CN111635340A - Benzene sulfonyl chloride production process method without wastewater discharge - Google Patents

Benzene sulfonyl chloride production process method without wastewater discharge Download PDF

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CN111635340A
CN111635340A CN202010601794.2A CN202010601794A CN111635340A CN 111635340 A CN111635340 A CN 111635340A CN 202010601794 A CN202010601794 A CN 202010601794A CN 111635340 A CN111635340 A CN 111635340A
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water
benzene
layering
hydrochloric acid
reaction
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朱雪松
张福祥
刘仕通
马龙
于海洋
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Zhenjiang Huilong Chemical Co ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/74—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D5/00—Fertilisers containing magnesium

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a benzene sulfonyl chloride production process method with zero wastewater discharge, which takes benzene and chlorosulfonic acid as raw materials and prepares a benzene sulfonyl chloride finished product through chlorosulfonation reaction, hydrolytic dilution, standing layering, rinsing layering and reduced pressure distillation; wherein, hydrogen chloride generated in the chlorosulfonation reaction and the hydrolysis dilution process is absorbed by a falling film absorption tower under the conditions of micro negative pressure, first external water and second external water for reuse to form a hydrochloric acid solution with the concentration of 30 percent; rinsing and layering the material after standing and layering by adopting second external water, and completely reusing the rinsed second external water for the falling film absorption process of the hydrogen chloride; wherein the mass of the first additional water and the second additional water is equal to the mass of water used for absorbing hydrogen chloride generated in the chlorosulfonation reaction and hydrolysis dilution processes to form a hydrochloric acid solution with the concentration of 30%; the invention fully utilizes the second external water addition, realizes zero discharge of wastewater, reduces the consumption of water resources, reduces environmental pollution and reduces the wastewater treatment cost.

