CN106278800A - Toluene and the method for methanol side chain alkylation - Google Patents
Toluene and the method for methanol side chain alkylation Download PDFInfo
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Abstract
A kind of method that the invention mainly relates to toluene and methanol side chain alkylation, mainly solves to there is, in prior art, the problem that use ratio of methanol is low.The present invention, by using with toluene and methanol as raw material, under conditions of being enough to make the reaction of raw material generation side chain alkylation, makes raw material contact with catalyst and obtains ethylbenzene and styrene；Described catalyst be particle size be that the technical scheme of the X molecular sieve of 20～900 nanometers preferably solves this problem, can be used for methylbenzene methanol side chain alkylation reaction and prepare in ethylbenzene and cinnamic commercial production.
Description
Technical field
A kind of method that the present invention relates to toluene and methanol side chain alkylation.
Background technology
Styrene monomer is a kind of important Organic Chemicals, is mainly used in polystyrene, ABS
The production of the products such as resin, butadiene-styrene rubber, unsaturated-resin.Additionally, can be additionally used in pharmacy, dye
Expecting or produce farm chemical emulgent and dressing agent etc., purposes is quite varied.Styrene series resin
Yield is only second to PE, PVC in synthetic resin and comes in third.Major part technical benzene ethylene at present
It is to be generated ethylbenzene by benzene and ethylene through Friedel-Craft reaction, then gets through catalytic dehydrogenation.This method stream
Journey compared with long, side reaction is many, energy consumption is high, cost of material account for produce variable cost 85%, produce into
This is higher.Toluene and methanol alkylation are to produce a cinnamic route having potential application foreground.
X-type and y-type zeolite that Sidorenko in 1967 etc. exchange with alkali metal ion first are catalyst
Success is by toluene and methanol-fueled CLC ethylbenzene and styrene.Compared with traditional handicraft, the method has
There are the advantages such as raw material sources are wide, low cost, energy consumption are low, pollution is few.Thus this reacts once report
Just being subject to the people's attention, the research about this respect also begins to increase.
The catalyst of methylbenzene methanol side chain alkylation preparation of styrene belongs to solid base catalyst, but is catalyzed
Process is a soda acid concerted catalysis reaction, and takes as the leading factor with the catalysis of basic active position.The acid of catalyst
Property potential energy play the effect of stable toluene phenyl ring, and alkalescence potential energy activation Toluene and the methyl base of methanol
Group.First methanol is decomposed into formaldehyde in alkali in the heart, and toluene adsorbs on acid site, its pendant methyl
Being activated by alkali center, then formaldehyde and the methyl reaction activated produce styrene, part styrene
Generation ethylbenzene is reacted with the hydrogen produced.If catalyst alkalescence is too strong, formaldehyde can be made to decompose further,
Produce more hydrogen and ethylbenzene simultaneously；If acidity of catalyst is too strong, then the alkane of phenyl ring can occur
Base and toluene disproportionation, generate benzene and dimethylbenzene, it requires that catalyst has suitable soda acid
Joining, the existence of phenyl ring simultaneously requires that catalyst has certain spatial hole structure.
The reaction of methylbenzene methanol side chain alkylation conducts extensive research on multiple catalysts.Many
Molecular sieve such as X, Y, L, β, ZSM-5, and some basic anhydride such as MgO, MgO-TiO2、
And CaO-TiO2The research that is all in the news is applied to be catalyzed in the reaction of methylbenzene methanol side chain alkylation, as
JOURNAL OF CATALYSIS 173,490 500 (1998) and CN101623649A,
CN101623650A.Result of study finds, wants to reach preferable side chain alkylation catalytic effect,
Catalyst must is fulfilled for following 4 requirements: catalyst is it is necessary to have enough basic center activate first
Alcohol is changed into methylating reagent formaldehyde；There is weak Lewis acid site to stablize toluene and to polarize it
Methyl；Toluene and methanol to have a good stoichiometric adsorption equilibrium on a catalyst；Urge
Agent must have micropore canals structure.Therefore, the result of study of some zeolite catalysis activity is shown,
The X-type zeolite of alkali metal cation-exchanged is the catalyst of relative efficiency.The reaction of y-type zeolite is lived
Property inferior to X-type zeolite.And other reactivity such as zeolites such as L, β, ZSM-5 types is the most undesirable,
And some do not have the basic anhydride of microcellular structure, such as MgO, MgO-TiO2And CaO-TiO2Deng
The lowest activity.At present, major part document report for methylbenzene methanol side chain alkylation Fau
Type molecular sieve catalyst is all conventional X and Y zeolite catalyst, and sieve particle size is all
Micron order.
