CN104496866B - A kind of continuous process for sulfonation synthesizing p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester - Google Patents

A kind of continuous process for sulfonation synthesizing p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester Download PDF

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CN104496866B
CN104496866B CN201410775922.XA CN201410775922A CN104496866B CN 104496866 B CN104496866 B CN 104496866B CN 201410775922 A CN201410775922 A CN 201410775922A CN 104496866 B CN104496866 B CN 104496866B
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sulfonation
still
antifebrin
reaction
chlorosulfonic acid
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CN104496866A (en
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胡章云
杜志超
李学坤
陆建祥
李军
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Zhejiang Qicai Eco Technology Co Ltd
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Zhejiang Qicai Eco Technology Co Ltd
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Abstract

The invention discloses a kind of continuous process for sulfonation synthesizing p-Aminophenyl-β-hydroxyethyl sulfone sulfate, reacting for raw material including with chlorosulfonic acid and antifebrin, being contacted after atomization respectively by the antifebrin of chlorosulfonic acid and molten state when feeding intake carries out described reaction.The invention provides a kind of continuous process for sulfonation synthesizing p-Aminophenyl-β-hydroxyethyl sulfone sulfate, this technique is with the antifebrin of molten state as raw material, react with spray pattern and the chlorosulfonic acid being all spray pattern, reaction temperature is easily controlled, avoid the generation of accessory substance parachloroanilinum, and raw material antifebrin conversion ratio is high.This technological operation is easy, with short production cycle, reaction process is controlled, artificial demand is few, low cost, it is easy to industrialized production.

Description

A kind of continuous process for sulfonation synthesizing p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester
Technical field
The present invention relates to the production technical field of dyestuff intermediate, be specifically related to a kind of synthesis p-aminophenyl The continuous process for sulfonation of base-beta-hydroxyethyl sulfone sulfate.
Background technology
P-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester is important Organic Ingredients and reactive dye intermediate, It is widely used, as being used for manufacturing Reactive dye red M-3BE, active red 3BS, reactive blue 3GF etc..
About p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester technical study existing more patent, literary composition both at home and abroad Offer report, as the Chinese patent literature of Publication No. CN1869017A disclosed by by mol ratio Beta-hydroxyethyl sulfuryl aniline and sulfuric acid for 1:1~1.2 mix, and obtain reaction material, by reaction material in 110~200 DEG C are dried solidification, obtain solidfied material, described solidfied material in movable reactor in 150~180 DEG C of Depressor responses 4-7 hour, obtain described product;And for example Publication No. CN101520359A Chinese patent disclose the production method of a kind of p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, the method By paranitrochlorobenzene, mercaptoethanol adds in DMF, is slow added into NaOH, four rub That ratio is 1:1-1.2:1.5-2:1, reacts 3-5h after adding NaOH again, and reaction temperature is 50-80 DEG C, Enter to filter, decompression distillation, obtain primary product, by this primary product, tungstates, hydrogen peroxide, add Entering stills for air blowing, react 1-3h at 95-100 DEG C, cooled, crystallization, vacuum filtration isolates oxidation Crystallization material, the most hydrogenated reaction of oxidizing and crystallizing material, esterification obtains p-aminophenyl-beta-hydroxyethyl sulfone Sulfuric ester.
At present, the many employings of sulfonation operation during domestic and international p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester produces Batch process:
First the chlorosulfonic acid measured is added in sulphonation kettle, then the antifebrin measured (is brought down a fever Ice) put in sulphonation kettle and react, sulfonating reaction is exothermic reaction, with less than-10 DEG C during refrigeration Brine ice, lowered the temperature by jacket reactor, control temperature, make reaction be smoothed out, instead Having substantial amounts of hydrogen chloride gas during Ying, be designed with two grades of water and absorb, hydrogen chloride gas is dissolved in water Producing the industrial hydrochloric acid of 30-31%, feed intake control temperature about 45 degree, charging time 3 hours, Feed intake complete, keep thermotonus 2 hours, then drip thionyl chloride, carry out chlorosulfonation, dropping Thionyl chloride controls temperature about 45 degree, within about 3 hours, adds, and adds reaction 2 hours, then adds Enter in frozen water dilution hydrolysis.
In the production process of this operation intermittently operated existing problems have following some:
1, batch process reaction, it is chip solid that raw material antifebrin needs to first pass through cooling section, so After slowly solid is joined in sulphonation kettle and reacts with chlorosulfonic acid, solid first to dissolve and to react, locally again Heat can be produced, cause local reaction temperature too high, thus cause accessory substance parachloroanilinum to exceed standard, both Increase energy consumption and affect again conversion rate of products;
2, the reaction mass transfer weak effect of batch process, temperature is not easily controlled, and the waste gas of generation is not easy Get rid of;
3, the batch process reaction time is long, increases the production cycle, there is the shortcoming that synthesis is relatively costly.
