CN106622338B - Catalyst and application thereof for the reaction of methylbenzene methanol side chain alkylation - Google Patents
Catalyst and application thereof for the reaction of methylbenzene methanol side chain alkylation Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst and application thereof for the reaction of methylbenzene methanol side chain alkylation, mainly solves the problems, such as to be currently used for that the catalyst that methylbenzene methanol side chain alkylation ethylbenzene and styrene react is low to the utilization rate of methanol, toluene conversion is low and poor catalyst stability.The present invention passes through a kind of catalyst for the reaction of methylbenzene methanol side chain alkylation and its application, the catalyst is to be modified X or Y molecular sieve as active component, using at least one of Al, P, B, and at least one of at least one of at least one of rare earth element, alkali metal element, platinum group are used as modified component, it is prepared in a manner of ion exchange or dipping, and surface is carried out to molecular sieve using Si oxide and is modified；It is contacted using toluene and methanol as raw material with the catalyst, reaction generates the technical solution of ethylbenzene and styrene, preferably solves the problems, such as this, can be used for methylbenzene methanol side chain alkylation reaction and prepare in the industrial production of ethylbenzene and styrene.
Description
Technical field
The present invention relates to a kind of catalyst and application thereof for the reaction of methylbenzene methanol side chain alkylation.
Background technique
Styrene is a kind of important Organic Chemicals, mainly for the production of polystyrene, butadiene-styrene rubber, ABS resin,
The products such as unsaturated-resin, it may also be used for the fields such as pharmacy, pesticide and dyestuff, it is widely used.Currently, most technical benzene second
The production of alkene is carried out in two steps.Firstly, benzene and ethylene are raw through Friedel-Craft alkylated reaction under the action of catalyst
At ethylbenzene, then ethylbenzene generates styrene through catalytic dehydrogenation.The route raw material is at high cost, and process flow is long, and equipment investment is big, and
And energy consumption is higher.It is that one for producing styrene has potential application foreground by methylbenzene methanol side chain alkylation synthesizing styrene
Route, Sidorenko in 1967 etc. report the X-type and Y type molecular sieve that toluene, methanol can be exchanged in alkali metal ion for the first time
Side chain alkylation occurs on catalyst and reacts step generation styrene.Compared to traditional styrene synthetic route, which is used
Coal Chemical Industry Route has good industrial development valence since raw material sources are extensive, at low cost, reaction condition is mild, energy consumption is lower
Value and application prospect, cause great concern.
Methylbenzene methanol side chain alkylation is acted synergistically by soda acid and is completed.The mechanism of reaction is that base catalysis Methanol Decomposition obtains
For formaldehyde as reaction intermediate, the methyl that activation Toluene is gone back in basic active position becomes carbanion, and carbanion then occurs to first
The Adol-type of aldehyde reacts, and obtains styrene after product dehydration.Part styrene occurs to add hydrogen anti-with the hydrogen generated is reacted
Ethylbenzene should be generated.The catalyst of methylbenzene methanol side chain alkylation reaction belongs to solid base catalyst, needs sufficient intensity and quantity
Alkali center formaldehyde and activation Toluene methyl c h bond generated with catalysis methanol dehydrogenation generate methyl carbanion.Meanwhile toluene
The still soda acid concerted catalysis reaction based on the catalysis of basic active position of methanol side chain alkylation reaction process.It is demonstrated experimentally that individually
Basic active position catalysis methylbenzene methanol side chain alkylation efficiency it is very low.In reaction process, toluene molecule needs are inhaled by Lewis acid
Stabilization is echoed, otherwise toluene conversion is lower.But if the alkalinity of catalyst is too strong, methanol and intermediate product formaldehyde be easy into
One step resolves into CO and hydrogen；If acidity of catalyst is too strong, the main alkylated reaction that phenyl ring occurs generates benzene and diformazan
Benzene.Therefore, catalyst needs that there is suitable soda acid to match.In addition, the adsorption equilibrium of toluene and methanol is also to influence toluene first
One of the factor of alcohol side chain alkylation reaction, suitable cellular structure and cage size are conducive to the adsorption equilibrium of toluene and methanol.
