CN109651206A - A method of chlorosulfonation is carried out using sulfur trioxide - Google Patents
A method of chlorosulfonation is carried out using sulfur trioxide Download PDFInfo
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- CN109651206A CN109651206A CN201910030249.XA CN201910030249A CN109651206A CN 109651206 A CN109651206 A CN 109651206A CN 201910030249 A CN201910030249 A CN 201910030249A CN 109651206 A CN109651206 A CN 109651206A
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- sulfur trioxide
- chlorosulfonic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/08—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with halogenosulfonic acids
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Abstract
The present invention relates to a kind of methods for carrying out chlorosulfonation using sulfur trioxide, and steps are as follows: will be dissolved in organic solvent by chlorosulfonation substance, villaumite then is added according to the ratio of Ar-H and chloride ion molar ratio 1: 2, and set 110-150 DEG C of reaction temperature；After reaching reaction temperature condition, after reaching reaction temperature condition, the chlorosulfonic acid of chlorosulfonic acid theory additive amount 0.1-2% is added in sulfonation reactor as initiator, lead to sulfur trioxide gas into chlorosulfonic acid synthesizer again to start to carry out sulfonating reaction, or leads to sulfur trioxide gas and hydrogen chloride gas directly into chlorosulfonic acid synthesizer and then start to carry out sulfonating reaction；Sulfonating reaction byproduct in process hydrogen chloride gas is constantly entered in chlorosulfonic acid synthesizer by pipeline, continual is passed through sulfur trioxide gas synthetic reaction with extraneous；The advantages of this method is: not using chlorosulfonic acid in reaction process directly, reaction is easily handled, and due to being water-less environment, sulfate is directly precipitated, and hydrogen chloride directly returns in reaction kettle, and product is easily handled.
Description
Technical field
The present invention relates to a kind of methods for carrying out chlorosulfonation using sulfur trioxide, belong to chlorosulfonation technology neck
Domain.
Background technique
Chlorosulfonation is introducing the chlorosulfonyl (- SO into organic molecule2Cl sulfonic acid chloride (R-SO) is formed2Cl mistake)
Journey.It is a kind of substitution reaction, and a hydrogen atom in reactant is changed into chlorosulfonyl after the reaction.Aromatic compound
(Ar-H) chlorosulfonation is generally with chlorosulfonic acid (ClSO3H) and the concentrated sulfuric acid is as chlorosulfonation reagent.
1. chlorosulfonic acid method:
Aromatic compound is reacted with excessive chlorosulfonic acid (molar ratio 1: 6), and reaction equation is as follows:
Ar-H+2ClSO3H→Ar-SO3H+2HCl
Latter reaction equation is balanced reaction, if sulfuric acid is converted in time, reaction can be promoted to carry out to the right, be conducive to react into
Row is complete.This method can generate a large amount of spent acid waste water, be difficult to handle in environmental protection, and the yield of product is declined.
2. sulphate method
Aromatic compound first uses concentrated acid sulfonation, is then finally produced with phosphorus oxychloride or phosphorus trichloride chlorination again
Object.Reaction equation is as follows:
Ar-SO3H+POCl3→Ar-SO2Cl+HCl+HPO3
Previous reaction equation is balanced reaction, there is water generation in system.To make reaction completely, usually grasp under vacuum
Make, is conducive to the chlorination of next step with the water generated except dereaction, and after removing water.Usually make fully reacting, the concentrated sulfuric acid needs
It is excessive, and contain water in the concentrated sulfuric acid, phosphorus oxychloride meets water and is decomposed into phosphoric acid and hydrogen chloride, this greatly reduces the effect of reaction
Rate, and the hydrogen chloride and phosphoric acid that generate are difficult to handle.