Therefore, a kind of p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester sulphur that can realize continuous operation is developed Metallization processes has important Practical significance.
Summary of the invention
The invention provides a kind of continuous sulfonation work synthesizing p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester Skill, this technique is with the antifebrin of molten state as raw material, with spray pattern and the chlorine being all spray pattern Sulfonic acid reacts, and reaction temperature is easily controlled, it is to avoid the generation of accessory substance parachloroanilinum, and former Material antifebrin conversion ratio is high.This technological operation is easy, with short production cycle, reaction process is controlled, people Work demand is few, low cost, it is easy to industrialized production.
A kind of continuous process for sulfonation synthesizing p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, including with chlorine sulphur Acid and antifebrin are that raw material reacts, when feeding intake by the antifebrin of chlorosulfonic acid and molten state respectively Contact after atomization and carry out described reaction.
Antifebrin is first placed in the medial launder that temperature is maintained at about 125 DEG C, keeps it to melt State, then got to sulfonation batching kettle by feed pump by flow controller, through the second atomization distributor with Atomization shape sprays into sulfonation batching kettle continuously, it is ensured that the good dispersion of material, the design of this atomization distributor Specification is according to material matched design, and matching is good, chlorosulfonic acid is effectively ensured and is fully contacted with antifebrin Reaction.Key in this technique seeks to must assure that antifebrin is in molten condition, otherwise cannot Realize the continuous operation of this technology.
Described chlorosulfonic acid carries out sulfonating reaction after contacting with antifebrin, after sulfonating reaction, then with dichloro Sulfoxide carries out chlorosulfonation, specifically comprises the following steps that
A, chlorosulfonic acid spray into sulfonation batching kettle through the first atomization distributor continuously with atomization shape;Melt Antifebrin sprays into sulfonation batching kettle through the second atomization distributor continuously with atomization shape and reacts, reaction During by circulating pump keep material circulate between sulfonation batching kettle and still external heat exchanger;
B, when sulfonation batching kettle liquid level reaches predetermined altitude, material enter sulfonation maturation still react, In course of reaction, chlorosulfonic acid is added in the consumption according to antifebrin;
C, when sulfonation maturation still liquid level reaches predetermined altitude, material enter sulfonation intensification still, material warp Described sulfonating reaction is completed after adding thermal response;
D, when sulfonation intensification still liquid level reaches predetermined altitude, material enters chlorosulfonation still and instills continuously Thionyl chloride react;
E, when chlorosulfonation still liquid level reaches predetermined altitude, material enter chlorosulfonation maturation still react, Until completing described chlorosulfonation.
The relevant chemical equation of the present invention is as follows:
1. sulfonating reaction:
2. chlorosulfonation
Reaction 1:
Reaction 2:
The present invention uses continuous sulfonation method to synthesize p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, process route For: with melted antifebrin and chlorosulfonic acid as initiation material, first it is atomized, the most successively warp Crossing sulfonation batching kettle, sulfonation maturation still, sulfonation intensification still carries out sulfonating reaction, then through chlorosulfonation still, Dropping thionyl chloride, completes the whole production process of continuous sulfonation through chlorosulfonation maturation still.By to sulphur The optimization of the particular design and technique of changing reactor overcomes trivial operations in traditional handicraft, production cycle Long, raw material antifebrin charge temperature is wayward, easily emits pot, and artificial demand is big, and cost is high Defect.
In the present invention, described sulfonation batching kettle be batching kettle be also reactor, utilize circulating pump not The recycle stock stopped, controls reaction by cycle heat exchange and carries out promoting reaction under optimum temperature.
Sulfonating reaction is mainly in sulfonation batching kettle, sulfonation maturation still, sulfonation intensification still, chlorosulfonation continuously Still, is carried out in chlorosulfonation maturation still, and chlorosulfonic acid and antifebrin are divided by the atomization above sulfonation batching kettle Cloth device enters reaction, and non-reacted parts can be entered sulfonation maturation still, sulfonation intensification still by predetermined flow export Reacting, in the most whole continuous sulfonating reaction, chlorosulfonic acid with the mass ratio of antifebrin is again 2.21~3.88:1.
As preferably, in step A, to be atomized chlorosulfonic acid and the matter of antifebrin that shape sprays into continuously Amount ratio is 1.29~3.88:1.
In step B, the material in sulfonation batching kettle, the most a small amount of antifebrin No reaction is not completely, needs to proceed reaction in sulfonation maturation still, according to acetyl in course of reaction Chlorosulfonic acid is added in the consumption of aniline.Sampled analysis, when in material, antifebrin consumes the most completely, can Add chlorosulfonic acid to react with antifebrin further, as preferably, in sulfonation maturation still, required Chlorosulfonic acid be 0.005~0.016:1 with the mass ratio of material from sulfonation batching kettle;Sulfonation is ripe The liquid level of still reaches predetermined altitude required time and is about 1~4h.
