CN102824923B - Catalyst for liquid phase synthesis of ethylbenzene, preparation method and application thereof - Google Patents
Catalyst for liquid phase synthesis of ethylbenzene, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for liquid phase synthesis of ethylbenzene, a preparation method and application of the catalyst. The preparation method comprises the steps of mixing sodium aluminate, sodium hydroxide, water, tetraethylammonium bromide, tetraethylammonium hydroxide and silica sol; crystallizing the mixture at 100-170 DEG C; dropwise adding aluminum chloride or zinc chloride solution on the obtained product, and crystallizing at 100-170 DEG C; drying and calcining to obtain beta molecular sieve; subjecting the beta molecular sieve to ion exchange in ammonium nitrate solution, drying and calcining to obtain H-beta molecular sieve; impregnating the obtained product in zirconium nitrate or titanium nitrate solution, and drying; impregnating the obtained product in lanthanum nitrate or cerium nitrate solution, drying and calcining to obtain molecular sieve material. In ethylbenzene synthesis reaction from benzene and ethylene, the catalyst has ethylene conversion rate above 97%, ethylbenzene selectivity above 95%, no xylene in product, and long operation time.
Description
Technical field
The present invention relates to a kind of preparation and application through the modified molecular screen of liquid phase method synthesizing ethyl benzene reaction for ethene and benzene.
Background technology
Ethylbenzene is to produce cinnamic raw material, and styrene can be used for producing the organic synthesis materials such as polystyrene, butadiene-styrene rubber, ABS resin and SBS.It is raw material that industrial ethylbenzene mainly be take benzene and ethene, under catalyst action, through alkylated reaction, makes.The progress of ethylbenzene synthetic technology has very important significance, and key is wherein exactly to develop efficient catalyst.
The technique that ethylbenzene alkylation adopts in the world mainly contains alchlor liquid catalytic, molecular sieve gas-phase catalysis and molecular sieve liquid catalytic.Wherein, alchlor liquid catalytic started from before the seventies, due to very strong corrosivity, gave plant maintenance and instead became liquid post processing to bring very large inconvenience, substantially no longer adopted now.From technical standpoint, development environment close friend's solid acid catalyst just meets trend.1976, Mobil and Badger company developed ZSM-5 molecular sieve catalyst cooperatively for vapor phase method synthesizing ethyl benzene, and had realized industrialization in 1980.That this method has is corrosion-free, pollution-free, energy consumption is low and ethene air speed advantages of higher.But it is high that this method also has reaction temperature, the easy coking and deactivation of catalyst, the shortcoming such as in product, by-product xylene content is high, and the regeneration period is short.1989, Unocal-ABB Lummus-Crest announced the liquid phase ethylbenzene technique based on active Y zeolite catalyst.First nineteen ninety is realized after industrialization in Japan by Lummus/UOP, and it is in the ascendance in new device in recent years.This method is compared with vapor phase method to be had reaction temperature and is easy to control, and catalyst carbon deposit is few, and good stability, life-span are long, non-xylol in product, the advantage such as separation process is simple, and equipment can all adopt carbon steel, and investment cost is lower.
At present, along with the development of technology, the ethylbenzene new technology of some companies has adopted β zeolite as catalyst.β zeolite is a kind of high silicon large pore molecular sieve of three-dimensional twelve-ring channel system, and its 3 D pore canal can communicate, thereby is difficult for stopping up inactivation.And β zeolite acidity is moderate, there are a certain proportion of strong acidic site and weak acid position.The structure of β zeolite and acidity become a kind of suitable alkylation solid acid catalyst.But the conventional beta zeolitic acid intensity of commercially producing is weak and acid site density is lower, causes their inactivations in alkylated reaction very fast.Therefore, conventional beta zeolite is carried out to modification, improve its acid strength or acid site density, make it better be applied to alkylated reaction very necessary.
Patent ZL02151177.2 and ZL02155114.6 disclose a kind of beta-molecular sieve catalyst of processing successively modification through high-temperature water vapor and organic acid, and it can be used for preparing ethylbenzene by liquid phase alkylation of ethylene reaction.This catalyst is active, stability no matter, or the performance after regeneration is all obviously better than untreated beta-molecular sieve.