Summary of the invention
The problem being prior art and having that use ratio of methanol is low to be solved by this invention, it is provided that a kind of
New toluene and the method for methanol side chain alkylation.The method has the advantages that use ratio of methanol is high.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of toluene and first
The method of alcohol side chain alkylation, with toluene and methanol as raw material, makes raw material generation side chain alkane being enough to
Under conditions of glycosylation reaction, make raw material contact with catalyst and obtain ethylbenzene and styrene；Described catalysis
Agent be particle size be the X molecular sieve of 20～900 nanometers.
In technique scheme, it is preferable that the particle size of described catalyst is 50～700 nanometers.
It is highly preferred that the particle size of described catalyst is 80～500 nanometers.Most preferably, described catalysis
The particle size of agent is 80～250 nanometers.
In technique scheme, it is preferable that described X molecular sieve SiO2/Al2O3It is 1～5.More excellent
Selection of land, described X molecular sieve SiO2/Al2O3It is 2～3.
In technique scheme, it is preferable that described X molecular sieve successively with the solution containing potassium ion,
Solution containing rubidium ion and the solution containing cesium ion carry out ion and exchange at least one times.
In technique scheme, it is preferable that the described solution containing potassium ion, the solution containing rubidium ion
It is 0.5～2.5 mol/L with the concentration of the solution containing cesium ion；Exchange temperature is 50～90 DEG C, often
Secondary swap time 1～3 hours, solid-liquid weight ratio is 1:(5～10).
In technique scheme, it is preferable that after exchange, potassium ion, rubidium ion and cesium ion with point
In son sieve, the ion-exchange degree of sodium ion is 10～90%.
In technique scheme, it is preferable that described in be enough to make raw material generation side chain alkylation react
Condition is: toluene and methanol molar ratio are (2～7): 1, and reaction temperature is 350～500 DEG C, reaction pressure
Power is 0～0.5MP, and raw material weight air speed is 1～8 hour-1。
Heretofore described particle size is that the preparation method of the X molecular sieve of 20～900 nanometers is as follows:
Silicon source, aluminum source, alkali and water is made to form mixture.In mixture, the mol ratio of each component is as follows:
n(Na2O):n(SiO2):n(Al2O3):n(H2O)=(2～7): (2～3): (1): (80～150).By mixture in
60～150 DEG C of ultrasonic crystallizations 0.5～10 hours, product obtains described nanometer X through filtration washing and divides
Son sieve.Wherein, silicon source can be selected from Ludox, silicon dioxide or tetraethyl orthosilicate.Aluminum source is permissible
Selected from sodium aluminate, aluminium oxide or aluminum isopropylate..Alkali can be selected from sodium hydroxide.
According to the present invention, the nanometer X molecular sieve of preparation is 0.5～2.5 by concentration the most successively
The solution containing potassium ion of mol/L, the solution containing rubidium ion and the solution containing cesium ion carry out ion
Exchange, exchange temperature is 50～90 DEG C, and each swap time is 1～3 hour, and solid-liquid weight ratio is
1:(5～10).The described solution preferred version containing potassium ion is selected from potassium hydroxide solution or potassium nitrate
At least one in solution, the described solution preferred version containing rubidium ion is selected from rubidium hydroxide or nitre
At least one in acid rubidium, the described solution preferred version containing cesium ion is selected from Cesium hydrate. or nitre
At least one in acid caesium.After ion exchange, in potassium ion, rubidium ion and cesium ion and molecular sieve
The ion-exchange degree of sodium ion is 10～90%.