In the present invention, the reaction temperature of described sulfonation batching kettle is 10~50 DEG C, pressure be-0.01~ -0.1MPa;The reaction temperature of sulfonation maturation still is 10~50 DEG C, and pressure is-0.01~-0.1MPa;Sulphur The reaction temperature changing intensification still is 50~60 DEG C, and pressure is-0.01~-0.1MPa.
As preferably, the temperature in sulfonation batching kettle and sulfonation maturation still is 35~50 DEG C, and pressure is -0.02~-0.06MPa;Reaction temperature in sulfonation intensification still is 55 DEG C, pressure be-0.02~ -0.06MPa。
Liquid level in sulfonation intensification still reaches predetermined altitude required time and is about 1~4h, subsequently into chlorine sulphur Changing still, in still, the quality of thionyl chloride dropping with the mass ratio from sulfonation intensification still material is 0.55~1.66:1, preferred mass ratio is 0.55~1.38:1.
Liquid level in chlorosulfonation still reaches predetermined altitude required time 2~6h, becomes subsequently into chlorosulfonation Ripe still, in still, liquid level reaches predetermined altitude required time is 2~6h.
As preferably, the reaction temperature of described chlorosulfonation still is 20~70 DEG C, pressure be-0.01~ -0.1Mpa;The reaction temperature of chlorosulfonation maturation still 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 antifebrin flow-control, at 600kg/h, is passed through in sulfonation batching kettle Chlorosulfonic acid flow-control is 900~2700kg/h, and thionyl chloride flow-control is 526~1585kg/h.
In the present invention, the predetermined altitude in each still is arranged at the position of the automatic flow export of this still;On State the waste gas produced in the reaction of each step all to enter absorption plant and absorb.
In the present invention, sulfonation batching kettle, sulfonation maturation still, the reaction between sulfonation intensification still influences each other, The most collaborative;Chlorosulfonation still, the reaction between chlorosulfonation maturation still is also the most collaborative promotion, such energy Enough realize steadily carrying out of continuous reaction, it is to avoid batch process processing ease emits the phenomenon of pot and occurs.
The material obtained after above-mentioned continuous process for sulfonation enters medial launder, then through frozen water dilution, pressure The operations such as filter, sub-reduction, be condensed, esterification, pulverizing, obtain end product.
Compared with prior art, the present invention has the following advantages:
The present invention uses the antifebrin continuous feed of molten condition, with chlorosulfonic acid successive reaction, liquid The process do not dissolved of antifebrin, reaction temperature is relatively more steady, greatly reduces disabling arylamine pair The generation of chloroaniline, it is ensured that product quality meets environmental requirement.By special atomization distributor device Design, increases mass transfer effect, fully by reaction mass antifebrin and chlorosulfonic acid in sulfonation batching kettle Contact, to ensure carrying out completely of described continuous sulfonating reaction, further increases the conversion ratio of reaction.
Present invention achieves the serialization of whole set process, consider from technical standpoint, it is necessary to use molten The antifebrin of state by flow controller and chlorosulfonic acid continuous feed, by advanced technological design from And be capable of continuity method and produce, shorten the production cycle, use Automated condtrol to ammonia simultaneously Base phenyl-beta-hydroxyethyl sulfone sulfate process for sulfonation has had brand-new development;From the point of view of economy, Decrease artificial, shorten reaction time, reduce cost to a certain extent;From the angle of environment Considering, whole process for sulfonation uses continuous closed production, environmentally friendly.Sulfonation method operation continuously Simplicity, sulfonating reaction conversion ratio is high, and the production cycle shortens more than 80%, and charging simultaneously is easily controlled, Artificial demand is few, and security is high, low cost.
Accompanying drawing explanation
Fig. 1 is the flow chart of the continuous process for sulfonation of synthesis p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester;
In figure, 1-antifebrin transfer tank, 2-antifebrin feed pump, 3-sulfonation circulation heat exchanger, 4-sulfonation circulating pump, 5-sulfonation batching kettle, 6-sulfonation maturation still, 7-sulfonation intensification still, 8-chlorosulfonation still, 9-chlorosulfonation maturation still, 10-sulfonated bodies medial launder, a-antifebrin feed pipe, b-chlorosulfonic acid feed pipe, C-first is atomized distributor, and d-second is atomized distributor, the automatic effuser of e-sulfonation material, and f-goes frozen water dilute Releasing still, g-thionyl chloride charge pipe, h-removes spareslots.