Patent ZL02155598.2 also will be through organic acid-treated beta-molecular sieve catalyst for olefin alkylation reaction.This catalyst is to obtain after citric acid treatment by pure beta-molecular sieve or through the beta-molecular sieve of binding agent moulding.Compare untreated beta-molecular sieve, catalyst selectivity and stability after processing obviously increase.
Patent ZL03146474.2 and 03146476.9 is by the SiO processing
2with or/Al
2o
3the composite forming with nano-beta molecular sieve, as catalyst, is applied to alkene and isoparaffin alkylated reaction, compares conventional beta molecular sieve, the principal product on this composite catalyst selectively and stability obviously increase.
The beta-molecular sieve that patent ZL99102571.7 adopt to implant ZSM-12, add La modification carries out alkylated reaction, and this catalyst can be simultaneously for gas phase and liquid phase reactor, and has high ethylbenzene selectivity and low methylbenzene selective simultaneously.
Patent 200610169664.6 discloses a kind of nano-beta molecular sieve through IIIA, IVA, IIIB, IVB, La system and Ac lanthanide modified, and this catalyst has stronger acidity, for alkylated reaction, has longer life-span and the selectivity of product of Geng Gao.
Patent 200610169665.0 discloses that a kind of this catalyst is compared traditional catalyst through IIIA, IVA, the element modified beta-molecular sieve of VIIIB, IVB, and alkylated reaction selectivity improves more than 20%.
Summary of the invention:
The object of the present invention is to provide a kind of Catalysts and its preparation method of benzene alkylation liquid phase method synthesizing ethyl benzene.Utilize the molecular sieve catalyst that the method obtains to there is high acid strength and strong acid center density.
The catalyst of liquid phase method synthesizing ethyl benzene provided by the invention is a kind of high stability, and for the catalyst of fixed bed reaction, its preparation process is as follows:
Aluminium source, NaOH, water, template are mixed and stirred, make working solution, above-mentioned working solution and silicon source are mixed to get to reactant mixture, become sol-gel state, after crystallization, under stirring, certain density chlorination metal salt solution is dropwise dripped on slurries, after aging, crystallization, filtration, washing, dry and roasting, this molecular sieve is immersed in certain density ammonium salt solution and carries out ion-exchange, after drying and roasting, obtain H-beta-molecular sieve.Again H-beta-molecular sieve be impregnated in the solution of the certain density IVB of containing element and floods, dry after, then put it into and certain densityly containing in the solution of rare earth element, flood, then be dried with roasting and obtain molecular screen material.
In method provided by the invention, said molecular sieve is beta-molecular sieve.
In method provided by the invention, said silicon source is selected from solid silicone, Ludox or positive esters of silicon acis, is preferably Ludox.Said aluminium source is selected from aluminium hydroxide, boehmite or sodium aluminate, is preferably sodium aluminate.Said template is tetraethylammonium bromide or tetraethyl ammonium hydroxide.
In method provided by the invention, said chlorination slaine is zinc chloride and liquor alumini chloridi, preferably liquor alumini chloridi.
In method provided by the invention, said ammonium salt is ammonium nitrate or ammonium sulfate, preferably ammonium nitrate solution.
In method provided by the invention, the solution of the said IVB of containing element is zirconium nitrate or Titanium Nitrate solution, preferably zirconium nitrate solution.
In method provided by the invention, the said solution containing rare earth element is lanthanum nitrate or cerous nitrate solution, preferably lanthanum nitrate hexahydrate.
