CN107445806A - Complexation-crystallization method separating-purifying metacresol and paracresol method - Google Patents
Complexation-crystallization method separating-purifying metacresol and paracresol method Download PDFInfo
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- CN107445806A CN107445806A CN201710580781.XA CN201710580781A CN107445806A CN 107445806 A CN107445806 A CN 107445806A CN 201710580781 A CN201710580781 A CN 201710580781A CN 107445806 A CN107445806 A CN 107445806A
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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
- C07C37/685—Processes comprising at least two steps in series
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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
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
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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
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
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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
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
- C07C39/06—Alkylated phenols
- C07C39/07—Alkylated phenols containing only methyl groups, e.g. cresols, xylenols
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Abstract
The present invention relates to a kind of complexation-crystallization method separating-purifying metacresol and paracresol method；The paracresol of high-purity is first obtained by complexation-crystallization using triethylene diamine as complexing agent, again using this filtrate in operating as reactant, the use of sodium acetate is that complexing agent therefrom purifies metacresol by complexation-crystallization, in order to improve whole process yield, the filtrate in sodium acetate method is recirculated back to the first step and is continuing with as reactant.This method can obtain metacresol and paracresol product of the purity more than 99.5% simultaneously, by the way that filtrate rectifying Posterior circle is used, maximally utilised raw material, the whole process yield of the flow is can reach more than 99%.The organic solvent and complexing agent used in course of reaction can recycle on stream, discharged without " three wastes ", reached green purpose.In addition, the complexing agent selected in the present invention is compared with prior art, reacts gentleer with temperature conditionss required during decrease temperature crystalline, greatly reduce energy consumption.
Description
Technical field
The invention belongs to field of chemical separation and purification.More specifically to between complexation-crystallization method separating-purifying/to first
Phenol mixture, so as to obtain the method for the metacresol and paracresol product of high-purity simultaneously.
Background technology
The metacresol and paracresol of high-purity are important fine-chemical intermediate, therefore for a long time ,/paracresol
Separation be always chemical field hot subject.Metacresol is production agricultural chemicals, antioxidant, spices, phenolic resin, vitamin
E, the important source material of dyestuff, fluorescent whitening agent, solvent, plasticizer and fire retardant etc..Due to using metacresol to be produced as raw material
Downstream product there is vast potential for future development, therefore China is protected for the demand of metacresol with 8~10% annual growth
Hold rapid growth.And paracresol is then widely used in medicine, herbicide, antioxidant, agricultural chemicals, the synthesis of spices and dyestuff.
The boiling point of metacresol (202.9 DEG C) and paracresol (202.5 DEG C) very close to, it is impossible to carried out with traditional rectificating method
Separation.Although the fusing point of metacresol (10.9 DEG C) and paracresol (34.7 DEG C) difference is larger, congruent melting area and high viscosity stream be present
The shortcomings that body, limits the application of conventional crystallization methods.Wide coverage and the compartment first mainly applied in industry in document at present
The method of phenol and paracresol is broadly divided into Physical and the major class of chemical method two.The physical method of compartment/paracresol mainly includes
Adsorption method of separation, extraction, crystallisation and film osmosis etc.；Chemical method then mainly includes alkylation process and reaction-crystallization method
Deng.Wherein, the selection of high-efficiency adsorbent and prepare more difficult in adsorption method of separation, adsorbance is limited and needs a large amount of strippants；Extraction
Substantial amounts of organic solvent need to be used by following the example of, and easily environment is polluted；High voltage junction crystallization and recrystallization method can be produced to equipment
It is required that the problem of higher or use a large amount of organic solvents；The technical matters of film osmosis is still immature, can not also be applied to big rule
Mould industrial production；Though alkylation process can realize between/separation of paracresol high-purity, there is also complex process, equipment and operation
The shortcomings that somewhat expensive；And complexation-crystallization rule has the advantages that product purity is high, easy to operate, green, compartment/
Paracresol field has very high research and application prospect.
The technology on complexation-crystallization method compartment/paracresol mixture delivered at present, such as《Chemical industry in Jiangsu Province》1997
05 phase, 21；《Modern chemical industry》, the 6th phase of volume 17,28；Patent document US3855195, CN104098445A, JP2010059137
Paracresol and urea method purification metacresol are purified etc. research piperazine method is focused primarily upon, is not only seldom related to for new complexing agent
Exploration, and single product can only be obtained, the waste of raw material be caused, without economy and the feature of environmental protection.Therefore, research is sought
New efficient complexing agent is looked for, is designed while obtains metacresol and the process route of two kinds of products of paracresol is to make complexation-crystallization method
Compartment/paracresol realizes the urgent problem to be solved of industrial applications.