Detailed description of the invention
By the following specific examples further illustrate the invention:
Embodiment 1
Opening sulfonation circulating pump 4, regulation chlorosulfonic acid flow is 1500kg/h, by chlorosulfonic acid feed pipe b Get to sulfonation batching kettle 5 from chlorosulfonic acid transfer tank by feed pump, enter the still mouth dress of sulfonation batching kettle There is the first atomization distributor c, can moment chlorosulfonic acid be atomized so that it is spray into sulfonation dispensing being atomized shape Still 5, the flow simultaneously regulating melted antifebrin is 600kg/h, by antifebrin feed pipe a Get to sulfonation batching kettle 5 from antifebrin transfer tank 1 by antifebrin feed pump 2, enter sulfonation Antifebrin, equipped with the second atomization distributor d, can be atomized so that it is with mist moment by the still mouth of batching kettle Changing shape and spray into sulfonation batching kettle 5, the chlorosulfonic acid of atomization and the antifebrin of atomization are at sulfonation batching kettle 5 Interior haptoreaction, opens the outer sulfonation circulation heat exchanger 3 connected of sulfonation batching kettle 5, controls heat exchanger Interior temperature of charge at 35 DEG C, ceaselessly recycle stock, open waste gas absorbing system simultaneously, absorb and produce Hydrogen chloride gas;After 1 hour, sulfonation material liquid level rises to automatic flow export, enters sulfonation and becomes Ripe still 6, opens the folder jacket water of sulfonation maturation still, controls temperature of charge 35 DEG C, and stirring is reacted, Sampling detection sulfonation terminal, if terminal less than, open the chlorosulfonic acid charging valve on sulfonation maturation still, Control flow 10.5kg/h.Through 1.5 hours, material liquid level rose to automatic flow export, and material enters Enter sulfonation intensification still 7, open sulfonation intensification still jacket steam, make temperature of charge rise to 55 DEG C, stir Mixing reaction, after 1.5 hours, material liquid level rises to automatic flow export, enters chlorosulfonation still 8, opens Thionyl chloride flow regulator, control flow is 600kg/h, by thionyl chloride charge pipe g by dichloro Sulfoxide is passed through chlorosulfonation still 8, opening clamp jacket water, controls temperature 50 C, after 4 hours, material Liquid level rises to automatic flow export, enters chlorosulfonation maturation still 9, continues stirring reaction, after 4 hours, Material liquid level rises to automatic flow export, and material enters sulfonated bodies medial launder 10, waits frozen water dilution. Put frozen water 20 tons at frozen water dilution still, sulfonation material slowly put into dilution, controls flow 3500kg/h, Dilution time 3 hours, dilutes complete, enters filter press press filtration, collects filter cake and treats sub-reduction, also In former still, adding the solution of sodium bisulfite 4 tons of 27%, regulation pH is 8-9, controls temperature 20-30 DEG C, being slowly added into by sulfonation filter cake, control pH with the liquid caustic soda solution of 30% is 8-9 simultaneously, Add filter cake, stirring reaction 1 hour, material is proceeded to condensation kettle, is warmed up to 65 DEG C, is passed through epoxy Ethane 800kg, adds for about 3 hours, period with 40% sulphur acid for adjusting pH be 8-9, after terminal arrives, Expect condensation to filter into centrifuge, then material is dried through flash distillation machine, obtain the condensation material being dried 4895kg, puts into esterifying kettle by 1240kg condensation material, adds the sulfuric acid 500kg of 100%, open and steam Vapour is warmed up to 170 DEG C, insulation reaction 3 hours, and sample analysis terminal, after terminal arrives, enters pulverizer Pulverize to obtain finished product.Product receipts amount 1433kg, yield 90.66%.
