CN1508105A - Method for preparing ethylbenzene by liquid phase alkylation of ethylene - Google Patents
Method for preparing ethylbenzene by liquid phase alkylation of ethylene Download PDFInfo
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Abstract
The present invention relates to a method for preparing ethylbenzene by utilizing ethylene liquid-phase alkylation, and is characterized by that it adopts ethylene and benzene as raw material, and uses beta-zeolite molecular sieve as catalyst, before the catalyst is used, firstly, the high-temp. steam can be used to treat the catalyst, then the organic acid is used to treat the catalyst, its reaction temp. is 200-270 deg.C, reaction pressure is 3.0-4.0 MPa, the mole ratio of benzene and ethylene is 3-10, the ethylene can produce liquid-phase alkylation reaction to obtain ethylbenzene.
Description
Technical field
The present invention relates to a kind of method of ethene liquid-phase alkylation system ethylbenzene, particularly about using the method for beta-zeolite molecular sieve as catalyzer ethene liquid-phase alkylation system ethylbenzene.
Background technology
Ethylbenzene is important petrochemical materials, is mainly used in production high polymer monomer-vinylbenzene.It can be produced with various productive method of chemical engineering, and traditional catalyzer has crystallization and noncrystalline silicon-dioxide, boron fluoride, aluminum oxide, phosphoric acid, aluminum chloride and solid phosphoric acid catalyst.All there are shortcomings such as seriously corroded, facility investment is big, the three wastes are many in these conventional catalyst technologies.In recent years, people have carried out extensive and deep research to molecular sieve, and some companies constantly are devoted to utilize molecular sieve to produce the new technology of ethylbenzene as catalyzer.Wherein having obtained great commercial a kind of method is in the presence of a kind of solid acid ZSM-5 zeolite catalyst, carries out vapor phase alkylation with ethene and benzene.For example U.S. Pat 3751504, US 3751506, US 4016218 and US 4547605 all are described in detail this.Liquid-phase condition uses down various molecular sieve catalysts by benzene and ethylene alkylation system ethylbenzene, and it is low to have temperature of reaction, and by product dimethylbenzene growing amount advantage such as less especially.For example U.S. Pat 4891458 has been reported and has been used unmodified beta-zeolite molecular sieve catalyst synthesizing ethyl benzene under the liquid phase alkylation reaction condition.Later studies show that, there is a significant disadvantage in unmodified beta-zeolite molecular sieve as the catalyzer of synthesizing ethyl benzene: poor catalyst stability, regeneration period weak point and regenerability are poor.For this reason, domestic and international many investigators have successively proposed multiple method to the β Zeolite modifying, to overcome the above-mentioned shortcoming of unmodified β zeolite in the synthesizing ethyl benzene reaction.Wherein representational method of modifying is as follows: U.S. Pat 5227558 has reported that the beta-zeolite molecular sieve catalyst liquid-phase alkylation that adopts the steam treatment modification produces the method for ethylbenzene, though have good transformation efficiency in the document, but ethylbenzene selectivity descends very fast, and does not relate to the catalyst regeneration performance.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the past to exist in benzene and the ethene liquid phase alkylation reaction in the document, and the problem of catalyst stability and regenerability difference provides a kind of method of new ethene liquid-phase alkylation system ethylbenzene.This method is used for benzene and ethene liquid phase alkylation reaction, has when can keep high activity of catalyst, can significantly improve the characteristics of catalyst stability and regenerability.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of ethene liquid-phase alkylation system ethylbenzene, with ethene and benzene is reaction raw materials, in temperature of reaction is 200～270 ℃, reaction pressure is 3.0～4.0MPa, benzene/ethylene molar ratio is 3～10, and the weight ethylene air speed is 0.2～2.0 hour
-1Under the condition, reaction raw materials contacts with catalyzer liquid phase alkylation reaction generation ethylbenzene takes place, and used catalyzer contains 70～90% silica alumina ratio SiO by weight percentage
2/ Al
2O
3Be 10～50 β zeolite and 10～30% binding agent aluminum oxide or silicon-dioxide, before using, handles with steam-treated and organic acid successively by used catalyzer, drying, roasting obtain required finished product then, wherein the steam-treated condition is used steam-treated 1～20 hour for being under 400～650 ℃ of conditions in normal pressure, temperature; The organic acid treatment condition are for being that the organic acid soln of 0.05～3.0 mol is to carry out acid treatment under 40～100 ℃ in temperature with concentration, and the time is 1～20 hour, and the weight ratio of organic acid soln and catalyzer is 1～20.
