CN103319299B - Solid acid catalysis prepares the method for phenyl ethylbenzene ethane capacitor insulation oil - Google Patents

Abstract

The invention discloses a kind of method that solid acid catalysis prepares phenyl ethylbenzene ethane capacitor insulation oil, it is characterized in that: under 110 DEG C ~ 150 DEG C and UV-irradiation or radical initiator initiation, 2 ~ 10mol ethylbenzene and 1mol chlorine reaction are generated alpha-chloro ethylbenzene and β-Chloroethyl benzene, the mixture that reaction generates directly obtains phenyl ethylbenzene ethane with mixture hybrid reaction at 60 DEG C ~ 150 DEG C of 1 ~ 20g solid acid catalyst and 2 ~ 10mol ethylbenzene without being separated.Adopt the present invention, obtained phenyl ethylbenzene ethane capacitor insulation oil has all good characteristics of normal temperature transformer oil phenyl xylyl ethane, and its condensation point is significantly less than the condensation point of phenyl xylyl ethane, make it have unique resistance to low temperature, be suitable for especially being used as low temperature capacitor transformer oil.

Description

Solid acid catalysis prepares the method for phenyl ethylbenzene ethane capacitor insulation oil

Technical field

The invention belongs to the preparation method of the compound of a carbon containing and hydrogen, relate to a kind of method that solid acid catalysis prepares phenyl ethylbenzene ethane capacitor insulation oil.Phenyl ethylbenzene ethane (being called for short PEPE) product prepared by the present invention is mainly used as capacitor insulation oil, is particularly useful as low temperature capacitor transformer oil.

Background technology

Capacitor insulation oil is one of critical material manufacturing High-performance power electrical condenser, and its quality determines the reliability of high-voltage fence safe and highly efficient operation.At present, full film power capacitor all adopts diarylethane type [comprising: phenyl xylyl ethane (being called for short PXE) and phenyl ethylbenzene ethane (being called for short PEPE)] and benzyl toluene type capacitor insulation oil.The synthetic method preparing phenyl ethylbenzene ethane and phenyl xylyl ethane is similar, be corresponding aromatic hydrocarbons (the corresponding ethylbenzene of synthesis of phenyl ethylbenzene ethane, the corresponding dimethylbenzene of synthesis of phenyl xylyl ethane) under catalyst action, carry out Fu-Ke (Friedel-Crafts) alkylated reaction with alkylating reagent vinylbenzene, this is well-known in the art.In prior art, with ethylbenzene and vinylbenzene for raw material, adopt the method for solid acid catalysis method synthesis of phenyl ethylbenzene ethane type capacitor insulation oil, mainly contain US Patent No. 5073655, US5866733, Chinese patent CN1412166A, CN101898931A etc. disclose and adopt the synthesis of molecular sieve of MCM-22, zeolite beta, ZSM-12 and Al-MCM-41 mesopore molecular sieve to be the method that catalyst vinylbenzene and alkylating aromatic hydrocarbon prepare diarylethane, but not mentioned catalyst recirculation result of use.A.B. Dixit and G.D. Yadav reports and adopts Zeo-karb to be that catalyst dimethylbenzene and alkylated styrene reaction prepare diarylethane, very fast inactivation in catalyst recirculation use procedure.(the composition research of ethylbenzene and alkylated styrene product under solid superacid as catalyst such as Chen Shengzong, Hunan University's journal, 1994,21(1), 81-86.) report with solid super-strong acid SO42-/ZrO2 as catalyst vinylbenzene and ethylbenzene Friedel-Crafts alkylation synthesis of phenyl ethylbenzene ethane, target product yield is the highest is no more than 80%, and not mentioned catalyst recirculation service condition in literary composition.At present, there is vinylbenzene and easily become styrene oligomer at solid acid catalyst surface aggregate and cause the technical problem of catalyst deactivation in solid acid catalysis method of the prior art, also there is catalyzer manufacture and reclaiming process complexity, the shortcoming that cost is high, these defects make solid acid catalysis method still fail so far in the synthesis of phenyl ethylbenzene ethane, realize suitability for industrialized production application.

In addition, Chinese patent CN 1288452A then looks for another way to have invented and replaces traditional alkylating agent vinylbenzene with α-methylbenzylalcohol as alkylating agent, develop the novel process that is prepared diarylethane, but cause the selectivity of diarylethane lower because α-methylbenzylalcohol reactive behavior is not high, be no more than 60%, practicality is poor.

Summary of the invention

Object of the present invention is intended to overcome above-mentioned deficiency of the prior art, solve existing solid acid catalysis method to there is vinylbenzene and easily become styrene oligomer at solid acid catalyst surface aggregate and cause the technical problem of catalyst deactivation, can not recycle, also there is catalyst regeneration process complexity, the shortcoming that cost is high, there is provided that a kind of catalyzer can recycle, technique is simple, cost is low, with ethylbenzene and chlorine be raw material, solid acid catalysis prepares the method for phenyl ethylbenzene ethane capacitor insulation oil.