Description

Benzene sulfonyl chloride production process method without wastewater discharge
Technical Field
The invention relates to the technical field of benzene sulfonyl chloride production, and particularly relates to a benzene sulfonyl chloride production process method with zero wastewater discharge.
Background
The prior benzene sulfonyl chloride is mainly prepared by the reaction of excessive chlorosulfonic acid and pure benzene, hydrogen chloride generated in the reaction is absorbed by water to prepare by-product hydrochloric acid with the concentration of 30 percent, the excessive chlorosulfonic acid needs to be hydrolyzed after the reaction, the pure sulfuric acid generated in the reaction process is diluted to prepare sulfuric acid solution with the mass concentration of 60-65 percent, and the materials also need to be rinsed by a large amount of water in the rinsing process, so that more rinsing wastewater can be generated and can be directly discharged generally, the operation pollutes the environment and increases the treatment cost, and the production process of the benzene sulfonyl chloride needs to be further improved.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a benzene sulfonyl chloride production process method with zero wastewater discharge, which takes benzene and chlorosulfonic acid as raw materials and prepares a benzene sulfonyl chloride finished product through chlorosulfonation reaction, hydrolytic dilution, standing layering, rinsing layering and reduced pressure distillation; wherein, hydrogen chloride generated in the chlorosulfonation reaction and the hydrolysis dilution process is absorbed by a falling film absorption tower under the conditions of micro negative pressure, first external water and second external water for reuse to form a hydrochloric acid solution with the concentration of 30 percent; a certain amount of hydrochloric acid solution with the concentration of 30 percent is used as hydrolysis diluent and is dripped into the sulfonation liquid after the chlorosulfonation reaction for hydrolysis and dilution reaction, so that the sulfuric acid in the sulfonation liquid is finally diluted to the mass concentration of 60-65 percent, and the residual hydrochloric acid solution with the concentration of 30 percent returns to a hydrochloric acid storage tank to obtain a byproduct hydrochloric acid; rinsing and layering the material after standing and layering by adopting second external water, and completely reusing the rinsed second external water for the falling film absorption process of the hydrogen chloride; wherein the mass of the first additional water and the second additional water is equal to the mass of water used for absorbing hydrogen chloride generated in the chlorosulfonation reaction and hydrolysis dilution processes to form a hydrochloric acid solution with the concentration of 30%;
the specific production process conditions comprise:
(1) the feed molar ratio is as follows: benzene and chlorosulfonic acid are 1: 2.5-3;
(2) chlorosulfonation reaction: the dripping time of benzene is 3-5 h; the stirring speed is 50-70 r/m, the reaction temperature is 25-55℃,
Hydrolysis and dilution: controlling the dripping speed of the hydrochloric acid to be slow firstly and then fast, wherein the dripping amount is 50-200kg/h, the stirring speed is 30-45 r/min, and the reaction temperature is less than or equal to 50 ℃;
standing and layering: standing for 1-1.5 h;
rinsing and layering: washing off polar substances in the coarse material by adding water in the second part to change the coarse material into a semitransparent color;
and (3) reduced pressure distillation: the vacuum degree is more than or equal to 0.096MPa, the distillation temperature is 160 ℃ and 180 ℃, and the distillation speed is 130 kg/h;
falling film type hydrogen chloride absorption: the vacuum degree is 0.01-0.02MPa, and the water spraying amount is 4-8m3/h。
Preferably, the mass of the first external water is equal to that of the water in the byproduct hydrochloric acid, and the mass of the second external water is equal to that of the water in the hydrolysis diluent.
Preferably, the content of chlorosulfonic acid in the raw materials is more than or equal to 98.5 percent, and the content of benzene is more than or equal to 99.8 percent.
Preferably, the content of the benzene sulfonyl chloride finished product is more than or equal to 99.5 percent, and the content of the diphenyl sulfone is less than or equal to 0.10 percent.
The reaction process of the chlorosulfonation reaction is as follows:
Figure BDA0002558775810000021
the reaction process of hydrolysis dilution is as follows:
HSO3Cl+H2O→H2SO4+HCl
H2SO4+H2O→H2SO4·H2O
hydrogen chloride generated in the chlorosulfonation reaction and hydrolysis dilution processes is absorbed by a falling film absorption tower under the conditions of micro negative pressure, first external water and second external water for reuse to form a hydrochloric acid solution with the concentration of 30%; the dosage of the hydrochloric acid solution (hydrolysis diluent) with the concentration of 30 percent added in the hydrolysis dilution process is calculated according to a chemical equation, the water quantity is divided into two parts, the first part is water required for hydrolyzing excessive chlorosulfonic acid, the second part is water required for diluting pure sulfuric acid to the concentration of 60-65 percent, and the mass sum of the two parts of water is equal to the mass of the water in the hydrolysis diluent; in addition, the dropping of the hydrochloric acid can also slow down the decomposition of the benzene sulfonyl chloride, and the sulfuric acid at the bottom can be separated completely by utilizing the specific gravity of the 60-65% concentration sulfuric acid which is greater than that of the benzene sulfonyl chloride; adding second external water into the hydrolyzed and diluted material for rinsing, standing for layering after rinsing, and introducing all rinsing wastewater into a falling film type absorption tower to serve as absorption water for HCl; in order to achieve the purpose of zero wastewater in the process, the dosage of the first externally added water and the second externally added water is strictly controlled, so that the quality of the externally added water can just absorb HCl generated in a reaction system into hydrochloric acid with the concentration of 30%, and zero wastewater discharge in the whole reaction process is realized; and (3) distilling the rinsed materials under reduced pressure, putting the head and tail materials into a small receiver in the distillation process, returning the head and tail materials into a bleaching kettle for continuous rinsing, putting the clear and transparent fine materials into a large receiver, and then packaging.
