CN104496866A - Continuous sulfonating process for synthesizing p-aminophenyl-beta-hydroxyethyl sulfone sulphate - Google Patents
Continuous sulfonating process for synthesizing p-aminophenyl-beta-hydroxyethyl sulfone sulphate Download PDFInfo
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Abstract
The invention discloses a continuous sulfonating process for synthesizing p-aminophenyl-beta-hydroxyethyl sulfone sulphate. The process comprises the steps: performing reaction on chlorosulfonic acid and acetanilide which serve as raw materials; respectively atomizing chlorosulfonic acid and molten-state acetanilide and contacting with each other during feeding to perform reaction. According to the continuous sulfonating process for synthesizing p-aminophenyl-beta-hydroxyethyl sulfone sulphate, the molten-state acetanilide is used as a raw material, and the reaction on the acetanilide in an atomizing state and chlorosulfonic acid which is also in an atomizing state are carried out and the reaction temperature is easily controlled, so that the production of byproducts such as parachloroaniline is avoided, and the conversion rate of acetanilide serving as a raw material is high. The process is convenient to operate, short in production period, controllable in reaction process, less in labor demands, low in cost and easy for industrial production.
Description
Technical field
The present invention relates to the production technical field of dyestuff intermediate, be specifically related to a kind of continuous process for sulfonation synthesizing p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester.
Background technology
P-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester is important organic raw material and reactive dyestuffs intermediate, is widely used, as the manufacture of Reactive dye red M-3BE, reactive red 3BS, Reactive blue 3GF etc.
About p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester technical study existing more patent, bibliographical information both at home and abroad, if publication number is disclose beta-hydroxyethyl sulfuryl aniline by being 1:1 ~ 1.2 in the Chinese patent literature of CN1869017A and sulfuric acid mixes by mol ratio, obtain reaction material, reaction material is carried out dry solidification in 110 ~ 200 DEG C, obtain cured article, described cured article in 150 ~ 180 DEG C of Depressor response 4-7 hour, obtains described product in movable reactor, and for example publication number is the production method that the Chinese patent of CN101520359A discloses a kind of p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, the method is by p-Nitrophenyl chloride, mercaptoethanol adds in DMF, slowly add sodium hydroxide again, the mol ratio of four is 1:1-1.2:1.5-2:1, 3-5h is reacted again after adding sodium hydroxide, temperature of reaction is 50-80 DEG C, enter to filter, underpressure distillation, obtain primary product, by this primary product, tungstate, hydrogen peroxide, add stills for air blowing, 1-3h is reacted at 95-100 DEG C, through cooling, crystallization, vacuum filtration isolates oxidizing and crystallizing material, oxidizing and crystallizing material is again through hydrogenation reaction, esterification obtains p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester.
At present, the sulfonation operation many employings interrupter method in domestic and international p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester production:
First the chlorsulfonic acid measured is added in sulphonation kettle, again the Acetanilide measured (antifebrin) is dropped in sulphonation kettle and react, sulfonation reaction is thermopositive reaction, with the icy salt solution of less than-10 DEG C during refrigeration, lowered the temperature by jacket reactor, control temperature, reaction is carried out smoothly, a large amount of hydrogen chloride gas is had in reaction process, design adopts secondary water to absorb, the industrial hydrochloric acid of hydrogen chloride gas water-soluble production 30-31%, feed intake control temperature about 45 degree, charging time 3 hours, feed intake complete, keep thermotonus 2 hours, then thionyl chloride is dripped, carry out chlorosulphonation, drip thionyl chloride control temperature about 45 degree, within about 3 hours, add, add reaction 2 hours, then dilution hydrolysis in frozen water is joined.
In the production process of this operation periodical operation existing problems have following some:
1, interrupter method reaction, raw material Acetanilide needs first to cut into slices as chip solid through overcooling, then slowly solid is joined in sulphonation kettle and react with chlorsulfonic acid, solid first will dissolve and react, local can produce heat, cause local reaction temperature too high, thus cause by product p-Chlorobenzoic acid amide to exceed standard, not only increase energy consumption but also affect conversion rate of products;
2, the reaction mass transfer weak effect of interrupter method, temperature is not easy to control, and the waste gas of generation is not easy to get rid of;
3, interrupter method long reaction time, increases the production cycle, there is the shortcoming that synthesis cost is higher.
Therefore, develop a kind of p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester process for sulfonation that can realize operate continuously and there is important Practical significance.
Summary of the invention
The invention provides a kind of continuous process for sulfonation synthesizing p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, this technique with the Acetanilide of molten state for raw material, react with atomizing state and the chlorsulfonic acid being all atomizing state, temperature of reaction easily controls, avoid the generation of by product p-Chlorobenzoic acid amide, and raw material Acetanilide transformation efficiency is high.This technological operation is easy, with short production cycle, reaction process is controlled, artificial demand is few, cost is low, is easy to suitability for industrialized production.
Synthesize a continuous process for sulfonation for p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, comprise with chlorsulfonic acid and Acetanilide for raw material reacts, when feeding intake, the Acetanilide of chlorsulfonic acid and molten state is contacted respectively after atomization and carry out described reaction.
