CN109776276A - A method of M-and P-cresols mixture is separated using selective oxidation catalyst - Google Patents
A method of M-and P-cresols mixture is separated using selective oxidation catalyst Download PDFInfo
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- CN109776276A CN109776276A CN201910212279.2A CN201910212279A CN109776276A CN 109776276 A CN109776276 A CN 109776276A CN 201910212279 A CN201910212279 A CN 201910212279A CN 109776276 A CN109776276 A CN 109776276A
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Abstract
The present invention provides a kind of methods using selective oxidation catalyst separation M-and P-cresols mixture, oxidation processes can be carried out to the mixture of M-and P-cresols using the catalyst of selective oxidation in the method, metacresol in mixture is fully oxidized as quinone compounds, and paracresol does not react.After oxidation reaction is handled, since quinone compounds (186-187 DEG C) and paracresol (202-203 DEG C) boiling-point difference are away from obvious, being kept completely separate for paracresol can be realized by rectifying.Separation method according to the present invention is since oxidation reaction uses oxygen or air as oxidant, and as mild as a dove, operation is simple, production cost is low, easy to industrialized production for reaction condition.In addition, the quinone compounds that reaction generates are important the raw material of dyestuff and antioxidant, high value added utilization may be implemented, there is good economic benefit.
Description
Technical field
The invention belongs to chemical fields, in particular to a kind of using the separation M-and P-cresols mixing of selective oxidation catalyst
The method of object.
Background technique
Paracresol is important fine chemical material and auxiliary agent, synthetic plastic, dyestuff, in terms of have it is important
Purposes, medically also by the raw material as disinfectant, preservative etc..Therefore, the preparation of pure paracresol monomer is standby always
It is concerned.But in the industrial production, paracresol is general and metacresol is sold as mixture, required pure paracresol
Monomer needs just obtain by further separating-purifying.During separating cresols, because of metacresol and paracresol
Boiling point differs only by 0.4 DEG C, and fusing point differs 24.6 DEG C, and common distillation or distillation technology are difficult to be isolated, this just needs to find conjunction
Suitable mode separates it.
Traditional separating technology mainly includes following several: 1) azeotropic method separates paracresol according to the principle of azeotropic
With the mixture of metacresol.Firstly, a certain amount of water is added into the mixture of paracresol and metacresol, sodium cresylate is added,
The azeotropic substance of a low boiling point is formed by cresols and water, the method for recycling rectifying distills it from tower top, at this time
It is relatively pure paracresol that tower bottom, which remains remaining,.The shortcomings that azeotropic method is that energy consumption is higher, and generates a large amount of phenol wastewater.
2) extraction, i.e., according to paracresol and metacresol, the difference of solubility separates the mixing of metacresols and paracresol in different solutions
Object.The extractant being often used includes the organic solvents such as N- methylpyrrolidone, dimethyl sulfone, and needs during dissociation extraction
A large amount of benzene.Benzene is toxic organic solvent, and bigger to the pollution of environment, does not meet environmental-friendly development strategy.
3) adsorption separation method is, the isomers progress selectively absorption point of paracresol different according to the absorption property of different adsorbents
From, then dissolved under certain conditions with different solvents, it is then separable to obtain the paracresol of high-purity.State's outgoing
Have been carried out the large-scale production of the method up to country, but the method to the selection of molecular sieve and prepare it is more demanding, at present in state
Industrial requirement inside has not yet been reached.4) high pressure crystal partition method, the fusing point based on paracresol and metacresol can be with the increasings of pressure
It increases, the technology then separated according to the fusing point difference of the two greatly.But the general pressure of separation condition will reach
100-300MPa, condition is harsh, is unfavorable for being mass produced.5) complexometric extraction crystallisation, be using isopropyl ether, n-butyl ether or
Isoamyl ether makees solvent, and extractant is anthalazine.It is soluble in water that paracresol is reacted to the precipitating generated with extractant, to complex compound
Dissolved, during dissolution, because extractant is water-soluble, and paracresol cannot, therefore with water and organic solvent by its
Extraction and separation, then paracresol is isolated by way of rectifying.The method generates a large amount of waste water, and there are organic solvent pollution rings
Border problem.6) class chelate partition method is according to the difference of position of the alkyl on phenyl ring on cresols isomer, with class chela
It closes object and reacts with it generation precipitating, to isolate metacresol and paracresol.But class chelate dosage is big, price is high, so
The application of method can not be extensive.7) complex partition method, being can be with certain chemical combination using metacresol in mixture cresol or paracresol
Object occurs complex reaction and generates different compounds, carries out method of the separation to separate mixture cresol to compound.Urea crystals method
It is one of the most widely used method in complex partition method.But this method there are reaction rates relatively slow, reaction complexing rate
Low disadvantage, and reactant in complexation process needs repeatedly washing, and uses a large amount of organic solvents, there are complex steps,
The problem of higher cost.8) hydrocarbylation method occurs that isobutene and the mixture of mixed phenol under conditions of acidic catalyst
The hydrocarbonylation product of alkylated reaction, generation has different boiling point and gap larger, is used using the biggish boiling-point difference of its span
The method of rectification under vacuum separates the product of acquisition.Hydrocarbylation method combines physics and chemical two kinds of means are separated,
Include three steps: first alkylated reaction, then rectifying separates, then carries out dealkylation.This method is due to obtained product
Purity is higher, manufacture craft is simple, environmental pollution is smaller, thus have become industrial the most widely used paracresol,
Metacresol partition method.But complex steps, equipment investment constrain greatly production scale, it is difficult to realize large-scale production.
