CN105399600A - Method for preparing parachlorotoluene - Google Patents
Method for preparing parachlorotoluene Download PDFInfo
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- CN105399600A CN105399600A CN201510862514.2A CN201510862514A CN105399600A CN 105399600 A CN105399600 A CN 105399600A CN 201510862514 A CN201510862514 A CN 201510862514A CN 105399600 A CN105399600 A CN 105399600A
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- parachlorotoluene
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- chlorination
- toluene
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Abstract
The invention provides a method for preparing parachlorotoluene. The method comprises the following steps of adding raw materials of methylbenzene and catalysts into a reaction kettle, and feeding chlorine into the reaction kettle to subject methylbenzene and chlorine to a liquid phase ring chlorination reaction; performing aeration after the reaction is completed, removing chlorine and hydrogen chloride remaining in reaction liquid, and rectifying the reaction liquid to separate out un-reacted methylbenzene and a small quantity of dichlorotoluene to obtain mixed chlorotoluene; separating mixed chlorotoluene through a melt crystallization method to obtain high-purity parachlorotoluene. According to the method, AlCl3 loaded L-shaped molecular sieve based catalysts are used for catalyzing methylbenzene for selective chlorination, the reaction rate is high, the catalytic activity is high, selectivity of parachlorotoluene is good, the requirement for process conditions is low, and the catalyst use amount is small; the catalyst is high in activity and capable of being recycled, and a good industrial prospect is achieved.
Description
Technical field
The invention belongs to organic chemical industry field, specifically a kind of method preparing parachlorotoluene.
Background technology
Toluene is under the effects such as lewis acid catalyst iron trichloride, butter of antimony, aluminum chloride, and react in the liquid phase with chlorine, the aromatic ring mono-substituted products monochlorotoluene of generation is the mixture of ortho-chlorotolu'ene and parachlorotoluene.If do catalysis with iron trichloride, in monochlorotoluene mixture, the ratio of parachlorotoluene and ortho-chlorotolu'ene is about 0.5 ~ 0.55:1.
In toluene ring chlorizate, parachlorotoluene is the important intermediate of producing the fine chemical products such as agricultural chemicals, medicine, dyestuff, and the purposes of ortho-chlorotolu'ene is much smaller, uses greatly as solvent at a low price.
All the time, people improve the method for contraposition proportion of products when striving to find toluene ring chlorination reaction, United States Patent (USP) (US4031144) report iron trichloride and sulfur dichloride do catalysis, toluene and chlorine carry out ring chlorination reaction in the liquid phase, parachlorotoluene in product: ortho-chlorotolu'ene=0.9 ~ 0.97:1.Toluene ring chlorination lewis acid catalyst, make promotor (US4069263 with the derivative of thianthrene or thianthrene simultaneously, US4250122), parachlorotoluene in mono chlorinated product: ortho-chlorotolu'ene=1.4:1, although the method obtains higher to neighbour's ratio, but reaction need be carried out under about 0 DEG C condition, severe reaction conditions, and promotor not easily synthesizes.European patent (292,824) report lewis acid catalyst, thiazides compounds makes promotor, parachlorotoluene in toluene and chlorine ring chlorizate: ortho-chlorotolu'ene=1.2 ~ 1.5:1.Although parachlorotoluene ratio is significantly improved, thiazides compounds is met a small amount of water in the reaction and can be decomposed, and causes inactivation, is difficult to industrial application.
Summary of the invention
For solving the problem, the invention discloses a kind of method preparing parachlorotoluene.
In order to reach above object, the invention provides following technical scheme:
A kind of method preparing parachlorotoluene, it is characterized in that step is as follows: join in reactor by methylbenzene raw material and catalyzer, chlorine is passed in reactor, toluene and chlorine is made to carry out liquid phase ring chlorination reaction, after reacting completely, aeration, remove the chlorine and hydrogen chloride gas that remain in reaction solution, reaction solution falls after unreacted toluene and a small amount of toluene dichloride to obtain mixed-chlorotoluene through rectifying separation, then mixed-chlorotoluene adopts fused junction crystallization to be separated and obtains highly purified parachlorotoluene, and the preparation method of described catalyzer is as follows: N
2under protection, by AlCl
3join in distilled water with zeolite L molecular sieve, temperature controls at 40 ~ 60 DEG C, return stirring 2 ~ 4h, after reaction terminates, by dry obtained after sample filtering.
As preferably, the add-on of described catalyzer is 0.1% ~ 2% of toluene quality; Described chlorination reaction temperature is 30 ~ 50 DEG C; The described chlorination reaction time is 6 ~ 12h.
As preferably, described AlCl
3with the amount of substance of zeolite L molecular sieve and mass ratio be: 1 ~ 3mmol:10g; The mass volume ratio of zeolite L molecular sieve and distilled water is: 1g:15 ~ 20ml; Described drying for standby at referring to 80 DEG C dry 12h for subsequent use.