First Acetanilide is placed on temperature and remains in the medial launder of about 125 DEG C, keep its molten state, sulfonation batching kettle is got to by fresh feed pump again by flow director, sulfonation batching kettle is sprayed into continuously to be atomized shape through the second atomization sparger, ensure the good dispersity of material, the design specification of this atomization sparger is according to material matching Design, and matching is good, effectively ensures chlorsulfonic acid and the abundant contact reacts of Acetanilide.Key in this technique is wanted to guarantee that Acetanilide is in molten state exactly, otherwise cannot realize the continuous operation of this technology.
Carry out sulfonation reaction after described chlorsulfonic acid contacts with Acetanilide, after sulfonation reaction, then carry out chlorosulfonation with thionyl chloride, concrete steps are as follows:
A, chlorsulfonic acid spray into sulfonation batching kettle through the first atomization sparger continuously to be atomized shape; The Acetanilide of melting sprays into sulfonation batching kettle through the second atomization sparger continuously react be atomized shape, is circulated in reaction process by recycle pump maintenance material between sulfonation batching kettle and still external heat exchanger;
B, when sulfonation batching kettle liquid level reaches predetermined height, material enters the ripe still of sulfonation and reacts, and chlorsulfonic acid is added in the consumption according to Acetanilide in reaction process;
C, when the ripe still liquid level of sulfonation reaches predetermined height, material enters sulfonation intensification still, and material completes described sulfonation reaction after reacting by heating;
D, when sulfonation intensification still liquid level reaches predetermined height, material enters chlorosulphonation still and reacts with the thionyl chloride instilled continuously;
E, when chlorosulphonation still liquid level reaches predetermined height, material enters the ripe still of chlorosulphonation and reacts, until complete described chlorosulfonation.
Relevant chemical reaction equation of the present invention is as follows:
1. sulfonation reaction:
2. chlorosulfonation
Reaction 1:
Reaction 2:
The present invention adopts continuous sulfonation method to synthesize p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, operational path is: with the Acetanilide of melting and chlorsulfonic acid for starting raw material, first be atomized, then successively through oversulfonate batching kettle, the ripe still of sulfonation, sulfonation intensification still carries out sulfonation reaction, then through chlorosulphonation still, drip thionyl chloride, complete the whole production process of continuous sulfonation through the ripe still of chlorosulphonation.By overcoming trivial operations in traditional technology to the particular design of sulfonation reaction still and the optimization of technique, the production cycle is long, and raw material Acetanilide charge temperature is wayward, easily emits pot, and artificial demand is large, the defect that cost is high.
In the present invention, described sulfonation batching kettle is batching kettle is also reactor, utilizes recycle pump ceaselessly recycle stock, controls reaction carry out promoting reaction under optimum temps by cycle heat exchange.
Continuous sulfonation reaction is mainly at sulfonation batching kettle, the ripe still of sulfonation, sulfonation intensification still, chlorosulphonation still, carry out in the ripe still of chlorosulphonation, chlorsulfonic acid and Acetanilide enter reaction by the atomization sparger above sulfonation batching kettle, non-reacted parts can enter the ripe still of sulfonation by predetermined spout, sulfonation intensification still reacts again, and therefore in whole continuous sulfonation reaction, the mass ratio of chlorsulfonic acid and Acetanilide is 2.21 ~ 3.88:1.
As preferably, in steps A, to be atomized the mass ratio of chlorsulfonic acid that shape sprays into continuously and Acetanilide for 1.29 ~ 3.88:1.
In step B, from the material in sulfonation batching kettle, wherein only have a small amount of Acetanilide not react completely, need to proceed reaction in the ripe still of sulfonation, chlorsulfonic acid is added in the consumption according to Acetanilide in reaction process.Through sampling analysis, in material during the non-completely consumed of Acetanilide, can add chlorsulfonic acid and react with Acetanilide further, as preferably, in the ripe still of sulfonation, required chlorsulfonic acid is 0.005 ~ 0.016:1 with the mass ratio from the material of sulfonation batching kettle; The liquid level of the ripe still of sulfonation reaches predetermined height required time and is about 1 ~ 4h.
In the present invention, the temperature of reaction of described sulfonation batching kettle is 10 ~ 50 DEG C, and pressure is-0.01 ~-0.1MPa; The temperature of reaction of the ripe still of sulfonation is 10 ~ 50 DEG C, and pressure is-0.01 ~-0.1MPa; The temperature of reaction of sulfonation intensification still is 50 ~ 60 DEG C, and pressure is-0.01 ~-0.1MPa.
As preferably, the temperature in sulfonation batching kettle and the ripe still of sulfonation is 35 ~ 50 DEG C, and pressure is-0.02 ~-0.06MPa; Temperature of reaction in sulfonation intensification still is 55 DEG C, and pressure is-0.02 ~-0.06MPa.
Liquid level in sulfonation intensification still reaches predetermined height required time and is about 1 ~ 4h, then enters chlorosulphonation still, and in still, the quality that thionyl chloride drips is 0.55 ~ 1.66:1 with the mass ratio from sulfonation intensification still material, and preferred mass ratio is 0.55 ~ 1.38:1.
Liquid level in chlorosulphonation still reaches predetermined height required time at 2 ~ 6h, and then enter the ripe still of chlorosulphonation, in still, liquid level reaches predetermined height required time is 2 ~ 6h.
