CN102909067B - Two zeolite-containing catalyst for ethene and benzene alkylation, and preparation method and application thereof - Google Patents

Two zeolite-containing catalyst for ethene and benzene alkylation, and preparation method and application thereof Download PDF

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CN102909067B
CN102909067B CN201110217563.2A CN201110217563A CN102909067B CN 102909067 B CN102909067 B CN 102909067B CN 201110217563 A CN201110217563 A CN 201110217563A CN 102909067 B CN102909067 B CN 102909067B
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CN102909067A (en
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徐会青
刘全杰
贾立明
王伟
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The invention discloses a two zeolite-containing catalyst for ethene and benzene alkylation, and a preparation method and an application thereof. The catalyst comprises a phosphor-modified BETA zeolite, a phosphor-modified ZSM-5 zeolite and a rare earth metal oxide. On the basis of the weight of the catalyst, the total content of the phosphor-modified BETA zeolite and the phosphor-modified ZSM-5 zeolite is 10%-90.0%; the content of the rare earth metal oxide is 1%-20%; and the balance is an inorganic refractory oxide, wherein the weight content ratio of the phosphor-modified BETA zeolite to the phosphor-modified ZSM-5 zeolite is 1 : 10-10 : 1. The catalyst provided by the invention is used for alkylation reactions of benzene and ethylene, and has higher reaction activity and selectivity.

Description

Containing the ethene of two kinds of zeolites and benzene alkylation catalyst and preparation method and application
Technical field
The invention discloses Catalysts and its preparation method and application that a kind of ethene and benzene alkylation reaction prepare ethylbenzene, specifically, be a kind ofly prepare Catalysts and its preparation method and the application of ethylbenzene with low-concentration ethane and benzene alkylation reaction in petrochemical industry by-product dry gas.
Background technology
Ethylbenzene is a kind of important Organic Chemicals, of many uses, be produce cinnamic raw material, for the production of ion exchange resin, unsaturated polyester resin, agricultural emulsifier and coating etc., can also be with a wide range of applications in fields such as automobile, household electrical appliances, light industrys.Styrene occupies the 3rd of world's olefin monomer output, and development in recent years is comparatively rapid, and market has driven the sustainable growth of ethylbenzene output to cinnamic thriving demand.Therefore, open up the new source of all raw materials in ethylbenzene production, find new the having great importance with more cheap approach that ethylbenzene is produced.
Ethylbenzene mainly adopts ethene and benzene catalytic alkylation reaction to synthesize, and ethylbenzene building-up process generally comprises two reactions, i.e. the alkylated reaction of benzene and ethene and the transalkylation reaction of many ethylbenzene and benzene.Along with the development of petrochemical processing industry, a large amount of refinery exhausts containing low concentration ethene are produce ethylbenzene to provide new raw material sources.Make full use of various source and variable concentrations, especially low-concentration ethane and benzene alkylation and produce ethylbenzene, the dependence of producing for China's pure ethylene resource in short supply for the cost of material of reduction ethylbenzene production, the economy improving ethylbenzene production plants and minimizing ethylbenzene has great importance.
Zeolite has a wide range of applications in a lot of field, in alkylated reaction technical development process, also from the transformed zeolite catalyst of non-zeolite catalysts.Using zeolite catalyst to carry out alkylated reaction is the earliest, since Mobil-Badger invention in 1978 uses zeolite catalyst, adopted the benzene alkylation technique of zeolite catalyst to develop rapidly.From the nineties in 20th century, the production of ethylbenzene completes from traditional AlCl 3for the Friedel-Crafts benzene-alkylation technique of catalyst is to the transformation of zeolite catalysis technique.