Content of the present invention is: solid acid catalysis prepares the method for phenyl ethylbenzene ethane capacitor insulation oil, it is characterized in that comprising the following steps:

A, prepare Chloroethyl benzene:

2 ~ 10mol ethylbenzene is added reactor A, stirring, the temperature of 110 DEG C ~ 150 DEG C, and under UV-irradiation or 2 ~ 10g radical initiator initiation, with 1 ~ 4 hour (being preferably at the uniform velocity), 1mol chlorine is passed in reactor A, after chlorine has passed into, continue reaction 1 ~ 3 hour, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid and discharge, obtain the mixture of alpha-chloro ethylbenzene, β-Chloroethyl benzene and ethylbenzene, mixture is incubated or lowers the temperature or be down to room temperature, for subsequent use;

Described radical initiator is one or more the mixture in Diisopropyl azodicarboxylate, tertbutyl peroxide, benzoyl peroxide, dicumyl peroxide; Also other radical initiators and free radical initiation method can be adopted;

B, prepare phenyl ethylbenzene ethane capacitor insulation oil:

2 ~ 10mol ethylbenzene and 1 ~ 20g solid acid catalyst are joined in reactor B and mixes, control temperature is 60 DEG C ~ 130 DEG C, to join in reactor B mixing react disposable for the mixture in reactor A, reaction 1 ~ 8 hour is continued at 60 DEG C ~ 150 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, the by-product hydrochloric acid obtained is discharged, filtering separation reclaims solid acid catalyst, filtrate passes through alkali cleaning again, the many alkylate by-products of excessive ethyl benzo removing high boiling point are reclaimed in washing and (normal pressure or decompression) rectifying, remaining thing is obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refining, i.e. obtained phenyl ethylbenzene ethane finished product (i.e. phenyl ethylbenzene ethane capacitor insulation oil),

Described solid acid catalyst is that (products production enterprise and product type can be Zeo-karb: the D001 macroporous strong-acid cation-exchange resin of resin company limited of Chengdu Nankai, the JHSK-8 gel-type strong-acid cation-exchange resin of Shijiazhuang Ji Hai resin Science and Technology Ltd., the D61 large hole strong acid styrene system cation exchange resin of resin company limited of Tianjin Nankai university), X-type zeolite, y-type zeolite, zeolite beta, mordenite, zeolite L, ZSM-5, ZSM-11, ZSM-18, ZSM-12, MCM-41, one or more mixture in super acids SO42-/ZrO2, also can be that other can the catalyzer of catalysis Friedel-Crafts alkylation.

In content of the present invention: to join in reactor B mixing and carry out reaction by disposable for the mixture in reactor A and can replace with described in step b: with 1 ~ 4 hour the mixture in reactor A is added dropwise in reactor B to mix and reacts.

In content of the present invention: to join in reactor B mixing and carry out reaction by disposable for the mixture in reactor A and can also replace with described in step b: with 2 hours the mixture in reactor A divided to join for three times in reactor B to mix and react, and interval time is identical, add 1/3 of described mixture total amount at every turn.

The chemical equation of synthesis of phenyl ethylbenzene ethane of the present invention is as follows:

Compared with prior art, the present invention has features and beneficial effect:

(1) the present invention is adopted, the vinylbenzene of easily polymerization is not used to make raw material, and adopting cinnamic industrial production raw material---ethylbenzene is raw material, avoids prior art to adopt vinylbenzene to be that raw material easily produces polymerization side reactions, thus affects the quality of product phenyl ethylbenzene ethane.

(2) adopt the present invention, the yield of phenyl ethylbenzene ethane is 68.81% ~ 87.14%, and adopts vinylbenzene to be very low or almost do not have through gas chromatographic detection yield in the comparative example of raw material.This result shows: ethylbenzene and chlorine reaction resultant alpha-chloro ethylbenzene, the activity that β-Chloroethyl benzene reacts compared with vinylbenzene are higher, the ethylbenzene making catalytic activity low and cinnamic catalyzer such as Zeo-karb, X-type zeolite, y-type zeolite, zeolite beta, mordenite, zeolite L, ZSM-5, ZSM-11, ZSM-18, ZSM-12, MCM-41, super acids SO42-/ZrO2 etc. all can use and show high catalytic activity, widened the range of choice of catalyzer, and target product selectivity is high.

(3) the present invention is adopted, the solid acid catalyst Zeo-karb, X-type zeolite, y-type zeolite, zeolite beta, mordenite, zeolite L, ZSM-5, ZSM-11, ZSM-18, the ZSM-12 that use, MCM-41, super acids SO42-/ZrO2 etc. are all recyclable recycles, and yield remains unchanged substantially, catalyst activity remains unchanged, reclaiming process is simple, reduces production cost.

(4) preparation technology of the present invention is simple, and operation is easy, easily operates, practical.

Concrete enforcement

Embodiment given below is intended so that the invention will be further described; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.

Embodiment 1-1:

4mol ethylbenzene is added reactor A, under stirring, 120 DEG C and UV-irradiation initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 3 hours, after chlorine has passed into, continue reaction 2 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, is down to room temperature, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Disposable for the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene adding in the reactor B filling 5mol ethylbenzene and 10g JHSK-8 gel-type strong-acid cation-exchange resin, 6g mordenite mixture at 60 DEG C is reacted, after mixing, reaction is continued 4 hours at 80 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims JHSK-8 gel-type strong-acid cation-exchange resin, mordenite, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 151.7g(theoretical yield is 210g), yield 72.24%.

The JHSK-8 gel-type strong-acid cation-exchange resin of recovery, mordenite catalyst are recycled 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 72.01%, 71.82% and 72.38%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 1-2:

5mol ethylbenzene is added reactor A, under stirring, 110 DEG C and 5g Diisopropyl azodicarboxylate initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 3 hours, after chlorine has passed into, continue reaction 2 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, is down to room temperature, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Disposable for the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene adding in the reactor B filling 5mol ethylbenzene and 20g zeolite beta mixture at 60 DEG C is reacted, after mixing, reaction is continued 8 hours at 70 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims zeolite beta, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 153.6g(theoretical yield is 210g), yield 73.14%.