Embodiment 2
Opening sulfonation circulating pump 4, regulation chlorosulfonic acid flow is 1500kg/h, by chlorosulfonic acid feed pipe b Get to sulfonation batching kettle 5 from chlorosulfonic acid transfer tank by feed pump, enter the still mouth dress of sulfonation batching kettle There is the first atomization distributor c, can moment chlorosulfonic acid be atomized so that it is spray into sulfonation dispensing being atomized shape Still 5, the flow simultaneously regulating melted antifebrin is 600kg/h, by antifebrin feed pipe a Get to sulfonation batching kettle 5 from antifebrin transfer tank 1 by antifebrin feed pump 2, enter sulfonation Antifebrin, equipped with the second atomization distributor d, can be atomized so that it is with mist moment by the still mouth of batching kettle Changing shape and spray into sulfonation batching kettle 5, the chlorosulfonic acid of atomization and the antifebrin of atomization are at sulfonation batching kettle 5 Interior haptoreaction, opens the outer sulfonation circulation heat exchanger 3 connected of sulfonation batching kettle 5, controls heat exchanger Interior temperature of charge at 40 DEG C, ceaselessly recycle stock, open waste gas absorbing system simultaneously, absorb and produce Hydrogen chloride gas;After 1 hour, sulfonation material liquid level rises to automatic flow export, enters sulfonation and becomes Ripe still 6, opens the folder jacket water of sulfonation maturation still, controls temperature of charge 40 DEG C, and stirring is reacted, Sampling detection sulfonation terminal, if terminal less than, open the chlorosulfonic acid charging valve on sulfonation maturation still, Control flow 12kg/h.Through 1.5 hours, material liquid level rose to automatic flow export, and material enters Sulfonation intensification still 7, opens sulfonation intensification still jacket steam, makes temperature of charge rise to 55 DEG C, stirring Reaction, after 1.5 hours, material liquid level rises to automatic flow export, enters chlorosulfonation still 8, opens two Chlorine sulfoxide flow regulator, control flow is 600kg/h, opening clamp jacket water, controls temperature 50 C, After 4 hours, material liquid level rises to automatic flow export, enters chlorosulfonation maturation still 9, continues stirring Reaction, after 4 hours, material liquid level rises to automatic flow export, and material enters sulfonated bodies medial launder 10, Wait frozen water dilutes.Put frozen water 20 tons at frozen water dilution still, sulfonation material slowly put into dilution, Control flow 3500kg/h, dilution time 3 hours, dilute complete, enter filter press press filtration, collect Sub-reduction treated by filter cake, in reduction kettle, adds the solution of sodium bisulfite 4 tons of 27%, regulates PH8-9, Control temperature 20-30 DEG C, sulfonation filter cake is slowly added into, control with the liquid caustic soda solution of 30% simultaneously PH8-9, adds filter cake, stirring reaction 1 hour, material is proceeded to condensation kettle, is warmed up to 65 DEG C, Being passed through oxirane 800kg, about 3h to add, period regulates PH8-9 with the sulfuric acid of 40%, and terminal arrives After, expect condensation to filter into centrifuge, then material is dried through flash distillation machine, obtain the condensation material being dried 4970kg, puts into esterifying kettle by 1240kg condensation material, adds the sulfuric acid 500kg of 100%, open and steam Vapour is warmed up to 170 DEG C, insulation reaction 3 hours, and sample analysis terminal, after terminal arrives, enters pulverizer Pulverize to obtain finished product.Product receipts amount 1433kg, yield 92.05%.
Embodiment 3
Opening sulfonation circulating pump 4, regulation chlorosulfonic acid flow is 2000kg/h, by chlorosulfonic acid feed pipe b Get to sulfonation batching kettle 5 from chlorosulfonic acid transfer tank by feed pump, enter the still mouth dress of sulfonation batching kettle There is the first atomization distributor c, can moment chlorosulfonic acid be atomized so that it is spray into sulfonation dispensing being atomized shape Still 5, the flow simultaneously regulating melted antifebrin is 600kg/h, by antifebrin feed pipe a Get to sulfonation batching kettle 5 from antifebrin transfer tank 1 by antifebrin feed pump 2, enter sulfonation Antifebrin, equipped with the second atomization distributor d, can be atomized so that it is with mist moment by the still mouth of batching kettle Changing shape and spray into sulfonation batching kettle 5, the chlorosulfonic acid of atomization and the antifebrin of atomization are at sulfonation batching kettle 5 Interior haptoreaction, opens the outer sulfonation circulation heat exchanger 3 connected of sulfonation batching kettle 5, controls heat exchanger Interior temperature of charge at 40 DEG C, ceaselessly recycle stock, open waste gas absorbing system simultaneously, absorb and produce Hydrogen chloride gas;After 1 hour, sulfonation material liquid level rises to automatic flow export, enters sulfonation and becomes Ripe still 6, opens the folder jacket water of sulfonation maturation still, controls temperature of charge 40 DEG C, and stirring is reacted, Sampling detection sulfonation terminal, if terminal less than, open the chlorosulfonic acid charging valve on sulfonation maturation still, Control flow 12kg/h.Through 1.5 hours, material liquid level rose to automatic flow export, and material enters Sulfonation intensification still 7, opens sulfonation intensification still jacket steam, makes temperature of charge rise to 55 DEG C, stirring Reaction, after 1.5 hours, material liquid level rises to automatic flow export, enters chlorosulfonation still 8, opens two Chlorine sulfoxide flow regulator, control flow is 600kg/h, opening clamp jacket water, control temperature 50 C, 4 After hour, material liquid level rises to automatic flow export, enters chlorosulfonation maturation still 9, continues stirring anti- Should, after 4 hours, material liquid level rises to automatic flow export, and material enters sulfonated bodies medial launder 10, Wait frozen water dilutes.Put frozen water 20 tons at frozen water dilution still, sulfonation material slowly put into dilution, Control flow 3500kg/h, dilution time 3 hours, dilute complete, enter filter press press filtration, collect filter Sub-reduction treated by cake, in reduction kettle, adds the solution of sodium bisulfite 4 tons of 27%, regulates PH8-9, Control temperature 20-30 DEG C, sulfonation filter cake is slowly added into, control with the liquid caustic soda solution of 30% simultaneously PH8-9, adds filter cake, stirring reaction 1 hour, material is proceeded to condensation kettle, is warmed up to 65 DEG C, Being passed through oxirane 800kg, within about 3 hours, add, period regulates PH8-9 with the sulfuric acid of 40%, eventually After point arrives, expect condensation to filter into centrifuge, then material is dried through flash distillation machine, obtain the contracting being dried Close material 5083kg, 1240kg condensation material is put into esterifying kettle, adds the sulfuric acid 500kg of 100%, open Open steam and be warmed up to 170 DEG C, insulation reaction 3 hours, sample analysis terminal, after terminal arrives, enters powder Finished product pulverized to obtain by broken machine.Product receipts amount 1433kg, yield 94.14%.
