阅读说明：本技术 一种母液套用的对苯基苯酚生产工艺 (Production process of p-phenylphenol for mother liquor recycling ) 是由 任建坡 张兵兵 沈志红 车立光 李灏 马丹丹 于 2019-11-14 设计创作，主要内容包括：本发明涉及有机合成、资源回收利用和环境保护领域,提供了一种母液套用的对苯基苯酚生产工艺。本发明将反应产生的碱熔母液套用于联苯4磺酸的钠化反应,由于钠化反应体系中含有未反应的硫酸,碱熔母液中的亚硫酸钠与硫酸反应生成二氧化硫和硫酸钠,硫酸钠的钠离子用于钠化反应,并补加氢氧化钠调节体系PH值,析出联苯4磺酸钠,二氧化硫用于碱熔后未反应氢氧化钠的中和,未反应的尾气二氧化硫用于吡啶酸车间的尾气吸收,降低公司亚硫酸钠产品的消耗,实现废液、废气的全利用,减少三废处理成本,提升反应的原子经济型,节能降耗,绿色环保。(The invention relates to the fields of organic synthesis, resource recycling and environmental protection, and provides a production process of p-phenylphenol for mother liquor recycling. According to the invention, the alkali fusion mother liquor generated by the reaction is applied to the sodium treatment reaction of biphenyl 4 sulfonic acid, the sodium treatment reaction system contains unreacted sulfuric acid, sodium sulfite in the alkali fusion mother liquor reacts with the sulfuric acid to generate sulfur dioxide and sodium sulfate, sodium ions of the sodium sulfate are used for the sodium treatment reaction, sodium hydroxide is added to adjust the pH value of the system, sodium biphenyl 4 sulfonate is separated out, the sulfur dioxide is used for neutralizing the unreacted sodium hydroxide after alkali fusion, the unreacted tail gas sulfur dioxide is used for tail gas absorption of a pyridine acid workshop, the consumption of sodium sulfite products of a company is reduced, the full utilization of waste liquor and waste gas is realized, the three-waste treatment cost is reduced, the atomic economy of the reaction is improved, the energy is saved, the consumption is reduced, and the.)

1. A production process of p-phenylphenol for mother liquor recycling is characterized by comprising the following steps:

(1) heating the sulfonation mother liquor B obtained in the last reaction to evaporate water vapor, condensing to obtain circulating water, cooling and crystallizing the residual sulfonation mother liquor B to separate out sodium sulfate crystals, and filtering to obtain a sodium sulfate product and a filtrate F;

(2) adding the biphenyl, the new biphenyl and the concentrated sulfuric acid which are not reacted in the previous reaction into a reaction kettle for sulfonation reaction at the reaction temperature of 135-150 ℃, reacting for 3 hours, adding the circulating water obtained in the step (1) after the reaction is finished for dissolving, filtering to obtain the unreacted biphenyl and a filtrate A, transferring the filtrate A into a sodium treatment kettle, adding the alkali fusion mother liquor obtained in the previous reaction for sodium treatment to generate sulfur dioxide gas, supplementing sodium hydroxide into the sodium treatment kettle until the solution is neutral, and centrifuging to obtain biphenyl-4-sodium sulfonate solid and a sulfonation mother liquor B;

(3) transferring the biphenyl-4-sodium sulfonate solid obtained in the step (2) into an alkali fusion kettle, adding sodium hydroxide to perform alkali fusion reaction for 2 hours at the temperature of 160-340 ℃, adding the circulating water obtained in the step (1) to dissolve after the alkali fusion reaction to obtain a mixed solution C, transferring the mixed solution C into a neutralization kettle, introducing sulfur dioxide gas generated in the step (2) into the neutralization kettle, neutralizing sodium hydroxide which is not completely reacted in the alkali fusion to obtain a mixed solution D, and introducing sulfur dioxide tail gas into a sodium hydroxide solution to absorb to obtain a sodium sulfite solution M;

(4) and (4) mixing the neutral mixed solution D obtained in the step (3) with an organic solvent, transferring the mixture to a continuous layered extraction system for extraction to obtain an organic phase E and an alkali fusion mother liquor F, and distilling the organic phase F to obtain the organic solvent and a p-phenylphenol product.