The preparation method of molecular sieve catalyst provided by the invention comprises the following steps:
(1) at 30-50 ℃, a certain amount of sodium aluminate, NaOH, water, tetraethylammonium bromide or tetraethyl ammonium hydroxide are mixed and stirred in colloid generating kettle, then add a certain amount of Ludox, become uniform sol-gel, continue to stir 10 minutes; He Lv source, silicon source is with SiO
2and Al
2o
3meter, mol ratio is 10-40; Tetraethylammonium bromide or tetraethyl ammonium hydroxide, with (TEA)
2o and SiO
2meter, mol ratio is 0.1-0.6; NaOH, with Na
2o and SiO
2meter, mol ratio is 0.05-0.2; Water, with H
2o and SiO
2meter, mol ratio is 10-20;
(2) mixture obtaining in step (1) is poured in crystallizing kettle into crystallization 48-96 hour at 100-170 ℃;
(3) under stirring, the aluminium chloride of 10% (wt) or liquor zinci chloridi are dropwise dripped on the product that step (2) obtains, stir aging 4-6 hour, be transferred in crystallizing kettle crystallization 24-48 hour at 100-170 ℃; After crystallization finishes, the product obtaining is filtered, be washed with distilled water to pH=10, then at 90-120 ℃, be dried 12 hours, 560-600 ℃ of roasting 4 hours, obtains beta-molecular sieve;
(4) in the ammonium nitrate solution that beta-molecular sieve step (3) being obtained is 10-20% in mass concentration, carry out ion-exchange, then 90-120 ℃ dry 12 hours, 560-600 ℃ of roasting 4 hours, obtains H-beta-molecular sieve;
(5) zirconium nitrate or Titanium Nitrate solution that product step (4) being obtained is put into 3% (wt) flood 12 hours, then at 90-120 ℃, are dried 12 hours;
(6) lanthanum nitrate or cerous nitrate solution that product step (5) being obtained is put into 1.5% (wt) flood, then 90-120 ℃ dry 12 hours, 560-600 ℃ of roasting 4 hours, obtains molecular screen material.
Molecular sieve catalyst of the present invention is for take the preparation of the ethylbenzene that benzene and ethene is raw material, and reaction condition is temperature 180-250 ℃, pressure 2-5MPa, benzene weight space velocity 1-6h
-1, benzene alkene mol ratio is 2-6.
With prior art, compare, catalyst feature provided by the invention is to have higher acid strength and strong acid distribution density, make this catalyst there is higher catalytic activity and catalytic efficiency, at benzene and ethene, prepare in reacting of ethylbenzene, conversion of ethylene reaches more than 97%, ethylbenzene selectivity reaches more than 95%, non-xylol in product, and one way is long the duration of runs.
The specific embodiment
Embodiment 1
At 30 ℃, 9 grams of sodium aluminates, 2 grams of NaOH, 60 grams of tetraethylammonium bromides are dissolved in 200ml deionized water, under agitation add 120 grams of Ludox, continue to stir 1 hour, make into uniform sol-gel.Moved in crystallizing kettle, in 100 ℃ of crystallization.After 96 hours, under stirring, the liquor alumini chloridi of 10% (wt) is dropwise dripped on slurries, stir after 6 hours, be transferred in crystallizing kettle, in 100 ℃ of crystallization 48 hours.After crystallization finishes, the product obtaining is filtered, be washed with distilled water to pH=10.Then at 120 ℃, be dried 12 hours, 560 ℃ of roastings 4 hours, obtain beta-molecular sieve.Again the beta-molecular sieve obtaining is carried out to ion-exchange in concentration is the ammonium nitrate solution of 20% (wt), then 120 ℃ dry 12 hours, 560 ℃ of roastings 4 hours, obtain H-beta-molecular sieve.The zirconium nitrate solution of again H-beta-molecular sieve being put into 3% (wt) floods 12 hours, then at 120 ℃, is dried 12 hours.The lanthanum nitrate hexahydrate of dried product being put into 1.5% (wt) floods, then 120 ℃ dry 12 hours, 560 ℃ of roastings 4 hours, obtain molecular screen material A.