The content of the invention
The present invention relates to a kind of complexation-crystallization method separating-purifying metacresol and paracresol method；First using triethylene diamine as network
Mixture obtains the paracresol of high-purity by complexation-crystallization, then using this filtrate in operating as reactant, uses sodium acetate
Metacresol is therefrom purified by complexation-crystallization for complexing agent, in order to improve whole process yield, the filtrate in sodium acetate method is recirculated back to
The first step is continuing with as reactant.This method can obtain metacresol and paracresol production of the purity more than 99.5% simultaneously
Product, by the way that filtrate rectifying Posterior circle is used, raw material is maximally utilised, the whole process yield of the flow is can reach 99%
More than.The organic solvent and complexing agent used in course of reaction can recycle on stream, discharge, reach without " three wastes "
Green purpose.In addition, the complexing agent selected in the present invention is compared with prior art, it is required when reacting with decrease temperature crystalline
Temperature conditionss it is gentleer, greatly reduce energy consumption.
Technical scheme is as follows:
A kind of complexation-crystallization method separating-purifying metacresol and paracresol method；It is characterized in that step is as follows：
1) paracresol complexation-crystallization：Between raw material is mixed/paracresol added in reactor after weighing volume, measure with it is former
It is 2.0 to expect mixture cresol volume ratio:1~3.0:1 solvent n-butyl ether is added in reactor, and the two is well mixed so that cresols is complete
It is dissolved in entirely in n-butyl ether；It is 0.7 to add thereto again with paracresol mol ratio:1~0.9:1 complexing agent triethylene diamine or six
Water triethylene diamine, react 2~4h in 90 DEG C of heating water baths and under conditions of stirring；After reaction terminates, reaction solution is moved into and tied
Decrease temperature crystalline is carried out in brilliant device, cooling rate is 5~15 DEG C/h, and crystallization final temperature is -10~10 DEG C, reaches -10~10 DEG C
Constant temperature keeps 2~4h afterwards；
2) filtration washings, rectifying：The reaction solution after decrease temperature crystalline is filtered to obtain filtrate and filter cake using vavuum pump,
Toluene is reused as detergent washing repeatedly is carried out to filter cake and filtered, obtain final filtrate and filter cake, filtrate be solvent with
The mixture of mixture cresol 1, respectively after rectifying separation, overhead product obtains n-butyl ether, and return to n-butyl ether groove makes as solvent circulation
With toluene recycles as extractant, and tower reactor product is that mixture cresol 1 is continuing with as the raw material of separation metacresol；
3) decomplexings extract：Weigh in step 2) filter cake quality that finally gives and with deionized water in decomposer is crystallized
Dissolving, it is 1 to add with deionized water quality ratio:1 toluene is added in liquid separation groove, layering as extractant after being well mixed
Complexing agent is dissolved in lower floor's aqueous phase afterwards, and paracresol is then dissolved in upper organic phase, and organic phase is separated from the water；
4) rectifying：The upper organic phase obtained to step 3) carries out rectifying, and overhead distillate is extractant toluene, returns
Recycled in crystallization decomposer, be then product paracresol in tower reactor；
5) evaporates：Lower floor's aqueous phase that step 3) obtains is evaporated crystallization to reclaim the water triethylene diamine of complexing agent six
And recycle；
6) metacresols complexation-crystallization：Using the mixture cresol 1 that step 2) obtains as separation metacresol raw material in the reactor
It is 1.0 to be dissolved in its volume ratio:1~2.0:1 toluene or benzene solvent, then complexing agent sodium acetate is added into reactor, add
Complexing agent and raw material in metacresol mol ratio be 2.1:1；Reacted under 20~40 DEG C of water bath conditions, course of reaction
In, reactant is stirred using electric mixer；After reacting 8~12h, decrease temperature crystalline in crystallizer, cooling rate are transferred to
For 5~15 DEG C/h, crystallization final temperature is -20~0 DEG C and keeps 3~5h；
7) filtration washings, rectifying：Crystallization Separation is out obtained into filtrate and filter cake by filtering, used during suction filtration
Toluene washs suction filtration to filter cake and obtains final filtrate and filter cake repeatedly；Filtrate rectifying is separated, the solvent that recovery tower top distillates
Toluene, return and recycled in toluene groove, tower reactor product mixture cresol 2 is mixed and recycled with raw material in step 1)；
8) decomplexings extract：The filter cake that step 7) is finally given, which is weighed, to be put into crystal separator, adds deionized water,
Filter cake is completely dissolved in water with magnetic stirrer, add the toluene with the quality such as water, after being well mixed using point
Liquid funnel carries out extracting operation to it, and complexing agent is dissolved in lower floor's aqueous phase after layering, and metacresol is then dissolved in upper organic phase, will be organic
It is mutually separated from the water；
9) rectifying：Rectifying separating step 8) obtained upper organic phase, tower top primary product is toluene, can be returned after processing
Return in crystal separator and recycled as extractant；Tower kettle product is then product metacresol；
10) evaporates：The lower floor's aqueous phase obtained to step 8), which is evaporated, crystallizes and takes off the crystallization water, obtains anhydrous sodium acetate,
It is recovered into sodium acetate groove and is recycled as complexing agent.
