CN106631651A - Preparation method of benzyl methylbenzene - Google Patents
Preparation method of benzyl methylbenzene Download PDFInfo
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- CN106631651A CN106631651A CN201611154348.1A CN201611154348A CN106631651A CN 106631651 A CN106631651 A CN 106631651A CN 201611154348 A CN201611154348 A CN 201611154348A CN 106631651 A CN106631651 A CN 106631651A
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- benzyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
Abstract
The invention relates to a preparation method of benzyl methylbenzene. The method comprises the following steps: adding concentrated sulfuric acid into calcium bentonite, stirring under reflux, and drying to obtain solid activated clay; dissolving ZnCl2 in an acetonitrile solution, adding the prepared activated clay, stirring at room temperature for 24 hours, filtering, and activating at 120 DEG C for 4 hours, thereby obtaining an activated-clay-supported ZnCl2 solid acid catalyst; adding the activated-clay-supported ZnCl2 solid acid catalyst into a benzyl chloride-methylbenzene alkylation reaction system, carrying out catalytic reaction, and filtering to recover the catalyst; and carrying out reduced pressure distillation and refinement on the benzyl methylbenzene crude product, thereby obtaining the benzyl methylbenzene. The catalyst has the advantages of abundant raw material sources, low cost, simple preparation technique and low energy consumption due to no need of high-temperature activation, and can be easily separated from the product; and when being used for carrying out synthetic reaction of benzyl methylbenzene, the catalyst has the advantages of high reaction conversion rate, high selectivity, mild conditions, low equipment corrosion and small environmental pollution, can be easily recovered and reutilized, and thus, has wide application prospects.
Description
Technical field
The invention belongs to organic synthesis field, and in particular to a kind of preparation method of benzyl toluene.
Background technology
Benzyl toluene is the product that toluene is obtained in the presence of acidic with benzyl chloride reaction, mainly including monobenzyl
Toluene (Monobenzyl Toluene, be abbreviated as MBT) and double benzyl toluenes (Dibenzyl Toluene, be abbreviated as DBT) two
Kind.Industrially, monobenzyl toluene and double benzyl toluenes press 3:1 mixing can be used as the insulating oil of power capacitor, trade name
C101, the country is also referred to as M/DBT.It is adapted to the excellent properties and feature that make full film power capacitor because C101 has, thus
Used more and more widely in industry.Single, double benzyl toluene can be additionally used in matching somebody with somebody for SAS series power capacitor insulating oils
System, and industrially use as excellent heat carrier.Therefore, the application prospect of benzyl toluene is very wide.
The catalyst that production benzyl toluene is adopted mainly has：Lewis acid (AlCl3, BF3, TiCl4, FeCl3Deng) and proton
Acid (HF, H2SO4, H3PO4Deng) two classes.At present, A1C13、FeCl3It is still wide in the synthesis of benzyl toluene Deng conventional homogeneous catalyst
It is general to use.For example, the synthetic method of a kind of monobenzyl toluene of low chlorine content disclosed in CN90110008.0 and double benzyl toluenes,
The method adopts ferric trichloride FeCl3Carry out catalyzing and synthesizing for benzyl toluene.These traditional homogeneous catalysts all exist and produce
Thing separates that difficult, catalyst cannot be recycled, equipment corrosion is serious, accessory substance is more, poor selectivity the shortcomings of, in production process
In can produce a large amount of waste water and unserviceable accessory substance, cause serious environmental pollution and the wasting of resources.Therefore, research and develop
Selective high, heterogeneous catalysis that is being easily isolated is subject to the common concern of people.
At present, both at home and abroad the relevant catalyst for the synthesis of monobenzyl toluene is reported and is concentrated mainly on ionic liquid, miscellaneous many
The heterogeneous catalysis of the loaded modified type of acid, solid super-strong acid, molecular sieve, alkaline earth oxide and metal halide, such as
CN102558230A and EP0306961A1 have been reported respectively using quaternary phosphine salt acidic ion liquid and SiO2/Al2O3Molecular sieve
Carry out catalyzing and synthesizing for benzyl toluene.But heteropoly acid and metal halide supported catalyst cannot all overcome equipment corrosion to ask
Topic, and there is preparation cost height in solid super-strong acid, molecular sieve and ionic liquid etc., the problems such as complex process.Therefore, industry
On urgently develop the new new technology for synthesizing benzyl toluene, reduce catalyst cost, reduce environmental pollution and equipment corrosion,
Improve product yield and selectivity.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation process is simple, raw materials for production low cost, equipment corrosion
Property little, easy recovery, the repeatable efficient heterogeneous solid acid catalyst for the utilizing method that synthesizes benzyl toluene.
