CN101781175B - Method for separating 2,4-Dichlorophenol and 2,6-Dichlorophenol - Google Patents
Method for separating 2,4-Dichlorophenol and 2,6-Dichlorophenol Download PDFInfo
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- chlorophenesic acid
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- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 30
- HOLHYSJJBXSLMV-UHFFFAOYSA-N 2,6-dichlorophenol Chemical compound OC1=C(Cl)C=CC=C1Cl HOLHYSJJBXSLMV-UHFFFAOYSA-N 0.000 title abstract description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 239000000706 filtrate Substances 0.000 claims abstract description 22
- 239000012065 filter cake Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012043 crude product Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 123
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 21
- 238000001953 recrystallisation Methods 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 17
- 238000000605 extraction Methods 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 239000012044 organic layer Substances 0.000 claims description 9
- 238000013517 stratification Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 abstract description 12
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 abstract description 11
- 238000000926 separation method Methods 0.000 abstract description 6
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000013341 scale-up Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- -1 Dichlorophenoxy Chemical group 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010494 dissociation reaction Methods 0.000 description 5
- 230000005593 dissociations Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- TWWCTGIBOJFDNL-UHFFFAOYSA-N C1(=CC=CC=C1)O.ClC1=CC=CC(=C1)Cl Chemical compound C1(=CC=CC=C1)O.ClC1=CC=CC(=C1)Cl TWWCTGIBOJFDNL-UHFFFAOYSA-N 0.000 description 1
- 239000005588 Oxadiazon Substances 0.000 description 1
- CHNUNORXWHYHNE-UHFFFAOYSA-N Oxadiazon Chemical compound C1=C(Cl)C(OC(C)C)=CC(N2C(OC(=N2)C(C)(C)C)=O)=C1Cl CHNUNORXWHYHNE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- JFIOVJDNOJYLKP-UHFFFAOYSA-N bithionol Chemical compound OC1=C(Cl)C=C(Cl)C=C1SC1=CC(Cl)=CC(Cl)=C1O JFIOVJDNOJYLKP-UHFFFAOYSA-N 0.000 description 1
- 229960002326 bithionol Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- XITQUSLLOSKDTB-UHFFFAOYSA-N nitrofen Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC1=CC=C(Cl)C=C1Cl XITQUSLLOSKDTB-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for separating 2,4-Dichlorophenol and 2,6-Dichlorophenol, comprising the following steps: dissolving the mixture of the 2,4-Dichlorophenol and the 2,6-Dichlorophenol in an organic solvent, adding alkalic organism, stirring and reacting at the temperature of 40-80 DEG C until the reaction liquid is clear, cooling the reaction liquid after the reaction is finished, standing and precipitating crystals, filtering to obtain a filter cake A and a filtrate A, and retaining the 2,4-Dichlorophenol in the filtrate A, wherein the filter cake A is a crude product of the 2,6-Dichlorophenol; the alkalic organism is triethylene diamine, morpholine, piperazidine, ethylpiperazine or methyl piperazine; and the organic solvent is ethanol, methanol, acetone or ethyl acetate. The invention has higher separation efficiency and only need crystallization for one time; the total yield of the 2,4-Dichlorophenol is 90-95%, and the purity thereof is 96-99%; the total yield of the 2,6-Dichlorophenol is 77-89%, and the purity thereof is 90-99%; and the invention has the advantages of simple operation, good repeatability and low implementation cost, and is favor of industrialized scale-up.
Description
(1) technical field
The present invention relates to a kind of method being separated 2,4 dichloro phenol and 2,6-chlorophenesic acid.
(2) background technology
2,4 dichloro phenol is a kind of important fine chemical product, is mainly used in agricultural chemicals, medicine, Additives Products.Because domestic santochlor phenol Downstream Products put more effort in recent years, particularly mould inhibitor TCS and agricultural chemicals oxadiazon are succeeded in developing in China, bring fabulous opportunity to the application and development of China's 2,4 dichloro phenol.
2,4 dichloro phenol on pesticide industry, be mainly used in production sterilant phenol line phosphorus and weedicide, methyl esters remove straw mulch, nitrofen, Dichlorophenoxy acid and ester class thereof; For the production of insect repellent bithionol on medicine industry; For the production of sanitas TCS in Auxiliaries Industry.And the domestic 2,4 dichloro phenol consumption for the production of Dichlorophenoxy acid and ester herbicide thereof is more stable, and increase with the annual growth of 8% ~ 10%.