Embodiment 2
At 40 ℃, 3 grams of sodium aluminates, 4 grams of NaOH are placed in to 200 grams of tetraethyl ammonium hydroxides (20%wt), then add in 100ml deionized water, under agitation add 120 grams of Ludox, continue to stir 1 hour, make into uniform sol-gel.Moved in crystallizing kettle, in 150 ℃ of crystallization.After 48 hours, under stirring, the liquor zinci chloridi of 10% (wt) is dropwise dripped on slurries, stir after 4 hours, be transferred in crystallizing kettle, in 150 ℃ of crystallization 24 hours.After crystallization finishes, the product obtaining is filtered, be washed with distilled water to pH=10.Then 90 ℃ dry 12 hours, 580 ℃ of roastings 4 hours, obtain beta-molecular sieve.Again the beta-molecular sieve obtaining is carried out to ion-exchange in concentration is the ammonium nitrate solution of 15% (wt), then 90 ℃ dry 12 hours, 580 ℃ of roastings 4 hours, obtain H-beta-molecular sieve.The zirconium nitrate solution of again H-beta-molecular sieve being put into 3% (wt) floods 12 hours, then at 90 ℃, is dried 12 hours.The cerous nitrate solution of dried product being put into 1.5% (wt) floods, then 90 ℃ dry 12 hours, 580 ℃ of roastings 4 hours, obtain molecular screen material B.
Embodiment 3
At 40 ℃, 6 grams of sodium aluminates, 3 grams of NaOH are placed in to 150 grams of tetraethyl ammonium hydroxides (20%wt), then add in 80ml deionized water, under agitation add 120 grams of Ludox, continue to stir 1 hour, make into uniform sol-gel.Moved in crystallizing kettle, in 170 ℃ of crystallization.After 48 hours, under stirring, the liquor alumini chloridi of 10% (wt) is dropwise dripped on slurries, stir after 6 hours, be transferred in crystallizing kettle, in 170 ℃ of crystallization 24 hours.After crystallization finishes, the product obtaining is filtered, be washed with distilled water to pH=10.Then 110 ℃ dry 12 hours, 600 ℃ of roastings 4 hours, obtain beta-molecular sieve.Again the beta-molecular sieve obtaining is carried out to ion-exchange in concentration is the ammonium nitrate solution of 10% (wt), then 110 ℃ dry 12 hours, 600 ℃ of roastings 4 hours, obtain H-beta-molecular sieve.The Titanium Nitrate solution of again H-beta-molecular sieve being put into 3% (wt) floods 12 hours, then at 110 ℃, is dried 12 hours.The lanthanum nitrate hexahydrate of dried product being put into 1.5% (wt) floods, then 110 ℃ dry 12 hours, 600 ℃ of roastings 4 hours, obtain molecular screen material C.
Embodiment 4
At 50 ℃, 11 grams of sodium aluminates, 0.5 gram of NaOH, 30 grams of tetraethylammonium bromides are dissolved in 250ml deionized water, under agitation add 120 grams of Ludox, continue to stir 1 hour, make into uniform sol-gel.Moved in crystallizing kettle, in 140 ℃ of crystallization.After 72 hours, under stirring, the liquor zinci chloridi of 10% (wt) is dropwise dripped on slurries, stir after 6 hours, be transferred in crystallizing kettle, in 140 ℃ of crystallization 24 hours.After crystallization finishes, the product obtaining is filtered, be washed with distilled water to pH=10.Then 100 ℃ dry 12 hours, 560 ℃ of roastings 4 hours, obtain beta-molecular sieve.Again the beta-molecular sieve obtaining is carried out to ion-exchange in concentration is the ammonium nitrate solution of 20% (wt), then 100 ℃ dry 12 hours, 560 ℃ of roastings 4 hours, obtain H-beta-molecular sieve.The Titanium Nitrate solution of again H-beta-molecular sieve being put into 3% (wt) floods 12 hours, then at 100 ℃, is dried 12 hours.The lanthanum nitrate hexahydrate of dried product being put into 1.5% (wt) floods, then 100 ℃ dry 12 hours, 560 ℃ of roastings 4 hours, obtain molecular screen material D.
