阅读说明：本技术 一种连续快速制备双酚s的方法 (Method for continuously and rapidly preparing bisphenol S ) 是由 骆建轻 周以鸿 李仲新 陈志勇 殷栎 于 2021-08-21 设计创作，主要内容包括：本发明公开了一种连续快速制备双酚S的方法,以苯磺酸与苯酚先进行反应,再与硫酸反应,在双酚S的粗制过程中抑制异构体2,4’-BPS,能够减少精制过程中添加其他溶剂,对环保性问题进行改善,同时增加双酚S回收率及纯度,同时使用活性炭、海泡石的双重净化,减少异构体的同时对废料内的有害物质进行吸收,减少环保处理问题,同时活性炭、海泡石能重复回收利用,大大节省了工艺时间、节约了生产成本,使得双酚S的提纯能够快速连续的进行。(The invention discloses a method for continuously and rapidly preparing bisphenol S, which comprises the steps of firstly reacting benzenesulfonic acid with phenol and then reacting with sulfuric acid, inhibiting isomer 2, 4' -BPS in the rough preparation process of bisphenol S, reducing the addition of other solvents in the refining process, improving the environmental protection problem, increasing the recovery rate and purity of bisphenol S, simultaneously using double purification of active carbon and sepiolite, reducing isomers, absorbing harmful substances in waste materials, reducing the environmental protection treatment problem, recycling the active carbon and the sepiolite repeatedly, greatly saving the process time, saving the production cost and enabling the purification of the bisphenol S to be carried out rapidly and continuously.)

1. A method for continuously and rapidly preparing bisphenol S is characterized by comprising the following steps:

s1, reacting phenol and benzenesulfonic acid at 40-150 ℃ for 1-2h under normal pressure in an inert atmosphere, adding concentrated sulfuric acid after the reaction is finished, introducing the concentrated sulfuric acid into a reduced pressure refining device, slowly raising the temperature to 170-180 ℃, and reacting for 10-24h to obtain a first treatment solution, wherein the molar ratio of the phenol to the concentrated sulfuric acid to the benzenesulfonic acid is (2: 1-1.5): 0.02-0.4;

s2, controlling the reflux ratio to enable water in the first treatment liquid to be brought out in a decompression mode, and decompressing to recover redundant phenol after water generated in the reaction in the first treatment liquid is completely separated to obtain a bisphenol S crude product;

and S3, refining the prepared bisphenol S crude product to obtain a bisphenol S finished product.

2. The method of claim 1, wherein the refining in step S3 comprises the steps of:

adding the bisphenol S crude product into a methanol water solution, stirring and reacting at 80-85 ℃ for 10-30min, and dripping an alkali solution to adjust the pH value to 6-7 to obtain a second treatment solution;

adding activated carbon into the second treatment solution, reacting for 1-2h at the temperature of 80-85 ℃, and filtering while hot to obtain a first filtrate;

and slowly cooling the first filtrate, separating out crystals, cooling to 25-35 ℃, filtering out solids, rinsing the obtained solids with 30% methanol aqueous solution, and drying to obtain refined bisphenol S, wherein the refined bisphenol S is used as a finished product of the bisphenol S.

3. The method for continuously and rapidly preparing bisphenol S according to claim 2, wherein the method for preparing activated carbon comprises the steps of:

putting the carbon raw material into an acid solution, soaking for 12-24h, taking out, and sintering at 200-350 ℃ in an argon atmosphere to obtain a first treatment material;

cooling the first treatment material to 40-60 ℃, putting the first treatment material into salicylic acid solution with the mass fraction of 30-70%, soaking for 1-5h, filtering, and drying at the temperature of 200-400 ℃ to obtain the activated carbon.

4. The method according to claim 3, wherein the acidic solution comprises the following components in percentage by mass:

10-12% of carbonic acid, 5-15% of sulfuric acid and the balance of deionized water.

5. The method according to claim 3, wherein the acidic solution comprises the following components in percentage by mass:

10-12% of carbonic acid, 5-8% of nitric acid, 1-5% of fruit acid and the balance of deionized water.