In the technique scheme, the temperature of reaction preferable range is 220～250 ℃, and the reaction pressure preferable range is 3.0～3.5MPa, and benzene/ethylene molar ratio preferable range is 5～6, and weight ethylene air speed preferable range is 0.3～1.5 hour
-1The silica alumina ratio SiO of β zeolite
2/ Al
2O
3Preferable range is 20～40, and steam treatment condition optimization scheme is at normal pressure, and temperature is under 450～550 ℃ of conditions, uses steam-treated 2～10 hours.The organic acid concentration preferable range is 0.2～2.5 mol, and organic acid-treated temperature preferable range is 65～95 ℃, and organic acid-treated time preferable range is 3～16 hours, and the weight ratio preferable range of organic acid soln and catalyzer is 2～10.The organic acid preferred version is selected from oxalic acid, toxilic acid, formic acid, acetic acid, hexanodioic acid, phthalic acid, terephthalic acid, succsinic acid, tartrate, oxysuccinic acid or citric acid.Organic acid more preferably scheme is a citric acid.After acid treatment, maturing temperature is 450～650 ℃, and roasting time is 1～10 hour.
Because the method for modifying that the catalyzer that uses among the present invention adopts steam treatment and organic acid washing to combine has improved the hydrothermal stability of beta-zeolite molecular sieve on the one hand and has regulated the strong faintly acid distribution of beta-zeolite molecular sieve; Removed amorphous substance in the beta-zeolite molecular sieve duct on the other hand or removed the materials such as non-framework aluminum that get off, played modification, the water repelling property of catalyzer and regenerability are significantly increased molecular sieve pore passage from framework of molecular sieve; The burnt ability of appearance of catalyzer is improved greatly, and activity stability has had very big improvement.Use the catalyzer that uses in the inventive method 200～270 ℃ of temperature, pressure 3.0～4.0MPa, benzene/ethylene molar ratio is 3～10, weight ethylene air speed 0.2～2.0 hour
-1Under the condition, through reaction in 500 hours, its conversion of ethylene can reach 98～100%, and ethylbenzene selectivity can reach 92.9～93.8%.Catalyzer is after regeneration, and its reactivity worth can be recovered as before, has obtained good technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Get the former powder of 50 gram sodium type beta-zeolite molecular sieves, its silica alumina ratio SiO
2/ Al
2O
3Be 25, the former powder of this sodium type beta-zeolite molecular sieve is exchanged with ammonium nitrate solution, obtain ammonium type beta-zeolite molecular sieve after the oven dry, ammonium type beta-zeolite molecular sieve and aluminum oxide are mixed by 80/20 weight ratio, and obtaining diameter through extrusion, oven dry and roasting is 1.6 millimeters strip hydrogen type catalyst.
Above-mentioned catalyzer is used steam treatment 6 hours under 520 ℃ condition.Handled 7 hours down at 50 ℃ with the citric acid solution of 0.5 mol, the ratio of the weight of citric acid solution and catalyzer is 5 again, and dry back obtains finished catalyst 480 ℃ of following roastings 3 hours.
Get the above-mentioned catalyzer that makes 2 grams, be positioned in the fixed-bed reactor.220 ℃ of temperature, pressure 3.5MPa, benzene/ethylene molar ratio is 6/1, weight ethylene air speed 1.5 hours
-1Under the condition, conversion of ethylene is 100%, and ethylbenzene selectivity is 93.8%, and after reaction in 500 hours, its conversion of ethylene is 99%, and ethylbenzene selectivity is 92.9%.Reaction proceeds to 490 hours, has just detected ethene in the reaction product, illustrates that activity of such catalysts has good stability.Regenerability for evaluate catalysts, reacted catalyzer has carried out in-situ regeneration in reactor, regeneration condition is: adopt the gas mixture (total flux is 250 ml/min) of normal pressure, air and nitrogen to regenerate, 400 ℃ logical 30% air 1 hour, again at 480 ℃, logical respectively 60% and 90% air each 1 hour 550 ℃ logical 100% air 3 hours, is cooled to 220 ℃ at last then.(benzene/ethylene molar ratio is 6/1 for 220 ℃ of temperature, pressure 3.5MPa, weight ethylene air speed 1.5 hours under the reaction conditions before regeneration again
-1) the regenerated catalyzer is continued reaction, conversion of ethylene is 100%, and ethylbenzene selectivity is 93.7%, and after reaction in 500 hours, its conversion of ethylene is 99% again, and ethylbenzene selectivity is 92.6%.Reaction proceeds to 487 hours, has just detected ethene in the reaction product, illustrates that the regenerability of catalyzer is good, and reactivity worth can be recovered as before.