Summary of the invention
In view of the problems of the existing technology, M-and P-cresols is separated using selective oxidation catalyst the present invention provides a kind of
The method of mixture, in the method using the catalyst of selective oxidation can the mixture to M-and P-cresols carry out at oxidation
Reason, the metacresol in mixture is fully oxidized as quinone compounds, and paracresol does not react.It is handled through oxidation reaction
Afterwards, since quinone compounds (186-187 DEG C) and paracresol (202-203 DEG C) boiling-point difference are away from obvious, rectifying can be passed through
Realize being kept completely separate for paracresol.
Specifically, it is according to the present invention separation M-and P-cresols mixture method the following steps are included:
1) oxidation of M-and P-cresols mixture: M-and P-cresols mixture, catalyst and solvent are added in autoclave,
It closes reaction kettle and opens stirring, be filled with oxygen or air to specified pressure, kept for 2-10 hours after being warming up to reaction temperature.Instead
It is cooled to room temperature after answering, vent gas simultaneously opens reaction kettle collection reaction post mother liquor；
2) rectifying separates: carrying out vacuum distillation processing, removal reaction dissolvent and reaction life to mother liquor obtained in step 1)
At water, reaction dissolvent recovery collects remaining solid mixture and tower bottom of rectifying tower is added.
1.0 meters of rectifying tower height used,2.0 centimetres, glass spring filler, tower body is kept the temperature using heat insulating cloth, and tower reactor uses
Electric heating cover heating and magnetic agitation, tower head heating tape temperature control, condenser use tap water when steaming front-end volatiles and changeover portion
Condensation cooling, and realized in fraction needed for rectifying using hot water constant temperature water circulation.Receive the trident dovetail pipe of sample part with
Diaphragm pump is connected, and shows vacuum degree according to vacuum meter.
The magnetic agitation started in tower reactor is stirred, and is opened vacuum diaphragm pump and slowly depressurized, when system vacuum degree reaches
To 5-10Pa or so and keep after stablizing, solids in heat tower reactor.Rise with temperature, gradually collect front-end volatiles, changeover portion and
Paracresol；If paracresol purity is lower than 95%, secondary rectifying can be carried out according to same technique until purity reach 99% with
On.
Preferably, catalyst described in step 1) is CuCl, and the dosage of the catalyst is to account for weight in reaction system
About 2wt% to about 8wt%, preferably from about 2.5wt% are to about 5wt%, even more preferably about 3wt% to about 5wt%.
Preferably, in M-and P-cresols mixture described in step 1) molar ratio of metacresol and paracresol be 50:1 extremely
0.01:1, preferably 25:1 are to 0.05:1, more preferably 15:1 to 0.1:1.
Preferably, oxygen pressure described in step 1) is 0.1 to 5MPa, more preferably 0.5 to 3MPa, more preferably 0.5
To 1.5MPa.Also air can be used instead of oxygen, air pressure 0.5-5.0MPa.
Beneficial effect
Separation method according to the present invention uses air as oxidant, reaction condition nor room temperature due to oxidation reaction
With operation is simple, production cost is low, easy to industrialized production.In addition, the quinone compounds that reaction generates are important dye
The raw material of material and antioxidant, may be implemented high value added utilization, have good economic benefit.
Detailed description of the invention
Fig. 1 is the schematic diagram for indicating the device of spiral-screen column process used in rectifying separating step in embodiment 1；
Appended drawing reference: 1. condensers；2. tower head；3.5.10. temperature control point；4. insulation belt；6. tower body；7. tower reactor；8. magnetic force
Adjuster；9. stirring magneton；11. heating mantle；12. connecing sample device.