6. The method according to claim 4, further comprising the steps of, after drying the purified bisphenol S:

stirring refined bisphenol S in ethanol water solution at 75-80 ℃ for reaction for 10-30min, and adjusting the pH value to 6-7 to obtain a third treatment solution;

adding hydrophobic sepiolite into the third treatment liquid, cooling to 50-60 ℃, preserving heat for 1-2h, and filtering to obtain a second filtrate;

and slowly cooling the second filtrate to 25-30 ℃, waiting for 10-30min after crystals are separated out, filtering to obtain a solid, washing the obtained solid with 20-30% of an organic solvent, and drying to obtain the secondary refined bisphenol S as the bisphenol S finished product.

7. The method for continuously and rapidly preparing bisphenol S according to claim 6, wherein the preparation method of the hydrophobic sepiolite comprises the following steps:

the sepiolite and the heteropoly acid aqueous solution are mixed according to the proportion of 1: 10, stirring and reacting at 70-80 ℃ for 30-60min, cooling to 30-40 ℃, washing with an organic solvent, washing with deionized water, crushing, and drying to obtain a second treatment material;

silane coupling agent and ethanol solution according to the ratio of 1: 2-10, and mixing the second treatment material according to a solid-liquid ratio of 1: 5-10, putting into the hydrolysate, stirring and reacting at 60-80 ℃ for 10-30min, and then carrying out suction filtration and drying to obtain the hydrophobic sepiolite.

8. The method for continuously and rapidly preparing bisphenol S according to claim 7, wherein the method for preparing the heteropoly acid aqueous solution comprises the following steps:

mixing heteropoly acid and carbonic acid solution, performing ultrasonic dispersion at 20-40 ℃ for 30-50min, and adjusting the pH value to 1-2 to obtain a mixed solution;

keeping the temperature of the mixed solution and standing for 12-24h until crystals are precipitated, filtering, washing and drying the crystals, and then mixing the crystals in a solid-liquid ratio of 1-3: 10 in proportion into deionized water to obtain heteropoly acid aqueous solution;

the heteropoly acid is at least two of sodium molybdate, sodium silicate, sodium phosphate and sodium tungstate.

9. The method according to claim 7, wherein the organic solvent comprises the following components in percentage by mass:

10-15% of ethanol, 5-8% of diethyl ether and the balance of deionized water.

10. The method according to claim 7, wherein the silane coupling agent comprises the following components in percentage by mass:

50-80% of alkyl silane, and the balance of polyether silane.

Technical Field

The invention relates to the technical field of organic chemical industry, in particular to a method for continuously and rapidly preparing bisphenol S.

Background

Bisphenol S: chemical name 4,4, -dihydroxydiphenyl sulfone (abbreviated as BPS), english name 4,4' -sulfophenylenedienol, CAS number: 80-09-1, which has excellent heat resistance, light resistance and oxidation resistance. Bisphenol S can be used as a monomer to synthesize polymer materials such as high molecular polyether sulfone, polysulfone ether ketone and the like, and can be used as an intermediate for preparing flame retardants with excellent performance (tetrabromobisphenol S, octabromoS ether and the like) and color developers of thermal pressure sensitive recording paper. Due to wide application and good performance of bisphenol S, the market demand rises year by year, and the bisphenol S has great market prospect.

The current process routes for preparing bisphenol S mainly include the following steps:

1) hydrolyzing 4, 4-dichlorodiphenyl sulfone serving as a raw material under the action of alkali to generate sodium salt, and then acidifying to prepare bisphenol S. The reaction equation is as follows:

the raw material 4, 4-dichlorodiphenyl sulfone is not easy to obtain, the alkali fusion reaction condition is harsh, and the salt-containing wastewater is much in production, so that the route is fresh and industrialized.

2) Preparing 4, 4-dihydroxy diphenyl sulfide intermediate with phenol and sulfur dioxide as raw materials, and oxidizing with hydrogen peroxide to prepare bisphenol S. The reaction equation is as follows:

although the method can prepare bisphenol S with high content, the intermediate 4, 4-dihydroxy diphenyl sulfide needs to be prepared firstly, so that the process flow is overlong, the production cost is increased, the raw material sulfur dioxide is not easy to store and transport, and the operation and operation are safe in production, so that the route is also rarely industrialized.