[comparative example 1]
Get the former powder of 50 gram sodium type beta-zeolite molecular sieves, its silica alumina ratio SiO
2/ Al
2O
3Be 25, the former powder of this sodium type beta-zeolite molecular sieve is exchanged with ammonium nitrate solution, obtain ammonium type beta-zeolite molecular sieve after the oven dry, ammonium type beta-zeolite molecular sieve and aluminum oxide are mixed by 80/20 weight ratio, and obtaining diameter through extrusion, oven dry and roasting is 1.6 millimeters strip hydrogen type catalyst.
Get the above-mentioned catalyzer that makes 2 grams, be positioned in the fixed-bed reactor.220 ℃ of temperature, pressure 3.5MPa, benzene/ethylene molar ratio is 6/1, weight ethylene air speed 1.5 hours
-1Under the condition, conversion of ethylene is 100%, and ethylbenzene selectivity is 91.5%, and after reaction in 500 hours, its conversion of ethylene is 94%, and ethylbenzene selectivity is 90.2%.Reaction proceeds to 200 hours, has just detected ethene in the reaction product, and the activity of such catalysts less stable is described.Be the regenerability of evaluate catalysts, reacted catalyzer has carried out in-situ regeneration by the regeneration condition of embodiment 1 in reactor, be cooled to 220 ℃ then.Under the identical reaction conditions before regeneration, the regenerated catalyzer is continued reaction again, conversion of ethylene is 98%, and ethylbenzene selectivity is 91.4%, and after reaction in 500 hours, its conversion of ethylene is 90% again, and ethylbenzene selectivity is 88.2%.Reaction proceeds to 150 hours, has just detected ethene in the reaction product, illustrates that the regenerability of catalyzer is relatively poor.
[comparative example 2]
Get the former powder of 50 gram sodium type beta-zeolite molecular sieves, its silica alumina ratio SiO
2/ Al
2O
3Be 25, the former powder of this sodium type beta-zeolite molecular sieve is exchanged with ammonium nitrate solution, after drying and the roasting, under the condition of 550 ℃ of normal pressures, handled 2 hours, the beta-zeolite molecular sieve of dealuminzation is again through the exchange of the ammonium nitrate solution under twice acidic conditions, the dealuminzation ammonium type beta-zeolite molecular sieve that obtains and aluminum oxide are mixed by 80/20 weight ratio, and obtaining diameter through extrusion, oven dry and roasting is 1.6 millimeters strip hydrogen type catalyst.
Get the above-mentioned catalyzer that makes 2 grams, be positioned in the fixed-bed reactor.220 ℃ of temperature, pressure 3.5MPa, benzene/ethylene molar ratio is 6/1, weight ethylene air speed 1.5 hours
-1Under the condition, conversion of ethylene is 99%, and ethylbenzene selectivity is 91.3%, and after reaction in 500 hours, its conversion of ethylene is 92%, and ethylbenzene selectivity is 89.7%.Reaction proceeds to 263 hours, has just detected ethene in the reaction product, and the activity of such catalysts less stable is described.Be the regenerability of evaluate catalysts, reacted catalyzer has carried out in-situ regeneration by the regeneration condition of embodiment 1 in reactor, be cooled to 220 ℃ then.Under the identical reaction conditions before regeneration, the regenerated catalyzer is continued reaction again, conversion of ethylene is 98%, and ethylbenzene selectivity is 90.6%, and after reaction in 500 hours, its conversion of ethylene is 90% again, and ethylbenzene selectivity is 89.5%.Reaction proceeds to 238 hours, has just detected ethene in the reaction product, illustrates that the regenerability of catalyzer is relatively poor.
[comparative example 3]
Get the former powder of 50 gram sodium type beta-zeolite molecular sieves, its silica alumina ratio SiO
2/ Al
2O
3Be 25, the former powder of this sodium type beta-zeolite molecular sieve is exchanged with ammonium nitrate solution, obtain ammonium type beta-zeolite molecular sieve after the oven dry, when ammonium type beta-zeolite molecular sieve mixes by 80/20 weight ratio with aluminum oxide, add a certain amount of ammonium fluoride, obtaining fluorine content through extrusion, oven dry and roasting is 3 (weight %), and diameter is 1.6 millimeters strip hydrogen type catalyst.