The zeolite beta catalyst of recovery is recycled 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 72.94%, 73.07% and 72.91%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 1-3:

6mol ethylbenzene is added reactor A, under stirring, 130 DEG C and UV-irradiation initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 4 hours, after chlorine has passed into, continue reaction 1 hour, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, insulation, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Disposable for the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene adding in the reactor B filling 10mol ethylbenzene and 5g zeolite L, 10g ZSM-12 mixture at 100 DEG C is reacted, after mixing, reaction is continued 8 hours at 100 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims zeolite L, ZSM-12, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 152.4g(theoretical yield is 210g), yield 72.57%.

Embodiment 1-4:

10mol ethylbenzene is added reactor A, under stirring, 120 DEG C and 10g dicumyl peroxide initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 3 hours, after chlorine has passed into, continue reaction 2 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, is cooled to 100 DEG C, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Disposable for the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene adding in the reactor B filling 9mol ethylbenzene and 2gD61 large hole strong acid styrene system cation exchange resin, 12g MCM-41 mixture at 120 DEG C is reacted, after mixing, reaction is continued 1.5 hours at 150 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims D61 large hole strong acid styrene system cation exchange resin, MCM-41, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 161.1g(theoretical yield is 210g), yield 76.71%.

The D61 large hole strong acid styrene system cation exchange resin of recovery, MCM-41 catalyst recirculation are used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 76.31%, 76.60% and 76.63%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 1-5:

2mol ethylbenzene is added reactor A, under stirring, 120 DEG C and 2g benzoyl peroxide initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 1 hour, after chlorine has passed into, continue reaction 3 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, is cooled to 80 DEG C, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Disposable for the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene adding in the reactor B filling 2mol ethylbenzene and 6g super acids SO42-/ZrO2 mixture at 80 DEG C is reacted, after mixing, reaction is continued 3.5 hours at 100 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims super acids SO42-/ZrO2, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 154.3g(theoretical yield is 210g), yield 73.48%.

The super acids SO42-/ZrO2 catalyst recirculation of recovery is used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 73.20%, 73.33% and 73.59%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 1-6:

4mol ethylbenzene is added reactor A, under stirring, 150 DEG C and UV-irradiation initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 2 hours, after chlorine has passed into, continue reaction 3 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, insulation, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Disposable for the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene adding in the reactor B filling 5mol ethylbenzene and 12g y-type zeolite, 5g zeolite beta mixture at 130 DEG C is reacted, after mixing, reaction is continued 5 hours at 130 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims y-type zeolite, zeolite beta, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 157.8g(theoretical yield is 210g), yield 75.14%.

The y-type zeolite of recovery, zeolite beta catalyst are recycled 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 94.99%, 75.67% and 75.49%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 1-7:

10mol ethylbenzene is added reactor A, under stirring, 120 DEG C and 1g Diisopropyl azodicarboxylate, 6g tertbutyl peroxide initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 1 hour, after chlorine has passed into, continue reaction 3 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, is down to room temperature, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Disposable for the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene adding in the reactor B filling 7mol ethylbenzene and 15g X-type zeolite mixture at 110 DEG C is reacted, after mixing, reaction is continued 1 hour at 150 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims X-type zeolite, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 158.2g(theoretical yield is 210g), yield 75.33%.

The X-type zeolite catalyst of recovery is recycled 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 74.96%, 75.45% and 75.22%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 1-8:

7mol ethylbenzene is added reactor A, under stirring, 110 DEG C and UV-irradiation initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 2 hours, after chlorine has passed into, continue reaction 2 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, insulation, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Disposable for the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene adding in the reactor B filling 3mol ethylbenzene and 20gD001 macroporous strong-acid cation-exchange resin mixture at 110 DEG C is reacted, after mixing, reaction is continued 5 hours at 110 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims D001 macroporous strong-acid cation-exchange resin, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 147.6g(theoretical yield is 210g), yield 70.29%.

The D001 macroporous strong-acid cation-exchange resin catalyst of recovery is recycled 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 70.29%, 69.97% and 70.38%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 1-9:

10mol ethylbenzene is added reactor A, under stirring, 140 DEG C and 1g Diisopropyl azodicarboxylate, 3g dicumyl peroxide initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 4 hours, after chlorine has passed into, continue reaction 3 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, insulation, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Disposable for the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene adding in the reactor B filling 10mol ethylbenzene and 1g D001 macroporous strong-acid cation-exchange resin, 10g y-type zeolite, 1g zeolite L, 4g ZSM-18 mixture at 120 DEG C is reacted, after mixing, reaction is continued 3 hours at 140 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims D001 macroporous strong-acid cation-exchange resin, y-type zeolite, zeolite L, ZSM-18, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 144.5g(theoretical yield is 210g), yield 68.81%.

The D001 macroporous strong-acid cation-exchange resin of recovery, y-type zeolite, zeolite L, ZSM-18 catalyst recirculation are used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 68.43%, 68.91% and 68.98%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 1-10:

5mol ethylbenzene is added reactor A, under stirring, 130 DEG C and UV-irradiation initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 3 hours, after chlorine has passed into, continue reaction 2 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, is cooled to 60 DEG C, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Disposable for the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene adding in the reactor B filling 5mol ethylbenzene and 1g mordenite, 10g ZSM-12,3g MCM-41 mixture at 60 DEG C is reacted, after mixing, reaction is continued 7 hours at 60 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims mordenite, ZSM-12, MCM-41, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 147.9g(theoretical yield is 210g), yield 70.43%.

