CN102824923A - 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 PDF

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CN102824923A
CN102824923A CN2011101637687A CN201110163768A CN102824923A CN 102824923 A CN102824923 A CN 102824923A CN 2011101637687 A CN2011101637687 A CN 2011101637687A CN 201110163768 A CN201110163768 A CN 201110163768A CN 102824923 A CN102824923 A CN 102824923A
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molecular sieve
catalyst
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CN102824923B (en
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周玮
马中义
李正
赵胤
邓广金
李树丰
孟庆茹
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China Petroleum and Natural Gas Co Ltd
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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

A kind of catalyst of liquid phase method synthesizing ethyl benzene and preparation thereof and application
Technical field
The present invention relates to a kind of preparation and application that is used for ethene and benzene through the modified molecular screen of liquid phase method synthesizing ethyl benzene reaction.
Background technology
Ethylbenzene is to produce cinnamic raw material, and styrene can be used for producing organic synthesis materials such as polystyrene, butadiene-styrene rubber, ABS resin and SBS.Ethylbenzene is raw material with benzene and ethene mainly in the industry, under catalyst action, makes through alkylated reaction.The progress of ethylbenzene synthetic technology has very important significance, and key wherein is exactly to develop catalyst efficiently.
The technology that the ethylbenzene alkylation is adopted in the world mainly contains alchlor liquid catalytic, molecular sieve gas-phase catalysis and molecular sieve liquid catalytic.Wherein, the alchlor liquid catalytic started from before the seventies, because very strong corrosivity is brought very big inconvenience to plant maintenance and the post processing of anti-one-tenth liquid, no longer adopted basically now.From technical standpoint, the friendly solid acid catalyst of development environment just meets trend.1976, Mobil and Badger company developed the ZSM-5 molecular sieve catalyst cooperatively and have been used for the vapor phase method synthesizing ethyl benzene, and had realized industrialization in 1980.This method has that no burn into is pollution-free, energy consumption is low and ethene air speed advantages of higher.Shortcomings such as but this method also has the reaction temperature height, and catalyst is prone to coking and deactivation, and the by-product xylene content is high in the product, and the regeneration period is short.1989, Unocal-ABB Lummus-Crest announced the liquid phase ethylbenzene technology based on active Y zeolite catalyst.Nineteen ninety, at first after Japan realizes industrialization, it was in the ascendance in new device in recent years by Lummus/UOP.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 the product, 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 the β zeolite as catalyst.The 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 the β zeolite acidity is moderate, and a certain proportion of strong acidic site and weak acid position are arranged.The structure of β zeolite makes it become a kind of suitable alkylation solid acid catalyst with acid.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, the conventional beta zeolite is carried out modification, improve its acid strength or acid site density, make its better application very necessary in alkylated reaction.
Patent ZL02151177.2 and ZL02155114.6 disclose and have a kind ofly handled the beta-molecular sieve catalyst of modification successively through high-temperature water vapor and organic acid, and it can be used for the reaction of ethene liquid-phase alkylation system ethylbenzene.No matter active, stable this catalyst is, and still the performance after the regeneration all obviously is superior to untreated beta-molecular sieve.
Patent ZL02155598.2 also will be used for olefin alkylation reaction through organic acid-treated beta-molecular sieve catalyst.This catalyst is to obtain after citric acid treatment with pure beta-molecular sieve or through the beta-molecular sieve of binding agent moulding.Compare the beta-molecular sieve that is untreated, the catalyst processed selectivity obviously increases with stability.
The SiO that patent ZL03146474.2 and 03146476.9 will handle 2With or/Al 2O 3The composite of forming with nano-beta molecular sieve is applied to alkene and isoparaffin alkylated reaction as catalyst, compares the conventional beta molecular sieve, principal product selectivity on this composite catalyst and obviously increase of stability.
