CN101195593A - Industrial production method of alkylbenzene sulfonyl chloride - Google Patents
Industrial production method of alkylbenzene sulfonyl chloride Download PDFInfo
- Publication number
- CN101195593A CN101195593A CNA200710044413XA CN200710044413A CN101195593A CN 101195593 A CN101195593 A CN 101195593A CN A200710044413X A CNA200710044413X A CN A200710044413XA CN 200710044413 A CN200710044413 A CN 200710044413A CN 101195593 A CN101195593 A CN 101195593A
- Authority
- CN
- China
- Prior art keywords
- sulfonyl chloride
- alkylbenzene
- chlorosulfonic acid
- reaction
- acid
- 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.)
- Granted
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an industrialized production process of alkyl benzenesulfonyl chloridebenzene sulfonyl chloride, which uses tubular reactor to continuously or kettle-type intermittently sulfonate alkyl benzene and liquid sulfur trioxide in the solvent as liquid sulfur dioxide, liquid wax, ligarine, and halohydrocarbon of C1-C4, 90-120# solvent oil and alkane of C4-C8 or the like, directly treats the reaction product and chlorosulfonic acid with acyl chlorination via a tubular reactor continuously or a kettle intermittently, to generate alkyl benzenesulfonyl chloridebenzene sulfonyl chloride, washes alkyl benzenesulfonyl chloridebenzene sulfonyl chloride, removes acid, and desolventizes to generate product alkyl benzenesulfonyl chloridebenzene sulfonyl chloride. The invention avoids generating hydrochloride gas, to support tube continuous production, reduce dangerous chemical in production system, reduce equipment investment, and improve economic benefit, which replaces chlorosulfonic acid with sulfur trioxide to process sulphonation to realize clean production and reduce material cost.
Description
Technical Field
The invention relates to an industrial production method of alkyl benzene sulfonyl chloride, in particular to a novel process for continuously or intermittently producing alkyl benzene sulfonyl chloride by utilizing liquid sulfur trioxide and chlorosulfonic acid in a solvent.
Background
Alkyl benzene sulfonyl chloride generated by the chlorosulfonation reaction of alkyl benzene (benzene, toluene, ethylbenzene and the like) is an important fine chemical product, is an important intermediate in the industries of medicines, dyes, pigments and plastic auxiliaries and has very wide application.
There are several methods for industrially producing alkylbenzenesulfonyl chloride, but most of them are formed by reacting alkylbenzene with excess chlorosulfonic acid and then hydrolyzing excess chlorosulfonic acid, but different auxiliaries such as phosphorus oxychloride, inorganic ammonium salts, alkali metals or alkaline earth metals, etc. are added during sulfonation in consideration of the amount of isomers, and there are some changes in reaction temperature and hydrolysis manner, etc. in the related art, see german patent DE 1172258, DE1112978, US patent US3686300, japanese patent JP 56-46860, chinese patent CN1824649, CN1405151, CN1049213C, CN1436773A, etc.
In the process flow (figure 1) of the traditional process, alkylbenzene directly reacts with excessive chlorosulfonic acid, so that a large amount of waste sulfuric acid and waste hydrochloric acid are generated, the treatment is difficult, and the three wastes are polluted greatly; the separation of the materials and the waste acid is difficult in the later period; meanwhile, the use of a large amount of chlorosulfonic acid causes the synthesis cost to be overhigh and the production lacks competitiveness; in the large-scale production process, the safety of the production apparatus is very poor due to the use of a large amount of chlorosulfonic acid in the batch reaction system.
Disclosure of Invention
The invention aims to provide an industrial production process of alkyl benzene sulfonyl chloride, which aims to reduce the pollution to the environment, improve the safety of a production device and reduce the production cost.
The technical scheme of the invention is as follows:
1) and (3) sulfonation reaction: in the presence of a solvent, under the condition of-20-80 ℃, continuously sulfonating by using a pipeline reactor or intermittently sulfonating in a kettle way;
2) acyl chlorination reaction: and (2) directly reacting the product generated in the sulfonation reaction 1) with chlorosulfonic acid, performing acyl chlorination reaction continuously or intermittently in a kettle manner by using a pipeline reactor at the temperature of-20-80 ℃ to generate alkylbenzene sulfonylchloride, hydrolyzing slightly excessive chlorosulfonic acid, and then separating acid and desolventizing to generate alkylbenzene sulfonyl chloride.
