Environment-friendly dispersing agent for preparing p-(beta-hydroxyethyl sulfone sulfate) aniline and application of environment-friendly dispersing agent

Abstract

The invention provides an environment-friendly dispersing agent for preparing p-(beta-hydroxyethyl sulfone sulfate) aniline and application of the environment-friendly dispersing agent. The environment-friendly dispersing agent is prepared from the following components in parts by weight: 50 to 60 parts of dispersing agent, 15 to 25 parts of ion exchange resin, 5 to 15 parts of surfactant, 5 to 12 parts of lubricant and 0.1 to 1 part of defoaming agent. The environment-friendly dispersing agent provided by the invention is safe and environment-friendly in components, can effectively reduce the content of parachloroaniline impurities in preparation (para-ester) of p-(beta-hydroxyethyl sulfone sulfate) aniline produced in the current preparation process of p-(beta-hydroxyethyl sulfone sulfate) aniline, reduces the consumption of thionyl chloride, reduces the cost, can also reduce the amount of three wastes, and is beneficial to environmental protection. The method is suitable for industrial production.

Description

Technical Field

[0001] The invention belongs to the technical field of preparation of reactive dye intermediates, and particularly relates to an environmentally friendly dispersant for preparing p-(β-hydroxyethyl sulfone sulfate) aniline and application thereof. Background Art

[0002] p-(β-Sulfato ethyl sulfonyl)anilin (para base ester) is one of the most important intermediates of reactive dyes and is used to synthesize reactive dyes such as EF, KM, M, KN and ME. At present, reactive dyes are developing rapidly and have become the second largest category of dyes. With the improvement of people's requirements for the green and environmental protection of printing and dyeing textile products, the requirements for banned aromatic amines in textile products are becoming more and more stringent. At present, standards for banned aromatic amines in dyes and dye intermediates have been formulated. In 2015, the new national standard GB / T 21895-2015 for para esters was issued, which clearly requires that the content of p-chloroaniline in the product be below 500 mg / kg. Moreover, many domestic and foreign printing and dyeing textile product manufacturers require that the p-chloroaniline content in dyes should be less than 20 mg / kg (GB19601-2013 Limits and determination of 23 toxic aromatic amines in dye products), which requires that the p-chloroaniline content in the raw material p-(β-hydroxyethyl sulfone sulfate) aniline product of synthetic dyes should be less than 200 mg / kg. However, the sulfonation reaction experienced by such active dye intermediates during the preparation process is a solid-liquid phase reaction, with a slow reaction rate and prone to producing impurities such as isomers, resulting in a low product yield. In particular, p-chloroaniline is easily produced when preparing p-(β-hydroxyethyl sulfone sulfate) aniline, and the sulfonation reaction is often not well controlled, which will cause the p-chloroaniline impurity in p-(β-hydroxyethyl sulfone sulfate) aniline to reach 900-1000 mg / kg, seriously affecting the quality and use of the product.

[0003] At present, many methods for producing p-(β-hydroxyethyl sulfone sulfate) aniline adopt sulfonation reaction, using high sulfur trioxide chlorosulfonic acid (SO3 content> 68.7%), when the mass ratio of thionyl chloride to chlorosulfonic acid is greater than 0.341:1, the p-chloroaniline content in p-(β-hydroxyethyl sulfone sulfate) aniline can be reduced, but it is unstable. At the same time, 4 tons of activated carbon (tons / tons of activated carbon used for p-(β-hydroxyethyl sulfone sulfate) aniline per unit consumption) with a volume of 0.1% of the reducing liquid should be added in the reduction process to remove the impurity p-chloroaniline, but the reduction process will produce a water content of about 51%. HW49 hazardous waste 8 tons / ton of waste activated carbon; at the same time, the use of thionyl chloride is too large, which will cause more recovery byproduct 30% hydrochloric acid to be produced in the production process; a large amount of activated carbon needs to be added in the reduction process to adsorb and remove the impurity p-chloroaniline, and the reduction liquid is filtered and then alkylated with ethylene oxide, and then sulfuric acid esterified after alkylation, so that the p-chloroaniline content in the para-ester product can be less than 500mg / kg to meet market demand; the p-chloroaniline content in the final product p-(β-hydroxyethyl sulfone sulfate) aniline is controlled at 200-500mg / kg. This technology has the problems of large use of thionyl chloride, high cost, large amount of three wastes (especially a large amount of hazardous waste waste activated carbon), and high content of p-chloroaniline impurities in the product, resulting in the quality of p-(β-hydroxyethyl sulfone sulfate) aniline meeting the national standard requirements, but it is difficult to meet the green environmental protection requirements of many downstream printing and dyeing textile product manufacturers that the p-chloroaniline content in the dyes should be less than 20mg / kg.

