WO1995010497A1 - Procede de production d'un diol - Google Patents
Procede de production d'un diol Download PDFInfo
- Publication number
- WO1995010497A1 WO1995010497A1 PCT/JP1994/001664 JP9401664W WO9510497A1 WO 1995010497 A1 WO1995010497 A1 WO 1995010497A1 JP 9401664 W JP9401664 W JP 9401664W WO 9510497 A1 WO9510497 A1 WO 9510497A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- reaction
- carboxylic acid
- acid
- mixture
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 33
- -1 diol compound Chemical class 0.000 title claims description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 129
- 239000000203 mixture Substances 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 25
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 239000005751 Copper oxide Substances 0.000 claims abstract description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007791 liquid phase Substances 0.000 claims abstract description 10
- 239000011787 zinc oxide Substances 0.000 claims abstract description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011541 reaction mixture Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 61
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 13
- 238000005886 esterification reaction Methods 0.000 claims description 12
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 9
- 150000001735 carboxylic acids Chemical class 0.000 claims description 9
- 239000001361 adipic acid Substances 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims description 7
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 5
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 239000012374 esterification agent Substances 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 12
- 238000007327 hydrogenolysis reaction Methods 0.000 abstract description 11
- 150000002009 diols Chemical class 0.000 abstract description 8
- 150000002148 esters Chemical class 0.000 abstract description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052804 chromium Inorganic materials 0.000 abstract description 4
- 239000011651 chromium Substances 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 30
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229940043375 1,5-pentanediol Drugs 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229940005605 valeric acid Drugs 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- PNPPVRALIYXJBW-UHFFFAOYSA-N 6-oxohexanoic acid Chemical compound OC(=O)CCCCC=O PNPPVRALIYXJBW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- IAJILQKETJEXLJ-QTBDOELSSA-N aldehydo-D-glucuronic acid Chemical compound O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O IAJILQKETJEXLJ-QTBDOELSSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- SIDJSMSAPAAIAM-UHFFFAOYSA-N dioxane-3,3-diol Chemical compound OC1(O)CCCOO1 SIDJSMSAPAAIAM-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229940097043 glucuronic acid Drugs 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000006194 liquid suspension Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 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
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
Definitions
- the present invention relates to a method for esterifying a carboxylic acid mixture separated from a liquid-phase air oxidation reaction solution of cyclohexane, and then hydrolyzing the resulting esterified product with hydrogen to obtain 1,6-hexanediol, It relates to a method for producing diol compounds such as 1,5-pentanediol and 1,4-butanediol.
- diol compounds such as 1,5-pentanediol and 1,4-butanediol.
- Such a diol compound is a useful compound used for a polyurethane elastomer, a synthetic resin additive, a pharmaceutical and agricultural chemical intermediate, and the like.
- Cyclohexanol and cyclohexanone which are useful as synthetic raw materials for ⁇ -caprolactam, are produced industrially by liquid-phase air oxidation of cyclohexane.
- Diol compounds such as xandiol are produced by esterifying a carboxylic acid mixture, which is a by-product of this oxidation reaction, with alcohol, and then hydrolyzing the resulting ester with hydrogen.
- carboxylic acids are produced as by-products, for example, capronic acid, valeric acid, butyric acid, propionic acid, and acetic acid as monobasic acids.
- Adipic acid, glutaric acid, succinic acid, etc. are generated as basic acids, and ⁇ -oxocaproic acid or its cyclized product, ie, ⁇ -caprolactone, is generated as oxyacid.
- a mixture of these carboxylic acids is obtained by extracting the above oxidation reaction solution with water or by adding sodium hydroxide or sodium carbonate aqueous solution. It is known that they are separated and recovered by washing with a solution (for example, see catalyst,, 5, 341 (1991)).
- the water-extracted carboxylic acid mixture is esterified with an alcohol, particularly a diol such as 1,6-hexanediol, and then hydrogenated.
- an alcohol particularly a diol such as 1,6-hexanediol
- the esterified product is hydrogenolyzed with hydrogen at a reaction temperature of 200 to 350 ° C under a pressure higher than atmospheric pressure, and diol is obtained from the obtained reaction solution.
- a method for separating species is known (see Japanese Patent Publication No. 49-27164).
- the sodium salt of carboxylic acid obtained by the above-described alkaline washing is neutralized to form a mixture of a carboxylic acid mainly composed of adipic acid and oxyproproic acid.