The present invention technical solution be:
A kind of preparation method of benzyl toluene, it is comprised the following steps that：
The preparation of A, active clay loaded solid acid catalyst
Water 270g, concentrated sulfuric acid 30g are added in 1000mL four-hole bottles, calcium base swelling 30g is subsequently adding, 6h is refluxed, is down to
The static 12h of room temperature, filters, 120 DEG C of drying 8h；Solid active carclazyte is obtained, it is standby as catalyst carrier；
B, active clay loaded ZnCl2The preparation of solid acid catalyst
By ZnCl2In being dissolved in acetonitrile solution, the atlapulgite for adding step A to prepare is stirred at room temperature 24 hours, filters, then at 120
DEG C activation 4 hours, obtain active clay loaded ZnCl2Solid acid catalyst；
C, alkylated reaction
By active clay loaded ZnCl2Solid acid catalyst is added in benzyl chloride and the alkylation reaction system of toluene and carries out
Catalytic reaction, catalyst amount is the 2%-4% of benzyl chloride quality, and benzyl chloride is 1 with the mol ratio of toluene:1-1:10, reaction
Temperature is 100 DEG C -120 DEG C, and the reaction time is -8 hours 4 hours, and catalyst is recovered by filtration, and obtains benzyl toluene crude product；
It is D, refined
Benzyl toluene crude product is passed through vacuum distillation, refined, benzyl toluene is obtained.
Further, atlapulgite described in step B and ZnCl2Mass ratio be 10:1.
Further, catalyst amount is the 4% of benzyl chloride quality in step C.
Further, benzyl chloride and the mol ratio of toluene are 1:3-1:6.
Further, reaction temperature is 110 DEG C in step C, and the reaction time is 7 hours.
The invention has the beneficial effects as follows：
The catalyst abundant raw material source that the present invention is adopted, with low cost, preparation process is simple is low without the need for high-temperature activation energy consumption,
Easily separate with product；The synthetic reaction of benzyl toluene is carried out using the catalyst, reaction conversion ratio is high, selectivity is strong, condition temperature
It is little with, equipment corrosion, catalyst easily reclaim and it is repeatable utilize, environmental pollution is little, preferably solves current benzyl toluene synthesis
The problems that used catalyst is present, have broad application prospects.
Embody as follows：
First, catalyst preparation process is simple, without the need for special installation.The solid acid for synthesizing benzyl toluene of previous literature report
Catalyst preparation process is complicated, generally requires the steps such as dipping, kneading, shaping, high-temperature activation, and need kneader, forming machine,
The special catalyst preparation equipment such as Muffle furnace.The catalyst that the present invention is used is due to without the need for processing and forming, and activation temperature is low,
Can meet preparation using Conventional batch reactor and drying plant to require.
2nd, Catalyst Production low cost, energy consumption is little.The solid acid catalyst of document report is using molecular sieve, zirconium oxide etc.
For carrier, catalyst raw material high cost, and activation of catalyst generally require 300 DEG C～600 DEG C high temperature, and energy consumption is big.The present invention is adopted
It is carrier, catalyst preparation low cost, and activation temperature low (120 DEG C) with atlapulgite with low cost, greatly reduces and urge
Agent prepares energy resource consumption.Compared with the quaternary phosphine salt acidic ionic liquid catalysts of document report, production cost is more for this technique
It is low.
3rd, catalytic reaction yield and selective height.The present invention adopts the larger atlapulgite of specific surface area for carrier, increases
Chain carrier, high catalytic efficiency, simultaneously because catalyst surface has moderate acidity, reduces how Benzylation by-product
The generation of thing, the selectivity of target product is high.Single double benzyl toluene total recoverys are up to 91%-96%.
4th, catalyst is easily separated, recyclable to use again, and technique tends to greenization.This technique avoids traditional FeCl3、AlCl3
Reclaim difficult Deng homogeneous catalyst, the shortcomings of pollution and equipment corrosion are big, catalyst can be urged by simple filtration or sedimentation separation
Agent repeated multiple times can be used, with good environmental benefit.