Generally obtain product 2,4 dichloro phenol and 2,6-chlorophenesic acid by the direct chlorination of phenol, but the equiprobability of 2,4 dichloro phenol and the generation of 2,6-chlorophenesic acid in the reaction, so the purity of 2,4-these phenol of dichloro obtained like this is lower.Current many products mostly use content lower than 90% 2,4 dichloro phenol so that the yield of derived product produced is low, the refuse of generation is more.Along with to the pay attention to day by day of environmental protection and the requirement to converted products purity, these manufacturers will use the 2,4 dichloro phenol of high-content instead gradually.Below the molecular structure of 2,6-chlorophenesic acid and 2,4 dichloro phenol:
2,6-chlorophenesic acid 2,4 dichloro phenol
Can be found out by the molecular structure of above-mentioned 2,6-chlorophenesic acid, 2,4 dichloro phenol, both structural formulas are quite similar, and its boiling point is respectively 218 DEG C and 210 DEG C.Traditional separating and purifying method has: fractional crystallization, essence are slipped, dissociation extraction, fractionation by adsorption and utilize the physical properties difference of the ammonia salt of two kinds of phenol to be separated.
(1) rectifying is main tradition purification mode.Some factories adopt rectifying means separating-purifying 2; 4-chlorophenesic acid; but under chlorinated phenol is in the condition of high temperature for a long time in rectifying, the arborescens raffinate that part chlorinated phenol is formed adds load to aftertreatment and environment protection, and the boiling point difference of each isomers is very little.Nature difference less causing adopts traditional rectificating method to be difficult to reach the separating effect of expection.In addition, therefore the rectifying at substantial energy be not desirable method.
(2) people such as Hermann A once reported and utilizes zeolite adsorption to be separated 2,4-chlorophenesic acid, application zeolite does sorbent material separation chlorinated phenol can from containing 2,4-chlorophenesic acid and 2,2 are isolated in the mixture of 6-chlorophenesic acid, 4-chlorophenesic acid, but the method complicated operation, efficiency are low, are not suitable for industrialization.
(3) foreign patent reports physical properties separation 2,4 dichloro phenol and 2, the 6-chlorophenesic acid mixed phenol of the ammonia salt utilizing two kinds of phenol.The method is with after ammonia treatment mixed phenol, and feed liquid will separate the solid-phase layer being rich in 2,4-Dichlorophenol and the water layer being rich in 2,6-Dichlorophenol, and further processing two-phase can by 2, and 4,2,6-mixed phenols are separated.The shortcoming of the method is that yield is low, and unsuitable industrialization.
(4) have people with dissociation extraction be separated 2,4,2,6-chlorophenesic acid.2,4-chlorophenesic acid, 2,6-chlorophenesic acid dissociation constant is 18 and 160 respectively, acid difference can make 2,6-chlorophenesic acid preferential salt formation enters aqueous phase, and when the organic solution of material and mutual convection current and inorganic base aqueous solution constantly contact, 2,6-chlorophenesic acid just proceed to aqueous phase gradually like this, and organic phase can obtain purer 2,4 dichloro phenol.Its shortcoming is that appointed condition requirement is higher, invests corresponding comparatively large, complicated operation, and will use a large amount of organic solvent and alkali.
(5) foreign patent reports and utilizes the method for dissociation extraction dehydrated precipitate to be separated 2, and 4,2,6-dichlorophenol mixtures.To estimate 2 of preferential salt formation in mixed phenol, based on the molar equivalent of 6-chlorophenesic acid, quantitatively add NaOH and remove whole moisture gradually, 2,6-chlorophenesic acid just can be precipitated out under the condition not having aqueous phase with sodium-salt form from organic phase, thus reaches the object of separating-purifying.This method is less, simple to operate than simple dissociation extraction facility investment, but still keeps away a large amount of organic solvent of unavoidable use, and its product purity is also undesirable.
It is large to there is power consumption in above separation method, and post-processing difficulty is large, and appointed condition requires higher, invests corresponding comparatively large, the shortcomings such as complicated operation.Therefore comparatively economic, the simple separation method of more deep research one is needed.Object of the present invention is exactly the principle utilizing molecular recognition, is meticulously considering on low power consuming, environmental friendliness, the simple basis of technique, provides a kind of method being separated 2,6-chlorophenesic acid and 2,4 dichloro benzene phenol mixture.
(3) summary of the invention
The technical problem to be solved in the present invention is to provide one to utilize Molecular Recognition Principle to be separated the method for 2,4 dichloro phenol and 2,6-dichlorophenol mixture simply, efficiently.