3) The bisphenol S is prepared by using phenol and sulfuric acid as raw materials through sulfonation and dehydration, and the equation is as follows:

the method is an industrial mainstream route, phenol and sulfuric acid are firstly sulfonated to generate p-hydroxybenzene sulfonic acid and water in actual production, and the p-hydroxybenzene sulfonic acid and phenol are continuously decolorized to generate bisphenol S when the system is continuously heated and depressurized for dewatering. Phenol is required to be supplemented for many times in the decompression reaction process, so that water generated in the system is completely taken out, the technical process is complicated, phenol odor is easily overflowed in the operation environment, operators have poisoning accidents, and a large amount of isomers of the BPS, namely 2, 4' -BPS, are generated in the production process. Therefore, the purpose of removing water from the system by carrying water in a solvent method is proposed in the literature, but the method introduces a new solvent and is not environment-friendly.

With the rapid development of market economy, people tend to be stronger than ever before to happy life, and the requirements of the chemical production process on safety and environmental protection are more and more strict, so that a solution is urgently needed to solve the problems in the industrial route 3.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a method for continuously and rapidly preparing bisphenol S.

In order to solve the technical problems, the invention adopts the following technical scheme,

a method for continuously and rapidly preparing bisphenol S comprises the following steps:

s1, reacting phenol and benzenesulfonic acid at 40-150 ℃ for 1-2h under normal pressure in an inert atmosphere, adding concentrated sulfuric acid after the reaction is finished, introducing the concentrated sulfuric acid into a reduced pressure refining device, slowly raising the temperature to 170-180 ℃, and reacting for 10-24h to obtain a first treatment solution, wherein the molar ratio of the phenol to the concentrated sulfuric acid is 2: 1-1.5;

the molar ratio of the phenol to the benzenesulfonic acid is 1: 0.02-0.2;

s2, controlling the reflux ratio to enable water in the first treatment liquid to be brought out in a decompression mode, and decompressing to recover redundant phenol after water generated in the reaction in the first treatment liquid is completely separated to obtain a bisphenol S crude product;

and S3, refining the prepared bisphenol S crude product to obtain a bisphenol S finished product.

Preferably, the refining in step S3 includes the steps of:

adding the bisphenol S crude product into a methanol water solution, stirring and reacting at 80-85 ℃ for 10-30min, and dripping an alkali solution to adjust the pH value to 6-7 to obtain a second treatment solution;

adding activated carbon into the second treatment solution, reacting for 1-2h at the temperature of 80-85 ℃, and filtering while hot to obtain a first filtrate;

and slowly cooling the first filtrate, separating out crystals, cooling to 25-35 ℃, filtering out solids, rinsing the obtained solids with 30% methanol aqueous solution, and drying to obtain refined bisphenol S, wherein the refined bisphenol S is used as a finished product of the bisphenol S.

Preferably, the preparation method of the activated carbon comprises the following steps:

putting the carbon raw material into an acid solution, soaking for 12-24h, taking out, and sintering at 200-350 ℃ in an argon atmosphere to obtain a first treatment material;

cooling the first treatment material to 40-60 ℃, putting the first treatment material into salicylic acid solution with the mass fraction of 30-70%, soaking for 1-5h, filtering, and drying at the temperature of 200-400 ℃ to obtain the activated carbon.

Preferably, the acidic solution comprises the following components in percentage by mass:

10-12% of carbonic acid, 5-15% of sulfuric acid and the balance of deionized water.

Preferably, the acidic solution comprises the following components in percentage by mass:

10-12% of carbonic acid, 5-8% of nitric acid, 1-5% of fruit acid and the balance of deionized water.

Preferably, the step of drying to obtain the purified bisphenol S further comprises the steps of:

stirring refined bisphenol S in ethanol water solution at 75-80 ℃ for reaction for 10-30min, and adjusting the pH value to 6-7 to obtain a third treatment solution;

adding hydrophobic sepiolite into the third treatment liquid, cooling to 50-60 ℃, preserving heat for 1-2h, and filtering to obtain a second filtrate;

and slowly cooling the second filtrate to 25-30 ℃, waiting for 10-30min after crystals are separated out, filtering to obtain a solid, washing the obtained solid with 20-30% of an organic solvent, and drying to obtain the secondary refined bisphenol S as the bisphenol S finished product.