Embodiment 4
Opening sulfonation circulating pump 4, regulation chlorosulfonic acid flow is 2500kg/h, by chlorosulfonic acid feed pipe b Get to sulfonation batching kettle 5 from chlorosulfonic acid transfer tank by feed pump, enter the still mouth dress of sulfonation batching kettle There is the first atomization distributor c, can moment chlorosulfonic acid be atomized so that it is spray into sulfonation dispensing being atomized shape Still 5, the flow simultaneously regulating melted antifebrin is 600kg/h, by antifebrin feed pipe a Get to sulfonation batching kettle 5 from antifebrin transfer tank 1 by antifebrin feed pump 2, enter sulfonation Antifebrin, equipped with the second atomization distributor d, can be atomized so that it is with mist moment by the still mouth of batching kettle Changing shape and spray into sulfonation batching kettle 5, the chlorosulfonic acid of atomization and the antifebrin of atomization are at sulfonation batching kettle 5 Interior haptoreaction, opens the outer sulfonation circulation heat exchanger 3 connected of sulfonation batching kettle 5, controls heat exchanger Interior temperature of charge at 40 DEG C, ceaselessly recycle stock, open waste gas absorbing system simultaneously, absorb and produce Hydrogen chloride gas;After 1 hour, sulfonation material liquid level rises to automatic flow export, enters sulfonation and becomes Ripe still 6, opens the folder jacket water of sulfonation maturation still, controls temperature of charge 40 DEG C, and stirring is reacted, Sampling detection sulfonation terminal, if terminal less than, open the chlorosulfonic acid charging valve on sulfonation maturation still, Control flow 12kg/h.Through 1.5 hours, material liquid level rose to automatic flow export, and material enters Sulfonation intensification still 7, opens sulfonation intensification still jacket steam, makes temperature of charge rise to 55 DEG C, stirring Reaction, after 1.5 hours, material liquid level rises to automatic flow export, enters chlorosulfonation still 8, opens two Chlorine sulfoxide flow regulator, control flow is 600kg/h, opening clamp jacket water, control temperature 50 C, 4 After hour, material liquid level rises to automatic flow export, enters chlorosulfonation maturation still 9, continues stirring anti- Should, after 4 hours, material liquid level rises to automatic flow export, and material enters sulfonated bodies medial launder 10, Wait frozen water dilutes.Put frozen water 20 tons at frozen water dilution still, sulfonation material slowly put into dilution, Control flow 3500kg/h, dilution time 3 hours, dilute complete, enter filter press press filtration, collect filter Sub-reduction treated by cake, in reduction kettle, adds the solution of sodium bisulfite 4 tons of 27%, regulates PH8-9, Control temperature 20-30 DEG C, sulfonation filter cake is slowly added into, control with the liquid caustic soda solution of 30% simultaneously PH8-9, adds filter cake, stirring reaction 1 hour, material is proceeded to condensation kettle, is warmed up to 65 DEG C, Being passed through oxirane 800kg, within about 3 hours, add, period regulates PH8-9 with the sulfuric acid of 40%, eventually After point arrives, expect condensation to filter into centrifuge, then material is dried through flash distillation machine, obtain the contracting being dried Close material 4970kg, 1240kg condensation material is put into esterifying kettle, adds the sulfuric acid 500kg of 100%, open Open steam and be warmed up to 170 DEG C, insulation reaction 3 hours, sample analysis terminal, after terminal arrives, enters powder Finished product pulverized to obtain by broken machine.Product receipts amount 1433kg, yield 92.05%.
