CN101891587A - Preparation method of m-trichlorobenzene - Google Patents
Preparation method of m-trichlorobenzene Download PDFInfo
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- CN101891587A CN101891587A CN 201010234536 CN201010234536A CN101891587A CN 101891587 A CN101891587 A CN 101891587A CN 201010234536 CN201010234536 CN 201010234536 CN 201010234536 A CN201010234536 A CN 201010234536A CN 101891587 A CN101891587 A CN 101891587A
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- trichlorobenzene
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Abstract
The invention provides a preparation method of m-trichlorobenzene, which relates to the technical field of chemical industry. Any one of 1,2,3-trichlorobenzene and 1,2,4-trichlorobenzene is simply isomerized under the action of aluminum chloride used as a catalyst and then continuously refined twice to obtain the m-trichlorobenzene of which the purity can reach 99%. In the invention, the 1,2,3-trichlorobenzene and the 1,2,4-trichlorobenzene which are used as raw materials and the aluminum chloride which is used as the catalyst are cheap and can be obtained easily, and organic solvents do not need to be added additionally, thus the production cost is lower.
Description
Technical field
The present invention relates to chemical technology field, particularly synthetic the and separation method of m-trichlorobenzene.
Background technology
M-trichlorobenzene is the industrial chemicals and the reaction intermediate of the industrial widespread use of a class, traditional synthetic method be utilize mixture that the benzene direct chlorination obtains multiple replacement then rectifying obtain, this method productive rate is low and degree of purity of production is not high.Orthodichlorobenzene continues mainly to obtain 1 and 1,2 after the chlorination, the mixture of 4-trichlorobenzene, and how the m-trichlorobenzene that is converted into that this mixture is simple and easy to do is one of industrial technical barrier.
Summary of the invention
The object of the invention is to provide a kind of synthetic method that forms highly purified m-trichlorobenzene.
Step of the present invention comprises:
1) with 1 and 1,2, any and aluminum trichloride (anhydrous) mixing at least in the 4-trichlorobenzene mixture;
2) add entry, and stir;
3) mixed solution slowly is warming up to 190 ± 10 ℃;
4) mixed solution is incubated 5～6 hours under whipped state;
5) in mixed solution, add hydrochloric acid, and stir;
6) slowly be heated to 90 ± 5 ℃, and continue to be stirred to reaction under the keeping warm mode and finish;
7) mixed solution is transferred in the separating funnel washes, is 4～5 until the oil reservoir pH value;
8) washing the oil reservoir material with aqueous sodium hydroxide washes, is 7 ± 0.3 until the oil reservoir pH value, obtains the m-trichlorobenzene crude product;
9) the m-trichlorobenzene crude product is transferred to rectifying in the negative pressure rectifier unit; The negative pressure of described rectifying column is 40～50mmHg, and the rectifying column height is 2 meters, and the control reflux ratio is 4～5;
10) the rectifying product is transferred to the sweating crystallization obtains pure m-trichlorobenzene in the crystallizer; Described sweating crystallization onset temperature is 5 ± 1 ℃, and heat-up rate is to raise 1 ℃ in per 10 minutes, ℃ stops to heat up up to temperature to 63.4.
The present invention is 1 and 1,2, and any of 4-trichlorobenzene refiningly obtains purity and can reach 99% m-trichlorobenzene by double after the simple isomerization under the catalyst action of aluminum chloride.The present invention is with the 1 and 1,2 of cheapness, and the 4-trichlorobenzene is that raw material directly prepares, and raw material is easy to get; Catalyzer is an aluminum chloride, and this catalyzer is cheap and easy to get; The present invention does not need to add organic solvent in addition, and production cost is lower.
In addition, economize in raw materials in order to be beneficial to, aluminum trichloride (anhydrous) that adds in the step 1) and 1 and 1,2, the mass ratio of any the total mass at least in the 4-trichlorobenzene mixture is 25: 100.
Step 2) 1 and 1,2 in water that adds in and the step 1), the mass ratio of any the total mass at least in the 4-trichlorobenzene mixture is 3.2～3.5: 100.