Specific embodiment
The preparation of A, active clay loaded solid acid catalyst
Water 270g, concentrated sulfuric acid 30g are added in 1000mL four-hole bottles, calcium base swelling 30g is subsequently adding, 6h is refluxed, is down to
The static 12h of room temperature, filters, 120 DEG C of drying 8h；Solid active carclazyte is obtained, it is standby as catalyst carrier；
B, active clay loaded ZnCl2The preparation of solid acid catalyst
By ZnCl2In being dissolved in acetonitrile solution, the atlapulgite of step A preparation, the atlapulgite and ZnCl are added2Mass ratio
For 10:1, it is stirred at room temperature 24 hours, filter, activate 4 hours then at 120 DEG C, obtain active clay loaded ZnCl2Solid acid is urged
Agent；
C, alkylated reaction
By active clay loaded ZnCl2Solid acid catalyst is added in benzyl chloride and the alkylation reaction system of toluene and carries out
Catalytic reaction, catalyst amount is the 2%-4% of benzyl chloride quality, and benzyl chloride is 1 with the mol ratio of toluene:1-1:10, reaction
Temperature is 100 DEG C -120 DEG C, and the reaction time is -8 hours 4 hours, and catalyst is recovered by filtration, and obtains benzyl toluene crude product；
It is D, refined
Benzyl toluene crude product is passed through vacuum distillation, refined, benzyl toluene is obtained.
In following examples, the conversion ratio of benzyl chloride is reacted by chromatographic and starts the benzyl chloride with the end of
Cubage：
Benzyl chloride conversion ratio (%)=(benzyl chloride content-reaction afterchlorinate benzyl content before reaction) front benzyl chloride content of ÷ reactions ×
100%；
Embodiment 1
The preparation of A, active clay loaded solid acid catalyst
Water 270g, concentrated sulfuric acid 30g are added in 1000mL four-hole bottles, calcium base swelling 30g is subsequently adding, 6h is refluxed, is down to
The static 12h of room temperature, filters, 120 DEG C of drying 4h；Solid active carclazyte is obtained, it is standby as catalyst carrier；
B, active clay loaded ZnCl2The preparation of solid acid catalyst
Weigh anhydrous ZnCl21.0g, in being dissolved in 30ml acetonitriles, is stirred well to ZnCl2Quan Rong, is added thereto to the preparation of step A
Atlapulgite 10.0g, stirring 24 hours is stirred at room temperature, filter, solid n-hexane 10mL × 3 time wash, 120 DEG C of drying 4h,
Obtain active clay loaded ZnCl2Solid acid catalyst (F/C catalyst)；
The preparation of C, benzyl toluene
Take F/C catalyst 3.2g to add in 500mL four-hole bottles, then add toluene 290g, be warming up to 110 DEG C, benzyl chloride 80g is added dropwise
Reacted, 6h is dripped off, then reacted 1h, cooling is stopped reaction；Catalyst is recovered by filtration, liquid 150mL × 3 are washed, 150mL
5% sodium hydrate aqueous solution is washed, and toluene is reclaimed in vacuum distillation；Residue rectification under vacuum respectively obtain monobenzyl toluene (MBT) and
Double benzyl toluene (DBT) cuts.Benzyl chloride conversion ratio, monobenzyl toluene yield, double benzyl toluene yields and single double benzyl toluenes
Total recovery is as shown in table 1.
Embodiment 2
The preparation of A, active clay loaded solid acid catalyst
Water 270g, concentrated sulfuric acid 30g are added in 1000mL four-hole bottles, calcium base swelling 30g is subsequently adding, 6h is refluxed, is down to
The static 12h of room temperature, filters, 120 DEG C of drying 8h；Solid active carclazyte is obtained, it is standby as catalyst carrier；
B, active clay loaded ZnCl2The preparation of solid acid catalyst
Weigh anhydrous ZnCl21.0g, in being dissolved in 30ml acetonitriles, is stirred well to ZnCl2Quan Rong, is added thereto to the preparation of step A
Atlapulgite 10.0g, stirring 24 hours is stirred at room temperature, filter, solid n-hexane 10mL × 3 time wash, 120 DEG C of drying 4h,
Obtain active clay loaded ZnCl2Solid acid catalyst (F/C catalyst)；
The preparation of C, benzyl toluene
Take F/C catalyst 3.2g to add in 500mL four-hole bottles, then add toluene 320g, be warming up to 110 DEG C, benzyl chloride 80g is added dropwise
Reacted, 5h is dripped off, then reacted 1h, cooling is stopped reaction；Catalyst is recovered by filtration, liquid 150mL × 3 are washed, 150mL
5% sodium hydrate aqueous solution is washed, and toluene is reclaimed in vacuum distillation；Residue rectification under vacuum respectively obtain monobenzyl toluene (MBT) and
Double benzyl toluene (DBT) cuts.Benzyl chloride conversion ratio, monobenzyl toluene yield, double benzyl toluene yields and single double benzyl toluenes
Total recovery is as shown in table 1.