The mordenite of recovery, ZSM-12, MCM-41 catalyst recirculation are used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 70.31%, 70.46% and 70.23%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 2-1:

4mol ethylbenzene is added reactor A, under stirring, 140 DEG C and UV-irradiation initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 3 hours, after chlorine has passed into, continue reaction 2 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, is incubated or lowers the temperature or be down to room temperature, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

The mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene was added dropwise in the reactor B filling 4mol ethylbenzene and 10gJHSK-8 gel-type strong-acid cation-exchange resin mixture at 120 DEG C with 3 hours and reacts, after mixing, reaction is continued 3 hours at 120 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims JHSK-8 gel-type strong-acid cation-exchange resin, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 168.2g(theoretical yield is 210g), yield 80.1%.

The JHSK-8 gel-type strong-acid cation-exchange resin catalyst of recovery is recycled 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 80.41%, 80.62% and 79.84%, and yield remains unchanged substantially, and catalyst activity remains unchanged.

Comparative example 2-1:

8mol ethylbenzene and 10gJHSK-8 gel-type strong-acid cation-exchange resin are dropped in reactor, is uniformly mixed and is heated to 120 DEG C, 1mol vinylbenzene was added dropwise in reactor in 3 hours.After dropwising, continue reaction 3 hours at 120 DEG C, gas chromatographic detection almost generates without phenyl ethylbenzene ethane.

Embodiment 2-2:

6mol ethylbenzene is added reactor A, under stirring, 130 DEG C and UV-irradiation initiation, at the uniform velocity 1mol chlorine was passed in reactor with 4 hours, after chlorine has passed into, continue reaction 3 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, insulation, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

With 3 hours the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene is added dropwise in the reactor B filling 2mol ethylbenzene and 20g y-type zeolite (commercially available) mixture at 110 DEG C and reacts, after mixing, reaction is continued 4 hours at 110 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims y-type zeolite, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 179.3g(theoretical yield is 210g), yield 85.38%.

The y-type zeolite catalyst recirculation of recovery is used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 85.41%, 85.65% and 85.33%, and yield remains unchanged substantially, and catalyst activity remains unchanged.

Comparative example 2-2:

8mol ethylbenzene and 20gY type zeolite (commercially available) are dropped in reactor, is uniformly mixed and is heated to 110 DEG C, 1mol vinylbenzene was added dropwise in reactor A in 4 hours.After dropwising, continue reaction 3 hours at 120 DEG C, gas chromatographic detection major part vinylbenzene is unconverted, and the yield generating phenyl ethylbenzene ethane only has about 10%.

Embodiment 2-3:

4mol ethylbenzene is added reactor A, under stirring, 140 DEG C and UV-irradiation initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 3 hours, after chlorine has passed into, continue reaction 2 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, insulation, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

With 3 hours the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene is added dropwise in the reactor B filling 4mol ethylbenzene and 10g zeolite beta (commercially available) mixture at 100 DEG C and reacts, after mixing, reaction is continued 3 hours at 100 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims zeolite beta, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 183g(theoretical yield is 210g), yield 87.14%.

The zeolite beta catalyst of recovery is recycled 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 87.04%, 86.96% and 86.87%, and yield remains unchanged substantially, and catalyst activity remains unchanged substantially.

Comparative example 2-3:

8mol ethylbenzene and 10g zeolite beta (commercially available) are dropped in reactor, is uniformly mixed and is heated to 100 DEG C, 1mol vinylbenzene was added dropwise in reactor in 3 hours.After dropwising, continue reaction 3 hours at 100 DEG C, gas chromatographic detection major part vinylbenzene is unconverted, and the yield generating phenyl ethylbenzene ethane only has about 7% ~ 8%.

Embodiment 2-4:

5mol ethylbenzene is added reactor A, under stirring, 145 DEG C and UV-irradiation initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 3 hours, after chlorine has passed into, continue reaction 1 hour, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, insulation, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

5mol ethylbenzene is filled at 130 DEG C and 20g ZSM-18(is commercially available with within 2 hours, to be added dropwise to by the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene) react in the reactor B of mixture, after mixing, reaction is continued 3 hours at 130 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims ZSM-18, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 167g(theoretical yield is 210g), yield 79.52%.

The ZSM-18 catalyst recirculation of recovery is used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 80.14%, 79.63% and 79.8%, and yield remains unchanged substantially, and catalyst activity remains unchanged.

Comparative example 2-4:

By 10mol ethylbenzene and 20gZSM-18(commercially available) drop in reactor, be uniformly mixed and be heated to 130 DEG C, 1mol vinylbenzene was added dropwise in reactor in 2 hours.After dropwising, continue reaction 3 hours at 130 DEG C, gas chromatographic detection major part vinylbenzene is unconverted, and the yield generating phenyl ethylbenzene ethane only has about 6% ~ 8%.

Embodiment 2-5:

6mol ethylbenzene is added reactor A, under stirring, 150 DEG C and UV-irradiation initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 2 hours, after chlorine has passed into, continue reaction 1 hour, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, is cooled to 100 DEG C, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

4mol ethylbenzene is filled at 110 DEG C and 5g super acids SO42-/ZrO2 specifically will indicate source with within 4 hours, to be added dropwise to by the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene) react in the reactor B of mixture, after mixing, reaction is continued 2 hours at 110 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims super acids SO42-/ZrO2, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 180.1g(theoretical yield is 210g), yield 85.71%.

The super acids SO42-/ZrO2 catalyst recirculation of recovery is used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 85.41%, 86.01% and 85.83%, and yield remains unchanged substantially, and catalyst activity remains unchanged.