The beta-molecular sieve that patent ZL99102571.7 adopted and implant ZSM-12, added the La modification carries out alkylated reaction, and this catalyst can be used for gas phase and liquid phase reactor simultaneously, 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, is used 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, VIIIB, the element modified beta-molecular sieve of IVB, and alkylated reaction selects performance to improve 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.The molecular sieve catalyst that utilizes this method to obtain has 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, is used for fixing a catalyst for reaction, and its preparation process is following:
Aluminium source, NaOH, water, template are mixed and stirred, process working solution, above-mentioned working solution is mixed obtaining reactant mixture with the silicon source; Become the sol-gel state, after the crystallization, under stirring; Dropwise drip to certain density chlorination metal salt solution on the slurries; After aging, crystallization, filtration, washing, drying and roasting, this molecular sieve is immersed in carries out ion-exchange in the certain density ammonium salt solution, after drying and roasting, obtain the H-beta-molecular sieve.Again the H-beta-molecular sieve impregnated in the solution of the certain density IVB of containing element and flood, after the drying, put it into again in the certain density solution that contains rare earth element and flood, carry out drying and roasting again and obtain molecular screen material.
In the method provided by the invention, said molecular sieve is a beta-molecular sieve.
In the 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 the method provided by the invention, said chlorination slaine is zinc chloride and liquor alumini chloridi, preferred liquor alumini chloridi.
In the method provided by the invention, said ammonium salt is ammonium nitrate or ammonium sulfate, preferred ammonium nitrate solution.
In the method provided by the invention, the solution of the said IVB of containing element is zirconium nitrate or Titanium Nitrate solution, preferred zirconium nitrate solution.
In the method provided by the invention, the said solution that contains rare earth element is lanthanum nitrate or cerous nitrate solution, preferred lanthanum nitrate hexahydrate.
The preparation method of molecular sieve catalyst provided by the invention comprises the following steps:
(1) under 30-50 ℃, a certain amount of sodium aluminate, NaOH, water, tetraethylammonium bromide or tetraethyl ammonium hydroxide are mixed in colloid generating kettle and stir, add a certain amount of Ludox again, become uniform sol-gel, continue to stir 10 minutes; Silicon source and aluminium source are with SiO 2And Al 2O 3Meter, mol ratio is 10-40; Tetraethylammonium bromide or tetraethyl ammonium hydroxide are with (TEA) 2O and SiO 2Meter, mol ratio is 0.1-0.6; NaOH is with Na 2O and SiO 2Meter, mol ratio is 0.05-0.2; Water is with H 2O and SiO 2Meter, mol ratio is 10-20;
(2) mixture that obtains in the step (1) is poured in the crystallizing kettle, in 100-170 ℃ of following crystallization 48-96 hour;
(3) under stirring, the aluminium chloride of 10% (wt) or liquor zinci chloridi are dropwise dripped on the product that step (2) obtains, stirred aging 4-6 hour, be transferred in the crystallizing kettle, in 100-170 ℃ of following crystallization 24-48 hour; After crystallization finishes, the product that obtains is filtered, be washed with distilled water to pH=10, carried out drying 12 hours at 90-120 ℃ then, 560-600 ℃ of roasting 4 hours obtains beta-molecular sieve;
(4) beta-molecular sieve that step (3) is obtained carries out ion-exchange in mass concentration is the ammonium nitrate solution of 10-20%, then 90-120 ℃ of drying 12 hours, 560-600 ℃ of roasting 4 hours obtains the H-beta-molecular sieve;
(5) product that step (4) is obtained is put into zirconium nitrate or the Titanium Nitrate solution dipping 12 hours of 3% (wt), then 90-120 ℃ of drying 12 hours;
(6) lanthanum nitrate or cerous nitrate solution that the product that step (5) is obtained is put into 1.5% (wt) flood, and then 90-120 ℃ of drying 12 hours, 560-600 ℃ of roasting 4 hours obtains molecular screen material.
It is the preparation of the ethylbenzene of raw material that molecular sieve catalyst of the present invention is used for benzene and 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.
Compare with prior art; Catalyst characteristics provided by the invention are to have higher acid strength and strong acid distribution density, make this catalyst have higher catalytic activity and catalytic efficiency, prepare in the reaction of ethylbenzene at benzene and ethene; Conversion of ethylene reaches more than 97%; Ethylbenzene selectivity reaches more than 95%, non-xylol in the product, and one way is long the duration of runs.