As preferably, described ring chlorination reaction adopts the mode of tower ring chlorination or the chlorination of autoclave ring to carry out, and ring chlorination plant material is lass lining, and its aspect ratio is 2 ~ 10 ︰ 1.
As preferably, the purification of parachlorotoluene is the method adopting fusion-crystallization, and the temperature of its crystallization is at-30 DEG C ~ 10 DEG C.
As preferably, the add-on of described catalyzer is 1% of toluene quality; Described chlorination reaction temperature is 65 DEG C; The described chlorination reaction time is 10h.
The beneficial effect that the present invention obtains is:
The present invention adopts AlCl
3the L-type molecular sieve catalyst catalysis Toluene selective chlorination of load, speed of reaction is fast, and catalytic activity is high, and parachlorotoluene selectivity is good, and require low to processing condition, the consumption of catalyzer is few; The activity of catalyzer is high, can recycled for multiple times, there is good industrial prospect.
Embodiment
Below in conjunction with embodiment, illustrate the present invention further, following embodiment should be understood and be only not used in for illustration of the present invention and limit the scope of the invention.
Embodiment one
Prepare the method for parachlorotoluene, step is as follows: N
2under protection, by AlCl
3join in distilled water with zeolite L molecular sieve, AlCl
3with the amount of substance of zeolite L molecular sieve and mass ratio be: 1mmol:10g; The mass volume ratio of zeolite L molecular sieve and distilled water is: 1g:15ml; At 40 DEG C, return stirring 2h, after reaction terminates, by the sample dry 12h at 80 DEG C after filtration, the catalyzer of obtained chlorination reaction; Join in reactor by methylbenzene raw material and catalyzer, the add-on of catalyzer is 0.1% of toluene quality; In reactor, pass into chlorine, make toluene and chlorine carry out liquid phase ring chlorination reaction, chlorination reaction temperature is 50 DEG C; The chlorination reaction time is 6h.Chlorination reaction adopts the mode of tower ring chlorination or the chlorination of autoclave ring to carry out, ring chlorination plant material is lass lining, its aspect ratio is 2 ︰ 1, after reacting completely, aeration, remove the chlorine and hydrogen chloride gas that remain in reaction solution, reaction solution falls after unreacted toluene and a small amount of toluene dichloride to obtain mixed-chlorotoluene through rectifying separation, then mixed-chlorotoluene adopts fused junction crystallization to be separated and obtains highly purified parachlorotoluene, and the temperature of crystallization is at-30 DEG C.
After measured, toluene conversion 97%, parachlorotoluene content 71.3% in product, ortho-chlorotolu'ene content 27.8%.
Embodiment two
Prepare the method for parachlorotoluene, step is as follows: N
2under protection, by AlCl
3join in distilled water with zeolite L molecular sieve, AlCl
3with the amount of substance of zeolite L molecular sieve and mass ratio be: 3mmol:10g; The mass volume ratio of zeolite L molecular sieve and distilled water is: 1g:20ml; At 60 DEG C, return stirring 4h, after reaction terminates, by the sample dry 12h at 80 DEG C after filtration, the catalyzer of obtained chlorination reaction; Join in reactor by methylbenzene raw material and catalyzer, the add-on of catalyzer is 2% of toluene quality; In reactor, pass into chlorine, make toluene and chlorine carry out liquid phase ring chlorination reaction, chlorination reaction temperature is 40 DEG C; The chlorination reaction time is 12h.Chlorination reaction adopts the mode of tower ring chlorination or the chlorination of autoclave ring to carry out, ring chlorination plant material is lass lining, its aspect ratio is 10 ︰ 1, after reacting completely, aeration, remove the chlorine and hydrogen chloride gas that remain in reaction solution, reaction solution falls after unreacted toluene and a small amount of toluene dichloride to obtain mixed-chlorotoluene through rectifying separation, then mixed-chlorotoluene adopts fused junction crystallization to be separated and obtains highly purified parachlorotoluene, and the temperature of crystallization is at 10 DEG C.
After measured, toluene conversion 98%, parachlorotoluene content 72.2% in product, ortho-chlorotolu'ene content 26.5%.