A variety of catalysis materials are attempted for the reaction of methylbenzene methanol side chain alkylation.Different types of modified molecular screen such as X,
Y, USY, L, β, ZSM-5 and basic anhydride such as MgO, CaO, MgO-TiO2、CaO-TiO2It is applied to methylbenzene methanol Deng studied
The catalyst of side chain alkylation reaction, all shows certain catalytic performance.As US 4463204 is reported through K, Cs ion exchange
Modified X or Y type molecular sieve methylbenzene methanol side chain alkylation reaction in improve toluene conversion and specific 90% ethylbenzene,
Styrene overall selectivity.US 4140726 reports the X or Y zeolite catalyst modified through K, Rb, Cs and B, P, has
Higher toluene conversion, but ethylbenzene, styrene overall selectivity are not ideal enough.US 8318999B2 report through Cs and Ga,
B, one of Co element modified X-type molecular sieve catalyst, the method increase selectivity of styrene.CN 101623650A
Ion exchange is carried out to X or Y type molecular sieve using K, Cs, and the method for loading B, P and alkali or alkaline earth metal improves
The stability of catalyst.CN 101623649A to through alkali metals modified X or Y type molecular sieve again at high temperature use ammonia treatment, mention
The high activity and stability of catalyst.These reported modified X or Y type molecular sieve are reacted in methylbenzene methanol side chain alkylation
In achieve certain catalytic effect.But how to take into account toluene conversion and use ratio of methanol is methylbenzene methanol pendant alkyl group
Change the important technology problem in reaction.Report that catalyst obtains high toluene conversion and high methanol utilization rate aspect still at the same time
It is not ideal enough, still there is biggish gap for industrial requirement, and have the shortcomings that hydrothermal stability is not high.Therefore,
Suitable toluene conversion and use ratio of methanol can be combined by developing in the reaction of methylbenzene methanol side chain alkylation, ethylbenzene,
The catalyst that selectivity of styrene is high and hydrothermal stability is high is to realize methylbenzene methanol side chain alkylation preparing ethylbenzene by reaction, benzene second
One of the key factor of alkene industrialized production.In addition, higher selectivity of styrene also advantageously improves economic benefit.
Summary of the invention
It is anti-the technical problem to be solved by the present invention is to be currently used for methylbenzene methanol side chain alkylation ethylbenzene and styrene
The problem of catalyst answered is low to the utilization rate of methanol, toluene conversion is low and poor catalyst stability provides a kind of new
For the catalyst that methylbenzene methanol side chain alkylation ethylbenzene and styrene react, the method for preparing catalyst is easy, in toluene
Methanol side chain alkylation reaction in simultaneously toluene conversion with higher and higher use ratio of methanol, have ethylbenzene, benzene second
The advantage that alkene selectivity is high and catalyst performance stabilised is high.
In order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of be used for methylbenzene methanol side chain alkane
The catalyst of base ethylbenzene and styrene reaction, includes following components:
A) at least one of X molecular sieve or Y molecular sieve；With load modified component thereon:
B) mass ratio of at least one of Al, P and B, the element and molecular sieve carrier is (0.05~10): 100；
C) mass ratio of at least one of alkali metal element, the element and molecular sieve carrier is (0.1~20): 100；
D) mass ratio of at least one of platinum group, the element and molecular sieve carrier is (0.05~10): 100；
E) mass ratio of at least one of rare earth element, the element and molecular sieve carrier is (0.05~10): 100；
F) mass ratio of the oxide of Si, the Si element and molecular sieve carrier is (0.1~10): 100.
In above-mentioned technical proposal, the molecular sieve is selected from SiO2/Al2O3For in 2~5 X molecular sieve or Y molecular sieve extremely
Few one kind, preferred embodiment is X molecular sieve；In modified component Al, P, B, at least one of preferred embodiment Al, P, B, with molecule
The mass ratio for sieving carrier is preferably (0.05~10): 100, more preferable scheme is (0.1~2): 100；Alkali metal element be selected from K,
At least one of Rb or Cs, more preferable scheme are Cs, the mass ratio of alkali metal element and molecular sieve carrier be preferably (0.1~
20): 100, more preferable scheme is (0.5~10): 100；Platinum group is selected from least one of Ru, Rh or Pt, platinum group
Mass ratio with molecular sieve carrier is preferably (0.05~10): 100, more preferable scheme is (0.1~2): 100；Rare earth element choosing
From at least one of La, Ce, Pr, Nd, one of preferred embodiment La, Ce, more preferable scheme is Ce, rare earth element with point
The mass ratio of son sieve carrier is preferably (0.05~10): 100, more preferable scheme is (0.1~2): 100；Si member in Si oxide
The mass ratio of element and molecular sieve carrier is (0.1~10): 100, preferred embodiment is (0.5~5): 100.
In above-mentioned technical proposal, Si oxide source is preferably methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, aminomethyl phenyl
Silicone oil, methylchlorophenyl silicone oil, MethylethoxylsiliconFluid Fluid, methyl vinyl silicon oil, methylhydroxy silicone oil, tetramethoxy-silicane,
The silicon-containing compounds such as tetraethoxysilane, tetrapropoxysilane, four butoxy silanes；Most preferably methyl-silicone oil, ethyl silicon oil,
At least one of phenyl silicone oil, tetraethoxysilane and four butoxy silanes.
A kind of catalyst reacted for methylbenzene methanol side chain alkylation ethylbenzene and styrene according to the present invention, can
It is prepared using following steps:
A) molecular sieve and the solution containing the modifying element are subjected to ion exchange or dipping；
B) molecular sieve is surface modified using silicon-containing compound, forms Si oxide in molecular sieve surface after roasting and covers
Cap rock；
C) modified molecular sieve is dried, roasted, formed.
