CN1268402A - Catalyst for producing ethylbenzene and its preparation method - Google Patents

Catalyst for producing ethylbenzene and its preparation method Download PDF

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Publication number
CN1268402A
CN1268402A CN99113574A CN99113574A CN1268402A CN 1268402 A CN1268402 A CN 1268402A CN 99113574 A CN99113574 A CN 99113574A CN 99113574 A CN99113574 A CN 99113574A CN 1268402 A CN1268402 A CN 1268402A
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Prior art keywords
benzene
catalyzer
ethylene
ethylbenzene
ethene
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CN1110364C (en
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杨为民
孙洪敏
杨书江
陆敏侠
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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention relates to a catalyst in the production of ethylbenzene and its preparation method. It uses ZSM-5 zeolite catalyst to proceed steam treatment and catalyst pre-carbon deposition 0.2-5% (wt) so that the following 4 requirements are achieved; high ethylene conversion rate, high ethyl benzene plus diethyl benzene selectivity, good stability of catalyst and low dimethyl benzene content in the product. It can be used in industrial production.

Description

Be used to produce the Catalysts and its preparation method of ethylbenzene
The present invention relates to be used for the Catalysts and its preparation method that benzene alkylation with ethylene is produced ethylbenzene.
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 wherein having obtained great commercial a kind of method is in the presence of a kind of solid acid ZSM-5 zeolite catalyst, with ethene benzene is carried out vapor-phase alkylation.Use unmodified ZSM-5 zeolite as benzene and the alkylating catalyzer of ethene gas phase among early stage U.S. Pat 3751504 and the US3751506.Studies show that afterwards, unmodified ZSM-5 molecular sieve has three significant disadvantage as the catalyzer of synthesizing ethyl benzene: the catalyzer life cycle is short, and it is lower that ethylbenzene adds the diethylbenzene selectivity, by product xylene content height.For this reason, domestic and international many investigators have successively proposed multiple method to the ZSM-5 Zeolite modifying, to overcome the above-mentioned shortcoming of unmodified ZSM-5 zeolite in the synthesizing ethyl benzene reaction.Wherein representational method of modifying is as follows: US3962364 has introduced a kind of catalyzer that the ZSM-5 zeolite is carried out modification with phosphoric.By modification, catalyzer has obtained certain raising to the selectivity of benzene and ethylene reaction and the stability of catalyzer, but its conversion of ethylene the highest still be 98%, the selectivity that ethylbenzene adds diethylbenzene is up to 98.99%.Ethylbenzene adds the selectivity of diethylbenzene when introduce adopting steam-treated to improve catalyzer among the US4016218 to be used to react, and its selectivity can reach 99.5%, but does not relate to conversion of ethylene and catalyst stability problem.Introduce a kind of benzene alkylation with ethylene among the Chinese patent CN1074392A and produced the ZSM-5 zeolite catalyst of ethylbenzene.Adopt the rare-earth lanthanum oxide modified catalyst of 0.2～3.0% (weight) in this patent, when being used for the benzene alkylation with ethylene reaction, its conversion of ethylene and ethylbenzene add the diethylbenzene selectivity and all can reach more than 99%, and catalyzer has stability preferably.The content that does not all relate to by product dimethylbenzene in the product in above-mentioned three pieces of documents, Gong Ye demand is that the requirement catalyzer has the selectivity that better stability and higher conversion of ethylene and ethylbenzene add diethylbenzene in addition, and requires the by product xylene content low.
One of purpose of the present invention is in order to overcome in the conventional art, do not relate to by-product xylene content and conversion of ethylene and benzene and add the relatively low and stable not too high shortcoming of diethylbenzene selectivity, a kind of new catalyzer that is used for benzene alkylation with ethylene production ethylbenzene is provided, this catalyzer has high conversion of ethylene and ethylbenzene adds the diethylbenzene selectivity, have satisfactory stability simultaneously, particularly have the low characteristics of by product xylene content in the product.
Two of purpose of the present invention provides one of a kind of acquisition above-mentioned purpose Preparation of catalysts method, adapts with one of purpose.
One of purpose of the present invention is to realize by following technical scheme: a kind of catalyzer that is used for benzene alkylation with ethylene production ethylbenzene, contain following composition by weight percentage:
A) 50～70% silica alumina ratio SiO 2/ Al 2O 3It is 30～250 ZSM-5 zeolite;
B) 29～49% binding agent silicon-dioxide or aluminum oxide;
C) 0.2～5% carbon.