2. The process for producing P-phenylphenol for mother liquor recycling according to claim 1, wherein the step (1) comprises mixing the sulfonation mother liquor B obtained from the previous reaction and the filtrate P obtained from the previous reaction, heating to evaporate water vapor, condensing to obtain circulating water, cooling and crystallizing the remaining sulfonation mother liquor B to separate out sodium sulfate crystals, and filtering to obtain a sodium sulfate product and the filtrate P.

3. The process for producing p-phenylphenol for mother liquor recycling according to claim 1, wherein the sodium sulfite solution M in the step (3) is used for absorption of chlorine and carbon dioxide mixed tail gas in pyridine acid plant.

4. The process for producing p-phenylphenol for use in the mother liquor as claimed in claim 1, wherein the organic solvent used in step (4) is methyl isobutyl ketone.

Technical Field

The invention relates to the fields of organic synthesis, resource recycling and environmental protection, in particular to a production process of p-phenylphenol for mother liquor recycling.

Background

The p-phenylphenol is an important novel fine chemical intermediate and is widely applied to the fields of dyes, medicines, preservatives, coatings, printing and dyeing auxiliaries, photosensitive materials and the like.

The p-phenylphenol production technology comprises the recovery of p-phenylphenol from distillation residues generated in phenol production by a sulfonation method, the alkali fusion method of diphenyl sulfone, the biphenyl sulfonation method, the synthesis method of cyclohexanone and phenol, and the like. The biphenyl sulfonation alkali fusion method uses biphenyl as a raw material, produces biphenyl-4-sulfonic acid through sulfonation, and obtains p-phenylphenol through alkali fusion, neutralization, extraction and distillation. The biphenyl sulfonation alkali fusion method is adopted to produce the p-phenylphenol, the technology is mature, and the production method has the defects of overlong route, harsh alkali fusion reaction conditions, more three wastes, low yield and the like, and needs to be further improved and perfected in production and practice.

In the Shuoshi paper of yellow lance, synthesis of p-phenylphenol from biphenyl, biphenyl is used as a raw material, and is sulfonated with sulfuric acid to produce biphenyl-4-sulfonic acid, and the target compound p-phenylphenol is obtained by salting out with sodium chloride, sulfonating with concentrated sulfuric acid, and alkali-melting with sodium hydroxide. In the step of biphenyl sulfonation, diluting water and washing water added in the sulfonation process of p-phenyl benzenesulfonic acid are replaced by mother liquor generated after the last reaction is finished; similarly, in the sodium p-phenylphenylsulfonate alkali fusion step, the mother liquor after the last alkali fusion reaction is replaced by dilution water, and the yield of the product reaches 90 percent in terms of biphenyl after the mother liquor recycling process is used. However, the mother liquor in the process is indiscriminately used and has the following problems: (1) the sulfonated mother liquor contains by-products such as sulfuric acid, hydrochloric acid, sodium chloride and the like, although a part of the sulfonated mother liquor can be used for dilution water, the sulfonated mother liquor still needs to be treated and neutralized to obtain mixed salt of sodium chloride and sodium sulfate, and the mixed salt is not easy to separate; (2) sodium chloride, hydrochloric acid, sodium sulfite and p-phenylphenol are remained in the alkali fusion mother liquor, and when the alkali fusion mother liquor is applied to alkali fusion dilution water, sulfur dioxide gas is generated during the neutralization reaction by adding hydrochloric acid along with the accumulation of sodium sulfate, so that the environment is polluted. The mother liquor applying process in the process is not thorough, and the recycling efficiency is low.

The existing pyridine acid workshop adopts sodium chlorate as an oxidant to produce pyridine acid, mixed gas tail gas of chlorine and carbon dioxide can be generated, the tail gas is treated by adopting sodium sulfite at present, the sodium sulfite is purchased externally, and the cost of each ton of sodium sulfite is 3000 yuan.