Specific embodiment
Hereinafter, will be described in detail the present invention.Before doing so, it should be appreciated that in this specification and appended
Claims used in term should not be construed as being limited to general sense and dictionary meanings, and inventor should allowed
On the basis of the appropriate principle for defining term to carry out best interpretations, according to meaning corresponding with technical aspect of the invention and generally
Thought explains.Therefore, description presented herein is not intended to limitation originally merely for the sake of the preferred embodiment for illustrating purpose
The range of invention, it will thus be appreciated that without departing from the spirit and scope of the present invention, it can be obtained by it
His equivalents or improved procedure.
The catalyst described in the step 1) of the method for separation M-and P-cresols mixture according to the present invention is CuCl.
It is surprisingly found by the inventors that CuCl is highly effective to the selective catalysis effect of M-and P-cresols mixture, and use other types
Catalyst cannot achieve the effect that CuCl catalyst.The CuCl catalyst amount is the pact for accounting for weight in reaction system
2wt% to about 8wt%, preferably from about 2.5wt% are to about 5wt%, even more preferably about 3wt% to about 5wt%.When dosage is less than
When 2wt%, catalytic effect is unobvious, and the reaction time is too long；When dosage is greater than 8wt%, then it is easy to produce more by-product, together
When be subsequent removing catalyst the step of make troubles.
Preferably, in M-and P-cresols mixture described in step 1) molar ratio of metacresol and paracresol be 50:1 extremely
0.01:1, preferably 25:1 are to 0.05:1, more preferably 15:1 to 0.1:1.When metacresol and paracresol are greater than 15:1, i.e., between
The amount of cresols is excessive, then reaction efficiency substantially reduces；When metacresol and paracresol are less than 0.1:1, paracresol can compare
Serious side reaction, reaction efficiency is equally bad, thus only in above range of the invention when, effect is best.
Following embodiment is enumerated only as the example of embodiment of the present invention, does not constitute any limit to the present invention
System, it will be appreciated by those skilled in the art that modification in the range of without departing from essence and design of the invention each falls within the present invention
Protection scope.Unless stated otherwise, reagent and instrument used in the following embodiment are commercially available product.
Embodiment 1
1) oxidation of M-and P-cresols mixture: by M-and P-cresols mixture (1.08g, metacresol: paracresol=1:1, mole
Than), catalyst (4.5wt%) and solvent (acetonitrile: 80ml and water: 4ml) be added in autoclave, close reaction kettle and simultaneously open
Stirring, is filled with oxygen to 1.0MPa, is kept for hour 8 hours after being warming up to 40 DEG C.It is cooled to room temperature after reaction, vent gas
And it opens reaction kettle and collects reaction post mother liquor；
Measure conversion ratio and yield by high performance liquid chromatography or silica gel column chromatography: high performance liquid chromatography uses Eclipe
Plus C18 column (250mm × 4.6mm, 5.0um), it is automatic in the Waters 1525 and 2707 with 2489UV-Vis detector
High performance liquid chromatography is carried out on sample injector, the standard sample by certification is used to determine the characteristic of product.Silicagel column uses 200-
The silica gel (petrol ether/ethyl acetate) of 300 mesh carries out column chromatography analysis.
The nuclear magnetic data of metacresol oxidation product is as follows:
1H NMR(600MHz,CDCl3)δ:6.71-6.78(m,2H),6.63(s,1H),2.07(s,3H)；
13C NMR(150MHz,CDCl3)δ:187.8,187.6,145.9,136.6,136.5,133.4,15.9.
2) rectifying separates: being evaporated under reduced pressure (0.01MPa, 50 DEG C) processing, removal reaction dissolvent and reaction life to mother liquor
At water, reaction dissolvent recovery collects the remaining total 1.0g of solid mixture, wherein paracresol content 55wt%, methyl
1,4-benzoquinone 43wt%, remaining as solid residue.Solid mixture is collected after repeatedly reacting and amounts to 150g, and rectifying tower is added
Kettle.
The magnetic agitation started in tower reactor is stirred, and is opened vacuum diaphragm pump and slowly depressurized, when system vacuum degree reaches
To 5-10Pa or so and keep after stablizing, solids in heat tower reactor.Rise with temperature, gradually collect front-end volatiles, changeover portion and
Paracresol.Condenser is cooled down when steaming front-end volatiles and changeover portion using originally water condensation, and 60 are used in fraction needed for rectifying
DEG C hot water constant temperature water circulation is realized.If the paracresol purity collected is lower than 95%, secondary fine can be carried out according to same technique
It evaporates until purity reaches 99% or more.Design parameter is according to parameter listed by number 1 in the following table 1.
