前,可以首先通过如DE-A-199 63 435实施例2和3描述的连续蒸馏处理所述粗制氢化产物。然而,优选在不进行通过蒸馏的预先处理的情况下实施根据本发明的对所述粗制氢化产物的纯化。
本发明还提供了一种催化剂,其含有担载于二氧化钛成形体上的钌,该二氧化钛成形体是在成形前或成形后通过用0.1~30重量%的二氧化钛可微溶于其中的酸处理市售二氧化钛而得到的,该催化剂被用于本发明方法中。钌可以以纯金属形式或作为其化合物例如氧化物或硫化物使用。
通过本身已知的方法施加所述催化活性的钌,优选施加于作为载体材料的预制TiO2上。
优选用于所述含钌催化剂的二氧化钛载体可以如DE 197 38 464中所述通过在成形前或成形后使用基于二氧化钛为0.1~30重量%的所述二氧化钛可微溶于其中的酸处理市售二氧化钛而获得。优选使用锐钛矿形式的二氧化钛。合适的酸的实例是甲酸、磷酸、硝酸、乙酸和硬脂酸。
可以使用一个或多个浸渍步骤以钌盐溶液形式将所述活性成分钌施加于以这种方式获得的二氧化钛载体上。然后干燥所述被浸渍的载体,如果需要的话进行煅烧。然而,也可以优选通过碳酸钠从钌盐溶液中将钌沉淀在作为粉末存在于含水悬浮液中的二氧化钛上。洗涤所述沉淀物,干燥,如果需要的话煅烧和成形。此外,可以以本身已知的方法(化学气相沉积)将挥发性钌化合物例如乙酰丙酮钌或羰基钌成为气相并施加于所述载体上。
以此方式获得的担载催化剂可以是所有已知的成品形状。实例是挤出型材、球状物或颗粒。使用前,所述钌催化剂前体通过用含氢气气体、优选在100℃以上处理而还原。在所述催化剂用于本发明的方法之前,优选通过含氧气气体混合物、优选空气/氮气混合物在0~50℃、优选室温下使该催化剂钝化。还可以将所述催化剂以氧化形式安装在氢化反应器中,并可以在反应条件下使其还原。
基于含有催化活性金属和载体的催化剂的总重量,本发明催化剂的钌含量为0.1~10重量%,优选2~6重量%。基于所述催化剂的总重量,本发明的催化剂的硫含量可以为0.01~1重量%,通过库仑定量法测量硫。
所述钌表面积为1~20m2/g,优选5~15m2/g,BET表面积(根据DIN 66131测量的)为5~500m2/g,优选50~200m2/g。
本发明催化剂的孔体积为0.1~1ml/g。此外,所述催化剂的切削硬度为1~100N。
根据本发明用于分解存在于粗制TMP中的三烷基甲酸铵的上述担载于二氧化钛上的含钌催化剂还适用于氢化TMP的前体(2,2-二羟甲基丁醛)。
使用相同催化剂用于氢化二羟甲基丁醛和用于分解所述三烷基甲酸铵是特别经济的,因为在此情况下,三烷基甲酸铵的分解可以在WO 98/28253中描述的氢化方法的氢化反应器中进行,而不需要附加的反应器。然而,通过本发明方法分解三烷基甲酸铵可以同样在独立的反应器中进行。
在本发明方法中,三烷基甲酸铵的分解一般在100~250℃、优选120~180℃下进行。所用压力一般高于1×106Pa,优选在2×106~15×106Pa范围内。
本发明方法可以连续或间歇地进行,优选连续工艺。
在连续工艺中,来自所述氢化方法或有机Cannizzaro方法的粗制三羟甲基烷的量优选为约0.05~约3kg/l催化剂·h,更优选为约0.1~约1kg/l催化剂·h。
本发明方法在氢化条件下进行,即,使用从外部来源添加的氢化气体。
作为氢化气体,可以使用含有游离氢气并且不含有害量的催化剂毒物例如CO的任何气体。例如,可以使用来自重整装置的废气。优选使用纯氢气。
下面通过实施例来说明本发明的方法。
实施例
I.通过WO 98/28253的方法制备粗制TMP
在包括两个通过溢流管相互连接的可加热搅拌容器和总容量为72升的设备中供入新鲜的甲醛水溶液(4300g/l 40%浓度的水溶液)和正丁醛(1800g/h),并以45%浓度的水溶液形式供入作为催化剂的新鲜三甲胺(130g/h)。保持该反应器在40℃下。
将输出物直接供入具有放在上面的柱(11bar加热蒸汽)的降膜蒸发器的上部,并在大气压下对其进行分馏,以得到主要由正丁醛、乙基丙烯醛、甲醛、水和三甲胺组成的低沸点塔顶产物和高沸点塔底产物。
将塔顶产物连续浓缩并循环到上述反应器中。
将来自所述蒸发器的高沸点塔底产物(约33.5kg/h)与新鲜三甲胺催化剂(50g/h,45%浓度的水溶液)连续混合,并供入装有无规填料并且空体积为12升的可加热管式反应器中。保持该反应器在40℃下。
将来自所述后反应器的输出物连续供入另一蒸馏器的上部,就是说,除去甲醛(11bar加热蒸汽),在那里进行分馏,以得到主要由乙基丙烯醛、甲醛、水和三甲胺组成的低沸点塔顶产物和高沸点塔底产物。将所述低沸点塔顶产物(27kg/h)连续浓缩并循环到第一搅拌容器中,同时收集所述高沸点塔底产物。
以此方式得到的塔底产物主要由水以及二羟甲基丁醛、甲醛和痕量单羟甲基丁醛组成。然后将其连续氢化。为此目的,在90bar和115℃下,在以循环/下流方式操作的主反应器和以循环方式操作的下游后反应器中氢化该反应溶液。所述催化剂以类似于DE 19809418中催化剂J的方法制备。其含有40%的CuO、20%的Cu和40%的TiO2。所用设备包含10m长的被加热的主反应器(内径:27mm)和5.3m长的被加热的后反应器(内径:25mm)。围绕环路的流量为25l/h的液体,设定反应器的进料为4kg/h。因此,取出4kg/h的氢化产物。所述氢化产物具有以下组成:22.6重量%的TMP、1.93重量%的二羟甲基丁醛、1.4重量%的甲醇、1.1重量%的甲基丁醇、0.7重量%的乙基丙二醇、1.2重量%的TMP与甲醛和甲醇的加合物、<0.1重量%的TMP甲酸酯、1.2重量%的TMP-二甲基丁醛缩醛、2.9重量%的高沸点物、0.57重量%的三甲基甲酸铵和66.2重量%的水。