In above-mentioned technical proposal, the modified metal component precursor of catalyst can be selected from chloride, hydroxide or nitrate
One of；Al elemental constituent precursor can be selected from NaAlO2Or KAlO2；B, P element component precursor can be selected from boric acid, phosphoric acid or alkali
Metal salt；Drying temperature is 90 DEG C~150 DEG C, and drying time is 1~24 hour, and maturing temperature is 400 DEG C~650 DEG C, roasting
Time is 1~24 hour；Si oxide surface modification process using silicon-containing compound and molecular sieve heat in organic solvent into
Row, organic solvent can be selected from one of toluene or hexamethylene.
Application of the catalyst according to the present invention in methylbenzene methanol side chain alkylation ethylbenzene and styrene reaction, can
Using including following processing step:
Using toluene and methanol as raw material, toluene and methanol molar ratio are (0.1~10) in raw material: 1, be in reaction temperature
350 DEG C~500 DEG C, material quality air speed is 0.1~5.0h-1Under conditions of, raw material is with generating ethylbenzene after catalyst haptoreaction
And styrene.
Compared with prior art, the present invention has the advantages that significant and high-lighting effect.Methylbenzene methanol side chain alkylation is anti-
Acid and basic sites carry out concerted catalysis in requisition for catalyst, and wherein basic sites play main work in Benzyl Side-Chain alkylated reaction
With.The X-type molecular sieve of alkali metals modified can make methylbenzene methanol side chain alkylation reactivity be significantly improved, and alkali metal carries out
After ion exchange, by electronics transfer, the framework of molecular sieve oxygen of band part negative electrical charge can be used as Lewis alkali center, impregnate simultaneously
Become Benzyl Side-Chain alkylation as the new basic center with appropriate intensity in the metal oxide in molecular sieve pore passage
There is the new active sites of reaction the addition of the meta-aluminate compared with strong basicity to enhance catalyst alkali centered active site, keep catalysis anti-
Answer toluene conversion with higher.Modifying element can be such that molecular sieve matches with suitable soda acid.Rare earth element and molecule
There are stronger active forces between sieve skeleton frame O atom, can dramatically increase the positive charge of framework of molecular sieve Al atom, increase Al and phase
Active force between adjacent O atom effectively stabilizes the skeleton Al of molecular sieve, avoids the removing of skeleton Al, is conducive to stablize
The skeleton structure of molecular sieve improves the hydrothermal stability of catalyst.Molecular sieve outer surface is because be difficult to realize toluene and methanol
The intermediate formaldehyde of adsorption equilibrium, methanol and generation resolves into CO and hydrogen in molecular sieve outer surface, reduces methanol feedstock
Utilization rate.Using relative inertness Si oxide covering molecular sieve outer surface, can to avoid the decomposition of material benzenemethanol,
Improve raw material availability.The method for preparing catalyst is easy, with higher simultaneously in the reaction of methylbenzene methanol side chain alkylation
Toluene conversion and higher use ratio of methanol have ethylbenzene, selectivity of styrene high, and resource utilization is higher and catalyst
The good advantage of stability.
The reaction of methylbenzene methanol side chain alkylation carries out on the continuously flowing miniature catalyst reaction device of quartz tube reactor.It produces
Object analysis use Agilent 7890A gas chromatograph on-line checking reactants and products to form and calculate the conversion ratio of reaction with
And selectivity of product.The catalyst prepared using method provided by the invention is for methylbenzene methanol side chain alkylation ethylbenzene and benzene
Ethylene reaction, toluene conversion reach 15%, and use ratio of methanol is up to 60%, ethylbenzene, styrene overall selectivity > 95%.Catalyst
Better performances and stability height, achieve preferable technical effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieve, returned in 500mL hexamethylene with methyl-silicone oil
Stream 4 hours, 110 DEG C drying 4 hours in an oven after filtering, then roasted 4 hours at 600 DEG C in Muffle furnace.By gained sample
Product carry out ion exchange 2 hours in the aqueous solution of 500mL potassium nitrate at 60 DEG C, exchange 2 times, then at 60 DEG C,
It is carried out ion exchange 2 hours in the aqueous solution of 500mL cesium nitrate, exchanges 2 times, filtered after exchange, in an oven 110 DEG C of dryings 4
Hour.Prepare containing appropriate potassium metaaluminate, boric acid, ruthenium trichloride, cerous nitrate aqueous solution 100mL, by the molecule after ion exchange
Sieve stirs 4 hours at 60 DEG C in the above solution to be impregnated, then evaporating water.110 DEG C drying 4 hours in an oven,
It is roasted 4 hours at 600 DEG C in Muffle furnace again after drying, obtains catalyst A, be ground into 40~60 mesh particles for catalyst
Evaluation.The mass ratio of modifying element contained by catalyst A and molecular sieve carrier are as follows: Al 1%, B 1%, K 2%, Cs 6%, Ru
0.8%, Ce 1%, Si 2%.
