CN108586192A - A method of preparing ortho-chlorotolu'ene - Google Patents
A method of preparing ortho-chlorotolu'ene Download PDFInfo
- Publication number
- CN108586192A CN108586192A CN201810682893.0A CN201810682893A CN108586192A CN 108586192 A CN108586192 A CN 108586192A CN 201810682893 A CN201810682893 A CN 201810682893A CN 108586192 A CN108586192 A CN 108586192A
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- CN
- China
- Prior art keywords
- dichlorotoleune
- method described
- chlorotolu
- ene
- palladium catalyst
- 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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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
Abstract
The present invention provides a kind of method preparing dichlorotoleune, is related to the preparation field of orgnnic comopounds.The present invention is with 2,3 dichlorotoleune, 2,4 dichlorotoleune and 2, more than one in 5 dichlorotoleune are raw material, and load type palladium is catalyst, and continuous fixed bed reaction or continuous prepares ortho-chlorotolu'ene.The present invention is raw material using 2,3 dichlorotoleune of industry byproduct, 2,4 dichlorotoleune and 2,5 dichlorotoleune, and load type palladium catalyst is selectively good, and usage time is long, and ortho-chlorotolu'ene yield is high.
Description
Technical field
The present invention relates to a kind of preparation methods of ortho-chlorotolu'ene, more particularly to 2,3- dichlorotoleune, 2,4- dichloromethanes
More than one in benzene and 2,5- dichlorotoleune are that catalytic material reduction prepares ortho-chlorotolu'ene.
Background technology
2,3 dichloro toluene, 2,4 di chloro toluene, 2,5- dichlorotoleune are the side reaction productions obtained in the industrial production of part
Object, and exist as a mixture substantially, it is only used at present as solvent, causes great waste.So to the mixture
Processing to environmental protection and obtain economic benefit it is all significant.
Ortho-chlorotolu'ene is a kind of important industrial chemicals intermediate, is widely used in the side such as pesticide, medicine, dyestuff and paint
Face.It is mid-boiling point organic solvent of good performance again.There are good market prospects.For example, adjacent toluene halide is increasingly applied
In terms of organic synthesis；Using ortho-chlorotolu'ene as raw material, alchlor is catalyst, can direct synthetizing thiazolium class agriculture chemicals fungicide；
Ortho-chlorotolu'ene can be used as high-pressure grease and oils with product of the dichloro alkanes through condensation reaction；Ortho-chlorotolu'ene is in sodium hydroxide alkali
Hydrolysis metacresol and o-cresol under the conditions of property, yield is up to 80% or more；Ortho-chlorotolu'ene is under the conditions of Lewis acid catalysts
Further halogenation it can prepare 2,6-halogeno toluenes, 2,4-halogeno toluenes.
Invention content
The problem of for above-mentioned side reaction product waste, the present invention provides one kind with 2,3- dichlorotoleune, 2,4- dichloros
Toluene and 2, more than one in 5- dichlorotoleune are raw material, and hydrogen is reducing agent, and load type palladium catalyst catalysis reduction prepares adjacent
The method of chlorotoluene.
It is as follows：
1, the synthesis of load type palladium catalyst：Carrier impregnation adsorbs palladium source aqueous solution, in 100-120 DEG C of drying after drying.
Wherein, it is preferred that carrier is silicon carbide or activated carbon, and silicon-carbide particle specific surface area is more than 100m2/ g, diameter
2-4mm or carrier are activated carbon.It is 0.1~5% that palladium rate is born after load.
Wherein, it is preferred that palladium source aqueous solution is 5% tetramminepalladous chloride aqueous solution.
2, catalytic reduction reaction：（1）Load type palladium catalyst is added in the reactor；（2）Logical hydrogen emptying；（3）It keeps
Atmosphere of hydrogen, 0.01~0.10MPa of reaction pressure, 120~250 DEG C of temperature, are passed through raw material；（4）Rectifying product obtains adjacent chloromethane
Benzene.
Wherein, catalytic reduction reaction is continuous fixed bed reaction or continuous, and raw material dichlorotoleune mass space velocity is（0.2-1.5）h-1,
Feed hydrogen is 0.2-2 with dichlorotoleune molar ratio：1.
Advantageous effect：
One, catalytic selectivity is good
2,3- dichlorotoleune, 2,4-DCT and 2,5- dichlorotoleune scheme through the invention, selectively can only restore
One halogeno-group, and only retain the halogeno-group at methylbenzyl ortho position.
Two, high conversion rate
Percent 50 or more reaction product is ortho-chlorotolu'ene.
Three, side reaction product recycles
2,3- dichlorotoleune, 2,4-DCT and 2, for 5- dichlorotoleune as side reaction product, recycling can be abundant
Using raw material, meet the standard of Green Chemistry, and product ortho-chlorotolu'ene also generates new as important Chemical Manufacture intermediate
Economic value.
Four, catalyst service life is long, can effectively be catalyzed more than 1000 hours.
Specific implementation mode
The present invention is described in further detail with reference to embodiment, but embodiments of the present invention are not limited to
This, while its shown data does not represent the limitation to feature of present invention range.
Embodiment 1
1,25g specific surface areas are more than 100m2/ g, diameter 2-4mm silicon carbide cylindrical particles, dipping absorption contain 5% tetramminepalladous chloride
Aqueous solution 10ml, it is for use after being dried 5 hours in 110 DEG C after natural drying.