Fig. 1 is the schematic diagram for indicating the device of spiral-screen column process used in rectifying separating step in the present embodiment.
Embodiment 2 to 4
Paracresol is separated according to the identical mode of embodiment 1, design parameter is according to listed by number 2 to 4 in the following table 1.
As it can be seen that pure paracresol can be obtained after rectification process, purity can satisfy the purity of production 99% or more
It is required that.
Embodiment 5 to 14: cuprous chloride catalyst compares the catalysis oxidation result of M-and P-cresols mixture.
The oxidation of M-and P-cresols mixture is carried out according to the identical mode of step 1) in embodiment 1, response parameter is under
It is listed in table 2.
Table 2
It can be seen that the conversion that metacresol can be efficiently realized using CuCl according to the data of embodiment 5 to 14.
Claims (8)
1. it is a kind of separate M-and P-cresols mixture method the following steps are included:
1) oxidation of M-and P-cresols mixture: M-and P-cresols mixture, catalyst and solvent are added in autoclave, are closed
Reaction kettle simultaneously opens stirring, is filled with oxygen or air to specified pressure, is kept for 2-10 hours after being warming up to reaction temperature, reaction knot
It is cooled to room temperature after beam, vent gas simultaneously opens reaction kettle collection reaction post mother liquor；
2) rectifying separates: vacuum distillation processing is carried out to mother liquor obtained in step 1), what removal reaction dissolvent and reaction generated
Water, reaction dissolvent recovery collect remaining solid mixture and tower bottom of rectifying tower are added；
The magnetic agitation started in tower reactor is stirred, and is opened vacuum diaphragm pump and slowly depressurized, when system vacuum degree reaches 5-
10Pa or so is simultaneously kept after stablizing, and solids in heat tower reactor rises with temperature, gradually collects front-end volatiles, changeover portion and to first
Phenol；If paracresol purity is lower than 95%, secondary rectifying can be carried out according to same technique until purity reaches 99% or more.
2. the method for separation M-and P-cresols mixture according to claim 1, which is characterized in that be catalyzed described in step 1)
Agent is CuCl, and the dosage of the catalyst is the about 2wt% to about 8wt%, preferably from about 2.5wt% for accounting for weight in reaction system
To about 5wt%, even more preferably about 3wt% to about 5wt%.
3. the method for separation M-and P-cresols mixture according to claim 1, which is characterized in that right between described in step 1)
The molar ratio of metacresol and paracresol is 50:1 to 0.01:1 in cresols mixture.
4. the method for separation M-and P-cresols mixture according to claim 3, which is characterized in that the M-and P-cresols mixing
The molar ratio of metacresol and paracresol is 25:1 to 0.05:1 in object.
5. the method for separation M-and P-cresols mixture according to claim 3, which is characterized in that the M-and P-cresols mixing
The molar ratio of metacresol and paracresol is 15:1 to 0.1:1 in object.
6. the method for separation M-and P-cresols mixture according to claim 1, which is characterized in that oxygen described in step 1)
Pressure is 0.1 to 5MPa, more preferably 0.5 to 3MPa, more preferably 0.5 to 1.5MPa, and air also can be used and replace oxygen,
Air pressure 0.5-5.0MPa.
7. the method for separation M-and P-cresols mixture according to claim 6, which is characterized in that oxygen described in step 1)
Pressure is 0.5 to 3MPa.
8. the method for separation M-and P-cresols mixture according to claim 6, which is characterized in that oxygen described in step 1)
Pressure is 0.5 to 1.5MPa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111470952A (en) * | 2020-04-30 | 2020-07-31 | 厦门中坤化学有限公司 | Method for preparing high-purity m-cresol by selectively oxidizing m-p-mixed cresol |
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| CN105061156A (en) * | 2015-09-01 | 2015-11-18 | 侯颖 | Method for effectively separating and preparing m-cresol |
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| CN107445806A (en) * | 2017-07-17 | 2017-12-08 | 天津大学 | Complexation-crystallization method separating-purifying metacresol and paracresol method |
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| CN105061156A (en) * | 2015-09-01 | 2015-11-18 | 侯颖 | Method for effectively separating and preparing m-cresol |
| CN105949037A (en) * | 2016-03-23 | 2016-09-21 | 中国科学院过程工程研究所 | Refining method of crude phenol from coking |
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| CN111470952A (en) * | 2020-04-30 | 2020-07-31 | 厦门中坤化学有限公司 | Method for preparing high-purity m-cresol by selectively oxidizing m-p-mixed cresol |
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