Embodiment 5
At 30 ℃, 6 grams of sodium aluminates, 3 grams of NaOH are placed in to 150 grams of tetraethyl ammonium hydroxides (20%wt), then add in 80ml deionized water, under agitation add 120 grams of Ludox, continue to stir 1 hour, make into uniform sol-gel.Moved in crystallizing kettle, in 150 ℃ of crystallization.After 48 hours, under stirring, the liquor alumini chloridi of 10% (wt) is dropwise dripped on slurries, stir after 6 hours, be transferred in crystallizing kettle, in 150 ℃ of crystallization 48 hours.After crystallization finishes, the product obtaining is filtered, be washed with distilled water to pH=10.Then 110 ℃ dry 12 hours, 580 ℃ of roastings 4 hours, obtain beta-molecular sieve.Again the beta-molecular sieve obtaining is carried out to ion-exchange in concentration is the ammonium nitrate solution of 15% (wt), then 110 ℃ dry 12 hours, 580 ℃ of roastings 4 hours, obtain H-beta-molecular sieve.The Titanium Nitrate solution of again H-beta-molecular sieve being put into 3% (wt) floods 12 hours, then at 110 ℃, is dried 12 hours.The cerous nitrate solution of dried product being put into 1.5% (wt) floods, then 110 ℃ dry 12 hours, 580 ℃ of roastings 4 hours, obtain molecular screen material E.
Embodiment 6
At 40 ℃, 9 grams of sodium aluminates, 2 grams of NaOH, 60 grams of tetraethylammonium bromides are dissolved in 200ml deionized water, under agitation add 120 grams of Ludox, continue to stir 1 hour, make into uniform sol-gel.Moved in crystallizing kettle, in 120 ℃ of crystallization.After 72 hours, under stirring, the liquor alumini chloridi of 10% (wt) is dropwise dripped on slurries, stir after 6 hours, be transferred in crystallizing kettle, in 120 ℃ of crystallization 48 hours.After crystallization finishes, the product obtaining is filtered, be washed with distilled water to pH=10.Then 120 ℃ dry 12 hours, 580 ℃ of roastings 4 hours, obtain beta-molecular sieve.Again the beta-molecular sieve obtaining is carried out to ion-exchange in concentration is the ammonium nitrate solution of 20% (wt), then 120 ℃ dry 12 hours, 580 ℃ of roastings 4 hours, obtain H-beta-molecular sieve.The zirconium nitrate solution of again H-beta-molecular sieve being put into 3% (wt) floods 12 hours, then at 120 ℃, is dried 12 hours.The cerous nitrate solution of dried product being put into 1.5% (wt) floods, then 120 ℃ dry 12 hours, 580 ℃ of roastings 4 hours, obtain molecular screen material F.
Comparative example 1
At 30 ℃, 9 grams of sodium aluminates, 2 grams of NaOH, 60 grams of tetraethylammonium bromides are dissolved in 200ml deionized water, under agitation add 120 grams of Ludox, continue to stir 1 hour, make into uniform sol-gel.Moved in crystallizing kettle, in 100 ℃ of crystallization.After 96 hours, the product obtaining is filtered, be washed with distilled water to pH=10.Then 120 ℃ dry 12 hours, 560 ℃ of roastings 4 hours, obtain beta-molecular sieve.Again the beta-molecular sieve obtaining is carried out to ion-exchange in concentration is the ammonium nitrate solution of 20% (wt), then 120 ℃ dry 12 hours, 560 ℃ of roastings 4 hours, obtain molecular screen material A-1.
Comparative example 2
At 40 ℃, 6 grams of sodium aluminates, 3 grams of NaOH are placed in to 150 grams of tetraethyl ammonium hydroxides (20%wt), then add in 80ml deionized water, under agitation add 120 grams of Ludox, continue to stir 1 hour, make into uniform sol-gel.Moved in crystallizing kettle, in 170 ℃ of crystallization.After 48 hours, the product obtaining is filtered, be washed with distilled water to pH=10.Then at 110 ℃, be dried 12 hours, 600 ℃ of roastings 4 hours, obtain beta-molecular sieve.Again the beta-molecular sieve obtaining is carried out to ion-exchange in concentration is the ammonium nitrate solution of 10% (wt), then 110 ℃ dry 12 hours, 600 ℃ of roastings 4 hours, obtain molecular screen material C-1.
