CN106631685B - A kind of separation method of phenol and quinone mixture - Google Patents
A kind of separation method of phenol and quinone mixture Download PDFInfo
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- CN106631685B CN106631685B CN201610687899.8A CN201610687899A CN106631685B CN 106631685 B CN106631685 B CN 106631685B CN 201610687899 A CN201610687899 A CN 201610687899A CN 106631685 B CN106631685 B CN 106631685B
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- phenol
- benzoquinone
- separation method
- organic amine
- separation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/88—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/10—Separation; Purification; Stabilisation; Use of additives
Abstract
The present invention relates to the separation methods of a kind of phenol and 1,4-benzoquinone to be conducive to 1,4-benzoquinone Precipitation reaching separating effect by the way that organic amine or nitrogen-containing heterocycle compound are added in reaction system.Organic amine compound or nitrogen-containing heterocycle compound are added into oxidation of phenol liquid, stirs at a certain temperature, cooling is stood, and as the reduction 1,4-benzoquinone of temperature is gradually precipitated, 1,4-benzoquinone is obtained by filtration.The technical solution realizes the simple separation of phenol and 1,4-benzoquinone at low temperature, and isolated 1,4-benzoquinone purity 95% or so can be used as reduction raw material and use, and separation yield is up to 80% or more.
Description
Technical field
The present invention relates to the separation methods of a kind of phenol and 1,4-benzoquinone.
Background technique
Hydroquinone (C6H6O2) also known as quinhydrones, be a kind of important fine chemical material and intermediate, medicine, pesticide,
The fields such as dyestuff, rubber, chemical fertilizer, water process and liquid crystal polymer are widely used, such as polymerization inhibitor, pigment, dyestuff, food additive
Add agent etc..Domestic ten thousand t/a of the market demand about 3-4 to hydroquinone at present, can also increase every year according to certain speed, to benzene
Diphenol has good market prospects.
There are mainly two types of the production technologies of domestic hydroquinone: aniline oxidizing process and phenol hydroxylation method.Wherein, aniline aoxidizes
Method is due to three wastes problem, it will is gradually eliminated；Phenol hydroxylation method there are hydroquinones selectively low (about 45%), by-product neighbour's benzene
The problem of diphenol, constrains the yield of hydroquinone.
Researcher domestic in recent years begins one's study oxidation of phenol technique, and research emphasis is that how to improve oxidation of phenol anti-
The selectivity answered in order to guarantee the highly selective conversion ratio for having to control phenol of oxidation reaction, therefore both contained in oxidation solution
There is phenol also to contain 1,4-benzoquinone, needs to separate 1,4-benzoquinone and carry out sequential reduction process again.
Document report at present about phenol and 1,4-benzoquinone separation is less, and US4235790 describes a kind of separation method, leads to
It crosses into mixture and hydroquinone is added in (phenol and 1,4-benzoquinone), hydroquinone can have an effect with 1,4-benzoquinone and generate quinone hydrogen
Quinone, quinhydrone can be precipitated from solution, so that phenol and 1,4-benzoquinone be separated, this method can efficiently separate phenol and right
Benzoquinones, but quinhydrone is difficult to be decomposed into 1,4-benzoquinone and hydroquinone again, if directly carrying out reduction and subsequent using quinhydrone
It is relatively low that separation (precipitation, decoking, crystallization etc.) will cause yield.Main cause is the hydroquinone of introducing in subsequent separation process height
Warm heated portion switchs to tar, to reduce the total recovery of reaction.
CN104761440 provides a kind of separation method, passes through (phenol and 1,4-benzoquinone) addition promotion pair into mixture
Benzoquinones aggregation/self assembly promotor realizes Precipitation of the 1,4-benzoquinone under room temperature or low temperature, to realize the effect of separation
Fruit.Since the promotor being previously mentioned in patent is all that oneself synthesis can not directly be bought, the practicability of this method is not high, difficult
To promote.