[0004] CN103497127B discloses a method for synthesizing p-β-hydroxyethyl sulfone sulfate aniline, comprising the following steps: uniformly mixing p-β-hydroxyethyl sulfone acetanilide with a catalytic amount of sulfonic acid dispersant, adding it to sulfuric acid for esterification and deacetic acidization reaction, and obtaining the p-β-hydroxyethyl sulfone sulfate aniline after the reaction is complete through treatment. The synthetic method changes the state of the material reaction process by adding a sulfonic acid dispersant as a modification aid in the reaction system, so that the material changes from the original peptization state to the foaming peptization state, improves the efficiency of the reaction, reduces the reaction energy consumption, improves the material crushing effect, and finally reduces the content of insoluble matter in the product, so that the final material changes from the original solid particles to non-solid particles with micropores, which is more conducive to the preparation of later dyes. The invention is mainly an innovation of the synthetic esterification process of p-(β-hydroxyethyl sulfone sulfate) aniline, and changes the application diffusion performance.

[0005] CN101633630A discloses a preparation process of p-β-hydroxyethyl sulfone sulfate aniline, wherein p-β-hydroxyethyl sulfone acetanilide with water and sulfuric acid with a content of 95-98% are directly subjected to a reduced pressure esterification reaction to obtain a p-β-hydroxyethyl sulfone sulfate aniline semi-finished product, and the p-β-hydroxyethyl sulfone sulfate aniline semi-finished product is added to water for pulping, and then filtered, and the filter cake is dried to obtain p-β-hydroxyethyl sulfone sulfate aniline. The preparation process of the invention can produce high-quality p-β-hydroxyethyl sulfone sulfate aniline, shorten the production time, save drying equipment, simplify the process and reduce the secondary transfer of materials; and sulfuric acid does not need to be added in excess, reducing the post-processing process and cost. The invention is mainly an innovation of the synthetic esterification process of p-(β-hydroxyethyl sulfone sulfate) aniline, using the esterification reaction of the tide-grade alkylated material and sulfuric acid.

[0006] However, the above processes are all innovations in the esterification process of the synthesis of p-(β-hydroxyethyl sulfone sulfate) aniline, and do not involve improvements in the sulfonation process.

[0007] CN104496866B discloses a continuous sulfonation process for synthesizing p-aminophenyl-β-hydroxyethyl sulfone sulfate, which uses molten acetanilide as raw material, reacts with chlorosulfonic acid in an atomized state, and the reaction temperature is easily controlled, thereby avoiding the generation of byproduct p-chloroaniline, and the raw material acetanilide conversion rate is high. The process is simple to operate, has a short production cycle, a controllable reaction process, a small amount of labor demand, and low cost, and is easy to industrial production. However, it is necessary to use special equipment to atomize the raw materials, which increases the production cost. And the invention is mainly an innovation of the key dangerous process of the synthesis sulfonation process (containing chlorination reaction) of p-(β-hydroxyethyl sulfone sulfate) aniline, and adopts the innovation of continuous reaction, but the synthesis sulfonation and chlorination process of p-(β-hydroxyethyl sulfone sulfate) aniline can only be produced by intermittent method at present, and the continuous production mode of pipeline reactor cannot be implemented.

[0008] Since the current method for producing p-(β-hydroxyethyl sulfone sulfate) aniline in the sulfonation process during the synthesis of p-(β-hydroxyethyl sulfone sulfate) aniline has the problems of high p-chloroaniline content, high cost and many three wastes in the product, and there is no method that can effectively solve the problem. Therefore, how to provide a p-(β-hydroxyethyl sulfone sulfate) aniline production method that can effectively reduce p-chloroaniline, reduce production costs and three wastes has become a problem to be solved urgently. Summary of the invention

[0009] In view of the deficiencies of the prior art, the object of the present invention is to provide an environmentally friendly dispersant for preparing p-(β-hydroxyethyl sulfone sulfate) aniline and its application. The environmentally friendly dispersant provided by the present invention has safe and environmentally friendly components, can effectively reduce the content of p-chloroaniline impurities in the preparation of p-(β-hydroxyethyl sulfone sulfate) aniline obtained by the current p-(β-hydroxyethyl sulfone sulfate) aniline preparation process, reduce the amount of thionyl chloride used, reduce costs, and can also reduce the amount of three wastes, and is suitable for industrial production.

[0010] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0011] In a first aspect, the present invention provides an environmentally friendly dispersant for preparing para-(β-hydroxyethyl sulfone sulfate)aniline, wherein the environmentally friendly dispersant comprises, by weight, 50-60 parts of a dispersant, 15-25 parts of an ion exchange resin, 5-15 parts of a surfactant, 5-12 parts of a lubricant, and 0.1-1 parts of a defoaming agent.

[0012] The amount of the dispersant can be 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts or 60 parts, the amount of the ion exchange resin can be 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts or 25 parts, the amount of the surfactant can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts The number of parts of the lubricant can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts or 12 parts, etc., the number of parts of the defoaming agent can be 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts or 1 parts, etc., but are not limited to the values ​​listed above, and other values ​​not listed within the above numerical range are equally applicable.