Preferably, the preparation method of the hydrophobic sepiolite comprises the following steps:

the sepiolite and the heteropoly acid aqueous solution are mixed according to the proportion of 1: 10, stirring and reacting at 70-80 ℃ for 30-60min, cooling to 30-40 ℃, washing with an organic solvent, washing with deionized water, crushing, and drying to obtain a second treatment material;

silane coupling agent and ethanol solution according to the ratio of 1: 2-10, and mixing the second treatment material according to a solid-liquid ratio of 1: 5-10, putting into the hydrolysate, stirring and reacting at 60-80 ℃ for 10-30min, and then carrying out suction filtration and drying to obtain the hydrophobic sepiolite.

Preferably, the preparation method of the heteropoly acid aqueous solution comprises the following steps:

mixing heteropoly acid and carbonic acid solution, performing ultrasonic dispersion at 20-40 ℃ for 30-50min, and adjusting the pH value to 1-2 to obtain a mixed solution;

keeping the temperature of the mixed solution and standing for 12-24h until crystals are precipitated, filtering, washing and drying the crystals, and then mixing the crystals in a solid-liquid ratio of 1-3: 10 in proportion into deionized water to obtain heteropoly acid aqueous solution;

the heteropolyacid is at least two of sodium molybdate, sodium silicate, sodium phosphate and sodium tungstate.

Preferably, the organic solvent comprises the following components:

10-15% of ethanol, 5-8% of diethyl ether and the balance of deionized water.

Preferably, the silane coupling agent comprises the following components in percentage by mass:

50-80 parts of alkyl silane, and the balance of polyether silane.

Compared with the prior art, the invention has the advantages that:

1. benzene sulfonic acid and phenol are reacted firstly and then are reacted with sulfuric acid, so that the isomer 2, 4' -BPS is inhibited in the crude process of bisphenol S, the addition of other solvents in the refining process can be reduced, and the problem of environmental protection is improved;

2. increase bisphenol S rate of recovery and purity, use the dual purification of active carbon, sepiolite simultaneously, absorb the harmful substance in the waste material when reducing the isomer, reduce environmental protection processing problem, active carbon, sepiolite can reuse simultaneously, have saved process time greatly, have practiced thrift manufacturing cost for the purification of bisphenol S can be fast continuous going on.

Drawings

Fig. 1 is a graph comparing the removal rate of phenol in wastewater after the sepiolite in examples 1, 2 and 6 of the present invention is reused for 1, 3, 5 and 7 times.

Detailed Description

The invention is further described in the following description and specific examples, but the scope of the invention is not limited thereby.

Example 1

A method for continuously and rapidly preparing bisphenol S comprises the following steps:

s1, reacting phenol and benzenesulfonic acid at 80 ℃ for 1.5h under normal pressure in a nitrogen atmosphere, adding concentrated sulfuric acid after the reaction is finished, introducing the concentrated sulfuric acid into a reduced-pressure refining device, slowly raising the temperature to 175 ℃, and reacting for 18h to obtain a first treatment solution, wherein the molar ratio of the phenol to the concentrated sulfuric acid to the benzenesulfonic acid is 2: 1.3: 0.2.

s2, controlling the reflux ratio to enable water in the first treatment liquid to be brought out in a decompression mode, and decompressing to recover redundant phenol after water generated in the reaction in the first treatment liquid is completely separated to obtain a bisphenol S crude product;

s3, adding the bisphenol S crude product into a methanol water solution, stirring and reacting for 25min at 80 ℃, and dripping an alkali solution to adjust the pH value to 7 to obtain a second treatment solution;

adding activated carbon into the second treatment solution, reacting for 2h at the temperature of 85 ℃, and filtering while hot to obtain a first filtrate;

slowly cooling the first filtrate, separating out crystals, filtering out solids after cooling to 30 ℃, rinsing the obtained solids by using 30% methanol aqueous solution, and drying to obtain primary refined bisphenol S;

stirring and reacting the primary refined bisphenol S in an ethanol water solution at 75 ℃ for 25min, and adjusting the pH value to 6 to obtain a third treatment solution;

adding hydrophobic sepiolite into the third treatment liquid, cooling to 55 ℃, preserving heat for 1.8h, and filtering to obtain a second filtrate;

and (3) slowly cooling the second filtrate to 25 ℃, waiting for 15min after crystals are separated out, filtering out solids, washing the solids with an organic solvent, and drying to obtain a bisphenol S finished product.