Embodiment 7
The molecular screen material that the present embodiment explanation makes by method provided by the invention is beta-molecular sieve.
The thing of molecular sieve is measured mutually the Lab-X-ray DIFFRACTON METER type X-ray diffractometer of the Japanese SHIMADZU of employing company and is measured, Cu Ka (0.154nm) target, transmitted intensity 1.5kcps, tube voltage 40kV, tube current 30mA, scanning 2 θ scope 10-80 °, sweep speed 2 θ/min, 0.02 ° of step-length, parallel light path, 1.0 ° of entrance slits (2 θ).From table 1 data, the molecular screen material that embodiment 1-6 and comparative example 1,2 prepare is beta-molecular sieve.
Table 1
Embodiment 8
The molecular screen material that the present embodiment explanation makes by method provided by the invention has higher acid strength and strong acid center density.
The acid strength of molecular sieve is measured and is adopted NH
3-TPD, the NH that utilizes Mass Spectrometer Method desorption to go out
3signal.With total desorption calculated by peak area acid strength, with AT, represent, the total desorption peaks area in comparative example A-1 calculates by 1; The density that recently represents strong acid center with the area of 300 ℃ of later desorption peaks and 300 ℃ of former desorption peaks, represents with AI.From table 2 data, compare ratio molecular sieve, embodiment molecular sieve has higher acid strength and strong acid density.
Table 2
| AT | AI | |
| Embodiment 1A | 1.8 | 1.6 |
| Embodiment 2B | 1.3 | 1.2 |
| Embodiment 3C | 1.5 | 1.6 |
| Embodiment 4D | 1.3 | 1.1 |
| Embodiment 5E | 1.4 | 1.2 |
| Embodiment 6F | 1.5 | 1.2 |
| Comparative example 1A-1 | 1 | 0.8 |
| Comparative example 2C-1 | 1.1 | 1 |
Embodiment 9
The present embodiment is to use above-mentioned catalyst to prepare the embodiment of ethylbenzene.Raw material is benzene and the ethene that benzene alkene mol ratio is 6, and catalyst amount is 20g.Specific experiment process is as follows: experiment is carried out on the fixed bed reactors of continuous-flow, and fresh benzene is by Microscale plunger pump injecting reactor, and ethene is controlled by gas flowmeter, after mixing, enters reactor with benzene.Experiment is at 250 ℃, 5MPa, and benzene weight space velocity is 6h
-1condition under carry out, the initial activity of catalyst and the activity experiment of running after 200 hours the results are shown in Table 3.From experimental result, can find out, compare ratio catalyst, the embodiment catalyst with higher acid strength and strong acid density has higher conversion of ethylene and ethylbenzene selectivity.
Table 3
Embodiment 10
The experiment condition of the present embodiment is: 210 ℃, and 3.3MPa, benzene weight space velocity is 3h
-1, benzene alkene mol ratio is 4.
All the other conditions are with embodiment 9.Specific experiment the results are shown in Table 4.
Table 4
Embodiment 11
The experiment condition of the present embodiment is: 180 ℃, and 2MPa, benzene weight space velocity is 1h
-1, benzene alkene mol ratio is 2.
All the other conditions are with embodiment 9.Specific experiment the results are shown in Table 5.