As preferably, the temperature of reaction of described chlorosulphonation still is 20 ~ 70 DEG C, and pressure is-0.01 ~-0.1Mpa; The temperature of reaction of the ripe still of chlorosulphonation is 20 ~ 70 DEG C, and pressure is-0.01 ~-0.1Mpa.Further preferably, chlorosulfonation temperature is 30 DEG C ~ 50 DEG C, and pressure is-0.02 ~-0.06MPa.
As preferably, described Acetanilide flow control is at 600kg/h, and pass into chlorsulfonic acid flow control in sulfonation batching kettle at 900 ~ 2700kg/h, thionyl chloride flow control is at 526 ~ 1585kg/h.
In the present invention, the predetermined height in each still is all arranged on the position of the automatic spout of this still; The waste gas produced in above-mentioned each step reaction all enters absorption unit and absorbs.
In the present invention, sulfonation batching kettle, the ripe still of sulfonation, the reaction between sulfonation intensification still influences each other, works in coordination with mutually; Chlorosulphonation still, the reaction between the ripe still of chlorosulphonation is also collaborative mutually promotion, can realize steadily carrying out of continuous reaction like this, avoid interrupter method processing ease and emit the phenomenon of pot to occur.
The material obtained after above-mentioned continuous process for sulfonation enters medial launder, and then through frozen water dilution, press filtration, sub-reduction, condensation, esterification, the operations such as pulverizing, obtain final product.
Compared with prior art, the present invention has the following advantages:
The present invention adopts the Acetanilide continuously feeding of molten state, and with chlorsulfonic acid successive reaction, the process that liquid Acetanilide does not dissolve, temperature of reaction is relatively more steady, greatly reduces the generation of forbidding arylamine p-Chlorobenzoic acid amide, guarantees that quality product meets environmental requirement.By the design of special atomization distributor device, reaction mass Acetanilide and chlorsulfonic acid are increased mass transfer effect in sulfonation batching kettle, fully contacts, to ensure carrying out completely of described continuous sulfonation reaction, further increase the transformation efficiency of reaction.
Present invention achieves the serialization of whole set process, consider from technical standpoint, the Acetanilide of molten state must be adopted by flow director and chlorsulfonic acid continuously feeding, continuous processing can be realized produce by the technological design of advanced person, shorten the production cycle, adopt Automated condtrol simultaneously, make p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester process for sulfonation have brand-new development; Consider from the angle of economy, decrease manually, shorten reaction time, reduce cost to a certain extent; Consider from the angle of environment, whole process for sulfonation adopts continuous closed production, environmentally friendly.Continuous sulfonation method is easy and simple to handle, and sulfonation reaction transformation efficiency is high, and the production cycle shortens more than 80%, and charging simultaneously easily controls, and artificial demand is few, and security is high, and cost is low.
Accompanying drawing explanation
Fig. 1 is the schema of the continuous process for sulfonation of synthesis p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester;
In figure, 1-Acetanilide transfer tank, 2-Acetanilide fresh feed pump, 3-sulfonation circulation heat exchanger, 4-sulfonation recycle pump, 5-sulfonation batching kettle, the ripe still of 6-sulfonation, 7-sulfonation intensification still, 8-chlorosulphonation still, the ripe still of 9-chlorosulphonation, 10-sulfonated bodies medial launder, a-Acetanilide feed-pipe, b-chlorsulfonic acid feed-pipe, c-first is atomized sparger, and d-second is atomized sparger, the automatic outlet pipe of e-sulfonation material, f-deicing water dilution still, g-thionyl chloride filling tube, h-removes spareslots.
Embodiment
By the following specific examples further illustrate the invention:
Embodiment 1
Open sulfonation recycle pump 4, chlorsulfonic acid flow is regulated to be 1500kg/h, sulfonation batching kettle 5 is got to from chlorsulfonic acid transfer tank by fresh feed pump by chlorsulfonic acid feed-pipe b, the still mouth entering sulfonation batching kettle is equipped with the first atomization sparger c, instantaneously chlorsulfonic acid can be atomized, it is made to spray into sulfonation batching kettle 5 to be atomized shape, regulate the flow of the Acetanilide of melting to be 600kg/h simultaneously, sulfonation batching kettle 5 is got to from Acetanilide transfer tank 1 by Acetanilide fresh feed pump 2 by Acetanilide feed-pipe a, the still mouth entering sulfonation batching kettle is equipped with the second atomization sparger d, instantaneously Acetanilide can be atomized, it is made to spray into sulfonation batching kettle 5 to be atomized shape, the chlorsulfonic acid of atomization and Acetanilide contact reacts in sulfonation batching kettle 5 of atomization, open the outer sulfonation circulation heat exchanger 3 connected of sulfonation batching kettle 5, in control interchanger, temperature of charge is at 35 DEG C, ceaselessly recycle stock, open waste gas absorbing system simultaneously, absorb the hydrogen chloride gas produced, after 1 hour, sulfonation material liquid level rises to automatic spout, enter the ripe still 6 of sulfonation, open the chuck water coolant of the ripe still of sulfonation, control temperature of charge 35 DEG C, stirring reaction, sampling detects sulfonation terminal, if terminal to feed in raw material