CN113979858A - Method for preparing chloroisobutyryl chloride by continuous chlorination - Google Patents
Method for preparing chloroisobutyryl chloride by continuous chlorination Download PDFInfo
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- CN113979858A CN113979858A CN202111203628.8A CN202111203628A CN113979858A CN 113979858 A CN113979858 A CN 113979858A CN 202111203628 A CN202111203628 A CN 202111203628A CN 113979858 A CN113979858 A CN 113979858A
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- CN
- China
- Prior art keywords
- chloride
- chloroisobutyryl
- continuous
- chlorine
- chloroisobutyryl chloride
- 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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- DTZKVZKYSZUBAG-UHFFFAOYSA-N 2-chloro-2-methylpropanoyl chloride Chemical compound CC(C)(Cl)C(Cl)=O DTZKVZKYSZUBAG-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000460 chlorine Substances 0.000 claims abstract description 32
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 17
- DGMOBVGABMBZSB-UHFFFAOYSA-N 2-methylpropanoyl chloride Chemical compound CC(C)C(Cl)=O DGMOBVGABMBZSB-UHFFFAOYSA-N 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000007599 discharging Methods 0.000 claims abstract description 5
- 238000004064 recycling Methods 0.000 claims abstract description 4
- 238000004821 distillation Methods 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims 1
- 238000001577 simple distillation Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- BSMGLVDZZMBWQB-UHFFFAOYSA-N 2-methyl-1-phenylpropan-1-one Chemical compound CC(C)C(=O)C1=CC=CC=C1 BSMGLVDZZMBWQB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/62—Preparation of carboxylic acid halides by reactions not involving the carboxylic acid halide group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/64—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing chloroisobutyryl chloride by continuous chlorination, which comprises the following steps: (I): adding a mixture of isobutyryl chloride and sulfuric acid (catalyst) into a continuous reaction device, replacing air in the device with nitrogen, heating to 40-75 ℃, and continuously introducing chlorine, wherein the content of chlorine in tail gas is 0%; (II): discharging through a continuous reaction device to obtain more than 99% of crude chloroisobutyryl chloride, carrying out reduced pressure distillation on the crude chloroisobutyryl chloride to obtain a product, and recycling the kettle residue to the continuous reaction device. According to the method for preparing chloroisobutyryl chloride by continuous chlorination, cheap and easily-obtained sulfuric acid is used as a catalyst, isobutyryl chloride and chlorine react in a continuous device, the reaction rate of the chlorine participating in the reaction is 100%, the content of the chlorine in tail gas is 0%, the obtained crude chloroisobutyryl chloride is simply distilled to obtain high-purity chloroisobutyryl chloride, and residual liquid is recycled.
Description
Technical Field
The invention relates to the technical field of chloroisobutyryl chloride, in particular to a method for preparing chloroisobutyryl chloride by continuous chlorination.
Background
Chloroisobutyryl chloride is an intermediate for producing a photoinitiator and is used for preparing the photoinitiator, the chloroisobutyryl chloride is also called chloroisobutyryl chloride or isobutyryl chloride, phenyl isopropyl ketone can be synthesized by isobutyryl chloride and benzene under the catalysis of AlCl3, the chloroisobutyryl chloride is an important intermediate of 2-hydroxy-2-methyl-1-phenyl acetone which is a new generation of photocuring coating photoinitiators, isobutyryl chloride is also an important intermediate in the aspects of pesticides and medicines, and a proper amount of phosphorus trichloride is added into thionyl chloride, so that the yield can be further improved.
In the preparation process of chloroisobutyryl chloride in the market, isobutyryl chloride and chlorine are mainly used for chlorination reaction, the purity of a crude product is low (generally lower than 95%), a rectification mode is needed for purification, the chlorine in tail gas needs to be absorbed by a special tail gas absorption device, and the reaction rate of chlorine participation is generally about 90%, so that the production cost is high and the environmental protection pressure is high.
Disclosure of Invention
The invention aims to provide a method for preparing chloroisobutyryl chloride by continuous chlorination, so as to solve the problems that isobutyryl chloride and chlorine react to perform chlorination reaction in the existing preparation process of chloroisobutyryl chloride on the market, the purity of a crude product is low (generally lower than 95 percent), the crude product needs to be purified by adopting a rectification mode, the chlorine in tail gas needs to be absorbed by adopting a special tail gas absorption device, the reaction rate of the chlorine participating in the tail gas is generally about 90 percent, the production cost is high, and the environmental protection pressure is high.
In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing chloroisobutyryl chloride by continuous chlorination comprises the following steps:
(I): adding a mixture of isobutyryl chloride and sulfuric acid (catalyst) into a continuous reaction device, replacing air in the device with nitrogen, heating to 40-75 ℃, and continuously introducing chlorine, wherein the content of chlorine in tail gas is 0%.
(II): discharging through a continuous reaction device to obtain more than 99% of crude chloroisobutyryl chloride, carrying out reduced pressure distillation on the crude chloroisobutyryl chloride to obtain a product, and recycling the kettle residue to the continuous reaction device.