- a method is also known in which the esterified product is hydrogenolyzed with hydrogen at a reaction temperature of 240 to 290 ° C. under a pressure of g / cm 2 to obtain a diol compound (see Japanese Patent Publication No. 53-33567).
- the resulting esterified product is hydrogenolyzed with hydrogen to form a diol such as 1,6-hexanediol.
- an alcohol containing a diol as a reaction product as a main component is used as an esterifying agent.
- esterification of the above carboxylic acid mixture without a catalyst requires a high temperature of 200 ° C or higher, and the reaction is carried out under high pressure when monohydric alcohols such as methanol and ethanol are used. This is because industrially, equipment costs are high and the danger is high, which is not desirable. Also, a catalyst such as sulfuric acid must be used to perform esterification at lower temperatures. It may be used, but in this case, problems such as separation of the catalyst and treatment of the waste liquid occur, so that it is not preferable as an industrial production method.
- diols such as 1,6-hexanediol and the like can be used as esterifying agents because they have a significantly higher boiling point than lower monovalent alcohols and can be esterified under normal pressure and no catalyst conditions.
- Compounds are preferably used.
- a hydrogenolysis reaction solution containing 50% or more of a 1,6-hexanediol or other diol compound is itself a target substance, and therefore, when another alcohol is used for esterification, The necessary separation operation can be omitted, and it is more preferably used.
- the resulting esterified product is hydrogenolyzed with hydrogen to form a diol compound such as 1,6-hexanediol.
- a copper-chromium-based catalyst is widely used as a hydrogenation catalyst.
- this copper-chromium catalyst contains harmful chromium.
- Special dust-proofing is required for the handling of the catalyst, and the treatment of wastewater and wastewater discharged in the process is necessary. It has disadvantages such as the need for special equipment.
- the reaction is performed under the conditions of liquid suspension. In this case, since the catalyst components partially dissolve in the reaction solution, there is a problem in the treatment of the distillation bottom after distilling and separating diol compounds such as 1,6-hexanediol from the reaction solution. ing.
- JP-A-63-141937 proposes a method for producing lauryl alcohol from methyl laurate using a catalyst comprising copper oxide and zinc oxide.
- a catalyst comprising copper oxide and zinc oxide.
- the activity of the catalyst is higher than that of the copper-chromium catalyst, but there is a problem that its filtration and separation properties are extremely low. are doing.
- Japanese Patent Publication No. 58-50775 proposes a method for producing a corresponding alcohol from coconut fatty acid methyl ester using a catalyst in which copper oxide and iron oxide are supported on aluminum oxide. I have. However, when this catalyst is applied to the above-mentioned production of 1,6-hexanediol, there is a problem that the filtration and separation of this catalyst is equivalent to that of a copper-chromium catalyst, but its activity is considerably low. Have. Disclosure of the invention
- the present invention relates to a method for producing a diol compound by esterifying a mixture of carboxylic acids separated from a liquid-phase air oxidation reaction solution of cyclohexane and then hydrocracking the resulting ester with hydrogen to produce a diol compound.
- Highly efficient, industrially efficient production of diol compounds using a hydrogenation catalyst that is easy to separate by filtration and contains no harmful chromium It is intended to provide a method.
- the present inventors have conducted intensive studies on a known chromium-free copper-based catalyst to achieve the above object, and as a result, carried out a hydrocracking reaction using a known chromium-free copper-based catalyst in combination. Then, surprisingly, they found that the activity of the catalyst was extremely high, and it was found that filtration and separation of the catalyst from the reaction solution were extremely easy, thereby completing the present invention.
- the method for producing a diol compound of the present invention comprises the steps of esterifying a carboxylic acid mixture separated from a liquid air oxidation reaction solution of cyclohexane with an alcohol, and hydrolyzing the resulting ester with hydrogen.
- a catalyst containing copper oxide and zinc oxide as main components hereinafter referred to as catalyst (A)
- a catalyst in which copper oxide and iron oxide are supported on aluminum oxide hereinafter referred to as catalyst (B)
- catalyst (A) a catalyst containing copper oxide and zinc oxide as main components
- catalyst (B) a catalyst in which copper oxide and iron oxide are supported on aluminum oxide
- the combination of catalyst (A) and catalyst (B) will be referred to as combined catalyst in the presence of a combined catalyst comprising: is there.