Embodiment 5
Opening sulfonation circulating pump 4, regulation chlorosulfonic acid flow is 2000kg/h, by chlorosulfonic acid feed pipe b Get to sulfonation batching kettle 5 from chlorosulfonic acid transfer tank by feed pump, enter the still mouth dress of sulfonation batching kettle There is the first atomization distributor c, can moment chlorosulfonic acid be atomized so that it is spray into sulfonation dispensing being atomized shape Still 5, the flow simultaneously regulating melted antifebrin is 600kg/h, by antifebrin feed pipe a Get to sulfonation batching kettle 5 from antifebrin transfer tank 1 by antifebrin feed pump 2, enter sulfonation Antifebrin, equipped with the second atomization distributor d, can be atomized so that it is with mist moment by the still mouth of batching kettle Changing shape and spray into sulfonation batching kettle 5, the chlorosulfonic acid of atomization and the antifebrin of atomization are at sulfonation batching kettle 5 Interior haptoreaction, opens the outer sulfonation circulation heat exchanger 3 connected of sulfonation batching kettle 5, controls heat exchanger Interior temperature of charge at 45 DEG C, ceaselessly recycle stock, open waste gas absorbing system simultaneously, absorb and produce Hydrogen chloride gas;After 1 hour, sulfonation material liquid level rises to automatic flow export, enters sulfonation and becomes Ripe still 6, opens the folder jacket water of sulfonation maturation still, controls temperature of charge 50 DEG C, and stirring is reacted, Sampling detection sulfonation terminal, if terminal less than, open the chlorosulfonic acid charging valve on sulfonation maturation still, Control flow 15kg/h.Through 1.5 hours, material liquid level rose to automatic flow export, and material enters Sulfonation intensification still 7, opens sulfonation intensification still jacket steam, makes temperature of charge rise to 55 DEG C, stirring Reaction, after 1.5 hours, material liquid level rises to automatic flow export, enters chlorosulfonation 8, opens dichloro Sulfoxide flow regulator, control flow is 700kg/h, opening clamp jacket water, control temperature 50 C, 4 After hour, material liquid level rises to automatic flow export, enters chlorosulfonation maturation still 9, continues stirring anti- Should, after 4 hours, material liquid level rises to automatic flow export, and material enters sulfonated bodies medial launder 10, Wait frozen water dilutes.Put frozen water 20 tons at frozen water dilution still, sulfonation material slowly put into dilution, Control flow 3500kg/h, dilution time 3 hours, dilute complete, enter filter press press filtration, collect filter Sub-reduction treated by cake, in reduction kettle, adds the solution of sodium bisulfite 4 tons of 27%, regulates PH8-9, Control temperature 20-30 DEG C, sulfonation filter cake is slowly added into, control with the liquid caustic soda solution of 30% simultaneously PH8-9, adds filter cake, stirring reaction 1 hour, material is proceeded to condensation kettle, is warmed up to 65 DEG C, Being passed through oxirane 800kg, within about 3 hours, add, period regulates PH8-9 with the sulfuric acid of 40%, eventually After point arrives, expect condensation to filter into centrifuge, then material is dried through flash distillation machine, obtain the contracting being dried Close material 5083kg, 1240kg condensation material is put into esterifying kettle, adds the sulfuric acid 500kg of 100%, open Open steam and be warmed up to 170 DEG C, insulation reaction 3 hours, sample analysis terminal, after terminal arrives, enters powder Finished product pulverized to obtain by broken machine.Product receipts amount 1433kg, yield 94.14%.
Embodiment 6
Opening sulfonation circulating pump 4, regulation chlorosulfonic acid flow is 2500kg/h, by chlorosulfonic acid feed pipe b Get to sulfonation batching kettle 5 from chlorosulfonic acid transfer tank by feed pump, enter the still mouth dress of sulfonation batching kettle There is the first atomization distributor c, can moment chlorosulfonic acid be atomized so that it is spray into sulfonation dispensing being atomized shape Still 5, the flow simultaneously regulating melted antifebrin is 600kg/h, by antifebrin feed pipe a Get to sulfonation batching kettle 5 from antifebrin transfer tank 1 by antifebrin feed pump 2, enter sulfonation Antifebrin, equipped with the second atomization distributor d, can be atomized so that it is with mist moment by the still mouth of batching kettle Changing shape and spray into sulfonation batching kettle 5, the chlorosulfonic acid of atomization and the antifebrin of atomization are at sulfonation batching kettle 5 Interior haptoreaction, opens the outer sulfonation circulation heat exchanger 3 connected of sulfonation batching kettle 5, controls heat exchanger Interior temperature of charge at 50 DEG C, ceaselessly recycle stock, open waste gas absorbing system simultaneously, absorb and produce Hydrogen chloride gas;After 0.5 hour, sulfonation material liquid level rises to automatic flow export, enters sulfonation Ripe still 6, opens the folder jacket water of sulfonation maturation still, controls temperature of charge 50 DEG C, and stirring is reacted, Sampling detection sulfonation terminal, if terminal less than, open the chlorosulfonic acid charging valve on sulfonation maturation still, Control flow 12kg/h.Through 1 hour, material liquid level rose to automatic flow export, and material enters sulphur Changing intensification still 7, open sulfonation intensification still jacket steam, make