CN111018754A - Para-ester synthesis process capable of recycling hydrogen chloride - Google Patents
Para-ester synthesis process capable of recycling hydrogen chloride Download PDFInfo
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- CN111018754A CN111018754A CN201911312831.1A CN201911312831A CN111018754A CN 111018754 A CN111018754 A CN 111018754A CN 201911312831 A CN201911312831 A CN 201911312831A CN 111018754 A CN111018754 A CN 111018754A
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Abstract
The invention discloses a para-ester synthesis process for recycling hydrogen chloride, which is characterized by comprising the following steps: (1) preparing chlorosulfonic acid; absorbing hydrogen chloride gas generated in the chlorosulfonation link by an original HCl absorption tower, and analyzing to generate pure hydrogen chloride gas; reacting the hydrogen chloride gas and pure sulfur trioxide gas in a primary reaction tower to obtain gaseous chlorosulfonic acid; condensing the gaseous chlorosulfonic acid, then feeding the condensed gaseous chlorosulfonic acid into a secondary reaction tower, and fully reacting a side reaction product in the primary reaction tower with excessive sulfur trioxide and hydrogen chloride to further generate chlorosulfonic acid; (2) preparing para-ester; preparing chlorosulfonated materials in a sulfonation reaction kettle; diluting and filtering, and then carrying out reduction reaction, condensation reaction and esterification reaction to prepare the para-ester. The method recycles hydrogen chloride generated in the chlorosulfonation link to react with sulfur trioxide gas to prepare chlorosulfonic acid which is used as a raw material in the chlorosulfonation link to further prepare para-ester, thereby realizing cyclic utilization.
Description
Technical Field
The invention belongs to the technical field of para-ester synthesis processes, and particularly relates to a para-ester synthesis process for recycling hydrogen chloride.
Background
Para-ester, also called 'para aminophenyl- β -hydroxyethyl sulfone sulfate', is an important intermediate for producing reactive dyes, mainly used for manufacturing KM or M series reactive dyes, and is suitable for the varieties of reactive turquoise blue (KN-G), reactive black (KN-B), reactive bright yellow (M-5G), reactive golden yellow (KM-G), reactive bright red (KM-2B, KM-8B) and the like.
The existing synthesis methods of para-ester mainly comprise three types: 1. acetanilide route, 2, p-nitrochlorobenzene route, 3, nitrobenzene route. In the above synthetic routes, the yield of nitrobenzene route is not high and the industrial value is not great. The p-nitrochlorobenzene route is low in cost, but is in the technical exploration stage at present. The acetanilide route is currently the predominant route for the production of para-esters.
In the production process of para-ester, chlorosulfonation process is necessary, so that chlorosulfonic acid is widely used. In actual production, the required chlorosulfonic acid is often required to be directly prepared, while in the preparation process of the chlorosulfonic acid, hydrogen chloride is often used for preparation, and a large amount of hydrochloric acid gas is often contained in waste gas discharged after reaction; meanwhile, a certain amount of hydrochloric acid gas is correspondingly generated in the chlorosulfonation reaction in which chlorosulfonic acid participates. In the existing para-ester synthesis process, hydrochloric acid gas is discharged, or hydrochloric acid is not used for preparing other products after collection, so that reasonable recovery and utilization of hydrogen chloride cannot be realized, discharged waste gas often contains more hydrogen chloride, resource waste is caused, environmental pollution is caused greatly, and cyclic utilization of resources cannot be realized.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a para-ester synthesis process for recycling hydrogen chloride, which comprises the steps of recovering hydrogen chloride generated in a chlorosulfonation link, introducing the hydrogen chloride into an analytical tower, analyzing the hydrogen chloride by hydrochloric acid to produce pure HCl gas, reacting the pure HCl gas with pure sulfur trioxide gas to prepare chlorosulfonic acid, using the chlorosulfonic acid as a raw material of the chlorosulfonation link to further prepare para-ester, and realizing recycling.
In order to realize the aim, the para-ester synthesis process for recycling hydrogen chloride comprises the following steps:
(1) preparing chlorosulfonic acid;
s11: in the chlorosulfonation step in the sulfonation reaction kettle, the generated hydrogen chloride gas is absorbed by an original HCl absorption tower and then preheated to enter an analytical tower, so that pure hydrogen chloride gas is generated;
s12: reacting the hydrogen chloride gas obtained by resolving hydrochloric acid with pure sulfur trioxide gas in a primary reaction tower to obtain gaseous chlorosulfonic acid;
s13: condensing the gaseous chlorosulfonic acid, then feeding the condensed gaseous chlorosulfonic acid into a secondary reaction tower, fully reacting a side reaction product in the primary reaction tower with excessive sulfur trioxide and hydrogen chloride to further generate chlorosulfonic acid, and absorbing the residual hydrogen chloride tail gas and then feeding the residual hydrogen chloride tail gas into the original HCl absorption tower again;
(2) preparing para-ester;
adding chlorosulfonic acid and acetanilide with set amount into the sulfonation reaction kettle, reacting to obtain a sulfonated substance, adding thionyl chloride, and reacting to prepare a chlorosulfonated substance; diluting and filtering, then carrying out reduction reaction, condensation reaction and esterification reaction, finally crushing and packaging the product after esterification reaction, and preparing the para-ester.
Further, the reaction temperature in the primary reaction tower is 110-230 ℃.
Further, in step S12, the equation for the first reaction is as follows:
SO3+HCl＝HSO3heat of Cl + ion
2HSO3Cl+SO3＝S2O5Cl2+H2SO4
S2O5Cl2+H2SO4＝HS2O5Cl2 ++HSO4 -
Among them, HS2O5Cl2 +And HSO4 -Is the byproduct.
Further, in step S13, the byproduct reacts with hydrogen chloride gas to generate chlorosulfonic acid, and the formula of the secondary reaction is as follows:
HS2O5Cl2 ++HSO4 -＝3HSO3Cl。
further, the molar ratio of the acetanilide, the chlorosulfonic acid and the thionyl chloride is 0.45-0.46: 1: 0.46-0.47.
Further, the preparation of the chlorosulfonated material comprises the following steps:
adding chlorosulfonic acid and acetanilide into a low-temperature sulfonation pot to react to obtain a sulfonated substance; the feeding temperature is controlled to be 25-35 ℃, and the feeding time is 4-5 hours; after the feeding is finished, maintaining for 4-5 hours, and controlling the temperature at 25-35 ℃;
transferring the sulfonated substance prepared in the low-temperature sulfonation pot into a high-temperature sulfonation pot for high-temperature sulfonation; the temperature of the high-temperature sulfonation is 45-48 ℃, and the high-temperature sulfonation is maintained for 1-2 hours;
and adding thionyl chloride for reaction, controlling the time to be 4-5 hours, maintaining the temperature at 55-60 ℃ for 2-3 hours after the thionyl chloride is added, and cooling to 40-50 ℃ for discharging.
Further, the condensation reaction comprises the following steps:
pumping the reducing solution into a condensation reaction device, vacuumizing, closing a vacuum valve, filling nitrogen, heating to 55-60 ℃ and adding a set amount of sodium phosphate, wherein the pressure in the pot is positive;
adding ethylene oxide, controlling the reaction temperature at 45-50 ℃, and controlling the time for adding the ethylene oxide at 3-4 hours;
and after the ethylene oxide is added, heating to 50 ℃ and maintaining for 3-4 hours, sampling and analyzing after maintaining, and discharging when the circulating water is cooled to 25-30 ℃ after the circulating water is qualified.