In this embodiment, the preparation method of sepiolite includes the following steps:

the sepiolite and the heteropoly acid aqueous solution are mixed according to the proportion of 1: mixing the raw materials according to a solid-liquid ratio of 10, stirring and reacting for 50min at 75 ℃, cooling to 35 ℃, washing with an organic solvent, washing with deionized water, crushing, and drying to obtain a second treatment material;

silane coupling agent and ethanol solution according to the ratio of 1: 8, hydrolyzing the second treatment material according to a solid-to-liquid ratio of 1: 9, putting the mixture into the hydrolysate, stirring the mixture at the temperature of 80 ℃ for reaction for 20min, and then carrying out suction filtration and drying to obtain the hydrophobic sepiolite.

The silane coupling agent is 70% of octadecyl silane and 30% of polyether polysiloxane;

the preparation method of the heteropoly acid aqueous solution comprises the following steps:

mixing sodium molybdate and sodium silicate according to the proportion of 1: 1, mixing the mixture with carbonic acid solution, performing ultrasonic dispersion at 30 ℃ for 40min, and adjusting the pH value to 1 to obtain mixed solution;

and (3) keeping the temperature of the mixed solution and standing for 15 hours until crystals are separated out, filtering, washing and drying the crystals, and then mixing the crystals in a solid-to-liquid ratio of 2: 10 in proportion into deionized water to obtain heteropoly acid aqueous solution;

the organic solvent is 20% ethanol solution.

Comparative example 1

This comparative example differs from example 1 in that:

s1, reacting phenol and benzenesulfonic acid at 80 ℃ for 1.5h under normal pressure in a nitrogen atmosphere, adding concentrated sulfuric acid after the reaction is finished, introducing the concentrated sulfuric acid into a reduced-pressure refining device, slowly raising the temperature to 175 ℃, and reacting for 18h to obtain a first treatment solution, wherein the molar ratio of the phenol to the concentrated sulfuric acid to the benzenesulfonic acid is 2: 1.3: 0.2.

s2, controlling the reflux ratio to enable water in the first treatment liquid to be brought out in a decompression mode, and decompressing to recover redundant phenol after water generated in the reaction in the first treatment liquid is completely separated to obtain a bisphenol S crude product;

s3, adding the bisphenol S crude product into a methanol water solution, stirring and reacting for 25min at 80 ℃, and dripping an alkali solution to adjust the pH value to 7 to obtain a second treatment solution;

adding activated carbon into the second treatment solution, reacting for 2h at the temperature of 85 ℃, and filtering while hot to obtain a first filtrate;

and slowly cooling the first filtrate, separating out crystals, filtering out solids after cooling to 30 ℃, rinsing the obtained solids by using 30% methanol aqueous solution, and drying to obtain the refined bisphenol S.

Comparative example 2

This comparative example differs from example 1 in that:

s1, adding concentrated sulfuric acid into phenol, introducing into a reduced pressure refining device, and reacting at 175 ℃ for 18 hours to obtain a first treatment solution, wherein the molar ratio of the phenol to the concentrated sulfuric acid is 2: 1.3;

comparative example 3

This comparative example differs from example 1 in that:

in this example, the silane coupling agent was 50% octadecylsilane and 50% polyether polysiloxane;

comparative example 4

This comparative example differs from example 1 in that:

in this example, the silane coupling agent was 70% octadecyltrimethoxysilane and 30% polyether polysiloxane.

Comparative example 5

This comparative example differs from example 1 in that:

in this example, the silane coupling agent was octadecylsilane.