Get the above-mentioned catalyzer that makes 2 grams, be positioned in the fixed-bed reactor.220 ℃ of temperature, pressure 3.5MPa, benzene/ethylene molar ratio is 6/1, weight ethylene air speed 1.5 hours
-1Under the condition, conversion of ethylene is 100%, and ethylbenzene selectivity is 93.5%, and after reaction in 500 hours, its conversion of ethylene is 96%, and ethylbenzene selectivity is 92.2%.Reaction proceeds to 320 hours, has just detected ethene in the reaction product, and the activity of such catalysts less stable is described.Be the regenerability of evaluate catalysts, reacted catalyzer has carried out in-situ regeneration by the regeneration condition of embodiment 1 in reactor, be cooled to 220 ℃ then.Under the identical reaction conditions before regeneration, the regenerated catalyzer is continued reaction again, conversion of ethylene is 98%, and ethylbenzene selectivity is 93.1%, and after reaction in 500 hours, its conversion of ethylene is 93% again, and ethylbenzene selectivity is 90.4%.Reaction proceeds to 290 hours, has just detected ethene in the reaction product, illustrates that the regenerability of catalyzer is relatively poor.
[embodiment 2]
The diameter that makes according to embodiment 1 is 1.6 millimeters a strip hydrogen type catalyst, under 470 ℃ condition, with steam treatment 8 hours.Handled 7 hours down at 50 ℃ with the citric acid solution of 0.5 mol, the ratio of the weight of citric acid solution and catalyzer is 5 again, and dry back obtains finished catalyst 480 ℃ of following roastings 3 hours.
Get the above-mentioned catalyzer that makes 2 grams, be positioned in the fixed-bed reactor.220 ℃ of temperature, pressure 3.5MPa, benzene/ethylene molar ratio is 6/1, weight ethylene air speed 1.5 hours
-1Under the condition, conversion of ethylene is 100%, and ethylbenzene selectivity is 93.6%, and after reaction in 500 hours, its conversion of ethylene is 99%, and ethylbenzene selectivity is 92.7%.Reaction proceeds to 485 hours, has just detected ethene in the reaction product, illustrates that activity of such catalysts has good stability.Be the regenerability of evaluate catalysts, reacted catalyzer has carried out in-situ regeneration by the regeneration condition of embodiment 1 in reactor, be cooled to 220 ℃ then.Under the identical reaction conditions before regeneration, the regenerated catalyzer is continued reaction again, conversion of ethylene is 100%, and ethylbenzene selectivity is 93.6%, and after reaction in 500 hours, conversion of ethylene is 98% again, and ethylbenzene selectivity is 92.5%.Reaction proceeds to 481 hours, has just detected ethene in the reaction product.The regenerability that catalyzer is described is good, and reactivity worth can be recovered as before.
[embodiment 3]
The diameter that makes according to embodiment 1 is 1.6 millimeters a strip hydrogen type catalyst, under 470 ℃ condition, with steam treatment 8 hours.Handled 4 hours down at 50 ℃ with the citric acid solution of 1.0 mol, the ratio of the weight of citric acid solution and catalyzer is 5 again, and dry back obtains finished catalyst 480 ℃ of following roastings 3 hours.
Get the above-mentioned catalyzer that makes 2 grams, be positioned in the fixed-bed reactor.220 ℃ of temperature, pressure 3.5MPa, benzene/ethylene molar ratio is 6/1, weight ethylene air speed 1.5 hours
-1Under the condition, conversion of ethylene is 100%, and ethylbenzene selectivity is 93.8%, and after reaction in 500 hours, its conversion of ethylene is 99%, and ethylbenzene selectivity is 92.6%.Reaction proceeds to 480 hours, has just detected ethene in the reaction product, illustrates that activity of such catalysts has good stability.Be the regenerability of evaluate catalysts, reacted catalyzer has carried out in-situ regeneration by the regeneration condition of embodiment 1 in reactor, be cooled to 220 ℃ then.Under the identical reaction conditions before regeneration, the regenerated catalyzer is continued reaction again, conversion of ethylene is 100%, and ethylbenzene selectivity is 93.7%, and after reaction in 500 hours, conversion of ethylene is 98% again, and ethylbenzene selectivity is 92.4%.Reaction proceeds to 476 hours, has just detected ethene in the reaction product.The regenerability that catalyzer is described is good, and reactivity worth can be recovered as before.