1 and 1,2 in hydrochloric acid and the step 1) in the step 5), any the total mass ratio at least in the 4-trichlorobenzene mixture is 3mL: 1g.
The mass percent concentration that adds hydrochloric acid in the step 5) is 1%.
Each with 1 and 1,2 in aqueous sodium hydroxide solution and the step 1) in the step 8), the mass ratio of any the total mass at least in the 4-trichlorobenzene mixture is 1: 4.
The mass percent concentration of aqueous sodium hydroxide solution is 10% in the step 8).
Embodiment
Concrete reaction formula of the present invention is:
Following formula is represented: raw material can be 1 or 1,2, and 4-trichlorobenzene, or both mixtures, catalyzer are aluminum chloride, and product is a m-trichlorobenzene.
Concrete steps are as follows:
1, with 100g 1 and 100g 1,2, the 4-trichlorobenzene mixes, and forms the 200g mixture, adds in the reaction vessel stirring at normal temperature 5 ± 1 minutes more in the lump with the 50g aluminum trichloride (anhydrous);
Also 200g 1 and 50g aluminum trichloride (anhydrous) can be blended in the reaction vessel, or with 200g 1,2,4-trichlorobenzene and 50g aluminum trichloride (anhydrous) are blended in the reaction vessel.
2, in system, add 6.8g water in 5 ± 1 minutes.Churning time after water injection is 5 ± 1 minutes;
3, in 30 ± 10 minutes, system temperature is elevated to 190 ± 10 ℃;
4, mixed solution stirred 5～6 hours down at 190 ± 10 ℃;
5, adding 600mL, mass percent concentration in 30 ± 10 minutes in mixed solution is 1% hydrochloric acid, and stirs;
6, slowly be heated to 90 ± 5 ℃ in 15 ± 3 minutes after, constant temperature stirred 60 ± 5 minutes;
7, mixed solution is transferred in the separating funnel, washes until oil reservoir PH=4～5 with 640mL at every turn;
8, be that 10% aqueous sodium hydroxide solution repeatedly washs organic layer with mass percent concentration, each 50mL is until PH=7;
9, mix products is transferred in the negative pressure rectifier unit carries out negative pressure rectifying with 2 meters rectifying columns under 40～50mmHg, the control reflux ratio is 4～5;
10, the rectifying product is transferred in the crystallizer and slowly cools to 5 ℃ earlier, the back raise 1 ℃ in per ten minutes, when temperature rises to 63.4 ℃, can obtain the m-trichlorobenzene of content 〉=99%.
Claims (7)
1. the preparation method of m-trichlorobenzene, its step comprises:
1) with 1 and 1,2, in the 4-trichlorobenzene mixture any mixes with aluminum trichloride (anhydrous) at least;
2) add entry, and stir;
3) mixed solution slowly is warming up to 190 ± 10 ℃;
4) mixed solution is incubated 5～6 hours under whipped state;
5) in mixed solution, add hydrochloric acid, and stir;
6) slowly be heated to 90 ± 5 ℃, and continue to be stirred to reaction under the keeping warm mode and finish;
7) mixed solution is transferred in the separating funnel washes, is 4～5 until the oil reservoir pH value;
8) washing the oil reservoir material with aqueous sodium hydroxide washes, is 7 ± 0.3 until the oil reservoir pH value, obtains the m-trichlorobenzene crude product;
9) the m-trichlorobenzene crude product is transferred to rectifying in the negative pressure rectifier unit; The negative pressure of described rectifying column is 40～50mmHg, and the rectifying column height is 2 meters, and the control reflux ratio is 4～5;
10) the rectifying product is transferred to the sweating crystallization obtains pure m-trichlorobenzene in the crystallizer; Described sweating crystallization onset temperature is 5 ± 1 ℃, and heat-up rate is to raise 1 ℃ in per 10 minutes, ℃ stops to heat up up to temperature to 63.4.
2. according to the described method of claim 1, it is characterized in that the aluminum trichloride (anhydrous) and 1 and 1,2 that add in the step 1), the mass ratio of any the total mass at least in the 4-trichlorobenzene mixture is 25: 100.