Example 2

This example differs from example 1 in that:

the preparation method of the heteropoly acid aqueous solution comprises the following steps:

mixing sodium molybdate, sodium silicate and sodium tungstate according to the proportion of 1: 1: 1, mixing the mixture with carbonic acid solution, performing ultrasonic dispersion at 30 ℃ for 40min, and adjusting the pH value to 1 to obtain mixed solution;

and (3) keeping the temperature of the mixed solution and standing for 15 hours until crystals are separated out, filtering, washing and drying the crystals, and then mixing the crystals in a solid-to-liquid ratio of 2: 10 in proportion into deionized water to obtain heteropoly acid aqueous solution;

the organic solvent is 20% ethanol solution.

Example 3

This example differs from example 1 in that:

the preparation method of the heteropoly acid aqueous solution comprises the following steps:

mixing sodium molybdate and sodium silicate according to the proportion of 1: 1, mixing the mixture with carbonic acid solution, performing ultrasonic dispersion at 30 ℃ for 40min, and adjusting the pH value to 1 to obtain mixed solution;

and (3) keeping the temperature of the mixed solution and standing for 15 hours until crystals are separated out, filtering, washing and drying the crystals, and then mixing the crystals in a solid-to-liquid ratio of 2: 10 in proportion into deionized water to obtain heteropoly acid aqueous solution;

the organic solvent is a mixture of 12% ethanol, 8% diethyl ether and 80% deionized water.

Example 4

This example differs from example 3 in that:

the preparation method of the activated carbon is optimized on the basis of the embodiment 3, and the specific steps are as follows:

putting the carbon raw material into an acid solution, soaking for 15h, taking out, and sintering at 300 ℃ in an argon atmosphere to obtain a first treatment material;

cooling the first treatment material to 50 ℃, soaking the first treatment material in a salicylic acid solution with the mass fraction of 50% for 2 hours, and drying the first treatment material at the temperature of 300 ℃ to obtain activated carbon;

in this example, the acidic solution comprises the following components:

12% of carbonic acid;

8% of sulfuric acid;

80% of deionized water.

Comparative example 6

This comparative example differs from example 4 in that:

putting the carbon raw material into an acid solution, soaking for 15h, taking out, and sintering at 300 ℃ in an argon atmosphere to obtain a first treatment material;

and cooling the first treatment material to 50 ℃, soaking the first treatment material in a sulfuric acid solution with the mass fraction of 50% for 2 hours, and drying the first treatment material at the temperature of 300 ℃ to obtain the activated carbon.

Comparative example 7

This comparative example differs from example 4 in that:

putting the carbon raw material into an acid solution, soaking for 15h, taking out, and sintering at 300 ℃ in an argon atmosphere to obtain a first treatment material;

and cooling the first treatment material to 50 ℃, putting the first treatment material into a mixed solution of 25 mass percent of sulfuric acid and 25 mass percent of salicylic acid, soaking for 2 hours, and drying at the temperature of 300 ℃ to obtain the activated carbon.

Comparative example 8

This comparative example differs from example 4 in that:

in this example, the acidic solution comprises the following components:

12% of carbonic acid;

8% of hydrochloric acid;

80% of deionized water.

Example 5

This comparative example differs from example 4 in that:

in this example, the acidic solution comprises the following components:

comparative example 9

This comparative example differs from example 5 in that:

in this example, the acidic solution comprises the following components:

example 6

This embodiment is different from the embodiment 5 in that,

in this embodiment, the organic solvent used for preparing the hydrophobic sepiolite includes the following components:

15% of ethanol;

5% of diethyl ether;

80% of deionized water.

Comparative example 10

This comparative example differs from example 6 in that:

in this embodiment, the organic solvent used for preparing the hydrophobic sepiolite includes the following components:

20% of diethyl ether;

80% of deionized water.

