CN1033637C - 1.2,4-trichlorobenzene separating and purifying method from mixed trichlorobenzene - Google Patents
1.2,4-trichlorobenzene separating and purifying method from mixed trichlorobenzene Download PDFInfo
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- CN1033637C CN1033637C CN 93117343 CN93117343A CN1033637C CN 1033637 C CN1033637 C CN 1033637C CN 93117343 CN93117343 CN 93117343 CN 93117343 A CN93117343 A CN 93117343A CN 1033637 C CN1033637 C CN 1033637C
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- trichlorobenzene
- mixed
- emulsion
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- washing
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/392—Separation; Purification; Stabilisation; Use of additives by crystallisation; Purification or separation of the crystals
Abstract
The present invention discloses a method of separating and purifying high-purity 1, 2, 4-trichlorobenzene from mixed trichlorobenzene, particularly from mixed trichlorobenzene whose proportion of 1, 2, 4-trichlorobenzene is from 65 to 90% obtained by pyrolysis or alkaline hydrolysis of pesticide lindane byproduct-BHC ineffective body by using recrystallization with solvent and washing with emulsion. Alkane, alcohol, aromatic hydrocarbons, halogenated hydrocarbons, halogenated aryl hydrocarbons or mixture of alkane, alcohol, aromatic hydrocarbons, halogenated hydrocarbons and halogenated aryl hydrocarbons is used as solvent, common emulsifying agent solution is used as emulsion, recrystallization temperature is-10 DEG C-13 DEG C, the purity of 1, 2, 4-trichlorobenzene in final product obtained is over 99%, and the present invention not only solves problem of producing lindane, but also meets the demand of high-purity 1, 2, 4-trichlorobenzene in the market.
Description
The present invention relates to a kind of solvent crystallization partition method of mixed trichlorobenzene
Contain three kinds of isomerss in the mixed trichlorobenzene, they are respectively: 1,2, and 4-trichlorobenzene, 1 and 1,3,5-trichlorobenzene.To purify out three kinds of isomerss separation in the mixed trichlorobenzene very difficult.Beautiful, day, add etc. state adopt zeolite adsorption method of analysis dna purity from mixed trichlorobenzene only reach 97% 1,2,4-trichlorobenzene (US 4,798,913, US4,089,909).This separation method is the operating procedure complexity not only, and product purity is low.Domestic have unit trying the employing rectification method at present, contain 1 from the invalid body of agricultural chemicals lindane by product-phenyl-hexachloride through what cracking or alkaline hydrolysis obtained, 2, separate in the mixed trichlorobenzene of 4-trichlorobenzene 65～90% (I) and purify 1,2, the 4-trichlorobenzene, this method cost of investment is high, the equipment complexity, product purity is limited, and economic benefit is not good enough.
The objective of the invention is to propose the easy maturation of a kind of technology, with low cost from mixed trichlorobenzene, particularly from (I), separate purify out purity greater than 99% 1,2, the method for 4-trichlorobenzene
The object of the present invention is achieved like this: the present invention adopts the solvent recrystallization separating and purifying method of emulsion washing in addition, concrete operation is, at first will contain 1,2, the interior temperature drop to 0 of the mixed trichlorobenzene raw material of 4-trichlorobenzene 65～92% [(particularly use (I) for raw material)] ℃～14 ℃, with contain in the raw material 8～35% non-1,2,4 trichlorobenzene (1,2,3-trichlorobenzene and/or 1,3, the 5-trichlorobenzene) and other halogenated aryl hydrocarbons be organic solvent, or add a certain amount of alkane again, or alcohol or aromatic hydrocarbon, or halogenated alkane, or halogenated aryl hydrocarbon, or their organic solvents such as mixture, but the organic solvent total content is no more than 35%, add and account for pure 1 of raw material weight 2～5%, 2,4-trichlorobenzene crystal is a crystal seed, system temperature is reduced to-10 ℃～13 ℃, keep reaction 10～15 hours, purity is arranged greater than 97%, in addition greater than 99% 1,2,4-trichlorobenzene crystal is separated out, filtering separation is taken out crystal, if this moment 1,2,4-trichlorobenzene crystal purity is also less than 99% (greater than 97%), be that wash temperature remains between 0 ℃～14 ℃, again with the clean emulsion of cold water on 0.1%～2% common emulsion (as the washing powder emulsion) washing crystal 1～10 minute just with concentration, after separate dry make purity greater than 99% 1,2,4-trichlorobenzene purified product, fusing point are 16 ℃～17.15 ℃.