Has the advantages that:
the method fully utilizes the second external water added in the benzene sulfonyl chloride rinsing process, and the second external water after rinsing is completely reused in the falling film absorption process of the hydrogen chloride, the mass of the first external water and the second external water is equal to the mass of water used for absorbing the hydrogen chloride generated in the chlorosulfonation reaction and hydrolysis dilution processes to form a hydrochloric acid solution with the concentration of 30 percent, so that the zero discharge of wastewater is realized, the consumption of water resources is reduced, the environmental pollution is reduced, and the wastewater treatment cost is reduced; by adding 30% hydrochloric acid solution in calculated amount into the sulfonation liquid after sulfonation reaction, not only can the excessive chlorosulfonic acid in the sulfonation liquid be hydrolyzed into sulfuric acid and hydrogen chloride, but also the sulfonation liquid and pure sulfuric acid generated by hydrolysis can be just diluted into 60-65% sulfuric acid solution, and the sulfuric acid solution can be used for producing magnesium sulfate fertilizer; therefore, the benzene sulfonyl chloride production process method has good application prospect.
Drawings
FIG. 1 is a schematic diagram of the process for producing benzenesulfonyl chloride of the present invention.
Detailed Description
For the purpose of enhancing understanding of the present invention, the present invention will be further described in detail with reference to the following examples, which are provided for illustration only and are not to be construed as limiting the scope of the present invention.
Referring to fig. 1, the process for producing benzenesulfonyl chloride of the present invention comprises chlorosulfonation, hydrolysis dilution, standing for layering, rinsing for layering, and vacuum distillation, wherein hydrogen chloride gas generated during chlorosulfonation and hydrolysis dilution is made into 30% hydrochloric acid by falling film absorption tower, a part of hydrochloric acid is used for hydrolysis of chlorosulfonic acid and dilution of sulfuric acid, and the rest of hydrochloric acid is fed into a hydrochloric acid storage tank; standing and layering to generate 60-65% sulfuric acid solution, sending the sulfuric acid solution into a sulfuric acid storage tank for storage to produce magnesium sulfate fertilizer, sending the crude material of benzene sulfonyl chloride into a rinsing kettle, adding second external water, introducing all rinsing wastewater generated in the rinsing process into a falling film type absorption tower to serve as absorption water of HCl, and absorbing the HCl into 30% hydrochloric acid together with the first external water, wherein no wastewater is generated in the whole production process, and the purpose of zero wastewater production is realized; and (3) standing and layering after rinsing, and further feeding the materials into a distillation kettle for distillation to obtain a benzenesulfonyl chloride finished product meeting the quality index.
Example 1
Production control conditions are as follows:
(1) the feed molar ratio is as follows: benzene: chlorosulfonic acid 1: 2.5; wherein, 3000kg of benzene and 11186kg of chlorosulfonic acid;
(2) and (3) sulfonation reaction: the dripping time of benzene is 3 h; stirring speed of 60 r/min, reaction temperature of 25 deg.C,
Hydrolysis and dilution: controlling the dripping speed of the hydrochloric acid to be slow firstly and then fast, wherein the total dripping amount of the hydrochloric acid is 4838kg, the stirring speed is 35 r/min, and the reaction temperature is less than or equal to 50 ℃;
standing and layering: standing for 1 h;
rinsing and layering: washing off polar substances in the coarse material by adding water in the second part to change the coarse material into a semitransparent color;
and (3) reduced pressure distillation: the vacuum degree is not less than 0.096MPa, the distillation temperature is 160-;
falling film type hydrogen chloride absorption: the vacuum degree is 0.01MPa, and the water spraying amount is 5m3/h；
Example 2
Production control conditions are as follows:
(1) the feed molar ratio is as follows: benzene: chlorosulfonic acid 1: 3; wherein, 3000kg of benzene and 13423kg of chlorosulfonic acid are contained;
(2) and (3) sulfonation reaction: the dripping time of benzene is 4 h; the stirring speed is 65 r/min, the reaction temperature is 55℃,
Hydrolysis and dilution: controlling the dripping speed of the hydrochloric acid to be slow firstly and then fast, wherein the total dripping amount of the hydrochloric acid is 6779kg, the stirring speed is 45 r/min, and the reaction temperature is less than or equal to 50 ℃;
standing and layering: standing for 1.5 h;
rinsing and layering: washing off polar substances in the coarse material by adding water in the second part to change the coarse material into a semitransparent color;
and (3) reduced pressure distillation: the vacuum degree is not less than 0.096MPa, the distillation temperature is 160-;
falling film type hydrogen chloride absorption: the vacuum degree is 0.02MPa, and the water spraying amount is 7m3/h；
Table 1 shows the material quality calculations in the production processes of examples 1-2;
TABLE 1 quality of materials in examples 1-2 production runs (kg)
Figure BDA0002558775810000051
Figure BDA0002558775810000061
As is clear from the data in Table 1, in example 1-2, the mass of the first external water was controlled to be equal to that of the water in the by-product hydrochloric acid, and the mass of the second external water was controlled to be 65% H2SO4The quality sum of the solution water and the hydrolysis water is equal, the sum of the external water amount and the quality of the water in the hydrolysis diluent and the quality of the water in the byproduct hydrochloric acid can be equal, no wastewater discharge is realized, all the external water is used as much as possible without being discharged, no treatment cost is generated, and the method has good application prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (6)