[0013] During the production of acetanilide used in the sulfonation process of para-(β-hydroxyethyl sulfone sulfate) aniline production, local acetanilide is prone to generate high temperature at the contact point with chlorosulfonic acid, which will cause the acetanilide to hydrolyze to produce a small amount of aniline. The produced aniline reacts with the hydrogen chloride gas produced by the sulfonation reaction to form para-chloroaniline impurities. The above-mentioned environmentally friendly dispersant can make the surface product of the reaction between acetanilide and chlorosulfonic acid diffuse rapidly in the sulfonation liquid by utilizing the dispersant component, so that the heat energy generated by the reaction is quickly absorbed by the low-temperature refrigerant in the interlayer of the sulfonation kettle, thereby reducing the hydrolysis of acetanilide to produce aniline, thereby reducing the amount of aniline produced during the sulfonation process reaction, and promoting the diffusion of acetanilide can also effectively increase the reaction rate, reduce the amount of thionyl chloride used, and reduce the production cost; by using ion exchange resin, it can effectively The ion exchange resin absorbs the p-chloroaniline impurity, and the ion exchange resin is insoluble in the reaction solution, and can be easily removed with the activated carbon during filtration in the reduction process, thereby effectively reducing the p-chloroaniline impurity content. In addition, since hydrogen chloride must be produced in the sulfonation process, this is inevitable, and the long-term presence of hydrogen chloride in the sulfonation material is an important factor in the generation of p-chloroaniline, the present invention can effectively eliminate the foam caused by the hydrogen chloride gas produced by the sulfonation process reaction by using a surfactant, a lubricant, and a defoaming agent, increase fluidity, and enable the hydrogen chloride gas to quickly leave the reaction system, thereby reducing the content of hydrogen chloride in the reaction system, further reducing the generation of p-chloroaniline, and removing the interference of hydrogen chloride on the reaction system, thereby increasing the reaction rate and reducing the use of thionyl chloride.

[0014] Preferably, the environmentally friendly dispersant comprises, by weight, 55-58 parts of dispersant, 18-20 parts of ion exchange resin, 8-11 parts of surfactant, 8-10 parts of lubricant, and 0.2-0.5 parts of defoaming agent.

[0015] Preferably, the dispersant comprises trisodium citrate and / or citric acid, preferably trisodium citrate.

[0016] The dispersant can effectively promote the solid-phase raw materials in the sulfonation process of para-(β-hydroxyethyl sulfone sulfate) aniline production to dissolve quickly into the sulfonating agent strong acid, thereby increasing the reaction speed and effectively reducing the generation of para-chloroaniline impurities; and the dispersant component is present in the sulfonation-producing contaminant dilute sulfuric acid and alkylation wastewater in the synthesis process of para-(β-hydroxyethyl sulfone sulfate) aniline, and can provide a carbon source during the environmentally friendly treatment of the dilute sulfuric acid and alkylation wastewater, thereby effectively improving the biochemical treatment effect and reducing the cost of three waste treatment.

[0017] Preferably, the ion exchange resin comprises sodium polystyrene sulfonate.

[0018] The ion exchange resin can adsorb the p-chloroaniline impurity produced during the sulfonation reaction of p-(β-hydroxyethyl sulfone sulfate) aniline, and can be easily removed by filtering in the reduction process, thereby reducing the cost of three waste treatment.

[0019] Preferably, the surfactant comprises sodium dodecylbenzene sulfonate and / or sodium dodecyl sulfate.

[0020] The above-mentioned surfactant can reduce the surface tension of the material, has the properties of wetting, penetration and emulsification, and can promote the dispersion of solid phase materials.

[0021] Preferably, the lubricant comprises maltodextrin.

[0022] The lubricant can increase the stability and lubricity of the product, and at the same time enhance the dispersibility and solubility of the raw materials and sulfonation products during sulfonation.

[0023] Preferably, the defoaming agent comprises polydimethylsilane.

[0024] The defoamer can effectively remove bubbles generated during the sulfonation reaction of p-(β-hydroxyethyl sulfone sulfate) aniline, so that the hydrogen chloride gas generated during the sulfonation reaction quickly leaves the reaction system, thereby increasing the reaction rate and reducing the generation of impurities.

[0025] Preferably, the environmentally friendly dispersant also includes 0.3-1 parts of pH adjuster by weight, such as 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts or 1 parts, but is not limited to the values ​​listed above, and other values ​​not listed within the above numerical range are also applicable.

[0026] The pH adjuster combined with the dispersant components can make the overall dispersant neutral or nearly neutral, avoiding the pH changes of other components when they are subjected to extreme conditions, which may affect the transportation, storage and use of the dispersant, thereby ensuring the safety of the dispersant.

[0027] Preferably, the pH adjuster comprises sodium formate.

[0028] In a second aspect, the present invention provides the use of the environmentally friendly dispersant for preparing p-(β-hydroxyethyl sulfone sulfate)aniline as described above in the preparation of dye intermediates.