The substituent on the benzene ring of the alkylbenzene is alkyl containing 0-10 carbon atoms.
The solvent in the sulfonation reaction 1) of the preparation method comprises liquid sulfur dioxide, liquid paraffin, petroleum ether and C1～C4Halogenated hydrocarbon, 90-120 # solvent oil or C4～C8An alkane; the weight percentage concentration of the liquid sulfur trioxide is 1-100%, the weight percentage concentration of the alkylbenzene is 1-100%, and the molar ratio of the alkylbenzene to the liquid sulfur trioxide is 1: 0.5-2.5.
The dosage of chlorosulfonic acid in the acyl chlorination reaction 2) is as follows: the molar ratio of the alkylbenzene to the chlorosulfonic acid is 1: 0.5-3.5.
The process flow of the production process of the alkylbenzene sulfonyl chloride is shown in figure 2, and the reaction formula is as follows
Through the pipeline continuous production, the dangerous chemical substances of the production system can be greatly reduced, the intrinsic safety of the system is realized, the investment of the device is reduced, and the economic benefit is improved. By replacing part of chlorosulfonic acid with liquid sulfur trioxide, not only can the production cost be greatly reduced, but also the discharge of waste acid and waste gas can be greatly reduced, and the purpose of emission reduction is achieved.
The solvent participates in the reaction, so that the whole process is liquefied, the possibility is provided for the pipeline continuous process, and the direct separation of waste acid can be directly realized.
Meanwhile, the preparation method can realize the byproduct of the alkylbenzene sulfonic acid, and greatly improve the operation efficiency of the device.
The invention has the beneficial effects that:
the invention uses liquid-phase sulfur trioxide as a sulfonating agent instead, which is the most economic synthesis mode in organic synthesis, does not produce any pollution, only connects sulfur trioxide to a benzene ring, is a green clean synthesis process, and is qualitatively leap compared with the traditional sulfonation by using chlorosulfonic acid. The product alkyl benzene sulfonic acid further reacts with chlorosulfonic acid without generating hydrogen chloride gas, and completely without generating waste hydrochloric acid, and the byproduct sulfuric acid is greatly reduced compared with the traditional process, thereby having obvious clean production characteristics. Meanwhile, the energy consumption is greatly reduced due to the adoption of the pipelining reaction. The sulfur trioxide has relatively small molecular weight and the price is less than half of that of chlorosulfonic acid, so that the sulfur trioxide is used for substituting chlorosulfonic acid for sulfonation, thereby greatly reducing the production cost. In addition, the use of the solvent in the new process greatly reduces the activity of the liquid sulfur trioxide, makes direct sulfonation possible and improves the yield. Meanwhile, the solvent can directly play a part of positioning role along with the change of the proportion of the solvent.
The production process of the invention has no hydrogen chloride gas generated in the whole reaction process, can realize pipeline continuous reaction, has stable production and easy control, and has less amount of dangerous chemicals stored in a system with the same production scale and good intrinsic safety. The method avoids the defects of poor intrinsic safety and high energy consumption caused by the adoption of intermittent reaction, difficulty in production control, more unorganized hydrogen chloride emission, and large amount of dangerous chemicals stored in a system with the same production scale in the traditional process.
Drawings
FIG. 1: a flow chart of the traditional production process of alkyl benzene sulfonyl chloride.
FIG. 2: the invention relates to a production process flow chart of alkyl benzene sulfonyl chloride.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
Cooling a benzene (liquid paraffin) solution with the flow rate of 39kg/h and the concentration of 20% by a metering pump, then injecting the cooled benzene (liquid paraffin) solution and a liquid sulfur trioxide (liquid paraffin) solution with the flow rate of 16kg/h and the concentration of 50% after pre-cooling into a 500ml four-neck flask continuous sulfonation pipeline reactor with a stirrer, a thermometer and a charging opening, and controlling the temperature to react at 50-60 ℃. The reacted feed liquid and chlorosulfonic acid with the flow rate of 11.6kg/h enter a continuous chlorination pipeline reactor together, the reaction temperature is controlled to be 60-70 ℃, the reaction product enters a continuous desolventizing system after the reaction is finished, and the product enters a crystallization system after the solvent is removed to separate a benzenesulfonyl chloride product with the purity of 16.4kg/h, wherein the product purity is 97%, and the yield is 90.1%.