The production process of the p-phenylphenol needs to be developed, the by-products in a workshop are comprehensively utilized, the three wastes are avoided, and the production yield of the p-phenylphenol is improved.

Disclosure of Invention

In order to overcome the problems in the prior art, the invention provides a novel p-phenylphenol production process for efficiently recycling mother liquor, the mother liquor is completely recycled, and the process is economic and environment-friendly.

The invention provides a production process of p-phenylphenol for mother liquor recycling, which comprises the following steps:

(1) heating the sulfonation mother liquor B obtained in the last reaction to evaporate water vapor, condensing to obtain circulating water, cooling and crystallizing the residual sulfonation mother liquor B to separate out sodium sulfate crystals, and filtering to obtain a sodium sulfate product and a filtrate F;

(2) adding the biphenyl, the new biphenyl and the concentrated sulfuric acid which are not reacted in the previous reaction into a reaction kettle for sulfonation reaction at the reaction temperature of 135-150 ℃, reacting for 3 hours, adding the circulating water obtained in the step (1) after the reaction is finished for dissolving, filtering to obtain the unreacted biphenyl and a filtrate A, transferring the filtrate A into a sodium treatment kettle, adding the alkali fusion mother liquor obtained in the previous reaction for sodium treatment to generate sulfur dioxide gas, supplementing sodium hydroxide into the sodium treatment kettle until the solution is neutral, and centrifuging to obtain biphenyl-4-sodium sulfonate solid and a sulfonation mother liquor B;

(3) transferring the biphenyl-4-sodium sulfonate solid obtained in the step (2) into an alkali fusion kettle, adding sodium hydroxide to perform alkali fusion reaction for 2 hours at the temperature of 160-340 ℃, adding the circulating water obtained in the step (1) to dissolve after the alkali fusion reaction to obtain a mixed solution C, transferring the mixed solution C into a neutralization kettle, introducing sulfur dioxide gas generated in the step (2) into the neutralization kettle, neutralizing sodium hydroxide which is not completely reacted in the alkali fusion to obtain a mixed solution D, and introducing sulfur dioxide tail gas into a sodium hydroxide solution to absorb to obtain a sodium sulfite solution M;

(4) and (4) mixing the neutral mixed solution D obtained in the step (3) with an organic solvent, transferring the mixture to a continuous layered extraction system for extraction to obtain an organic phase E and an alkali fusion mother liquor F, and distilling the organic phase F to obtain the organic solvent and a p-phenylphenol product.

Further, in the step (1), the sulfonation mother liquor B obtained in the last reaction and the filtrate F obtained in the last reaction are mixed, heated to evaporate water vapor, condensed to obtain circulating water, the residual sulfonation mother liquor B is cooled to crystallize to separate out sodium sulfate crystals, and the sodium sulfate product and the filtrate F are obtained through filtration.

Further, the sodium sulfite solution M in the step (3) is used for absorbing chlorine and carbon dioxide mixed tail gas in a pyridine acid plant.

Further, the organic solvent in the step (4) is methyl isobutyl ketone.