[embodiment 2]
Weigh 100g silica alumina ratio SiO2/Al2O3For 2 NaX type molecular sieve, flow back in 500mL hexamethylene with methyl-silicone oil
4 hours, 90 DEG C drying 24 hours in an oven after filtering, then roasted 24 hours at 400 DEG C in Muffle furnace.By gained sample
It at 60 DEG C, carries out ion exchange 2 hours, exchanges 2 times in the aqueous solution of 500mL potassium nitrate, then at 60 DEG C,
It is carried out ion exchange 2 hours in the aqueous solution of 500mL cesium nitrate, exchanges 2 times, filtered after exchange, in an oven 90 DEG C of dryings 24
Hour.Prepare containing appropriate potassium metaaluminate, boric acid, ruthenium trichloride, cerous nitrate aqueous solution 100mL, by the molecule after ion exchange
Sieve stirs 4 hours at 60 DEG C in the above solution to be impregnated, then evaporating water.90 DEG C drying 24 hours in an oven,
It is roasted 24 hours at 400 DEG C in Muffle furnace again after drying, obtains catalyst B, be ground into 40~60 mesh particles for being catalyzed
Agent evaluation.The mass ratio of modifying element contained by catalyst B and molecular sieve carrier are as follows: Al 0.1%, B 0.1%, K 0.5%, Cs
0.5%, Ru 0.1%, Ce 0.1%, Si 0.5%.
[embodiment 3]
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.9 NaX type molecular sieve, returned in 500mL hexamethylene with methyl-silicone oil
Stream 4 hours, 150 DEG C drying 1 hour in an oven after filtering, then roasted 1 hour at 650 DEG C in Muffle furnace.By gained sample
Product carry out ion exchange 2 hours in the aqueous solution of 500mL potassium nitrate at 60 DEG C, exchange 2 times, then at 60 DEG C,
It is carried out ion exchange 2 hours in the aqueous solution of 500mL cesium nitrate, exchanges 2 times, filtered after exchange, in an oven 150 DEG C of dryings 1
Hour.Prepare containing appropriate potassium metaaluminate, boric acid, ruthenium trichloride, cerous nitrate aqueous solution 100mL, by the molecule after ion exchange
Sieve stirs 4 hours at 60 DEG C in the above solution to be impregnated, then evaporating water.150 DEG C drying 1 hour in an oven,
It is roasted 1 hour at 650 DEG C in Muffle furnace again after drying, obtains catalyst C, be ground into 40~60 mesh particles for catalyst
Evaluation.The mass ratio of modifying element contained by catalyst C and molecular sieve carrier are as follows: Al 2%, B 2%, K 5%, Cs 10%, Ru
2%, Ce 2%, Si 5%.
[embodiment 4]
Weigh 100g silica alumina ratio SiO2/Al2O3For 2 NaX type molecular sieve, flow back in 500mL hexamethylene with methyl-silicone oil
4 hours, 110 DEG C drying 4 hours in an oven after filtering, then roasted 4 hours at 600 DEG C in Muffle furnace.By gained sample
It at 60 DEG C, carries out ion exchange 2 hours, exchanges 2 times in the aqueous solution of 500mL potassium nitrate, then at 60 DEG C,
It is carried out ion exchange 2 hours in the aqueous solution of 500mL cesium nitrate, exchanges 2 times, filtered after exchange, in an oven 110 DEG C of dryings 4
Hour.Prepare containing appropriate potassium metaaluminate, boric acid, ruthenium trichloride, cerous nitrate aqueous solution 100mL, by the molecule after ion exchange
Sieve stirs 4 hours at 60 DEG C in the above solution to be impregnated, then evaporating water.110 DEG C drying 4 hours in an oven,
It is roasted 4 hours at 600 DEG C in Muffle furnace again after drying, obtains catalyst D, be ground into 40~60 mesh particles for catalyst
Evaluation.The mass ratio of modifying element contained by catalyst D and molecular sieve carrier are as follows: Al 0.05%, B 0.05%, K 0.1%, Cs
0.3%, Ru 0.05%, Ce 0.05%, Si 0.1%.