Detergent toluene temperature is -10~10 DEG C in the step 2).
Detergent toluene temperature is -20~0 DEG C in the step 7).
The quality of detergent used in washing is gained filter cake quality after suction filtration every time every time in the step 2) or step 7)
1~3 times.
Complexing agent sodium acetate used in the step 6) is anhydrous sodium acetate.
The invention provides between a kind of high-recovery, green separating-purifying/method of paracresol mixture.Relatively
Other separation methods, the present invention can obtain two kinds of products of metacresol and paracresol of high-purity simultaneously, and raw material can be in flow
Middle recycling, in the absence of the waste of raw material, the rate of recovery is improved to greatest extent；Whole technological process does not produce " three wastes ",
Equipment requirement is low, belongs to environmentally friendly green separation technique.
The present invention effect be：Metacresol and paracresol product of the purity more than 99.5% can be obtained simultaneously, pass through by
Filtrate rectifying Posterior circle uses, and has maximally utilised raw material, the whole process yield of the flow is can reach more than 99%.Reaction
During the organic solvent that uses and complexing agent can recycle on stream, discharged without " three wastes ", reached green ring
The purpose of guarantor.In addition, the complexing agent selected in the present invention is compared with prior art, react and temperature strip required during decrease temperature crystalline
Part is gentleer, greatly reduces energy consumption.
The present invention effect be：Metacresol and paracresol product of the purity more than 99.5% can be obtained simultaneously, pass through by
Filtrate rectifying Posterior circle uses, and has maximally utilised raw material, the whole process yield of the flow is can reach more than 99%.Reaction
During the organic solvent that uses and complexing agent can recycle on stream, discharged without " three wastes ", reached green ring
The purpose of guarantor.In addition, the complexing agent selected in the present invention is compared with prior art, react and temperature strip required during decrease temperature crystalline
Part is gentleer, greatly reduces energy consumption.
Brief description of the drawings
Fig. 1 is triethylene diamine-sodium acetate coupled method separation metacresol and paracresol flow chart, illustrates designed technique
Two kinds of products of metacresol and paracresol can be obtained simultaneously, and raw material can recycle, ensure that in high yield with it is green.
Embodiment
With reference to specific embodiment, the present invention is further illustrated, but the present invention is not imposed any restrictions；This
Invention methods described can be completed on the process route in including but not limited to figure.