- the combined catalyst can be efficiently separated from the hydrogenolysis reaction mixture by filtration.
- 2A and 2B show the particle size distribution of the catalyst (A) described in Comparative Example 3 before and after the reaction, respectively.
- 3A and 3B show the particle size distribution of the catalyst (B) described in Comparative Example 2 before and after the reaction, respectively.
- the carboxylic acid mixture used in the present invention is prepared by subjecting cyclohexane to liquid phase air oxidation to produce cyclohexanol and cyclohexanone. It is separated and recovered by the method described in (1).
- monobasic acids such as cabronic acid, valeric acid and butyric acid, adipic acid, glutaric acid, and After separating an aqueous phase containing a dibasic acid such as succinic acid and an oxyacid such as oxycabroic acid as a main component, the aqueous phase is concentrated to obtain cyclohexanol and cyclohexane. Hexanone and a carboxylic acid mixture containing almost no monobasic acid can be recovered.
- the cyclohexanone oxidation reaction solution is washed with an aqueous sodium hydroxide solution, and the washing solution is neutralized with dilute sulfuric acid. Then, by extracting and concentrating with methylisobutyl ketone, a carboxylic acid mixture containing dibasic acids such as adipic acid, glutaric acid and succinic acid and oxyacids such as oxycabroic acid as a main component is obtained. They can also be collected.
- the esterified product used in the present invention is a mixture of a dibasic acid such as adipic acid, glutaric acid, and succinic acid, and a carboxylic acid containing an oxyacid such as oxycaproic acid, which is separated and recovered by the method described above.
- a dibasic acid such as adipic acid, glutaric acid, and succinic acid
- a carboxylic acid containing an oxyacid such as oxycaproic acid
- the alcohol may be, for example, a monohydric alcohol such as methanol, ethanol, propanol, and butanol, or 1,4-butanediol, 1,5 — Pentanediol, and 1,6-hexanediol Diols such as phenols can be used.
- 1,6-hexanediol in order to carry out the esterification under conditions of normal pressure and no catalyst, it is necessary to use a remarkably high boiling alcohol without using a lower alcohol. It is preferable to use 1,6-hexanediol, and particularly preferably, the above esterified product hydrogenolysis reaction solution containing 50% or more of 1,6-hexanediol is used.
- the amount of alcohol used in the esterification reaction is such that the hydroxyl group of the alcohol is 1.2 to 1.5 times equivalent to the acid value (AV value) of the raw sulfonic acid mixture. Is set. If this ratio is less than 1.2 times, the esterification reaction rate will be too slow to complete the reaction, and the resulting esterification reaction mixture will have a high AV value and will be used as a raw material for hydrocracking. would be undesirable. If the AV value of the esterified compound is 5 mg-KOH / g or more, the action of the acidic substance significantly dissolves the components of the hydrogenation catalyst and reduces the activity. If the ratio is more than 1.5 times, the reaction is not hindered, but the processing volume of the reaction solution increases and the equipment becomes large, requiring a large amount of energy to recover the target diol compound. Become like
- the AV value of the reaction solution is 5 mg—KOH or less, preferably 2 mg—KOH / It is preferable to carry out the reaction until the amount becomes less than g. Since the esterification reaction is a flat mouth reaction, the reaction can be completed quickly if the generated water is removed by vaporization with an inert gas such as nitrogen gas.
- the hydrocracking reaction of the present invention is carried out by hydrocracking the ester obtained as described above with hydrogen.
- This hydrocracking reaction is usually carried out at a reaction temperature of 250 to 300 ° C, preferably 270 to 300 ° C, and a hydrogen pressure of 200 to 300 kg at the above reaction temperature. / cm 2 , preferably 250-300 kg cm 2 . If the reaction temperature is higher than 300 ° C, the amount of by-product water increases, and if the hydrogen pressure is higher than 300 kg / cm 2, it is not preferable because the safety of the device must be considered.
- the above-mentioned catalyst is used in the presence of a catalyst (A) containing copper oxide and zinc oxide as main components and a catalyst (B) in which copper oxide and iron oxide are supported on aluminum oxide.
- a hydrogenolysis reaction of the esterified product with hydrogen is performed.