Table 5
Claims (5)
1. a preparation method for the catalyst of liquid phase method synthesizing ethyl benzene, is characterized in that:
Its preparation process is as follows:
(1) at 30-50 ℃, sodium aluminate, NaOH, water, tetraethylammonium bromide or tetraethyl ammonium hydroxide are mixed and stirred in colloid generating kettle, then add Ludox, become uniform sol-gel, continue to stir 10 minutes; He Lv source, silicon source is with SiO
2and Al
2o
3meter, mol ratio is 10-40; Tetraethylammonium bromide or tetraethyl ammonium hydroxide, with (TEA)
2o and SiO
2meter, mol ratio is 0.1-0.6; NaOH, with Na
2o and SiO
2meter, mol ratio is 0.05-0.2; Water, with H
2o and SiO
2meter, mol ratio is 10-20;
(2) mixture obtaining in step (1) is poured in crystallizing kettle into crystallization 48-96 hour at 100-170 ℃;
(3) under stirring, by 10%(wt) aluminium chloride or liquor zinci chloridi dropwise drip on the product that step (2) obtains, stir aging 4-6 hour, be transferred in crystallizing kettle crystallization 24-48 hour at 100-170 ℃; After crystallization finishes, the product obtaining is filtered, be washed with distilled water to pH=10, then at 90-120 ℃, be dried 12 hours, 560-600 ℃ of roasting 4 hours, obtains beta-molecular sieve;
(4) in the ammonium nitrate solution that beta-molecular sieve step (3) being obtained is 10-20% in mass concentration, carry out ion-exchange, then 90-120 ℃ dry 12 hours, 560-600 ℃ of roasting 4 hours, obtains H-beta-molecular sieve;
(5) product step (4) being obtained is put into 3%(wt) zirconium nitrate or Titanium Nitrate solution flood 12 hours, then dry 12 hours at 90-120 ℃;
(6) product step (5) being obtained is put into 1.5%(wt) lanthanum nitrate or cerous nitrate solution flood, then 90-120 ℃ dry 12 hours, 560-600 ℃ of roasting 4 hours, obtains molecular screen material.
2. according to preparation method claimed in claim 1, it is characterized in that: silicon source is selected from solid silicone, Ludox or positive esters of silicon acis, and aluminium source is selected from aluminium hydroxide, boehmite or sodium aluminate, and template is tetraethylammonium bromide or tetraethyl ammonium hydroxide.
3. according to preparation method claimed in claim 1, it is characterized in that: ammonium salt is ammonium nitrate or ammonium sulfate.
4. a catalyst for liquid phase method synthesizing ethyl benzene, is characterized in that: prepared by preparation method according to claim 1.
5. an application for the catalyst of liquid phase method synthesizing ethyl benzene claimed in claim 4, is characterized in that:
Molecular sieve catalyst is applied to take benzene and as raw material, prepares reacting of ethylbenzene with ethene, and reaction condition is temperature 180-250 ℃, pressure 2-5MPa, benzene weight space velocity 1-6h
-1, benzene alkene mol ratio is 2-6.
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| CN105983439A (en) * | 2015-02-10 | 2016-10-05 | 中国石油天然气股份有限公司 | Molecular sieve catalysts for benzene alkylation and their preparation methods and use |
| CN109759043B (en) * | 2019-02-13 | 2021-08-13 | 郑州大学 | Solid acid catalyst, preparation method thereof and preparation method of p-hydroxyphenylglycine |
| CN111744539A (en) * | 2019-03-28 | 2020-10-09 | 中国石油化工股份有限公司 | Preparation method of catalyst used in method for preparing ethylbenzene by benzene-ethylene gas phase alkylation |
| CN111744545A (en) * | 2019-03-28 | 2020-10-09 | 中国石油化工股份有限公司 | Preparation method of catalyst used in method for preparing ethylbenzene by benzene-ethylene liquid phase alkylation |
| CN114433198A (en) * | 2020-10-30 | 2022-05-06 | 中国石油天然气股份有限公司 | Alkylated molecular sieve catalyst and preparation method thereof |
| CN115501903B (en) * | 2021-06-23 | 2024-03-29 | 中国石油化工股份有限公司 | graphene/ZSM-5 molecular sieve compound and synthetic method and application thereof |
| CN114345401B (en) * | 2022-01-10 | 2023-06-02 | 万华化学集团股份有限公司 | Preparation method of p-hydroxyphenoxyethanol |
| CN115364893B (en) * | 2022-08-08 | 2023-09-15 | 蚌埠学院 | Preparation method and application of BETA-ZSM composite type hierarchical pore molecular sieve |
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| US4891458A (en) * | 1987-12-17 | 1990-01-02 | Innes Robert A | Liquid phase alkylation or transalkylation process using zeolite beta |
| CN101491758A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Catalyst for H2 selective oxidation in styrene production |
| CN102040462A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for producing styrene by ethylbenzene dehydrogenation-hydrogen selective oxidization |
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