Further, reducing liquid: ethylene oxide: molar ratio of sodium phosphate, 1: 0.52-0.53: 0.0014.
further, the esterification reaction comprises the following steps: slowly adding sulfuric acid into the condensation compound, stirring for 8-16 minutes at the temperature of 200-;
further, the molar ratio of the condensation compound to the sulfuric acid is 1: 1.03-1.06.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) according to the synthesis process of the para-ester by recycling the hydrogen chloride, the hydrogen chloride generated in the chlorosulfonation link is recycled and enters an analytical tower, the pure HCl gas is produced after hydrochloric acid is analyzed, and the pure HCl gas reacts with the pure sulfur trioxide gas to prepare chlorosulfonic acid which is used as a raw material in the chlorosulfonation link to further prepare the para-ester, so that the cyclic utilization is realized.
(2) The synthesis process of para-ester by recycling hydrogen chloride adopts a gas phase synthesis method, the produced chlorosulfonic acid has high purity, and the chlorosulfonic acid with high purity can be obtained by the separation function of a primary reaction tower and can reach more than 99.5 percent; and the gas utilization rate is high, the tail gas is less, sulfur dioxide is not contained, and the requirement can be met only by absorbing the tail gas with hydrochloric acid.
(3) The synthesis process of para-ester by recycling hydrogen chloride has the advantages of low system power consumption, greatly reduced gas amount and over 50 percent reduction of the power consumption of chlorosulfonic acid due to the direct adoption of pure sulfur trioxide gas.
(4) The synthesis process of the para-ester by recycling the hydrogen chloride optimizes the molar ratio of the acetanilide, the chlorosulfonic acid and the thionyl chloride, reduces the dosage of the chlorosulfonic acid compared with the mixture ratio of the three in the prior art, replaces part of the chlorosulfonic acid with the thionyl chloride, and improves the yield of the para-ester by optimizing the mixture ratio.
(5) According to the para-ester synthesis process by recycling hydrogen chloride, sodium phosphate is added as a buffering agent in the condensation reaction link of the para-ester synthesis method, so that the pH value is stabilized, and hydrolysis of ethylene oxide is inhibited, so that the use amount of ethylene oxide is reduced, and the cost is reduced. And the yield is further improved by adjusting the mass molar ratio of the reduction product, the ethylene oxide and the phosphate.
(6) According to the synthesis process of the para-ester by recycling the hydrogen chloride, the thionyl chloride is added on the basis of the chlorosulfonic acid, so that the yield is improved (the original yield is improved to 82 percent), the sulfonation reaction rate is accelerated, the reaction is stable, the sulfonation reaction efficiency is high, side reactions are less, the environmental effect is good, the yield of the sulfonation reaction is effectively improved, the generation of side products is reduced, the discharge amount of waste water is reduced, the material consumption is reduced, and the product quality is improved.
Drawings
FIG. 1 is a flow chart of a process for recycling hydrogen chloride to prepare chlorosulfonic acid, which is involved in a para-ester synthesis process for recycling hydrogen chloride in an embodiment of the invention;
FIG. 2 is a material weighing and calculating diagram of chlorosulfonic acid synthesis link involved in the para-ester synthesis process by recycling hydrogen chloride in the embodiment of the present invention;
FIG. 3 is a material weighing diagram of a chlorination desorption link involved in the para-ester synthesis process by recycling hydrogen chloride according to an embodiment of the present invention;
FIG. 4 is a flow chart of a process for synthesizing para-ester by recycling hydrogen chloride according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Fig. 1 is a flow chart of a process for recycling hydrogen chloride to prepare chlorosulfonic acid according to a process for synthesizing para-ester by recycling hydrogen chloride of the embodiment of the present invention, and fig. 4 is a flow chart of a process for synthesizing para-ester by recycling hydrogen chloride of the embodiment of the present invention. With reference to fig. 1 and 4, the process for synthesizing para-ester by recycling hydrogen chloride according to the present invention comprises the following steps;
(1) preparation of chlorosulfonic acid
S11: in the chlorosulfonation link in the para-ester synthesis process, the generated hydrogen chloride gas is absorbed by an original HCl absorption tower, preheated and enters an analytical tower, and cooled and dried to generate pure hydrogen chloride gas;
s12: reacting hydrogen chloride gas resolved from hydrochloric acid with pure sulfur trioxide gas in a primary reaction tower to obtain gaseous chlorosulfonic acid; the reaction temperature in the primary reaction tower is 110-230 ℃, and preferably 110-150 ℃.
S13: condensing the gaseous chlorosulfonic acid, then feeding the condensed gaseous chlorosulfonic acid into a secondary reaction tower, and fully reacting a byproduct in the primary reaction tower with excessive sulfur trioxide and hydrogen chloride to further generate chlorosulfonic acid.
In step S11, hydrochloric acid having a concentration of about 31% is absorbed by the absorption tower, and is preheated by a hydrochloric acid pump through a preheater and enters the desorption tower to be distributed and then performs heat and mass transfer with hot HCl gas, and efficient heat and mass transfer processes occur when the hydrochloric acid passes through the packing and the internals in the downward flow process under the action of gravity. At the same time, the solution is continuously heated by steam in a thermosiphon natural circulation reboiler, and the gas is distilled and separated and flows upwards. The separated HCl gas is cooled by primary cooling and secondary cooling, frozen and demixed by a demister to produce pure HCl, and the condensed acid is returned to the tower or the concentrated acid tank.
In step S12, the equation for the first reaction is as follows:
SO3+HCl＝HSO3heat of Cl + ion
2HSO3Cl+SO3＝S2O5Cl2+H2SO4
S2O5Cl2+H2SO4＝HS2O5Cl2 ++HSO4 -
Wherein pure sulfur trioxide and hydrogen chloride form chlorosulfonic acid and release heat, and wherein chlorosulfonic acid and excess sulfur trioxide form a by-product S, since the sulfur trioxide introduced is usually in excess2O5Cl2And H2SO4Further generation ofTo HS2O5Cl2 +And HSO4 -。
Further, in step S13, a side reaction product HS2O5Cl2 +And HSO4 -Continuously reacting with hydrogen chloride gas to generate chlorosulfonic acid, wherein the formula corresponding to the secondary reaction is as follows:
HS2O5Cl2 ++HSO4 -＝3HSO3Cl
in addition, after the reaction of the step S13, excessive sulfur trioxide and hydrogen chloride tail gas are respectively absorbed, wherein hydrogen chloride returns to the hydrochloric acid absorption tower, and other waste gases are discharged. Condensing chlorosulfonic acid, removing impurities and separating to obtain a finished product of chlorosulfonic acid; the tail gas is washed by sulfuric acid and then enters an original hydrochloric acid absorption device, and is absorbed by two times of washing by dilute acid and water without increasing emission.
Fig. 2 and fig. 3 are a material weighing diagram of a chlorosulfonic acid synthesis link and a material weighing diagram of a chlorination desorption link, respectively, relating to a p-ester synthesis process for recycling hydrogen chloride according to an embodiment of the present invention. Referring to fig. 2, sulfur trioxide gas and hydrogen chloride gas react in a synthesis tower (primary reaction tower) to generate chlorosulfonic acid, which is condensed by a cooler (condenser) and then enters an auxiliary tower (secondary reaction tower). As shown in fig. 3, the temperature for desorption in the desorption tower is preferably 100-120 ℃, and the desorbed pure hydrogen chloride gas is cooled by water and then cooled by low temperature, dried and then enters the synthesis tower (primary reaction tower); and discharging the other part of the dilute acid in the desorption tower from the tower bottom, primarily cooling the dilute acid by a preheater, cooling the dilute acid to below 40 ℃ by secondary dilute acid, returning the dilute acid to the dilute acid tank again, and pumping the dilute acid to the original HCl absorption tower.
