CN101781175A - 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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- CN101781175A CN101781175A CN200910156611A CN200910156611A CN101781175A CN 101781175 A CN101781175 A CN 101781175A CN 200910156611 A CN200910156611 A CN 200910156611A CN 200910156611 A CN200910156611 A CN 200910156611A CN 101781175 A CN101781175 A CN 101781175A
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- chlorophenesic acid
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- chlorophenesic
- dichlorophenol
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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 48
- 238000000034 method Methods 0.000 title claims abstract description 32
- HOLHYSJJBXSLMV-UHFFFAOYSA-N 2,6-dichlorophenol Chemical compound OC1=C(Cl)C=CC=C1Cl HOLHYSJJBXSLMV-UHFFFAOYSA-N 0.000 title abstract description 9
- 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 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000000706 filtrate Substances 0.000 claims abstract description 22
- 239000012065 filter cake Substances 0.000 claims abstract description 21
- 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
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012043 crude product Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims abstract description 12
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 117
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 31
- 238000001953 recrystallisation Methods 0.000 claims description 20
- 239000002904 solvent Substances 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 18
- 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
- -1 ethyl piperazidine Chemical compound 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000012044 organic layer Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000284 extract Substances 0.000 claims description 7
- 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 4
- 238000005352 clarification Methods 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 9
- 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 11
- 239000000047 product Substances 0.000 description 9
- 238000010494 dissociation reaction Methods 0.000 description 5
- 230000005593 dissociations Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- SCWBSTVOWDDYHH-UHFFFAOYSA-N 4-amino-2,6-dichlorophenol;4-aminophenol Chemical compound NC1=CC=C(O)C=C1.NC1=CC(Cl)=C(O)C(Cl)=C1 SCWBSTVOWDDYHH-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 101100489867 Mus musculus Got2 gene Proteins 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- BQJCRHHNABKAKU-KBQPJGBKSA-N morphine Chemical compound O([C@H]1[C@H](C=C[C@H]23)O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4O BQJCRHHNABKAKU-KBQPJGBKSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000003905 agrochemical Substances 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
- 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
- 229960005181 morphine Drugs 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
- 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
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent 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
- 230000000295 complement effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 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
- 238000004519 manufacturing process Methods 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
- 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
- 235000012976 tarts Nutrition 0.000 description 1
Landscapes
- 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 separation 2,4 dichloro phenol and 2, the method for 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, auxiliary agent product.Because domestic in recent years santochlor phenol derived product exploitation puts more effort, particularly mould inhibitor TCS and agricultural chemicals oxadiazon are succeeded in developing in China, have brought fabulous opportunity for the application and the development of China's 2,4 dichloro phenol.
2,4 dichloro phenol is mainly used in production sterilant phenol line phosphorus on pesticide industry and weedicide, methyl esters remove straw mulch, nitrofen, Dichlorophenoxy acid and ester class thereof; On medicine industry, be used to produce the insect repellent bithionol; On Auxiliaries Industry, be used to produce sanitas TCS.And the domestic 2,4 dichloro phenol consumption that is used to produce Dichlorophenoxy acid and ester herbicide thereof is more stable, and increases with 8%～10% annual growth.
Generally the direct chlorination by phenol obtains product 2,4 dichloro phenol and 2, the 6-chlorophenesic acid, but in this reaction 2,4 dichloro phenol and 2, the equiprobability that the 6-chlorophenesic acid generates, thus obtain like this 2, the purity of this phenol of 4-dichloro is lower.Current many products mostly use content to be lower than 90% 2,4 dichloro phenol, so that the yield of the derived product of producing is low, the refuse of generation is more.Along with to the pay attention to day by day of environmental protection with to the requirement of converted products purity, these manufacturers will use high-load 2,4 dichloro phenol gradually instead.Below be 2, the molecular structure of 6-chlorophenesic acid and 2,4 dichloro phenol:
2,6-chlorophenesic acid 2,4 dichloro phenol
By above-mentioned 2, the molecular structure of 6-chlorophenesic acid, 2,4 dichloro phenol as can be seen, both structural formulas are quite similar, its boiling point is respectively 218 ℃ and 210 ℃.Traditional separating and purifying method has: fractional crystallization, smart slide, dissociation extraction, fractionation by adsorption and utilize the physical properties difference of the ammonia salt of two kinds of phenol to separate.