Embodiment 1：
1) paracresol complexation-crystallization：Between raw material is mixed/paracresol (metacresol 60%, paracresol 40%) weighing volume
Add afterwards in reactor, it is 2.0 to measure with raw material mixture cresol volume ratio:1 solvent n-butyl ether is added in reactor, and the two is mixed
Close uniformly so that cresols is completely dissolved in n-butyl ether.It is 0.9 to add thereto again with paracresol mol ratio:1 complexing agent
DABCO·6H2O, react 2h in 90 DEG C of heating water baths and under conditions of being stirred vigorously.After reaction terminates, reaction solution is moved into and tied
Decrease temperature crystalline is carried out in brilliant device, cooling rate is 10 DEG C/h, and crystallization final temperature is -10 DEG C, and constant temperature is kept after reaching -10 DEG C
3h；
2) filtration washings, rectifying：The reaction solution after decrease temperature crystalline is filtered to obtain filtrate and filter cake using vavuum pump,
- 10 DEG C of toluene are reused as detergent carry out filter cake washing to filter and obtain final filtrate and filter cake 5 times, wherein, every time
Wash 2 times that toluene quality used in filter cake is gained filter cake quality after filtering every time.Filtrate is the mixing of solvent and mixture cresol 1
Thing, respectively after rectifying separation, overhead product can obtain n-butyl ether, returns to n-butyl ether groove and is recycled as solvent, toluene can be made
Recycled for extractant, tower reactor product is that raw material of the mixture cresol 1 then as separation metacresol is continuing with；
3) decomplexings extract：Weigh in step 2) filter cake quality that finally gives and with deionized water in decomposer is crystallized
Dissolving, deionized water are 2.0 with filter cake quality ratio:1, it is 1 to add with deionized water quality ratio:1 toluene as extractant,
Added after well mixed in separatory funnel, complexing agent is dissolved in lower floor's aqueous phase after layering, and paracresol is then dissolved in upper organic phase, will have
Machine is mutually separated from the water；
4) rectifying：The upper organic phase obtained to step 3) carries out rectifying, and overhead distillate is extractant toluene, returns
It can be recycled in crystallization decomposer, be then product paracresol in tower reactor；
5) evaporates：Lower floor's aqueous phase that step 3) obtains is evaporated crystallization to reclaim complexing agent DABCO6H2O is simultaneously followed
Ring uses；
6) metacresols complexation-crystallization：Using the mixture cresol 1 that step 2) obtains as separation metacresol raw material in the reactor
It is 2.0 to be dissolved in its volume ratio:1 toluene solvant, then complexing agent sodium acetate is added into reactor, complexing agent and the original of addition
The mol ratio of metacresol is 2.1 in material:1.Reacted under 20 DEG C of water bath conditions, in course of reaction, use electric mixer
Reactant is stirred vigorously.After reacting 12h, decrease temperature crystalline in crystallizer is transferred to, cooling rate is 10 DEG C/h, and crystallization terminates
Temperature is 0 DEG C and keeps 4h；
7) filtration washings, rectifying：Crystallization Separation is out obtained into filtrate and filter cake by filtering, 0 is used during suction filtration
DEG C toluene filter cake is washed repeatedly 4 times and obtains final filtrate and filter cake, toluene quality used in washing is filters every time every time
3 times of gained filter cake quality afterwards.Filtrate rectifying is separated, the solvent toluene that recovery tower top distillates, returning to circulate in toluene groove makes
With tower reactor product mixture cresol 2 is mixed and recycled with raw material in step 1)；
8) decomplexings extract：Filter cake is weighed and is put into crystal separator, it is 2.0 to add with filter cake quality ratio:1 go from
Sub- water, filter cake is completely dissolved in water with magnetic stirrer, add the toluene with the quality such as water, make after well mixed
Extracting operation is carried out to it with separatory funnel, complexing agent is dissolved in lower floor's aqueous phase after layering, and metacresol is then dissolved in upper organic phase, will
Organic phase is separated from the water；
9) rectifying：Rectifying separating step 8) obtained upper organic phase, tower top primary product is toluene, can be returned after processing
Return in crystal separator and recycled as extractant；Tower kettle product is then product metacresol；
10) evaporates：The lower floor's aqueous phase obtained to step 8), which is evaporated, crystallizes and takes off the crystallization water, can obtain anhydrous acetic acid
Sodium, it is recovered into sodium acetate groove and is recycled as complexing agent.
The purity and the purity and once through yield of once through yield and metacresol product of paracresol product are analyzed, analysis result is shown in
Table 1.
Embodiment 2：
Experimental provision and operating process are the same as embodiment 1, simply in step 1), complexing agent DABCO6H2O is replaced by
DABCO, analysis result are shown in Table 1.
Embodiment 3：
Experimental provision and operating process are the same as embodiment 1, simply in step 1), the volume of solvent n-butyl ether and raw material mixture cresol
Than being replaced by 2.5:1, the complexing agent DABCO6H of addition2O is changed to 0.8 with the paracresol mol ratio in raw material mixture cresol:1,
Reaction time is changed into 3h, and cooling rate is 5 DEG C/h, and constant temperature keeps 2h after reaching -10 DEG C；In step 2), first used in each washing
Benzene quality is identical for gained filter cake quality after suction filtration every time, and analysis result is shown in Table 1.