The chlorosulfonation link in the para-ester synthesis process adopts the steps of mixing and preheating pure sulfur trioxide gas from a sulfur trioxide evaporator and hydrogen chloride gas (resolved from hydrochloric acid), then feeding the mixture into a synthesis tower to synthesize gaseous chlorosulfonic acid, and then removing impurities and separating the gaseous chlorosulfonic acid by an auxiliary tower and a condenser to obtain a chlorosulfonic acid finished product. The hydrogen chloride generated in the chlorosulfonation link is recycled and enters an analytical tower, pure HCl gas is produced after hydrochloric acid is analyzed, and the pure HCl gas reacts with pure sulfur trioxide gas to prepare chlorosulfonic acid which is used as a raw material of the chlorosulfonation link to realize cyclic utilization. The process lays a foundation for purifying various byproduct HCl in production, fully realizes the cyclic utilization of HCl and is a clean production process.
The chlorosulfonation link in the para-ester synthesis process of the invention adopts a gas phase synthesis method, and the produced chlorosulfonic acid has high purity. The primary reaction tower has a separation function, so that chlorosulfonic acid with high purity can be obtained, and the purity can reach more than 99.5%; the tail gas is less, sulfur dioxide is not contained, and the requirement can be met only by absorbing the tail gas with hydrochloric acid; the gas utilization rate is high; the system has low power consumption, and the gas quantity is greatly reduced and the power consumption of the chlorosulfonic acid is reduced by more than 50 percent because the pure sulfur trioxide gas is directly adopted.
(2) Preparation of para-ester
With reference to the block diagram of the para-ester synthesis process using hydrogen chloride cyclically in fig. 2, the para-ester preparation process of the present invention comprises the following steps:
s21: adding chlorosulfonic acid and acetanilide with a set amount into a sulfonation reaction kettle, reacting to obtain a sulfonated substance, adding thionyl chloride, and reacting to prepare a chlorosulfonated substance;
the molar ratio of the acetanilide to the chlorosulfonic acid to the thionyl chloride is 0.45-0.46: 1: 0.46-0.47;
s22: diluting chlorosulfonated matter and then carrying out suction filtration;
s23: adding pyronitrite, adjusting the stable pH value, and carrying out reduction reaction to obtain a reducing solution;
s24: sodium phosphate is taken as a buffering agent, sulfuric acid and ethylene oxide are added, and condensation reaction is carried out to obtain a condensation product;
s25: carrying out suction filtration on the condensation product;
s26: adding sulfuric acid into the product after suction filtration to perform esterification reaction;
s27: and crushing and packaging the product after the esterification reaction to prepare the para-ester.
Specifically, step S21 includes the following steps:
s211: adding chlorosulfonic acid and acetanilide into a low-temperature sulfonation pot to react to obtain a sulfonated substance; the feeding temperature is controlled to be 25-35 ℃, and the feeding time is 4-5 hours; after the feeding is finished, maintaining for 4-5 hours, and controlling the temperature at 25-35 ℃;
s212: transferring the sulfonated substance prepared in the low-temperature sulfonation pot into a high-temperature sulfonation pot for high-temperature sulfonation; the temperature of the high-temperature sulfonation is 45-48 ℃, and the high-temperature sulfonation is maintained for 1-2 hours;
s213: adding thionyl chloride for reaction. And controlling the time for adding the thionyl chloride within 4-5 hours, maintaining the temperature at 55-60 ℃ for 2-3 hours after the thionyl chloride is added, and then cooling to 40-50 ℃ for discharging.
In step S23, sodium metabisulfite is added into chlorosulfonated product, stirred until the sodium metabisulfite is completely dissolved, alkali liquor is adopted to adjust the pH value to keep alkalinity, the pH value is preferably 7.0-7.5, the reaction temperature is preferably controlled to be 31-35 ℃, and after the reaction is finished, the chlorosulfonated product is transferred to a condensation reaction kettle to carry out the next reaction.
Further, step S24 specifically includes the following steps:
s241: pumping the reducing solution into a condensation reaction device, vacuumizing, heating, and adding a set amount of sodium phosphate;
s242: adding ethylene oxide, controlling the reaction temperature at 45-50 ℃, and controlling the time for adding the ethylene oxide at 3-4 hours;
s243: and after the ethylene oxide is added, heating to 50 ℃ and maintaining for 3-4 hours, sampling and analyzing after maintaining, and discharging when the circulating water is cooled to 25-30 ℃ after the circulating water is qualified.
The method comprises the steps of adding ethylene oxide into a reducing solution, wherein the molar ratio of the reducing solution to the ethylene oxide to sodium phosphate is 1: 0.52-0.53: 0.0014, more preferably 1: 0.525: 0.0014, controlling the pH value to be 7.5-8 in the process of adding the ethylene oxide in step S42, and maintaining the pH value to be in an alkaline environment all the time in the process of maintaining in step S43, wherein the product obtained after condensation in step S4 is mainly p- β -hydroxyethyl sulfone acetanilide.
In the condensation reaction link of the para-ester synthesis method, sodium phosphate is added as a buffering agent to stabilize the pH value and inhibit the hydrolysis of ethylene oxide, so that the use amount of the ethylene oxide is reduced, and the cost is reduced. And by adjusting the molar ratio of the reduction product, ethylene oxide and phosphate, the ratio of the reduction product to the ethylene oxide to the phosphate is adjusted from the existing ratio of 1: 0.57: 0.00.14 to 1: 0.52-0.53: 0.0014, the yield is further improved.
Further, in step S26, slowly adding sulfuric acid into the condensate, stirring at 200-210 ℃ for 8-16 minutes, and discharging after keeping the time for 2-3 hours when the materials are dry powder. The molar ratio of the condensation compound to the sulfuric acid is 1: 1.03-1.06. The sulfuric acid is 100% sulfuric acid. In the esterification link of the para-ester synthesis method, the concentration of sulfuric acid is improved, 98% concentrated sulfuric acid commonly used in the prior art is optimized to 100% concentrated sulfuric acid, and the quality and the yield are further improved.
In the method for synthesizing the para-ester, the thionyl chloride is added on the basis of chlorosulfonic acid, so that the yield is improved (the original 75 percent is improved to over 82 percent), the rate of sulfonation reaction is accelerated, the reaction is stable, the sulfonation reaction efficiency is high, side reactions are less, the environmental effect is good, the yield of sulfonation reaction is effectively improved, the generation of side products is reduced, the discharge amount of waste water is reduced, the material consumption is reduced, and the product quality is improved. The mol ratio of the acetanilide, the chlorosulfonic acid and the thionyl chloride is optimized, compared with the mixture ratio of the acetanilide, the chlorosulfonic acid and the thionyl chloride in the prior art, the dosage of the chlorosulfonic acid is reduced, partial chlorosulfonic acid is replaced by the thionyl chloride, and the yield of the para-ester is improved by about 5 percent through the optimization of the mixture ratio.
This invention better explains the synthesis method of para-ester of the invention, provides the following specific examples:
example 1
(1) Preparation of chlorosulfonic acid
S11: in the chlorosulfonation link in the para-ester synthesis process, the generated hydrogen chloride gas is absorbed by an original HCl absorption tower, preheated and enters an analytical tower, and cooled and dried to generate pure hydrogen chloride gas;
s12: reacting hydrogen chloride gas resolved from hydrochloric acid with pure sulfur trioxide gas in a primary reaction tower to obtain gaseous chlorosulfonic acid; the reaction temperature in the primary reaction column was 110 ℃.