Preferably, the catalyst in step (1) is sulfuric acid (98%).
Preferably, the mass ratio of isobutyryl chloride to the catalyst in the step (1) is 100: 1-5.
Preferably, the reaction temperature in the step (1) is 40-75 ℃.
Preferably, the reaction rate of chlorine participation in the step (1) is 100%, and the content of chlorine in the tail gas is 0%.
Preferably, a continuous reaction device is adopted in the step (1) and continuous feeding and discharging are carried out.
Preferably, the content of the crude chloroisobutyryl chloride in the step (2) is 99% or more.
Preferably, the crude chloroisobutyryl chloride in the step (2) is simply distilled under reduced pressure, and the content of the distilled chloroisobutyryl chloride is more than 99%.
Preferably, the still residue (the main component is sulfuric acid) obtained in the step (2) is recycled to a continuous reaction device, and the comprehensive consumption of the sulfuric acid is 2 Kg/ton of product.
Compared with the prior art, the invention has the beneficial effects that: according to the method for preparing chloroisobutyryl chloride by continuous chlorination, cheap and easily-obtained sulfuric acid is used as a catalyst, isobutyryl chloride and chlorine react in a continuous device, the reaction rate of the chlorine participating in the reaction is 100%, the content of the chlorine in tail gas is 0%, the obtained crude chloroisobutyryl chloride is simply distilled to obtain high-purity chloroisobutyryl chloride, and residual liquid is recycled.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
the process for preparing chloroisobutyryl chloride by continuous chlorination comprises the following steps:
(I): adding a mixture of 99% of isobutyryl chloride and 6g of sulfuric acid catalyst (the feeding speed is 15g/h) into a continuous reaction device, replacing air in a kettle with nitrogen, heating to 60 ℃, keeping the temperature at 60-75 ℃, continuously introducing chlorine, and detecting the content of chlorine in tail gas of the reaction device.
(II): 606g of crude chloroisobutyryl chloride from the reaction device is simply distilled under reduced pressure of-0.095 MPa, the purity of the obtained chloroisobutyryl chloride is 99.2 percent, the yield is 98.1 percent, and the residual liquid is recycled.
Example two:
the process for preparing chloroisobutyryl chloride by continuous chlorination comprises the following steps:
(I): adding a mixture of 99% isobutyryl chloride and 12g sulfuric acid catalyst (the feeding speed is 15g/h) into a continuous reaction device, replacing the air in a kettle with nitrogen, heating to 55 ℃, keeping the temperature at 55-70 ℃, continuously introducing chlorine, and simultaneously detecting the chlorine content in the tail gas of the reaction device.
(II): 612g of crude chloroisobutyryl chloride from the reaction device is simply distilled under reduced pressure of-0.095 MPa, the purity of the obtained chloroisobutyryl chloride is 99.3 percent, the yield is 98.2 percent, and the residual liquid is recycled.
Example three:
the process for preparing chloroisobutyryl chloride by continuous chlorination comprises the following steps:
(I): replacing air in the kettle with nitrogen in the continuous reaction device, heating to 50 ℃, keeping the temperature at 50-65 ℃, continuously introducing chlorine, and simultaneously detecting the chlorine content in the tail gas of the reaction device.
(II): 618g of crude chloroisobutyryl chloride from the reaction device is simply distilled under reduced pressure of-0.095 MPa, the purity of the obtained chloroisobutyryl chloride is 99.2 percent, the yield is 98.3 percent, and the residual liquid is recycled.
Example four:
the process for preparing chloroisobutyryl chloride by continuous chlorination comprises the following steps:
(I): adding a mixture of 99% of isobutyryl chloride and 24g of sulfuric acid catalyst (the feeding speed is 15g/h) into a continuous reaction device, replacing air in a kettle with nitrogen, heating to 45 ℃, keeping the temperature at 45-60 ℃, continuously introducing chlorine, and detecting the content of chlorine in tail gas of the reaction device.
(II): 624g of crude chloroisobutyryl chloride from the reaction device is simply distilled under reduced pressure, the reduced pressure is-0.095 MPa, the purity of the obtained chloroisobutyryl chloride is 99.5 percent, the yield is 98.1 percent, and the residual liquid is recycled.
Example five:
the process for preparing chloroisobutyryl chloride by continuous chlorination comprises the following steps:
(I): adding a mixture of 99% isobutyryl chloride and 30g sulfuric acid catalyst (the feeding speed is 15g/h) into a continuous reaction device, replacing the air in the kettle with nitrogen, heating to 40 ℃, keeping the temperature at 40-55 ℃, continuously introducing chlorine, and simultaneously detecting the chlorine content in the tail gas of the reaction device.
(II): 630g of crude chloroisobutyryl chloride from the reaction device is simply distilled under reduced pressure of-0.095 MPa, the purity of the obtained chloroisobutyryl chloride is 99.6 percent, the yield is 98.0 percent, and the residual liquid is recycled.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in the process, method, article, or apparatus that comprises the element.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.