Example 2
Adding 920kg of toluene and 500kg of chloroform into a 3000L reaction kettle with a stirrer, a thermometer and a charging hole, starting stirring, dropping 1600kg of liquid sulfur trioxide/chloroform solution (wherein the concentration of sulfur trioxide is 50%) at the temperature of 60-70 ℃, keeping the temperature for 1 hour after dropping, then adding 1160kg of chlorosulfonic acid at the temperature of 60-70 ℃, and keeping the temperature for 1 hour after dropping and heating to 70-80 ℃. Cooling to 20 deg.C, adding small amount of water, washing, layering, and desolventizing solvent layer to obtain 1860kg of methyl benzenesulfonyl chloride product with purity of 95% and yield of 92.8%.
Example 3
Adding 10 g of liquid paraffin into a 500ml four-neck flask with a stirrer, a thermometer and a charging hole, starting stirring, then simultaneously dropwise adding 0.1mol of benzene and 0.05mol of liquid sulfur trioxide (containing 10 g of liquid paraffin), controlling the temperature to be minus 20-0 ℃ for reaction, after dropwise adding, keeping the temperature for 2 hours, then adding 0.35mol of chlorosulfonic acid at minus 20 ℃, after dropwise adding, heating to 60-70 ℃ and keeping the temperature for 2 hours. Cooling to 20 deg.c, washing with small amount of water, layering, and desolventizing in solvent layer to obtain benzenesulfonyl chloride product 16.4 g, purity 97% and yield 90.1%.
Example 4
Adding 0.1mol of toluene (containing 5 g of chloroform) into a 500ml four-neck flask with a stirrer, a thermometer and a charging hole, starting stirring, dropping 0.25mol of liquid sulfur trioxide (containing 100 g of chloroform) at the temperature of 60-80 ℃, keeping the temperature for 1 hour after dropping, then adding 0.05mol of chlorosulfonic acid at the temperature of 60-70 ℃, and keeping the temperature for 1 hour after dropping and heating to-20-0 ℃. Cooling to 20 ℃, adding a small amount of water for washing, layering, and desolventizing a solvent layer to obtain 18.6 g of the methyl benzene sulfonyl chloride product with the purity of 95% and the yield of 92.8%.
Claims (5)
1. An industrial production method of alkyl benzene sulfonyl chloride comprises the following steps:
1) and (3) sulfonation reaction: in the presence of a solvent, under the condition of-20-80 ℃, continuously sulfonating by using a pipeline reactor or intermittently sulfonating in a kettle way;
2) acyl chlorination reaction: and (2) directly reacting the product generated in the sulfonation reaction 1) with chlorosulfonic acid, performing acyl chlorination reaction continuously or intermittently in a kettle manner by using a pipeline reactor at the temperature of-20-80 ℃ to generate alkylbenzene sulfonyl chloride, hydrolyzing slightly excessive chlorosulfonic acid, and then separating acid and desolventizing to generate alkylbenzene sulfonyl chloride.
2. The method of claim 1, wherein the substituent on the benzene ring of the alkylbenzene is an alkyl group having 0 to 10 carbons.
3. The method of claim 1, wherein the solvent used in sulfonation 1) comprises liquid sulfur dioxide, liquid paraffin, petroleum ether, C1～C4Halogenated hydrocarbon, 90-120 # solvent oil or C4～C8An alkane.
4. The method of claim 1, wherein the liquid sulfur trioxide in the sulfonation reaction 1) is at a concentration of 1 to 100 wt%, the alkylbenzene is at a concentration of 1 to 100 wt%, and the molar ratio of the alkylbenzene to the liquid sulfur trioxide is 1: 0.5 to 2.5.