S13: condensing the gaseous chlorosulfonic acid, then feeding the condensed gaseous chlorosulfonic acid into a secondary reaction tower, and fully reacting a byproduct in the primary reaction tower with excessive sulfur trioxide and hydrogen chloride to further generate chlorosulfonic acid.
Respectively absorbing excessive sulfur trioxide and hydrogen chloride tail gas, wherein the hydrogen chloride returns to the hydrochloric acid absorption tower, and other waste gases are discharged. Condensing chlorosulfonic acid, removing impurities and separating to obtain a finished product of chlorosulfonic acid; the tail gas is washed by sulfuric acid and then enters an original hydrochloric acid absorption device, and is absorbed by two times of washing by dilute acid and water without increasing emission.
(2) Preparation of para-ester
S21: adding 100mol of preset chlorosulfonic acid and 45mol of acetanilide into a low-temperature sulfonation pot for reaction; the feeding temperature is controlled at 25 ℃, and the feeding time is 4 hours; after the feeding is finished, maintaining for 4 hours, and controlling the temperature at 25 ℃;
transferring the sulfonated substance prepared in the low-temperature sulfonation pot into a high-temperature sulfonation pot for high-temperature sulfonation; the temperature of high-temperature sulfonation is 45 ℃, and the sulfonation is maintained for 1 hour;
adding 46mol of thionyl chloride for reaction, controlling the time for adding the thionyl chloride to be 4 hours, maintaining the temperature at 55 ℃ for 2 hours after the thionyl chloride is added, cooling to 40 ℃, discharging, diluting the sulfonated substance, and performing suction filtration.
The molar ratio of acetanilide, chlorosulfonic acid and thionyl chloride is 0.45:1: 0.46.
S22: adding pyronitrite, adjusting the stable pH value to 7.5 by using liquid alkali, and carrying out reduction reaction to obtain reducing liquid;
s23: pouring 100mol of high-temperature reducing liquid into a condensation pot, sealing the condensation pot, vacuumizing (the negative pressure is-0.01 MPa), closing a vacuum valve, filling nitrogen, heating to 55 ℃, starting a material circulating pump, and adding 0.14mol of sodium phosphate;
the ethylene oxide feed tube was flushed with nitrogen to prevent plugging. 52mol of ethylene oxide is added, a dilute acid feeding valve is opened, and the pH value is controlled to be 7.5 during the ethylene oxide adding process, so that partial acid or partial alkali is not allowed. The temperature was controlled at 45 ℃. The epoxy time is 3 hours;
after the ethylene oxide is added, the temperature is raised to 50 ℃ and maintained for 3 hours, and the pH value is always maintained in an alkaline environment in the maintaining process. After the maintenance, sampling and analyzing are finished, and after the sample is qualified, circulating water is boiled and cooled to 25 ℃ for discharging.
Reducing liquid: ethylene oxide: the molar ratio of sodium phosphate is 1: 0.52: 0.0014.
s24: and (4) carrying out suction filtration on the condensation product, and adding sulfuric acid into the product after suction filtration to carry out esterification reaction. Adding 100mol of condensation centrifugal material, feeding dry powder, simultaneously opening an oil valve to feed oil, keeping the oil temperature at 200 ℃, stirring for 8 minutes, slowly adding 103mol of 100% acid, starting timing and maintaining for 2 hours when the material is to be dry powder, then sampling, and discharging after the material is qualified;
condensation product and condensation product: the molar ratio of 100% sulfuric acid was 1: 1.03.
S25: and crushing and packaging the product after the esterification reaction to prepare the para-ester.
The yield of the para-ester prepared in example 1 was measured to obtain the yield of 82% in this example.
Example 2
(1) Preparation of chlorosulfonic acid
S11: in the chlorosulfonation link in the para-ester synthesis process, the generated hydrogen chloride gas is absorbed by an original HCl absorption tower, preheated and enters an analytical tower, and cooled and dried to generate pure hydrogen chloride gas;
s12: reacting hydrogen chloride gas resolved from hydrochloric acid with pure sulfur trioxide gas in a primary reaction tower to obtain gaseous chlorosulfonic acid; the reaction temperature in the primary reaction tower was 150 ℃.
S13: condensing the gaseous chlorosulfonic acid, then feeding the condensed gaseous chlorosulfonic acid into a secondary reaction tower, and fully reacting a byproduct in the primary reaction tower with excessive sulfur trioxide and hydrogen chloride to further generate chlorosulfonic acid.
Respectively absorbing excessive sulfur trioxide and hydrogen chloride tail gas, wherein the hydrogen chloride returns to the hydrochloric acid absorption tower, and other waste gases are discharged. Condensing chlorosulfonic acid, removing impurities and separating to obtain a finished product of chlorosulfonic acid; the tail gas is washed by sulfuric acid and then enters an original hydrochloric acid absorption device, and is absorbed by two times of washing by dilute acid and water without increasing emission.
(2) Preparation of para-ester
S21: adding 100mol of preset chlorosulfonic acid and 45mol of acetanilide into a low-temperature sulfonation pot for reaction; the feeding temperature is controlled at 26 ℃, and the feeding time is 4.2 hours; after the feeding is finished, maintaining for 4 hours, and controlling the temperature at 27 ℃;
transferring the sulfonated substance prepared in the low-temperature sulfonation pot into a high-temperature sulfonation pot for high-temperature sulfonation; the temperature of high-temperature sulfonation is 45 ℃, and the sulfonation is maintained for 1 hour;
adding 47mol of thionyl chloride for reaction, controlling the time for adding the thionyl chloride to be 4.4 hours, maintaining the temperature at 55 ℃ for 2 hours after the thionyl chloride is added, cooling to 40 ℃, discharging, diluting the sulfonated substance, and performing suction filtration.
The molar ratio of the acetanilide, the chlorosulfonic acid and the thionyl chloride is 0.45:1: 0.47.
S22: adding pyronitrite, adjusting the stable pH value to 7.5 by using liquid alkali, and carrying out reduction reaction to obtain a reducing solution;
s23: pouring 100mol of high-temperature reducing liquid into a condensation pot, sealing the condensation pot, vacuumizing (the negative pressure is-0.01 MPa), closing a vacuum valve, filling nitrogen, heating to 55 ℃, starting a material circulating pump, and adding 0.14mol of sodium phosphate;
the ethylene oxide feed tube was flushed with nitrogen to prevent plugging. 52.1mol of ethylene oxide is added, a dilute acid feeding valve is opened, and the pH value is controlled to be 7.7 during the ethylene oxide adding process, so that partial acid or partial alkali is not allowed. The temperature was controlled at 45 ℃. The epoxy time is 3 hours;
after the ethylene oxide is added, the temperature is raised to 50 ℃ and maintained for 3 hours, and the pH value is always maintained in an alkaline environment in the maintaining process. After the maintenance, sampling and analyzing are finished, and after the sample is qualified, circulating water is boiled and cooled to 25 ℃ for discharging.
Reducing liquid: ethylene oxide: the molar ratio of sodium phosphate is 1: 0.521: 0.0014.
s24: and (4) carrying out suction filtration on the condensation product, and adding sulfuric acid into the product after suction filtration to carry out esterification reaction. Adding 100mol of condensation centrifugal material, feeding dry powder, simultaneously opening an oil valve to feed oil, keeping the oil temperature at 200 ℃, stirring for 10 minutes, slowly adding 104mol of 100% acid, starting timing and keeping for 2 hours when the material is to be dry powder, then sampling, and discharging after the material is qualified;
condensation product and condensation product: the molar ratio of 100% sulfuric acid was 1: 1.04.