- Examples of the catalyst (A) used in the hydrocracking reaction of the method of the present invention include a methanol synthesis catalyst, a cyclohexanol dehydrogenation catalyst, a CO low-temperature conversion catalyst, and a gas purification for removing hydrogen sulfide or CO.
- a commercially available copper-zinc catalyst can be used as the catalyst.
- Each of these catalysts contains copper oxide and zinc oxide as main components, but may contain carriers or binders such as alumina and clay.
- the catalyst (A) When the catalyst (A) is supplied as a molded article, it can be used by pulverizing it. When it is supplied as a powder, it can be used as it is. In each case, the particle size of the catalyst (A) powder is under a 200 mesh sieve, preferably having an average particle size of 1 to 50 m, and having an average particle size of 2 to 20 m. But more preferred.
- a catalyst (A) which is preferably used, for example, a gas which is commercially available from BASF Corporation purification catalyst R 3 - 12 (pellet molding composition: CuO 40% - ⁇ 40% - ⁇ 1 2 0 3 20%), and a low-temperature CO conversion catalyst G — 66 G (pellet molded product, composition: 30% CuO—60% ZnO—10% viscous material) commercially available from Nissan Guardola Co., Ltd. And a powder under a 200 mesh sieve
- the catalyst (B) used in the method of the present invention is described in A known catalyst prepared according to the methods disclosed in JP-A-7287, JP-B-58-50775, JP-A-52-156192 and the like, wherein copper oxide and iron oxide are supported on aluminum oxide Can be used.
- the average particle size of the catalyst is usually preferably 5 to 15 m.
- the above-mentioned catalyst is particularly suitable for the present invention because it contains copper as an active ingredient and is easily filtered and separated by itself.
- the dispersion of copper oxide is extremely good due to the action of zinc oxide, a part of the copper component is easily dissolved in the reaction solution, and this copper component is reduced with hydrogen during the reaction.
- the particle size of the copper component which is the active ingredient, becomes extremely small. As a result, the activity of the catalyst will be high, but it will be difficult to remove it by filtration.
- the filterability of the catalyst (B) is improved by the presence of iron oxide and aluminum oxide, but the activity is considered to be lower because the dispersibility of copper oxide is inferior to that of the catalyst (A).
- the copper component of the catalyst (A) is once dissolved during the reaction, and the co-existing copper component of the catalyst (B) is easily removed by filtration. It is conceivable that they are deposited, thereby increasing the activity of the combined catalyst and, at the same time, facilitating removal by filtration. This is inferred from the measurement of the particle size distribution of the catalyst, as shown in Figs. 1 to 3, where the particle size of the combined catalyst is larger after use than before use. Therefore, it is clear that the combination catalyst, the catalyst (A) and the catalyst (B) act as a catalyst having novel properties different from those of the catalyst (B).
- the hydrocracking reaction in the method of the present invention can be carried out in a general liquid phase suspension bed apparatus.
- the reaction can be carried out by a batch type reaction in which the raw material esterified product and the combined catalyst are charged into a pressure-resistant reactor, and the mixture is heated to a reaction temperature while being stirred under hydrogen pressure.
- a continuous reaction in which a combined catalyst is suspended in the esterified material as a raw material in advance, heated under hydrogen pressure, and then continuously introduced into the lower part of the reactor to carry out the reaction, can also be carried out.
- the amount of the combined catalyst used is usually preferably 0.1 to 3.0% by weight, more preferably 0.3 to 1.5% by weight, based on the esterified material. .
- the catalyst (combined catalyst) is separated by filtration from the reaction solution.
- the filtration can be easily performed using a usual filtration device, for example, a filter set filtration device.
- a diol compound such as 1,6-hexanediol can be easily separated by distillation from a reaction solution obtained by filtration, for example, using an ordinary vacuum distillation apparatus.
- 1,6-hexanediol, 1,5-pentanediol, 1,4-butanediol, etc. can be obtained as target products.
- the carboxylic acid mixture used in each Example and Comparative Example was prepared by a water extraction method from the liquid-phase air oxidation reaction solution of Hexahexane described in JP-B-49-27164.
- the extracted carboxylic acid mixture contained 26.8% by weight of adipic acid, 31.9% by weight of oxycaproic acid, 6.1% by weight of glucuronic acid, and 1.2% by weight of succinic acid.