5. The industrial process for preparing alkylbenzene sulfonic acid chloride according to claim 1, wherein the dosage of chlorosulfonic acid in the acyl chlorination reaction 2) is as follows: the molar ratio of the alkylbenzene to the chlorosulfonic acid is 1: 0.5-3.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710044413XA CN101195593B (en) | 2007-07-31 | 2007-07-31 | Industrial production method of alkylbenzene sulfonyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710044413XA CN101195593B (en) | 2007-07-31 | 2007-07-31 | Industrial production method of alkylbenzene sulfonyl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101195593A true CN101195593A (en) | 2008-06-11 |
| CN101195593B CN101195593B (en) | 2010-12-08 |
Family
ID=39546239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710044413XA Active CN101195593B (en) | 2007-07-31 | 2007-07-31 | Industrial production method of alkylbenzene sulfonyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101195593B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489488A (en) * | 2011-11-14 | 2012-06-13 | 锦州开元石化有限责任公司 | Process for recycling alkylbenzene sulfonate filter residues |
| CN102746199A (en) * | 2012-07-13 | 2012-10-24 | 江苏丰山集团有限公司 | Method for recovering paratoluensulfonyl chloride from waste water generated by producing aryloxy phenoxy propionic acid herbicide |
| CN103304451A (en) * | 2013-05-13 | 2013-09-18 | 台州市前进化工有限公司 | Preparation method of aromatic hydrocarbon sulfonyl chloride derivative |
| CN111377837A (en) * | 2020-03-18 | 2020-07-07 | 湖南吴赣药业有限公司 | Green synthesis method of p-acetamido-benzenesulfonyl chloride |
| CN111718286A (en) * | 2020-07-23 | 2020-09-29 | 邓博天 | Industrial production method of aromatic hydrocarbon sulfonyl chloride with power supply group |
| CN113277965A (en) * | 2021-05-21 | 2021-08-20 | 金华双宏化工有限公司 | Method for continuously synthesizing paratoluensulfonyl chloride by using microchannel reactor |
| CN113582883A (en) * | 2021-08-03 | 2021-11-02 | 金华双宏化工有限公司 | Method for continuously synthesizing p-toluenesulfonyl chloride |
| CN115710204A (en) * | 2022-11-21 | 2023-02-24 | 金华双宏化工有限公司 | Method for continuously synthesizing benzene sulfonyl chloride |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86105852A (en) * | 1986-07-14 | 1988-02-03 | 吉林化工学院 | The production method of heavy alkylbenzene sulfonic acid |
-
2007
- 2007-07-31 CN CN200710044413XA patent/CN101195593B/en active Active
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489488A (en) * | 2011-11-14 | 2012-06-13 | 锦州开元石化有限责任公司 | Process for recycling alkylbenzene sulfonate filter residues |
| CN102746199A (en) * | 2012-07-13 | 2012-10-24 | 江苏丰山集团有限公司 | Method for recovering paratoluensulfonyl chloride from waste water generated by producing aryloxy phenoxy propionic acid herbicide |
| CN103304451A (en) * | 2013-05-13 | 2013-09-18 | 台州市前进化工有限公司 | Preparation method of aromatic hydrocarbon sulfonyl chloride derivative |
| CN111377837A (en) * | 2020-03-18 | 2020-07-07 | 湖南吴赣药业有限公司 | Green synthesis method of p-acetamido-benzenesulfonyl chloride |
| CN111718286A (en) * | 2020-07-23 | 2020-09-29 | 邓博天 | Industrial production method of aromatic hydrocarbon sulfonyl chloride with power supply group |
| CN113277965A (en) * | 2021-05-21 | 2021-08-20 | 金华双宏化工有限公司 | Method for continuously synthesizing paratoluensulfonyl chloride by using microchannel reactor |
| CN113582883A (en) * | 2021-08-03 | 2021-11-02 | 金华双宏化工有限公司 | Method for continuously synthesizing p-toluenesulfonyl chloride |
| CN113582883B (en) * | 2021-08-03 | 2022-11-04 | 金华双宏化工有限公司 | Method for continuously synthesizing p-toluenesulfonyl chloride |
| CN115710204A (en) * | 2022-11-21 | 2023-02-24 | 金华双宏化工有限公司 | Method for continuously synthesizing benzene sulfonyl chloride |