valve less than, the chlorsulfonic acid opened on the ripe still of sulfonation, control flow 10.5kg/h.Through 1.5 hours, material liquid level rises to automatic spout, material enters sulfonation intensification still 7, open sulfonation intensification still jacket steam, temperature of charge is made to rise to 55 DEG C, stirring reaction, after 1.5 hours, material liquid level rises to automatic spout, enter chlorosulphonation still 8, open thionyl chloride flow regulator, control flow is 600kg/h, by thionyl chloride filling tube g, thionyl chloride is passed into chlorosulphonation still 8, opening clamp jacket water, control temperature 50 DEG C, after 4 hours, material liquid level rises to automatic spout, enter the ripe still 9 of chlorosulphonation, continue stirring reaction, after 4 hours, material liquid level rises to automatic spout, material enters sulfonated bodies medial launder 10, wait frozen water dilutes.Frozen water 20 tons is put at frozen water dilution still, sulfonation material is slowly put into dilution, control flow 3500kg/h, dilution time 3 hours, dilute complete, enter pressure filter press filtration, collect filter cake and treat sub-reduction, in reduction kettle, add the sodium sulfite solution 4 tons of 27%, adjustment pH is 8-9, control temperature 20-30 DEG C, sulfonation filter cake is slowly added, be 8-9 with the liquid caustic soda solution control pH of 30% simultaneously, add filter cake, stirring reaction 1 hour, material is proceeded to condensation kettle, be warmed up to 65 DEG C, pass into oxyethane 800kg, within about 3 hours, add, period with 40% sulphur acid for adjusting pH be 8-9, after terminal arrives, condensation material is entered whizzer to filter, again that material is dry through flash distillation machine, obtain dry condensation material 4895kg, 1240kg condensation material is dropped into esterifying kettle, add the sulfuric acid 500kg of 100%, open steam and be warmed up to 170 DEG C, insulation reaction 3 hours, sampling analysis terminal, after terminal arrives, enter pulverizer and pulverize to obtain finished product.Product receipts amount 1433kg, yield 90.66%.
Embodiment 2
Open sulfonation recycle pump 4, chlorsulfonic acid flow is regulated to be 1500kg/h, sulfonation batching kettle 5 is got to from chlorsulfonic acid transfer tank by fresh feed pump by chlorsulfonic acid feed-pipe b, the still mouth entering sulfonation batching kettle is equipped with the first atomization sparger c, instantaneously chlorsulfonic acid can be atomized, it is made to spray into sulfonation batching kettle 5 to be atomized shape, regulate the flow of the Acetanilide of melting to be 600kg/h simultaneously, sulfonation batching kettle 5 is got to from Acetanilide transfer tank 1 by Acetanilide fresh feed pump 2 by Acetanilide feed-pipe a, the still mouth entering sulfonation batching kettle is equipped with the second atomization sparger d, instantaneously Acetanilide can be atomized, it is made to spray into sulfonation batching kettle 5 to be atomized shape, the chlorsulfonic acid of atomization and Acetanilide contact reacts in sulfonation batching kettle 5 of atomization, open the outer sulfonation circulation heat exchanger 3 connected of sulfonation batching kettle 5, in control interchanger, temperature of charge is at 40 DEG C, ceaselessly recycle stock, open waste gas absorbing system simultaneously, absorb the hydrogen chloride gas produced, after 1 hour, sulfonation material liquid level rises to automatic spout, enter the ripe still 6 of sulfonation, open the chuck water coolant of the ripe still of sulfonation, control temperature of charge 40 DEG C, stirring reaction, sampling detects sulfonation terminal, if terminal to feed in raw material valve less than, the chlorsulfonic acid opened on the ripe still of sulfonation, control flow 12kg/h.Through 1.5 hours, material liquid level rises to automatic spout, material enters sulfonation intensification still 7, open sulfonation intensification still jacket steam, temperature of charge is made to rise to 55 DEG C, stirring reaction, after 1.5 hours, material liquid level rises to automatic spout, enter chlorosulphonation still 8, open thionyl chloride flow regulator, control flow is 600kg/h, opening clamp jacket water, control temperature 50 DEG C, after 4 hours, material liquid level rises to automatic spout, enter the ripe still 9 of chlorosulphonation, continue stirring reaction, after 4 hours, material liquid level rises to automatic spout, material enters sulfonated bodies medial launder 10, wait frozen water dilutes.Frozen water 20 tons is put at frozen water dilution still, sulfonation material is slowly put into dilution, control flow 3500kg/h, dilution time 3 hours, dilute complete, enter pressure filter press filtration, collect filter cake and treat sub-reduction, in reduction kettle, add the sodium sulfite solution 4 tons of 27%, regulate PH8-9, control temperature 20-30 DEG C, sulfonation filter cake is slowly added, simultaneously with 30% liquid caustic soda solution control PH8-9, add filter cake, stirring reaction 1 hour, material is proceeded to condensation kettle, be warmed up to 65 DEG C, pass into oxyethane 800kg, about 3h adds, period with 40% sulfuric acid regulate PH8-9, after terminal arrives, condensation material is entered whizzer to filter, again that material is dry through flash distillation machine, obtain dry condensation material 4970kg, 1240kg condensation material is dropped into esterifying kettle, add the sulfuric acid 500kg of 100%, open steam and be warmed up to 170 DEG C, insulation reaction 3 hours, sampling analysis terminal, after terminal arrives, enter pulverizer and pulverize to obtain finished product.Product receipts amount 1433kg, yield 92.05%.