Research Thinking of the present invention is: 2, the physico-chemical property of 4-chlorophenesic acid and 2,6-chlorophenesic acid is quite similar, but their sterie configuration and acidity have certain difference, this species diversity makes them different from the ability that specific alkaline organic combines, thus occurs the phenomenon of selective binding.
For solving the technology of the present invention problem, the present invention adopts following technical scheme:
A kind of separation 2, 4-chlorophenesic acid and 2, the method of 6-chlorophenesic acid, described method comprises the following steps: (1) first detects 2, 4-chlorophenesic acid and 2, in the mixture of 6-chlorophenesic acid 2, the content of 6-chlorophenesic acid, by 2, 4-chlorophenesic acid and 2, the mixture of 6-chlorophenesic acid is dissolved in organic solvent, add alkaline organic, stirring reaction at 40 ~ 80 DEG C of temperature, clarify to reaction solution, reaction terminates, reaction solution is cooled to-10 ~ 40 DEG C, leave standstill crystallize out, filtration obtains filter cake A and filtrate A, 2, 4-chlorophenesic acid is stayed in filtrate A, filter cake A is 2, 6-chlorophenesic acid crude product, described alkaline organic is triethylene diamine, morpholine, piperazine, ethyl piperazidine or methylpiperazine, in the mixture of described alkaline organic and 2,4 dichloro phenol and 2,6-chlorophenesic acid, the ratio of the amount of substance of 2,6-chlorophenesic acid is 1.2 ~ 1.5: 1, described organic solvent is ethanol, methyl alcohol, acetone or ethyl acetate.
Described method also comprises step (2): filter cake A recrystallization solvent recrystallization step (1) obtained, obtain compound crystal, compound crystal adds hydrochloric acid, stir fully reaction, then extract with extraction solvent, stratification is got organic layer distillation and is obtained 2,6-chlorophenesic acid; Described recrystallization solvent is ethanol, methyl alcohol, acetone or ethyl acetate; Described extraction solvent is sherwood oil, benzene, chloroform or ethyl acetate.
The filtrate A distillation that described step (1) obtains obtains 2,4 dichloro phenol.
The time of the standing crystallize out in described step (1) is 6-10 days.
The volumetric usage of organic solvent counts 3 ~ 4ml/g with the quality of the mixture of 2,4 dichloro phenol and 2,6-chlorophenesic acid in described step (1).
In described step (2), the mass concentration of hydrochloric acid is 5 ~ 20wt%.
In described step (2) in hydrochloric acid hydrogenchloride and 2,4 dichloro phenol and 2,6-chlorophenesic acid mixture in the amount of substance ratio of 2,6-chlorophenesic acid that records be 1 ~ 2: 1.
The preferred triethylene diamine of alkaline organic of the present invention, morpholine or piperazine.
Organic solvent preferred alcohol of the present invention, methyl alcohol or acetone.
Recrystallization solvent preferred alcohol of the present invention, methyl alcohol or acetone.
The preferred sherwood oil of extraction solvent of the present invention, benzene or chloroform.
Comparatively concrete, recommend method of the present invention to carry out according to following steps:
(1) first 2 are detected, 4-chlorophenesic acid and 2, in the mixture of 6-chlorophenesic acid 2, the content of 6-chlorophenesic acid, by 2,4 dichloro phenol and 2, the mixture of 6-chlorophenesic acid is dissolved in organic solvent, add alkaline organic, at 40 ~ 80 DEG C of temperature, stirring reaction 1 ~ 2 minute, clarifies to reaction solution, reaction terminates, reaction solution is cooled to-10 ~ 40 DEG C, leaves standstill 6-10 days crystallize outs, filters and obtains filter cake A and filtrate A, filtrate A distillation obtains 2,4-chlorophenesic acid, filter cake A is 2,6-chlorophenesic acid crude product; Described alkaline organic is triethylene diamine, morpholine, piperazine, ethyl piperazidine or methylpiperazine; In the mixture of described alkaline organic and 2,4 dichloro phenol and 2,6-chlorophenesic acid, the ratio of the amount of substance of 2,6-chlorophenesic acid is 1.2 ~ 1.5: 1; Described organic solvent is ethanol, methyl alcohol, acetone or ethyl acetate; The volumetric usage of described organic solvent with, the quality of the mixture of 4-chlorophenesic acid and 2,6-chlorophenesic acid counts 3 ~ 4ml/g;
(2) filter cake A recrystallization solvent recrystallization step (1) obtained, obtain compound crystal, compound crystal adds 5 ~ 20wt% hydrochloric acid, stirs and fully reacts, hydrogenchloride and 2 in hydrochloric acid, the amount of substance ratio of 2, the 6-chlorophenesic acid recorded in the mixture of 4-chlorophenesic acid and 2,6-chlorophenesic acid is 1 ~ 2: 1, then extract with extraction solvent, stratification, gets organic layer distillation and obtains 2,6-chlorophenesic acid; Described recrystallization solvent is ethanol, methyl alcohol, acetone or ethyl acetate; Described extraction solvent is sherwood oil, benzene, chloroform or ethyl acetate.