[embodiment 4]
The diameter that makes according to embodiment 1 is 1.6 millimeters a strip hydrogen type catalyst, under 470 ℃ condition, with steam treatment 8 hours.Handled 2 hours down at 50 ℃ with the citric acid solution of 3.0 mol, the ratio of the weight of citric acid solution and catalyzer is 5 again, and dry back obtains finished catalyst 480 ℃ of following roastings 3 hours.
Get the above-mentioned catalyzer that makes 2 grams, be positioned in the fixed-bed reactor.220 ℃ of temperature, pressure 3.5MPa, benzene/ethylene molar ratio is 6/1, weight ethylene air speed 1.5 hours
-1Under the condition, conversion of ethylene is 100%, and ethylbenzene selectivity is 93.5%, and after reaction in 500 hours, its conversion of ethylene is 99%, and ethylbenzene selectivity is 92.4%.Reaction proceeds to 482 hours, has just detected ethene in the reaction product, illustrates that activity of such catalysts has good stability.Be the regenerability of evaluate catalysts, reacted catalyzer has carried out in-situ regeneration by the regeneration condition of embodiment 1 in reactor, be cooled to 220 ℃ then.Under the identical reaction conditions before regeneration, the regenerated catalyzer is continued reaction again, conversion of ethylene is 100%, and ethylbenzene selectivity is 93.7%, and after reaction in 500 hours, conversion of ethylene is 98% again, and ethylbenzene selectivity is 92.4%.Reaction proceeds to 479 hours, has just detected ethene in the reaction product.The regenerability that catalyzer is described is good, and reactivity worth can be recovered as before.
[embodiment 5]
The diameter that makes according to embodiment 1 is 1.6 millimeters a strip hydrogen type catalyst, under 520 ℃ condition, with steam treatment 6 hours.Handled 7 hours down at 50 ℃ with the tartaric acid solution of 0.5 mol, the ratio of the weight of citric acid solution and catalyzer is 5 again, and dry back obtains finished catalyst 480 ℃ of following roastings 3 hours.
Get the above-mentioned catalyzer that makes 2 grams, be positioned in the fixed-bed reactor.220 ℃ of temperature, pressure 3.5MPa, benzene/ethylene molar ratio is 6/1, weight ethylene air speed 1.5 hours
-1Under the condition, conversion of ethylene is 100%, and ethylbenzene selectivity is 94.3%, and after reaction in 500 hours, its conversion of ethylene is 97%, and ethylbenzene selectivity is 93.2%.Reaction proceeds to 450 hours, has just detected ethene in the reaction product, illustrates that activity of such catalysts has good stability.Be the regenerability of evaluate catalysts, reacted catalyzer has carried out in-situ regeneration by the regeneration condition of embodiment 1 in reactor, be cooled to 220 ℃ then.Under the identical reaction conditions before regeneration, the regenerated catalyzer is continued reaction again, conversion of ethylene is 100%, and ethylbenzene selectivity is 94.2%, and after reaction in 500 hours, conversion of ethylene is 97% again, and ethylbenzene selectivity is 93.1%.Reaction proceeds to 443 hours, has just detected ethene in the reaction product, illustrates that the regenerability of catalyzer is good, and reactivity worth can be recovered as before.
[embodiment 6]
The diameter that makes according to embodiment 1 is 1.6 millimeters a strip hydrogen type catalyst, under 550 ℃ condition, with steam treatment 4 hours.Handled 4 hours down at 90 ℃ with the acetum of 0.5 mol, the ratio of the weight of citric acid solution and catalyzer is 10 again, and dry back obtains finished catalyst 480 ℃ of following roastings 3 hours.