(1) rectifying is main tradition purification mode.Some factories adopt the rectifying means to separate and purify 2; the 4-chlorophenesic acid; but chlorinated phenol is in rectifying under the condition of high temperature for a long time, and the arborescens raffinate that the part chlorinated phenol forms has increased load for aftertreatment and environment protection, and the boiling point difference of each isomers is very little.Nature difference is less to cause adopting traditional rectificating method to be difficult to reach the separating effect of expection.In addition, rectifying expends a large amount of energy, is not the ideal method therefore.
(2) people such as Hermann A once reported and utilizes zeolite adsorption to separate 2, the 4-chlorophenesic acid, the application zeolite is done sorbent material separation chlorinated phenol can be from containing 2,4-chlorophenesic acid and 2, isolate 2 in the mixture of 6-chlorophenesic acid, the 4-chlorophenesic acid, but this method complicated operation, efficient are low, are not suitable for industrialization.
(3) foreign patent has been reported the physical properties separation 2,4 dichloro phenol and 2 of the ammonia salt that utilizes two kinds of phenol, 6-chlorophenesic acid mixed phenol.This method is that feed liquid will be told and be rich in 2 with behind the ammonia treatment mixed phenol, the solid-phase layer of 4-two chlorophenols and be rich in 2, and the water layer of 6-two chlorophenols can be with 2,4,2 to the further processing of two-phase, and the 6-mixed phenol is separated.The shortcoming of this method is that yield is low, and unsuitable industrialization.
(4) there is the human dissociation extraction to separate 2,4,2, the 6-chlorophenesic acid.2,4-chlorophenesic acid, 2,6-chlorophenesic acid dissociation constant is respectively 18 and 160, tart difference can make 2, the preferential salify of 6-chlorophenesic acid enters water, and when the organic solution of material and mutually convection current and inorganic base aqueous solution constantly contact 2, the 6-chlorophenesic acid just changes water gradually over to like this, and organic phase can obtain purer 2,4 dichloro phenol.Its shortcoming is that appointed condition is had relatively high expectations, invest corresponding bigger, complicated operation, and will use a large amount of organic solvents and alkali.
(5) foreign patent has been reported and has been utilized the dissociation extraction sedimentary method of dewatering to separate 2,4,2, the 6-dichlorophenol mixture.To estimate preferential salifiable 2 in the mixed phenol, the molar equivalent of 6-chlorophenesic acid is the basis, quantitatively adds NaOH and removes whole moisture, 2 gradually, the 6-chlorophenesic acid can just be precipitated out from organic phase under the condition that does not have water with sodium-salt form, separates the purpose of purifying thereby reach.This method is littler, simple to operate than simple dissociation extraction facility investment, but still keeps away a large amount of organic solvents of unavoidable use, and its product purity is also undesirable.
Above separation method exists power consumption big, and post-processing difficulty is big, and appointed condition is had relatively high expectations, invest corresponding bigger, shortcomings such as complicated operation.Therefore need one of more deep research comparatively economy, simple separation method.Purpose of the present invention is exactly to utilize the principle of molecular recognition, considering meticulously on low power consuming, environmental friendliness, the simple basis of technology, provides a kind of separation 2, the method for 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 a kind of molecular recognition principle of utilizing simply, efficiently to separate 2,4 dichloro phenol and 2, the method for 6-dichlorophenol mixture.
Research thinking of the present invention is: 2,4-chlorophenesic acid and 2, the physico-chemical property of 6-chlorophenesic acid is quite similar, but their sterie configuration and acidity have certain difference, this species diversity makes them different with specific alkaline organic bonded ability, thereby the phenomenon of selective binding occurs.