The specific embodiment
Embodiment 1
Under 30 ℃, 9 gram sodium aluminates, 2 gram NaOH, 60 gram tetraethylammonium bromides are dissolved in the 200ml deionized water, under agitation add Ludox 120 grams, continue to stir 1 hour, make into uniform sol-gel.It is moved in the crystallizing kettle, in 100 ℃ of crystallization.After 96 hours, under stirring, the liquor alumini chloridi of 10% (wt) is dropwise dripped on the slurries, stir after 6 hours, be transferred in the crystallizing kettle, in 100 ℃ of crystallization 48 hours.Crystallization after finishing is filtered the product that obtains, and is washed with distilled water to pH=10.Carried out drying 12 hours at 120 ℃ then, 560 ℃ of roastings 4 hours obtain beta-molecular sieve.Again the beta-molecular sieve that obtains is carried out ion-exchange in concentration is the ammonium nitrate solution of 20% (wt), then 120 ℃ of dryings 12 hours, 560 ℃ of roastings 4 hours obtain the H-beta-molecular sieve.Again the H-beta-molecular sieve is put into the zirconium nitrate solution dipping 12 hours of 3% (wt), then 120 ℃ of dryings 12 hours.The lanthanum nitrate hexahydrate of dried product being put into 1.5% (wt) floods, and then 120 ℃ of dryings 12 hours, 560 ℃ of roastings 4 hours obtain molecular screen material A.
Embodiment 2
Under 40 ℃, 3 gram sodium aluminates, 4 gram NaOH are placed 200 gram tetraethyl ammonium hydroxides (20%wt), add again in the 100ml deionized water, under agitation add Ludox 120 grams, continue to stir 1 hour, make into uniform sol-gel.It is moved in the crystallizing kettle, in 150 ℃ of crystallization.After 48 hours, under stirring, the liquor zinci chloridi of 10% (wt) is dropwise dripped on the slurries, stir after 4 hours, be transferred in the crystallizing kettle, in 150 ℃ of crystallization 24 hours.Crystallization after finishing is filtered the product that obtains, and is washed with distilled water to pH=10.Then 90 ℃ of dryings 12 hours, 580 ℃ of roastings 4 hours obtain beta-molecular sieve.Again the beta-molecular sieve that obtains is carried out ion-exchange in concentration is the ammonium nitrate solution of 15% (wt), then 90 ℃ of dryings 12 hours, 580 ℃ of roastings 4 hours obtain the H-beta-molecular sieve.Again the H-beta-molecular sieve is put into the zirconium nitrate solution dipping 12 hours of 3% (wt), then 90 ℃ of dryings 12 hours.The cerous nitrate solution of dried product being put into 1.5% (wt) floods, and then 90 ℃ of dryings 12 hours, 580 ℃ of roastings 4 hours obtain molecular screen material B.
Embodiment 3
Under 40 ℃, 6 gram sodium aluminates, 3 gram NaOH are placed 150 gram tetraethyl ammonium hydroxides (20%wt), add again in the 80ml deionized water, under agitation add Ludox 120 grams, continue to stir 1 hour, make into uniform sol-gel.It is moved in the crystallizing kettle, in 170 ℃ of crystallization.After 48 hours, under stirring, the liquor alumini chloridi of 10% (wt) is dropwise dripped on the slurries, stir after 6 hours, be transferred in the crystallizing kettle, in 170 ℃ of crystallization 24 hours.Crystallization after finishing is filtered the product that obtains, and is washed with distilled water to pH=10.Then 110 ℃ of dryings 12 hours, 600 ℃ of roastings 4 hours obtain beta-molecular sieve.Again the beta-molecular sieve that obtains is carried out ion-exchange in concentration is the ammonium nitrate solution of 10% (wt), then 110 ℃ of dryings 12 hours, 600 ℃ of roastings 4 hours obtain the H-beta-molecular sieve.Again the H-beta-molecular sieve is put into the Titanium Nitrate solution dipping 12 hours of 3% (wt), then 110 ℃ of dryings 12 hours.The lanthanum nitrate hexahydrate of dried product being put into 1.5% (wt) floods, and then 110 ℃ of dryings 12 hours, 600 ℃ of roastings 4 hours obtain molecular screen material C.