The invention has the beneficial effects that: (1) the production process for the p-phenylphenol by using the mother liquor can be used for mechanically using the sulfonated mother liquor generated by the reaction, sodium sulfate crystals and circulating water are gradually separated, the circulating water is recycled, the sodium sulfate crystals are sold, the waste liquid treatment cost is reduced, and the company benefits are improved; (2) according to the production process for the p-phenylphenol, which is used for mother liquor indiscriminately, the alkali fusion mother liquor generated by reaction is indiscriminately used for the sodium treatment reaction of the biphenyl 4 sulfonic acid, and is superior to the sodium treatment reaction system containing unreacted sulfuric acid, the sodium sulfite in the alkali fusion mother liquor reacts with the sulfuric acid to generate sulfur dioxide and sodium sulfate, sodium ions of the sodium sulfate are used for the sodium treatment reaction, sodium hydroxide is supplemented to adjust the pH value of the system, the biphenyl 4 sodium sulfonate is separated out, one part of the sulfur dioxide is used for neutralizing the unreacted sodium hydroxide after alkali fusion, and on the other hand, the sulfur dioxide is absorbed by the sodium hydroxide and then used for treating chlorine and carbon dioxide tail gas in a pyridine acid workshop, so; (3) the production process of the p-phenylphenol used for mother liquor in the invention makes full use of sodium sulfate and sodium sulfite mixed salt solution which is difficult to separate, separates sodium sulfate crystals, reduces the treatment cost of three wastes, improves the atom economy of reaction, saves energy, reduces consumption, and is green and environment-friendly; (4) the yield of the p-phenylphenol product produced by the p-phenylphenol production process mechanically applied to the mother liquor is 97.2 percent, the purity of the p-phenylphenol product is 99.8 percent, the purity of the sodium sulfate crystal is more than 99.1 percent, and the product quality is high.

Drawings

FIG. 1 is a process diagram for the production of p-phenylphenol

FIG. 2 is a diagram of a process for producing p-phenylphenol by recycling mother liquor.

Detailed Description

Please refer to fig. 1 to understand embodiment 1 and refer to fig. 2 to understand embodiments 2-5.

Example 1

The production process of p-phenylphenol comprises the following steps:

(1) 154g of biphenyl and 200.05g of concentrated sulfuric acid are added into a reaction kettle for sulfonation reaction at the temperature of 135 ℃ and 150 ℃ for 3 hours, 500g of water is added after the reaction is finished for dissolution, 3.08g of unreacted biphenyl and 850.97g of filtrate A are obtained by filtration, the filtrate A is completely transferred into a sodium treatment kettle, 81.64g of sodium hydroxide is added for sodium treatment, the solution in the sodium treatment kettle is neutral, and 250.88g of biphenyl-4-sodium sulfonate solid and 681.73g of sulfonation mother liquor B are obtained by centrifugation;

(2) transferring all the biphenyl-4-sodium sulfonate solid obtained in the step (1) into an alkali fusion kettle, adding 128g of sodium hydroxide to perform alkali fusion reaction at the temperature of 160-340 ℃ for 2h, adding 500g of water to dissolve after the alkali fusion reaction to obtain a mixed solution C, transferring the mixed solution C into a neutralization kettle, adding 150g of sulfuric acid (with the mass fraction of 42.5%) to neutralize sodium hydroxide which is not completely reacted in the alkali fusion until the pH value is 7, and obtaining a neutral mixed solution D;

(3) and (3) mixing the neutral mixed solution D obtained in the step (2) with 300g of organic solvent, transferring the mixture to a continuous layered extraction system for extraction to obtain an organic phase E and 78.38g of alkali fusion mother liquor F, and distilling the organic phase F to obtain 297g of organic solvent and 161.5g of p-phenylphenol product. The yield of the p-phenylphenol product is 95% and the purity of the p-phenylphenol product is 99.8% based on biphenyl.

Example 2

The production process of the p-phenylphenol used for the first mother liquor comprises the following steps:

(1) 681.73g of sulfonation mother liquor B obtained in example 1 are heated to evaporate water vapor, 540.29g of circulating water is obtained by condensation, 117.44g of sodium sulfate crystals are separated out by cooling and crystallizing the residual sulfonation mother liquor B, and a sodium sulfate product and 24g of filtrate F are obtained by filtration. The purity of the sodium sulfate crystal is 99.6 percent;

(2) adding 3.08g of unreacted biphenyl, 150.92g of biphenyl and 200.05g of concentrated sulfuric acid in the example 1 into a reaction kettle for sulfonation reaction at the reaction temperature of 135-150 ℃ for 3h, adding 500g of circulating water in the step (1) after the reaction is finished for dissolving, filtering to obtain 3.08g of unreacted biphenyl and a filtrate A, transferring the filtrate A into a sodium treatment kettle, adding 782.38g of alkali melt mother liquor obtained in the example 1 for sodium treatment to generate 62.21g of sulfur dioxide gas, supplementing 4.24g of sodium hydroxide into the sodium treatment kettle until the solution is neutral, and centrifuging to obtain 250.88g of biphenyl-4-sodium sulfonate solid and 1383.25g of sulfonated mother liquor B;