For solving the technology of the present invention problem, the present invention adopts following technical scheme:
A kind of separation 2,4 dichloro phenol and 2, the method for 6-chlorophenesic acid, described method may further comprise the steps: (1) detects 2 earlier, 4-chlorophenesic acid and 2, in the mixture of 6-chlorophenesic acid 2, the content of 6-chlorophenesic acid, with 2,4-chlorophenesic acid and 2, the mixture of 6-chlorophenesic acid is dissolved in the organic solvent, adds alkaline organic, stirring reaction under 40～80 ℃ of temperature, to the reaction solution clarification, reaction finishes, and reaction solution is cooled to-10～40 ℃, leave standstill and separate out crystal, filtration obtains filter cake A and filtrate A, and 2,4 dichloro phenol is stayed among the filtrate A, filter cake A is 2,6-chlorophenesic acid crude product; Described alkaline organic is triethylene diamine, morpholine, piperazine, ethyl piperazidine or methylpiperazine; Described alkaline organic and 2,4 dichloro phenol and 2, in the mixture of 6-chlorophenesic acid 2, the ratio of the amount of substance of 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): the filter cake A recrystallization solvent recrystallization with step (1) obtains, get compound crystal, and compound crystal adds hydrochloric acid, stir fully reaction, with the extraction solvent extraction, standing demix is got the organic layer distillation and is obtained 2, the 6-chlorophenesic acid then; 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.
It is 6-10 days that leaving standstill in the described step (1) separated out the crystalline time.
The volume of organic solvent consumption is with 2,4 dichloro phenol and 2 in the described step (1), and the quality of the mixture of 6-chlorophenesic acid is counted 3～4ml/g.
The mass concentration of hydrochloric acid is 5～20wt% in the described step (2).
Hydrogenchloride and 2,4 dichloro phenol and 2 in the hydrochloric acid in the described step (2), record in the mixture of 6-chlorophenesic acid 2, the amount of substance ratio of 6-chlorophenesic acid is 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) detects earlier 2,4 dichloro phenol and 2, in the mixture of 6-chlorophenesic acid 2, the content of 6-chlorophenesic acid is with 2,4 dichloro phenol and 2, the mixture of 6-chlorophenesic acid is dissolved in the organic solvent, adds alkaline organic, and stirring reaction is 1～2 minute under 40～80 ℃ of temperature, to the reaction solution clarification, reaction finishes, and reaction solution is cooled to-10～40 ℃, leave standstill and separated out crystal in 6-10 days, filter and obtain filter cake A and filtrate A, filtrate A distillation obtains 2, the 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; Described alkaline organic and 2,4 dichloro phenol and 2, in the mixture of 6-chlorophenesic acid 2, the ratio of the amount of substance of 6-chlorophenesic acid is 1.2～1.5: 1; Described organic solvent is ethanol, methyl alcohol, acetone or ethyl acetate; Described volume of organic solvent consumption is with, 4-chlorophenesic acid and 2, and the quality of the mixture of 6-chlorophenesic acid is counted 3～4ml/g;
(2) the filter cake A recrystallization solvent recrystallization that step (1) is obtained, get compound crystal, compound crystal adds 5～20wt% hydrochloric acid, stirs fully reaction, hydrogenchloride and 2 in the hydrochloric acid, 4-chlorophenesic acid and 2, record in the mixture of 6-chlorophenesic acid 2, the amount of substance ratio of 6-chlorophenesic acid is 1～2: 1, extract with extraction solvent then, standing demix is got the organic layer distillation and is obtained 2, the 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 is counted 3～4ml/g with the quality of filter cake A, and the consumption of extraction solvent is 1: 1～2 with the volume ratio (being the volume of hydrochloric acid) of the mother liquor that is extracted in the described step (2).
Compared with prior art, present method is based on the ultimate principle of supramolecule assembling, utilize being complementary on the topology between host molecule and the guest molecule, make 2, the 6-chlorophenesic acid optionally forms stable molecular crystal with alkaline organic, thereby realize centrifugation efficiently and rapidly, its advantage mainly is:
A) isolating efficiency ratio is higher.Because the high selectivity of molecular recognition only needs primary crystallization, the total recovery that can realize 2,4 dichloro phenol is between 90%-95%, and purity is between 96%-99%; 2, the total recovery of 6-chlorophenesic acid is between 77%-89%, and purity is between 90%-99%.
B) simple to operate, good reproducibility, implementation cost is low, helps industry and amplifies.