S25: and crushing and packaging the product after the esterification reaction to prepare the para-ester.
The yield of the para-ester prepared in example 2 was measured to obtain the yield of 87% in this example.
Example 3
(1) Preparation of chlorosulfonic acid
S11: in the chlorosulfonation link in the para-ester synthesis process, the generated hydrogen chloride gas is absorbed by an original HCl absorption tower, preheated and enters an analytical tower, and cooled and dried to generate pure hydrogen chloride gas;
s12: reacting hydrogen chloride gas resolved from hydrochloric acid with pure sulfur trioxide gas in a primary reaction tower to obtain gaseous chlorosulfonic acid; the reaction temperature in the primary reaction tower was 170 ℃.
S13: condensing the gaseous chlorosulfonic acid, then feeding the condensed gaseous chlorosulfonic acid into a secondary reaction tower, and fully reacting a byproduct in the primary reaction tower with excessive sulfur trioxide and hydrogen chloride to further generate chlorosulfonic acid.
Respectively absorbing excessive sulfur trioxide and hydrogen chloride tail gas, wherein the hydrogen chloride returns to the hydrochloric acid absorption tower, and other waste gases are discharged. Condensing chlorosulfonic acid, removing impurities and separating to obtain a finished product of chlorosulfonic acid; the tail gas is washed by sulfuric acid and then enters an original hydrochloric acid absorption device, and is absorbed by two times of washing by dilute acid and water without increasing emission.
(2) Preparation of para-ester
S21: adding 100mol of preset chlorosulfonic acid and 46mol of acetanilide into a low-temperature sulfonation pot for reaction; the feeding temperature is controlled at 28 ℃, and the feeding time is 4.4 hours; after the feeding is finished, maintaining for 5 hours, and controlling the temperature at 29 ℃;
transferring the sulfonated substance prepared in the low-temperature sulfonation pot into a high-temperature sulfonation pot for high-temperature sulfonation; the temperature of high-temperature sulfonation is 45 ℃, and the sulfonation is maintained for 1 hour;
adding 46mol of thionyl chloride for reaction, controlling the time for adding the thionyl chloride to be 4.4 hours, maintaining the temperature at 57 ℃ for 2 hours after the thionyl chloride is added, cooling to 40 ℃, discharging, diluting the sulfonated substance, and performing suction filtration.
The molar ratio of acetanilide, chlorosulfonic acid and thionyl chloride was 0.46:1: 0.46.
S22: adding pyronitrite, adjusting the stable pH value to 7.5 by using liquid alkali, and carrying out reduction reaction to obtain reducing liquid;
s23: pouring 100mol of high-temperature reducing liquid into a condensation pot, sealing the condensation pot, vacuumizing (the negative pressure is-0.01 MPa), closing a vacuum valve, filling nitrogen, heating to 55 ℃, starting a material circulating pump, and adding 0.14mol of sodium phosphate;
the ethylene oxide feed tube was flushed with nitrogen to prevent plugging. 52.2mol of ethylene oxide is added, a dilute acid feeding valve is opened, and the pH value is controlled to be 7.8 during the ethylene oxide adding process, so that partial acid or partial alkali is not allowed. The temperature was controlled at 45 ℃. The epoxy time is 3 hours;
after the ethylene oxide is added, the temperature is raised to 50 ℃ and maintained for 3 hours, and the pH value is always maintained in an alkaline environment in the maintaining process. After the maintenance, sampling and analyzing are finished, and after the sample is qualified, circulating water is boiled and cooled to 25 ℃ for discharging.
Reducing liquid: ethylene oxide: the molar ratio of sodium phosphate is 1: 0.522: 0.0014.
s24: and (4) carrying out suction filtration on the condensation product, and adding sulfuric acid into the product after suction filtration to carry out esterification reaction. Adding 100mol of condensation centrifugal material, feeding dry powder, simultaneously opening an oil valve to feed oil, keeping the oil temperature at 200 ℃, stirring for 10 minutes, slowly adding 104mol of 100% acid, starting timing and keeping for 2 hours when the material is to be dry powder, then sampling, and discharging after the material is qualified;
condensation product and condensation product: the molar ratio of 100% sulfuric acid was 1: 1.04.
S25: and crushing and packaging the product after the esterification reaction to prepare the para-ester.
The yield of the para-ester prepared in example 3 was measured to obtain the yield of 85% in this example.
Example 4
(1) Preparation of chlorosulfonic acid
S11: in the chlorosulfonation link in the para-ester synthesis process, the generated hydrogen chloride gas is absorbed by an original HCl absorption tower, preheated and enters an analytical tower, and cooled and dried to generate pure hydrogen chloride gas;
s12: reacting hydrogen chloride gas resolved from hydrochloric acid with pure sulfur trioxide gas in a primary reaction tower to obtain gaseous chlorosulfonic acid; the reaction temperature in the primary reaction tower was 180 ℃.
S13: condensing the gaseous chlorosulfonic acid, then feeding the condensed gaseous chlorosulfonic acid into a secondary reaction tower, and fully reacting a byproduct in the primary reaction tower with excessive sulfur trioxide and hydrogen chloride to further generate chlorosulfonic acid.
Respectively absorbing excessive sulfur trioxide and hydrogen chloride tail gas, wherein the hydrogen chloride returns to the hydrochloric acid absorption tower, and other waste gases are discharged. Condensing chlorosulfonic acid, removing impurities and separating to obtain a finished product of chlorosulfonic acid; the tail gas is washed by sulfuric acid and then enters an original hydrochloric acid absorption device, and is absorbed by two times of washing by dilute acid and water without increasing emission.
(2) Preparation of para-ester
S21: adding 100mol of preset chlorosulfonic acid and 46mol of acetanilide into a low-temperature sulfonation pot for reaction; the feeding temperature is controlled at 30 ℃, and the feeding time is 4.6 hours; after the feeding is finished, maintaining for 4 hours, and controlling the temperature at 30 ℃;
transferring the sulfonated substance prepared in the low-temperature sulfonation pot into a high-temperature sulfonation pot for high-temperature sulfonation; the temperature of high-temperature sulfonation is 46 ℃, and the sulfonation is maintained for 1 hour;
adding 47mol of thionyl chloride for reaction, controlling the time for adding the thionyl chloride to be 4.4 hours, maintaining the temperature at 60 ℃ for 2 hours after the thionyl chloride is added, cooling to 40 ℃, discharging, diluting the sulfonated substance, and performing suction filtration.
The molar ratio of acetanilide, chlorosulfonic acid and thionyl chloride was 0.46:1: 0.47.
S22: adding pyronitrite, adjusting the stable pH value to 7.5 by using liquid alkali, and carrying out reduction reaction to obtain reducing liquid;
s23: pouring 100mol of high-temperature reducing liquid into a condensation pot, sealing the condensation pot, vacuumizing (the negative pressure is-0.01 MPa), closing a vacuum valve, filling nitrogen, heating to 55 ℃, starting a material circulating pump, and adding 0.14mol of sodium phosphate;
the ethylene oxide feed tube was flushed with nitrogen to prevent plugging. 52.3mol of ethylene oxide is added, a dilute acid feeding valve is opened, and the pH value is controlled to be 8.0 during the ethylene oxide adding process, so that partial acid or partial alkali is not allowed. The temperature was controlled at 45 ℃. The epoxy time is 3 hours;
after the ethylene oxide is added, the temperature is raised to 50 ℃ and maintained for 4 hours, and the pH value is always maintained in an alkaline environment in the maintaining process. After the maintenance, sampling and analysis are finished, and after the sample is qualified, circulating water is started to cool to 28 ℃ for discharging.