[0029] In a third aspect, the present invention further provides a method for preparing p-(β-hydroxyethyl sulfone sulfate)aniline, the preparation method comprising the following steps:

[0030] (1) adding acetanilide to chlorosulfonic acid and simultaneously adding the environmentally friendly dispersant as described above to carry out a sulfonation reaction, and then mixing with thionyl chloride to react to obtain p-acetamidobenzenesulfonyl chloride;

[0031] (2) mixing 4-acetamidobenzenesulfonyl chloride with a reducing agent for reaction, then adding activated carbon for adsorption to obtain sodium 4-acetamidobenzenesulfinate, and then alkylating and esterifying to obtain the p-(β-hydroxyethyl sulfone sulfate) aniline.

[0032] The preparation method adopts the environmentally friendly dispersant, which can effectively reduce the content of p-chloroaniline in the product, reduce the amount of raw material thionyl chloride, reduce the amount of activated carbon used for adsorbing p-chloroaniline impurities in the reduction reaction (the existing technology requires the addition of more than 0.1%), reduce the amount of hazardous waste and waste activated carbon, reduce production costs, and also reduce the amount of three wastes and treatment costs.

[0033] Preferably, the specific step of adding the environmentally friendly dispersant as described above in step (1) is: when the amount of acetanilide added reaches 45-55% (e.g., 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54% or 55%) of the total amount of acetanilide added, 2-3kg (e.g., 2kg, 2.1kg, 2.2kg, 2.3kg, 2.4kg, 2.5kg, 2.6kg, 2.7kg, 2.8kg, 2.9kg or 3kg) of para-(β-hydroxyethyl sulfone sulfate) aniline is added. agent; when the amount of acetanilide added reaches 75-85% (e.g., 75%, 76%, 78%, 79%, 80%, 81%, 82%, 83%, 84% or 85%) of the total amount of acetanilide added, 1.5-3kg (e.g., 1.5kg, 1.6kg, 1.7kg, 1.8kg, 1.9kg, 2kg, 2.1kg, 2.2kg, 2.3kg, 2.4kg, 2.5kg, 2.6kg, 2.7kg, 2.8kg, 2.9kg or 3kg, etc.) of para-(β-hydroxyethyl sulfone sulfate) aniline is added.

[0034] The above-mentioned ton consumption means the amount of raw materials consumed per production of 1 ton of product (p-(β-hydroxyethyl sulfone sulfate) aniline).

[0035] The specific addition time, time-divided addition method and addition amount can effectively ensure that the yield of the impurity p-chloroaniline is as low as possible without affecting the normal progress of the reaction.

[0036] Preferably, the amount of activated carbon added in step (2) is 0.03-0.07% of the volume of the reducing solution obtained after the mixing reaction, such as 0.03%, 0.04%, 0.05%, 0.06%, etc., but is not limited to the values ​​listed above. Other values ​​not listed within the above numerical range are also applicable.

[0037] The amount of activated carbon added is significantly reduced compared to the prior art, which can not only maintain the adsorption and removal effect of 4-chloroaniline, but also effectively reduce the amount of waste activated carbon generated, thereby reducing the subsequent treatment costs of the three wastes.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] The invention provides an environmentally friendly dispersant for preparing p-(β-hydroxyethyl sulfone sulfate) aniline. By utilizing dispersant components, the surface product of the reaction between acetanilide and chlorosulfonic acid can be rapidly diffused in a sulfonation liquid, and the heat energy generated by the reaction can be rapidly absorbed by a low-temperature refrigerant in a sulfonation kettle interlayer, thereby reducing the generation of aniline by hydrolysis of acetanilide, thereby reducing the amount of aniline generated during the reaction in the sulfonation process, and promoting the diffusion of acetanilide can also effectively improve the reaction rate, reduce the amount of thionyl chloride used, and reduce the production cost; by adopting an ion exchange resin, p-chloroaniline impurities can be effectively absorbed, and the ion exchange resin is insoluble in the reaction liquid, and can be easily removed with activated carbon during filtration in a reduction process, thereby effectively reducing the content of p-chloroaniline impurities; by using a surfactant, a lubricant, and a defoaming agent, the foam brought by hydrogen chloride gas generated by the sulfonation process reaction can be effectively eliminated, the fluidity can be increased, the hydrogen chloride gas can be rapidly separated from the reaction system, the content of hydrogen chloride in the reaction system is reduced, the generation of p-chloroaniline is further reduced, and the interference of hydrogen chloride on the reaction system is eliminated, the reaction rate is improved, and the use of thionyl chloride is reduced. DETAILED DESCRIPTION

[0040] In order to further explain the technical means and effects adopted by the present invention, the technical solution of the present invention is further described below in conjunction with the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.

[0041] In the following examples, sodium polystyrene sulfonate was purchased from Elest (Shanghai) New Material Technology Co., Ltd., model number YLT-1;

[0042] Polydimethylsilane was purchased from Jiangsu Jianyu Additive Technology Co., Ltd. with model number JY-861.

[0043] Example 1

[0044] This embodiment provides an environmentally friendly dispersant, and the specific components (by weight) are as follows:

[0045] 57 parts of trisodium citrate, 19 parts of sodium polystyrene sulfonate, 1.7 parts of sodium dodecylbenzene sulfonate, 8.5 parts of sodium lauryl sulfate, 9 parts of maltodextrin, 0.6 parts of sodium formate, and 0.3 parts of polydimethylsilane.