- the esterified product of the carboxylic acid mixture was prepared by esterifying 1000 kg of the corresponding carboxylic acid mixture with 850 kg of a hydrogenolysis reaction solution containing 50% or more of 6-hexanediol.
- the obtained ester contains 3.1% by weight of 1,6-hexanediol, 1.1% by weight of 5-pentanediol and 0.06% by weight of 1,4-butanediol, and has an acid value (AV) of 0.8.
- mg—KOH Z g and its gentification value (SV) was 343 mg—KOH Z g.
- the hydrocracking reaction solution was prepared by the method described in Example 1 of JP-A-3-115237, and was composed of 61.1% by weight of 1,6-hexanediol and 1,5-pentane. It contained 8.5% by weight of diol and 0.8% by weight of -1,4-butanediol.
- catalyst (A) a gas which is commercially available from BASF Corporation purification catalyst R 3 one 12 (Perez DOO molding composition: CuO A0% - 40% ZnO - A1 2 0 3 20%) was triturated 200 mesh A fine powder (average particle size of 8.3 ⁇ m before reaction) passed through a sieve was prepared, and was prepared as a catalyst (B) by the method described in JP-B-58-50775, Example 1, CuO 30% -Fe 2 0 3 30 % - AI2O3 consisting of 40% powder of the catalyst (before reaction average particle size 9.7 zm) was prepared.
- the particle size of the combined catalyst is determined by washing the combined catalyst separated by the filtration operation with a small amount of methanol, drying, dispersing in ethanol, and centrifugal sedimentation type particle size distribution analyzer (SA-CA3: Shimadzu Corporation) Was used for the measurement.
- Table 1 shows the results of the analysis.
- a low-temperature CO conversion catalyst G-66G (a pellet molded product, commercially available from Nissan Gasdora Co., Ltd., composition: CuO 30% —ZnO 60) % —Viscosity material 10%) and used as fine powder (average particle size before reaction 6.7 01) passed through a 200 mesh sieve, and catalysts (A) and (B) The same reaction and analysis as in Example 1 were performed, except that the mixing weight ratio was changed as described in Table 1. Table 1 shows the results of the analysis.
- Example 2 The same reaction and analysis as in Example 2 were performed, except that the catalyst used in Example 2 was changed to the catalyst (A) alone. Table 1 shows the results of the analysis.
- the method of the present invention can simultaneously overcome the problems of the activity and the filter separation property of the conventional catalyst. That is, the oxidation reaction product of cyclohexane according to the method of the present invention.
- the esterified product of the carboxylic acid mixture separated from water is hydrogenolyzed with hydrogen in the presence of a specific combination catalyst that has excellent catalytic activity, is easy to separate by filtration, and does not contain chromium.
- a specific combination catalyst that has excellent catalytic activity, is easy to separate by filtration, and does not contain chromium.
- Diol compounds such as hexanediol can be easily obtained.
- the target compound and the catalyst can be easily separated by filtration.
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94929004A EP0673909B1 (en) | 1993-10-08 | 1994-10-05 | Process for producing diol compound |
US08/448,488 US5710349A (en) | 1993-10-08 | 1994-10-05 | Process for producing diol compounds |
DE69417720T DE69417720T2 (de) | 1993-10-08 | 1994-10-05 | Verfahren zur herstellung von diolen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP5/253205 | 1993-10-08 | ||
JP25320593 | 1993-10-08 |
Publications (1)
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WO1995010497A1 true WO1995010497A1 (fr) | 1995-04-20 |
Family
ID=17248019