II.孔隙率的测量
根据DIN 66133通过压汞法测量所述催化剂的孔隙率。
III.BET表面积的测量
根据DIN 66131测量所述催化剂的BET表面积。
IV.切削硬度的测量
为了测量切削硬度,用切割器分开样品。为了切开样品而对切割器施加的力为切削硬度(N(牛顿))。
V.通过离子色谱法测量所述甲酸盐含量
根据DEV ISO 10304-2通过离子色谱法测量所述甲酸盐含量。
实施例1:Ru/TiO2催化剂的制备
将121.3g亚硝酰基硝酸钌溶液(Ru含量:10.85重量%)用水稀释到90ml.将250g如DE 19738463实施例3中描述生产的二氧化钛挤出型材(其为1.5mm挤出型材,BET表面积为104m2/g,孔隙率为0.36ml/g)用钌溶液缓慢浸渍。然后将潮湿的挤出型材在100℃下干燥2小时,在120℃下干燥16小时。通过用10标准l/h的氢气和10标准l/h的氮气在300℃下还原达4小时而使得该催化剂活化。然后在室温下通过空气/氮气混合物钝化该催化剂。
所述成品催化剂挤出型材的Ru含量为4.2重量%,BET表面积为103m2/g,孔体积为0.26ml/g,钌表面积为12m2/g,切削硬度为21.2N。
实施例1~4
所用的如上所述制备的TMP具有如下组成:22.6重量%的TMP、1.93重量%的二羟甲基丁醛、1.4重量%的甲醇、1.1重量%的甲基丁醇、0.7重量%的乙基丙二醇、1.2重量%的TMP与甲醛和甲醇的加合物、<0.1重量%的TMP甲酸酯、1.2重量%的TMP二甲基丁醛缩醛、2.9重量%的高沸点物、0.57重量%的三甲基甲酸铵和66.2重量%的水。在180℃和90bar下,在如表1给出的于180和25bar下预还原的催化剂存在下,用氢气处理180ml该粗制溶液。1小时后,通过气相色谱法测量二羟甲基丁醛的含量。通过离子色谱法测定所述甲酸盐浓度。所得结果概括于表1中。
编号 | 催化剂 | 成形体 | 催化剂量[g] | DMB3面积%1 | 甲酸盐重量%2 | 甲酸盐转化率[%] |
起始材料 | 1.93 | 0.57 | - | |||
1 | Cu/TiO2(DE 19809418) | 3×3mm球状物 | 18.6 | <0.05 | 0.39 | 32 |
2 | Ni/SiO2/Al2O3/ZrO2(EP 0672 452) | 1.5mm挤出型材 | 12.7 | <0.05 | 0.51 | 11 |
3 | Co/MnO2/P2O5(EP 0742045) | 4mm挤出型材 | 21.3 | <0.05 | 0.18 | 68 |
4 | Ru/TiO2 | 1.5mm挤出型材 | 14.8 | <0.05 | 0.006 | 99 |
1 GC分析(无水检测)
2 通过离子色谱法测量
3 DMB=2,2-二甲基丁醛
从该表可以看出,于150℃下在根据本发明使用的钌催化剂上以高转化率催化分解甲酸铵,这些催化剂比铜、镍和钴催化剂明显更有效。废气分析显示甲烷是所述甲酸盐分解作用的主要产物。
Claims (7)
1、一种从通过甲醛与高级醛缩合获得的羟甲基烷中除去三烷基甲酸铵的方法,其包括在升高的温度下、在含氢气气体存在下、在含有担载于二氧化钛上的钌的催化剂上分解三烷基甲酸铵。
2、根据权利要求1的方法,其中所述催化剂的钌含量为0.1~10重量%。
3、根据权利要求1或2的方法,其中使用通过在成形前或成形后用0.1~30重量%的二氧化钛可微溶于其中的酸处理市售二氧化钛而获得的二氧化钛成形体。
4、根据权利要求1~3中任一项的方法,其中所述方法在100~250℃下进行。
5、根据权利要求1~4中任一项的方法,其中所述方法在1×106~15×106Pa的压力下进行。
6、根据权利要求1~5中任一项的方法,其中所述方法在所述氢化工艺的氢化反应器中进行。
7、含有担载于二氧化钛成形体上的钌的催化剂,其中所述二氧化钛成形体是通过在成形前或成形后用0.1~30重量%的二氧化钛可微溶于其中的酸处理市售二氧化钛而获得的。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10334489.6 | 2003-07-29 | ||
DE10334489A DE10334489A1 (de) | 2003-07-29 | 2003-07-29 | Verfahren zur hydrierenden Zersetzung von Ammoniumformiaten in polyolhaltigen Reaktionsgemischen |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1829674A true CN1829674A (zh) | 2006-09-06 |
CN100383097C CN100383097C (zh) | 2008-04-23 |
Family
ID=34088904
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2004800220241A Expired - Fee Related CN100383097C (zh) | 2003-07-29 | 2004-07-07 | 氢化分解含有多元醇的反应混合物中的甲酸铵的方法 |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1651586A1 (zh) |