Embodiment three
Prepare the method for parachlorotoluene, step is as follows: N
2under protection, by AlCl
3join in distilled water with zeolite L molecular sieve, AlCl
3with the amount of substance of zeolite L molecular sieve and mass ratio be: 2mmol:10g; The mass volume ratio of zeolite L molecular sieve and distilled water is: 1g:18ml; At 50 DEG C, return stirring 3h, after reaction terminates, by the sample dry 12h at 80 DEG C after filtration, the catalyzer of obtained chlorination reaction; Join in reactor by methylbenzene raw material and catalyzer, the add-on of catalyzer is 1% of toluene quality; In reactor, pass into chlorine, make toluene and chlorine carry out liquid phase ring chlorination reaction, chlorination reaction temperature is 40 DEG C; The chlorination reaction time is 8h.Chlorination reaction adopts the mode of tower ring chlorination or the chlorination of autoclave ring to carry out, ring chlorination plant material is lass lining, its aspect ratio is 5 ︰ 1, after reacting completely, aeration, remove the chlorine and hydrogen chloride gas that remain in reaction solution, reaction solution falls after unreacted toluene and a small amount of toluene dichloride to obtain mixed-chlorotoluene through rectifying separation, then mixed-chlorotoluene adopts fused junction crystallization to be separated and obtains highly purified parachlorotoluene, and the temperature of crystallization is at-5 DEG C.
After measured, toluene conversion 98%, parachlorotoluene content 72.8% in product, ortho-chlorotolu'ene content 26.1%.
Technique means disclosed in the present invention program is not limited only to the technique means disclosed in above-mentioned embodiment, also comprises the technical scheme be made up of above technical characteristic arbitrary combination.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (6)
1. prepare the method for parachlorotoluene for one kind, it is characterized in that step is as follows: join in reactor by methylbenzene raw material and catalyzer, chlorine is passed in reactor, toluene and chlorine is made to carry out liquid phase ring chlorination reaction, after reacting completely, aeration, remove the chlorine and hydrogen chloride gas that remain in reaction solution, reaction solution falls after unreacted toluene and a small amount of toluene dichloride to obtain mixed-chlorotoluene through rectifying separation, then mixed-chlorotoluene adopts fused junction crystallization to be separated and obtains highly purified parachlorotoluene, and the preparation method of described catalyzer is as follows: N
2under protection, by AlCl
3join in distilled water with zeolite L molecular sieve, temperature controls at 40 ~ 60 DEG C, return stirring 2 ~ 4h, after reaction terminates, by dry obtained after sample filtering.
2. prepare the method for parachlorotoluene as claimed in claim 1, it is characterized in that, the add-on of described catalyzer is 0.1% ~ 2% of toluene quality; Described chlorination reaction temperature is 30 ~ 50 DEG C; The described chlorination reaction time is 6 ~ 12h.
3. prepare the method for parachlorotoluene as claimed in claim 1, it is characterized in that, described AlCl
3with the amount of substance of zeolite L molecular sieve and mass ratio be: 1 ~ 3mmol:10g; The mass volume ratio of zeolite L molecular sieve and distilled water is: 1g:15 ~ 20ml; Described drying for standby at referring to 80 DEG C dry 12h for subsequent use.
4. prepare the method for parachlorotoluene as claimed in claim 1, it is characterized in that, described ring chlorination reaction adopts the mode of tower ring chlorination or the chlorination of autoclave ring to carry out, and ring chlorination plant material is lass lining, and its aspect ratio is 2 ~ 10 ︰ 1.
5. prepare the method for parachlorotoluene as claimed in claim 1, it is characterized in that, the purification of parachlorotoluene is the method adopting fusion-crystallization, and the temperature of its crystallization is at-30 DEG C ~ 10 DEG C.
6. prepare the method for parachlorotoluene as claimed in claim 3, it is characterized in that, the add-on of described catalyzer is 1% of toluene quality; Described chlorination reaction temperature is 65 DEG C; The described chlorination reaction time is 10h.
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| CN201510862514.2A CN105399600A (en) | 2015-12-01 | 2015-12-01 | Method for preparing parachlorotoluene |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734551A (en) * | 2019-01-10 | 2019-05-10 | 江苏琦衡农化科技有限公司 | A kind of oriented chlorination of toluene prepares the production technology of p-chlorotoluene |
| CN114773146A (en) * | 2022-05-19 | 2022-07-22 | 常州新东化工发展有限公司 | Method for synthesizing 2, 4-dichlorotoluene and 3, 4-dichlorotoluene by directionally chlorinating p-chlorotoluene with supported catalyst |
| CN115108883A (en) * | 2021-03-17 | 2022-09-27 | 山东泰和水处理科技股份有限公司 | Preparation method of benzyl chloride |
-
2015
- 2015-12-01 CN CN201510862514.2A patent/CN105399600A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734551A (en) * | 2019-01-10 | 2019-05-10 | 江苏琦衡农化科技有限公司 | A kind of oriented chlorination of toluene prepares the production technology of p-chlorotoluene |
| CN115108883A (en) * | 2021-03-17 | 2022-09-27 | 山东泰和水处理科技股份有限公司 | Preparation method of benzyl chloride |
| CN114773146A (en) * | 2022-05-19 | 2022-07-22 | 常州新东化工发展有限公司 | Method for synthesizing 2, 4-dichlorotoluene and 3, 4-dichlorotoluene by directionally chlorinating p-chlorotoluene with supported catalyst |
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