According to the present invention, the condition that toluene and methanol side chain alkylation react is: toluene rubs with methanol
Your ratio is (2～7): 1, and reaction temperature is 350～500 DEG C, and reaction pressure is 0～0.5MP, raw material
Weight space velocity is 1～8 hour-1。
The inventive method can be carried out in continuous flow reactor of fixed bed, and its process is summarized as follows:
Taking the desired amount of catalyst and put into the flat-temperature zone of reactor, catalyst bottom quartz sand is filled.?
Under the temperature of setting, pressure, by toluene and methanol mixed, deliver to preheater and nitrogen with micro pump
Enter reactor upper end after mixing gasifying, flow through beds and carry out catalytic reaction, product
Directly enter gas chromatogram with valve injection to be analyzed.
The activity and selectivity of catalyst calculates according to below equation:
The inventive method selects nano X-type molecular sieve to be that catalyst material, beneficially reaction molecular are dividing
Diffusion in sub-sieve catalyst duct, decreases the decomposition of methanol, thus is effectively increased methanol profit
By rate.It addition, according to ionic radius increase order (potassium, rubidium, caesium), with containing potassium, rubidium,
The solution continuous process of caesium carries out ion exchange to nanometer X molecular sieve, substantially increases ion exchange
Degree, thus further increase catalytic effect.Use the inventive method, at toluene and Methanol Molar
Ratio is 5:1, and reaction temperature is 415 DEG C, and reaction pressure is 0MPa, and raw material weight air speed is 2.5
Hour-1Under conditions of, use ratio of methanol can be up to 54%, achieves preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Sodium hydroxide is dissolved in distilled water, then sodium aluminate is joined in sodium hydroxide solution, stir
Mix to clarification.Then Ludox is joined in above-mentioned solution, the mol ratio of each material in mixture
For n (Na2O):n(SiO2):n(Al2O3):n(H2O)=2.92:2:1:96.Stir after addition, finally
Put in the stainless steel autoclave with teflon lined, 80 DEG C of water bath sonicator crystallization 2.5
Hour, synthetic product obtains nanometer X molecular sieve through filtration washing.Synthesizing nano X molecular sieve
SiO2/Al2O3Ratio is 2.10, and average particle size particle size is 800nm.
Take 10 grams of above-mentioned molecular sieve, at 80 DEG C, at the KNO of 100 milliliter of 1 mol/L3In solution
Carry out ion to exchange 2 hours, exchange 2 times；Then at the RbNO of 50 milliliter of 1 mol/L3Molten
Liquid carries out ion exchange, exchanges 2 times；Finally at the CsNO of 50 milliliter of 1 mol/L3Solution
In carry out ion exchange, exchange 2 times；Filter latter 100 DEG C to be dried 10 hours.After exchange, catalysis
In agent, in alkali metal ion exchange molecular sieve, the ion-exchange degree of sodium ion is 83.4%
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5:1,2.5 hours-1Liquid air speed, 415 DEG C, N2Flow velocity
Carrying out activity rating under conditions of 10 ml/min, the results are shown in Table 1.
[embodiment 2]
Sodium hydroxide is dissolved in distilled water, then sodium aluminate is joined in sodium hydroxide solution, stir
Mix to clarification.Then Ludox is joined in above-mentioned solution, the mol ratio of each material in mixture
For n (Na2O):n(SiO2):n(Al2O3):n(H2O)=3.57:2:1:96.Stir after addition, finally
Put in the stainless steel autoclave with teflon lined, 80 DEG C of water bath sonicator crystallization 2.5
Hour, synthetic product obtains nanometer X molecular sieve through filtration washing.Synthesizing nano X molecular sieve
SiO2/Al2O3Ratio is 2.07, and average particle size particle size is 650nm.