[0046] Mix the above ingredients.

[0047] Example 2

[0048] This embodiment provides an environmentally friendly dispersant, and the specific components (by weight) are as follows:

[0049] 55 parts of trisodium citrate, 20 parts of sodium polystyrene sulfonate, 1 part of sodium dodecylbenzene sulfonate, 7 parts of sodium lauryl sulfate, 10 parts of maltodextrin, 1 part of sodium formate, and 0.5 parts of polydimethylsilane.

[0050] Mix the above ingredients.

[0051] Example 3

[0052] This embodiment provides an environmentally friendly dispersant, and the specific components (by weight) are as follows:

[0053] 58 parts of trisodium citrate, 18 parts of sodium polystyrene sulfonate, 11 parts of sodium lauryl sulfate, 8 parts of maltodextrin, 0.3 parts of sodium formate, and 0.2 parts of polydimethylsilane.

[0054] Mix the above ingredients.

[0055] Example 4

[0056] This embodiment provides an environmentally friendly dispersant, and the specific components (by weight) are as follows:

[0057] 60 parts of trisodium citrate, 15 parts of sodium polystyrene sulfonate, 2 parts of sodium dodecylbenzene sulfonate, 13 parts of sodium lauryl sulfate, 5 parts of maltodextrin, 1 part of sodium formate, and 1 part of polydimethylsilane.

[0058] Mix the above ingredients.

[0059] Example 5

[0060] This embodiment provides an environmentally friendly dispersant, and the specific components (by weight) are as follows:

[0061] 50 parts of trisodium citrate, 25 parts of sodium polystyrene sulfonate, 0.5 parts of sodium dodecylbenzene sulfonate, 4.5 parts of sodium lauryl sulfate, 12 parts of maltodextrin, 0.3 parts of sodium formate, and 0.1 parts of polydimethylsilane.

[0062] Mix the above ingredients.

[0063] Example 6

[0064] This embodiment provides an environmentally friendly dispersant. The specific components are the same as those of Embodiment 1 except that trisodium citrate is replaced by an equal amount of dispersant MF.

[0065] Example 7

[0066] This embodiment provides an environmentally friendly dispersant, and the specific ingredients are consistent with those of Example 1 except that trisodium citrate is replaced with an equal amount of dispersant NN0.

[0067] Example 8

[0068] This embodiment provides an environmentally friendly dispersant. The specific ingredients are the same as those in Example 1 except that sodium polystyrene sulfonate is replaced by an equal amount of macroporous adsorption resin (A-722MP, produced by Shanghai Kaiyin Chemical Co., Ltd.).

[0069] Example 9

[0070] This embodiment provides an environmentally friendly dispersant. The specific ingredients are the same as those in Example 1 except that polydimethylsilane is replaced by an equal amount of a polyether defoamer (GPE polyether defoamer, produced by Suzhou Hengkang New Materials Co., Ltd.).

[0071] Comparative Example 1

[0072] This comparative example provides an environmentally friendly dispersant, and the specific ingredients are consistent with those of Example 1 except that trisodium citrate is not added and the reduced portion is distributed to other ingredients in proportion.

[0073] Comparative Example 2

[0074] This comparative example provides an environmentally friendly dispersant, and the specific ingredients are consistent with Example 1 except that sodium polystyrene sulfonate is not added and the reduced part is distributed to other ingredients in proportion.

[0075] Comparative Example 3

[0076] This comparative example provides an environmentally friendly dispersant, and the specific components are consistent with those of Example 1 except that polydimethylsilane is not added and the reduced portion is distributed to other components in proportion.

[0077] Application Example 1

[0078] This application example provides a method for preparing p-(β-hydroxyethyl sulfone sulfate) aniline, and the specific steps are as follows:

[0079] (1) Sulfonation and chlorination reactions

[0080] A quantitative amount of 0.306 kg of chlorosulfonic acid is added to a four-mouth standard ground-mouth glass flask through a standard ground-mouth stoppered separatory funnel, and a slightly negative pressure hydrogen chloride water absorption and recovery of hydrochloric acid and a tail gas treatment circulating water plastic vacuum pump absorption device are turned on. The sulfonation stirring and interlayer automatic ice water cooling are started, and when the temperature in the sulfonation four-mouth glass flask is controlled to drop to below 20° C., 0.1078 kg of acetanilide is slowly added at a uniform speed from the feed port, and the reaction temperature is controlled at 30° C. by adjusting the cooling water of the outer jacket. When the amount of acetanilide added reaches 50%, 0.0054 kg of the environmentally friendly dispersant provided in Example 1 is added, and when the amount of acetanilide added reaches 80%, 0.0032 kg of the environmentally friendly dispersant provided in Example 1 is added. After the addition is completed, stir for 0.5 hours and prepare for the chlorination reaction. Slowly heat to 50°C through an insulated electric heating bowl outside a four-mouth standard ground glass flask. 0.1 kg of thionyl chloride is slowly added dropwise to the sulfonated liquid through a standard ground-mouth stoppered separatory funnel. The temperature is controlled at about 50°C. After the addition is completed, keep warm at 50°C for 0.5 hours, hydrolyze and dilute to obtain 4-acetamidobenzenesulfonyl chloride.