Embodiment 3
The preparation of A, active clay loaded solid acid catalyst
Water 270g, concentrated sulfuric acid 30g are added in 1000mL four-hole bottles, calcium base swelling 30g is subsequently adding, 6h is refluxed, is down to
The static 12h of room temperature, filters, 120 DEG C of drying 8h；Solid active carclazyte is obtained, it is standby as catalyst carrier；
B, active clay loaded ZnCl2The preparation of solid acid catalyst
Weigh anhydrous ZnCl21.0g, in being dissolved in 30ml acetonitriles, is stirred well to ZnCl2Quan Rong, is added thereto to the preparation of step A
Atlapulgite 10.0g, stirring 24 hours is stirred at room temperature, filter, solid n-hexane 10mL × 3 time wash, 120 DEG C of drying 4h,
Obtain active clay loaded ZnCl2Solid acid catalyst (F/C catalyst)；
The preparation of C benzyl toluenes
Take F/C catalyst 2.4g to add in 500mL four-hole bottles, then add toluene 174g, be warming up to 100 DEG C, benzyl chloride 80g is added dropwise
Reacted, 6h is dripped off, then reacted 2h, cooling is stopped reaction；Catalyst is recovered by filtration, liquid 150mL × 3 are washed, 150mL
5% sodium hydrate aqueous solution is washed, and toluene is reclaimed in vacuum distillation；Residue rectification under vacuum respectively obtain monobenzyl toluene (MBT) and
Double benzyl toluene (DBT) cuts.Benzyl chloride conversion ratio, monobenzyl toluene yield, double benzyl toluene yields and single double benzyl toluenes
Total recovery is as shown in table 1.
Embodiment 4
The preparation of A, active clay loaded solid acid catalyst
Water 270g, concentrated sulfuric acid 30g are added in 1000mL four-hole bottles, calcium base swelling 30g is subsequently adding, 6h is refluxed, is down to
The static 12h of room temperature, filters, 120 DEG C of drying 8h；Solid active carclazyte is obtained, it is standby as catalyst carrier；
B, active clay loaded ZnCl2The preparation of solid acid catalyst
Weigh anhydrous ZnCl21.0g, in being dissolved in 30ml acetonitriles, is stirred well to ZnCl2Quan Rong, is added thereto to the preparation of step A
Atlapulgite 10.0g, stirring 24 hours is stirred at room temperature, filter, solid n-hexane 10mL × 3 time wash, 120 DEG C of drying 4h,
Obtain active clay loaded ZnCl2Solid acid catalyst (F/C catalyst)；
The preparation of C, benzyl toluene
Take F/C catalyst 1.6g to add in 500mL four-hole bottles, then add toluene 240g, be warming up to 120 DEG C, benzyl chloride 80g is added dropwise
Reacted, 3.5h is dripped off, then reacted 0.5h, cooling is stopped reaction；Catalyst is recovered by filtration, liquid 150ml × 3 are washed,
The sodium hydrate aqueous solutions of 150mL 5% are washed, and toluene is reclaimed in vacuum distillation；Residue rectification under vacuum respectively obtains monobenzyl toluene
And double benzyl toluene (DBT) cut (MBT).Benzyl chloride conversion ratio, monobenzyl toluene yield, double benzyl toluene yields and single double benzyls
Base toluene total recovery is as shown in table 1.
Embodiment 5
According to embodiment 1 method synthesize benzyl toluene, except for the difference that the consumption of catalyst be 2.4g, benzyl chloride conversion ratio, list
Benzyl toluene yield, double benzyl toluene yields and single double benzyl toluene total recoverys are as shown in table 1.
