CN101891587B - Preparation method of m-trichlorobenzene - Google Patents
Preparation method of m-trichlorobenzene Download PDFInfo
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- CN101891587B CN101891587B CN2010102345361A CN201010234536A CN101891587B CN 101891587 B CN101891587 B CN 101891587B CN 2010102345361 A CN2010102345361 A CN 2010102345361A CN 201010234536 A CN201010234536 A CN 201010234536A CN 101891587 B CN101891587 B CN 101891587B
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- China
- Prior art keywords
- trichlorobenzene
- mixture
- mixed solution
- rectifying
- total mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000002360 preparation method Methods 0.000 title claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 230000035900 sweating Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 abstract 2
- 238000007670 refining Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for preparing m-trichlorobenzene includes such steps as isomerizing any one of 1, 2, 3-trichlorobenzene and 1, 2, 4-trichlorobenzene in the presence of catalyst of aluminium trichloride, and refining twice to obtain m-trichlorobenzene with purity up to 99%. The invention takes cheap 1, 2, 3-trichlorobenzene and 1, 2, 4-trichlorobenzene as raw materials and aluminium trichloride as a catalyst, is cheap and easy to obtain, does not need to be additionally added with an organic solvent, and has lower production cost.
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 widespread use in one type of industry, traditional compound method be utilize the benzene direct chlorination obtain multiple substituted mixture 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 technical barrier in the industry.
Summary of the invention
The object of the invention is to provide a kind of compound 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 oil reservoir pH value;
8) washing the oil reservoir material with aqueous sodium hydroxide washes, is 7 ± 0.3 until 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 said rectifying volumn is 40～50mmHg, and the rectifying volumn 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 mold; Said 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 through double after the simple isomerizing 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 following:
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 can 200g 1 and 50g aluminum trichloride (anhydrous) 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, in mixed solution, adding 600mL, mass percent concentration in 30 ± 10 minutes 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, using mass percent concentration is that 10% aqueous sodium hydroxide solution repeatedly washs organic layer, and each 50mL is until pH=7;
9, mix products is transferred in the negative pressure rectifier unit under 40～50mmHg, carries out negative pressure rectifying with 2 meters rectifying volumns, the control reflux ratio is 4～5;
10, the rectifying product is transferred in the mold 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 oil reservoir pH value;
8) washing the oil reservoir material with aqueous sodium hydroxide washes, is 7 ± 0.3 until 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 said rectifying volumn is 40～50mmHg, and the rectifying volumn 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 mold; Said 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 said 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 said 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 said 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 said methods, it is characterized in that the mass percent concentration of adding hydrochloric acid in the step 5) is 1%.
6. according to the said method of claim 1, it is characterized in that in the step 8) at every turn with 1 and 1,2 in aqueous sodium hydroxide solution and the step 1), the mass ratio of any the total mass at least in the 4-trichlorobenzene mixture is 1: 4.
7. according to claim 1 or 6 said 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 CN101891587A (en) | 2010-11-24 |
| CN101891587B true 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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| 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 |
| CN116178101A (en) * | 2023-01-03 | 2023-05-30 | 江苏聚由新材料科技有限公司 | Method for synthesizing 1,3, 5-trichlorobenzene by isomerising 1,2, 3-trichlorobenzene |
Citations (3)
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (3)
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| JP平1-311032A 1989.12.15 |
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| CN101891587A (en) | 2010-11-24 |
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| C06 | Publication | ||
| PB01 | Publication | ||
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| C14 | Grant of patent or utility model | ||
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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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| CF01 | Termination of patent right due to non-payment of annual fee | ||
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Granted publication date: 20120523 Termination date: 20160719 |