(4) embodiment
Further specify the technical scheme of invention below with concrete embodiment, but protection scope of the present invention is not limited thereto.
2,4 chlorophenesic acid, 2 in the embodiment of the invention, 6-dichlorophenol mixture are the products that is obtained by the direct catalytic chlorination of phenol, from the chemical plant, Shangyu
Detection method is high performance liquid chromatography in the embodiment of the invention, Tianjin, island LC-10AT type high performance liquid chromatograph.
Example 1:
In the 200ml beaker, add 150ml ethanol and 50g 2,4 chlorophenesic acid, 2, the 6-dichlorophenol mixture, detect (down with) wherein 2 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 morphine quinoline, and 70 ℃ of stirring heating 2 minutes to solution is clarified.The greenhouse was placed 7 days down, had colourless crystalline transparent to separate out, and decompress filter obtains filter cake crystal 3 1.5g and filtrate, this crystal is 2, and 6-chlorophenesic acid crude product is 2, the mixture of 6-chlorophenesic acid and morphine quinoline, 2,4 dichloro phenol is then stayed in the filtrate, can obtain highly purified 2 by distillation again, 4-chlorophenesic acid 22.8g, yield is 91%, and purity is 96% (high performance liquid chromatography detects, down together).With 100ml ethanol with 2,6-chlorophenesic acid crude product carries out recrystallization one time, join that normal temperature fully reacts in 10% dilute hydrochloric acid solution of 60ml, add the 60ml sherwood oil again and extract, standing demix is got organic layer and can be got 2 by distillation, 6-chlorophenesic acid 20.4g, yield is 82%, and purity is 93% (high performance liquid chromatography detects, down together).
Example 2:
In the 500ml beaker, add 200ml methyl alcohol and 50g 2,4 chlorophenesic acid, 2,6-dichlorophenol mixture, 2,4 dichloro phenol and 2 wherein after testing, the content of 6-chlorophenesic acid is respectively 60% and 40%, and then adding the 16g triethylene diamine, 60 ℃ of stirring heating 2 minutes to solution is clarified.The greenhouse was placed 6 days down, had colourless crystalline transparent to separate out, and decompress filter obtains filter cake crystal 3 0.8g and filtrate, this crystal is 2,6-chlorophenesic acid crude product is 2, the mixture of 6-chlorophenesic acid and triethylene diamine, and 2, the 4-chlorophenesic acid is then stayed in the filtrate, can obtain highly purified 2,4 dichloro phenol 28.0g by distillation again, yield is 93%, and purity is 98%.With 2,6-chlorophenesic acid crude product carries out recrystallization one time with 100ml methyl alcohol, joins that normal temperature fully reacts in 10% dilute hydrochloric acid solution of 60ml, add 60ml benzene again and extract, standing demix is got organic layer and can be got 2 by distillation, 6-chlorophenesic acid 15.4g, yield are 77%, and purity is 96%.
Example 3:
In the 200ml beaker, add 150ml ethanol and 50g 2,4 chlorophenesic acid, 2,6-dichlorophenol mixture, 2,4 dichloro phenol and 2 wherein after testing, the content of 6-chlorophenesic acid is respectively 60% and 40%, and then adding the 12.5g piperazine, 70 ℃ of stirring heating 2 minutes to solution is clarified.Placed 8 days under the room temperature, have colourless crystalline transparent to separate out, decompress filter obtains filter cake crystal 3 0.5g and filtrate, this crystal is 2,6-chlorophenesic acid crude product is 2, the mixture of 6-chlorophenesic acid and piperazine, and 2, the 4-chlorophenesic acid is then stayed in the filtrate, can obtain highly purified 2,4 dichloro phenol 29.1g by distillation again, yield is 97%, and purity is 98%.With 2,6-chlorophenesic acid crude product carries out recrystallization one time with 100ml acetone, joins that normal temperature fully reacts in 10% dilute hydrochloric acid solution of 60ml, add the 60ml chloroform again and extract, standing demix is got organic layer and can be got 2 by distillation, 6-chlorophenesic acid 17.0g, yield are 85%, and purity is 99%.