JP (1) | JP2007500138A (zh) |
KR (1) | KR20060054364A (zh) |
CN (1) | CN100383097C (zh) |
BR (1) | BRPI0412987A (zh) |
DE (1) | DE10334489A1 (zh) |
MX (1) | MXPA06000481A (zh) |
WO (1) | WO2005019145A1 (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5566450B2 (ja) * | 2009-04-07 | 2014-08-06 | ビーエーエスエフ ソシエタス・ヨーロピア | 1,6−ヘキサンジオールおよびカプロラクトンの製造方法 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1952738A1 (de) * | 1968-12-17 | 1970-07-09 | Leuna Werke Veb | Verfahren zur Herstellung von Trimethylolpropan |
DE3217751A1 (de) * | 1982-05-12 | 1983-11-17 | Degussa Ag, 6000 Frankfurt | Presslinge aus pyrogen hergestelltem titandioxid, verfahren zu ihrer herstellung sowie ihre verwendung |
US4647592A (en) * | 1984-01-05 | 1987-03-03 | Exxon Research & Engineering Company | Start-up with ruthenium catalysts |
DE3715035A1 (de) * | 1987-05-06 | 1988-11-17 | Basf Ag | Verfahren zur gewinnung von trialkylaminen und methylformiat bei der herstellung von trimethylolalkanen |
US5484757A (en) * | 1994-06-02 | 1996-01-16 | Norton Chemical Process Products Corp. | Titania-based catalyst carriers |
JPH11504255A (ja) * | 1995-04-17 | 1999-04-20 | エンゲルハード・コーポレーシヨン | 成形組成物 |
DE19530528C2 (de) * | 1995-08-19 | 1998-12-10 | Dornier Gmbh | Verwendung eines Ru/TiO¶2¶-Metall-Trägerkatalysators für die Methanisierung von Kohlendioxid |
WO1999011615A1 (de) * | 1997-09-03 | 1999-03-11 | Basf Aktiengesellschaft | Als katalysator geeignete formmassen |
JPH11124348A (ja) * | 1997-10-22 | 1999-05-11 | Koei Chem Co Ltd | トリメチロールアルカンを製造する方法 |
US6235797B1 (en) * | 1999-09-03 | 2001-05-22 | Battelle Memorial Institute | Ruthenium on rutile catalyst, catalytic system, and method for aqueous phase hydrogenations |
DE10152525A1 (de) * | 2001-10-24 | 2003-05-08 | Basf Ag | Verfahren zur Zersetzung von Ammoniumformiaten in polyolhaltigen Reaktionsgemischen |
-
2003
- 2003-07-29 DE DE10334489A patent/DE10334489A1/de not_active Withdrawn
-
2004
- 2004-07-07 EP EP04740714A patent/EP1651586A1/de not_active Withdrawn
- 2004-07-07 MX MXPA06000481A patent/MXPA06000481A/es active IP Right Grant
- 2004-07-07 BR BRPI0412987-3A patent/BRPI0412987A/pt not_active IP Right Cessation
- 2004-07-07 CN CNB2004800220241A patent/CN100383097C/zh not_active Expired - Fee Related
- 2004-07-07 KR KR1020067001926A patent/KR20060054364A/ko not_active Application Discontinuation
