CN1225918A - Process for synthesizing cyclohexandiol by coproduct of epoxy-cyclohexane from cyclohexane oxidation - Google Patents
Process for synthesizing cyclohexandiol by coproduct of epoxy-cyclohexane from cyclohexane oxidation Download PDFInfo
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- CN1225918A CN1225918A CN 98112736 CN98112736A CN1225918A CN 1225918 A CN1225918 A CN 1225918A CN 98112736 CN98112736 CN 98112736 CN 98112736 A CN98112736 A CN 98112736A CN 1225918 A CN1225918 A CN 1225918A
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- cyclohexane
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Abstract
The method for synthesizing cyclohexandiol by using epoxy cyclohexane which is a by-product obtained from oxidation of cyclohexane is characterized by that in the presence of 0.05%-1% acidic material, making the material containing epoxy cyclohexane implement hydrolysis reaction at 40-80 deg.C, after said reaction is completed, adopting the steps of neutralizing, filtering, concentraating, crystallizing and drying to obtain the trans-1,2-cyclohexandiol with purity of greater than 99%.
Description
The present invention relates to a kind of method by cyclohexane oxidation by-product epoxy cyclohexane mixture synthesizing cyclohexane 1 glycol.
Cyclohexane oxidation is produced in pimelinketone, the hexalin technology, while by-product lightweight oil, wherein epoxy cyclohexane content is 10～50%, press the method that the CN-1180702A patent is introduced, recyclable content reaches the epoxy cyclohexane product more than 95%, and by-product epoxy cyclohexane content is 20～50% mixed solution simultaneously.The synthesizing cyclohexane 1 glycol process that the present invention studied both can directly use regular epoxy cyclohexane product to be raw material, also can use low epoxy cyclohexane content mixed solution to be raw material, all can reach promising result.
It is reported, the domestic report that does not have quinite to conduct a research as yet at present, and abroad for the research of cyclohexanediol, being confined to the tetrahydrobenzene is starting raw material, makes epoxy cyclohexane through epoxidation reaction, and then the synthesizing cyclohexane 1 glycol.For example: (1) epoxy cyclohexane is under acidic conditions, pressurized hydrolysis in organic solvent, temperature of reaction is 130～150 ℃ (DE2749984), becoming to adopt the Nafion-H sulfate resin is catalyzer, epoxy cyclohexane reacted two hours at normal temperatures with water in tetrahydrofuran (THF), also can obtain cyclohexanediol (OlahGA, Fung AP, MeidarD.Synthesis, 1981, (4): 280～282), as can be known, its reaction scheme is long, complex process from above-mentioned introduction, also need use other organic raw material, synthetic costing an arm and a leg.
The object of the present invention is to provide a kind of method by cyclohexane oxidation by product epoxy hexanaphthene synthesizing cyclohexane 1 glycol.
The present invention is achieved in that (epoxy cyclohexane content height does not all influence reaction result to the mixture that epoxy cyclohexane content 〉=20% is above.Component in the mixture is except that the epoxy hexanaphthene, for the organic substance of hydrolysis reaction does not take place).Reaction is hydrolyzed under 0.05%～1% (weight ratio) an acidic catalyst existence condition, the an acidic catalyst range of choice is wider, can be acids such as sulfuric acid, phosphoric acid, hydrochloric acid, strong-acid ion exchange resin and Lewis acid, also can use materials such as zinc chloride or aluminum chloride, the add-on of water is preferably: epoxy cyclohexane: water (mol ratio) is 1: 8～10.Temperature of reaction is controlled at 40～80 ℃ of scopes, with 60 ℃ be the best, this reaction is for strong exothermal reaction, for guaranteeing that temperature of reaction is constant, epoxy cyclohexane must slowly add.
After reaction finishes, use mineral alkali, as sulfuric acid catalyst in the hydrated barta neutralization reaction liquid, produce barium sulfate precipitate, and remove with filtering method, remove organic solvent in the reaction solution with distillating method then, cyclohexanediol then remains in the aqueous solution, again through extraction, concentrate, Crystallization Separation and drying, get final product purity greater than 99% cyclohexanediol product.
The inventive method has the advantage that has made full use of the epoxy cyclohexane that reclaims from lightweight oil, and it is not high for epoxy cyclohexane content requirement in the raw material, need not to add any specific organic solvent, reaction conditions gentleness, reaction conversion ratio height (greater than 99%), yield height (greater than 85%), characteristics such as technology is simple, and production cost is low, product purity height (greater than 99%), can satisfy with the cyclohexanediol is the demand of the various fine chemical products of raw material production.