2,25g hydrogenation catalysts are filled in diameter 20mm cylindrical reactors, are warming up to 200 DEG C, lead to hydrogen after one hour,
Atmosphere of hydrogen is kept,；Keep reaction pressure 0.05MPa, with 0.3ml/h be continuously added to 2,3- dichlorotoleune, 2,4-DCT,
2,5- dichlorotoleune mixtures, reaction sample after 1 hour, use gas chromatographic analysis.
Its result is as follows：
Embodiment 2
Change 2,3 dichloro toluene, 2,4 di chloro toluene, the 2,5- dichlorotoleune mixtures in embodiment 1 into 2,5- dichloromethanes
Benzene, other are the same as embodiment 1.
Its result is as follows：
Embodiment 3
Silicon carbide loaded palladium catalyst in embodiment 1 is replaced with into activated carbon supported palladium catalyst, other are the same as embodiment 1.
Its result is as follows：
It can be seen that activated carbon supported palladium catalyst, catalytic selectivity effect is not so good as silicon carbide loaded palladium catalyst, industrial production
Preferentially select activated carbon supported palladium catalyst provided by the invention.
Embodiment 4
It changes the step（2）Reaction time is 240h, 480h.Other are the same as embodiment 1.
Its result is as follows：
Claims (7)
1. a kind of method of synthesis ortho-chlorotolu'ene, characterized in that load type palladium catalyst is with 2,3- dichlorotoleune, 2,4- dichloromethanes
Benzene and 2, one or more of 5- dichlorotoleune are raw material, and hydrogen is reducing agent, and catalysis reduction generates ortho-chlorotolu'ene.
2. according to the method described in claim 1, it is characterized in that, realized by following steps：(1) load is added in the reactor
Type palladium catalyst；（2）Logical hydrogen emptying；（3）Atmosphere of hydrogen, reaction pressure 0.01-0.10MPa, 120-250 DEG C of temperature are kept,
It is passed through raw material dichlorotoleune；（4）Rectifying product obtains adjacent toluene halide.
3. according to the method described in claim 2, it is characterized in that, the catalytic reduction reaction be continuous fixed bed reaction or continuous.
4. according to the method described in claim 2, it is characterized in that, the raw material dichlorotoleune mass space velocity be 0.2-1.5h-1；
The hydrogen is 0.2-2 with dichlorotoleune molar ratio：1.
5. according to the method described in claim 1, it is characterized in that：The load type palladium catalyst is silicon carbide load palladium catalysis
Agent or activated carbon supported palladium catalyst, it is 0.1-5% to bear palladium rate.
6. according to the method described in claim 5, it is characterized in that：The silicon carbide loaded palladium catalyst is by following methods system
It is standby：Silicon-carbide particle dipping absorption palladium source aqueous solution, in 100-120 DEG C of drying after drying.
7. according to the method described in claim 6, it is characterized in that：The palladium source aqueous solution is that 5-10% tetramminepalladous chlorides are water-soluble
Liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810682893.0A CN108586192A (en) | 2018-06-28 | 2018-06-28 | A method of preparing ortho-chlorotolu'ene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810682893.0A CN108586192A (en) | 2018-06-28 | 2018-06-28 | A method of preparing ortho-chlorotolu'ene |
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| CN108586192A true CN108586192A (en) | 2018-09-28 |
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| CN201810682893.0A Pending CN108586192A (en) | 2018-06-28 | 2018-06-28 | A method of preparing ortho-chlorotolu'ene |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4749817A (en) * | 1986-08-22 | 1988-06-07 | Standard Chlorine Of Delaware, Inc. | Hydrodechlorination of chlorinated benzenes |
| US5545779A (en) * | 1993-10-13 | 1996-08-13 | Bayer Aktiengesellschaft | Process for the hydrodehalogenation of halogenated benzenes |
| US5625110A (en) * | 1994-07-26 | 1997-04-29 | Leuna-Katalysatoren Gmbh | Hydrodehalogenation catalyst |
| US6482996B1 (en) * | 1999-09-09 | 2002-11-19 | Bayer Aktiengesellschaft | Method for the production or preparation of 2,6-dichlorotoluol |
| CN103102243A (en) * | 2013-03-08 | 2013-05-15 | 江苏超跃化学有限公司 | Method for preparing chlorotoluene |
-
2018
- 2018-06-28 CN CN201810682893.0A patent/CN108586192A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4749817A (en) * | 1986-08-22 | 1988-06-07 | Standard Chlorine Of Delaware, Inc. | Hydrodechlorination of chlorinated benzenes |
| US5545779A (en) * | 1993-10-13 | 1996-08-13 | Bayer Aktiengesellschaft | Process for the hydrodehalogenation of halogenated benzenes |
| US5625110A (en) * | 1994-07-26 | 1997-04-29 | Leuna-Katalysatoren Gmbh | Hydrodehalogenation catalyst |
| US6482996B1 (en) * | 1999-09-09 | 2002-11-19 | Bayer Aktiengesellschaft | Method for the production or preparation of 2,6-dichlorotoluol |
| CN103102243A (en) * | 2013-03-08 | 2013-05-15 | 江苏超跃化学有限公司 | Method for preparing chlorotoluene |
Non-Patent Citations (1)
| Title |
|---|
| 朱洪法 编: "《催化剂载体》", 30 April 1980 * |
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Application publication date: 20180928 |
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