[embodiment 5]
Weigh 100g silica alumina ratio SiO2/Al2O3For 5 NaY type molecular sieve, flow back in 500mL hexamethylene with methyl-silicone oil
4 hours, 110 DEG C drying 4 hours in an oven after filtering, then roasted 4 hours at 600 DEG C in Muffle furnace.By gained sample
It at 60 DEG C, is carried out ion exchange 2 hours in the aqueous solution of 500mL cesium nitrate, exchanges 2 times, filtered after exchange, in an oven
110 DEG C drying 4 hours.Prepare containing appropriate potassium metaaluminate, boric acid, ruthenium trichloride, cerous nitrate aqueous solution 100mL, ion is handed over
Molecular sieve after changing stirs 4 hours at 60 DEG C in the above solution to be impregnated, then evaporating water.110 DEG C in an oven
It is 4 hours dry, it is roasted 4 hours at 600 DEG C in Muffle furnace again after dry, obtains catalyst E, be ground into 40~60 mesh particles
For evaluating catalyst.The mass ratio of modifying element contained by catalyst E and molecular sieve carrier are as follows: Al 10%, B 10%, Cs
20%, Ru 10%, Ce 10%, Si 10%.
[embodiment 6]
Weigh 100g silica alumina ratio SiO2/Al2O3For 5 NaY type molecular sieve, returned in 500mL toluene with tetraethoxysilane
Stream 4 hours, 110 DEG C drying 4 hours in an oven after filtering, then roasted 4 hours at 600 DEG C in Muffle furnace.By gained sample
Product carry out ion exchange 2 hours in the aqueous solution of 500mL rubidium nitrate at 60 DEG C, exchange 2 times, then at 60 DEG C,
It is carried out ion exchange 2 hours in the aqueous solution of 500mL cesium nitrate, exchanges 2 times, filtered after exchange, in an oven 110 DEG C of dryings 4
Hour.Prepare containing appropriate boric acid, phosphoric acid, radium chloride, lanthanum nitrate aqueous solution 100mL, by the molecular sieve after ion exchange upper
It states to stir 4 hours at 60 DEG C in solution and be impregnated, then evaporating water.110 DEG C drying 4 hours in an oven, after dry
It is roasted 4 hours at 600 DEG C in Muffle furnace again, obtains catalyst F, be ground into 40~60 mesh particles for evaluating catalyst.
The mass ratio of modifying element contained by catalyst F and molecular sieve carrier are as follows: B 1%, P 1%, Rb 2%, Cs 6%, Rh 0.8%,
La 1%, Si 2%.
[embodiment 7]
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieve, at 60 DEG C, in 500mL cesium hydroxide
It is carried out ion exchange 2 hours in aqueous solution, exchanges 2 times, filtered after exchange, in an oven 110 DEG C drying 4 hours.It prepares containing suitable
The aqueous solution 100mL for measuring phosphoric acid, chloroplatinic acid, cerous nitrate, the molecular sieve after ion exchange is stirred at 60 DEG C in the above solution
It mixes 4 hours and is impregnated, then evaporating water.110 DEG C drying 4 hours in an oven, after drying again in Muffle furnace in 600 DEG C
Lower roasting 4 hours, gained sample and four butoxy silanes is flowed back 4 hours in 500mL hexamethylene, after filtering in an oven
110 DEG C drying 4 hours, then roasted 4 hours at 600 DEG C in Muffle furnace, obtain catalyst G, be ground into 40~60 mesh particles
For evaluating catalyst.The mass ratio of modifying element contained by catalyst G and molecular sieve carrier are as follows: P 1%, Cs 6%, Pt
0.8%, Ce 1%, Si 2%.
[embodiment 8]
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieve, at 60 DEG C, in the water of 500mL cesium chloride
It is carried out ion exchange 2 hours in solution, exchanges 2 times, filtered after exchange, in an oven 110 DEG C drying 4 hours.It prepares containing appropriate
Boric acid, palladium chloride, lanthanum nitrate aqueous solution 100mL, the molecular sieve after ion exchange is stirred 4 at 60 DEG C in the above solution
Hour is impregnated, then evaporating water.110 DEG C drying 4 hours in an oven, after drying again in Muffle furnace at 600 DEG C
Roasting 4 hours, gained sample and methyl-silicone oil are flowed back 4 hours in 500mL ether, 110 DEG C of dryings 4 in an oven after filtering
Hour, then roasted 4 hours at 600 DEG C in Muffle furnace, catalyst H is obtained, is ground into 40~60 mesh particles for catalyst
Evaluation.The mass ratio of modifying element contained by catalyst H and molecular sieve carrier are as follows: B 1%, Cs 6%, Pd 0.8%, La 1%,
Si 2%.
[embodiment 9]
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieve, returned in 500mL hexamethylene with methyl-silicone oil
Stream 4 hours, 110 DEG C drying 4 hours in an oven after filtering, then roasted 4 hours at 600 DEG C in Muffle furnace.By gained sample
Product carry out ion exchange 2 hours in the aqueous solution of 500mL cesium nitrate at 60 DEG C, exchange 2 times, filter after exchange, in baking oven
In 110 DEG C drying 4 hours.Prepare containing appropriate sodium metaaluminate, boric acid, cesium hydroxide, chloroplatinic acid, cerous nitrate aqueous solution 100mL,
Molecular sieve after ion exchange is stirred 4 hours at 60 DEG C in the above solution and is impregnated, then evaporating water.In baking oven
In 110 DEG C drying 4 hours, roasted 4 hours at 600 DEG C in Muffle furnace again after dry, obtain catalyst I, be ground into 40~
60 mesh particles are used for evaluating catalyst.The mass ratio of modifying element contained by catalyst I and molecular sieve carrier are as follows: Al 1%, B
1%, Cs 8%, Pt 0.8%, Ce 1%, Si 2%.