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Application Number | Title | Priority Date | Filing Date |
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PCT/JP1994/001664 WO1995010497A1 (fr) | 1993-10-08 | 1994-10-05 | Procede de production d'un diol |
Country Status (5)
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US (1) | US5710349A (ja) |
EP (1) | EP0673909B1 (ja) |
DE (1) | DE69417720T2 (ja) |
ES (1) | ES2131707T3 (ja) |
WO (1) | WO1995010497A1 (ja) |
Families Citing this family (6)
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JP2000505468A (ja) * | 1996-03-01 | 2000-05-09 | ビーエーエスエフ アクチェンゲゼルシャフト | 99%を越える純度を有する1,6―ヘキサンジオールの製法 |
MY118128A (en) * | 1996-03-01 | 2004-09-30 | Basf Ag | The preparation of 1, 6-hexanediol and caprolactone |
DE19929831A1 (de) * | 1999-06-30 | 2001-01-04 | Basf Ag | Verfahren zur Herstellung von Hexandiol |
US6455742B1 (en) | 1999-09-02 | 2002-09-24 | Wisconsin Alumni Research Foundation | Method for catalytically reducing carboxylic acid groups to hydroxyl groups in hydroxycarboxylic acids |
US7964114B2 (en) * | 2007-12-17 | 2011-06-21 | Sud-Chemie Inc. | Iron-based water gas shift catalyst |
US8759594B2 (en) | 2009-04-08 | 2014-06-24 | Basf Se | Method for producing 1,6-hexanediol by hydrogenation of oligo- and polyesters |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58500993A (ja) * | 1981-04-29 | 1983-06-23 | デイビ マツキ− (ロンドン) リミテツド | アルキルアルコールの生成方法 |
JPS61106528A (ja) * | 1984-09-17 | 1986-05-24 | ザ・ハルコン・エス・デイ−・グル−プ・インコ−ポレ−テツド | アルコ−ル及び/又はエステルの気相形成法 |
JPS63141937A (ja) * | 1986-12-03 | 1988-06-14 | Kao Corp | 高級アルコ−ルの製造法 |
JPH01305042A (ja) * | 1988-06-02 | 1989-12-08 | Kao Corp | アルコールの製造法 |
JPH03186349A (ja) * | 1989-10-17 | 1991-08-14 | Engelhard Corp | 水素化触媒、該触媒の製造方法及び使用方法 |
JPH03220143A (ja) * | 1990-01-22 | 1991-09-27 | Kao Corp | アルコールの製造法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2524892A (en) * | 1948-06-26 | 1950-10-10 | Petrolite Corp | Processes for breaking petroleum emulsions |
JPS4927164A (ja) * | 1972-07-07 | 1974-03-11 | ||
JPS5333567B2 (ja) * | 1974-06-12 | 1978-09-14 | ||
JPS52156192A (en) * | 1976-06-22 | 1977-12-26 | Kao Corp | Production of cu:fe catalyst |
JPS5850775B2 (ja) * | 1979-03-30 | 1983-11-12 | 花王株式会社 | 銅−鉄−アルミニウム触媒の製法 |
JPH0699345B2 (ja) * | 1989-09-29 | 1994-12-07 | 宇部興産株式会社 | 1,6―ヘキサンジオールの製造法 |
-
1994
- 1994-10-05 WO PCT/JP1994/001664 patent/WO1995010497A1/ja active IP Right Grant
- 1994-10-05 DE DE69417720T patent/DE69417720T2/de not_active Expired - Lifetime
- 1994-10-05 US US08/448,488 patent/US5710349A/en not_active Expired - Lifetime
- 1994-10-05 ES ES94929004T patent/ES2131707T3/es not_active Expired - Lifetime
- 1994-10-05 EP EP94929004A patent/EP0673909B1/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58500993A (ja) * | 1981-04-29 | 1983-06-23 | デイビ マツキ− (ロンドン) リミテツド | アルキルアルコールの生成方法 |
JPS61106528A (ja) * | 1984-09-17 | 1986-05-24 | ザ・ハルコン・エス・デイ−・グル−プ・インコ−ポレ−テツド | アルコ−ル及び/又はエステルの気相形成法 |
JPS63141937A (ja) * | 1986-12-03 | 1988-06-14 | Kao Corp | 高級アルコ−ルの製造法 |
JPH01305042A (ja) * | 1988-06-02 | 1989-12-08 | Kao Corp | アルコールの製造法 |
JPH03186349A (ja) * | 1989-10-17 | 1991-08-14 | Engelhard Corp | 水素化触媒、該触媒の製造方法及び使用方法 |
JPH03220143A (ja) * | 1990-01-22 | 1991-09-27 | Kao Corp | アルコールの製造法 |
Non-Patent Citations (1)
Title |
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See also references of EP0673909A4 * |
Also Published As
Publication number | Publication date |
---|---|
DE69417720D1 (de) | 1999-05-12 |
EP0673909A4 (en) | 1996-11-20 |
DE69417720T2 (de) | 1999-07-29 |
ES2131707T3 (es) | 1999-08-01 |
EP0673909B1 (en) | 1999-04-07 |
EP0673909A1 (en) | 1995-09-27 |
US5710349A (en) | 1998-01-20 |
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