- 2004-07-07 WO PCT/EP2004/007396 patent/WO2005019145A1/de active Application Filing
- 2004-07-07 JP JP2006521423A patent/JP2007500138A/ja not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
CN100383097C (zh) | 2008-04-23 |
MXPA06000481A (es) | 2006-04-05 |
KR20060054364A (ko) | 2006-05-22 |
EP1651586A1 (de) | 2006-05-03 |
WO2005019145A1 (de) | 2005-03-03 |
BRPI0412987A (pt) | 2006-10-03 |
DE10334489A1 (de) | 2005-02-24 |
JP2007500138A (ja) | 2007-01-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1021636C (zh) | 用于醛加氢的改性的铜-氧化锌催化剂 | |
EP2349972B1 (en) | Integrated process for the production of vinyl acetate from acetic acid via ethylene | |
CA2968981C (en) | Process for production of hexanetriol from 5-hydroxymethylfurfural | |
EP2015860B1 (en) | Process for the removal of hydrogen cyanide and formic acid from synthesis gas | |
Zhang et al. | The cascade synthesis of α, β-unsaturated ketones via oxidative C–C coupling of ketones and primary alcohols over a ceria catalyst | |
RU2736494C2 (ru) | Способ получения метанола | |
CN102388009A (zh) | 生产1,6-己二醇的方法 | |
CN101945847A (zh) | 生产6-羟基己酸酯的方法 | |
Joo et al. | Migration and reduction of formate to form methanol on CuZnO catalysts | |
US4628128A (en) | Process for the preparation of ethylene glycol by catalytic hydrogenation | |
CN1181025C (zh) | 通过氢化改进多元醇的比色指数 | |
CN111465591A (zh) | 使用非均相催化剂通过氧化酯化产生甲基丙烯酸甲酯的方法 | |
CN1429217A (zh) | 使烃环氧化的方法 | |
CN100383097C (zh) | 氢化分解含有多元醇的反应混合物中的甲酸铵的方法 | |
US3404098A (en) | Platinum group metal catalysts supported on rare earth carbonates | |
CN1260193C (zh) | 甲酸铵在含有多元醇的反应混合物中的分解方法 | |
EP0778257B1 (en) | Process for producing benzyl acetate and benzyl alcohol | |
Cheng et al. | Selective Upcycling of Polyethylene Terephthalate towards High‐valued Oxygenated Chemical Methyl p‐Methyl Benzoate using a Cu/ZrO2 Catalyst | |
Ischia et al. | Synthesis, characterization and photocatalytic activity of TiO 2 powders prepared under different gelling and pressure conditions | |
US20070197837A1 (en) | Method for the hydrodecomposition of ammonium formates in polyolcontaining reaction mixtures | |
CN1191227C (zh) | 一种丁酸丁酯的制备方法 | |
CN106103394B (zh) | 甲酸盐分解的方法 | |
CN1267633A (zh) | 笑气的制备方法 | |
KR102639461B1 (ko) | 글리세롤의 프로판올로의 촉매 전환 방법 | |
JPS5929170B2 (ja) | β−フエニルエチルアルコ−ルおよび酢酸β−フエニルエチルの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080423 Termination date: 20090807 |