Get the above-mentioned catalyzer that makes 2 grams, be positioned in the fixed-bed reactor.220 ℃ of temperature, pressure 3.5MPa, benzene/ethylene molar ratio is 6/1, weight ethylene air speed 1.5 hours
-1Under the condition, conversion of ethylene is 100%, and ethylbenzene selectivity is 94.6%, and after reaction in 500 hours, its conversion of ethylene is 99%, and ethylbenzene selectivity is 93.5%.Reaction proceeds to 467 hours, has just detected ethene in the reaction product, illustrates that activity of such catalysts has good stability.Be the regenerability of evaluate catalysts, reacted catalyzer has carried out in-situ regeneration by the regeneration condition of embodiment 1 in reactor, be cooled to 220 ℃ then.Under the identical reaction conditions before regeneration, the regenerated catalyzer is continued reaction again, conversion of ethylene is 100%, and ethylbenzene selectivity is 94.5%, and after reaction in 500 hours, conversion of ethylene is 98% again, and ethylbenzene selectivity is 93.3%.Reaction proceeds to 463 hours, has just detected ethene in the reaction product, illustrates that the regenerability of catalyzer is good, and reactivity worth can be recovered as before.
[embodiment 7]
The diameter that makes according to embodiment 1 is 1.6 millimeters a strip hydrogen type catalyst, under 450 ℃ condition, with steam treatment 10 hours.Handled 15 hours down at 65 ℃ with the phthalic acid solution of 0.5 mol, the ratio of the weight of citric acid solution and catalyzer is 3 again, and dry back obtains finished catalyst 480 ℃ of following roastings 3 hours.
Get the above-mentioned catalyzer that makes 2 grams, be positioned in the fixed-bed reactor.220 ℃ of temperature, pressure 3.5MPa, benzene/ethylene molar ratio is 6/1, weight ethylene air speed 1.5 hours
-1Under the condition, conversion of ethylene is 100%, and ethylbenzene selectivity is 94.4%, and after reaction in 500 hours, its conversion of ethylene is 99%, and ethylbenzene selectivity is 93.7%.Reaction proceeds to 455 hours, has just detected ethene in the reaction product, illustrates that activity of such catalysts has good stability.Be the regenerability of evaluate catalysts, reacted catalyzer has carried out in-situ regeneration by the regeneration condition of embodiment 1 in reactor, be cooled to 220 ℃ then.Under the identical reaction conditions before regeneration, the regenerated catalyzer is continued reaction again, conversion of ethylene is 100%, and ethylbenzene selectivity is 94.0%, and after reaction in 500 hours, conversion of ethylene is 98% again, and ethylbenzene selectivity is 93.5%.Reaction proceeds to 450 hours, has just detected ethene in the reaction product, illustrates that the regenerability of catalyzer is good, and reactivity worth can be recovered as before.
[embodiment 8]
According to the catalyzer that each operation steps of embodiment 1 and condition preparation and examination make, change just that the weight ethylene air speed is 0.3 hour in the examination condition
-1, its result is: conversion of ethylene is 100%, ethylbenzene selectivity is 91.5%.Reaction proceeds to 500 hours, does not detect ethene in the reaction product yet, illustrates that catalyst stability is good, and the life-span is long.
[embodiment 9]
According to each operation steps of embodiment 1 and the catalyzer that condition prepares and examination makes, just change in the examination condition, temperature of reaction is 250 ℃, and reaction pressure is 3.0MPa, and benzene/ethylene molar ratio is 5, and the weight ethylene air speed is 0.3 hour
-1, its result is: conversion of ethylene is 100%, ethylbenzene selectivity is 90.8%.Reaction proceeds to 500 hours, does not detect ethene in the reaction product yet.
Claims (9)
1, a kind of method of ethene liquid-phase alkylation system ethylbenzene is a reaction raw materials with ethene and benzene, is 200～270 ℃ in temperature of reaction, and reaction pressure is 3.0～4.0MPa, and benzene/ethylene molar ratio is 3～10, and the weight ethylene air speed is 0.2～2.0 hour
-1Under the condition, reaction raw materials contacts with catalyzer liquid phase alkylation reaction generation ethylbenzene takes place, and used catalyzer contains 70～90% silica alumina ratio SiO by weight percentage
2/ Al
2O
3Be 10～50 β zeolite and 10～30% binding agent aluminum oxide or silicon-dioxide, it is characterized in that handling with steam-treated and organic acid successively before catalyzer uses, drying, roasting obtain required finished product then, wherein the steam-treated condition is used steam-treated 1～20 hour for being under 400～650 ℃ of conditions in normal pressure, temperature; The organic acid treatment condition are for being that the organic acid soln of 0.05～3.0 mol is to carry out acid treatment under 40～100 ℃ in temperature with concentration, and the time is 1～20 hour, and the weight ratio of organic acid soln and catalyzer is 1～20.
