CN102909067A - 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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CN102909067A
CN102909067A CN2011102175632A CN201110217563A CN102909067A CN 102909067 A CN102909067 A CN 102909067A CN 2011102175632 A CN2011102175632 A CN 2011102175632A CN 201110217563 A CN201110217563 A CN 201110217563A CN 102909067 A CN102909067 A CN 102909067A
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CN102909067B (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

The ethene and benzene alkylation catalyst and the preparation method and application that contain two kinds of zeolites
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 of Catalysts and its preparation method and application for preparing ethylbenzene with low-concentration ethane and benzene alkylation reaction in the petrochemical industry by-product dry gas.
Background technology
Ethylbenzene is a kind of important Organic Chemicals, of many uses, be to produce cinnamic raw material, can also for the production of ion exchange resin, unsaturated polyester resin, agricultural emulsifier and coating etc., be with a wide range of applications in fields such as automobile, household electrical appliances, light industrys.Styrene occupies the 3rd of world's polyolefin 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 the ethylbenzene production, the new and more cheap approach of seeking ethylbenzene production has great importance.
Ethylbenzene mainly adopts ethene and benzene catalytic alkylation reaction to synthesize, and the ethylbenzene building-up process generally comprises two reactions, i.e. the transalkylation reaction of the alkylated reaction of benzene and ethene and many ethylbenzene and benzene.Along with the development of petrochemical processing industry, a large amount of refinery exhausts that contain low concentration ethene provide new raw material sources for producing ethylbenzene.Take full advantage of various sources and variable concentrations, especially low-concentration ethane and benzene alkylation and produce ethylbenzene, have great importance for the cost of material that reduces ethylbenzene production, the economy that improves ethylbenzene production plants and the production of the minimizing ethylbenzene dependence for China's pure ethylene resource in short supply.
Zeolite has widely in a lot of fields to be used, and in alkylated reaction technical development process, also transforms zeolite catalyst from non-zeolite catalysts.Using the earliest zeolite catalyst to carry out alkylated reaction is that Mobil-Badger invention in 1978 has been used since the zeolite catalyst, adopts the benzene alkylation technique of zeolite catalyst to develop rapidly.Since the nineties in 20th century, the production of ethylbenzene has been finished from traditional AlCl 3Be the transformation to zeolite catalysis technique of the Friedel-Crafts benzene-alkylation technique of catalyst.
In the prior art, traditional alkylation process is mainly take the Hydrogen ZSM-5 zeolite as catalyst.US3750504 and US3751506 are take unmodified ZSM-5 zeolite as benzene with ethene gas phase alkylation catalyst, but the catalyst regeneration cycle is short, ethylization product (ethylbenzene) selectively lower, and xylene content is high in the product.For improving the ZSM-5 catalyst in the total reactivity worth of ethene and producing phenylethane from alkylation of benzene process, the researcher has adopted various method of modifying.The stability of the selective and catalyst of ethylization product when the steam treatment that adopts US4016218, US4429176 and US4594146 etc. improves catalyst for ethene and benzene alkylation.US3962364 adopts P elements that ZSM-5 zeolite is carried out modification, has improved to a certain extent ethylization selectivity of product and catalyst stability.CN97106449.0, CN97106448.2 and CN00111721.1 have improved catalyst performance to a certain extent when adopting the conventional ZSM-5 zeolite of alkaline earth/rare-earth oxide modification to be used for ethene and benzene alkylation, but still have alkylated reaction temperature high (400 ~ 420 ℃), cause the problems such as the dimethylbenzene impurity content is higher in energy consumption height, the product.And CN101584993A has improved the performance of catalyst to a certain extent by the specific condition modified ZSM-5 zeolite, but still there is higher problem in the alkylated reaction temperature.
Summary of the invention
For the deficiencies in the prior art, the purpose of this invention is to provide a kind of ethene and benzene alkylation reaction ethylbenzene catalyst system therefor processed and its preparation method and application.When this catalyst contains ethene dry gas low-concentration ethane and producing phenylethane from alkylation of benzene reaction for the refinery, has higher reactivity.