Embodiment 4：
Experimental provision and operating process are the same as embodiment 1, simply in step 1), the volume of solvent n-butyl ether and raw material mixture cresol
Than being replaced by 3.0:1, the complexing agent DABCO6H of addition2O is changed to 0.7 with the paracresol mol ratio in raw material mixture cresol:1,
Reaction time is changed into 4h, and cooling rate is 15 DEG C/h, and constant temperature keeps 4h after reaching -10 DEG C；In step 2), first used in each washing
Benzene quality is 3 times of gained filter cake quality after suction filtration every time, and analysis result is shown in Table 1.
Embodiment 5：
Experimental provision and operating process are the same as embodiment 1, simply in step 1), the volume of solvent n-butyl ether and raw material mixture cresol
Than being replaced by 2.5:1, the reaction time is changed into 4h, and crystallization final temperature is replaced by 0 DEG C, and constant temperature keeps 3h after reaching 0 DEG C；Step 2)
In, toluene temperature used in washing is 0 DEG C every time, and quality is identical with gained filter cake quality after suction filtration every time, and analysis result is shown in Table 1.
Embodiment 6：
Experimental provision and operating process are the same as embodiment 1, simply in step 1), the volume of solvent n-butyl ether and raw material mixture cresol
Than being replaced by 3.0:1, the complexing agent DABCO6H of addition2O is changed to 0.8 with the paracresol mol ratio in raw material mixture cresol:1,
Crystallization final temperature is replaced by 0 DEG C, and constant temperature keeps 3h after reaching 0 DEG C；In step 2), toluene temperature used in washing is 0 DEG C every time,
Quality is 3 times of gained filter cake quality after suction filtration every time, and analysis result is shown in Table 1.
Embodiment 7：
Experimental provision and operating process are the same as embodiment 1, simply in step 1), the volume of solvent n-butyl ether and raw material mixture cresol
Than being replaced by 3.0:1, the reaction time is changed into 3h, and crystallization final temperature is replaced by 10 DEG C, and constant temperature keeps 4h after reaching 10 DEG C；Step
2) in, toluene temperature used in washing is 10 DEG C every time, and quality is 3 times of gained filter cake quality after each filter, and analysis result is shown in
Table 1.
Embodiment 8：
Experimental provision and operating process are the same as embodiment 1, simply in step 1), the complexing agent DABCO6H of addition2O and original
Paracresol mol ratio in material mixture cresol is changed to 0.8:1, the reaction time is changed into 4h, and crystallization final temperature is replaced by 10 DEG C, reached
Constant temperature keeps 4h after to 10 DEG C；In step 2), toluene temperature is 10 DEG C used in washing every time, and analysis result is shown in Table 1.
Embodiment 9：
Experimental provision and operating process are the same as embodiment 1, simply in step 1), the volume of solvent n-butyl ether and raw material mixture cresol
Than being replaced by 2.5:1, the complexing agent DABCO6H of addition2O is changed to 0.7 with the paracresol mol ratio in raw material mixture cresol:1,
Crystallization final temperature is replaced by 10 DEG C, and constant temperature keeps 4h after reaching 10 DEG C；In step 2), toluene temperature used in suction filtration is 10 every time
DEG C, quality is identical with gained filter cake quality after suction filtration every time, and analysis result is shown in Table 1.
Embodiment 10：
Experimental provision and operating process are with embodiment 1, and simply in step 6), solvent toluene is replaced by benzene, and analysis result is shown in
Table 1.
Embodiment 11：
Experimental provision and operating process are the same as embodiment 1, simply in step 6), the volume of solvent toluene and raw material mixture cresol 1
Than being replaced by 1.0:1, the reaction time is changed into 8h, and crystallization final temperature is replaced by -20 DEG C, and cooling rate is 15 DEG C/h, reaches -20
Constant temperature keeps 3h after DEG C；In step 7), toluene temperature used in washing is -20 DEG C every time, and quality with filtering gained filter cake matter every time
Measure identical, analysis result is shown in Table 1.
Embodiment 12：
Experimental provision and operating process are the same as embodiment 1, simply in step 6), the volume of solvent toluene and raw material mixture cresol 1
Than being replaced by 1.5:1, the reaction time is changed into 10h, and crystallization final temperature is replaced by -10 DEG C, and constant temperature keeps 4h after reaching -10 DEG C；
In step 7), toluene temperature used in washing is -10 DEG C every time, and quality is filters 2 times of gained filter cake quality every time, analysis result
It is shown in Table 1.