| CN115710204B (en) * | 2022-11-21 | 2024-01-09 | 金华双宏化工有限公司 | Method for continuously synthesizing benzenesulfonyl chloride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101195593B (en) | 2010-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101195593A (en) | Industrial production method of alkylbenzene sulfonyl chloride | |
| CN111718286A (en) | Industrial production method of aromatic hydrocarbon sulfonyl chloride with power supply group | |
| CN101503383B (en) | Preparation of o-nitro p-methylsulfonylbenzoic acid | |
| WO2023010649A1 (en) | Method for continuous synthesis of p-toluenesulfonyl chloride | |
| TWI714964B (en) | Catalysts for the synthesis of alkanesulfonic acids | |
| CN105294653B (en) | The preparation technology of Vonoprazan fumarate | |
| CN102190592B (en) | Synthetic method of methanamide compound | |
| CN108191674A (en) | A kind of synthetic method of benzidine compound | |
| CN109721037B (en) | Novel process of bis (fluorosulfonyl) imide salt | |
| CN108084062A (en) | A kind of preparation method of 2,4- disubstituted benzenes sulfonic acid chloride | |
| JP6392994B2 (en) | Method for producing 9-fluorenone from fluorene | |
| Zhang et al. | A metal-free synthesis of 1, 1-diphenylvinylsulfides with thiols via thioetherification under continuous-flow conditions | |
| CN115285951B (en) | Preparation method and application of bis (fluorosulfonyl) imide salt electrolyte | |
| CN104130183A (en) | Synthetic method for 3-bromopyridine | |
| CN202201846U (en) | Tubular continuous naphthtalene-2,7-disulfonic acid nitrifying device in H acid production | |
| CN101585783B (en) | Preparing method of ortho-nitrobenzonitrile series compound | |
| CN101481349A (en) | Preparation of alkyl pyridine-2-sulfonic acid amide | |
| CN106854125B (en) | Method for preparing α -fluoro- β -ethynyl ketone compound containing two chiral centers | |
| CN117229187B (en) | Synthesis method of thioimine ester compound | |
| CN113563235B (en) | Synthetic method of 3- (halogenated phenoxy) benzenesulfonyl chloride derivative | |
| CN117050011B (en) | Method for synthesizing 2-methylquinoline by using vinyl acetate as raw material | |
| CN107674007A (en) | A kind of synthesis technique of reactive dye intermediate orthanilic acid | |
| CN111848476B (en) | Preparation method of thiotoluene diiso (thio) cyanate | |
| Li et al. | Synthesis of Diaryl Tellurides with Sodium Aryltellurites under Mild Conditions | |
| CN102304071A (en) | Method for synthesizing 4.4-dichlorodiphenyl sulfone by two-step process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: ZHEJIANG JIAHUA ENERGY CHEMICAL CO., LTD. Free format text: FORMER OWNER: ZHEJIANG JIAHUA GROUP CO., LTD. Effective date: 20110630 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 314021 NO. 5, WUJING ROAD, NANHU DISTRICT, JIAXING CITY, ZHEJIANG PROVINCE TO: 314201 NO. 2288, BINJIANG AVENUE, ZHAPU ECONOMIC DEVELOPMENT ZONE, JIAXING PORT DISTRICT, ZHEJIANG |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20110630 Address after: The 314201 Zhejiang Jiaxing port Zhapu Economic Development Zone Binjiang Road No. 2288 Patentee after: Zhejiang Jiahua Energy Chemical Co., Ltd. Address before: Wu Jing Lu, Jiaxing Nanhu District of Zhejiang Province, No. 5 314021 Patentee before: Zhejiang Jiahua Group Co., Ltd. |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20200213 Address after: 314201 room 318, building 1, south side of Zhongshan Road and west side of Washan Road, Jiaxing Port Area, Jiaxing City, Zhejiang Province Patentee after: Zhejiang Jiafu New Material Technology Co., Ltd Address before: The 314201 Zhejiang Jiaxing port Zhapu Economic Development Zone Binjiang Road No. 2288 Patentee before: Zhejiang Jiahua Energy Chemical Co., Ltd. |
|
| TR01 | Transfer of patent right |