The consumption of described recrystallization solvent counts 3 ~ 4ml/g with the quality of filter cake A, and in described step (2), the consumption of extraction solvent is 1: 1 ~ 2 with the volume ratio (i.e. the volume of hydrochloric acid) of the mother liquor be extracted.
Compared with prior art, present method is based on the ultimate principle of Supramolecular Assembling, utilize matching between host molecule and guest molecule in topology, make 2,6-chlorophenesic acid optionally forms stable molecular crystal with alkaline organic, thus realize centrifugation efficiently and rapidly, its advantage is mainly:
A) efficiency comparison be separated is high.Due to the high selectivity of molecular recognition, only need primary crystallization, can realize the total recovery of 2,4 dichloro phenol between 90%-95%, purity is between 96%-99%; The total recovery of 2,6-chlorophenesic acid is between 77%-89%, and purity is between 90%-99%.
B) simple to operate, reproducible, implementation cost is low, is conducive to industry and amplifies.
(4) embodiment
Further illustrate the technical scheme of invention below with concrete embodiment, but protection scope of the present invention is not limited thereto.
In the embodiment of the present invention, 2,4 chlorophenesic acid, 2,6-dichlorophenol mixtures are the products obtained by the direct catalytic chlorination of phenol, from chemical plant, Shangyu
In the embodiment of the present invention, detection method is high performance liquid chromatography, Shimadzu LC-10AT type high performance liquid chromatograph.
Example 1:
150ml ethanol and 50g 2 is added in 200ml beaker, 4 chlorophenesic acid, 2,6-dichlorophenol mixture, (lower with) wherein 2 is detected through high performance liquid chromatography, 4-chlorophenesic acid and 2, the content of 6-chlorophenesic acid is respectively 50% and 50%, and then adds 16g morpholine, and 70 DEG C of stirring heating are clarified to solution for 2 minutes.Place 7 days under greenhouse, have water white crystal to separate out, decompress filter obtains filter cake crystal 31.5g and filtrate, this crystal is 2,6-chlorophenesic acid crude product, is 2, the mixture of 6-chlorophenesic acid and morpholine, 2,4 dichloro phenol is then stayed in filtrate, then can obtain highly purified 2 by distillation, 4-chlorophenesic acid 22.8g, yield is 91%, and purity is 96% (high performance liquid chromatography detects, lower same).With 100ml ethanol by 2,6-chlorophenesic acid crude product carries out a recrystallization, join normal temperature in 10% dilute hydrochloric acid solution of 60ml fully to react, add 60ml sherwood oil again to extract, stratification, get organic layer and can obtain 2 by distillation, 6-chlorophenesic acid 20.4g, yield is 82%, and purity is 93% (high performance liquid chromatography detects, lower same).
Example 2:
200ml methyl alcohol and 50g 2,4 chlorophenesic acid, 2,6-dichlorophenol mixtures are added in 500ml beaker, wherein the content of 2,4 dichloro phenol and 2,6-chlorophenesic acid is respectively 60% and 40% after testing, and then adding 16g triethylene diamine, 60 DEG C of stirring heating are clarified to solution for 2 minutes.Place 6 days under greenhouse, have water white crystal to separate out, decompress filter obtains filter cake crystal 30.8g and filtrate, this crystal is 2,6-chlorophenesic acid crude product is the mixture of 2,6-chlorophenesic acid and triethylene diamine, and 2,4-chlorophenesic acid is then stayed in filtrate, then can obtain highly purified 2,4 dichloro phenol 28.0g by distillation, yield is 93%, and purity is 98%.With 100ml methyl alcohol, 2,6-chlorophenesic acid crude product is carried out a recrystallization, join normal temperature in 10% dilute hydrochloric acid solution of 60ml and fully react, add 60ml benzene again to extract, stratification, get organic layer and can obtain 2 by distillation, 6-chlorophenesic acid 15.4g, yield is 77%, and purity is 96%.