Can produce in the production of agricultural chemicals lindane and decuple the harmful and do not have the invalid body that desinsection is renderd a service to people and animals of effective phenyl-hexachloride composition, this has greatly limited the production of lindane (being effective body phenyl-hexachloride).The existing outlet of these invalid bodies is to contain 1,2 through cracking or alkaline hydrolysis generation, the thick mixed trichlorobenzene (I) of 4-trichlorobenzene 65～90%, though it can directly be sold as intermediate, market both at home and abroad is all very limited, and a large amount of overstocking becomes trouble and worry.Yet purity greater than 99% 1,2, the market requirement of 4-trichlorobenzene is all very big at home and abroad, only the U.S. will consume 3000 tons of santochlor every year and prepare highly purified 1,2, the 4-trichlorobenzene, therefore research and development from (I) the separation purification purity greater than 99% 1,2, the method for 4-trichlorobenzene has become the focus of this technical field.The solvent recrystallization of the present invention positively effect that compared with prior art has of the separating and purifying method of emulsion washing in addition is: the solvent recrystallization process for separating and purifying is easy sophisticated technology, used solvent and emulsion be common be easy to get inexpensive, the simple less investment of equipment, therefore production cost is low, easy to operate, and prepared 1,2,4-trichlorobenzene based on very high purity, surpass 99%, thereby the inventive method not only removed trouble and worry for the production development of lindane, the high-quality high purity 1 of enough urgent needs is provided to the domestic and international market again, 2,4-trichlorobenzene product.
Embodiment 1
Get and contain 1,2, the thick trichlorobenzene mixture liquid 200g of 4-trichlorobenzene 85% is with temperature drop to 12 in it ℃, with wherein 25% non-1,2, the trichlorobenzene of 4-position and other halogenated aryl hydrocarbon mixtures are organic solvent, add 5g pure 1,2,4-trichlorobenzene crystal crystal seed, temperature drop to 7 ℃ and kept 10 hours, filter out the crystal of separating out, cooling to 5 ℃ of washing powder emulsions with 0.8% concentration washs once, use the remaining emulsion of cold water flush away again, make crystal 1,2 through separating drying, 4-trichlorobenzene 85g, with its content of gas chromatographic analysis is 99.32, and yield is 50%, and mother liquor can use repeatedly
Embodiment 2
Get and contain 1,2, the mixed trichlorobenzene liquid 200g of 4-trichlorobenzene 91%, fall within the range of 14 ℃, with non-1,2,4 trichlorobenzene of 9% wherein is organic solvent, stir down and add pure 1,2,4-trichlorobenzene crystal crystal seed 5g continues to be cooled to 11.5 ℃, kept 11 hours, the crystal that filtration is separated out cools to 3 ℃ again, with the emulsion washing of 0.8% concentration, use the remaining emulsion of cold water flush away again, the drying separation makes crystal 1,2,4-trichlorobenzene 82g, its content of gas chromatographic analysis is 99.64%, and yield is 45%.Mother liquor can use repeatedly.
Embodiment 3
Get and contain 1,2, the mixed trichlorobenzene liquid 84g of 4-trichlorobenzene 85%, with temperature drop to 3 in it ℃, other adds 100ml dehydrated alcohol organic solvent, adds 1.7g pure 1,2,4-trichlorobenzene crystal crystal seed, temperature drops to 0 ℃, kept 10 hours, other operations are the same, make crystal 1,2,4-trichlorobenzene 30g, purity testing are 99.39%, and yield is 42%.