Reducing liquid: ethylene oxide: the molar ratio of sodium phosphate is 1: 0.523: 0.0014.
s24: and (4) carrying out suction filtration on the condensation product, and adding sulfuric acid into the product after suction filtration to carry out esterification reaction. Adding 100mol of condensation centrifugal material, feeding dry powder, simultaneously opening an oil valve to feed oil, keeping the oil temperature at 210 ℃, stirring for 10 minutes, slowly adding 105mol of 100% acid, starting timing and maintaining for 2 hours when the material is to be dry powder, then sampling, and discharging after the material is qualified;
condensation product and condensation product: the molar ratio of 100% sulfuric acid was 1: 1.05.
S25: and crushing and packaging the product after the esterification reaction to prepare the para-ester.
The yield of the para-ester prepared in example 4 was measured to obtain the yield of 85% in this example.
Example 5
(1) Preparation of chlorosulfonic acid
S11: in the chlorosulfonation link in the para-ester synthesis process, the generated hydrogen chloride gas is absorbed by an original HCl absorption tower, preheated and enters an analytical tower, and cooled and dried to generate pure hydrogen chloride gas;
s12: reacting hydrogen chloride gas resolved from hydrochloric acid with pure sulfur trioxide gas in a primary reaction tower to obtain gaseous chlorosulfonic acid; the reaction temperature in the primary reaction tower was 200 ℃.
S13: condensing the gaseous chlorosulfonic acid, then feeding the condensed gaseous chlorosulfonic acid into a secondary reaction tower, and fully reacting a byproduct in the primary reaction tower with excessive sulfur trioxide and hydrogen chloride to further generate chlorosulfonic acid.
Respectively absorbing excessive sulfur trioxide and hydrogen chloride tail gas, wherein the hydrogen chloride returns to the hydrochloric acid absorption tower, and other waste gases are discharged. Condensing chlorosulfonic acid, removing impurities and separating to obtain a finished product of chlorosulfonic acid; the tail gas is washed by sulfuric acid and then enters an original hydrochloric acid absorption device, and is absorbed by two times of washing by dilute acid and water without increasing emission.
(2) Preparation of para-ester
S21: adding 100mol of preset chlorosulfonic acid and 45.5mol of acetanilide into a low-temperature sulfonation pot for reaction; the feeding temperature is controlled at 30 ℃, and the feeding time is 4.6 hours; after the feeding is finished, maintaining for 4 hours, and controlling the temperature at 30 ℃;
transferring the sulfonated substance prepared in the low-temperature sulfonation pot into a high-temperature sulfonation pot for high-temperature sulfonation; the temperature of high-temperature sulfonation is 46 ℃, and the sulfonation is maintained for 1 hour;
adding 46mol of thionyl chloride for reaction, controlling the time for adding the thionyl chloride to be 4.4 hours, maintaining the temperature at 60 ℃ for 2 hours after the thionyl chloride is added, cooling to 40 ℃, discharging, diluting the sulfonated substance, and performing suction filtration.
The molar ratio of acetanilide, chlorosulfonic acid and thionyl chloride was 0.455:1: 0.46.
S22: adding pyronitrite, adjusting the stable pH value to 7.5 by using liquid alkali, and carrying out reduction reaction to obtain reducing liquid;
s23: pouring 100mol of high-temperature reducing liquid into a condensation pot, sealing the condensation pot, vacuumizing (the negative pressure is-0.01 MPa), closing a vacuum valve, filling nitrogen, heating to 55 ℃, starting a material circulating pump, and adding 0.14mol of sodium phosphate;
the ethylene oxide feed tube was flushed with nitrogen to prevent plugging. 52.4mol of ethylene oxide is added, a dilute acid feeding valve is opened, and the pH value is controlled to be 7.9 during the ethylene oxide adding process, so that partial acid or partial alkali is not allowed. The temperature was controlled at 45 ℃. The epoxy time is 3 hours;
after the ethylene oxide is added, the temperature is raised to 50 ℃ and maintained for 4 hours, and the pH value is always maintained in an alkaline environment in the maintaining process. After the maintenance, sampling and analysis are finished, and after the sample is qualified, circulating water is started to cool to 28 ℃ for discharging.
Reducing liquid: ethylene oxide: the molar ratio of sodium phosphate is 1: 0.524: 0.0014.
s24: and (4) carrying out suction filtration on the condensation product, and adding sulfuric acid into the product after suction filtration to carry out esterification reaction. Adding 100mol of condensation centrifugal material, feeding dry powder, simultaneously opening an oil valve to feed oil, keeping the oil temperature at 210 ℃, stirring for 12 minutes, slowly adding 106mol of 100% acid, starting timing and maintaining for 2 hours when the material is to be dry powder, then sampling, and discharging after the material is qualified;
condensation product and condensation product: the molar ratio of 100% sulfuric acid was 1: 1.06.
S25: and crushing and packaging the product after the esterification reaction to prepare the para-ester.
The yield of the para-ester prepared in example 5 was measured to obtain the yield of this example of 85%.
Example 6
(1) Preparation of chlorosulfonic acid
S11: in the chlorosulfonation link in the para-ester synthesis process, the generated hydrogen chloride gas is absorbed by an original HCl absorption tower, preheated and enters an analytical tower, and cooled and dried to generate pure hydrogen chloride gas;
s12: reacting hydrogen chloride gas resolved from hydrochloric acid with pure sulfur trioxide gas in a primary reaction tower to obtain gaseous chlorosulfonic acid; the reaction temperature in the primary reaction tower was 230 ℃.
S13: condensing the gaseous chlorosulfonic acid, then feeding the condensed gaseous chlorosulfonic acid into a secondary reaction tower, and fully reacting a byproduct in the primary reaction tower with excessive sulfur trioxide and hydrogen chloride to further generate chlorosulfonic acid.
Respectively absorbing excessive sulfur trioxide and hydrogen chloride tail gas, wherein the hydrogen chloride returns to the hydrochloric acid absorption tower, and other waste gases are discharged. Condensing chlorosulfonic acid, removing impurities and separating to obtain a finished product of chlorosulfonic acid; the tail gas is washed by sulfuric acid and then enters an original hydrochloric acid absorption device, and is absorbed by two times of washing by dilute acid and water without increasing emission.
(2) Preparation of para-ester
S21: adding 100mol of preset chlorosulfonic acid and 45.5mol of acetanilide into a low-temperature sulfonation pot for reaction; the feeding temperature is controlled at 30 ℃, and the feeding time is 4.6 hours; after the feeding is finished, maintaining for 4 hours, and controlling the temperature at 30 ℃;
transferring the sulfonated substance prepared in the low-temperature sulfonation pot into a high-temperature sulfonation pot for high-temperature sulfonation; the temperature of high-temperature sulfonation is 46 ℃, and the sulfonation is maintained for 1 hour;
adding 47mol of thionyl chloride for reaction, controlling the time for adding the thionyl chloride to be 4.6 hours, maintaining the temperature at 57 ℃ for 3 hours after the thionyl chloride is added, cooling to 42 ℃, discharging, diluting the sulfonated substance, and performing suction filtration.
The molar ratio of acetanilide, chlorosulfonic acid and thionyl chloride was 0.455:1: 0.47.