In prior art, traditional alkylation process mainly with Hydrogen ZSM-5 zeolite for catalyst.US3750504 and US3751506 is with unmodified ZSM-5 zeolite for benzene and ethene gas phase alkylation catalyst, but catalyst regeneration cycle is short, ethylation products (ethylbenzene) selective lower, and in product, xylene content is high.For improving ZSM-5 catalyst in ethene and the total reactivity worth of producing phenylethane from alkylation of benzene process, researcher have employed various method of modifying.The steam treatment that adopts US4016218, US4429176 and US4594146 etc. improves the stability of catalyst for the selective and catalyst of ethylation products when ethene and benzene alkylation.US3962364 adopts P elements to carry out modification to ZSM-5 zeolite, improves the selective and catalyst stability of ethylation products to a certain extent.CN97106449.0, CN97106448.2 and CN00111721.1 adopt alkaline earth/rare earth oxide-modified conventional ZSM-5 zeolite to improve catalyst performance to a certain extent when being used for ethene and benzene alkylation, but still there is alkylated reaction temperature high (400 ~ 420 DEG C), cause that energy consumption is high, the problems such as xylene impurities content is higher in product.And CN101584993A is by specific condition modified ZSM-5 zeolite, improve the performance of catalyst to a certain extent, but still there is higher problem in alkylated reaction temperature.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of ethene and benzene alkylation reaction ethylbenzene used catalyst and its preparation method and application.When this catalyst reacts containing low-concentration ethane in ethene dry gas and producing phenylethane from alkylation of benzene for refinery, there is higher reactivity.
Of the present invention contain two kinds of zeolites ethene and benzene alkylation catalyst in, containing P Modification BETA zeolite, phosphorous modified ZSM-5 zeolite and rare-earth oxide, with the weight of catalyst for benchmark, the total content of P Modification BETA zeolite and phosphorous modified ZSM-5 zeolite is 10% ~ 90.0%, rare-earth oxide content is 1% ~ 20%, surplus is inorganic refractory oxide, wherein the ratio of P Modification BETA zeolite and phosphorous modified ZSM-5 zeolite weight content is 1: 10 ~ 10:1, be preferably 10:1 ~ 1:1, be more preferably 10:1 ~ 2:1.
In catalyst of the present invention, the total content of P Modification BETA zeolite and phosphorous modified ZSM-5 zeolite is preferably 20.0% ~ 85.0%, most preferably is 30.0% ~ 80.0%; Rare-earth oxide content is preferably 1% ~ 15%, most preferably is 2% ~ 12%.Described rare earth element comprises one or more mixtures such as lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, dysprosium, gadolinium, erbium, thulium, yttrium, lutetium, is preferably lanthanum or/and cerium.Rare-earth oxide in catalyst adopts the aqueous solvent containing rare earth metal solubilized salt to flood the catalyst precarsor be made up of zeolite and inorganic refractory oxide, then drying and roasting obtains, rare earth metal solubilized salt, as chloride, nitrate and acetate etc., is preferably nitrate.
In catalyst of the present invention, the mol ratio of the silica/alumina of described P Modification BETA zeolite is 10 ~ 200; The mol ratio of the silica/alumina of phosphorous modified ZSM-5 zeolite is 20 ~ 300.Described P Modification BETA zeolite and phosphorous modified ZSM-5 zeolite are the h-type zeolites containing P elements.The zeolite of direct synthesis generally contains the cation of alkali metal or alkaline-earth metal, method by roasting after the ammonium ion exchange of routine obtains h-type zeolite, then load P elements obtains phosphorus-modified zeolite, BETA zeolite and ZSM-5 zeolite also can pass through conventional modification, as hydrothermal treatment consists, acid treatment etc.The weight content of P elements in P Modification BETA zeolite and phosphorous modified ZSM-5 zeolite is 0.01% ~ 10.0%, is preferably 0.1% ~ 10.0%.
Described inorganic refractory oxide is adhesive or plays skeleton function, is generally selected from one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and clay, is preferably aluminium oxide and/or kaolin, is more preferably aluminium oxide.