Example 4:
In the 200ml beaker, add 150ml acetone and 50g 2,4 chlorophenesic acid, 2,6-dichlorophenol mixture, 2,4 dichloro phenol and 2 wherein after testing, the content of 6-chlorophenesic acid is respectively 70% and 30%, and then adding the 15.7g ethyl piperazidine, 50 ℃ of stirring heating 2 minutes to solution is clarified.The greenhouse was placed 7 days down, had colourless crystalline transparent to separate out, and decompress filter obtains filter cake crystal 2 5.7g and filtrate, this crystal is 2,6-chlorophenesic acid crude product is 2, the mixture of 6-chlorophenesic acid and ethyl piperazidine, and 2, the 4-chlorophenesic acid is then stayed in the filtrate, can obtain highly purified 2,4 dichloro phenol 31.9g by distillation again, yield is 91%, and purity is 97%.With the 100ml ethyl acetate with 2,6-chlorophenesic acid crude product carries out recrystallization one time, join that normal temperature fully reacts in 10% dilute hydrochloric acid solution of 50ml, adding the 50ml ethyl acetate again extracts, standing demix is got organic layer and can be got 2,6-chlorophenesic acid 13.4g by distillation, yield is 89%, and purity is 93%.
Example 5:
In the 200ml beaker, add 150ml ethyl acetate and 50g2,4 chlorophenesic acid, 2,6-dichlorophenol mixture, 2,4 dichloro phenol and 2 wherein after testing, the content of 6-chlorophenesic acid is respectively 80% and 20%, and then adding the 7.2g methylpiperazine, 77 ℃ of stirring heating 2 minutes to solution is clarified.The greenhouse was placed 6 days down, had colourless crystalline transparent to separate out, and decompress filter obtains filter cake crystal 16.2g and filtrate, this crystal is 2,6-chlorophenesic acid crude product is 2, the mixture of 6-chlorophenesic acid and methylpiperazine, and 2, the 4-chlorophenesic acid is then stayed in the filtrate, can obtain highly purified 2,4 dichloro phenol 38.0g by distillation again, yield is 95%, and purity is 98%.With 2,6-chlorophenesic acid crude product carries out recrystallization one time with 50ml ethanol, joins that normal temperature fully reacts in 10% dilute hydrochloric acid solution of 30ml, add the 30ml sherwood oil again and extract, standing demix is got organic layer and can be got 2 by distillation, 6-chlorophenesic acid 7.8g, yield are 78%, and purity is 99%.
Claims (10)
1. one kind is separated 2,4 dichloro phenol and 2, the method for 6-chlorophenesic acid, it is characterized in that described method may further comprise the steps: (1) detects 2 earlier, 4-chlorophenesic acid and 2, in the mixture of 6-chlorophenesic acid 2, the content of 6-chlorophenesic acid, with 2,4-chlorophenesic acid and 2, the mixture of 6-chlorophenesic acid is dissolved in the organic solvent, adds alkaline organic, stirring reaction under 40～80 ℃ of temperature, to the reaction solution clarification, reaction finishes, and reaction solution is cooled to-10～40 ℃, leave standstill and separate out crystal, filtration obtains filter cake A and filtrate A, and 2,4 dichloro phenol is stayed among the filtrate A, filter cake A is 2,6-chlorophenesic acid crude product; Described alkaline organic is triethylene diamine, morpholine, piperazine, ethyl piperazidine or methylpiperazine; Described alkaline organic and 2,4 dichloro phenol and 2, in the mixture of 6-chlorophenesic acid 2, the ratio of the amount of substance of 6-chlorophenesic acid is 1.2～1.5: 1; Described organic solvent is ethanol, methyl alcohol, acetone or ethyl acetate.
2. the method for claim 1, it is characterized in that described method also comprises step (2): the filter cake A recrystallization solvent recrystallization that step (1) is obtained, get compound crystal, compound crystal adds hydrochloric acid, stir fully reaction, with the extraction solvent extraction, standing demix is got the organic layer distillation and is obtained 2, the 6-chlorophenesic acid then; Described recrystallization solvent is ethanol, methyl alcohol, acetone or ethyl acetate; Described extraction solvent is sherwood oil, benzene, chloroform or ethyl acetate.