[0081] (2) Hydrolysis reaction

[0082] After opening the hydrogen chloride water absorption and recovery of hydrochloric acid and the tail gas treatment circulating water plastic vacuum pump absorption device, start the stirring of the chlorinated material, cool the chlorinated material to 25°C with cold ice water, slowly add a certain amount of dilute sulfuric acid to the chlorinated material in the four-mouth standard ground glass flask through a standard ground mouth stoppered separatory funnel, and then slowly add 0°C water to hydrolyze the excess chlorosulfonic acid and thionyl chloride. The temperature is controlled at about 35°C. After hydrolysis is completed until there is basically no smoke in the four-mouth standard ground glass flask, and the acidity is controlled to be about 75%, dilute;

[0083] The hydrogen chloride and sulfur dioxide gases produced during the sulfonation, chlorination reaction and hydrolysis process are treated by using a circulating cooling water system to absorb the hydrogen chloride to produce hydrochloric acid and a tail gas absorption system.

[0084] (3) Dilution and filtration

[0085] Add a certain amount of 0-5°C chilled water to a 1000mL four-mouth standard ground glass flask for dilution, start stirring, and slowly add the sulfonated hydrolyzate to the 0-5°C chilled water in the inner pot of the four-mouth standard ground glass flask for dilution at a certain flow rate, and control the temperature in the flask below 5°C for dilution through the outer jacket of frozen brine, and control the dilution acidity between 27-29%. After dilution, filter, rinse, and squeeze the diluted liquid to obtain a 50-55% content of para-acetamidobenzenesulfonyl chloride filter cake. The gas generated during the dilution process enters the sulfonated tail gas absorption system for treatment. The gas generated during the dilution and filtration process is introduced into the hydrochloric acid production and tail gas absorption system through a slight negative pressure for treatment.

[0086] (4) Reduction process

[0087] The measured water and 0.45 kg of sodium sulfite are placed in a 1000 mL beaker and stirred. The outer jacket of the beaker is cooled with low-temperature cooling water. After the pH value is adjusted to neutral with sodium hydroxide, the acetylaminobenzenesulfonyl chloride filter cake obtained by dilution and filtration is added at a uniform speed, and 32% sodium hydroxide solution is added dropwise while adding the material. The temperature of the reducing liquid in the beaker is controlled at 30°C, and the pH value is controlled between 7.5-8. After the addition is completed, the reaction is stirred for 0.5 hour. After the pH stabilizes, the reducing liquid is heated to 45°C using an insulating electric heating bowl and the reaction is continued for 2 hours. The concentration of the reducing liquid is controlled at 19-21 g / 100 mL. 0.4 kg of activated carbon was added to the reducing material at 0.05% of the total volume of 0.8 L to adsorb impurities. After stirring at 45° C. for 1 hour, the mixture was filtered and the filter residue and waste activated carbon were rinsed with 40° C. hot water to obtain a refined aqueous solution of sodium p-acetamidobenzenesulfinate. The aqueous solution of sodium p-acetamidobenzenesulfinate was transferred to the alkylation process. The filtered activated carbon cake residue was 0.8 kg of hazardous waste waste activated carbon (its components were: about 51% water, about 48% activated carbon, very trace organic matter and sodium sulfate).

[0088] (5) Alkylation step (condensation)

[0089] The sodium p-acetamidobenzenesulfinate aqueous solution of the filtrate from the reduction process is added to a four-mouth standard ground glass flask for alkylation, and the pH is adjusted to between 7.5 and 8. The oxygen in the alkylation flask is replaced by nitrogen to remove oxygen. When the oxygen content in the flask is controlled to be 0%, the temperature is slowly raised to 40°C in an external water bath, and 0.0475 kg of ethylene oxide is slowly introduced into the sodium p-acetamidobenzenesulfinate aqueous solution in the alkylation flask, and the pH is adjusted to between 8 and 9.5 with dilute sulfuric acid. After the addition of ethylene oxide, the pH is adjusted to between 7.5 and 8.5 after the reaction is kept warm for 5 hours. After reaching the end point, the temperature is lowered to 40°C and filtered.

[0090] (6) Esterification process

[0091] The filtered product p-(β-hydroxyethyl sulfone)acetanilide obtained in the alkylation process was added to 0.047 kg of 98% sulfuric acid in proportion and then introduced into the esterification equipment. The temperature of the equipment interlayer was uniformly increased to control the temperature of the esterification material between 158-162°C. The esterification was hydrolyzed and esterified by reduced pressure distillation. After the esterification was completed, the esterification material was crushed to obtain 0.2 kg of the product p-(β-hydroxyethyl sulfone sulfate)aniline.