The preparation method of catalyst of the present invention, comprises the steps:
A) preparation of P Modification BETA zeolite and phosphorous modified ZSM-5 zeolite: BETA zeolite and ZSM-5 zeolite adopt dipping phosphorus-containing compound, then the method for drying and roasting introduces P elements, BETA zeolite and ZSM-5 zeolite can introduce P elements respectively, also introduce P elements after can mixing simultaneously, specifically can adopt as one of two kinds of modes;
Method 1: by the aqueous impregnation Hydrogen BETA zeolite containing inorganic phosphorus compound and Hydrogen ZSM-5 zeolite, dip time 1 ~ 24 hour, dipping temperature 0 ~ 90 DEG C, then through conventional drying and roasting, obtains phosphorus-modified zeolite; Inorganic phosphorus compound is as phosphoric acid or solubility microcosmic salt etc.
Method 2: organophosphorus compound is dissolved in organic solvent (as ethanol or toluene etc.), and under normal temperature, flood Hydrogen BETA zeolite and Hydrogen ZSM-5 zeolite, dip time 1 ~ 24 hour, through conventional drying and roasting, obtains phosphorus-modified zeolite;
B) abundant to above-mentioned modified molecular screen, inorganic refractory oxide, water and peptizing agent kneading is become plastic paste, through super-dry and calcination process after extruded moulding, obtain catalyst precarsor.
C) by step b) catalyst precarsor of gained joins in the solution containing rare-earth salts, at 60-120 DEG C, carries out impregnation process 0.5 ~ 2 hour, then filters, washs, dry and roasting, obtains alkylation catalyst of the present invention.
Inorganic refractory oxide described in step b) is selected from one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and clay, be preferably aluminium oxide and kaolin, be more preferably aluminium oxide, the precursor of aluminium oxide can be selected from boehmite, boehmite, diaspore, gibbsite and visit in aluminium stone one or more.Peptizing agent described in step (b) is inorganic acid or organic acid, is preferably inorganic acid, is more preferably hydrochloric acid and nitric acid, most preferably is nitric acid; Wherein the mass concentration of salpeter solution used is 1.0% ~ 30.0%, and be preferably 1.0% ~ 5.0%, consumption is that plastic block is as the criterion can make kneading material.Step (b) in order to be beneficial to extruded moulding, can adopt extrusion aid in shaping of catalyst process, such as graphite, starch, cellulose and sesbania powder etc.
Described in step c) described containing rare-earth compound be the salt being dissolvable in water water, such as chloride, nitrate and acetate etc., be preferably nitrate.The mass concentration of described solution is 1% ~ 20%, and be preferably 1% ~ 15%, described dipping temperature is 60 ~ 120 DEG C, and be preferably 70 ~ 100 DEG C, the impregnation process time is 0.5 ~ 2 hour, is preferably 1 ~ 1.5 hour.
Step a) and b) described in drying condition be that normal temperature ~ 300 DEG C keep 1h ~ 48h, wherein step a) described in method 1 can be identical with the drying condition described in method 2, also can be different.The roasting condition of step a) is 400 DEG C ~ 900 DEG C and keeps 0.5h ~ 10.0h, wherein step a) described in method 1 can be identical with the roasting condition described in method 2, also can be different.Catalyst roasting condition described in step b) is 300 DEG C ~ 600 DEG C and keeps 1h ~ 8h.
The drying of catalyst described in step c) and roasting condition can be this area normal condition, and such as drying condition is that normal temperature ~ 300 DEG C keep 1h ~ 48h, and roasting condition is 350 DEG C ~ 600 DEG C and keeps 1h ~ 10h.