In the ethene and benzene alkylation catalyst that contains two kinds of zeolites of the present invention, contain phosphorus modification BETA zeolite, phosphorous modified ZSM-5 zeolite and rare-earth oxide, take the weight of catalyst as benchmark, the total content of phosphorus 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 phosphorus modification BETA zeolite and phosphorous modified ZSM-5 zeolite weight content is 1: 10～10:1, be preferably 10:1～1:1, more preferably 10:1～2:1.
In the catalyst of the present invention, the total content of phosphorus 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 the catalyst adopts the aqueous solvent that contains rare earth metal solubilized salt to flood the catalyst precarsor of being made by zeolite and inorganic refractory oxide, then drying and roasting makes, rare earth metal solubilized salt such as chloride, nitrate and acetate etc. are preferably nitrate.
In the catalyst of the present invention, the mol ratio of the silica/alumina of described phosphorus modification BETA zeolite is 10 ~ 200; The mol ratio of the silica/alumina of phosphorous modified ZSM-5 zeolite is 20 ~ 300.Described phosphorus modification BETA zeolite and phosphorous modified ZSM-5 zeolite are the h-type zeolites that contains P elements.Directly synthetic zeolite generally contains the cation of alkali metal or alkaline-earth metal, can obtain h-type zeolite by the method for roasting after the ammonium ion exchange of routine, then the load P elements obtains phosphorus-modified zeolite, BETA zeolite and ZSM-5 zeolite also can be through conventional modifications, such as hydrothermal treatment consists, acid treatment etc.The weight content of P elements in phosphorus 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, generally is selected from one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and the clay, is preferably aluminium oxide and/or kaolin, more preferably aluminium oxide.
The preparation method of catalyst of the present invention comprises the steps:
A) preparation of phosphorus modification BETA zeolite and phosphorous modified ZSM-5 zeolite: BETA zeolite and ZSM-5 zeolite adopt the dipping phosphorus-containing compound, then the method for drying and roasting is introduced P elements, BETA zeolite and ZSM-5 zeolite can be introduced respectively P elements, introduce simultaneously P elements after also can mixing, specifically can adopt such as one of dual mode;
Method 1: will contain aqueous solution dipping Hydrogen BETA zeolite and the Hydrogen ZSM-5 zeolite of inorganic phosphorus compound, dip time 1 ~ 24 hour, then 0 ~ 90 ℃ of dipping temperature passes through conventional drying and roasting, gets phosphorus-modified zeolite; Inorganic phosphorus compound such as phosphoric acid or solubility microcosmic salt etc.
Method 2: organophosphorus compound is dissolved in the organic solvent (such as ethanol or toluene etc.), and floods Hydrogen BETA zeolite and Hydrogen ZSM-5 zeolite under the normal temperature, dip time 1 ~ 24 hour through conventional drying and roasting, gets phosphorus-modified zeolite;
B) the abundant kneading of above-mentioned modified molecular screen, inorganic refractory oxide, water and peptizing agent is become plastic paste, extruded moulding obtains catalyst precarsor by super-dry and calcination process.
C) with step b) catalyst precarsor of gained joins in the solution that contains rare-earth salts, at 60-120 ℃, carries out impregnation process 0.5 ~ 2 hour, then filters, washs, drying and roasting, obtains alkylation catalyst of the present invention.
Inorganic refractory oxide described in the step b) is selected from one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and the clay, be preferably aluminium oxide and kaolin, aluminium oxide more preferably, the precursor of aluminium oxide can be selected from boehmite, boehmite, diaspore, gibbsite and visit in the aluminium stone one or more.The described peptizing agent of step (b) is inorganic acid or organic acid, is preferably inorganic acid, and more preferably hydrochloric acid and nitric acid most preferably are nitric acid; Wherein the mass concentration of used salpeter solution is 1.0%～30.0%, is preferably 1.0%～5.0%, and consumption is can make the kneading material be as the criterion as plastic block.Step (b) in order to be beneficial to extruded moulding, can adopt extrusion aid in the shaping of catalyst process, such as graphite, starch, cellulose and sesbania powder etc.