[0092] Application Example 2-9

[0093] Application Examples 2-9 respectively provide a method for preparing p-(β-hydroxyethyl sulfone sulfate)aniline. In the specific steps, except that the environmentally friendly dispersant provided in Example 1 is replaced by an equal amount of the environmentally friendly dispersant provided in Examples 2-9, the rest is consistent with Application Example 1.

[0094] Application Example 10

[0095] This application example provides a method for preparing p-(β-hydroxyethyl sulfone sulfate) aniline. The specific steps are consistent with those of Application Example 1 except that 4.3 kg (ton consumption) of the environmentally friendly dispersant provided in Example 1 is added once when the amount of acetanilide added reaches 50%, and no dispersant is added subsequently.

[0096] Application Example 11

[0097] This application example provides a method for preparing para-(β-hydroxyethyl sulfone sulfate) aniline. In the specific steps, except that 1.5 kg (ton consumption) of the environmentally friendly dispersant provided in Example 1 is added when the amount of acetanilide added reaches 40%, and 3.5 kg (ton consumption) of the environmentally friendly dispersant provided in Example 1 is added when the amount of acetanilide added reaches 90%, the rest are consistent with Application Example 1.

[0098] Comparative Application Examples 1-3

[0099] Comparative Application Examples 1-3 respectively provide a method for preparing p-(β-hydroxyethyl sulfone sulfate)aniline. In the specific steps, except that the environmentally friendly dispersant provided in Example 1 is replaced by an equal amount of the environmentally friendly dispersant provided in Comparative Examples 1-3, the rest is consistent with Application Example 1.

[0100] Comparative Application Example 4

[0101] This comparative application example provides a method for preparing p-(β-hydroxyethyl sulfone sulfate)aniline. The specific steps are consistent with those of Application Example 1 except that the environmentally friendly dispersant provided in Example 1 is not added.

[0102] Comparative Application Example 5

[0103] This comparative application example provides a method for preparing p-(β-hydroxyethyl sulfone sulfate) aniline, and the specific steps are as follows:

[0104] (1) Sulfonation and chlorination reactions

[0105] A quantitative amount of 0.306 kg of chlorosulfonic acid was added to a four-mouth standard ground-mouth glass flask through a standard ground-mouth stoppered separatory funnel, and a micro-negative pressure hydrogen chloride water absorption device was turned on to recover hydrochloric acid and tail gas treatment circulating water plastic vacuum pump absorption device, and the sulfonation stirring and interlayer automatic ice water cooling were started. When the temperature in the sulfonation four-mouth glass flask was controlled to be below 20°C, 0.1092 kg of acetanilide was added slowly and uniformly from the feeding port, and the reaction temperature was controlled at 30°C by adjusting the outer jacket cooling water. After the addition was completed, the chlorination reaction was prepared after stirring for 0.5 hours, and the temperature was slowly raised to 50°C through the insulation electric heating bowl outside the four-mouth standard ground-mouth glass flask. The measured 0.103 kg of thionyl chloride was slowly added dropwise to the sulfonation solution through a standard ground-mouth stoppered separatory funnel, and the temperature was controlled at about 50°C. After the addition was completed, it was kept at 50°C for 0.5 hours, and then hydrolyzed and diluted to obtain 4-acetamidobenzenesulfonyl chloride.

[0106] (2) Hydrolysis reaction

[0107] Same as Application Example 1.

[0108] (3) Dilution and filtration

[0109] Same as Application Example 1.

[0110] (4) Reduction process

[0111] The measured water and 0.45 kg of sodium sulfite are placed in a 1000 mL beaker and stirred. The outer jacket of the beaker is cooled with cooling water. The pH value is adjusted to neutral with sodium hydroxide. The acetaminobenzenesulfonyl chloride filter cake obtained by dilution and filtration is added at a uniform rate, and 32% sodium hydroxide solution is added dropwise while adding the material. The temperature of the reducing liquid in the beaker is controlled at 30°C, and the pH value is controlled between 7.5-8. After the addition is completed, the reaction is stirred for 0.5 hour. After the pH stabilizes, the reducing liquid is heated to 45°C using an insulating electric heating bowl and the reaction is continued for 2 hours. The concentration of the reducing liquid is controlled between 19-21 g / 100 mL. 0.8 kg of activated carbon was added to the reducing material at 0.1% of the total volume of 0.8 L to adsorb impurities. After stirring at 45° C. for 1 hour, the mixture was filtered and the filter residue and waste activated carbon were rinsed with 40° C. hot water to obtain a refined aqueous solution of sodium p-acetamidobenzenesulfinate. The aqueous solution of sodium p-acetamidobenzenesulfinate was transferred to the alkylation process. The filtered activated carbon cake residue was 1.6 kg of hazardous waste waste activated carbon (its components were: about 51% water, about 48% activated carbon, very trace organic matter and sodium sulfate).

[0112] (5) Alkylation step (condensation)

[0113] Same as Application Example 1.

[0114] (6) Esterification process

[0115] Same as Application Example 1.