Take 10 grams of above-mentioned molecular sieve, at 80 DEG C, at the KNO of 100 milliliter of 1 mol/L3In solution
Carry out ion to exchange 2 hours, exchange 2 times；Then at the RbNO of 50 milliliter of 1 mol/L3Molten
Liquid carries out ion exchange, exchanges 2 times；Finally at the CsNO of 50 milliliter of 1 mol/L3Solution
In carry out ion exchange, exchange 2 times；Filter latter 100 DEG C to be dried 10 hours.After exchange, catalysis
In agent, in alkali metal ion exchange molecular sieve, the ion-exchange degree of sodium ion is 82.9%.
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5:1,2.5 hours-1Liquid air speed, 415 DEG C, N2Flow velocity
Carrying out activity rating under conditions of 10 ml/min, the results are shown in Table 1.
[embodiment 3]
Sodium hydroxide is dissolved in distilled water, then sodium aluminate is joined in sodium hydroxide solution, stir
Mix to clarification.Then Ludox is joined in above-mentioned solution, the mol ratio of each material in mixture
For n (Na2O):n(SiO2):n(Al2O3):n(H2O)=4.71:2:1:96.Stir after addition, finally
Put in the stainless steel autoclave with teflon lined, 80 DEG C of water bath sonicator crystallization 2.5
Hour, synthetic product obtains nanometer X molecular sieve through filtration washing.Synthesizing nano X molecular sieve
SiO2/Al2O3Ratio is 2.12, and average particle size particle size is 400nm.
Take 10 grams of above-mentioned molecular sieve, at 80 DEG C, at the KNO of 100 milliliter of 1 mol/L3In solution
Carry out ion to exchange 2 hours, exchange 2 times；Then at the RbNO of 50 milliliter of 1 mol/L3Molten
Liquid carries out ion exchange, exchanges 2 times；Finally at the CsNO of 50 milliliter of 1 mol/L3Solution
In carry out ion exchange, exchange 2 times；Filter latter 100 DEG C to be dried 10 hours.After exchange, catalysis
In agent, in alkali metal ion exchange molecular sieve, the ion-exchange degree of sodium ion is 86.7%.
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5:1,2.5 hours-1Liquid air speed, 415 DEG C, N2Flow velocity
Carrying out activity rating under conditions of 10 ml/min, the results are shown in Table 1.
[embodiment 4]
Sodium hydroxide is dissolved in distilled water, then sodium aluminate is joined in sodium hydroxide solution, stir
Mix to clarification.Then Ludox is joined in above-mentioned solution, the mol ratio of each material in mixture
For n (Na2O):n(SiO2):n(Al2O3):n(H2O)=5.85:2.8:1:105.Stir after addition,
After put in the stainless steel autoclave with teflon lined, 80 DEG C of water bath sonicator crystallization 2.5
Hour, synthetic product obtains nanometer X molecular sieve through filtration washing.Synthesizing nano X molecular sieve
SiO2/Al2O3Ratio is 2.88, and average particle size particle size is at 250nm.
Take 10 grams of above-mentioned molecular sieve, at 80 DEG C, at the KNO of 100 milliliter of 1 mol/L3In solution
Carry out ion to exchange 2 hours, exchange 2 times；Then at the RbNO of 50 milliliter of 1 mol/L3Molten
Liquid carries out ion exchange, exchanges 2 times；Finally at the CsNO of 50 milliliter of 1 mol/L3Solution
In carry out ion exchange, exchange 2 times；Filter latter 100 DEG C to be dried 10 hours.After exchange, catalysis
In agent, in alkali metal ion exchange molecular sieve, the ion-exchange degree of sodium ion is 83.7%.
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5:1,2.5 hours-1Liquid air speed, 415 DEG C, N2Flow velocity 10
Carrying out activity rating under conditions of ml/min, the results are shown in Table 1.
[embodiment 5]
Sodium hydroxide is dissolved in distilled water, then sodium aluminate is joined in sodium hydroxide solution, stir
Mix to clarification.Then Ludox is joined in above-mentioned solution, the mol ratio of each material in mixture
For n (Na2O):n(SiO2):n(Al2O3):n(H2O)=5.85:2.25:1:105.Stir after addition,
After put in the stainless steel autoclave with teflon lined, 80 DEG C of water bath sonicator crystallization 2.5
Hour, synthetic product obtains nanometer X molecular sieve through filtration washing.Synthesizing nano X molecular sieve
SiO2/Al2O3Ratio is 2.31, and average particle size particle size is 85nm.