[embodiment 10]
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieve, returned in 500mL hexamethylene with methyl-silicone oil
Stream 4 hours, 110 DEG C drying 4 hours in an oven after filtering, then roasted 4 hours at 600 DEG C in Muffle furnace.By gained sample
Product carry out ion exchange 2 hours in the aqueous solution of 500mL rubidium nitrate at 60 DEG C, exchange 2 times, then at 60 DEG C,
It is carried out ion exchange 2 hours in the aqueous solution of 500mL cesium nitrate, exchanges 2 times, filtered after exchange, in an oven 110 DEG C of dryings 4
Hour.Prepare containing appropriate potassium metaaluminate, phosphoric acid, ruthenium trichloride, lanthanum nitrate aqueous solution 100mL, by the molecule after ion exchange
Sieve stirs 4 hours at 60 DEG C in the above solution to be impregnated, then evaporating water.110 DEG C drying 4 hours in an oven,
It is roasted 4 hours at 600 DEG C in Muffle furnace again after drying, obtains catalyst J, be ground into 40~60 mesh particles for catalyst
Evaluation.The mass ratio of modifying element contained by catalyst J and molecular sieve carrier are as follows: Al 1%, P 1%, Rb 2%, Cs 6%, Ru
0.8%, La 1%, Si 2%.
[embodiment 11]
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieve, returned in 500mL hexamethylene with methyl-silicone oil
Stream 4 hours, 110 DEG C drying 4 hours in an oven after filtering, then roasted 4 hours at 600 DEG C in Muffle furnace.By gained sample
Product carry out ion exchange 2 hours in the aqueous solution of 500mL potassium nitrate at 60 DEG C, exchange 2 times, then in 500mL rubidium nitrate
Carried out ion exchange 2 hours in aqueous solution, exchange 2 times, then at 60 DEG C, carried out in the aqueous solution of 500mL cesium nitrate from
Son exchange 2 hours, exchanges 2 times, filters after exchange, in an oven 110 DEG C drying 4 hours.It prepares and contains appropriate potassium metaaluminate, boron
Acid, phosphoric acid, cesium nitrate, ruthenium trichloride, radium chloride, chloroplatinic acid, cerous nitrate, lanthanum nitrate aqueous solution 100mL, after ion exchange
Molecular sieve stir 4 hours impregnated at 60 DEG C in the above solution, then evaporating water.110 DEG C of dryings 4 in an oven
Hour, it is roasted 4 hours at 600 DEG C in Muffle furnace again after dry, obtains catalyst K, be ground into 40~60 mesh particles and be used for
Evaluating catalyst.The mass ratio of modifying element contained by catalyst K and molecular sieve carrier are as follows: Al 1%, B 1%, P 1%, K
1%, Rb 1%, Cs 6%, Ru 0.8%, Rh 0.8%, Pt 0.8%, Ce 1%, La 1%, Si 2%.
[embodiment 12]
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieve, returned in 500mL hexamethylene with methyl-silicone oil
Stream 4 hours, 110 DEG C drying 4 hours in an oven after filtering, then roasted 4 hours at 600 DEG C in Muffle furnace.By gained sample
Product carry out ion exchange 2 hours in the aqueous solution of 500mL potassium nitrate at 60 DEG C, exchange 2 times, then at 60 DEG C,
It is carried out ion exchange 2 hours in the aqueous solution of 500mL cesium nitrate, exchanges 2 times, filtered after exchange, in an oven 110 DEG C of dryings 4
Hour.Prepare containing appropriate potassium metaaluminate, boric acid, ruthenium trichloride, cerous nitrate, indium nitrate aqueous solution 100mL, after ion exchange
Molecular sieve stir 4 hours impregnated at 60 DEG C in the above solution, then evaporating water.110 DEG C of dryings 4 in an oven
Hour, it is roasted 4 hours at 600 DEG C in Muffle furnace again after dry, obtains catalyst L, be ground into 40~60 mesh particles and be used for
Evaluating catalyst.The mass ratio of modifying element contained by catalyst L and molecular sieve carrier are as follows: Al 1%, B 1%, K 2%, Cs
6%, Ru 0.8%, Ce 1%, Si 2%, In 1%.
[comparative example 1]
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieve, in the aqueous solution of 500mL cesium nitrate at 60 DEG C
Middle progress ion exchange 2 hours is exchanged 2 times, is filtered after exchange, in an oven 110 DEG C drying 4 hours, again in Muffle after drying
It is roasted 4 hours at 600 DEG C in furnace, obtains catalyst M, be ground into 40~60 mesh particles for evaluating catalyst.Catalyst M institute
Mass ratio containing modifying element and molecular sieve carrier are as follows: Cs 6%.