In the technique scheme, the preferable range of carbon amount is 0.2～3.0% by weight percentage, also can contain 0.1～5% in addition by weight percentage and be selected from phosphorus or/and the oxide compound of lanthanum in catalyzer.
Two of purpose of the present invention is to realize by following technical scheme: a kind of one of above-mentioned purpose Preparation of catalysts method that is used for, carry out according to the following steps:
(1) with the phosphorus of Hydrogen ZSM-5 zeolite, binding agent and non-imposed adding or the oxide compound mixing moulding of lanthanum, roasting under 500～650 ℃ of conditions;
(2) with above-mentioned forming composition under 400～650 ℃ of conditions, with steam-treated 1～20 hour;
(3) through the forming composition of above-mentioned processing, under 370～480 ℃ of conditions, carry out pre-carbon distribution with the mixture of benzene and ethene and handle, the deposition that makes carbon is 0.2～5% by weight percentage.
In the technique scheme, when pre-carbon distribution was handled, the mixture of benzene and ethene is with molar ratio computing benzene: ethene was 0.2～0.95, and its preferable range is 0.6～0.8.
Adopt steam-treated can make the α value drop to a certain value gradually among the present invention, and this α value is can be basically identical or lower with the α value of the catalyzer of unprocessed mistake from high value.It is acid active that alkylated reaction between benzene and the ethene requires alkylation catalyst to have, thereby catalyzer can have usually than higher α value.Have be not less than about 10 for example 40 or higher α value be typical, and have found that it also is useful that the α value is higher than 100 catalyzer in this reaction.The α value of zeolite is to compare with standard catalyst, is the active a kind of roughly symbol of catalyst cracking (acidity).It is with the α value of highly active sial catalyst for cracking as 1 (rate constant=0.016 second -1) be the relative rate constant of benchmark.Too high activity can since side reaction aggravate to produce and do not wish the by product dimethylbenzene that obtains.Because this reason, so 10～100 α value is normally comparatively suitable, although higher α value, for example 100～500 also is to use.
Generate in the alkylated reaction of ethylbenzene at benzene and ethene, the productive rate of many ethylbenzene and other by product normally reduces along with the increase of temperature.When temperature surpassed 480 ℃, the content of dimethylbenzene can increase, and therefore general temperature of reaction is controlled at 370～480 ℃.Benzene should be 1: 1 with the theoretical molar ratio of ethylene reaction, help generating purpose product ethylbenzene but benzene is excessive, so the material molar ratio of reaction usually all is that benzene/ethene is greater than 1.When benzene/ethylene molar ratio less than 1 the time, at high temperature will cause the raw material carbonization, form carbon deposits.Find after deliberation, in catalyzer, contain the generation that a certain amount of deposit carbon helps suppressing by product dimethylbenzene, has satisfactory stability simultaneously, can cause the carbon excess deposition too much but ethene is excessive, influence the catalyzer duct, thereby influence catalytic activity and selectivity, so benzene: the mol ratio of ethene should be controlled, generally be controlled between 0.2～0.95, better scope is 0.6～0.8, and the deposition that guarantees carbon like this is 0.2～5% by weight percentage.
Owing to adopt steam-treated, changed the acidity of ZSM-5 zeolite catalyst among the present invention, removed a part of strong acid center aluminium in the catalyzer, reduced strong acid center, the generation that helps improving selectivity and reduce by product dimethylbenzene.Use the carbon laydown method, the pore structure of having regulated the ZSM-5 zeolite catalyst has improved product ethylbenzene equally and has added the diethylbenzene selectivity, has reduced the content of dimethylbenzene, has increased the stability of catalyzer, has prolonged the work-ing life of catalyzer.Use catalyzer of the present invention 420 ℃ of temperature of reaction, reaction pressure 1.5MPa, benzene/ethylene molar ratio is 7: 1, weight ethylene air speed 2.5 hours -1Under the condition, example preferably, its conversion of ethylene is 99.8%, it is 99.8% that ethylbenzene adds the diethylbenzene selectivity, and xylene content only is 600PPm in the reaction product, under accelerated ageing conditions, its catalyst deactivation rate only is 0.07% per hour, has obtained effect preferably.
