CN105418358A - Method for preparing o-chlorotoluene - Google Patents
Method for preparing o-chlorotoluene Download PDFInfo
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- CN105418358A CN105418358A CN201510862679.XA CN201510862679A CN105418358A CN 105418358 A CN105418358 A CN 105418358A CN 201510862679 A CN201510862679 A CN 201510862679A CN 105418358 A CN105418358 A CN 105418358A
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- toluene
- reaction
- ortho
- chlorotolu
- chlorotoluene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing o-chlorotoluene. The method comprises the following steps: adding a raw material toluene and a FeCl3-loaded macroporous metal silica gel catalyst into a reaction kettle; introducing chlorine into the reaction kettle for a liquid-phase ring chlorination reaction between the toluene and chlorine; after the reaction is complete, aerating to remove residual chlorine and hydrogen chloride gas in the reaction liquid; rectifying the reaction liquid to separate out unreacted toluene and a little dichlorotoluene to obtain mixed chlorotoluene; and then, separating high-purity p-chlorotoluene from the mixed chlorotoluene by using a melt crystallization process. According to the method disclosed by the invention, the FeCl3-loaded macroporous metal silica gel catalyst is adopted for catalyzing the selective chlorination of toluene, the reaction is fast, the catalytic activity is high, the o-chlorotoluene selectivity is good, the requirements for the technological conditions are low, the catalyst consumption is low, the catalyst has high activity and can be recycled, and the method has a good industrial prospect.
Description
Technical field
The invention belongs to organic chemical industry field, specifically a kind of method preparing ortho-chlorotolu'ene.
Background technology
Ortho-chlorotolu'ene is a kind of important industrial chemicals intermediate, is widely used in the aspects such as agricultural chemicals, medicine, dyestuff and paint.It is again mid-boiling point organic solvent of good performance; At present, ortho-chlorotolu'ene is applied to organic synthesis aspect increasingly extensively.
Take ortho-chlorotolu'ene as raw material, aluminum chloride is catalyzer, can direct synthetizing thiazolium class agricultural bactericide; Ortho-chlorotolu'ene and dichloro alkanes can be used as high-pressure grease and oils through the product of condensation reaction; Ortho-chlorotolu'ene is at Sodium Hydroxide Alkaline Water Under solution synthesis meta-cresol and ortho-cresol, and yield can reach more than 80%; Ortho-chlorotolu'ene chlorination can prepare 2 further under Lewis acid catalyst condition, 6 – toluene dichloride, 2,4 – toluene dichloride etc.
Existingly prepare in ortho-chlorotolu'ene technology, mainly adopt common Lewis acid to be catalyzer, comprise SbCl
3, FeCl
3, AlCl
3deng, though Lewis acid catalyst better catalytic activity, when being used alone, corrodibility is strong, harsh to equipment requirements, and the three wastes are many, are unfavorable for that industrialization generates.
Molecular sieve is used as toluene cyclochlorination catalyst by many bibliographical informations in addition, and as patent CN104945222A, report with zinc chloride load HY molecular sieve for catalyzer, catalysis Toluene selective chlorination produces ortho-chlorotolu'ene.But molecular sieve lattice is easily broken ring by the acid that reaction produces, and catalyst life is short, when reusing after regeneration, in chlorizate, the ratio of ortho-chlorotolu'ene obviously declines, and chlorated liquid interposition content is high simultaneously, is difficult to obtain the high ortho-chlorotolu'ene of purity.
Summary of the invention
For solving the problem, the invention discloses a kind of method preparing ortho-chlorotolu'ene.
In order to reach above object, the invention provides following technical scheme:
A kind of method preparing ortho-chlorotolu'ene, comprise the following steps: methylbenzene raw material and catalyzer are joined in reactor, 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 FeCl
3join in dehydrated alcohol with macroporous silica gel, be warming up to 60 ~ 90 DEG C, return stirring 2 ~ 4h, after reaction terminates, by dry after sample filtering, the sample obtained is FeCl
3the macropore metal silica-gel catalyst of load.
As preferably, the add-on of described catalyzer is 0.1% ~ 2% of toluene quality; Described chlorination reaction temperature is 50 ~ 80 DEG C; The described chlorination reaction time is 6 ~ 12h.