3. the method for claim 1 is characterized in that the filtrate A distillation that described step (1) obtains obtains 2,4 dichloro phenol.
4. the method for claim 1 is characterized in that described volume of organic solvent consumption with 2,4 dichloro phenol and 2, and the quality of the mixture of 6-chlorophenesic acid is counted 3～4ml/g.
5. method as claimed in claim 2 is characterized in that the mass concentration of hydrochloric acid in the described step (2) is 5～20wt%.
6. method as claimed in claim 2 is characterized in that in the described step (2) hydrogenchloride and 2,4 dichloro phenol and 2 in the hydrochloric acid, and in the mixture of 6-chlorophenesic acid 2, the amount of substance ratio of 6-chlorophenesic acid is 1～2: 1.
7. the method for claim 1 is characterized in that it is 6-10 days that leaving standstill in the described step (1) separated out the crystalline time.
8. method as claimed in claim 1 or 2 is characterized in that described method carries out according to following steps:
(1) detects 2 earlier, 4-chlorophenesic acid and 2, in the mixture of 6-chlorophenesic acid 2, the content of 6-chlorophenesic acid is with 2,4 dichloro phenol and 2, the mixture of 6-chlorophenesic acid is dissolved in the organic solvent, add alkaline organic, stirring reaction is 1～2 minute under 40～80 ℃ of temperature, clarifies to reaction solution, reaction finishes, reaction solution is cooled to-10～40 ℃, leaves standstill to separate out crystal in 6-10 days, filters and obtains filter cake A and filtrate A, obtain 2 after the filtrate A distillation, the 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; Described alkaline organic and 2,4 dichloro phenol and 2, in the mixture of 6-chlorophenesic acid 2, the ratio of the amount of substance of 6-chlorophenesic acid is 1.2～1.5: 1; Described organic solvent is ethanol, methyl alcohol, acetone or ethyl acetate; Described volume of organic solvent consumption is with, 4-chlorophenesic acid and 2, and the quality of the mixture of 6-chlorophenesic acid is counted 3～4ml/g;
(2) the filter cake A recrystallization solvent recrystallization that step (1) is obtained, get compound crystal, compound crystal adds 5～20wt% hydrochloric acid, stirs fully reaction, hydrogenchloride and 2 in the hydrochloric acid, 4-chlorophenesic acid and 2, in the mixture of 6-chlorophenesic acid 2, the amount of substance ratio of 6-chlorophenesic acid is 1～2: 1, extract with extraction solvent then, standing demix is got the organic layer distillation and is obtained 2, the 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.
9. method as claimed in claim 8 is characterized in that the consumption of described recrystallization solvent is counted 3～4ml/g with the quality of filter cake A.
10. method as claimed in claim 8, the consumption that it is characterized in that described extraction solvent is 1: 1～2 with the volume ratio of the mother liquor that is extracted.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105859550A (en) * | 2016-05-06 | 2016-08-17 | 四川福思达生物技术开发有限责任公司 | Dicamba preparation process |
| CN105884573A (en) * | 2016-05-06 | 2016-08-24 | 四川福思达生物技术开发有限责任公司 | Preparation method of dicamba |
| 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 |
| CN109020787A (en) * | 2018-07-10 | 2018-12-18 | 青岛科技大学 | A kind of method of chlorophenol high-boiling components resource utilization |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412664B (en) * | 2008-11-06 | 2014-10-08 | 浙江工业大学 | Method for separating mixer of 2,4-dichlorophenol and 2,5-dichlorophenol |
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2009
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105859550A (en) * | 2016-05-06 | 2016-08-17 | 四川福思达生物技术开发有限责任公司 | Dicamba preparation process |
| CN105884573A (en) * | 2016-05-06 | 2016-08-24 | 四川福思达生物技术开发有限责任公司 | Preparation method of dicamba |
| 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 |
| CN109020787A (en) * | 2018-07-10 | 2018-12-18 | 青岛科技大学 | A kind of method of chlorophenol high-boiling components resource utilization |
| CN109020787B (en) * | 2018-07-10 | 2024-05-10 | 青岛科技大学 | Method for recycling chlorophenol high-boiling-point substances |
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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 |