temperature of charge rise to 55 DEG C, stirring is anti- Should, after 1 hour, material liquid level rises to automatic flow export, enters chlorosulfonation still 8, opens dichloro Sulfoxide flow regulator, control flow is 600kg/h, opening clamp jacket water, control temperature 45 C, 3.5 After hour, material liquid level rises to automatic flow export, enters chlorosulfonation maturation still 9, continues stirring anti- Should, after 3.5 hours, material liquid level rises to automatic flow export, and material enters sulfonated bodies medial launder 10, Wait frozen water dilutes.Put frozen water 20 tons at frozen water dilution still, sulfonation material slowly put into dilution, Control flow 3500kg/h, dilution time 3 hours, dilute complete, enter filter press press filtration, collect filter Sub-reduction treated by cake, in reduction kettle, adds the solution of sodium bisulfite 4 tons of 27%, regulates PH8-9, Control temperature 20-30 DEG C, sulfonation filter cake is slowly added into, control with the liquid caustic soda solution of 30% simultaneously PH8-9, adds filter cake, stirring reaction 1 hour, material is proceeded to condensation kettle, is warmed up to 65 DEG C, Being passed through oxirane 800kg, within about 3 hours, add, period regulates PH8-9 with the sulfuric acid of 40%, eventually After point arrives, expect condensation to filter into centrifuge, then material is dried through flash distillation machine, obtain the contracting being dried Close material 5120kg, 1240kg condensation material is put into esterifying kettle, adds the sulfuric acid 500kg of 100%, open Open steam and be warmed up to 170 DEG C, insulation reaction 3 hours, sample analysis terminal, after terminal arrives, enters powder Finished product pulverized to obtain by broken machine.Product receipts amount 1433kg, yield 94.84%.

Claims (6)

1. synthesize a continuous process for sulfonation for p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester, including with Chlorosulfonic acid and antifebrin are that raw material reacts, it is characterised in that by chlorosulfonic acid with melted when feeding intake The antifebrin of state contacts after carrying out sulfonating reaction respectively after atomization, then carries out chlorine with thionyl chloride Sulfonating reaction, in whole continuous sulfonating reaction, the mass ratio of chlorosulfonic acid and antifebrin be 2.21~ 3.88:1。
Synthesis p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester the most according to claim 1 continuous Process for sulfonation, it is characterised in that specifically comprise the following steps that
A, chlorosulfonic acid spray into sulfonation batching kettle through the first atomization distributor continuously with atomization shape;Melt Antifebrin sprays into sulfonation batching kettle through the second atomization distributor continuously with atomization shape and reacts, reaction During by circulating pump keep material circulate between sulfonation batching kettle and still external heat exchanger;
B, when sulfonation batching kettle liquid level reaches predetermined altitude, material enter sulfonation maturation still react, In course of reaction, chlorosulfonic acid is added in the consumption according to antifebrin;
C, when sulfonation maturation still liquid level reaches predetermined altitude, material enter sulfonation intensification still, material warp Described sulfonating reaction is completed after adding thermal response;
D, when sulfonation intensification still liquid level reaches predetermined altitude, material enters chlorosulfonation still and instills continuously Thionyl chloride react;
E, when chlorosulfonation still liquid level reaches predetermined altitude, material enter chlorosulfonation maturation still react, Until completing described chlorosulfonation.
Synthesis p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester the most according to claim 2 continuous Process for sulfonation, it is characterised in that in step A, to be atomized chlorosulfonic acid and the acetophenone that shape sprays into continuously The mass ratio of amine is 1.29~3.88:1.
Synthesis p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester the most according to claim 2 continuous Process for sulfonation, it is characterised in that in step D, the thionyl chloride of instillation with from sulfonation intensification still thing The mass ratio of material is 0.55~1.66:1.
Synthesis p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester the most according to claim 2 continuous Process for sulfonation, it is characterised in that
The reaction temperature of described sulfonation batching kettle is 10~50 DEG C, and pressure is-0.01~-0.1MPa;
The reaction temperature of described sulfonation maturation still is 10~50 DEG C, and pressure is-0.01~-0.1MPa;
The reaction temperature of described sulfonation intensification still is 50~60 DEG C, and pressure is-0.01~-0.1MPa;
The reaction temperature of described chlorosulfonation still is 20~70 DEG C, and pressure is-0.01~-0.1Mpa;
The reaction temperature of described chlorosulfonation maturation still is 20~70 DEG C, and pressure is-0.01~-0.1Mpa.
Synthesis p-aminophenyl-beta-hydroxyethyl sulfone sulfuric ester the most according to claim 2 continuous Process for sulfonation, it is characterised in that described antifebrin flow-control, at 600kg/h, is passed through sulfonation and joins Chlorosulfonic acid flow-control in material still 900~2700kg/h, thionyl chloride flow-control 526~ 1585kg/h。
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