Take 10 grams of above-mentioned molecular sieve, at 80 DEG C, at the KNO of 100 milliliter of 1 mol/L3In solution
Carry out ion to exchange 2 hours, exchange 2 times；Then at the RbNO of 50 milliliter of 1 mol/L3Molten
Liquid carries out ion exchange, exchanges 2 times；Finally at the CsNO of 50 milliliter of 1 mol/L3Solution
In carry out ion exchange, exchange 2 times；Filter latter 100 DEG C to be dried 10 hours.After exchange, catalysis
In agent, in alkali metal ion exchange molecular sieve, the ion-exchange degree of sodium ion is 85.7%.
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5:1,2.5 hours-1Liquid air speed, 415 DEG C, N2Flow velocity
Carrying out activity rating under conditions of 10 ml/min, the results are shown in Table 1.
[embodiment 6]
Sodium hydroxide is dissolved in distilled water, then takes sodium aluminate and join in sodium hydroxide solution, stir
Mix to clarification.Then Ludox is joined in above-mentioned solution, the mol ratio of each material in mixture
For n (Na2O):n(SiO2):n(Al2O3):n(H2O)=5.85:2:1:105.Stir after addition, finally
Put in the stainless steel autoclave with teflon lined, 80 DEG C of water bath sonicator crystallization 2.5
Hour, synthetic product obtains nanometer X molecular sieve through filtration washing.Synthesizing nano X molecular sieve
SiO2/Al2O3Ratio is 2.10, and average particle size particle size is 120nm.
Take 10 grams of above-mentioned molecular sieve, at 80 DEG C, at the KNO of 100 milliliter of 1 mol/L3In solution
Carry out ion to exchange 2 hours, exchange 2 times；Then at the RbNO of 50 milliliter of 1 mol/L3Molten
Liquid carries out ion exchange, exchanges 2 times；Finally at the CsNO of 50 milliliter of 1 mol/L3Solution
In carry out ion exchange, exchange 2 times；Filter latter 100 DEG C to be dried 10 hours.After exchange, catalysis
In agent, in alkali metal ion exchange molecular sieve, the ion-exchange degree of sodium ion is 86.7%.
By the beaded catalyst of catalyst tablet forming 40～60 mesh obtained above, load reactor,
Normal pressure, methylbenzene methanol mol ratio be 5:1,2.5 hours-1Liquid air speed, 415 DEG C, N2Flow velocity
Carrying out activity rating under conditions of 10 ml/min, the results are shown in Table 1.
[comparative example 1]
Take the common X molecular sieve (SiO of purchase2/Al2O3Ratio is 2.1, and average particle size particle size is 5 μm)
10 grams, at 80 DEG C, at the KNO of 100 milliliter of 1 mol/L3Carrying out ion in solution, to exchange 2 little
Time, exchange 2 times；Then at the RbNO of 50 milliliter of 1 mol/L3Solution carries out ion exchange,
Exchange 2 times；Finally at the CsNO of 50 milliliter of 1 mol/L3Solution carries out ion exchange, hands over
Change 2 times；Filter latter 100 DEG C to be dried 10 hours.After exchange, alkali metal ion exchange in catalyst
In molecular sieve, the ion-exchange degree of sodium ion is 82.9%.
According to the method for [embodiment 5], catalyst being carried out activity rating, the results are shown in Table 1.
[comparative example 2]
Nanometer X molecular sieve is prepared according to [embodiment 5].Take 10 grams of molecular sieve, at 80 DEG C,
The KNO of 100 milliliter of 1 mol/L3Solution carries out ion exchange 2 hours, exchange 3 times；So
After at the CsNO of 50 milliliter of 1 mol/L3Solution carries out ion exchange, exchanges 3 times；Filter
Latter 100 DEG C are dried 10 hours.After exchange, in catalyst alkali metal ion exchange molecular sieve in sodium from
The ion-exchange degree of son is 76.9%.