A kind of ethene provided by the invention and producing phenylethane from alkylation of benzene catalyst, for low-concentration ethane and producing phenylethane from alkylation of benzene process, it is characterized in that: low-concentration ethane is the dry gas produced in the petroleum refining process such as catalytic cracking, catalytic pyrolysis, in dry gas, the percent by volume of ethene is 8% ~ 55%, is generally 10% ~ 25%; Reaction temperature is 200 ~ 300 DEG C, and pressure is between 0.5 ~ 2.0MPa, and in dry gas, volume of ethylene air speed is 0.3 ~ 3.0h -1, the molecular proportion of benzene and ethene is between 3:1 ~ 20:1.
In ethene and benzene alkylation reaction process, two key factors affecting catalyst performance performance are acidity and pore structures of catalyst.Adopt two kinds of zeolites with the use of, be conducive to the diffusion of reactant and product, reduce secondary response generate accessory substance.Add rare earth component, effectively can stop the generation of some side reactions, reduce carbon distribution reaction, improve the stability of catalyst.Two kinds through P elements modified zeolite with the use of, the acid centre of two kinds of zeolites is worked in coordination, and is conducive to improving the selective of object product.Catalyst of the present invention with low-concentration ethane be raw material carry out alkylated reaction time, catalyst has active high, reaction temperature is low and object product selectivity is high feature.
Detailed description of the invention
20ml evaluating apparatus carries out the evaluation test of catalyst, in reaction temperature lower than 300 DEG C, pressure 0.7MPa, ethene air speed 0.5h -1, benzene and ethylene molecule than be 6 condition under catalyst performance evaluate.Conversion ratio and selective with mole for benchmark.
In embodiment, dry gas composition used is as shown in table 1.
Table 1 dry gas raw material composition (volumn concentration).
CH 4 C 2H 4 C 2H 6 C 3H 6 C 3H 8 H 2 N 2 CO X O 2 H 2S(mg/m 3)
26.0 20.9 18.8 1.4 0.5 10.4 16.6 4.2 1.1 308
Below by embodiment, the invention will be further described, but the present invention is not limited to this.
embodiment 1
The preparation process of catalyst E-1 of the present invention is as follows:
(1) configure the phosphate aqueous solution of 0.5mol/L, then adopt method and the BETA(SiO of incipient impregnation 2/ Al 2o 3mol ratio is 28) and ZSM-5(SiO 2/ Al 2o 3mol ratio is 75) two kinds of hydrogen type molecular sieves mix (its mass ratio is 8:1), and 80 DEG C of dippings are after 2 hours, through 120 DEG C of oven dry, roasting 5 hours in 550 DEG C of air, obtain BETA and ZSM-5 modified molecular screen, be designated as S-1, wherein the weight content of P elements in zeolite is 1.5%.
(2) modified molecular screen S-1 step (1) obtained and alumina powder, mix according to the butt of 60:40, then 100ml water and 2.5ml red fuming nitric acid (RFNA) (mass concentration is 66.5%) is added, abundant kneading, make it to become paste plastic, banded extruder is extruded the cylindrical bars that diameter is 1.5mm, and cylindrical bars at 100 DEG C dry 16 hours, then in air atmosphere, 550 DEG C of roastings obtain molecular sieve catalyst precursor D-1 of the present invention for 4 hours.
(3) by step 2) the molecular sieve catalyst precursor D-1 molecular sieve catalyst that obtains is flood in the lanthanum nitrate hexahydrate of 6% in mass concentration, at 90 DEG C dry 10 hours, then in air atmosphere, 500 DEG C of roastings must contain 7.8%(weight in 4 hours) the alkylation catalyst E-1 of lanthana.The evaluation result of this catalyst is in table 2.
embodiment 2
The preparation of catalyst E-2 of the present invention
(1) configure the ammonium dihydrogen phosphate aqueous solution of 0.5mol/L, then adopt method and the BETA(SiO of incipient impregnation 2/ Al 2o 3mol ratio is 28) and ZSM-5(SiO 2/ Al 2o 3mol ratio is 75) two kinds of hydrogen type molecular sieves mix (its mass ratio is 5:1), and 80 DEG C of dippings are after 2 hours, through 120 DEG C of oven dry, roasting 5 hours in 550 DEG C of air, obtain BETA and ZSM-5 modified molecular screen, be designated as S-2, wherein the weight content of P elements in zeolite is 2.5%.