Embodiment 4
Get and contain 1,2, the mixed trichlorobenzene liquid 49g of 4-trichlorobenzene 85%, with temperature drop to 5 in it ℃, other adds 5ml orthodichlorobenzene organic solvent, adds 2.45g pure 1,2,4-trichlorobenzene crystal crystal seed, temperature drops to 1 ℃, keep reaction 12 hours, other operations are the same, make crystal 1,2,4-trichlorobenzene crystal 13.7g, measuring its purity is 99.07%, yield is 32.89%.
Embodiment 5
Get and contain 1,2, the mixed trichlorobenzene liquid 52g of 4-trichlorobenzene 85%, with temperature drop to 0 in it ℃, other adds 10ml Skellysolve A organic solvent, adds 1.56g pure 1,2,4-trichlorobenzene crystal crystal seed, temperature drops to-1 ℃, keep reaction 15 hours, other operations are the same, make crystal 1,2,4-trichlorobenzene 15.2g, measuring its purity is 99.13%, yield is 34.38%.
Claims (4)
1. one kind from containing 1,2, separate in the mixed trichlorobenzene of 4-trichlorobenzene 85-91% and purify 1,2, the method of 4-trichlorobenzene, it is characterized in that adopting solvent recrystallization to add the method for purification of emulsion washing, its concrete operations are with interior temperature drop to 0～14 of the mixed trichlorobenzene raw material of 85-91% ℃, with contain in the raw material 9～15% 1,2,3-trichlorobenzene or 1,3,5-trichlorobenzene and other halogenated aryl hydrocarbons, the straight-chain paraffin of 5-6 carbon atom or its mixture, alcohol or its mixture of 1～3 carbon atom, various dichlorobenzene or its mixture, various trichlorobenzene or its mixture are organic solvent (the organic solvent total content is no more than 35%), add and to account for the pure 1,2 of raw material weight 2-5%, the 4-trichlorobenzene is a crystal seed, system temperature is reduced to-10～13 ℃, kept 10～15 hours, and filtered then and separate out content at 1,2 more than 97%, 4-trichlorobenzene crystal, between 0～14 ℃, be 0.1%～2% common emulsion washing crystal 1-10 minute, clean remaining emulsion with cold water again with concentration, after separate dry make purity greater than 99% 1,2,4-trichlorobenzene purified product.
2. purify 1,2 by the described separation of claim 1, the method for 4-trichlorobenzene is characterized in that, used mixed trichlorobenzene raw material be invalid cracking of agricultural chemicals lindane by product-phenyl-hexachloride or alkaline hydrolysis obtain contain 1,2, the mixed trichlorobenzene of 4-trichlorobenzene 85-91%.
3. purify 1,2 by the described separation of claim 1, the method for 4-trichlorobenzene is characterized in that the temperature of recrystallization is-8～12 ℃.
4. purify 1,2 by the described separation of claim 1, the method for 4-trichlorobenzene is characterized in that, the temperature of washing with emulsion is 0～8 ℃, and the concentration of washing emulsion is 0.8%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93117343 CN1033637C (en) | 1993-09-14 | 1993-09-14 | 1.2,4-trichlorobenzene separating and purifying method from mixed trichlorobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93117343 CN1033637C (en) | 1993-09-14 | 1993-09-14 | 1.2,4-trichlorobenzene separating and purifying method from mixed trichlorobenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1088569A CN1088569A (en) | 1994-06-29 |
| CN1033637C true CN1033637C (en) | 1996-12-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93117343 Expired - Fee Related CN1033637C (en) | 1993-09-14 | 1993-09-14 | 1.2,4-trichlorobenzene separating and purifying method from mixed trichlorobenzene |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105859517B (en) * | 2016-05-03 | 2018-11-02 | 四川福思达生物技术开发有限责任公司 | A kind of method that 1,2,4- trichloro-benzenes is purified in the mixture of trichloro-benzenes |
| CN110204418A (en) * | 2019-06-04 | 2019-09-06 | 江苏扬农化工集团有限公司 | A kind of method of highly effective hydrogenation dechlorination purification trichloro-benzenes |
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| CN1088569A (en) | 1994-06-29 |
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