As can be seen from the figure 1, it is,

the contents of the isomer 4,4 '-BPS and the isomer 2, 4' -BPS of the crude bisphenol S obtained in example 1 and comparative example 2 were measured, respectively, and the specific results are shown in Table 1:

TABLE 1

	Example 1	Comparative example 2
			2, 4' -BPS content (%)	0.02	2
4,4' -BPS content (%)	98	91

The purity and yield of the isomer 4,4' -BPS prepared using examples 1-6 and comparative examples 1-11 were determined, respectively, and the specific results are shown in Table 2:

TABLE 2

	4,4' -BPS purity (%)	4,4' -BPS yield (%)
			Comparative example 1	90.21	61.35
Comparative example 2	86.33	64.82
			Comparative example 3	91.05	72.37
Comparative example 4	88.62	67.59
			Comparative example 5	89.96	71.33
Comparative example 6	97.98	96.22
			Comparative example 7	97.88	96.12
Comparative example 8	97.92	93.71
			Comparative example 9	95.33	90.24
Comparative example 10	98.51	92.11
			Example 1	97.45	90.23
Example 2	97.62	89.71
			Example 3	97.84	91.33
Example 4	98.27	96.55
			Example 5	99.93	97.45
Example 6	99.98	97.64

The phenol content of the waste solutions produced after the production of examples 1, 2, 3, 6 and comparative examples 1, 3, 4, 5, 10 were measured, respectively, and the specific results are shown in table 3:

TABLE 3

	Phenol content (mg/L)
		Example 1	22.59
Example 2	36.57
		Example 3	19.65
Example 6	12.33
		Comparative example 1	876.68
Comparative example 3	432.75
		Comparative example 4	549.32
Comparative example 5	469.37
		Comparative example 10	49.52

Referring to tables 1-2, and the contents of the above comparative examples and examples, comparing example 1 with comparative example 2, it can be seen that example 1 inhibits the formation of isomer 2, 4 '-BPS using benzenesulfonic acid as an inhibitor on the basis of comparative example 2, and the content of isomer 2, 4' -BPS in the crude bisphenol S prepared is negligible;

comparing example 1 with comparative example 1, it is seen that in example 1, in addition to comparative example 1, the purity and yield of 4,4' -BPS are greatly improved by secondarily refining the bisphenol S after the filtration and purification of activated carbon with octadecylsilane and polyether polysiloxane and sepiolite modified with heteropoly acid;

comparing example 1 with comparative examples 3 to 5, it can be seen that the use of 70% octadecylsilane and 30% polyether polysiloxane as the surface modifier of sepiolite provides a better effect and the properties of sepiolite are more excellent;

comparing example 1 with example 2, it is known that in example 2, sodium tungstate component is added in preparation of heteropoly acid based on example 1, purity of refined 4,4' -BPS is improved, but yield is obviously reduced;

comparing example 1 and example 3, it is seen that example 3 improves the organic solvent used for improving sepiolite on the basis of example 1, the performance of sepiolite is optimized by using 12% ethanol and 8% diethyl ether as the organic solvent, and the purity of 4,4' -BPS is further improved;

comparing example 3, example 4 and comparative example 8, it can be seen that in example 4, the purification effect of bisphenol S by the prepared activated carbon is better by the improved manner of acid soaking-drying the activated carbon based on example 3 and soaking by using two components of carbonic acid and sulfuric acid;

comparing example 4 with comparative examples 6 to 7, it is known that the refining effect of bisphenol S is better compared to other acidic solvents or synthetic acidic solvents by using salicylic acid to soak and then dry during the activation process after primary sintering;

comparing example 4, example 5 and comparative example 9, it can be seen that comparative example 5 has the fruit acid component added in the acid solution component, and has better purification effect on sepiolite relative to bisphenol S;

comparing example 5, example 6 and comparative example 10, it is known that the use of a mixture of ethanol and diethyl ether as the organic solvent for the preparation of sepiolite gives the sepiolite a better purification effect;

referring to table 3, and the contents of the above comparative examples and examples, it can be seen that the sepiolite prepared by using the method of example 6 has the best effect of treating phenol-containing industrial waste during refining, and is most environmentally friendly, as compared to examples 1, 2, 3, and 6 and comparative examples 1, 3, 4, 5, and 10, and that the modified sepiolite of example 6 has the best repeated removal rate, as seen from fig. 1.

As can be seen from the above, example 6 is considered to be the most preferable example of the present invention because the purity and yield of bisphenol S obtained by the production method of example 6 are highest and the phenol content of the waste liquid after production is the least, compared to examples 1 to 5.

The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.