Claims (9)
1. A method for preparing chloroisobutyryl chloride by continuous chlorination is characterized by comprising the following steps:
(I): adding a mixture of isobutyryl chloride and sulfuric acid (catalyst) into a continuous reaction device, replacing air in the device with nitrogen, heating to 40-75 ℃, and continuously introducing chlorine, wherein the content of chlorine in tail gas is 0%.
(II): discharging through a continuous reaction device to obtain more than 99% of crude chloroisobutyryl chloride, carrying out reduced pressure distillation on the crude chloroisobutyryl chloride to obtain a product, and recycling the kettle residue to the continuous reaction device.
2. The process according to claim 1 for the continuous chlorination for the preparation of chloroisobutyryl chloride, characterized in that: the catalyst in the step (1) is sulfuric acid (98%).
3. The process according to claim 1 for the continuous chlorination for the preparation of chloroisobutyryl chloride, characterized in that: in the step (1), the mass ratio of isobutyryl chloride to the catalyst is 100: 1-5.
4. The process according to claim 1 for the continuous chlorination for the preparation of chloroisobutyryl chloride, characterized in that: the reaction temperature in the step (1) is 40-75 ℃.
5. The process according to claim 1 for the continuous chlorination for the preparation of chloroisobutyryl chloride, characterized in that: the reaction rate of chlorine participating in the step (1) is 100%, and the content of chlorine in the tail gas is 0%.
6. The process according to claim 1 for the continuous chlorination for the preparation of chloroisobutyryl chloride, characterized in that: and (2) adopting a continuous reaction device and continuously feeding and discharging materials in the step (1).
7. The process according to claim 1 for the continuous chlorination for the preparation of chloroisobutyryl chloride, characterized in that: the content of the crude chloroisobutyryl chloride in the step (2) is more than 99 percent.
8. The process according to claim 1 for the continuous chlorination for the preparation of chloroisobutyryl chloride, characterized in that: and (3) carrying out reduced pressure simple distillation on the crude chloroisobutyryl chloride in the step (2), wherein the content of the distilled chloroisobutyryl chloride is more than 99%.
9. The process according to claim 1 for the continuous chlorination for the preparation of chloroisobutyryl chloride, characterized in that: and (3) recycling the kettle residue (mainly comprising sulfuric acid) obtained in the step (2) to a continuous reaction device, wherein the comprehensive consumption of the sulfuric acid is 2 Kg/ton of the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111203628.8A CN113979858A (en) | 2021-10-15 | 2021-10-15 | Method for preparing chloroisobutyryl chloride by continuous chlorination |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111203628.8A CN113979858A (en) | 2021-10-15 | 2021-10-15 | Method for preparing chloroisobutyryl chloride by continuous chlorination |
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| Publication Number | Publication Date |
|---|---|
| CN113979858A true CN113979858A (en) | 2022-01-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111203628.8A Pending CN113979858A (en) | 2021-10-15 | 2021-10-15 | Method for preparing chloroisobutyryl chloride by continuous chlorination |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1444787A (en) * | 1972-12-27 | 1976-08-04 | ||
| US4169847A (en) * | 1976-07-07 | 1979-10-02 | Saurefabrik Schweizerhall | Process for the manufacture of α-chloroalkanoyl chlorides |
| DE2927353A1 (en) * | 1979-07-06 | 1981-01-29 | Hoechst Ag | METHOD FOR PRODUCING CHLORACETYL CHLORIDE |
| CN105480948A (en) * | 2015-12-16 | 2016-04-13 | 南京工业大学 | Method and system for recycling by-product hydrogen chloride in fatty acid or fatty acyl chloride chlorination production process |
| CN108276361A (en) * | 2018-02-01 | 2018-07-13 | 浙江扬帆新材料股份有限公司 | A kind of synthetic method of free radical photo-initiation |
| CN109651134A (en) * | 2019-02-13 | 2019-04-19 | 天津城建大学 | A kind of preparation method of photoinitiator 2- methyl -2- hydroxyl -1- phenylacetone |
-
2021
- 2021-10-15 CN CN202111203628.8A patent/CN113979858A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1444787A (en) * | 1972-12-27 | 1976-08-04 | ||
| US4169847A (en) * | 1976-07-07 | 1979-10-02 | Saurefabrik Schweizerhall | Process for the manufacture of α-chloroalkanoyl chlorides |
| DE2927353A1 (en) * | 1979-07-06 | 1981-01-29 | Hoechst Ag | METHOD FOR PRODUCING CHLORACETYL CHLORIDE |
| CN105480948A (en) * | 2015-12-16 | 2016-04-13 | 南京工业大学 | Method and system for recycling by-product hydrogen chloride in fatty acid or fatty acyl chloride chlorination production process |
| CN108276361A (en) * | 2018-02-01 | 2018-07-13 | 浙江扬帆新材料股份有限公司 | A kind of synthetic method of free radical photo-initiation |
| CN109651134A (en) * | 2019-02-13 | 2019-04-19 | 天津城建大学 | A kind of preparation method of photoinitiator 2- methyl -2- hydroxyl -1- phenylacetone |
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