[comparative example 2]
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieve, in the aqueous solution of 500mL potassium nitrate at 60 DEG C
Middle progress ion exchange 2 hours exchanges 2 times, and then at 60 DEG C, ion exchange 2 is carried out in the aqueous solution of 500mL cesium nitrate
Hour, it exchanges 2 times, is filtered after exchange, in an oven 110 DEG C drying 4 hours.Prepare the aqueous solution containing appropriate ruthenium trichloride
Molecular sieve after ion exchange is stirred 4 hours at 60 DEG C in the above solution and is impregnated, then evaporating water by 100mL.
110 DEG C drying 4 hours in an oven roast 4 hours at 600 DEG C in Muffle furnace again after dry, obtain catalyst n, grind
Evaluating catalyst is used at 40~60 mesh particles.The mass ratio of modifying element and molecular sieve carrier contained by catalyst n are as follows: K 2%,
Cs 6%, Ru 0.8%.
[comparative example 3]
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieve, in the aqueous solution of 500mL potassium nitrate at 60 DEG C
Middle progress ion exchange 2 hours exchanges 2 times, and then at 60 DEG C, ion exchange 2 is carried out in the aqueous solution of 500mL cesium nitrate
Hour, it exchanges 2 times, is filtered after exchange, in an oven 110 DEG C drying 4 hours.It prepares and contains appropriate boric acid, ruthenium trichloride, cerous nitrate
Aqueous solution 100mL, the molecular sieve after ion exchange is stirred 4 hours at 60 DEG C in the above solution and is impregnated, then
Evaporating water.110 DEG C drying 4 hours in an oven roast 4 hours at 600 DEG C in Muffle furnace again after dry, are catalyzed
Agent O is ground into 40~60 mesh particles for evaluating catalyst.The mass ratio of modifying element contained by catalyst O and molecular sieve carrier
Are as follows: B 1%, K 2%, Cs 6%, Ru 0.8%, Ce 1%.
[comparative example 4]
Weigh 100g silica alumina ratio SiO2/Al2O3For 2.1 NaX type molecular sieve, returned in 500mL hexamethylene with methyl-silicone oil
Stream 4 hours, 110 DEG C drying 4 hours in an oven after filtering, then roasted 4 hours at 600 DEG C in Muffle furnace.By gained sample
Product carry out ion exchange 2 hours in the aqueous solution of 500mL potassium nitrate at 60 DEG C, exchange 2 times, then at 60 DEG C,
It is carried out ion exchange 2 hours in the aqueous solution of 500mL cesium nitrate, exchanges 2 times, filtered after exchange, in an oven 110 DEG C of dryings 4
Hour.The aqueous solution 100mL containing appropriate ruthenium trichloride is prepared, by the molecular sieve after ion exchange in the above solution at 60 DEG C
Stirring is impregnated for 4 hours, then evaporating water.110 DEG C drying 4 hours in an oven, after drying again in Muffle furnace in 600
It is roasted 4 hours at DEG C, obtains catalyst P, be ground into 40~60 mesh particles for evaluating catalyst.Modified member contained by catalyst P
The mass ratio of element and molecular sieve carrier are as follows: K 2%, Cs 6%, Ru0.8%, Si 2%.
[embodiment 13]
5g catalyst A~P is taken to carry out methylbenzene methanol side chain alkylation reaction evaluating.Reaction temperature is 415 DEG C；Reaction pressure
For normal pressure；Methylbenzene methanol molar ratio is 4:1；Toluene mass space velocity is 1.0h-1, carrier gas N2Flow velocity is 10mL/min.In above-mentioned item
Catalysis reaction is carried out under part, reaction product is analyzed with gas chromatography.After reaction, methanol conversion 100%.Reaction knot
Fruit is listed in table 1.
Table 1*
| Catalyst | Toluene conversion (%) | Use ratio of methanol (%) | Ethylbenzene+selectivity of styrene (%) |
| A | 15.4 | 61.6 | 98.1 |
| B | 10.7 | 42.8 | 95.8 |
| C | 12.9 | 51.6 | 91.4 |
| D | 10.1 | 40.4 | 94.7 |
| E | 15.6 | 62.4 | 88.1 |
| F | 12.3 | 49.2 | 96.4 |
| G | 11.5 | 46.0 | 95.2 |
| H | 11.9 | 47.6 | 97.5 |
| I | 14.7 | 58.8 | 94.5 |
| J | 13.6 | 54.4 | 96.3 |
| K | 13.8 | 55.2 | 97.0 |
| L | 15.2 | 60.8 | 95.9 |
| Comparative example M | 5.5 | 22.0 | 89.2 |
| Comparative example N | 6.1 | 24.4 | 88.6 |
| Comparative example O | 6.3 | 25.2 | 89.2 |
| Comparative example P | 6.7 | 26.8 | 91.4 |
* it reacts 10 hours and is averaged
[embodiment 14]
5g catalyst A, M is taken to carry out methylbenzene methanol side chain alkylation reaction evaluating.Reaction temperature is 415 DEG C；Reaction pressure
For normal pressure；Methylbenzene methanol molar ratio is 4:1；Toluene mass space velocity is 1.0h-1, carrier gas N2Flow velocity is 10mL/min.In above-mentioned item
Catalysis reaction is carried out under part, reaction product is analyzed with gas chromatography.After reaction, methanol conversion 100%.Catalyst
One way is reacted 200 hours, and after Burning Coke on Catalyst regenerates 20 times, reaction result is listed in table 2.