In addition, there are also vapor stripping process to separate 1,4-benzoquinone, this method is mainly used in aniline oxidative synthesis to benzene two
In the technique of phenol, since aniline will not be steamed with vapor, it can be separated.But in oxidation of phenol technique phenol and
1,4-benzoquinone can be all distilled out of with vapor, and energy consumption is high, therefore this method is not suitable for the separation of phenol and 1,4-benzoquinone.
Summary of the invention
The object of the present invention is to provide the separation methods of a kind of phenol and 1,4-benzoquinone.By the way that organic amine is added in reaction system
Or nitrogen-containing heterocycle compound, be conducive to 1,4-benzoquinone Precipitation reaching separating effect.
Thinking of the invention: due in oxidation of phenol liquid between phenol and 1,4-benzoquinone there are certain combination so that phenol
In the presence of the dissolution of 1,4-benzoquinone in a solvent can be promoted, to be difficult to be precipitated from oxidation solution through cooling.Therefore, it is desirable to
Certain substance is added, it is made to form stronger active force between phenol, to destroy the binding force of phenol and 1,4-benzoquinone, restores
Or 1,4-benzoquinone original solubility in a solvent is further decreased, so that 1,4-benzoquinone is precipitated at a certain temperature, reach separation
The purpose of 1,4-benzoquinone.
Complete foregoing invention task technical solution it is as follows: to oxidation of phenol liquid (include phenol, solvent, catalyst, to benzene
Quinone and impurity) in organic amine compound or nitrogen-containing heterocycle compound is added, stir at a certain temperature, cooling is stood, with
The reduction 1,4-benzoquinone of temperature is gradually precipitated, and 1,4-benzoquinone is obtained by filtration.
Organic amine compound or nitrogen-containing heterocycle compound of the present invention, wherein organic amine compound can be
R3N (R=CnH2n+1, n=1~12), such as trimethylamine, tri-n-butylamine, trioctylamine；Nitrogen-containing heterocycle compound can for pyridine and its
Substitutive derivative (substituent can be halogen, alkyl, sulfonic group etc.), such as pyridine, picoline, chloro-pyridine.
In separation condition of the present invention, the molar ratio of organic amine or nitrogen-containing heterocycle compound and phenol can be 0.5
~2:1, preferably 1~1.5:1；Reaction temperature can be 0 DEG C~15 DEG C, preferably 0 DEG C~10 DEG C；Dwell temperature can be -10 DEG C
~5 DEG C, preferably -10 DEG C~0 DEG C.
The technical solution realizes the simple separation of phenol and 1,4-benzoquinone at low temperature, isolated 1,4-benzoquinone purity
95% or so, it can be used as reduction raw material and use, separation yield is up to 80% or more.
Specific embodiment
The following examples are intended to explain protrusion effect of the invention, rather than limitation of the invention further.
Embodiment 1
The synthetic method of oxidation of phenol liquid is briefly explained, subsequent embodiment is closed referring to the method by adjusting technological parameter
At the oxidation solution of different compositions.
By taking embodiment 1 as an example, phenol 10g is added into 50ml autoclave, ethyl alcohol 9.5g, copper chloride 0.5g are passed through 3MPa
Oxygen, 65 DEG C of insulation reaction 1.5hr, 6g containing phenol, 1,4-benzoquinone 3g, copper chloride 0.5g in obtained oxidation solution, ethyl alcohol 9.5g are miscellaneous
Matter and tar about 1g.
Use homemade 20g oxidation solution for raw material, wherein 6g containing phenol, 1,4-benzoquinone 3g, copper chloride 0.5g, ethyl alcohol 9.5g,
Impurity and tar about 1g.Tri-n-butylamine 15g is added into oxidation solution, the stir about 30min at 10 DEG C stops stirring, is down to -5 DEG C
It stands overnight, 1,4-benzoquinone 2.62g, purity 94.4%, separation yield 82.44% is obtained by filtration.
Embodiment 2
Use homemade 30g oxidation solution for raw material, wherein 10g containing phenol, 1,4-benzoquinone 6g, copper chloride 0.5g, methanol 12g,
Impurity and tar about 1.5g.Into oxidation solution be added pyridine 10.5g, stir about 25min, stops stirring at 5 DEG C, be down to 0 DEG C it is quiet
10h is set, 1,4-benzoquinone 5.36g, purity 95.2%, separation yield 85.04% is obtained by filtration.