Embodiment 4
Under 50 ℃, 11 gram sodium aluminates, 0.5 gram NaOH, 30 gram tetraethylammonium bromides are dissolved in the 250ml deionized water, under agitation add Ludox 120 grams, continue to stir 1 hour, make into uniform sol-gel.It is moved in the crystallizing kettle, in 140 ℃ of crystallization.After 72 hours, under stirring, the liquor zinci chloridi of 10% (wt) is dropwise dripped on the slurries, stir after 6 hours, be transferred in the crystallizing kettle, in 140 ℃ of crystallization 24 hours.Crystallization after finishing is filtered the product that obtains, and is washed with distilled water to pH=10.Then 100 ℃ of dryings 12 hours, 560 ℃ of roastings 4 hours obtain beta-molecular sieve.Again the beta-molecular sieve that obtains is carried out ion-exchange in concentration is the ammonium nitrate solution of 20% (wt), then 100 ℃ of dryings 12 hours, 560 ℃ of roastings 4 hours obtain the H-beta-molecular sieve.Again the H-beta-molecular sieve is put into the Titanium Nitrate solution dipping 12 hours of 3% (wt), then 100 ℃ of dryings 12 hours.The lanthanum nitrate hexahydrate of dried product being put into 1.5% (wt) floods, and then 100 ℃ of dryings 12 hours, 560 ℃ of roastings 4 hours obtain molecular screen material D.
Embodiment 5
Under 30 ℃, 6 gram sodium aluminates, 3 gram NaOH are placed 150 gram tetraethyl ammonium hydroxides (20%wt), add again in the 80ml deionized water, under agitation add Ludox 120 grams, continue to stir 1 hour, make into uniform sol-gel.It is moved in the crystallizing kettle, in 150 ℃ of crystallization.After 48 hours, under stirring, the liquor alumini chloridi of 10% (wt) is dropwise dripped on the slurries, stir after 6 hours, be transferred in the crystallizing kettle, in 150 ℃ of crystallization 48 hours.Crystallization after finishing is filtered the product that obtains, and is washed with distilled water to pH=10.Then 110 ℃ of dryings 12 hours, 580 ℃ of roastings 4 hours obtain beta-molecular sieve.Again the beta-molecular sieve that obtains is carried out ion-exchange in concentration is the ammonium nitrate solution of 15% (wt), then 110 ℃ of dryings 12 hours, 580 ℃ of roastings 4 hours obtain the H-beta-molecular sieve.Again the H-beta-molecular sieve is put into the Titanium Nitrate solution dipping 12 hours of 3% (wt), then 110 ℃ of dryings 12 hours.The cerous nitrate solution of dried product being put into 1.5% (wt) floods, and then 110 ℃ of dryings 12 hours, 580 ℃ of roastings 4 hours obtain molecular screen material E.
Embodiment 6
Under 40 ℃, 9 gram sodium aluminates, 2 gram NaOH, 60 gram tetraethylammonium bromides are dissolved in the 200ml deionized water, under agitation add Ludox 120 grams, continue to stir 1 hour, make into uniform sol-gel.It is moved in the crystallizing kettle, in 120 ℃ of crystallization.After 72 hours, under stirring, the liquor alumini chloridi of 10% (wt) is dropwise dripped on the slurries, stir after 6 hours, be transferred in the crystallizing kettle, in 120 ℃ of crystallization 48 hours.Crystallization after finishing is filtered the product that obtains, and is washed with distilled water to pH=10.Then 120 ℃ of dryings 12 hours, 580 ℃ of roastings 4 hours obtain beta-molecular sieve.Again the beta-molecular sieve that obtains is carried out ion-exchange in concentration is the ammonium nitrate solution of 20% (wt), then 120 ℃ of dryings 12 hours, 580 ℃ of roastings 4 hours obtain the H-beta-molecular sieve.Again the H-beta-molecular sieve is put into the zirconium nitrate solution dipping 12 hours of 3% (wt), then 120 ℃ of dryings 12 hours.The cerous nitrate solution of dried product being put into 1.5% (wt) floods, and then 120 ℃ of dryings 12 hours, 580 ℃ of roastings 4 hours obtain molecular screen material F.
Comparative Examples 1
Under 30 ℃, 9 gram sodium aluminates, 2 gram NaOH, 60 gram tetraethylammonium bromides are dissolved in the 200ml deionized water, under agitation add Ludox 120 grams, continue to stir 1 hour, make into uniform sol-gel.It is moved in the crystallizing kettle, in 100 ℃ of crystallization.After 96 hours, the product that obtains is filtered, be washed with distilled water to pH=10.Then 120 ℃ of dryings 12 hours, 560 ℃ of roastings 4 hours obtain beta-molecular sieve.Again the beta-molecular sieve that obtains is carried out ion-exchange in concentration is the ammonium nitrate solution of 20% (wt), then 120 ℃ of dryings 12 hours, 560 ℃ of roastings 4 hours obtain molecular screen material A-1.