Summary of the invention
It is an object of the invention to solve the deficiencies in the prior art, a kind of side that chlorosulfonation is carried out using sulfur trioxide is proposed
Method, this method are reacted with HCl the characteristics of can directly generating chlorosulfonic acid using sulfur trioxide, are reacted initially according to molar ratio
Addition is sulfonated substance and villaumite, and organic solvent is added, and hydrogen chloride gas initially need to be proportionally added in reaction, then leads to again
Enter sulfur trioxide gas to be reacted, by-product HCl is returned directly in chlorosulfonic acid synthesizer in subsequent reaction, no longer needs to add
Hydrogen chloride gas is as reaction raw materials.Reaction, which terminates pressure, to be increased, i.e. reaction terminates, and stop logical sulfur trioxide gas.The party
The advantages of method, is: using chlorosulfonic acid directly in reaction process, chlorosulfonic acid is difficult to store, transport, by-product dilute sulfuric acid, hydrochloric acid
Quantity is very big, is difficult to handle in environmental protection.Reaction is easily handled, and due to being water-less environment, sulfate is directly precipitated, and hydrogen chloride is direct
It returns in reaction kettle, product is easily handled.Reaction equation of the invention is as follows:
The technical solution adopted by the present invention to solve the technical problems is:
A method of chlorosulfonation being carried out using sulfur trioxide, the operating procedure of this method is as follows:
Step S1 will be dissolved in organic solvent, then according to Ar-H and chloride ion molar ratio 1: 2 first by chlorosulfonation substance
Ratio be added villaumite, set 110-150 DEG C of reaction temperature；
Step S2 after reaching reaction temperature condition, is added chlorosulfonic acid theory additive amount 0.1-2%'s in sulfonation reactor
Chlorosulfonic acid as initiator, then into chlorosulfonic acid synthesizer lead to sulfur trioxide gas start carry out sulfonating reaction, or directly to
Lead to sulfur trioxide gas in chlorosulfonic acid synthesizer and then hydrogen chloride gas starts to carry out sulfonating reaction；
Step S3, sulfonating reaction byproduct in process hydrogen chloride gas are constantly entered in chlorosulfonic acid synthesizer by pipeline, with
The external world is continual to be passed through sulfur trioxide gas synthetic reaction；
Step S4 keeps in reaction process the pressure of reaction kettle and chlorosulfonic acid synthesizer to stablize, and passes through pressure and controls three oxygen
Change the flux of sulphur gas, reaction terminates pressure in kettle and increases, and stops logical sulfur trioxide, after the sulfur trioxide gas that multi-pass enters enters
Processing system, by-product sulfate are directly precipitated, organic solvent evaporation separating and recovering.
Method of the invention, organic solvent can be dissolved in the solvent for being sulfonated substance to be any, and the solvent property is steady
It is fixed, chemical reaction and the variation of other chemical property can not occur at reaction conditions；It is preferred that ether, carbon dichloride, two sulphur
Change any one in carbon.
Method of the invention, villaumite can be free of the crystallization water for the various of sodium chloride, magnesium chloride, calcium chloride, lithium chloride etc.
Villaumite.
Method of the invention, villaumite preferably control partial size at 0.1~15 μm, are conducive to improve reaction speed.
Method of the invention, chlorosulfonation can use still reaction, and setting chlorosulfonic acid synthesizes outside sulfonating reaction kettle
Device, the two connection, sulfur trioxide are passed through chlorosulfonic acid synthesizer, synthesize with the hydrogen chloride gas overflowed in reaction process in chlorosulfonic acid
Reaction in device, the chlorosulfonic acid of generation reach after technique requires temperature through cooling and return to reaction kettle, reacted.It moves in circles.
Method of the invention, reaction process can constantly generate hydrogen chloride gas, can return in reaction kettle and be recycled.
Detailed description of the invention
Fig. 1 is reaction process material circulation schematic diagram of the invention.
In figure: 1, it goes to post-process, 2, sulfonation reactor, 3, hydrogen chloride, 4, chlorosulfonic acid, 5, sulfur trioxide, 6, pans, 7,
Circulating pump, 8, cooler, 9, chlorosulfonic acid synthesizer, 10, tail gas.
Specific embodiment
Below by specific embodiment, and in conjunction with the reaction process material of attached drawing 1 circulation schematic diagram, to technology of the invention
Scheme is described in further detail.
Embodiment:
By taking the production of the double benzene sulfonyl chlorides (OBSC) of 4 ' 4- oxos as an example, these embodiments are intended merely in detail following embodiment
Show technical concept and its exploitativeness of the invention, is not limiting the scope of the invention, utilizes the technology of the present invention
Conceive the equivalence replacement made and accommodation still within protection scope of the present invention.