Embodiment 13：
Experimental provision and operating process are the same as embodiment 1, simply in step 6), the volume of solvent toluene and raw material mixture cresol 1
Than being replaced by 1.5:1, reaction temperature is changed into 30 DEG C, and crystallization final temperature is replaced by -20 DEG C, and cooling rate is 15 DEG C/h, reach -
Constant temperature keeps 3h after 20 DEG C；In step 7), toluene temperature used in washing is -20 DEG C every time, and quality filters gained filter cake to be each
2 times of quality, analysis result is shown in Table 1.
Embodiment 14：
Experimental provision and operating process are the same as embodiment 1, simply in step 6), the volume of solvent toluene and raw material mixture cresol 1
Than being replaced by 1.0:1, reaction temperature is changed into 30 DEG C, and the reaction time is replaced by 10h, and cooling rate is 5 DEG C/h, permanent after reaching 0 DEG C
Temperature keeps 5h；In step 7), toluene quality used in washing is identical with filtering gained filter cake quality every time every time, and analysis result is shown in Table
1。
Metacresol content in raw material and product is determined with paracresol content by gas chromatography.The chromatograph used is peace
Prompt human relations 7890A type gas-chromatographies, using fid detector, carrier gas is provided by high pure nitrogen, nebulizer gas pressure 0.5MPa, required
Hydrogen and air are provided by hydrogen generator and air generator respectively.Due to metacresol and paracresol isomer use it is general
Logical polarity chromatographic column is difficult separation, and in order to reach preferable separating effect, chromatographic column selects chiral column Agilent CP-
Chirasil (200 DEG C, 25m × 0.25 μm of 250 μ m).
The embodiment experimental result of table 1
To sum up the form of implementation column and accompanying drawing can also clearly be found out, the technological process designed by the present invention can the same time-division
From the two kinds of products of metacresol and paracresol for obtaining high-purity, and raw material can be recycled in the technological process, have high return
Yield, it is green the advantages of.
The process of a kind of complexation-crystallization method separating-purifying metacresol and paracresol that the present invention is disclosed and proposed, ability
Field technique personnel can be by using for reference present disclosure, and the appropriate links such as condition route that change are realized, although the method and system of the present invention
Standby technology is described by preferred embodiment, and person skilled can substantially not depart from present invention, spirit
Methods and techniques described herein route is modified or reconfigured with scope, to realize final technology of preparing.It is special
Not it is pointed out that all similar replacements and apparent to those skilled in the art, the Ta Mendou of change
It is deemed to be included in spiritual, scope and content of the invention.
Claims (5)
1. a kind of complexation-crystallization method separating-purifying metacresol and paracresol method；It is characterized in that step is as follows：
1) paracresol complexation-crystallization：Between raw material is mixed/paracresol weigh volume after add reactor in, measure and mixed with raw material
Cresols volume ratio is 2.0:1~3.0:1 solvent n-butyl ether is added in reactor, and the two is well mixed so that cresols is completely molten
In n-butyl ether；It is 0.7 to add thereto again with paracresol mol ratio:1~0.9:1 complexing agent triethylene diamine or six water three
Ethylene diamine, react 2~4h in 90 DEG C of heating water baths and under conditions of stirring；After reaction terminates, reaction solution is moved into crystallizer
Middle carry out decrease temperature crystalline, cooling rate are 5~15 DEG C/h, and crystallization final temperature is -10~10 DEG C, permanent after reaching -10~10 DEG C
Temperature keeps 2~4h；
2) filtration washings, rectifying：The reaction solution after decrease temperature crystalline is filtered using vavuum pump to obtain filtrate and filter cake, then made
Washing suction filtration is carried out repeatedly to filter cake by the use of toluene as detergent and obtains final filtrate and filter cake, filtrate is solvent and mixture cresol
1 mixture, respectively after rectifying separation, overhead product obtains n-butyl ether, returns to n-butyl ether groove and is recycled as solvent, toluene
Recycled as extractant, tower reactor product is that mixture cresol 1 is continuing with as the raw material of separation metacresol；
3) decomplexings extract：Weigh the filter cake quality finally given in step 2) and dissolved with deionized water in decomposer is crystallized,