According to the method for [embodiment 5], catalyst being carried out activity rating, the results are shown in Table 1.
[comparative example 3]
Nanometer X molecular sieve is prepared according to [embodiment 5].Take 10 grams of molecular sieve, at 80 DEG C,
The CsNO of 50 milliliter of 1 mol/L3Solution carries out ion exchange 2 hours, exchange 2 times；Then
KNO 100 milliliter of 1 mol/L3Solution carries out ion exchange, exchanges 2 times；Finally exist
The RbNO of 50 milliliter of 1 mol/L3Solution carries out ion exchange, exchanges 2 times；Filter latter 100 DEG C
It is dried 10 hours.After exchange, the ion of sodium ion in alkali metal ion exchange molecular sieve in catalyst
Exchange degree is 78.6%.
According to the method for [embodiment 5], catalyst being carried out activity rating, the results are shown in Table 1.
Table 1
Claims (10)
1. a method for toluene and methanol side chain alkylation, with toluene with methanol as raw material, at foot
So that under conditions of the reaction of raw material generation side chain alkylation, making raw material contact with catalyst and obtain ethylbenzene
And styrene；Described catalyst be particle size be the X molecular sieve of 20～900 nanometers.
Toluene and the method for methanol side chain alkylation the most according to claim 1, it is characterised in that
The particle size of described catalyst is 50～700 nanometers.
Toluene and the method for methanol side chain alkylation the most according to claim 2, it is characterised in that
The particle size of described catalyst is 80～500 nanometers.
Toluene and the method for methanol side chain alkylation the most according to claim 3, it is characterised in that
The particle size of described catalyst is 80～250 nanometers.
Toluene and the method for methanol side chain alkylation the most according to claim 1, it is characterised in that
Described X molecular sieve SiO2/Al2O3It is 1～5.
Toluene and the method for methanol side chain alkylation the most according to claim 5, it is characterised in that
Described X molecular sieve SiO2/Al2O3It is 2～3.
Toluene and the method for methanol side chain alkylation the most according to claim 1, it is characterised in that
Described X molecular sieve is successively with the solution containing potassium ion, solution containing rubidium ion and molten containing cesium ion
Liquid carries out ion and exchanges at least one times.
Toluene and the method for methanol side chain alkylation the most according to claim 7, it is characterised in that
The described solution containing potassium ion, the solution containing rubidium ion and the concentration of solution containing cesium ion be 0.5～
2.5 mol/L；Exchange temperature is 50～90 DEG C, each swap time 1～3 hours, solid-liquid weight
Ratio is 1:(5～10).
Toluene and the method for methanol side chain alkylation the most according to claim 7, it is characterised in that
After exchange, potassium ion, rubidium ion and cesium ion with the ion-exchange degree of sodium ion in molecular sieve are
10～90%.
The most according to claim 1, toluene and the method for methanol side chain alkylation, its feature exists
In the described condition that be enough to make raw material generation side chain alkylation react it is: toluene with methanol molar ratio is
(2～7): 1, reaction temperature is 350～500 DEG C, and reaction pressure is 0～0.5MP, and raw material weight is empty
Speed is 1～8 hour-1。
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| CN109453802A (en) * | 2018-11-19 | 2019-03-12 | 内江师范学院 | Molecular sieve catalyst and preparation method thereof, the application in methanol and Benzyl Side-Chain alkylated reaction |
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| 王宇红等: "甲苯/甲醇在碱性沸石上侧链烷基化反应的研究 Ⅲ.X型沸石添加稀土元素La、Ce改性", 《天然气化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109453802A (en) * | 2018-11-19 | 2019-03-12 | 内江师范学院 | Molecular sieve catalyst and preparation method thereof, the application in methanol and Benzyl Side-Chain alkylated reaction |
| CN109453802B (en) * | 2018-11-19 | 2021-09-07 | 内江师范学院 | Molecular sieve catalyst, preparation method thereof and application thereof in side-chain alkylation reaction of methanol and toluene |
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