Comparative example 2-5:

10mol ethylbenzene and 5g super acids SO42-/ZrO2 are dropped in reactor, is uniformly mixed and is heated to 110 DEG C, 1mol vinylbenzene was added dropwise in reactor in 4 hours.After dropwising, reaction is continued 2 hours at 110 DEG C, after the completely consumed of gas chromatographic detection vinylbenzene, stopped reaction, by reaction mixture filtered and recycled super acids SO42-/ZrO2, can obtain phenyl ethylbenzene ethane 176g(theoretical yield through alkali cleaning, washing, rectifying is again 210g), yield 73.81%.The super acids SO42-/ZrO2 catalyst recirculation of recovery is used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 50. 14%, 33.01% and 9.83%, and catalyst activity obviously reduces.

Embodiment 2-6:

5mol ethylbenzene is added reactor A, under stirring, 110 DEG C and 4g Diisopropyl azodicarboxylate initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 4 hours, after chlorine has passed into, continue reaction 1 hour, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, is down to room temperature, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

With the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene to be added dropwise in 3 hours to fill 5mol ethylbenzene and 3g D001 macroporous strong-acid cation-exchange resin, 1g ZSM-5,10g ZSM-11,1g ZSM-18 mixture at 60 DEG C reactor B in react, after mixing, reaction is continued 8 hours at 60 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims D001 macroporous strong-acid cation-exchange resin, ZSM-5, ZSM-11, ZSM-18, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 181.6g(theoretical yield is 210g), yield 86.48%.

The D001 macroporous strong-acid cation-exchange resin of recovery, ZSM-5, ZSM-11, ZSM-18 catalyst recirculation are used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 86.39%, 85.95% and 86.31%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 2-7:

5mol ethylbenzene is added reactor A, under stirring, 140 DEG C and UV-irradiation initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 3 hours, after chlorine has passed into, continue reaction 2 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, is cooled to 100 DEG C, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

With the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene to be added dropwise in 3 hours to fill 4mol ethylbenzene and 10g X-type zeolite, 3g zeolite beta, 1g ZSM-5 mixture at 130 DEG C reactor B in react, after mixing, reaction is continued 1 hour at 150 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims X-type zeolite, zeolite beta, ZSM-5, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 174.9g(theoretical yield is 210g), yield 83.29%.

The X-type zeolite of recovery, zeolite beta, ZSM-5 catalyst recirculation are used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 83.42%, 83.10% and 83.55%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 2-8:

2mol ethylbenzene is added reactor A, under stirring, 120 DEG C and 2.5g Diisopropyl azodicarboxylate, 2.5g dicumyl peroxide initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 2 hours, after chlorine has passed into, continue reaction 3 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, is down to room temperature, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

With the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene to be added dropwise in 1 hour to fill 2mol ethylbenzene and 0.5g mordenite, 0.5g super acids SO42-/ZrO2 mixture at 60 DEG C reactor B in react, after mixing, reaction is continued 6 hours at 150 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims mordenite, super acids SO42-/ZrO2, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 166.3g(theoretical yield is 210g), yield 79.19%.

The mordenite of recovery, super acids SO42-/ZrO2 catalyst recirculation are used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 78.84%, 78.97% and 79.33%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 2-9:

10mol ethylbenzene is added reactor A, under stirring, 130 DEG C and 1g Diisopropyl azodicarboxylate, 1g tertbutyl peroxide initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 1 hour, after chlorine has passed into, continue reaction 3 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, insulation, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

With the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene to be added dropwise in 3 hours to fill 10mol ethylbenzene and 5gD61 large hole strong acid styrene system cation exchange resin, 8g zeolite L mixture at 110 DEG C reactor B in react, after mixing, reaction is continued 2 hours at 130 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims D61 large hole strong acid styrene system cation exchange resin, zeolite L, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 177.4g(theoretical yield is 210g), yield 84.48%.

The D61 large hole strong acid styrene system cation exchange resin of recovery, zeolite L catalyst recirculation are used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 84.07%, 83.82% and 83.93%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 2-10:

6mol ethylbenzene is added reactor A, under stirring, 140 DEG C and 4g benzoyl peroxide, 6g tertbutyl peroxide initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 2 hours, after chlorine has passed into, continue reaction 3 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, is down to room temperature, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

With 3 hours the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene is added dropwise in the reactor B filling 4mol ethylbenzene and 1g ZSM-18 mixture at 80 DEG C and reacts, after mixing, reaction is continued 6 hours at 120 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims ZSM-18, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 169.1g(theoretical yield is 210g), yield 80.53%.

The ZSM-18 catalyst recirculation of recovery is used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 79.99%, 79.70% and 80.48%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 3-1:

6mol ethylbenzene is added reactor A, under stirring, 130 DEG C and 10g Diisopropyl azodicarboxylate initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 1 hour, after chlorine has passed into, continue reaction 3 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, is down to room temperature, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Three times are divided by the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene and 1/3 total amount with 2 hours/time hour to add in the reactor B filling 5mol ethylbenzene and 5g super acids SO42-/ZrO2 mixture at 60 DEG C and react, after mixing, reaction is continued 1 hour at 150 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims super acids SO42-/ZrO2, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 163.5g(theoretical yield is 210g), yield 77.86%.

The super acids SO42-/ZrO2 catalyst recirculation of recovery is used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 78.05%, 78.01% and 77.81%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 3-2:

2mol ethylbenzene is added reactor A, under stirring, 120 DEG C and UV-irradiation initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 2 hours, after chlorine has passed into, continue reaction 3 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, is down to room temperature, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Divided three times with 2 hours by the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene and 1/3 total amount/time hour to add fill 5mol ethylbenzene at 70 DEG C and 20g ZSM-18(is commercially available) react in the reactor B of mixture, after mixing, reaction is continued 6 hours at 100 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims ZSM-18, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 161.2g(theoretical yield is 210g), yield 76.76%.