2, according to the method for the described ethene of claim 1 liquid-phase alkylation system ethylbenzene, it is characterized in that temperature of reaction is 220～250 ℃, reaction pressure is 3.0～3.5MPa, and benzene/ethylene molar ratio is 5～6, and the weight ethylene air speed is 0.3～1.5 hour
-1
3,, it is characterized in that the silica alumina ratio SiO of β zeolite according to the method for the described ethene of claim 1 liquid-phase alkylation system ethylbenzene
2/ Al
2O
3Be 20～40.
4,, it is characterized in that the steam-treated condition for being under 450～550 ℃ of conditions, with steam-treated 2～10 hours in normal pressure, temperature according to the method for the described ethene of claim 1 liquid-phase alkylation system ethylbenzene.
5,, it is characterized in that organic acid is selected from oxalic acid, toxilic acid, formic acid, acetic acid, hexanodioic acid, phthalic acid, terephthalic acid, succsinic acid, tartrate, oxysuccinic acid or citric acid according to the method for the described ethene of claim 1 liquid-phase alkylation system ethylbenzene.
6,, it is characterized in that organic acid is selected from citric acid according to the method for the described ethene of claim 5 liquid-phase alkylation system ethylbenzene.
7,, it is characterized in that organic acid concentration is 0.2～2.5 mol according to the method for the described ethene of claim 1 liquid-phase alkylation system ethylbenzene.
8,, it is characterized in that organic acid-treated temperature is 65～95 ℃ according to the method for the described ethene of claim 1 liquid-phase alkylation system ethylbenzene.
9,, it is characterized in that organic acid-treated time is 3～16 hours according to the method for the described ethene of claim 1 liquid-phase alkylation system ethylbenzene.
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|---|---|---|---|
| CNB021551146A CN1187299C (en) | 2002-12-17 | 2002-12-17 | Method for preparing ethylbenzene by liquid phase alkylation of ethylene |
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| CNB021551146A CN1187299C (en) | 2002-12-17 | 2002-12-17 | Method for preparing ethylbenzene by liquid phase alkylation of ethylene |
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| CN1187299C CN1187299C (en) | 2005-02-02 |
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| CN102872899A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Catalyst for preparation of ethylbenzene by ethanol and benzene vapor-phase alkylation |
| CN102875315A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene by ethanol and benzene vapor-phase alkylation |
| CN102872900A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Catalyst for dry gas and benzene alkylation to prepare ethylbenzene |
| CN105566050A (en) * | 2014-10-13 | 2016-05-11 | 中国石油化工股份有限公司 | Method for producing ethylbenzene from ethylene and benzene |
| CN115475653A (en) * | 2021-06-16 | 2022-12-16 | 中国石油化工股份有限公司 | Benzene and ethanol gas phase alkylation catalyst and preparation method and application thereof |
| CN115518672A (en) * | 2021-06-24 | 2022-12-27 | 中国石油化工股份有限公司 | Regenerated catalyst powder and alkaline substance treating agent containing same |
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2002
- 2002-12-17 CN CNB021551146A patent/CN1187299C/en not_active Expired - Lifetime
Cited By (9)
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| CN102872899A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Catalyst for preparation of ethylbenzene by ethanol and benzene vapor-phase alkylation |
| CN102875315A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene by ethanol and benzene vapor-phase alkylation |
| CN102872900A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Catalyst for dry gas and benzene alkylation to prepare ethylbenzene |
| CN102875315B (en) * | 2011-07-11 | 2015-12-09 | 中国石油化工股份有限公司 | The method of ethanol and benzene producing ethyl benzene through alkylation in gas phase |
| CN105566050A (en) * | 2014-10-13 | 2016-05-11 | 中国石油化工股份有限公司 | Method for producing ethylbenzene from ethylene and benzene |
| CN115475653A (en) * | 2021-06-16 | 2022-12-16 | 中国石油化工股份有限公司 | Benzene and ethanol gas phase alkylation catalyst and preparation method and application thereof |
| CN115475653B (en) * | 2021-06-16 | 2024-03-29 | 中国石油化工股份有限公司 | Benzene and ethanol gas phase alkylation catalyst and preparation method and application thereof |
| CN115518672A (en) * | 2021-06-24 | 2022-12-27 | 中国石油化工股份有限公司 | Regenerated catalyst powder and alkaline substance treating agent containing same |
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