Example 3:
150ml ethanol and 50g 2,4 chlorophenesic acid, 2,6-dichlorophenol mixtures are added in 200ml beaker, wherein the content of 2,4 dichloro phenol and 2,6-chlorophenesic acid is respectively 60% and 40% after testing, and then adding 12.5g piperazine, 70 DEG C of stirring heating are clarified to solution for 2 minutes.Ambient temperatare puts 8 days, and have water white crystal to separate out, decompress filter obtains filter cake crystal 30.5g and filtrate, this crystal is 2,6-chlorophenesic acid crude product is the mixture of 2,6-chlorophenesic acid and piperazine, and 2,4-chlorophenesic acid is then stayed in filtrate, then can obtain highly purified 2,4 dichloro phenol 29.1g by distillation, yield is 97%, and purity is 98%.With 100ml acetone, 2,6-chlorophenesic acid crude product is carried out a recrystallization, join normal temperature in 10% dilute hydrochloric acid solution of 60ml and fully react, add 60ml chloroform again to extract, stratification, get organic layer and can obtain 2 by distillation, 6-chlorophenesic acid 17.0g, yield is 85%, and purity is 99%.
Example 4:
150ml acetone and 50g 2,4 chlorophenesic acid, 2,6-dichlorophenol mixtures are added in 200ml beaker, wherein the content of 2,4 dichloro phenol and 2,6-chlorophenesic acid is respectively 70% and 30% after testing, and then adding 15.7g ethyl piperazidine, 50 DEG C of stirring heating are clarified to solution for 2 minutes.Place 7 days under greenhouse, have water white crystal to separate out, decompress filter obtains filter cake crystal 25.7g and filtrate, this crystal is 2,6-chlorophenesic acid crude product is the mixture of 2,6-chlorophenesic acid and ethyl piperazidine, and 2,4-chlorophenesic acid is then stayed in filtrate, then can obtain highly purified 2,4 dichloro phenol 31.9g by distillation, yield is 91%, and purity is 97%.By 100ml ethyl acetate by 2,6-chlorophenesic acid crude product carries out a recrystallization, join normal temperature in 10% dilute hydrochloric acid solution of 50ml fully to react, add 50ml ethyl acetate again to extract, stratification, gets organic layer and can obtain 2,6-chlorophenesic acid 13.4g by distillation, yield is 89%, and purity is 93%.
Example 5:
150ml ethyl acetate and 50g2 is added, 4 chlorophenesic acid, 2,6-dichlorophenol mixtures in 200ml beaker, wherein the content of 2,4 dichloro phenol and 2,6-chlorophenesic acid is respectively 80% and 20% after testing, and then adding 7.2g methylpiperazine, 77 DEG C of stirring heating are clarified to solution for 2 minutes.Place 6 days under greenhouse, have water white crystal to separate out, decompress filter obtains filter cake crystal 16.2g and filtrate, this crystal is 2,6-chlorophenesic acid crude product is the mixture of 2,6-chlorophenesic acid and methylpiperazine, and 2,4-chlorophenesic acid is then stayed in filtrate, then can obtain highly purified 2,4 dichloro phenol 38.0g by distillation, yield is 95%, and purity is 98%.With 50ml ethanol, 2,6-chlorophenesic acid crude product is carried out a recrystallization, join normal temperature in 10% dilute hydrochloric acid solution of 30ml and fully react, add 30ml sherwood oil again to extract, stratification, get organic layer and can obtain 2 by distillation, 6-chlorophenesic acid 7.8g, yield is 78%, and purity is 99%.
