Claims
- 1. A process for preparing 1,6-hexanediol from an aqueous carboxylic acid mixture comprising adipic acid, 6-hydroxy-caproic acid and small amounts of 1,4-cyclohexanediols, which aqueous carboxylic acid mixture is obtained as a by-product in the oxidation of cyclohexane to cyclohexanone/cyclohexanol using oxygen or oxygen-containing gases followed by water extraction, which process comprises esterifying the aqueous carboxylic acid mixture followed by catalytic hydrogenation,
- a) reacting monocarboxylic and dicarboxylic acid present in the aqueous carboxylic acid mixture with a low molecular weight alcohol to give an esterification mixture comprising the corresponding carboxylic ester;
- b) removing excess alcohol and low boilers from the esterification mixture in a first distillation stage;
- c) fractionating bottoms from the first distillation stage in a second distillation stage to give an ester fraction essentially free of 1,4-cyclohexanediols and a fraction comprising at least a major amount of the 1,4-cyclohexanediols;
- d) catalytically hydrogenating the ester fraction which is essentially free of 1,4-cyclohexanediols to produce a hydrogenation product; and
- e) isolating 1,6-hexanediol from the hydrogenation produce in a pure distillation stage.
- 2. A process as defined in claim 1, wherein the aqueous carboxylic acid mixture is dewatered prior to reaction of monocarboxylic acid and dicarboxylic acid present therein with the low molecular weight alcohol.
- 3. A process as defined in claim 1, wherein monocarboxylic and dicarboxylic acid present in the aqueous carboxylic acid mixture are reacted with an alkanol having from 1 to 3 carbon atoms.
- 4. A process as defined in claim 1, wherein monocarboxylic acid and dicarboxylic acid present in the aqueous carboxylic acid mixture are reacted with an alkanol having from 4 to 10 carbon atoms.
- 5. A process as defined in claim 1, wherein the low molecular weight alcohol is methanol, and in the second distillation stage (c), a methyl carboxylate fraction essentially free of 1,4-cyclohexanediols is obtained at the top of the column and a fraction comprising high boilers and 1,4-cyclohexanediols is obtained as bottoms, and the methyl carboxylate fraction is catalytically hydrogenated in the hydrogenation stage (d).
- 6. A process as defined in claim 1, wherein the low molecular weight alcohol is n- or i-butanol, and in the second distillation stage (c), the 1,4-cyclohexanediols are separated off at the top together with low boilers, and butyl carboxylates are obtained as a side stream or as bottoms and are catalytically hydrogenated in the hydrogenation stage (d).
- 7. A process as defined in claim 1, wherein alcohol is isolated in pure form from the product obtained by removing alcohol and low boilers from the esterification mixture in the first distillation stage (b), and this alcohol is recirculated to esterification stage (a).
- 8. A process as defined in claim 1, wherein bottoms from second distillation stage (c) are subjected at least partially to a renewed esterification by means of further addition thereto of low molecular weight alcohol and an esterification catalyst, followed by removing excess alcohol and low boilers from the renewed esterification in a first distillation stage, then fractionating bottoms from this first distillation stage in a second distillation stage to give a carboxylic ester fraction essentially free of 1,4-cyclohexanediols and a fraction comprising at least a major amount of 1,4-cyclohexanediols, followed by introducing the carboxylic ester fraction into the hydrogenation stage (d).
- 9. A process as defined in claim 1, wherein the hydrogenation in step (d) is carried out using a catalyst comprising as main catalytically active constituent a member selected from the group consisting of copper, cobalt and rhenium.
- 10. A process as defined in claim 1, wherein the hydrogenation in stage (d) is carried out using a catalyst which, in the oxidic form, has the composition Cu.sub.a Al.sub.b Zr.sub.c Mn.sub.d O.sub.x, where a>0, b>0, c.gtoreq.0, d>0, a>b/2, b>a/4, a>c and a>d and x is the number of oxygen ions required to maintain electrical neutrality of the formula unit.
Priority Claims (2)
Number |
Date |
Country |
Kind |
196 07 955 |
Mar 1996 |
DEX |
|
196 47 348 |
Nov 1996 |
DEX |
|
Parent Case Info
This application is the national phase of PCT/EP97/00980, filed Feb. 28, 1997, now WO97/31882.
PCT Information
Filing Document |
Filing Date |
Country |
Kind |
102e Date |
371c Date |
PCT/EP97/00980 |
2/28/1997 |
|
|
8/28/1998 |
8/28/1998 |
Publishing Document |
Publishing Date |
Country |
Kind |
WO97/31882 |
9/4/1997 |
|
|
US Referenced Citations (8)
Foreign Referenced Citations (6)
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Country |
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EPX |
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EPX |
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DEX |
2 060 548 |
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DEX |
23 21 101 |
Jul 1982 |
DEX |
28 19 593 |
Nov 1997 |
DEX |
Non-Patent Literature Citations (3)
Entry |
CA:112:178071 abs of JP01249735, Mar. 1988. |
CA:118:80490 abs of JP 04202150, Jan. 1990. |
CA:118:80489 abs of Jp04202149, Jan. 1990. |