3. according to the described method of claim 1, it is characterized in that step 2) in 1 and 1,2 in the water that adds and the step 1), the mass ratio of any the total mass at least in the 4-trichlorobenzene mixture is 3.2～3.5: 100.
4. according to the described method of claim 1, it is characterized in that in the step 5) 1 and 1,2 in the hydrochloric acid and step 1), any the total mass ratio at least in the 4-trichlorobenzene mixture is 3mL: 1g.
5. according to claim 1 or 4 described methods, it is characterized in that the mass percent concentration of adding hydrochloric acid in the step 5) is 1%.
6. according to the described method of claim 1, it is characterized in that using 1 and 1,2 in aqueous sodium hydroxide solution and the step 1) in the step 8), the mass ratio of any the total mass at least in the 4-trichlorobenzene mixture is 1: 4 at every turn.
7. according to claim 1 or 6 described methods, the mass percent concentration that it is characterized in that aqueous sodium hydroxide solution in the step 8) is 10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102345361A CN101891587B (en) | 2010-07-19 | 2010-07-19 | Preparation method of m-trichlorobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102345361A CN101891587B (en) | 2010-07-19 | 2010-07-19 | Preparation method of m-trichlorobenzene |
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| Publication Number | Publication Date |
|---|---|
| CN101891587A true CN101891587A (en) | 2010-11-24 |
| CN101891587B CN101891587B (en) | 2012-05-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2010102345361A Expired - Fee Related CN101891587B (en) | 2010-07-19 | 2010-07-19 | Preparation method of m-trichlorobenzene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112299974A (en) * | 2020-11-03 | 2021-02-02 | 宁夏瑞泰科技股份有限公司 | Method for synthesizing 2, 4-dichloroacetophenone by recycling acetophenone crystallization waste |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2123857A (en) * | 1937-09-29 | 1938-07-12 | Dow Chemical Co | Manufacture of 1,3-dichloro-and 1, 3, 5-trichlorobenzenes |
| US2742508A (en) * | 1953-05-22 | 1956-04-17 | Commercial Solvents Corp | Production of 1, 3, 5-trichlorobenzene from waste isomers of benzene hexachloride |
| US4629815A (en) * | 1980-07-01 | 1986-12-16 | Rhone-Poulenc Industries | Isomerization/rearrangement of polychlorobenzenes |
| JPH01311032A (en) * | 1988-06-06 | 1989-12-15 | Kureha Chem Ind Co Ltd | Transchlorination of aromatic polychloride |
-
2010
- 2010-07-19 CN CN2010102345361A patent/CN101891587B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2123857A (en) * | 1937-09-29 | 1938-07-12 | Dow Chemical Co | Manufacture of 1,3-dichloro-and 1, 3, 5-trichlorobenzenes |
| US2742508A (en) * | 1953-05-22 | 1956-04-17 | Commercial Solvents Corp | Production of 1, 3, 5-trichlorobenzene from waste isomers of benzene hexachloride |
| US4629815A (en) * | 1980-07-01 | 1986-12-16 | Rhone-Poulenc Industries | Isomerization/rearrangement of polychlorobenzenes |
| JPH01311032A (en) * | 1988-06-06 | 1989-12-15 | Kureha Chem Ind Co Ltd | Transchlorination of aromatic polychloride |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112299974A (en) * | 2020-11-03 | 2021-02-02 | 宁夏瑞泰科技股份有限公司 | Method for synthesizing 2, 4-dichloroacetophenone by recycling acetophenone crystallization waste |
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| Publication number | Publication date |
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| CN101891587B (en) | 2012-05-23 |
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| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20101124 Assignee: Jiangsu Pengyu Chemical Co., Ltd. Assignor: Yangzhou University Contract record no.: 2015320000547 Denomination of invention: Preparation method of m-trichlorobenzene Granted publication date: 20120523 License type: Exclusive License Record date: 20150713 |
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Granted publication date: 20120523 Termination date: 20160719 |