The described rare-earth compound that contains described in the step c) is the salt that is dissolvable in water water, and such as chloride, nitrate and acetate etc. is preferably nitrate.The mass concentration of described solution is 1% ~ 20%, is preferably 1% ~ 15%, and described dipping temperature is 60 ~ 120 ℃, is preferably 70 ~ 100 ℃, and 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 ℃ keep 1h ~ 48h, wherein the method 1 of step described in a) can be identical with method 2 described drying conditions, also can be different.The roasting condition of step a) is 400 ℃ ~ 900 ℃ and keeps 0.5h ~ 10.0h, and wherein the method 1 of step described in a) can be identical with method 2 described roasting conditions, also can be different.The described catalyst roasting condition of step b) is 300 ℃ ~ 600 ℃ and keeps 1h ~ 8h.
The drying of catalyst described in the step c) and roasting condition can be this area normal condition, and for example drying condition is normal temperature ~ 300 ℃ maintenance 1h ~ 48h, and roasting condition is 350 ℃ ~ 600 ℃ and keeps 1h ~ 10h.
A kind of ethene provided by the invention and producing phenylethane from alkylation of benzene catalyst, be used for low-concentration ethane and producing phenylethane from alkylation of benzene process, it is characterized in that: low-concentration ethane is the dry gas that produces in the petroleum refining processes such as catalytic cracking, catalytic pyrolysis, the percent by volume of ethene is 8% ~ 55% in the dry gas, is generally 10% ~ 25%; Reaction temperature is 200 ~ 300 ℃, and pressure is between 0.5 ~ 2.0MPa, and the volume of ethylene air speed is 0.3 ~ 3.0h in the dry gas -1, the molecular proportion of benzene and ethene is between 3:1 ~ 20:1.
In ethene and benzene alkylation reaction process, acidity and pore structure that two key factors that affect the catalyst performance performance are catalyst.Adopt being used of two kinds of zeolites, be conducive to the diffusion of reactant and product, reduce secondary response and generate accessory substance.Add rare earth component, can effectively stop the generation of some side reactions, reduce the carbon distribution reaction, improve the stability of catalyst.Two kinds are used through the P elements modified zeolite, and the acid centre of two kinds of zeolites is worked in coordination, and are conducive to improve the selective of purpose product.Catalyst of the present invention is when carrying out alkylated reaction take low-concentration ethane as raw material, and catalyst has the advantages that activity is high, reaction temperature is low and the purpose product selectivity is high.
The specific embodiment
Carry out the evaluation test of catalyst at the 20ml evaluating apparatus, be lower than 300 ℃ in reaction temperature, pressure 0.7MPa, ethene air speed 0.5h -1, benzene and ethylene molecule are than being that catalyst performance is estimated under 6 the condition.Conversion ratio reaches selectively take mole as benchmark.
Used dry gas forms as shown in table 1 among the embodiment.
Table 1 dry gas raw material forms (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
The invention will be further described below by embodiment, 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) then the phosphate aqueous solution of configuration 0.5mol/L adopts 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 ℃ of dippings are after 2 hours, through 120 ℃ of oven dry, roasting is 5 hours in 550 ℃ 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) the modified molecular screen S-1 and the alumina powder that step (1) are obtained, butt according to 60:40 mixes, then add 100ml water and 2.5ml red fuming nitric acid (RFNA) (mass concentration is 66.5%), abundant kneading, make it to become the paste plastic, extrude the cylindrical bars that diameter is 1.5mm at banded extruder, cylindrical bars descended dry 16 hours at 100 ℃, and then 550 ℃ of roastings obtained molecular sieve catalyst precursor D-1 of the present invention in 4 hours in air atmosphere.
(3) with step 2) the molecular sieve catalyst precursor D-1 molecular sieve catalyst that obtains floods in mass concentration is 6% lanthanum nitrate hexahydrate, 90 ℃ lower dry 10 hours, then 500 ℃ of roastings must contain 7.8%(weight in 4 hours in air atmosphere) the alkylation catalyst E-1 of lanthana.The evaluation result of this catalyst sees Table 2.