(2) modified molecular screen S-2 step (1) obtained and alumina powder, mix according to the butt of 20:80, then 100ml water and 2.5ml red fuming nitric acid (RFNA) (mass concentration is 66.5%) is added, abundant kneading, make it to become paste plastic, banded extruder is extruded the cylindrical bars that diameter is 1.5mm, and cylindrical bars at 100 DEG C dry 16 hours, then in air atmosphere, 550 DEG C of roastings obtain molecular sieve catalyst precursor D-2 of the present invention for 4 hours.
(3) by step 2) the molecular sieve catalyst precursor D-2 molecular sieve catalyst that obtains is flood in the lanthanum nitrate hexahydrate of 8% in mass concentration, at 90 DEG C dry 10 hours, then in air atmosphere, 500 DEG C of roastings must contain 9.6%(weight in 4 hours) the alkylation catalyst E-2 of lanthana.The evaluation result of this catalyst is in table 2.
embodiment 3
The preparation of catalyst E-3 of the present invention
The preparation process of catalyst E-3 of the present invention is with embodiment 1, and difference is that the ethanolic solution of triethyl phosphate used replaces phosphate aqueous solution, and the evaluation result of the catalyst E-3 of the present invention prepared is in table 2.
(1) configure the ethanolic solution of the etherophosphoric acid of 1.0mol/L, then adopt method and the BETA(SiO of incipient impregnation 2/ Al 2o 3mol ratio is 58) and ZSM-5(SiO 2/ Al 2o 3mol ratio is 105) two kinds of hydrogen type molecular sieves mix (its mass ratio is 8:1), and 80 DEG C of dippings are after 2 hours, through 120 DEG C of oven dry, roasting 5 hours in 550 DEG C of air, obtain BETA and ZSM-5 modified molecular screen, be designated as S-3, wherein the weight content of P elements in zeolite is 5.0%.
(2) modified molecular screen S-3 step (1) obtained and alumina powder, mix according to the butt of 30:70, then 100ml water and 2.5ml red fuming nitric acid (RFNA) (mass concentration is 66.5%) is added, abundant kneading, make it to become paste plastic, banded extruder is extruded the cylindrical bars that diameter is 1.5mm, and cylindrical bars at 100 DEG C dry 16 hours, then in air atmosphere, 550 DEG C of roastings obtain molecular sieve catalyst precursor D-3 of the present invention for 4 hours.
(3) by step 2) the molecular sieve catalyst precursor D-3 molecular sieve catalyst that obtains is flood in the lanthanum nitrate hexahydrate of 10% in mass concentration, at 90 DEG C dry 10 hours, then in air atmosphere, 500 DEG C of roastings must contain 9.6%(weight in 4 hours) the alkylation catalyst E-3 of lanthana.The evaluation result of this catalyst is in table 2.
embodiment 4
The preparation of catalyst E-4 of the present invention
The preparation process of catalyst E-4 of the present invention is with embodiment 1, and difference is containing 10.8%(weight) the alkylation catalyst E-4 of lanthana, the evaluation result of its catalyst E-4 is in table 2.
embodiment 5
The preparation process of catalyst E-5 of the present invention is with embodiment 2, and difference is that BETA and ZSM-5 quality is 4:1, and the evaluation result of its catalyst E-5 is in table 2.
embodiment 6
The preparation process of catalyst E-6 of the present invention is with embodiment 3, and difference is containing 3.8%(weight) lanthana, BETA and ZSM-5 quality is 8:1, and the evaluation result of its catalyst E-6 is in table 2.