Embodiment 1
100g diphenyl ether is added into reaction kettle, 100g ether is added as solvent, 137g sodium chloride is added under stiring,
Temperature setting be 115 DEG C, to reaction kettle outside be arranged chlorosulfonic acid synthesizer, be passed through sulfur trioxide gas and hydrogen chloride gas thereto
Body, reaction process refrigerant control reaction temperature, and the chlorosulfonic acid of generation is reduced to room temperature by heat exchange, returns to sulphur by liquid level difference
Change reactor and carry out sulfonating reaction, micro-positive pressure in reaction process holding system, reaction terminates, and pressure increases, and stops logical three oxidation
Sulphur gas, the inorganic salts crystallization in system, solvent evaporation recycling, solid are the double benzene sulfonyl chlorides (OBSC) of 4 ' 4- oxo of product,
Product yield 94%.
Embodiment 2
100g diphenyl ether is added into reaction kettle, 100g carbon dichloride is added as solvent, 130g chlorine is added under stiring
Change calcium, temperature setting is 125 DEG C, and chlorosulfonic acid synthesizer is arranged to reaction kettle top, is passed through sulfur trioxide gas and chlorine thereto
Change hydrogen, reaction process refrigerant controls reaction temperature, and the chlorosulfonic acid of generation is reduced to room temperature by heat exchange, passes through liquid level difference
It returns to sulfonation reactor and carries out sulfonating reaction, micro-positive pressure in reaction process holding system, reaction terminates, and pressure increases, and stops logical
Sulfur trioxide gas, the inorganic salts crystallization in system, solvent evaporation recycling, solid are the double benzene sulfonyl chlorides of 4 ' 4- oxo of product
(OBSC), product yield 95%.
Embodiment 3
100g diphenyl ether is added into reaction kettle, 100g carbon disulfide is added as solvent, 112g chlorine is added under stiring
Change magnesium, temperature setting is 135 DEG C, to reaction kettle outside chlorosulfonic acid synthesizer is set, think that a small amount of chlorine is added in chlorosulfonation kettle
Sulfonic acid, starting reaction are being passed through sulfur trioxide gas into the device that chlorosulfonic acid synthesizes, and reaction process refrigerant controls reaction temperature
The chlorosulfonic acid of degree, generation is reduced to room temperature by heat exchange, returns to sulfonation reactor by pipeline pump and carries out sulfonating reaction, reacted
Micro-positive pressure in journey holding system, reaction terminate, and pressure increases, and stop logical sulfur trioxide gas, and the inorganic salts crystallization in system is molten
Agent evaporation recycling, solid are the double benzene sulfonyl chlorides (OBSC) of 4 ' 4- oxo of product, product yield 96.5%.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form
Limitation, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.
Claims (6)
1. a kind of method for carrying out sulfonating reaction using sulfur trioxide, which is characterized in that the operating procedure of this method is as follows:
Step S1 will be dissolved in organic solvent first by chlorosulfonation substance, then according to the ratio of Ar-H and chloride ion molar ratio 1: 2
Villaumite is added in example, sets 110-150 DEG C of reaction temperature；
After reaching reaction temperature condition, the chlorine sulphur of chlorosulfonic acid theory additive amount 0.1-2% is added in step S2 in sulfonation reactor
Acid is used as initiator, then leads to sulfur trioxide gas into chlorosulfonic acid synthesizer and start to carry out sulfonating reaction, or directly to chlorine sulphur
Lead to sulfur trioxide gas in sour synthesizer and then hydrogen chloride gas starts to carry out sulfonating reaction；
Step S3, sulfonating reaction byproduct in process object hydrogen chloride gas, is constantly entered in chlorosulfonic acid synthesizer by pipeline, and outer
Boundary is continual to be passed through sulfur trioxide gas synthetic reaction；
Step S4 keeps in reaction process the pressure of reaction kettle and chlorosulfonic acid synthesizer to stablize, controls sulfur trioxide by pressure
The pressure of the flux of gas, reaction reaction was completed system increases, and stops logical sulfur trioxide, and the sulfur trioxide gas that multi-pass enters enters
After-treatment system, by-product sulfate are directly precipitated, organic solvent evaporation separating and recovering.