Table 2*
* it reacts 10 hours and is averaged.
Claims (9)
1. a kind of catalyst for the reaction of methylbenzene methanol side chain alkylation, includes following components:
A) at least one of X molecular sieve or Y molecular sieve；With load modified component thereon:
B) mass ratio of at least one of Al, P and B, the element and molecular sieve carrier is (0.05 ~ 10): 100；
C) mass ratio of at least one of alkali metal element, the element and molecular sieve carrier is (0.1 ~ 20): 100；
D) mass ratio of at least one of platinum group, the element and molecular sieve carrier is (0.05 ~ 10): 100；
E) mass ratio of at least one of rare earth element, the element and molecular sieve carrier is (0.05 ~ 10): 100；
F) mass ratio of the oxide of Si, the Si element and molecular sieve carrier is (0.5 ~ 10): 100,
The preparation method of the catalyst comprises the steps of:
A) molecular sieve and the solution containing the modifying element are subjected to ion exchange or dipping；
B) molecular sieve is surface modified using silicon-containing compound, forms the covering of Si oxide in molecular sieve surface after roasting
Layer；
C) modified molecular sieve is dried, roasted and formed.
2. the catalyst for the reaction of methylbenzene methanol side chain alkylation according to claim 1, it is characterised in that the molecule
Screened from SiO2/Al2O3For at least one of 2 ~ 5 X molecular sieve or Y molecular sieve.
3. the catalyst for the reaction of methylbenzene methanol side chain alkylation according to claim 1, it is characterised in that the molecule
Sieve is X molecular sieve.
4. the catalyst for the reaction of methylbenzene methanol side chain alkylation according to claim 1, it is characterised in that the modification
Group is selected from least one of Al and B, and the mass ratio of the element and molecular sieve carrier is (0.1 ~ 2): 100.
5. the catalyst for the reaction of methylbenzene methanol side chain alkylation according to claim 1, it is characterised in that the alkali gold
Belong to element and be selected from least one of K, Rb or Cs, the mass ratio of the element and molecular sieve carrier is (0.5 ~ 10): 100.
6. the catalyst for the reaction of methylbenzene methanol side chain alkylation according to claim 1, it is characterised in that the platinum group
Element is selected from least one of Ru, Rh or Pt, and the mass ratio of the element and molecular sieve carrier is (0.1 ~ 2): 100.
7. the catalyst for the reaction of methylbenzene methanol side chain alkylation according to claim 1, it is characterised in that the rare earth
Element is selected from least one of La or Ce, and the mass ratio of the element and molecular sieve carrier is (0.1 ~ 2): 100.
8. according to claim 1 for methylbenzene methanol side chain alkylation reaction catalyst, it is characterised in that the Si with
The mass ratio of molecular sieve carrier is (0.5 ~ 5): 100.
9. a kind of purposes of the catalyst for the reaction of methylbenzene methanol side chain alkylation, using toluene and methanol as raw material, in raw material
Toluene and methanol molar ratio are (0.1 ~ 10): 1, it is 350 DEG C ~ 500 DEG C in reaction temperature, material quality air speed is 0.1 ~ 5.0h-1
Under conditions of, raw material is with generating ethylbenzene and styrene after the described in any item catalyst haptoreactions of claim 1 ~ 8.
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| CN107866264B (en) * | 2017-11-21 | 2020-08-28 | 万华化学集团股份有限公司 | Catalyst for synthesizing DEMMA (DEMMA), and preparation method and application thereof |
| CN109529910B (en) * | 2018-11-29 | 2020-08-07 | 中国科学院大连化学物理研究所 | Catalyst for toluene methanol side-chain alkylation reaction and styrene preparation method |
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| CN102740969A (en) * | 2010-02-05 | 2012-10-17 | 弗纳技术股份有限公司 | Styrene production processes and catalysts for use therein |
| CN104557374A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Toluene/methanol side chain alkylation method |
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| CN102740969A (en) * | 2010-02-05 | 2012-10-17 | 弗纳技术股份有限公司 | Styrene production processes and catalysts for use therein |
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