The ZSM-18 catalyst recirculation of recovery is used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 76.88%, 76.35% and 76.69%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 3-3:

4mol ethylbenzene is added reactor A, under stirring, 120 DEG C and UV-irradiation initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 3 hours, after chlorine has passed into, continue reaction 2 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, is cooled to 60 DEG C, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Three times are divided by the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene and 1/3 total amount with 2 hours/time hour to add in the reactor B filling 6mol ethylbenzene and 10g zeolite beta (commercially available) mixture at 80 DEG C and react, after mixing, reaction is continued 5 hours at 130 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims zeolite beta, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 156.7g(theoretical yield is 210g), yield 74.62%.

The zeolite beta catalyst of recovery is recycled 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 74.33%, 74.29% and 74.69%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 3-4:

5mol ethylbenzene is added reactor A, under stirring, 110 DEG C and 5g Diisopropyl azodicarboxylate initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 4 hours, after chlorine has passed into, continue reaction 1 hour, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, is down to room temperature, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Three times are divided by the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene and 1/3 total amount with 2 hours/time hour to add in the reactor B filling 10mol ethylbenzene and 20g y-type zeolite (commercially available) mixture at 60 DEG C and react, after mixing, reaction is continued 8 hours at 60 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims y-type zeolite, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 156.9g(theoretical yield is 210g), yield 74.71%.

The y-type zeolite catalyst recirculation of recovery is used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 74.70%, 77.63% and 77.82%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 3-5:

3mol ethylbenzene is added reactor A, under stirring, 110 DEG C and UV-irradiation initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 3 hours, after chlorine has passed into, continue reaction 2 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, insulation, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Three times are divided by the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene and 1/3 total amount with 2 hours/time hour to add in the reactor B filling 9mol ethylbenzene and 10g D61 large hole strong acid styrene system cation exchange resin mixture at 100 DEG C and react, after mixing, reaction is continued 4.5 hours at 80 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims D61 large hole strong acid styrene system cation exchange resin, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 155.9g(theoretical yield is 210g), yield 74.24%.

The D61 large hole strong acid styrene system cation exchange resin catalyst recirculation of recovery is used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 74.31%, 74.36% and 77.26%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 3-6:

10mol ethylbenzene is added reactor A, under stirring, 140 DEG C and 8g dicumyl peroxide initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 4 hours, after chlorine has passed into, continue reaction 2 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, insulation, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Three times are divided by the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene and 1/3 total amount with 2 hours/time hour to add in the reactor B filling 2mol ethylbenzene and 10g ZSM-11,5gMCM-41 mixture at 110 DEG C and react, after mixing, reaction is continued 3.5 hours at 100 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims ZSM-11, MCM-41, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 162.5g(theoretical yield is 210g), yield 77.38%.

ZSM-11, MCM-41 catalyst recirculation of recovery is used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 77.39%, 77.40% and 77.20%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 3-7:

6mol ethylbenzene is added reactor A, under stirring, 120 DEG C and UV-irradiation initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 3 hours, after chlorine has passed into, continue reaction 2 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, insulation, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Three times are divided by the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene and 1/3 total amount with 2 hours/time hour to add in the reactor B filling 5mol ethylbenzene and 5g ZSM-5,5g ZSM-12 mixture at 120 DEG C and react, after mixing, reaction is continued 6 hours at 90 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims ZSM-5, ZSM-12, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 153.2g(theoretical yield is 210g), yield 72.95%.

ZSM-5, ZSM-12 catalyst recirculation of recovery is used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 72.87%, 73.01% and 73.02%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 3-8:

7mol ethylbenzene is added reactor A, under stirring, 130 DEG C and 2g benzoyl peroxide initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 3 hours, after chlorine has passed into, continue reaction 3 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, is down to room temperature, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Three times are divided by the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene and 1/3 total amount with 2 hours/time hour to add in the reactor B filling 7mol ethylbenzene and 10g mordenite, 1g zeolite L mixture at 70 DEG C and react, after mixing, reaction is continued 5 hours at 140 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims mordenite, zeolite L, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 157.4g(theoretical yield is 210g), yield 74.95%.

The mordenite of recovery, zeolite L catalyst recirculation are used 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 74.58%, 74.69% and 74.96%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 3-9:

4mol ethylbenzene is added reactor A, under stirring, 140 DEG C and UV-irradiation initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 1 hour, after chlorine has passed into, continue reaction 2 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, insulation, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Three times are divided by the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene and 1/3 total amount with 2 hours/time hour to add in the reactor B filling 5mol ethylbenzene and 1g JHSK-8 gel-type strong-acid cation-exchange resin, 2g X-type zeolite mixture at 130 DEG C and react, after mixing, reaction is continued 2 hours at 140 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims JHSK-8 gel-type strong-acid cation-exchange resin, X-type zeolite, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 156.9g(theoretical yield is 210g), yield 74.71%.