Embodiment 3
Use homemade 30g oxidation solution for raw material, wherein 8g containing phenol, 1,4-benzoquinone 6g, copper chloride 0.3g, dichloroethanes
14g, impurity and tar about 1.7g.Picoline 12g is added into oxidation solution, the stir about 35min at 8 DEG C stops stirring, and drops
It is stood overnight to -5 DEG C, 1,4-benzoquinone 5.28g, purity 94.1%, separation yield 82.8% is obtained by filtration.
Embodiment 4
Use homemade 20g oxidation solution for raw material, wherein 6g containing phenol, 1,4-benzoquinone 4g, copper chloride 0.3g, tetrachloroethanes
8.5g, impurity and tar about 1.2g.Triethylamine 9g is added into oxidation solution, the stir about 25min at 0 DEG C stops stirring, be down to-
10 DEG C of standing 12h, are obtained by filtration 1,4-benzoquinone 3.52g, purity 94.6%, separation yield 83.25%.
Embodiment 5-8
On that basis of example 1, using different organic amine compounds or the separating effect of nitrogen-containing heterocycle compound
Claims (8)
1. the separation method of a kind of phenol and 1,4-benzoquinone, which is characterized in that organic amine compound is added into oxidation of phenol liquid,
It stirs at a certain temperature, cooling is stood, and as the reduction 1,4-benzoquinone of temperature is gradually precipitated, 1,4-benzoquinone, organic amine is obtained by filtration
Class compound is R3N, R=CnH2n+1, n=1~12.
2. the separation method of a kind of phenol and 1,4-benzoquinone according to claim 1, which is characterized in that organic amine compound
For trimethylamine, tri-n-butylamine, trioctylamine.
3. the separation method of a kind of phenol and 1,4-benzoquinone according to claim 1, which is characterized in that organic amine compound with
The molar ratio of phenol is 0.5~2:1.
4. the separation method of a kind of phenol and 1,4-benzoquinone according to claim 3, which is characterized in that organic amine compound with
The molar ratio of phenol is 1~1.5:1.
5. the separation method of a kind of phenol and 1,4-benzoquinone according to claim 1, which is characterized in that the whipping temp is
0 DEG C~15 DEG C.
6. the separation method of a kind of phenol and 1,4-benzoquinone according to claim 5, which is characterized in that temperature is 0 DEG C~10
℃。
7. the separation method of a kind of phenol and 1,4-benzoquinone according to claim 1, which is characterized in that the dwell temperature
It is -10 DEG C~5 DEG C.
8. the separation method of a kind of phenol and 1,4-benzoquinone according to claim 7, which is characterized in that the dwell temperature
It is -10 DEG C~0 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4235790A (en) * | 1978-01-24 | 1980-11-25 | Hoechst Aktiengesellschaft | Process for separating p-benzoquinone from the reaction products of phenol oxidation as quinhydrone |
| CN104341274A (en) * | 2013-07-31 | 2015-02-11 | 中国石油化工股份有限公司 | Method for simultaneously producing dihydroxybenzene and benzoquinone |
| CN104761440A (en) * | 2014-09-17 | 2015-07-08 | 中国科学院青岛生物能源与过程研究所 | Separation / purification method of p-benzoquinone compound |
-
2016
- 2016-08-18 CN CN201610687899.8A patent/CN106631685B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4235790A (en) * | 1978-01-24 | 1980-11-25 | Hoechst Aktiengesellschaft | Process for separating p-benzoquinone from the reaction products of phenol oxidation as quinhydrone |
| CN104341274A (en) * | 2013-07-31 | 2015-02-11 | 中国石油化工股份有限公司 | Method for simultaneously producing dihydroxybenzene and benzoquinone |
| CN104761440A (en) * | 2014-09-17 | 2015-07-08 | 中国科学院青岛生物能源与过程研究所 | Separation / purification method of p-benzoquinone compound |
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