comparative example 1
The preparation of contrast medium C-1 of the present invention
According to method disclosed in CN101584993A embodiment 1, namely catalyst adopts alumina powder and ZSM-5 molecular sieve (SiO 2/ Al 2o 3mol ratio is 28) obtain contrast medium C-1 through extrusion, drying and roasting, it consists of: molecular sieve mass content 50.Result of the test is in table 2.
comparative example 2
According to method disclosed in CN101433859 embodiment 8, namely catalyst adopts alumina powder and the BETA molecular sieve (SiO through ammonium dihydrogen phosphate (ADP) modification 2/ Al 2o 3mol ratio is 28) obtain contrast medium C-2 through extrusion, drying and roasting, it consists of: molecular sieve mass content 70.Result of the test is in table 2.
comparative example 3
According to the preparation method of embodiment 1, difference is not containing lanthana.Its catalyst be numbered C-3, evaluation result is in table 2.
Table 2 differential responses temperature catalyst experimental result.
Numbering Temperature, DEG C Conversion of ethylene, % Ethylbenzene selectivity, % Xylene content, μ g/g
E-1 270 99.4 99.7 77
E-2 270 99.8 99.8 79
E-3 275 99.5 99.7 78
E-4 265 99.6 99.6 68
E-5 278 99.7 99.8 70
E-6 270 99.6 99.8 75
C-1 310 99.3 99.2 93
C-2 320 99.1 99.3 95
C-3 300 99.5 99.6 86
In the unstripped gas that catalyst of the present invention uses, ethylene contents is approximately 20%, and from the results shown in Table 2, the selective of ethylbenzene is greater than 99%, and the conversion ratio of ethene is also greater than 99%, in finished product in ethylbenzene xylene content also lower than 80 μ g/g.Reaction temperature, also lower than 280 DEG C (lower than comparative catalyst more than 30 DEG C), compared with contrast medium, has high, the selective excellent advantage of reactivity.

Claims (16)

1. the ethene containing two kinds of zeolites and benzene alkylation catalyst, it is characterized in that: containing P Modification BETA zeolite, phosphorous modified ZSM-5 zeolite and rare-earth oxide in catalyst, with the weight of catalyst for benchmark, the total content of P Modification BETA zeolite and phosphorous modified ZSM-5 zeolite is 10% ~ 90.0%, rare-earth oxide content is 1% ~ 20%, surplus is inorganic refractory oxide, and wherein the ratio of P Modification BETA zeolite and phosphorous modified ZSM-5 zeolite weight content is 1: 10 ~ 10:1; The weight content of P elements in P Modification BETA zeolite and phosphorous modified ZSM-5 zeolite is 0.01% ~ 10.0%.
2. according to catalyst according to claim 1, it is characterized in that: the ratio of P Modification BETA zeolite and phosphorous modified ZSM-5 zeolite weight content is 1: 10 ~ 1:1.
3. according to catalyst according to claim 1, it is characterized in that: the ratio of P Modification BETA zeolite and phosphorous modified ZSM-5 zeolite weight content is 10:1 ~ 2:1.
4. according to catalyst according to claim 1, it is characterized in that: the total content of P Modification BETA zeolite and phosphorous modified ZSM-5 zeolite is 20.0% ~ 85.0%.
5. according to catalyst according to claim 1, it is characterized in that: the total content of P Modification BETA zeolite and phosphorous modified ZSM-5 zeolite is 30.0% ~ 80.0%.
6. according to catalyst according to claim 1, it is characterized in that: rare-earth oxide content is 1% ~ 15%; Rare earth comprises one or more mixtures in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, dysprosium, gadolinium, erbium, thulium, yttrium, lutetium.
7. according to catalyst according to claim 1, it is characterized in that: rare-earth oxide content is 2% ~ 12%.
8. according to catalyst according to claim 1, it is characterized in that: the rare-earth oxide in catalyst adopts the aqueous solvent containing rare earth metal solubilized salt to flood the catalyst precarsor be made up of zeolite and inorganic refractory oxide, and then drying and roasting obtains.
