CN1194944C - Catalyst for liquid phase alkylation of ethylene to prepare ethylbenzene - Google Patents
Catalyst for liquid phase alkylation of ethylene to prepare ethylbenzene Download PDFInfo
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- CN1194944C CN1194944C CNB021511772A CN02151177A CN1194944C CN 1194944 C CN1194944 C CN 1194944C CN B021511772 A CNB021511772 A CN B021511772A CN 02151177 A CN02151177 A CN 02151177A CN 1194944 C CN1194944 C CN 1194944C
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The present invention relates to a catalyst used for preparing ethylbenzene by liquid phase alkylation of ethylene. The present invention mainly solves the problems of poor catalyst stability and poor reproducing performance of catalysts in liquid phase alkylation reaction of benzene and ethylene in the prior art. Beta-zeolite molecular sieves whose silica alumina ratio SiO2/Al2O3 is from 10 to 50 are adopted as catalysts, the catalysts are treated by high temperature water vapor before being used, and then the catalysts are treated by organic acid. The problems of the prior art are solved, and the present invention can be used for the industrial production of preparing ethylbenzene by liquid phase alkylation.
Description
Technical field
The present invention relates to a kind of catalyzer that is used for ethene liquid-phase alkylation system ethylbenzene, particularly about being used for the beta-zeolite molecular sieve catalyst of 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, US3751506, US4016218 and US4547605 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-molecular sieve catalyzer synthesizing ethyl benzene under the liquid phase alkylation reaction condition.Later studies show that, there is a significant disadvantage in unmodified beta-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-molecular sieve catalyzer liquid-phase alkylation that adopts the steam treatment modification produces the method for ethylbenzene.Though have good transformation efficiency in the document, ethylbenzene selectivity descends very fast, and does not relate to catalyzer.
Summary of the invention
Technical problem to be solved by this invention is to exist in benzene and the ethene liquid phase alkylation reaction in the document in the past, and the problem of catalyst stability and regenerability difference provides a kind of new catalyzer that is used for ethene liquid-phase alkylation system ethylbenzene.This catalyzer 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 catalyzer that is used for ethene liquid-phase alkylation system ethylbenzene, contain 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, wherein catalyzer is handled with steam-treated and organic acid successively, 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 silica alumina ratio SiO of β zeolite
2/ Al
2O
3Be 20～40, 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, and 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 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, therefore the water repelling property of catalyzer and regenerability have been 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 catalyzer of the present invention 220 ℃ of temperature, pressure 3.5MPa, benzene/ethylene molar ratio is 6/1, weight ethylene air speed 1.5 hours
-1Under the condition, through reaction in 500 hours, its conversion of ethylene was 98～100%, and ethylbenzene selectivity is 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.
Claims (9)
1, a kind of catalyzer that is used for ethene liquid-phase alkylation system ethylbenzene 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 catalyzer is successively with steam-treated and organic acid processing, 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,, it is characterized in that the silica alumina ratio SiO of β zeolite according to the described catalyzer that is used for ethene liquid-phase alkylation system ethylbenzene of claim 1
2/ Al
2O
3Be 20～40.
3,, 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 described catalyzer that is used for ethene liquid-phase alkylation system ethylbenzene of claim 1.
4,, 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 described catalyzer that is used for ethene liquid-phase alkylation system ethylbenzene of claim 1.
5, according to the described catalyzer that is used for ethene liquid-phase alkylation system ethylbenzene of claim 4, it is characterized in that organic acid is selected from citric acid.
6,, it is characterized in that organic acid concentration is 0.2～2.5 mol according to the described catalyzer that is used for ethene liquid-phase alkylation system ethylbenzene of claim 1.
7,, it is characterized in that organic acid-treated temperature is 65～95 ℃ according to the described catalyzer that is used for ethene liquid-phase alkylation system ethylbenzene of claim 1.
8,, it is characterized in that organic acid-treated time is 3～16 hours according to the described catalyzer that is used for ethene liquid-phase alkylation system ethylbenzene of claim 1.
9, according to the described catalyzer that is used for ethene liquid-phase alkylation system ethylbenzene of claim 1, the weight ratio that it is characterized in that organic acid soln and catalyzer is 2～10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021511772A CN1194944C (en) | 2002-12-11 | 2002-12-11 | Catalyst for liquid phase alkylation of ethylene to prepare ethylbenzene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021511772A CN1194944C (en) | 2002-12-11 | 2002-12-11 | Catalyst for liquid phase alkylation of ethylene to prepare ethylbenzene |
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| Publication Number | Publication Date |
|---|---|
| CN1506340A CN1506340A (en) | 2004-06-23 |
| CN1194944C true CN1194944C (en) | 2005-03-30 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11434183B2 (en) | 2018-07-23 | 2022-09-06 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Catalyst for preparing ethylbenzene from ethanol and benzene, preparation therefor and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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2002
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11434183B2 (en) | 2018-07-23 | 2022-09-06 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Catalyst for preparing ethylbenzene from ethanol and benzene, preparation therefor and use thereof |
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