Claims (8)
1. one kind is separated 2, 4-chlorophenesic acid and 2, the method of 6-chlorophenesic acid, it is characterized in that described method comprises the following steps: (1) first detects 2, 4-chlorophenesic acid and 2, in the mixture of 6-chlorophenesic acid 2, the content of 6-chlorophenesic acid, by 2, 4-chlorophenesic acid and 2, the mixture of 6-chlorophenesic acid is dissolved in organic solvent, add alkaline organic, stirring reaction at 40 ~ 80 DEG C of temperature, clarify to reaction solution, reaction terminates, reaction solution is cooled to-10 ~ 40 DEG C, leave standstill crystallize out, filtration obtains filter cake A and filtrate A, 2, 4-chlorophenesic acid is stayed in filtrate A, filtrate A distillation obtains 2, 4-chlorophenesic acid, filter cake A is 2,6-chlorophenesic acid crude product, described alkaline organic is triethylene diamine, in the mixture of described alkaline organic and 2,4 dichloro phenol and 2,6-chlorophenesic acid, the ratio of the amount of substance of 2,6-chlorophenesic acid is 1.2 ~ 1.5:1, described organic solvent is ethanol, methyl alcohol, acetone or ethyl acetate,
(2): filter cake A recrystallization solvent recrystallization step (1) obtained, obtain compound crystal, compound crystal adds hydrochloric acid, stir fully reaction, then with extraction solvent extraction, stratification is got organic layer distillation and is obtained 2,6-chlorophenesic acid; Described recrystallization solvent is ethanol, methyl alcohol, acetone or ethyl acetate; Described extraction solvent is sherwood oil, benzene, chloroform or ethyl acetate.
2. the method for claim 1, is characterized in that the volumetric usage of described organic solvent counts 3 ~ 4ml/g with the quality of the mixture of 2,4 dichloro phenol and 2,6-chlorophenesic acid.
3. the method for claim 1, is characterized in that the mass concentration of hydrochloric acid in described step (2) is 5 ~ 20wt%.
4. the method for claim 1, is characterized in that the amount of substance ratio of 2,6-chlorophenesic acid in the mixture of hydrogenchloride and 2,4 dichloro phenol and 2,6-chlorophenesic acid in hydrochloric acid in described step (2) is 1 ~ 2:1.
5. the method for claim 1, is characterized in that the time of the standing crystallize out in described step (1) is 6-10 days.
6. the method for claim 1, is characterized in that described method is carried out in accordance with the following steps:
(1) first 2 are detected, 4-chlorophenesic acid and 2, in the mixture of 6-chlorophenesic acid 2, the content of 6-chlorophenesic acid, by 2,4 dichloro phenol and 2, the mixture of 6-chlorophenesic acid is dissolved in organic solvent, add alkaline organic, at 40 ~ 80 DEG C of temperature, stirring reaction 1 ~ 2 minute, clarifies to reaction solution, reaction terminates, reaction solution is cooled to-10 ~ 40 DEG C, leaves standstill 6-10 days crystallize outs, filters and obtains filter cake A and filtrate A, filtrate A obtains 2 after distilling, 4-chlorophenesic acid, filter cake A is 2,6-chlorophenesic acid crude product; Described alkaline organic is triethylene diamine; In the mixture of described alkaline organic and 2,4 dichloro phenol and 2,6-chlorophenesic acid, the ratio of the amount of substance of 2,6-chlorophenesic acid is 1.2 ~ 1.5:1; Described organic solvent is ethanol, methyl alcohol, acetone or ethyl acetate; The volumetric usage of described organic solvent counts 3 ~ 4ml/g with the quality of the mixture of 2,4 dichloro phenol and 2,6-chlorophenesic acid;
(2) filter cake A recrystallization solvent recrystallization step (1) obtained, obtain compound crystal, compound crystal adds 5 ~ 20wt% hydrochloric acid, stirs and fully reacts, hydrogenchloride and 2 in hydrochloric acid, in the mixture of 4-chlorophenesic acid and 2,6-chlorophenesic acid, the amount of substance ratio of 2,6-chlorophenesic acid is 1 ~ 2:1, then extract with extraction solvent, stratification, gets organic layer distillation and obtains 2,6-chlorophenesic acid; Described recrystallization solvent is ethanol, methyl alcohol, acetone or ethyl acetate; Described extraction solvent is sherwood oil, benzene, chloroform or ethyl acetate.
7. method as claimed in claim 6, is characterized in that the consumption of described recrystallization solvent counts 3 ~ 4ml/g with the quality of filter cake A.
8. method as claimed in claim 6, the consumption that it is characterized in that described extraction solvent is 1:1 ~ 2 with the volume ratio of the mother liquor be extracted.
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| CN106139634A (en) * | 2016-08-31 | 2016-11-23 | 连云港致诚化工有限公司 | A kind of crystallization apparatus refined for chlorophenol |
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Application publication date: 20100721 Assignee: Wuzhou Tongxin Energy Materials Co.,Ltd. Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980054078 Denomination of invention: A method for separating 2,4-dichlorophenol and 2,6-dichlorophenol Granted publication date: 20150603 License type: Common License Record date: 20231226 |