The JHSK-8 gel-type strong-acid cation-exchange resin of recovery, X-type zeolite catalyst are recycled 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 74.70%, 74.89% and 74.58%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

Embodiment 3-10:

10mol ethylbenzene is added reactor A, under stirring, 120 DEG C and 1g Diisopropyl azodicarboxylate, 5g tertbutyl peroxide initiation, at the uniform velocity 1mol chlorine was passed in reactor A with 4 hours, after chlorine has passed into, continue reaction 3 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid discharge, insulation, the mixture of the alpha-chloro ethylbenzene obtained, β-Chloroethyl benzene and ethylbenzene;

Three times are divided by the mixture of the alpha-chloro ethylbenzene in reactor A, β-Chloroethyl benzene and ethylbenzene and 1/3 total amount with 2 hours/time hour to add in the reactor B filling 4mol ethylbenzene and 20gX type zeolite mixture at 110 DEG C and react, after mixing, reaction is continued 3 hours at 110 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, obtain by-product hydrochloric acid to discharge, filtering separation reclaims X-type zeolite, pass through alkali cleaning, washing and Atmospheric vacuum rectifying are reclaimed the many alkylate by-products of excessive ethyl benzo removing high boiling point and are obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refined and obtained phenyl ethylbenzene ethane finished product 153.2g(theoretical yield is 210g), yield 72.95%.

The X-type zeolite catalyst of recovery is recycled 3 times, is undertaken by aforesaid operations step, the yield of three circulations is respectively 72.99%, 72.67% and 72.88%.Yield remains unchanged substantially, and catalyst activity remains unchanged.

As can be seen from above-described embodiment and corresponding comparative example, adopting ethylbenzene partial oxidation product to be alkylating reagent compared to vinylbenzene is that alkylating reagent has that reactive behavior is high, selectivity good, target product yield is high, and adopts Fu-Ke alkylation solid acid catalyst also to have to recycle effective advantage.

Embodiment 4:

Solid acid catalysis prepares the method for phenyl ethylbenzene ethane capacitor insulation oil, comprises the following steps:

A, prepare Chloroethyl benzene:

6mol ethylbenzene is added reactor A, stirring, the temperature of 110 DEG C ~ 150 DEG C, and under UV-irradiation or 6g radical initiator initiation, with 2.5 hours (being preferably at the uniform velocity), 1mol chlorine is passed in reactor A, after chlorine has passed into, continue reaction 2 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid and discharge, obtain the mixture of alpha-chloro ethylbenzene, β-Chloroethyl benzene and ethylbenzene, mixture can be incubated or lower the temperature or be down to room temperature, for subsequent use;

B, prepare phenyl ethylbenzene ethane capacitor insulation oil:

6mol ethylbenzene and 10g solid acid catalyst are joined in reactor B and mixes, control temperature is 80 DEG C ~ 110 DEG C, to join in reactor B mixing react disposable for the mixture in reactor A, reaction 5 hours is continued at 80 DEG C ~ 120 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, the by-product hydrochloric acid obtained is discharged, filtering separation reclaims solid acid catalyst, filtrate passes through alkali cleaning again, the many alkylate by-products of excessive ethyl benzo removing high boiling point are reclaimed in washing and (can normal pressure or decompression) rectifying, remaining thing is obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refining, i.e. obtained phenyl ethylbenzene ethane finished product.

Embodiment 5:

Solid acid catalysis prepares the method for phenyl ethylbenzene ethane capacitor insulation oil, comprises the following steps:

A, prepare Chloroethyl benzene:

2mol ethylbenzene is added reactor A, stirring, the temperature of 110 DEG C ~ 150 DEG C, and under UV-irradiation or 2g radical initiator initiation, with 1 hour (being preferably at the uniform velocity), 1mol chlorine is passed in reactor A, after chlorine has passed into, continue reaction 1 hour, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid and discharge, obtain the mixture of alpha-chloro ethylbenzene, β-Chloroethyl benzene and ethylbenzene, mixture is incubated or lowers the temperature or be down to room temperature, for subsequent use;

B, prepare phenyl ethylbenzene ethane capacitor insulation oil:

2mol ethylbenzene and 1g solid acid catalyst are joined in reactor B and mixes, control temperature is 60 DEG C, to join in reactor B mixing react disposable for the mixture in reactor A, reaction is continued 8 hours at 60 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, the by-product hydrochloric acid obtained is discharged, filtering separation reclaims solid acid catalyst, filtrate passes through alkali cleaning again, the many alkylate by-products of excessive ethyl benzo removing high boiling point are reclaimed in washing and (normal pressure or decompression) rectifying, remaining thing is obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refining, i.e. obtained phenyl ethylbenzene ethane finished product.

Embodiment 6:

Solid acid catalysis prepares the method for phenyl ethylbenzene ethane capacitor insulation oil, comprises the following steps:

A, prepare Chloroethyl benzene:

10mol ethylbenzene is added reactor A, stirring, the temperature of 110 DEG C ~ 150 DEG C, and under UV-irradiation or 10g radical initiator initiation, with 4 hours (being preferably at the uniform velocity), 1mol chlorine is passed in reactor A, after chlorine has passed into, continue reaction 3 hours, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid and discharge, obtain the mixture of alpha-chloro ethylbenzene, β-Chloroethyl benzene and ethylbenzene, mixture is incubated or lowers the temperature or be down to room temperature, for subsequent use;

B, prepare phenyl ethylbenzene ethane capacitor insulation oil:

10mol ethylbenzene and 20g solid acid catalyst are joined in reactor B and mixes, control temperature is 110 DEG C ~ 130 DEG C, to join in reactor B mixing react disposable for the mixture in reactor A, reaction 1 hour is continued at 130 DEG C ~ 150 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, the by-product hydrochloric acid obtained is discharged, filtering separation reclaims solid acid catalyst, filtrate passes through alkali cleaning again, the many alkylate by-products of excessive ethyl benzo removing high boiling point are reclaimed in washing and (can normal pressure or decompression) rectifying, remaining thing is obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refining, i.e. obtained phenyl ethylbenzene ethane finished product.