It is 54.7% mixture 400ml that embodiment 1 gets epoxy cyclohexane content.Wherein the epoxy cyclohexane total amount is 2mol.In the 1000ml there-necked flask, add 200ml water, the meter water yield is 16.7mol, adding catalyzer is analytically pure vitriol oil 0.39g, puts flask in water bath with thermostatic control, drips mixture continuously to reaction flask, and open and stir thorough mixing reaction system, control rate of addition and water coolant are 60 ℃ for amount with constant temperature of reaction, react after 2.5 hours and finish, hydrated barta neutralization with sulfuric acid amount equivalent in the system removes by filter the barium sulfate precipitate thing.Remove the organic solvent of not participating in reaction with distillating method then.To distill again the back gained contain that the cyclohexanediol aqueous solution concentrates, Crystallization Separation, drying, obtaining purity is 99.40%, melting range is 102.1 ℃～104.2 ℃ a anti-form-1,2-cyclohexanediol product 94.1g, other is dissolved in the mother liquor 110g cyclohexanediol of having an appointment, can with following batch of cyclohexanediol aqueous solution that removes behind the organic solvent, reclaim wherein cyclohexanediol product.
In the present embodiment, the epoxy cyclohexane total recovery is 88.32%, and its once through yield is 41%.
Claims (3)
1, a kind of method by cyclohexane oxidation by-product epoxy cyclohexane synthesizing cyclohexane 1 glycol, it is characterized in that adopting acidic substance is catalyzer, makes the epoxy cyclohexane hydrolysis generate cyclohexanediol, process comprises:
(1) will contain the mixture (epoxy cyclohexane content be in 20%～98% scope all can) of epoxy cyclohexane, at one or more of materials such as the sulfuric acid of 0.05%～1% (wt), hydrochloric acid, phosphoric acid, strong-acid ion exchange resin, Lewis acid simultaneously under existence conditions, the water that adds epoxy cyclohexane total amount 100%～300% (wt) in the material, reacted 1～4 hour under 40 ℃～80 ℃ conditions, reaction solution neutralizes, filters with mineral alkali;
(2) concentrate, crystallization, drying; Recycling Mother Solution in the sepn process is used.
2, according to the method for claims 1 described synthesizing cyclohexane 1 glycol, it is characterized in that: an acidic catalyst add-on is 0.1%～0.5% (wt) of epoxy cyclohexane content in the mixture in the hydrolysis reaction, and the ratio of epoxy cyclohexane and water is 1: 1.4～1.5 (weight ratios).
3, the method for synthesizing cyclohexane 1 glycol according to claim 1, the optimum temps that it is characterized in that hydrolysis reaction is 60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98112736A CN1112341C (en) | 1998-11-17 | 1998-11-17 | Process for synthesizing cyclohexandiol by coproduct of epoxy-cyclohexane from cyclohexane oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98112736A CN1112341C (en) | 1998-11-17 | 1998-11-17 | Process for synthesizing cyclohexandiol by coproduct of epoxy-cyclohexane from cyclohexane oxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1225918A true CN1225918A (en) | 1999-08-18 |
| CN1112341C CN1112341C (en) | 2003-06-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98112736A Expired - Fee Related CN1112341C (en) | 1998-11-17 | 1998-11-17 | Process for synthesizing cyclohexandiol by coproduct of epoxy-cyclohexane from cyclohexane oxidation |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219762A (en) * | 2011-04-19 | 2011-10-19 | 武汉森茂精细化工有限公司 | Preparation process of 1,2-cyclohexanediol diglycidyl ether |
| CN102464579A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化学工业开发股份有限公司 | Method for preparing hexanedioic acid from cyclohexane oxidation byproducts |
| CN101704711B (en) * | 2009-10-27 | 2012-07-25 | 岳阳昌德化工实业有限公司 | Method for preparing 1,2-diol compound by using catalytic hydration of epoxide |
| CN102807472A (en) * | 2012-08-21 | 2012-12-05 | 南京工业大学 | New process for synthesizing 1,2-cyclohexanediol by hydrolyzing cyclohexene oxide |
| CN103864572A (en) * | 2012-12-18 | 2014-06-18 | 中国科学院大连化学物理研究所 | Method for preparing diol |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4943956B1 (en) * | 1970-11-27 | 1974-11-25 | ||
| JPS5136746B2 (en) * | 1971-09-22 | 1976-10-12 |
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1998
- 1998-11-17 CN CN98112736A patent/CN1112341C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704711B (en) * | 2009-10-27 | 2012-07-25 | 岳阳昌德化工实业有限公司 | Method for preparing 1,2-diol compound by using catalytic hydration of epoxide |
| CN102464579A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化学工业开发股份有限公司 | Method for preparing hexanedioic acid from cyclohexane oxidation byproducts |
| CN102464579B (en) * | 2010-11-05 | 2014-03-12 | 中国石油化学工业开发股份有限公司 | Method for preparing hexanedioic acid from cyclohexane oxidation byproducts |
| CN102219762A (en) * | 2011-04-19 | 2011-10-19 | 武汉森茂精细化工有限公司 | Preparation process of 1,2-cyclohexanediol diglycidyl ether |
| CN102807472A (en) * | 2012-08-21 | 2012-12-05 | 南京工业大学 | New process for synthesizing 1,2-cyclohexanediol by hydrolyzing cyclohexene oxide |
| CN103864572A (en) * | 2012-12-18 | 2014-06-18 | 中国科学院大连化学物理研究所 | Method for preparing diol |
| CN103864572B (en) * | 2012-12-18 | 2015-10-21 | 中国科学院大连化学物理研究所 | A kind of method preparing glycol |
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| CN1112341C (en) | 2003-06-25 |
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