Embodiment 3
Open sulfonation recycle pump 4, chlorsulfonic acid flow is regulated to be 2000kg/h, sulfonation batching kettle 5 is got to from chlorsulfonic acid transfer tank by fresh feed pump by chlorsulfonic acid feed-pipe b, the still mouth entering sulfonation batching kettle is equipped with the first atomization sparger c, instantaneously chlorsulfonic acid can be atomized, it is made to spray into sulfonation batching kettle 5 to be atomized shape, regulate the flow of the Acetanilide of melting to be 600kg/h simultaneously, sulfonation batching kettle 5 is got to from Acetanilide transfer tank 1 by Acetanilide fresh feed pump 2 by Acetanilide feed-pipe a, the still mouth entering sulfonation batching kettle is equipped with the second atomization sparger d, instantaneously Acetanilide can be atomized, it is made to spray into sulfonation batching kettle 5 to be atomized shape, the chlorsulfonic acid of atomization and Acetanilide contact reacts in sulfonation batching kettle 5 of atomization, open the outer sulfonation circulation heat exchanger 3 connected of sulfonation batching kettle 5, in control interchanger, temperature of charge is at 40 DEG C, ceaselessly recycle stock, open waste gas absorbing system simultaneously, absorb the hydrogen chloride gas produced, after 1 hour, sulfonation material liquid level rises to automatic spout, enter the ripe still 6 of sulfonation, open the chuck water coolant of the ripe still of sulfonation, control temperature of charge 40 DEG C, stirring reaction, sampling detects sulfonation terminal, if terminal to feed in raw material valve less than, the chlorsulfonic acid opened on the ripe still of sulfonation, control flow 12kg/h.Through 1.5 hours, material liquid level rises to automatic spout, material enters sulfonation intensification still 7, open sulfonation intensification still jacket steam, temperature of charge is made to rise to 55 DEG C, stirring reaction, after 1.5 hours, material liquid level rises to automatic spout, enter chlorosulphonation still 8, open thionyl chloride flow regulator, control flow is 600kg/h, opening clamp jacket water, control temperature 50 DEG C, after 4 hours, material liquid level rises to automatic spout, enter the ripe still 9 of chlorosulphonation, continue stirring reaction, after 4 hours, material liquid level rises to automatic spout, material enters sulfonated bodies medial launder 10, wait frozen water dilutes.Frozen water 20 tons is put at frozen water dilution still, sulfonation material is slowly put into dilution, control flow 3500kg/h, dilution time 3 hours, dilute complete, enter pressure filter press filtration, collect filter cake and treat sub-reduction, in reduction kettle, add the sodium sulfite solution 4 tons of 27%, regulate PH8-9, control temperature 20-30 DEG C, sulfonation filter cake is slowly added, simultaneously with 30% liquid caustic soda solution control PH8-9, add filter cake, stirring reaction 1 hour, material is proceeded to condensation kettle, be warmed up to 65 DEG C, pass into oxyethane 800kg, within about 3 hours, add, period with 40% sulfuric acid regulate PH8-9, after terminal arrives, condensation material is entered whizzer to filter, again that material is dry through flash distillation machine, obtain dry condensation material 5083kg, 1240kg condensation material is dropped into esterifying kettle, add the sulfuric acid 500kg of 100%, open steam and be warmed up to 170 DEG C, insulation reaction 3 hours, sampling analysis terminal, after terminal arrives, enter pulverizer and pulverize to obtain finished product.Product receipts amount 1433kg, yield 94.14%.
Embodiment 4
Open sulfonation recycle pump 4, chlorsulfonic acid flow is regulated to be 2500kg/h, sulfonation batching kettle 5 is got to from chlorsulfonic acid transfer tank by fresh feed pump by chlorsulfonic acid feed-pipe b, the still mouth entering sulfonation batching kettle is equipped with the first atomization sparger c, instantaneously chlorsulfonic acid can be atomized, it is made to spray into sulfonation batching kettle 5 to be atomized shape, regulate the flow of the Acetanilide of melting to be 600kg/h simultaneously, sulfonation batching kettle 5 is got to from Acetanilide transfer tank 1 by Acetanilide fresh feed pump 2 by Acetanilide feed-pipe a, the still mouth entering sulfonation batching kettle is equipped with the second atomization sparger d, instantaneously Acetanilide can be atomized, it is made to spray into sulfonation batching kettle 5 to be atomized shape, the chlorsulfonic acid of atomization and Acetanilide contact reacts in sulfonation batching kettle 5 of atomization, open the outer sulfonation circulation heat exchanger 3 connected of sulfonation batching kettle 5, in control interchanger, temperature of charge is at 40 DEG C, ceaselessly recycle stock, open waste gas absorbing system simultaneously, absorb the hydrogen chloride gas produced, after 1 hour, sulfonation material liquid level rises to automatic spout, enter the ripe still 6 of sulfonation, open the chuck water coolant of the ripe still of sulfonation, control temperature of charge 40 DEG C, stirring reaction, sampling detects sulfonation terminal, if terminal to feed in raw material valve less than, the chlorsulfonic acid opened on the ripe still of sulfonation, control flow 12kg/h.Through 1.5 hours, material liquid level rises to automatic spout, material enters sulfonation intensification still 7, open sulfonation intensification still jacket steam, temperature of charge is made to rise to 55 DEG C, stirring reaction, after 1.5 hours, material liquid level rises to automatic spout, enter chlorosulphonation still 8, open thionyl chloride flow regulator, control flow is 600kg/h, opening clamp jacket water, control temperature 50 DEG C, after 4 hours, material liquid level rises to automatic spout, enter the ripe still 9 of chlorosulphonation, continue stirring reaction, after 4 hours, material liquid level rises to automatic spout, material enters sulfonated bodies medial launder 10, wait frozen water dilutes.Frozen water 20 tons is put at frozen water dilution still, sulfonation material is slowly put into dilution, control flow 3500kg/h, dilution time 3 hours, dilute complete, enter pressure filter press filtration, collect filter cake and treat sub-reduction, in reduction kettle, add the sodium sulfite solution 4 tons of 27%, regulate PH8-9, control temperature 20-30 DEG C, sulfonation filter cake is slowly added, simultaneously with 30% liquid caustic soda solution control PH8-9, add filter cake, stirring reaction 1 hour, material is proceeded to condensation kettle, be warmed up to 65 DEG C, pass into oxyethane 800kg, within about 3 hours, add, period with 40% sulfuric acid regulate PH8-9, after terminal arrives, condensation material is entered whizzer to filter, again that material is dry through flash distillation machine, obtain dry condensation material 4970kg, 1240kg condensation material is dropped into esterifying kettle, add the sulfuric acid 500kg of 100%, open steam and be warmed up to 170 DEG C, insulation reaction 3 hours, sampling analysis terminal, after terminal arrives, enter pulverizer and pulverize to obtain finished product.Product receipts amount 1433kg, yield 92.05%.