Comparative example
A, active clay loaded ZnCl2The preparation of solid acid catalyst
Weigh anhydrous ZnCl21.0g, in being dissolved in 30ml acetonitriles, is stirred well to ZnCl2Quan Rong, is added thereto to atlapulgite
(commercially available) 10.0g, is stirred at room temperature stirring 24 hours, filters, and solid n-hexane 10mL × 3 time are washed, 120 DEG C of drying 4h, obtains
Active clay loaded ZnCl2Solid acid catalyst (F/C catalyst)；
The preparation of B, benzyl toluene
Take F/C catalyst 3.2g to add in 500mL four-hole bottles, then add toluene 320g, be warming up to 110 DEG C, benzyl chloride 80g is added dropwise
Reacted, 3h is dripped off, then reacted 1h, cooling is stopped reaction；Catalyst is recovered by filtration, liquid 150mL × 3 are washed, 150mL
5% sodium hydrate aqueous solution is washed, and toluene is reclaimed in vacuum distillation；Residue rectification under vacuum respectively obtain monobenzyl toluene (MBT) and
Double benzyl toluene (DBT) cuts.Benzyl chloride conversion ratio, monobenzyl toluene yield, double benzyl toluene yields and single double benzyl toluenes
Total recovery is as shown in table 1.
Table 1
Catalyst in embodiment 1- embodiment 5 is reusable after separating, using 5 times after, merely due to catalyst member
Loss product yield is declined slightly, and to supplement and can reach first using effect after raw catelyst.
The specific embodiment of the present invention is these are only, the present invention is not limited to, for those skilled in the art
For member, the present invention can have various modifications and variations.All any modifications within the spirit and principles in the present invention, made,
Equivalent, improvement etc., should be included within the scope of the present invention.
Claims (5)
1. a kind of preparation method of benzyl toluene, is characterized in that：
Comprise the following steps that：
The preparation of A, active clay loaded solid acid catalyst
Water 270g, concentrated sulfuric acid 30g are added in 1000mL four-hole bottles, calcium base swelling 30g is subsequently adding, 6h is refluxed, is down to
The static 12h of room temperature, filters, 120 DEG C of drying 8h；Solid active carclazyte is obtained, it is standby as catalyst carrier；
B, active clay loaded ZnCl2The preparation of solid acid catalyst
By ZnCl2In being dissolved in acetonitrile solution, the atlapulgite for adding step A to prepare is stirred at room temperature 24 hours, filters, then at 120
DEG C activation 4 hours, obtain active clay loaded ZnCl2Solid acid catalyst；
C, alkylated reaction
By active clay loaded ZnCl2Solid acid catalyst is added in benzyl chloride and the alkylation reaction system of toluene and carries out
Catalytic reaction, catalyst amount is the 2%-4% of benzyl chloride quality, and benzyl chloride is 1 with the mol ratio of toluene:1-1:10, reaction
Temperature is 100 DEG C -120 DEG C, and the reaction time is -8 hours 4 hours, and catalyst is recovered by filtration, and obtains benzyl toluene crude product；
It is D, refined
Benzyl toluene crude product is passed through vacuum distillation, refined, benzyl toluene is obtained.
2. the preparation method of benzyl toluene according to claim 1, is characterized in that：Atlapulgite described in step B with
ZnCl2Mass ratio be 10:1.
3. the preparation method of benzyl toluene according to claim 1, is characterized in that：Catalyst amount is chlorination in step C
The 4% of benzyl quality.
4. the preparation method of benzyl toluene according to claim 1, is characterized in that：Benzyl chloride is 1 with the mol ratio of toluene:
3-1:6。
5. the preparation method of benzyl toluene according to claim 1, is characterized in that：Reaction temperature is 110 DEG C in step C,
Reaction time is 7 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087588A (en) * | 2021-04-07 | 2021-07-09 | 常州新东化工发展有限公司 | Continuous rectification production process of benzyl aromatic oil |
| CN114014739A (en) * | 2021-11-09 | 2022-02-08 | 常州新东化工发展有限公司 | Preparation method for improving selectivity of dibenzyl toluene by solid acid catalysis |
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| CN103833509A (en) * | 2012-11-23 | 2014-06-04 | 中国石油天然气股份有限公司 | Method for catalysis synthesis of benzyl toluene through solid acid catalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087588A (en) * | 2021-04-07 | 2021-07-09 | 常州新东化工发展有限公司 | Continuous rectification production process of benzyl aromatic oil |
| CN114014739A (en) * | 2021-11-09 | 2022-02-08 | 常州新东化工发展有限公司 | Preparation method for improving selectivity of dibenzyl toluene by solid acid catalysis |
| CN114014739B (en) * | 2021-11-09 | 2023-10-13 | 常州新东化工发展有限公司 | Preparation method for improving dibenzyl toluene selectivity by solid acid catalysis |
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Application publication date: 20170510 |
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| RJ01 | Rejection of invention patent application after publication |