Embodiment 2
The preparation of catalyst E-2 of the present invention
(1) then the ammonium dihydrogen phosphate aqueous solution of configuration 0.5mol/L adopts 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 ℃ of dippings are after 2 hours, through 120 ℃ of oven dry, roasting is 5 hours in 550 ℃ 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) the modified molecular screen S-2 and the alumina powder that step (1) are obtained, butt according to 20:80 mixes, then add 100ml water and 2.5ml red fuming nitric acid (RFNA) (mass concentration is 66.5%), abundant kneading, make it to become the paste plastic, extrude the cylindrical bars that diameter is 1.5mm at banded extruder, cylindrical bars descended dry 16 hours at 100 ℃, and then 550 ℃ of roastings obtained molecular sieve catalyst precursor D-2 of the present invention in 4 hours in air atmosphere.
(3) with step 2) the molecular sieve catalyst precursor D-2 molecular sieve catalyst that obtains floods in mass concentration is 8% lanthanum nitrate hexahydrate, 90 ℃ lower dry 10 hours, then 500 ℃ of roastings must contain 9.6%(weight in 4 hours in air atmosphere) the alkylation catalyst E-2 of lanthana.The evaluation result of this catalyst sees 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 used triethyl phosphate replaces phosphate aqueous solution, and the evaluation result of the catalyst E-3 of the present invention for preparing sees Table 2.
(1) then the ethanolic solution of etherophosphoric acid of configuration 1.0mol/L adopts 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 ℃ of dippings are after 2 hours, through 120 ℃ of oven dry, roasting is 5 hours in 550 ℃ 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) the modified molecular screen S-3 and the alumina powder that step (1) are obtained, butt according to 30:70 mixes, then add 100ml water and 2.5ml red fuming nitric acid (RFNA) (mass concentration is 66.5%), abundant kneading, make it to become the paste plastic, extrude the cylindrical bars that diameter is 1.5mm at banded extruder, cylindrical bars descended dry 16 hours at 100 ℃, and then 550 ℃ of roastings obtained molecular sieve catalyst precursor D-3 of the present invention in 4 hours in air atmosphere.
(3) with step 2) the molecular sieve catalyst precursor D-3 molecular sieve catalyst that obtains floods in mass concentration is 10% lanthanum nitrate hexahydrate, 90 ℃ lower dry 10 hours, then 500 ℃ of roastings must contain 9.6%(weight in 4 hours in air atmosphere) the alkylation catalyst E-3 of lanthana.The evaluation result of this catalyst sees 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 to contain 10.8%(weight) the alkylation catalyst E-4 of lanthana, the evaluation result of its catalyst E-4 sees 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 are 4:1, and the evaluation result of its catalyst E-5 sees Table 2.
Embodiment 6
The preparation process of catalyst E-6 of the present invention is with embodiment 3, and difference is to contain 3.8%(weight) lanthana, BETA and ZSM-5 quality are 8:1, the evaluation result of its catalyst E-6 sees Table 2.
Comparative Examples 1
The preparation of contrast medium C-1 of the present invention
According to CN101584993A embodiment 1 disclosed method, 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 sees Table 2.
Comparative Examples 2
According to CN101433859 embodiment 8 disclosed methods, namely catalyst adopts alumina powder and through the BETA of ammonium dihydrogen phosphate (ADP) modification molecular sieve (SiO 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 sees Table 2.
Comparative Examples 3
According to the preparation method of embodiment 1, difference is not contain lanthana.Its catalyst be numbered C-3, evaluation result sees Table 2.
Table 2 differential responses temperature catalyst experimental result.
Numbering Temperature, ℃ 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
Ethylene contents is approximately 20% in the employed unstripped gas of catalyst of the present invention, from the results shown in Table 2, ethylbenzene selectively greater than 99%, the conversion ratio of ethene is also greater than 99%, in the finished product in the ethylbenzene xylene content also be lower than 80 μ g/g.Reaction temperature also is lower than 280 ℃ (comparison is lower more than 30 ℃ than catalyst), compares with contrast medium, has reactivity height, selective excellent advantage.