Embodiment 5
Open sulfonation recycle pump 4, chlorsulfonic acid flow is regulated to be 2000kg/h, sulfonation batching kettle 5 is got to from chlorsulfonic acid transfer tank by fresh feed pump by chlorsulfonic acid feed-pipe b, the still mouth entering sulfonation batching kettle is equipped with the first atomization sparger c, instantaneously chlorsulfonic acid can be atomized, it is made to spray into sulfonation batching kettle 5 to be atomized shape, regulate the flow of the Acetanilide of melting to be 600kg/h simultaneously, sulfonation batching kettle 5 is got to from Acetanilide transfer tank 1 by Acetanilide fresh feed pump 2 by Acetanilide feed-pipe a, the still mouth entering sulfonation batching kettle is equipped with the second atomization sparger d, instantaneously Acetanilide can be atomized, it is made to spray into sulfonation batching kettle 5 to be atomized shape, the chlorsulfonic acid of atomization and Acetanilide contact reacts in sulfonation batching kettle 5 of atomization, open the outer sulfonation circulation heat exchanger 3 connected of sulfonation batching kettle 5, in control interchanger, temperature of charge is at 45 DEG C, ceaselessly recycle stock, open waste gas absorbing system simultaneously, absorb the hydrogen chloride gas produced, after 1 hour, sulfonation material liquid level rises to automatic spout, enter the ripe still 6 of sulfonation, open the chuck water coolant of the ripe still of sulfonation, control temperature of charge 50 DEG C, stirring reaction, sampling detects sulfonation terminal, if terminal to feed in raw material valve less than, the chlorsulfonic acid opened on the ripe still of sulfonation, control flow 15kg/h.Through 1.5 hours, material liquid level rises to automatic spout, material enters sulfonation intensification still 7, open sulfonation intensification still jacket steam, temperature of charge is made to rise to 55 DEG C, stirring reaction, after 1.5 hours, material liquid level rises to automatic spout, enter chlorosulphonation 8, open thionyl chloride flow regulator, control flow is 700kg/h, opening clamp jacket water, control temperature 50 DEG C, after 4 hours, material liquid level rises to automatic spout, enter the ripe still 9 of chlorosulphonation, continue stirring reaction, after 4 hours, material liquid level rises to automatic spout, material enters sulfonated bodies medial launder 10, wait frozen water dilutes.Frozen water 20 tons is put at frozen water dilution still, sulfonation material is slowly put into dilution, control flow 3500kg/h, dilution time 3 hours, dilute complete, enter pressure filter press filtration, collect filter cake and treat sub-reduction, in reduction kettle, add the sodium sulfite solution 4 tons of 27%, regulate PH8-9, control temperature 20-30 DEG C, sulfonation filter cake is slowly added, simultaneously with 30% liquid caustic soda solution control PH8-9, add filter cake, stirring reaction 1 hour, material is proceeded to condensation kettle, be warmed up to 65 DEG C, pass into oxyethane 800kg, within about 3 hours, add, period with 40% sulfuric acid regulate PH8-9, after terminal arrives, condensation material is entered whizzer to filter, again that material is dry through flash distillation machine, obtain dry condensation material 5083kg, 1240kg condensation material is dropped into esterifying kettle, add the sulfuric acid 500kg of 100%, open steam and be warmed up to 170 DEG C, insulation reaction 3 hours, sampling analysis terminal, after terminal arrives, enter pulverizer and pulverize to obtain finished product.Product receipts amount 1433kg, yield 94.14%.