In above-described embodiment 1-6: described radical initiator is one or more the mixture in Diisopropyl azodicarboxylate, tertbutyl peroxide, benzoyl peroxide, dicumyl peroxide; Also other radical initiators and free radical initiation method can be adopted;

In above-described embodiment 1-6: described solid acid catalyst is that (products production enterprise and product type can be Zeo-karb: the D001 macroporous strong-acid cation-exchange resin of resin company limited of Chengdu Nankai, the JHSK-8 gel-type strong-acid cation-exchange resin of Shijiazhuang Ji Hai resin Science and Technology Ltd., the D61 large hole strong acid styrene system cation exchange resin of resin company limited of Tianjin Nankai university), X-type zeolite, y-type zeolite, zeolite beta, mordenite, zeolite L, ZSM-5, ZSM-11, ZSM-18, ZSM-12, MCM-41, one or more mixture in super acids SO42-/ZrO2, also can be that other can the catalyzer of catalysis Friedel-Crafts alkylation.

In above-described embodiment 1-6: to join in reactor B mixing and carry out reaction by disposable for the mixture in reactor A and can replace with described in step b: with 2.5 hours the mixture in reactor A is added dropwise in reactor B to mix and reacts.

In above-described embodiment 1-6: to join in reactor B mixing and carry out reaction by disposable for the mixture in reactor A and can replace with described in step b: with 1 hour the mixture in reactor A is added dropwise in reactor B to mix and reacts.

In above-described embodiment 1-6: to join in reactor B mixing and carry out reaction by disposable for the mixture in reactor A and can replace with described in step b: with 4 hours the mixture in reactor A is added dropwise in reactor B to mix and reacts.

In above-described embodiment 1-6: to join in reactor B mixing and carry out reaction by disposable for the mixture in reactor A and can also replace with described in step b: with 2 hours the mixture in reactor A divided to join for three times in reactor B to mix and react, and interval time is identical, add 1/3 of described mixture total amount at every turn.

In above-described embodiment: in the percentage adopted, do not indicate especially, be quality (weight) percentage; Described weight part can be all gram or kilogram.

In above-described embodiment: the processing parameter (temperature, time, concentration etc.) in each step and each amounts of components numerical value etc. are scope, and any point is all applicable.

The concrete same prior art of technology contents described in content of the present invention and above-described embodiment, described starting material are commercially available prod.

The invention is not restricted to above-described embodiment, all can implement described in content of the present invention and there is described good result.

Claims (3)

1. solid acid catalysis prepares the method for phenyl ethylbenzene ethane capacitor insulation oil, it is characterized in that comprising the following steps:

A, prepare Chloroethyl benzene:

2 ~ 10mol ethylbenzene is added reactor A, stirring, the temperature of 110 DEG C ~ 150 DEG C, and under UV-irradiation or 2 ~ 10g radical initiator initiation, with 1 ~ 4 hour, 1mol chlorine is passed in reactor A, after chlorine has passed into, continue reaction 1 ~ 3 hour, the hydrogen chloride gas water generated in reaction process absorbs and obtains by-product hydrochloric acid and discharge, obtain the mixture of alpha-chloro ethylbenzene, β-Chloroethyl benzene and ethylbenzene, for subsequent use;

Described radical initiator is one or more the mixture in Diisopropyl azodicarboxylate, tertbutyl peroxide, benzoyl peroxide, dicumyl peroxide;

B, prepare phenyl ethylbenzene ethane capacitor insulation oil:

2 ~ 10mol ethylbenzene and 1 ~ 20g solid acid catalyst are joined in reactor B and mixes, control temperature is 60 DEG C ~ 130 DEG C, to join in reactor B mixing react disposable for the mixture in reactor A, reaction 1 ~ 8 hour is continued at 60 DEG C ~ 150 DEG C, after gas chromatographic detection alpha-chloro ethylbenzene and β-Chloroethyl benzene completely consumed, stopped reaction, the hydrogen chloride gas water generated in reaction process absorbs, the by-product hydrochloric acid obtained is discharged, filtering separation reclaims solid acid catalyst, filtrate passes through alkali cleaning again, the many alkylate by-products of excessive ethyl benzo removing high boiling point are reclaimed in washing and rectifying, remaining thing is obtained phenyl ethylbenzene ethane crude product, adsorb through atlapulgite again, high vacuum degassing dehydration is refining, i.e. obtained phenyl ethylbenzene ethane finished product,

Described solid acid catalyst is Zeo-karb, X-type zeolite, y-type zeolite, zeolite beta, mordenite, zeolite L, ZSM-5, ZSM-11, ZSM-18, ZSM-12, MCM-41, super acids SO ₄ ^2-/ ZrO ₂in one or more mixture.

2. prepare the method for phenyl ethylbenzene ethane capacitor insulation oil by solid acid catalysis described in claim 1, it is characterized in that: to join in reactor B mixing and carry out reaction by disposable for the mixture in reactor A and replace with described in step b: with 1 ~ 4 hour the mixture in reactor A is added dropwise in reactor B to mix and reacts.

3. the method for phenyl ethylbenzene ethane capacitor insulation oil is prepared by solid acid catalysis described in claim 1, it is characterized in that: to join in reactor B mixing and carry out reaction by disposable for the mixture in reactor A and replace with described in step b: with 2 hours the mixture in reactor A divided to join for three times in reactor B to mix and react, and interval time is identical, add 1/3 of described mixture total amount at every turn.