2. the method for carrying out sulfonating reaction using sulfur trioxide according to claim 1, which is characterized in that the organic solvent
The inert organic solvents of substance are sulfonated for any energy dissolution, the inert organic solvents refer to that organic solvent property is stablized, energy
Enough variations that chemical reaction and other chemical property do not occur at reaction conditions.
3. the method for carrying out sulfonating reaction using sulfur trioxide according to claim 2, which is characterized in that the organic solvent
For any one in ether, carbon dichloride and carbon disulfide.
4. the method for carrying out sulfonating reaction using sulfur trioxide according to claim 1, which is characterized in that the villaumite is not
Villaumite containing the crystallization water, including sodium chloride, magnesium chloride, calcium chloride and lithium chloride.
5. the method for carrying out sulfonating reaction using sulfur trioxide according to claim 1, the partial size of the villaumite is 0.1~15
μm。
6. the method for carrying out sulfonating reaction using sulfur trioxide according to claim 1, which is characterized in that chlorosulfonation is adopted
With tank reactor, chlorosulfonic acid synthesizer, the two connection is arranged in tank reactor outside, and sulfur trioxide is passed through chlorosulfonic acid synthesis
Device reacts in chlorosulfonic acid synthesizer with the hydrogen chloride escaped in reaction process, and the chlorosulfonic acid of generation after cooling, reaches technique
It is required that returning to reaction kettle after temperature, reacted, is moved in circles.
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| CN201910030249.XA CN109651206A (en) | 2019-01-14 | 2019-01-14 | A method of chlorosulfonation is carried out using sulfur trioxide |
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| CN201910030249.XA CN109651206A (en) | 2019-01-14 | 2019-01-14 | A method of chlorosulfonation is carried out using sulfur trioxide |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50149643A (en) * | 1974-05-22 | 1975-11-29 | ||
| EP0053314A1 (en) * | 1980-11-27 | 1982-06-09 | Bayer Ag | Process for the chloro-sulphonation of biphenyl and diphenyl ether |
| CN1203188A (en) * | 1997-06-22 | 1998-12-30 | 中化四平联合化工总厂 | Process for synthesizing chlorosulfonic acid using high-concentration sulfur trioxide |
| CN101058408A (en) * | 2007-06-07 | 2007-10-24 | 浙江闰土股份有限公司 | Method of reclaiming and using high-pollution low-concentration waste acid |
| CN102633687A (en) * | 2012-04-05 | 2012-08-15 | 天津理工大学 | Method and technology for preparing p-substituted alkyl benzene sulfonyl chloride |
| 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 |
| CN105111111A (en) * | 2015-09-10 | 2015-12-02 | 泰兴市臻庆化工有限公司 | Preparation method for aryl sulfonyl chloride derivative |
| CN106187830A (en) * | 2016-07-06 | 2016-12-07 | 南通天泽化工有限公司 | A kind of preparation method of sulfaguanidine |
-
2019
- 2019-01-14 CN CN201910030249.XA patent/CN109651206A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50149643A (en) * | 1974-05-22 | 1975-11-29 | ||
| EP0053314A1 (en) * | 1980-11-27 | 1982-06-09 | Bayer Ag | Process for the chloro-sulphonation of biphenyl and diphenyl ether |
| CN1203188A (en) * | 1997-06-22 | 1998-12-30 | 中化四平联合化工总厂 | Process for synthesizing chlorosulfonic acid using high-concentration sulfur trioxide |
| CN101058408A (en) * | 2007-06-07 | 2007-10-24 | 浙江闰土股份有限公司 | Method of reclaiming and using high-pollution low-concentration waste acid |
| CN102633687A (en) * | 2012-04-05 | 2012-08-15 | 天津理工大学 | Method and technology for preparing p-substituted alkyl benzene sulfonyl chloride |
| 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 |
| CN105111111A (en) * | 2015-09-10 | 2015-12-02 | 泰兴市臻庆化工有限公司 | Preparation method for aryl sulfonyl chloride derivative |
| CN106187830A (en) * | 2016-07-06 | 2016-12-07 | 南通天泽化工有限公司 | A kind of preparation method of sulfaguanidine |
Non-Patent Citations (1)
| Title |
|---|
| 李磊等: "对氯苯磺酰氯的合成进展及改进方向", 《天津化工》 * |
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