It is 1 to add with deionized water quality ratio:1 toluene is added in liquid separation groove after being well mixed, is complexed after layering as extractant
Agent is dissolved in lower floor's aqueous phase, and paracresol is then dissolved in upper organic phase, and organic phase is separated from the water；
4) rectifying：The upper organic phase obtained to step 3) carries out rectifying, and overhead distillate is extractant toluene, returns to crystallization
Recycled in decomposer, be then product paracresol in tower reactor；
5) evaporates：Lower floor's aqueous phase that step 3) obtains is evaporated crystallization to reclaim the water triethylene diamine of complexing agent six and follow
Ring uses；
6) metacresols complexation-crystallization：The mixture cresol 1 that step 2) is obtained is dissolved in the reactor as the raw material of separation metacresol
It is 1.0 with its volume ratio:1~2.0:1 toluene or benzene solvent, then complexing agent sodium acetate, the network of addition are added into reactor
The mol ratio of mixture and metacresol in raw material is 2.1:1；Reacted under 20~40 DEG C of water bath conditions, in course of reaction, made
Reactant is stirred with electric mixer；After reacting 8~12h, decrease temperature crystalline in crystallizer is transferred to, cooling rate is 5~
15 DEG C/h, crystallization final temperature is -20~0 DEG C and keeps 3~5h；
7) filtration washings, rectifying：Crystallization Separation is out obtained into filtrate and filter cake by filtering, toluene is used during suction filtration
Wash suction filtration repeatedly to filter cake and obtain final filtrate and filter cake；Filtrate rectifying is separated, the solvent toluene that recovery tower top distillates,
Return and recycled in toluene groove, tower reactor product mixture cresol 2 is mixed and recycled with raw material in step 1)；
8) decomplexings extract：The filter cake that step 7) is finally given, which is weighed, to be put into crystal separator, is added ionized water, is used magnetic force
Agitator stirring makes filter cake be completely dissolved in water, adds the toluene with the quality such as water, separatory funnel is used after well mixed
Extracting operation is carried out to it, complexing agent is dissolved in lower floor's aqueous phase after layering, and metacresol is then dissolved in upper organic phase, by organic phase and water
It is separated；
9) rectifying：Rectifying separating step 8) obtained upper organic phase, tower top primary product is toluene, and knot is can return to after processing
Recycled in brilliant separator as extractant；Tower kettle product is then product metacresol；
10) evaporates：The lower floor's aqueous phase obtained to step 8), which is evaporated, crystallizes and takes off the crystallization water, anhydrous sodium acetate is obtained, by it
It is recovered into sodium acetate groove and is recycled as complexing agent.
2. the method as described in claim 1, it is characterized in that detergent toluene temperature is -10~10 DEG C in step 2).
3. the method as described in claim 1, it is characterized in that detergent toluene temperature is -20~0 DEG C in step 7).
4. the method as described in claim 1, it is characterized in that the quality of detergent used in washing every time in step 2) or step 7)
For 1~3 times of gained filter cake quality after suction filtration every time.
5. the method as described in claim 1, it is characterized in that the complexing agent sodium acetate used in step 6) is anhydrous sodium acetate.
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| CN115124408A (en) * | 2022-07-28 | 2022-09-30 | 天津大学 | Co-crystallization resolution method of cresol isomer mixture |
| CN115974656A (en) * | 2022-12-12 | 2023-04-18 | 南京工业大学 | Method for separating cresol isomer by membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108558609A (en) * | 2018-05-10 | 2018-09-21 | 江苏焕鑫新材料股份有限公司 | A kind of polyphenol mixture recycling purifying technique |
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| CN109776276A (en) * | 2019-03-20 | 2019-05-21 | 中国科学院青岛生物能源与过程研究所 | A method of M-and P-cresols mixture is separated using selective oxidation catalyst |
| CN111909004A (en) * | 2019-05-10 | 2020-11-10 | 陕西省石油化工研究设计院 | Method for separating m-cresol from p-cresol |
| CN115124408A (en) * | 2022-07-28 | 2022-09-30 | 天津大学 | Co-crystallization resolution method of cresol isomer mixture |
| CN115124408B (en) * | 2022-07-28 | 2023-07-25 | 天津大学 | Co-crystallization resolution method of cresol isomeride mixture |
| CN115974656A (en) * | 2022-12-12 | 2023-04-18 | 南京工业大学 | Method for separating cresol isomer by membrane |
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