S22: adding pyronitrite, adjusting the stable pH value to 7.5 by using liquid alkali, and carrying out reduction reaction to obtain reducing liquid;
s23: pouring 100mol of high-temperature reducing liquid into a condensation pot, sealing the condensation pot, vacuumizing (the negative pressure is-0.01 MPa), closing a vacuum valve, filling nitrogen, heating to 55 ℃, starting a material circulating pump, and adding 0.14mol of sodium phosphate;
the ethylene oxide feed tube was flushed with nitrogen to prevent plugging. 52.6mol of ethylene oxide is added, a dilute acid feeding valve is opened, and the pH value is controlled to be 7.8 during the ethylene oxide adding process, so that partial acid or partial alkali is not allowed. The temperature was controlled at 50 ℃. The epoxy time is 4 hours;
after the ethylene oxide is added, the temperature is raised to 50 ℃ and maintained for 4 hours, and the pH value is always maintained in an alkaline environment in the maintaining process. After the maintenance, sampling and analysis are finished, and after the sample is qualified, circulating water is started to cool to 28 ℃ for discharging.
Reducing liquid: ethylene oxide: the molar ratio of sodium phosphate is 1: 0.526: 0.0014.
s24: and (4) carrying out suction filtration on the condensation product, and adding sulfuric acid into the product after suction filtration to carry out esterification reaction. Adding 100mol of condensation centrifugal material, feeding dry powder, simultaneously opening an oil valve to feed oil, keeping the oil temperature at 210 ℃, stirring for 14 minutes, slowly adding 106mol of 100% acid, starting timing and keeping for 2 hours when the material is to be dry powder, then sampling, and discharging after the material is qualified;
condensation product and condensation product: the molar ratio of 100% sulfuric acid was 1: 1.06.
S25: and crushing and packaging the product after the esterification reaction to prepare the para-ester.
The yield of the para-ester prepared in example 6 was measured to obtain the yield of this example of 83%.
Example 7
(1) Preparation of chlorosulfonic acid
S11: in the chlorosulfonation link in the para-ester synthesis process, the generated hydrogen chloride gas is absorbed by an original HCl absorption tower, preheated and enters an analytical tower, and cooled and dried to generate pure hydrogen chloride gas;
s12: reacting hydrogen chloride gas resolved from hydrochloric acid with pure sulfur trioxide gas in a primary reaction tower to obtain gaseous chlorosulfonic acid; the reaction temperature in the primary reaction column was 210 ℃.
S13: condensing the gaseous chlorosulfonic acid, then feeding the condensed gaseous chlorosulfonic acid into a secondary reaction tower, and fully reacting a byproduct in the primary reaction tower with excessive sulfur trioxide and hydrogen chloride to further generate chlorosulfonic acid.
Respectively absorbing excessive sulfur trioxide and hydrogen chloride tail gas, wherein the hydrogen chloride returns to the hydrochloric acid absorption tower, and other waste gases are discharged. Condensing chlorosulfonic acid, removing impurities and separating to obtain a finished product of chlorosulfonic acid; the tail gas is washed by sulfuric acid and then enters an original hydrochloric acid absorption device, and is absorbed by two times of washing by dilute acid and water without increasing emission.
(2) Preparation of para-ester
S21: adding 100mol of preset chlorosulfonic acid and 45mol of acetanilide into a low-temperature sulfonation pot for reaction; the feeding temperature is controlled to be 35 ℃, and the feeding time is 4.8 hours; after the feeding is finished, maintaining for 5 hours, and controlling the temperature at 32 ℃;
transferring the sulfonated substance prepared in the low-temperature sulfonation pot into a high-temperature sulfonation pot for high-temperature sulfonation; the temperature of high-temperature sulfonation is 48 ℃, and the sulfonation is maintained for 1 hour;
adding 46.5mol of thionyl chloride for reaction, controlling the time for adding the thionyl chloride to be 4.6 hours, maintaining the temperature at 60 ℃ for 3 hours after the thionyl chloride is added, cooling to 45 ℃, discharging, diluting the sulfonated substance, and performing suction filtration.
The molar ratio of acetanilide, chlorosulfonic acid and thionyl chloride is 0.45:1: 0.465.
S22: adding pyronitrite, adjusting the stable pH value to 7.5 by using liquid alkali, and carrying out reduction reaction to obtain reducing liquid;
s23: pouring 100mol of high-temperature reducing liquid into a condensation pot, sealing the condensation pot, vacuumizing (the negative pressure is-0.01 MPa), closing a vacuum valve, filling nitrogen, heating to 60 ℃, starting a material circulating pump, and adding 0.14mol of sodium phosphate;
the ethylene oxide feed tube was flushed with nitrogen to prevent plugging. 52.8mol of ethylene oxide is added, a dilute acid feeding valve is opened, and the pH value is controlled to be 7.8 during the ethylene oxide adding process, so that partial acid or partial alkali is not allowed. The temperature was controlled at 50 ℃. The epoxy time is 4 hours;
after the ethylene oxide is added, the temperature is raised to 50 ℃ and maintained for 3 hours, and the pH value is always maintained in an alkaline environment in the maintaining process. After the maintenance, sampling and analysis are finished, and after the sample is qualified, circulating water is started to cool to 28 ℃ for discharging.
Reducing liquid: ethylene oxide: the molar ratio of sodium phosphate is 1: 0.528: 0.0014.
s24: and (4) carrying out suction filtration on the condensation product, and adding sulfuric acid into the product after suction filtration to carry out esterification reaction. Adding 100mol of condensation centrifugal material, feeding dry powder, simultaneously opening an oil valve to feed oil, keeping the oil temperature at 210 ℃, stirring for 16 minutes, slowly adding 105mol of 100% acid, starting timing and maintaining for 2 hours when the material is to be dry powder, then sampling, and discharging after the material is qualified;
condensation product and condensation product: the molar ratio of 100% sulfuric acid was 1: 1.05.
S25: and crushing and packaging the product after the esterification reaction to prepare the para-ester.
The yield of the para-ester prepared in example 7 was measured to obtain the yield of this example of 83%.
Example 8
(1) Preparation of chlorosulfonic acid
S11: in the chlorosulfonation link in the para-ester synthesis process, the generated hydrogen chloride gas is absorbed by an original HCl absorption tower, preheated and enters an analytical tower, and cooled and dried to generate pure hydrogen chloride gas;
s12: reacting hydrogen chloride gas resolved from hydrochloric acid with pure sulfur trioxide gas in a primary reaction tower to obtain gaseous chlorosulfonic acid; the reaction temperature in the primary reaction tower was 190 ℃.
S13: condensing the gaseous chlorosulfonic acid, then feeding the condensed gaseous chlorosulfonic acid into a secondary reaction tower, and fully reacting a byproduct in the primary reaction tower with excessive sulfur trioxide and hydrogen chloride to further generate chlorosulfonic acid.
Respectively absorbing excessive sulfur trioxide and hydrogen chloride tail gas, wherein the hydrogen chloride returns to the hydrochloric acid absorption tower, and other waste gases are discharged. Condensing chlorosulfonic acid, removing impurities and separating to obtain a finished product of chlorosulfonic acid; the tail gas is washed by sulfuric acid and then enters an original hydrochloric acid absorption device, and is absorbed by two times of washing by dilute acid and water without increasing emission.
(2) Preparation of para-ester
S21: adding 100mol of preset chlorosulfonic acid and 46mol of acetanilide into a low-temperature sulfonation pot for reaction; the feeding temperature is controlled to be 35 ℃, and the feeding time is 5 hours; after the feeding is finished, maintaining for 5 hours, and controlling the temperature at 35 ℃;
transferring the sulfonated substance prepared in the low-temperature sulfonation pot into a high-temperature sulfonation pot for high-temperature sulfonation; the temperature of high-temperature sulfonation is 48 ℃, and the sulfonation is maintained for 1 hour;
adding 46.5mol of thionyl chloride for reaction, controlling the time for adding the thionyl chloride to be 4.6 hours, maintaining the temperature at 60 ℃ for 2 hours after the thionyl chloride is added, cooling to 50 ℃, discharging, diluting the sulfonated substance, and performing suction filtration.