Comparative Examples 2
Under 40 ℃, 6 gram sodium aluminates, 3 gram NaOH are placed 150 gram tetraethyl ammonium hydroxides (20%wt), add again in the 80ml deionized water, under agitation add Ludox 120 grams, continue to stir 1 hour, make into uniform sol-gel.It is moved in the crystallizing kettle, in 170 ℃ of crystallization.After 48 hours, the product that obtains is filtered, be washed with distilled water to pH=10.Carried out drying 12 hours at 110 ℃ then, 600 ℃ of roastings 4 hours obtain beta-molecular sieve.Again the beta-molecular sieve that obtains is carried out ion-exchange in concentration is the ammonium nitrate solution of 10% (wt), then 110 ℃ of dryings 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 a beta-molecular sieve.
The thing of molecular sieve is measured the Lab-X-ray DIFFRACTON METER type X-ray diffractometer of the Japanese SHIMADZU of employing company mutually and is measured Cu Ka (0.154nm) target, transmitted intensity 1.5kcps; Tube voltage 40kV, tube current 30mA scans 10-80 ° of 2 θ scope; Sweep speed 2 θ/min; 0.02 ° of step-length, parallel light path, 1.0 ° of entrance slits (2 θ).Can know that from table 1 data the molecular screen material that embodiment 1-6 and Comparative Examples 1,2 prepare is a beta-molecular sieve.
Table 1
Figure BDA0000069117070000071
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 the Mass Spectrometer Method desorption to go out 3Signal.With total desorption calculated by peak area acid strength, represent that with AT the total desorption peaks area of comparative example A-1 calculates by 1; Recently represent the density of strong acid center with the desorption peaks after 300 ℃ and the area of 300 ℃ of former desorption peaks, represent with AI.Can know from table 2 data, compare the ratio molecular sieve, the 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 Examples 1A-1 1 0.8
Comparative Examples 2C-1 1.1 1
Embodiment 9
Present embodiment is to use the embodiment of above-mentioned Preparation of Catalyst ethylbenzene.Raw material is that benzene alkene mol ratio is 6 benzene and ethene, and catalyst amount is 20g.Concrete experimentation is following: experiment is carried out on the fixed bed reactors of continuous-flow, and fresh benzene is by micro-plunger displacement pump injecting reactor, and ethene is controlled by gas flowmeter, mixes the back with benzene and gets into reactor.Experiment is at 250 ℃, and 5MPa, benzene weight space velocity are 6h -1Condition under carry out, the initial activity of catalyst is seen table 3 with the activity experiment result of running after 200 hours.Can find out from experimental result, compare the ratio catalyst, the embodiment catalyst with higher acid strength and strong acid density has higher conversion of ethylene and ethylbenzene selectivity.
Table 3
Figure BDA0000069117070000091
Embodiment 10
The experiment condition of present embodiment is: 210 ℃, 3.3MPa, benzene weight space velocity are 3h -1, benzene alkene mol ratio is 4.
All the other conditions are with embodiment 9.Concrete experimental result is seen table 4.
Table 4
Figure BDA0000069117070000101
Embodiment 11
The experiment condition of present embodiment is: 180 ℃, 2MPa, benzene weight space velocity are 1h -1, benzene alkene mol ratio is 2.
All the other conditions are with embodiment 9.Concrete experimental result is seen table 5.