(3) transferring the biphenyl-4-sodium sulfonate solid obtained in the step (2) into an alkali fusion kettle, adding 128g of sodium hydroxide to perform alkali fusion reaction for 2 hours at the temperature of 160-;

(4) and (3) mixing the neutral mixed solution D obtained in the step (3) with 300g of organic solvent, transferring the mixture to a continuous layered extraction system for extraction to obtain an organic phase E and 713.64g of alkali fusion mother liquor F, and distilling the organic phase F to obtain 297g of organic solvent and 165.24g of p-phenylphenol product. The yield of the p-phenylphenol product is 97.2% and the purity of the p-phenylphenol product is 99.8% based on biphenyl.

(5) And (4) using the sodium sulfite solution M obtained in the step (3) for absorbing chlorine and carbon dioxide mixed tail gas in a pyridine acid workshop.

Example 3

The production process of the p-phenylphenol for the secondary mother liquor comprises the following steps:

(1) 1383.25g of sulfonation mother liquor B obtained in example 2 and 24g of filtrate F are heated to evaporate water vapor, 1176.23g of circulating water is obtained by condensation, the residual sulfonation mother liquor B is cooled to crystallize and separate out 110.10g of sodium sulfate crystals, and sodium sulfate products and 120.92g of filtrate F are obtained by filtration. The purity of the sodium sulfate crystal is 99.4 percent;

(2) adding 3.08g of unreacted biphenyl, 150.92g of biphenyl and 200.05g of concentrated sulfuric acid in the example 2 into a reaction kettle for sulfonation reaction at the reaction temperature of 135-150 ℃ for 3h, adding 500g of circulating water in the step (1) after the reaction is finished for dissolving, filtering to obtain 3.08g of unreacted biphenyl and a filtrate A, transferring the filtrate A into a sodium treatment kettle, adding 713.64g of alkali melt mother liquor obtained in the example 1 for sodium treatment to generate 62.21g of sulfur dioxide gas, supplementing 4.24g of sodium hydroxide into the sodium treatment kettle until the solution is neutral, and centrifuging to obtain 250.88g of biphenyl-4-sodium sulfonate solid and 1321.02g of sulfonated mother liquor B;

(3) transferring the biphenyl-4-sodium sulfonate solid obtained in the step (2) into an alkali fusion kettle, adding 128g of sodium hydroxide to perform alkali fusion reaction for 2 hours at the temperature of 160-340 ℃, adding 500g of circulating water to dissolve after the alkali fusion reaction to obtain a mixed solution C, transferring the mixed solution C into a neutralization kettle, introducing sulfur dioxide gas generated in the step (2) into the neutralization kettle, neutralizing sodium hydroxide which is not completely reacted in the alkali fusion to obtain a mixed solution D, and introducing sulfur dioxide tail gas into a sodium hydroxide solution to be absorbed to obtain a sodium sulfite solution M;

(4) and (3) mixing the neutral mixed solution D obtained in the step (3) with 300g of organic solvent, transferring the mixture to a continuous layered extraction system for extraction to obtain an organic phase E and 78.38g of alkali fusion mother liquor F, and distilling the organic phase F to obtain 297g of organic solvent and 165.24g of p-phenylphenol product. The yield of the p-phenylphenol product is 97.2% and the purity of the p-phenylphenol product is 99.8% based on biphenyl.