Embodiment 6
Open sulfonation recycle pump 4, chlorsulfonic acid flow is regulated to be 2500kg/h, sulfonation batching kettle 5 is got to from chlorsulfonic acid transfer tank by fresh feed pump by chlorsulfonic acid feed-pipe b, the still mouth entering sulfonation batching kettle is equipped with the first atomization sparger c, instantaneously chlorsulfonic acid can be atomized, it is made to spray into sulfonation batching kettle 5 to be atomized shape, regulate the flow of the Acetanilide of melting to be 600kg/h simultaneously, sulfonation batching kettle 5 is got to from Acetanilide transfer tank 1 by Acetanilide fresh feed pump 2 by Acetanilide feed-pipe a, the still mouth entering sulfonation batching kettle is equipped with the second atomization sparger d, instantaneously Acetanilide can be atomized, it is made to spray into sulfonation batching kettle 5 to be atomized shape, the chlorsulfonic acid of atomization and Acetanilide contact reacts in sulfonation batching kettle 5 of atomization, open the outer sulfonation circulation heat exchanger 3 connected of sulfonation batching kettle 5, in control interchanger, temperature of charge is at 50 DEG C, ceaselessly recycle stock, open waste gas absorbing system simultaneously, absorb the hydrogen chloride gas produced, after 0.5 hour, sulfonation material liquid level rises to automatic spout, enter the ripe still 6 of sulfonation, open the chuck water coolant of the ripe still of sulfonation, control temperature of charge 50 DEG C, stirring reaction, sampling detects sulfonation terminal, if terminal to feed in raw material valve less than, the chlorsulfonic acid opened on the ripe still of sulfonation, control flow 12kg/h.Through 1 hour, material liquid level rises to automatic spout, material enters sulfonation intensification still 7, open sulfonation intensification still jacket steam, temperature of charge is made to rise to 55 DEG C, stirring reaction, after 1 hour, material liquid level rises to automatic spout, enter chlorosulphonation still 8, open thionyl chloride flow regulator, control flow is 600kg/h, opening clamp jacket water, control temperature 45 DEG C, after 3.5 hours, material liquid level rises to automatic spout, enter the ripe still 9 of chlorosulphonation, continue stirring reaction, after 3.5 hours, material liquid level rises to automatic spout, material enters sulfonated bodies medial launder 10, wait frozen water dilutes.Frozen water 20 tons is put at frozen water dilution still, sulfonation material is slowly put into dilution, control flow 3500kg/h, dilution time 3 hours, dilute complete, enter pressure filter press filtration, collect filter cake and treat sub-reduction, in reduction kettle, add the sodium sulfite solution 4 tons of 27%, regulate PH8-9, control temperature 20-30 DEG C, sulfonation filter cake is slowly added, simultaneously with 30% liquid caustic soda solution control PH8-9, add filter cake, stirring reaction 1 hour, material is proceeded to condensation kettle, be warmed up to 65 DEG C, pass into oxyethane 800kg, within about 3 hours, add, period with 40% sulfuric acid regulate PH8-9, after terminal arrives, condensation material is entered whizzer to filter, again that material is dry through flash distillation machine, obtain dry condensation material 5120kg, 1240kg condensation material is dropped into esterifying kettle, add the sulfuric acid 500kg of 100%, open steam and be warmed up to 170 DEG C, insulation reaction 3 hours, sampling analysis terminal, after terminal arrives, enter pulverizer and pulverize to obtain finished product.Product receipts amount 1433kg, yield 94.84%.
Claims (8)
1. one kind is synthesized the continuous process for sulfonation of p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, comprise with chlorsulfonic acid and Acetanilide for raw material reacts, it is characterized in that, when feeding intake, the Acetanilide of chlorsulfonic acid and molten state is contacted respectively after atomization and carry out described reaction.
2. the continuous process for sulfonation of synthesis p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester according to claim 1, is characterized in that, carry out sulfonation reaction after described chlorsulfonic acid contacts with Acetanilide, after sulfonation reaction, then carries out chlorosulfonation with thionyl chloride.
3. the continuous process for sulfonation of synthesis p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester according to claim 2, it is characterized in that, concrete steps are as follows:
A, chlorsulfonic acid spray into sulfonation batching kettle through the first atomization sparger continuously to be atomized shape; The Acetanilide of melting sprays into sulfonation batching kettle through the second atomization sparger continuously react be atomized shape, is circulated in reaction process by recycle pump maintenance material between sulfonation batching kettle and still external heat exchanger;
B, when sulfonation batching kettle liquid level reaches predetermined height, material enters the ripe still of sulfonation and reacts, and chlorsulfonic acid is added in the consumption according to Acetanilide in reaction process;
C, when the ripe still liquid level of sulfonation reaches predetermined height, material enters sulfonation intensification still, and material completes described sulfonation reaction after reacting by heating;
D, when sulfonation intensification still liquid level reaches predetermined height, material enters chlorosulphonation still and reacts with the thionyl chloride instilled continuously;
E, when chlorosulphonation still liquid level reaches predetermined height, material enters the ripe still of chlorosulphonation and reacts, until complete described chlorosulfonation.
4. the continuous process for sulfonation of synthesis p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester according to claim 3, is characterized in that, in whole continuous sulfonation reaction, the mass ratio of chlorsulfonic acid and Acetanilide is 2.21 ~ 3.88:1.
5. the continuous process for sulfonation of synthesis p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester according to claim 4, is characterized in that, in steps A, to be atomized the mass ratio of chlorsulfonic acid that shape sprays into continuously and Acetanilide for 1.29 ~ 3.88:1.
6. the continuous process for sulfonation of synthesis p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester according to claim 3, is characterized in that, in step D, the thionyl chloride of instillation is 0.55 ~ 1.66:1 with the mass ratio from sulfonation intensification still material.