Claims (10)

1. ethene and benzene alkylation catalyst that contains two kinds of zeolites, it is characterized in that: contain phosphorus modification BETA zeolite, phosphorous modified ZSM-5 zeolite and rare-earth oxide in the catalyst, take the weight of catalyst as benchmark, the total content of phosphorus 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 phosphorus modification BETA zeolite and phosphorous modified ZSM-5 zeolite weight content is 1: 10～10:1, be preferably 10:1～1:1, more preferably 10:1～2:1.
2. according to catalyst claimed in claim 1, it is characterized in that: the total content of phosphorus modification BETA zeolite and phosphorous modified ZSM-5 zeolite is 20.0%～85.0%, is preferably 30.0%～80.0%.
3. according to catalyst claimed in claim 1, it is characterized in that: rare-earth oxide content is 1%～15%, is preferably 2%～12%; Rare earth comprises one or more mixtures in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, dysprosium, gadolinium, erbium, thulium, yttrium, the lutetium.
4. according to catalyst claimed in claim 1, it is characterized in that: the rare-earth oxide in the catalyst adopts the aqueous solvent that contains rare earth metal solubilized salt to flood the catalyst precarsor of being made by zeolite and inorganic refractory oxide, and then drying and roasting makes.
5. according to catalyst claimed in claim 1, it is characterized in that: the mol ratio of the silica/alumina of phosphorus modification BETA zeolite is 10 ~ 200; The mol ratio of the silica/alumina of phosphorous modified ZSM-5 zeolite is 20 ~ 300; The weight content of P elements in phosphorus modification BETA zeolite and phosphorous modified ZSM-5 zeolite is 0.01%～10.0%, is preferably 0.1%～10.0%.
6. according to catalyst claimed in claim 1, it is characterized in that: inorganic refractory oxide is selected from one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and the clay.
7. the preparation method of the described catalyst of the arbitrary claim of claim 1 to 6 is characterized in that comprising the steps:
(a) preparation of phosphorus modification BETA zeolite and phosphorous modified ZSM-5 zeolite: BETA zeolite and ZSM-5 zeolite adopt the dipping phosphorus-containing compound, then the method for drying and roasting is introduced P elements, BETA zeolite and ZSM-5 zeolite are introduced respectively P elements, introduce simultaneously P elements after perhaps mixing;
(b) the abundant kneading of modified molecular screen, inorganic refractory oxide, water and peptizing agent with step (a) becomes plastic paste, and extruded moulding obtains catalyst precarsor by super-dry and calcination process;
(c) with step (b) catalyst precarsor join in the solution that contains rare-earth salts, at 60-120 ℃, carried out impregnation process 0.5 ~ 2 hour, then filter, wash, drying and roasting, obtain alkylation catalyst.
8. in accordance with the method for claim 7, it is characterized in that: step (a) and (b) in drying condition be that normal temperature ~ 300 ℃ keep 1h ~ 48h, the roasting condition of step (a) is 400 ℃ ~ 900 ℃ and keeps 0.5h ~ 10.0h that the described catalyst roasting condition of step (b) is 300 ℃ ~ 600 ℃ and keeps 1h ~ 8h; The drying of catalyst described in the step (c) is normal temperature ~ 300 ℃ maintenance 1h ~ 48h, and roasting is 350 ℃ ~ 600 ℃ and keeps 1h ~ 10h.
9. the described catalyst of the arbitrary claim of claim 1 to 6 is used for low-concentration ethane and producing phenylethane from alkylation of benzene process, and it is characterized in that: reaction temperature is 200 ~ 300 ℃, and pressure is between 0.5 ~ 2.0MPa, and the volume of ethylene air speed is 0.3 ~ 3.0h in the dry gas -1, the molecular proportion of benzene and ethene is between 3:1 ~ 20:1.
10. according to application claimed in claim 9, its spy is: low-concentration ethane is the dry gas that produces in catalytic cracking, the catalytic pyrolysis, and the percent by volume of ethene is 8% ~ 55% in the dry gas, is preferably 10% ~ 25%.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107413375A (en) * 2017-04-12 2017-12-01 兰州理工大学 Benzene alkylation prepares the method for preparing catalyst of toluene

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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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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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107413375A (en) * 2017-04-12 2017-12-01 兰州理工大学 Benzene alkylation prepares the method for preparing catalyst of toluene

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