(5) The sodium sulfite solution M obtained in the step (3) is used for absorbing chlorine and carbon dioxide mixed tail gas in a pyridine acid workshop, so that the use is reduced

Example 4

The production process of the p-phenylphenol used for the third mother liquor comprises the following steps:

(1) 1321.02g of the sulfonation mother liquor B obtained in example 3 and 120.92g of the filtrate F are heated to evaporate water vapor, 1138.25 circulating water is obtained by condensation, 115.10g of sodium sulfate crystals are separated out by cooling and crystallizing the residual sulfonation mother liquor B, and sodium sulfate products and 67.67g of the filtrate F are obtained by filtration. The purity of the sodium sulfate crystal is 99.4 percent;

(2) adding 3.08g of unreacted biphenyl, 150.92g of biphenyl and 200.05g of concentrated sulfuric acid in the example 3 into a reaction kettle for sulfonation reaction at the reaction temperature of 135-150 ℃ for 3h, adding 500g of circulating water in the step (1) after the reaction is finished for dissolving, filtering to obtain 3.08g of unreacted biphenyl and a filtrate A, transferring the filtrate A into a sodium treatment kettle, adding 713.64g of alkali melt mother liquor obtained in the example 1 for sodium treatment to generate 62.21g of sulfur dioxide gas, supplementing 4.24g of sodium hydroxide into the sodium treatment kettle until the solution is neutral, and centrifuging to obtain 250.88g of biphenyl-4-sodium sulfonate solid and 1321.02g of sulfonated mother liquor B;

(3) transferring the biphenyl-4-sodium sulfonate solid obtained in the step (2) into an alkali fusion kettle, adding 128g of sodium hydroxide to perform alkali fusion reaction for 2 hours at the temperature of 160-340 ℃, adding 500g of circulating water to dissolve after the alkali fusion reaction to obtain a mixed solution C, transferring the mixed solution C into a neutralization kettle, introducing sulfur dioxide gas generated in the step (2) into the neutralization kettle, neutralizing sodium hydroxide which is not completely reacted in the alkali fusion to obtain a mixed solution D, and introducing sulfur dioxide tail gas into a sodium hydroxide solution to be absorbed to obtain a sodium sulfite solution M;

(4) and (3) mixing the neutral mixed solution D obtained in the step (3) with 300g of organic solvent, transferring the mixture to a continuous layered extraction system for extraction to obtain an organic phase E and 78.38g of alkali fusion mother liquor F, and distilling the organic phase F to obtain 297g of organic solvent and 165.24g of p-phenylphenol product. The yield of the p-phenylphenol product is 97.2% and the purity of the p-phenylphenol product is 99.8% based on biphenyl.

(5) And (4) using the sodium sulfite solution M obtained in the step (3) for absorbing chlorine and carbon dioxide mixed tail gas in a pyridine acid workshop.

Example 5

The production process of the p-phenylphenol used for the third mother liquor comprises the following steps:

(1) 1321.02g of sulfonation mother liquor B and 120.92g of filtrate F in example 3 are heated to evaporate water vapor, circulating water is obtained by condensation, the residual sulfonation mother liquor B is cooled to crystallize and separate out sodium sulfate crystals, and sodium sulfate products and filtrate F are obtained by filtration. The purity of the sodium sulfate crystals was 99.1%.

The other steps of this example were the same as in example 4 to obtain 165.24g of a p-phenylphenol product. The yield of the p-phenylphenol product is 97.2% and the purity of the p-phenylphenol product is 99.8% based on biphenyl.

The existing pyridine acid workshop adopts sodium chlorate as an oxidant to produce pyridine acid, mixed gas tail gas of chlorine and carbon dioxide can be generated, the tail gas is treated by adopting sodium sulfite at present, the sodium sulfite is purchased externally, and the cost of each ton of sodium sulfite is 3000 yuan. And the redundant sulfur dioxide gas generated by the para-phenylphenol production process mechanically applied to the mother liquor is absorbed by sodium hydroxide to generate sodium sulfite, and the sodium sulfite is used for tail gas absorption of a mixed gas of chlorine and carbon dioxide in a pyridine acid workshop, so that the cost consumption of purchased sodium sulfite is reduced, and the production cost of pyridine acid is reduced.

Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.