7. the continuous process for sulfonation of synthesis p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester according to claim 3, is characterized in that,
The temperature of reaction of described sulfonation batching kettle is 10 ~ 50 DEG C, and pressure is-0.01 ~-0.1MPa;
The temperature of reaction of the ripe still of described sulfonation is 10 ~ 50 DEG C, and pressure is-0.01 ~-0.1MPa;
The temperature of reaction of described sulfonation intensification still is 50 ~ 60 DEG C, and pressure is-0.01 ~-0.1MPa;
The temperature of reaction of described chlorosulphonation still is 20 ~ 70 DEG C, and pressure is-0.01 ~-0.1Mpa;
The temperature of reaction of the ripe still of described chlorosulphonation is 20 ~ 70 DEG C, and pressure is-0.01 ~-0.1Mpa.
8. the continuous process for sulfonation of synthesis p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester according to claim 3, it is characterized in that, described Acetanilide flow control is at 600kg/h, pass into chlorsulfonic acid flow control in sulfonation batching kettle at 900 ~ 2700kg/h, thionyl chloride flow control is at 526 ~ 1585kg/h.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107056663A (en) * | 2017-06-08 | 2017-08-18 | 新乡市锦源化工有限公司 | The synthetic method of para-ester |
| CN107266342A (en) * | 2017-08-04 | 2017-10-20 | 吴赣药业（苏州）有限公司 | A kind of industrial sulfanilamide (SN) production system |
| CN108440342A (en) * | 2018-03-15 | 2018-08-24 | 新乡市锦源化工有限公司 | Environment-friendly type is to the production method of beta-sulfuric ester ethyl sulfonyl aniline and to beta-sulfuric ester ethyl sulfonyl aniline |
| CN108440326A (en) * | 2018-04-23 | 2018-08-24 | 新乡市锦源化工有限公司 | The high-efficiency synthesis method and antifebrin of antifebrin |
| CN108465443A (en) * | 2018-04-23 | 2018-08-31 | 新乡市锦源化工有限公司 | The process units and system of the antifebrin route of para-ester |
| CN108530324A (en) * | 2018-06-12 | 2018-09-14 | 新乡市锦源化工有限公司 | The production technology and N-acetylsulfanilyl chloride of high-purity N-acetylsulfanilyl chloride |
| CN108640859A (en) * | 2018-06-12 | 2018-10-12 | 新乡市锦源化工有限公司 | The high-efficiency synthesis method and N-acetylsulfanilyl chloride of N-acetylsulfanilyl chloride |
| CN110724073A (en) * | 2019-10-28 | 2020-01-24 | 新乡市锦源化工有限公司 | Production process of p-acetamido-benzenesulfonyl chloride |
| CN111018753A (en) * | 2019-12-18 | 2020-04-17 | 荆门市丽康源纺织科技有限公司 | Para-ester synthesis process for recycling acetic acid |
| CN111039829A (en) * | 2019-12-09 | 2020-04-21 | 山东金德新材料有限公司 | Method for producing p-acetamido benzene sulfonyl chloride by two-temperature zone two-stage method based on continuous flow reaction |
| CN111056981A (en) * | 2019-12-18 | 2020-04-24 | 荆门市丽康源纺织科技有限公司 | Para-ester synthesis method and para-ester |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613308A (en) * | 2009-07-24 | 2009-12-30 | 重庆大学 | The method of synthesizing right-acetylsulphanilyl chloride with phosphorus pentachloride |
| CN102786446A (en) * | 2012-08-23 | 2012-11-21 | 楚源高新科技集团股份有限公司 | New production process for chlorosulfonation of para-ester by using thionyl chloride |
-
2014
- 2014-12-15 CN CN201410775922.XA patent/CN104496866B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613308A (en) * | 2009-07-24 | 2009-12-30 | 重庆大学 | The method of synthesizing right-acetylsulphanilyl chloride with phosphorus pentachloride |
| CN102786446A (en) * | 2012-08-23 | 2012-11-21 | 楚源高新科技集团股份有限公司 | New production process for chlorosulfonation of para-ester by using thionyl chloride |
Non-Patent Citations (3)
| Title |
|---|
| 关存钢等: "用雾化混合喷头使椰油醇与氯磺酸连续硫酸化", 《日用化学工业》 * |
| 崔林: "4-氨基苯基-β-羟乙基砜硫酸酯（对位酯）工艺改进研究", 《染料工业》 * |
| 王小泉: "喷雾法合成石油磺酸盐", 《中国优秀博士学位论文全文数据库 工程科技I辑》 * |
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| CN108440342A (en) * | 2018-03-15 | 2018-08-24 | 新乡市锦源化工有限公司 | Environment-friendly type is to the production method of beta-sulfuric ester ethyl sulfonyl aniline and to beta-sulfuric ester ethyl sulfonyl aniline |
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| CN108465443A (en) * | 2018-04-23 | 2018-08-31 | 新乡市锦源化工有限公司 | The process units and system of the antifebrin route of para-ester |
| CN108440326B (en) * | 2018-04-23 | 2020-10-20 | 新乡市锦源化工有限公司 | High-efficiency synthesis method of acetanilide and acetanilide |
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| CN110724073A (en) * | 2019-10-28 | 2020-01-24 | 新乡市锦源化工有限公司 | Production process of p-acetamido-benzenesulfonyl chloride |
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