As preferably, described FeCl
3with the amount of substance of macroporous silica gel and mass ratio be: 0.5 ~ 5mmol:10g; The mass volume ratio of macroporous silica gel and dehydrated alcohol is: 1g:10 ~ 15ml; 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 FeCl
3the macropore metal silica gel catalyst Toluene selective chlorination of load, speed of reaction is fast, and catalytic activity is high, and ortho-chlorotolu'ene 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 ortho-chlorotolu'ene, step is as follows: N
2under protection, by FeCl
3join in dehydrated alcohol with macroporous silica gel, FeCl
3with the amount of substance of macroporous silica gel and mass ratio be: 0.5mmol:10g; The mass volume ratio of macroporous silica gel and dehydrated alcohol is: 1g:10ml; Be warming up to 60 DEG C, return stirring 2h, after reaction terminates, by the sample dry 12h at 80 DEG C after filtration, the sample obtained is FeCl
3the macropore metal silica-gel catalyst of load; 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 98%, ortho-chlorotolu'ene content 72.3% in product, parachlorotoluene content 26.8%.
Embodiment two
Prepare the method for ortho-chlorotolu'ene, step is as follows: N
2under protection, by FeCl
3join in dehydrated alcohol with macroporous silica gel, FeCl
3with the amount of substance of macroporous silica gel and mass ratio be: 5mmol:10g; The mass volume ratio of macroporous silica gel and dehydrated alcohol is: 1g:15ml; Be warming up to 90 DEG C, return stirring 4h, after reaction terminates, by the sample dry 12h at 80 DEG C after filtration, the sample obtained is FeCl
3the macropore metal silica-gel catalyst of load; 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 80 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 97%, ortho-chlorotolu'ene content 71.2% in product, parachlorotoluene content 27.5%.
Embodiment three
Prepare the method for ortho-chlorotolu'ene, step is as follows: N
2under protection, by FeCl
3join in dehydrated alcohol with macroporous silica gel, FeCl
3with the amount of substance of macroporous silica gel and mass ratio be: 3mmol:10g; The mass volume ratio of macroporous silica gel and dehydrated alcohol is: 1g:12ml; Be warming up to 80 DEG C, return stirring 3h, after reaction terminates, by the sample dry 12h at 80 DEG C after filtration, the sample obtained is FeCl
3the macropore metal silica-gel catalyst of load; 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 60 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%, ortho-chlorotolu'ene content 73.5% in product, parachlorotoluene content 25.6%.
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 ortho-chlorotolu'ene for one kind, comprise the following steps: methylbenzene raw material and catalyzer are joined in reactor, 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 FeCl
3join in dehydrated alcohol with macroporous silica gel, be warming up to 60 ~ 90 DEG C, return stirring 2 ~ 4h, after reaction terminates, by dry after sample filtering, the sample obtained is FeCl
3the macropore metal silica-gel catalyst of load.
2. prepare the method for ortho-chlorotolu'ene 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 50 ~ 80 DEG C; The described chlorination reaction time is 6 ~ 12h.
3. prepare the method for ortho-chlorotolu'ene as claimed in claim 1, it is characterized in that, described FeCl
3with the amount of substance of macroporous silica gel and mass ratio be: 0.5 ~ 5mmol:10g; The mass volume ratio of macroporous silica gel and dehydrated alcohol is: 1g:10 ~ 15ml; Described drying for standby at referring to 80 DEG C dry 12h for subsequent use.
4. prepare the method for ortho-chlorotolu'ene 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 ortho-chlorotolu'ene 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 ortho-chlorotolu'ene 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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|---|---|---|---|
| CN201510862679.XA CN105418358A (en) | 2015-12-01 | 2015-12-01 | Method for preparing o-chlorotoluene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113896615A (en) * | 2021-11-18 | 2022-01-07 | 常州新东化工发展有限公司 | Method for adsorbing and purifying impurities by using high-purity benzyl chloride |
| CN114797710A (en) * | 2022-06-06 | 2022-07-29 | 常州新东化工发展有限公司 | Preparation method of chlorotoluene |
-
2015
- 2015-12-01 CN CN201510862679.XA patent/CN105418358A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113896615A (en) * | 2021-11-18 | 2022-01-07 | 常州新东化工发展有限公司 | Method for adsorbing and purifying impurities by using high-purity benzyl chloride |
| CN113896615B (en) * | 2021-11-18 | 2023-08-11 | 常州新东化工发展有限公司 | Method for adsorbing and purifying impurities by using high-purity benzyl chloride |
| CN114797710A (en) * | 2022-06-06 | 2022-07-29 | 常州新东化工发展有限公司 | Preparation method of chlorotoluene |
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