1. A benzene sulfonyl chloride production process method with zero wastewater discharge is characterized in that benzene and chlorosulfonic acid are used as raw materials, and benzene sulfonyl chloride finished products are prepared by chlorosulfonation reaction, hydrolytic dilution, standing layering, rinsing layering and reduced pressure distillation; wherein, hydrogen chloride generated in the chlorosulfonation reaction and the hydrolysis dilution process is absorbed by a falling film absorption tower under the conditions of micro negative pressure, first external water and second external water for reuse to form a hydrochloric acid solution with the concentration of 30 percent; a certain amount of hydrochloric acid solution with the concentration of 30 percent is used as hydrolysis diluent and is dripped into the sulfonation liquid after the chlorosulfonation reaction for hydrolysis and dilution reaction, so that the sulfuric acid in the sulfonation liquid is finally diluted to the mass concentration of 60-65 percent, and the residual hydrochloric acid solution with the concentration of 30 percent returns to a hydrochloric acid storage tank to obtain a byproduct hydrochloric acid; rinsing and layering the material after standing and layering by adopting second external water, and completely reusing the rinsed second external water for the falling film absorption process of the hydrogen chloride; wherein the mass of the first additional water and the second additional water is equal to the mass of water used for absorbing hydrogen chloride generated in the chlorosulfonation reaction and hydrolysis dilution processes to form a hydrochloric acid solution with the concentration of 30%;
the specific production process conditions comprise:
(1) the feed molar ratio is as follows: benzene: 1:2.5-3 parts of chlorosulfonic acid;
(2) and (3) sulfonation reaction: the dripping time of benzene is 3-5 h; the stirring speed is 50-70 r/m, the reaction temperature is 25-55℃,
Hydrolysis and dilution: controlling the dripping speed of hydrochloric acid to be slow firstly and then fast, wherein the dripping amount is 50-200kg/h, the stirring speed is 30-45 r/min, and the reaction temperature is less than or equal to 50 ℃;
standing and layering: standing for 1-1.5 h;
rinsing and layering: washing off polar substances in the coarse material by adding water in the second part to change the coarse material into a semitransparent color;
and (3) reduced pressure distillation: the vacuum degree is not less than 0.096MPa, the distillation temperature is 160-;
falling film type hydrogen chloride absorption: the vacuum degree is 0.01-0.02MPa, and the water spraying amount is 4-8m3/h。
2. The method for producing benzenesulfonyl chloride with zero wastewater discharge according to claim 1, wherein the mass of said first external water is equal to the mass of water in hydrochloric acid byproduct, and the mass of said second external water is equal to the mass of water in hydrolysis diluent.
3. The process for producing benzenesulfonyl chloride with zero wastewater discharge as claimed in claim 1, wherein the content of chlorosulfonic acid in raw material is not less than 98.5%, and the content of benzene is not less than 99.8%.
4. The method for producing benzene sulfonyl chloride with zero wastewater discharge according to claim 1, wherein the specific production process conditions comprise:
(1) the feed molar ratio is as follows: benzene: chlorosulfonic acid 1: 2.5; wherein, 3000kg of benzene and 11186kg of chlorosulfonic acid;
(2) and (3) sulfonation reaction: the dripping time of benzene is 3 h; stirring speed of 60 r/min, reaction temperature of 25 deg.C,
Hydrolysis and dilution: controlling the dripping speed of the hydrochloric acid to be slow firstly and then fast, wherein the total dripping amount of the hydrochloric acid is 4838kg, the stirring speed is 35 r/min, and the reaction temperature is less than or equal to 50 ℃;
standing and layering: standing for 1 h;
rinsing and layering: washing off polar substances in the coarse material by adding water in the second part to change the coarse material into a semitransparent color;
and (3) reduced pressure distillation: the vacuum degree is not less than 0.096MPa, the distillation temperature is 160-;
falling film type hydrogen chloride absorption: the vacuum degree is 0.01MPa, and the water spraying amount is 5m3/h。
5. The method for producing benzene sulfonyl chloride with zero wastewater discharge according to claim 1, wherein the specific production process conditions comprise:
(1) the feed molar ratio is as follows: benzene: chlorosulfonic acid 1: 3; wherein, 3000kg of benzene and 13423kg of chlorosulfonic acid are contained;
(2) and (3) sulfonation reaction: the dripping time of benzene is 4 h; the stirring speed is 65 r/min, the reaction temperature is 55℃,
Hydrolysis and dilution: controlling the dripping speed of the hydrochloric acid to be slow firstly and then fast, wherein the total dripping amount of the hydrochloric acid is 6779kg, the stirring speed is 45 r/min, and the reaction temperature is less than or equal to 50 ℃;
standing and layering: standing for 1.5 h;
rinsing and layering: washing off polar substances in the coarse material by adding water in the second part to change the coarse material into a semitransparent color;
and (3) reduced pressure distillation: the vacuum degree is not less than 0.096MPa, the distillation temperature is 160-;
falling film type hydrogen chloride absorption: the vacuum degree is 0.02MPa, and the water spraying amount is 7m3/h。
6. The process for producing benzene sulfonyl chloride with zero wastewater discharge according to claim 1, wherein the content of the finished benzene sulfonyl chloride is not less than 99.5%, and the content of diphenyl sulfone is not less than 0.10%.
CN202010601794.2A 2020-06-28 2020-06-28 Benzene sulfonyl chloride production process method without wastewater discharge Withdrawn CN111635340A (en)

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Application publication date: 20200908