The present invention is further elaborated below by embodiment.[embodiment 1]
To be mixed with 2 millimeters extrusion HZSM-5 (SiO of 35% (weight) alumina binder 2/ Al 2O 3=80 moles/mole) zeolite 10 grams were handled 2 hours at 500 ℃ with water vapor.Material benzene after will handling again: ethylene molar ratio is 0.8 mixture, under 420 ℃ and normal pressure, presses the weight space velocity 22.4 hours of benzene -1Handled 1.5 hours.Obtain the catalyst A that coke content is 1% (weight), the α value of this catalyzer is 80.[comparative example 1]
To be mixed with 2 millimeters extrusion HZSM-5 zeolites, 10 grams of 35% (weight) alumina binder, and handle 2 hours 50 minutes at 500 ℃ with water vapor, and make catalyst B, the α value of this catalyzer is 80.[comparative example 2]
To be mixed with 2 millimeters extrusion HZSM-5 zeolites, 10 grams of 35% (weight) alumina binder, handle 2 hours at 500 ℃ with water vapor.With the material after handling, again with 0.6 gram La (NO 3) 36H 2O is dissolved in the solution impregnation of 30 ml waters, drying, and 500 ℃ of roastings 10 hours, final catalyzer contained the lanthanum that 2% (weight) exists with the lanthanum trioxide form.The α value of this catalyzer C is 80.[comparative example 3]
To be mixed with 2 millimeters extrusion HZSM-5 zeolites, 10 grams of 35% (weight) alumina binder, with 0.7 gram (NH 4) 2HPO 4Be dissolved in the solution impregnation of 20 ml waters, drying about 15 hours of 500 ℃ of following roastings, makes catalyzer D, and the P that this catalyzer contains the oxidation state existence is 6% (weight), and its α value is 80.[embodiment 2]
On the pressurization static bed reaction unit of continuous flow, carry out the process that benzene and ethene vapor-phase alkylation are produced ethylbenzene.Evaluate catalysts A～D carries out the activity and the selectivity of alkylated reaction.Reaction conditions: 420 ℃ of temperature of reaction, reaction pressure 1.5MPa, benzene/ethene=7: 1 (moles/mole), ethene WHSV=2.5 hour -1, reaction result sees Table 1.As seen with the catalyzer of method of modifying preparation of the present invention, its ethylbenzene adds the diethylbenzene selectivity can reach 99.8% by table 1, and dimethylbenzene impurity only is 600PPm with respect to the content of ethylbenzene simultaneously.
Table 1
Catalyzer Conversion of ethylene, % Ethylbenzene adds diethylbenzene selectivity, % Dimethylbenzene/ethylbenzene, PPm
????A ???????99.8 ??????????99.8 ???????600
????B ???????99.8 ??????????99.2 ???????1500
????C ???????99.8 ??????????99.5 ???????1200
????D ???????99.8 ??????????98.5 ???????3000
[embodiment 3]
On the pressurization static bed reaction unit of continuous flow, the activity stability of evaluate catalysts A～D in alkylated reaction, i.e. catalyst life.For in the relatively shorter time, the comparative lifetime that compares different catalysts has adopted following catalysis aging condition: 420 ℃ of temperature of reaction, reaction pressure 0.5MPa, benzene: ethene (moles/mole)=2: 1, ethene WHSV=4 hour -1, the results are shown in Table 2.
Table 2
Catalyzer Initial conversion of ethylene, % 100 hours conversion of ethylene, % Per hour average deactivation rate, %
????A ??????90 ??????????83 ?????????0.07
????B ??????91 ??????????79 ?????????0.12
????C ??????89 ??????????80 ?????????0.09
????D ??????92 ??????????70 ?????????0.22
As seen catalyst A of the present invention has minimum deactivation rate, shows that it has best activity stability.[embodiment 4]
Under the operational condition of full scale plant (reaction conditions is with embodiment 2), on the continuous flow fixed bed reactor of computer controlled automatic, the alkylation properties of evaluate catalysts A sees Table 3.