The molar ratio of acetanilide, chlorosulfonic acid and thionyl chloride was 0.46:1: 0.465.
S22: adding pyronitrite, adjusting the stable pH value to 7.5 by using liquid alkali, and carrying out reduction reaction to obtain reducing liquid;
s23: pouring 100mol of high-temperature reducing liquid into a condensation pot, sealing the condensation pot, vacuumizing (the negative pressure is-0.01 MPa), closing a vacuum valve, filling nitrogen, heating to 60 ℃, starting a material circulating pump, and adding 0.14mol of sodium phosphate;
the ethylene oxide feed tube was flushed with nitrogen to prevent plugging. 53mol of ethylene oxide is added, a dilute acid feeding valve is opened, and the pH value is controlled to be 7.8 during the ethylene oxide adding process, so that partial acid or partial alkali is not allowed. The temperature was controlled at 50 ℃. The epoxy time is 4 hours;
after the ethylene oxide is added, the temperature is raised to 50 ℃ and maintained for 3 hours, and the pH value is always maintained in an alkaline environment in the maintaining process. After the maintenance, sampling and analysis are finished, and after the sample is qualified, circulating water is started to cool to 28 ℃ for discharging.
Reducing liquid: ethylene oxide: the molar ratio of sodium phosphate is 1: 0.53: 0.0014.
s24: and (4) carrying out suction filtration on the condensation product, and adding sulfuric acid into the product after suction filtration to carry out esterification reaction. Adding 100mol of condensation centrifugal material, feeding dry powder, simultaneously opening an oil valve to feed oil, keeping the oil temperature at 210 ℃, stirring for 10 minutes, slowly adding 105mol of 100% acid, starting timing and maintaining for 2 hours when the material is to be dry powder, then sampling, and discharging after the material is qualified;
condensation product and condensation product: the molar ratio of 100% sulfuric acid was 1: 1.05.
S25: and crushing and packaging the product after the esterification reaction to prepare the para-ester.
The yield of the para-ester prepared in example 8 was measured to obtain the yield of 82% in this example.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A para-ester synthesis process for recycling hydrogen chloride is characterized by comprising the following steps:
(1) preparing chlorosulfonic acid;
s11: in the chlorosulfonation step in the sulfonation reaction kettle, the generated hydrogen chloride gas is absorbed by an original HCl absorption tower and then preheated to enter an analytical tower, so that pure hydrogen chloride gas is generated;
s12: reacting the hydrogen chloride gas obtained by resolving hydrochloric acid with pure sulfur trioxide gas in a primary reaction tower to obtain gaseous chlorosulfonic acid;
s13: condensing the gaseous chlorosulfonic acid, then feeding the condensed gaseous chlorosulfonic acid into a secondary reaction tower, fully reacting a side reaction product in the primary reaction tower with excessive sulfur trioxide and hydrogen chloride to further generate chlorosulfonic acid, and absorbing the residual hydrogen chloride tail gas and then feeding the residual hydrogen chloride tail gas into the original HCl absorption tower again;
(2) preparing para-ester;
adding chlorosulfonic acid and acetanilide with set amount into the sulfonation reaction kettle, reacting to obtain a sulfonated substance, adding thionyl chloride, and reacting to prepare a chlorosulfonated substance; diluting and filtering, then carrying out reduction reaction, condensation reaction and esterification reaction, finally crushing and packaging the product after esterification reaction, and preparing the para-ester.
2. The process for synthesizing para-ester by recycling hydrogen chloride according to claim 1, wherein the reaction temperature in the primary reaction tower is 110-230 ℃.
3. The process for synthesizing esters of para-position by recycling hydrogen chloride as claimed in claim 1 or 2, wherein in step S12, the corresponding formula of the first reaction is as follows:
SO3+HCl＝HSO3heat of Cl + ion
2HSO3Cl+SO3＝S2O5Cl2+H2SO4
S2O5Cl2+H2SO4＝HS2O5Cl2 ++HSO4 -
Among them, HS2O5Cl2 +And HSO4 -Is the byproduct.
4. The process for synthesizing esters of para-position by recycling hydrogen chloride as claimed in any of claims 1 to 3, wherein in step S13, the by-product reacts with hydrogen chloride gas to generate chlorosulfonic acid, and the secondary reaction corresponds to the following formula:
HS2O5Cl2 ++HSO4 -＝3HSO3Cl。
5. the process for synthesizing esters of para-position by recycling hydrogen chloride as claimed in any of claims 1 to 4, wherein the molar ratio of acetanilide, chlorosulfonic acid and thionyl chloride is 0.45-0.46: 1: 0.46-0.47.
6. The process for synthesizing para-ester by recycling hydrogen chloride according to any one of claims 1 to 5, wherein the preparation of the chlorosulfide comprises the following steps:
adding chlorosulfonic acid and acetanilide into a low-temperature sulfonation pot to react to obtain a sulfonated substance; the feeding temperature is controlled to be 25-35 ℃, and the feeding time is 4-5 hours; after the feeding is finished, maintaining for 4-5 hours, and controlling the temperature at 25-35 ℃;
transferring the sulfonated substance prepared in the low-temperature sulfonation pot into a high-temperature sulfonation pot for high-temperature sulfonation; the temperature of the high-temperature sulfonation is 45-48 ℃, and the high-temperature sulfonation is maintained for 1-2 hours;
and adding thionyl chloride for reaction, controlling the time to be 4-5 hours, maintaining the temperature at 55-60 ℃ for 2-3 hours after the thionyl chloride is added, and cooling to 40-50 ℃ for discharging.
7. The process for the synthesis of para-ester by recycling hydrogen chloride according to any of claims 1 to 6, wherein the condensation reaction comprises the steps of:
pumping the reducing solution into a condensation reaction device, vacuumizing, closing a vacuum valve, filling nitrogen, heating to 55-60 ℃ and adding a set amount of sodium phosphate, wherein the pressure in the pot is positive;
adding ethylene oxide, controlling the reaction temperature at 45-50 ℃, and controlling the time for adding the ethylene oxide at 3-4 hours;
and after the ethylene oxide is added, heating to 50 ℃ and maintaining for 3-4 hours, sampling and analyzing after maintaining, and discharging when the circulating water is cooled to 25-30 ℃ after the circulating water is qualified.
8. The process for synthesizing para-ester by recycling hydrogen chloride according to claim 7, wherein the reducing solution: ethylene oxide: molar ratio of sodium phosphate, 1: 0.52-0.53: 0.0014.
9. the process for synthesizing para-ester by recycling hydrogen chloride according to claims 1-8, wherein the esterification reaction comprises the following steps: slowly adding sulfuric acid into the condensation compound, stirring for 8-16 minutes at the temperature of 200-.
10. The process for synthesizing para-ester by recycling hydrogen chloride according to claim 9, wherein the molar ratio of the condensate to sulfuric acid is 1: 1.03-1.06.
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| 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 |
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Address after: No.146, Hanjin Avenue, Shayang Town, Shayang County, Jingmen City, Hubei Province 448200 Applicant after: Hubei Likangyuan Chemical Co.,Ltd. Address before: 448200 Shayang County Economic Development Zone, Jingmen City, Hubei Province Applicant before: Jingmen likanyuan Textile Technology Co.,Ltd. |
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