9. according to catalyst according to claim 1, it is characterized in that: the mol ratio of the silica/alumina of P Modification BETA zeolite is 10 ~ 200; The mol ratio of the silica/alumina of phosphorous modified ZSM-5 zeolite is 20 ~ 300.
10. according to catalyst according to claim 1, it is characterized in that: the weight content of P elements in P Modification BETA zeolite and phosphorous modified ZSM-5 zeolite is 0.1% ~ 10.0%.
11., according to catalyst according to claim 1, is characterized in that: inorganic refractory oxide is selected from one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia and clay.
Described in 12. 1 kinds of arbitrary claims of claim 1 to 11, the preparation method of catalyst, is characterized in that comprising the steps:
The preparation of (a) P Modification BETA zeolite and phosphorous modified ZSM-5 zeolite: BETA zeolite and ZSM-5 zeolite adopt dipping phosphorus-containing compound, then the method for drying and roasting introduces P elements, BETA zeolite and ZSM-5 zeolite introduce P elements respectively, or introduce P elements after mixing simultaneously;
B abundant to the modified molecular screen of step (a), inorganic refractory oxide, water and peptizing agent kneading is become plastic paste by (), through super-dry and calcination process after extruded moulding, obtain catalyst precarsor;
(c) by step (b) catalyst precarsor join in the solution containing rare-earth salts, at 60-120 DEG C, carry out impregnation process 0.5 ~ 2 hour, then filter, wash, dry and roasting, obtain alkylation catalyst.
13. in accordance with the method for claim 12, it is characterized in that: step (a) and the drying condition in (b) are that normal temperature ~ 300 DEG C keep 1h ~ 48h, the roasting condition of step (a) is 400 DEG C ~ 900 DEG C and keeps 0.5h ~ 10.0h, and the catalyst roasting condition described in step (b) is 300 DEG C ~ 600 DEG C and keeps 1h ~ 8h; The drying of catalyst described in step (c) is that normal temperature ~ 300 DEG C keep 1h ~ 48h, and roasting is 350 DEG C ~ 600 DEG C and keeps 1h ~ 10h.
The application of catalyst described in the arbitrary claim of 14. claim 1 to 11, for low-concentration ethane and producing phenylethane from alkylation of benzene process, it is characterized in that: reaction temperature is 200 ~ 300 DEG C, pressure is between 0.5 ~ 2.0MPa, and in dry gas, volume of ethylene air speed is 0.3 ~ 3.0h -1, the molecular proportion of benzene and ethene is between 3:1 ~ 20:1.
15. according to application according to claim 14, and its spy is: low-concentration ethane is the dry gas produced in catalytic cracking, catalytic pyrolysis, and in dry gas, the percent by volume of ethene is 8% ~ 55%.
16. according to application according to claim 14, and its spy is: low-concentration ethane is the dry gas produced in catalytic cracking, catalytic pyrolysis, and in dry gas, the percent by volume of ethene is 10% ~ 25%.
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US20060100471A1 (en) * 2004-11-09 2006-05-11 Serra Alfaro Jose M Process for transalkylation of alkyl-aromatic hydrocarbons used in two reaction zones
CN101622327A (en) * 2007-01-19 2010-01-06 埃克森美孚化学专利公司 Adopt the liquid-phase alkylation of multiple catalyzer

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Publication number Priority date Publication date Assignee Title
CN85102764A (en) * 1985-04-01 1986-08-13 大连工学院 Zeolite catalyst modified by rare earth preparation and application
US20060100471A1 (en) * 2004-11-09 2006-05-11 Serra Alfaro Jose M Process for transalkylation of alkyl-aromatic hydrocarbons used in two reaction zones
CN101622327A (en) * 2007-01-19 2010-01-06 埃克森美孚化学专利公司 Adopt the liquid-phase alkylation of multiple catalyzer

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