Table 5
Figure BDA0000069117070000111

Claims (6)

1. the Preparation of catalysts method of a liquid phase method synthesizing ethyl benzene is characterized in that:
Its preparation process is following:
(1) under 30-50 ℃, sodium aluminate, NaOH, water, tetraethylammonium bromide or tetraethyl ammonium hydroxide are mixed in colloid generating kettle and stir, add Ludox again, become uniform sol-gel, continue to stir 10 minutes; Silicon source and aluminium source are with SiO 2And Al 2O 3Meter, mol ratio is 10-40; Tetraethylammonium bromide or tetraethyl ammonium hydroxide are with (TEA) 2O and SiO 2Meter, mol ratio is 0.1-0.6; NaOH is with Na 2O and SiO 2Meter, mol ratio is 0.05-0.2; Water is with H 2O and SiO 2Meter, mol ratio is 10-20;
(2) mixture that obtains in the step (1) is poured in the crystallizing kettle, in 100-170 ℃ of following crystallization 48-96 hour;
(3) under stirring, the aluminium chloride of 10% (wt) or liquor zinci chloridi are dropwise dripped on the product that step (2) obtains, stirred aging 4-6 hour, be transferred in the crystallizing kettle, in 100-170 ℃ of following crystallization 24-48 hour; After crystallization finishes, the product that obtains is filtered, be washed with distilled water to pH=10, carried out drying 12 hours at 90-120 ℃ then, 560-600 ℃ of roasting 4 hours obtains beta-molecular sieve;
(4) beta-molecular sieve that step (3) is obtained carries out ion-exchange in mass concentration is the ammonium nitrate solution of 10-20%, then 90-120 ℃ of drying 12 hours, 560-600 ℃ of roasting 4 hours obtains the H-beta-molecular sieve;
(5) product that step (4) is obtained is put into zirconium nitrate or the Titanium Nitrate solution dipping 12 hours of 3% (wt), then 90-120 ℃ of drying 12 hours;
(6) lanthanum nitrate or cerous nitrate solution that the product that step (5) is obtained is put into 1.5% (wt) flood, and then 90-120 ℃ of drying 12 hours, 560-600 ℃ of roasting 4 hours obtains molecular screen material.
2. according to the described preparation method of claim 1, it is characterized in that: the silicon source is selected from solid silicone, Ludox or positive esters of silicon acis, and the aluminium source is selected from aluminium hydroxide, boehmite or sodium aluminate, and template is tetraethylammonium bromide or tetraethyl ammonium hydroxide.
3. according to the described preparation method of claim 1, it is characterized in that: ammonium salt is ammonium nitrate or ammonium sulfate.
4. according to the described preparation method of claim 1, it is characterized in that: described chlorination slaine is zinc chloride or aluminium chloride, and described IVB family metal is zirconium or titanium, and described transition metal is lanthanum or cerium.
5. the catalyst of a liquid phase method synthesizing ethyl benzene is characterized in that: preparation method's preparation according to claim 1.
6. the Application of Catalyst of the described liquid phase method synthesizing ethyl benzene of claim 5 is characterized in that:
It is the reaction of feedstock production ethylbenzene that molecular sieve catalyst is applied to benzene and 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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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
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
CN114345401A (en) * 2022-01-10 2022-04-15 万华化学集团股份有限公司 Preparation method of p-hydroxyphenyloxyethanol
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
CN115364893A (en) * 2022-08-08 2022-11-22 蚌埠学院 Preparation method and application of BETA-ZSM composite hierarchical pore molecular sieve
CN115501903A (en) * 2021-06-23 2022-12-23 中国石油化工股份有限公司 graphene/ZSM-5 molecular sieve compound and synthesis method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4891458A (en) * 1987-12-17 1990-01-02 Innes Robert A Liquid phase alkylation or transalkylation process using zeolite beta
WO2008085265A1 (en) * 2007-01-09 2008-07-17 Catalytic Solutions, Inc. Ammonia scr catalyst and method of using the catalyst
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4891458A (en) * 1987-12-17 1990-01-02 Innes Robert A Liquid phase alkylation or transalkylation process using zeolite beta
WO2008085265A1 (en) * 2007-01-09 2008-07-17 Catalytic Solutions, Inc. Ammonia scr catalyst and method of using the catalyst
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

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN109759043A (en) * 2019-02-13 2019-05-17 郑州大学 A kind of preparation method of solid acid catalyst and preparation method thereof and D-pHPG
CN109759043B (en) * 2019-02-13 2021-08-13 郑州大学 Solid acid catalyst, preparation method thereof and preparation method of p-hydroxyphenylglycine
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
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
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
CN115501903A (en) * 2021-06-23 2022-12-23 中国石油化工股份有限公司 graphene/ZSM-5 molecular sieve compound and synthesis method and application thereof
CN114345401A (en) * 2022-01-10 2022-04-15 万华化学集团股份有限公司 Preparation method of p-hydroxyphenyloxyethanol
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
CN115364893A (en) * 2022-08-08 2022-11-22 蚌埠学院 Preparation method and application of BETA-ZSM composite hierarchical pore molecular sieve
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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