[0116] Effect comparison:

[0117] The p-(β-hydroxyethyl sulfone sulfate) aniline obtained in the above example was collected, and the content of p-chloroaniline in the reducing material and the product before adding activated carbon in step (4) of each method was detected according to GB19601-2013. The results are as follows:

[0118]

[0119] From the above results, it can be found that the environmentally friendly dispersant provided by the present invention can effectively reduce the content of p-chloroaniline impurities in the sulfonation production process of p-(β-hydroxyethyl sulfone sulfate) aniline, and reduce the amount of three wastes; by comparing application examples 1-5, it can be found that the present invention can further improve the effect of the environmentally friendly dispersant by controlling the ratio of each component; by comparing application examples 1 and 6-11, it can be found that the present invention can further reduce the content of p-chloroaniline impurities in the product by selecting specific dispersants, ion exchange resins and defoaming agents, and controlling the amount, timing and method of adding the environmentally friendly dispersant; by comparing application example 1 and comparative application examples 1-5, it can be found that the present invention can effectively reduce the content of p-chloroaniline impurities in the sulfonation production process of p-(β-hydroxyethyl sulfone sulfate) aniline, improve the yield and reduce the amount of three wastes compared with the prior art by adopting specific components.

[0120] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the environmentally friendly dispersant for preparing p-(β-hydroxyethyl sulfone sulfate) aniline and its application, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0121] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0122] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

Claims

1. An environmentally friendly dispersant for preparing p-(β-hydroxyethyl sulfone sulfate) aniline, characterized in that: The environmentally friendly dispersant comprises, by weight, 50-60 parts of dispersant, 15-25 parts of ion exchange resin, 5-15 parts of surfactant, 5-12 parts of lubricant, and 0.1-1 part of defoaming agent.

2. The environmentally friendly dispersant for preparing p-(β-hydroxyethyl sulfone sulfate) aniline according to claim 1, characterized in that: The environmentally friendly dispersant comprises, by weight, 55-58 parts of dispersant, 18-20 parts of ion exchange resin, 8-11 parts of surfactant, 8-10 parts of lubricant, and 0.2-0.5 parts of defoaming agent.

3. The environmentally friendly dispersant for preparing p-(β-hydroxyethyl sulfone sulfate) aniline according to claim 1 or 2, characterized in that: The dispersant comprises trisodium citrate and / or citric acid, preferably trisodium citrate; Preferably, the ion exchange resin comprises sodium polystyrene sulfonate.

4. The environmentally friendly dispersant for preparing p-(β-hydroxyethyl sulfone sulfate) aniline according to any one of claims 1 to 3, characterized in that: The surfactant includes sodium dodecylbenzene sulfonate and / or sodium dodecyl sulfate; Preferably, the lubricant comprises maltodextrin.

5. The environmentally friendly dispersant for preparing p-(β-hydroxyethyl sulfone sulfate) aniline according to any one of claims 1 to 4, characterized in that: The defoaming agent includes polydimethylsilane.

6. The environmentally friendly dispersant for preparing p-(β-hydroxyethyl sulfone sulfate) aniline according to any one of claims 1 to 5, characterized in that: The environmentally friendly dispersant also includes 0.3-1 parts of pH regulator by weight; Preferably, the pH adjuster comprises sodium formate.

7. Use of the environmentally friendly dispersant for preparing p-(β-hydroxyethyl sulfone sulfate)aniline according to any one of claims 1 to 6 in the preparation of dye intermediates.

8. A method for preparing p-(β-hydroxyethyl sulfone sulfate) aniline, characterized in that: The preparation method comprises the following steps: (1) adding acetanilide to chlorosulfonic acid, and simultaneously adding the environmentally friendly dispersant according to any one of claims 1 to 6, to carry out a sulfonation reaction, and then mixing with thionyl chloride to react, to obtain 4-acetamidobenzenesulfonyl chloride; (2) mixing 4-acetamidobenzenesulfonyl chloride with a reducing agent for reaction, then adding activated carbon for adsorption to obtain sodium 4-acetamidobenzenesulfinate, and then alkylating and esterifying to obtain the p-(β-hydroxyethyl sulfone sulfate) aniline.

9. The preparation method according to claim 8, characterized in that: The specific steps of adding the environmentally friendly dispersant for preparing p-(β-hydroxyethyl sulfone sulfate) aniline according to any one of claims 1-6 in step (1) are as follows: when the amount of acetanilide added reaches 45-55% of the total amount of acetanilide added, adding the environmentally friendly dispersant according to any one of claims 1-6 with a per ton consumption of 2-3 kg of p-(β-hydroxyethyl sulfone sulfate) aniline; when the amount of acetanilide added reaches 75-85% of the total amount of acetanilide added, adding the environmentally friendly dispersant according to any one of claims 1-6 with a per ton consumption of 1.5-3 kg of p-(β-hydroxyethyl sulfone sulfate) aniline.

10. The preparation method according to claim 8 or 9, characterized in that: The amount of activated carbon added in step (2) is 0.03-0.06% of the volume of the reducing solution obtained after the mixing reaction.

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