Table 3
Reaction times, hour Conversion of ethylene, % Ethylbenzene adds diethylbenzene selectivity, % Dimethylbenzene/ethylbenzene, PPm
????0～300 ?????99.8 ?????????99.8 ???????600
????300～700 ?????99.8 ?????????99.9 ???????550
????700～1000 ?????99.7 ?????????99.9 ???????500
The above results shows that catalyst A has high reactivity, highly selective and long life-span in the benzene alkylation with ethylene reaction.[embodiment 5]
To be mixed with 2 millimeters extrusion HZSM-5 (SiO of 35% (weight) alumina binder 2/ Al 2O 3=80 moles/mole) zeolite 10 gram was handled 4 hours at 450 ℃ with water vapor, and then use benzene: ethylene molar ratio is 0.95 mixture, 480 ℃ with normal pressure under, press the weight space velocity 22.4 hours of benzene -1Handled 6 hours, obtaining coke content is the catalyzer E of 5% (weight).[embodiment 6]
To be mixed with 2 millimeters extrusion HZSM-5 (SiO of 35% (weight) alumina binder 2/ Al 2O 3=40 moles/mole) zeolite 10 gram, use benzene earlier: ethylene molar ratio is 0.2 mixture, 370 ℃ with normal pressure under, press the weight space velocity 22.4 hours of benzene -1Handled 0.5 hour, and then handled 0.5 hour at 950 ℃ with water vapor, obtaining coke content is the catalyzer F of 0.2% (weight).[embodiment 7]
To be mixed with 2 millimeters extrusion HZSM-5 (SiO of 35% (weight) alumina binder 2/ Al 2O 3=40 moles/mole) zeolite 10 grams were handled 1 hour at 700 ℃ with water vapor, and then use benzene: ethylene molar ratio is 0.6 mixture, handled 0.6 hour with normal pressure at 450 ℃, and obtaining coke content is the catalyzer G of 3.0% (weight).[embodiment 8]
To be mixed with 2 millimeters extrusion HZSM-5 (SiO of 35% (weight) alumina binder 2/ Al 2O 3=160 moles/mole) zeolite 10 gram, use benzene earlier: ethylene molar ratio is 0.8 mixture, processing is 1.0 hours under 420 ℃ and normal pressure, after use (NH again 4) 2HPO 4Solution impregnation, oven dry, roasting in 500 ℃ of nitrogen was then handled 1 hour at 500 ℃ with water vapor, obtained containing coke 0.7% (weight), contained P 2O 5The catalyzer H of 2% (weight).[embodiment 9]
Under the reaction conditions identical with embodiment 2, investigated activity and the selectivity of catalyzer E～H in alkylated reaction, and investigated deactivation rate with the condition of embodiment 3, it the results are shown in Table 4.
Table 4
Catalyzer Conversion of ethylene % Ethylbenzene adds diethylbenzene selectivity, % Dimethylbenzene/ethylbenzene PPm Deactivation rate % hour -1
????E ?????99.6 ?????99.7 ??????860 ????0.085
????F ?????99.8 ?????99.6 ??????770 ????0.080
????G ?????99.7 ?????99.8 ??????650 ????0.072
????H ?????99.8 ?????99.6 ??????730 ????0.077

Claims (6)

1, a kind of catalyzer that is used for benzene alkylation with ethylene production ethylbenzene, contain following composition by weight percentage:
A) 50～70% silica alumina ratio SiO 2/ Al 2O 3It is 30～250 ZSM-5 zeolite;
B) 29～49% binding agent silicon-dioxide or aluminum oxide;
C) 0.2～5% carbon.
2, according to the described catalyzer that is used for benzene alkylation with ethylene production ethylbenzene of claim 1, it is characterized in that the amount of carbon is 0.2～3.0% by weight percentage.
3, according to the described catalyzer that is used for benzene alkylation with ethylene production ethylbenzene of claim 1, it is characterized in that also containing by weight percentage in the catalyzer 0.1～5% and be selected from phosphorus or/and the oxide compound of lanthanum.
4, produce ethylbenzene Preparation of catalysts method according to the described benzene alkylation with ethylene that is used for of claim 1, carry out according to the following steps:
(1) with the phosphorus of Hydrogen ZSM-5 zeolite, binding agent and non-imposed adding or the oxide compound mixing moulding of lanthanum, roasting under 500～650 ℃ of conditions;
(2) with above-mentioned forming composition under 400～650 ℃ of conditions, with steam-treated 1～20 hour;
(3) through the forming composition of above-mentioned processing, under 370～480 ℃ of conditions, carry out pre-carbon distribution with the mixture of benzene and ethene and handle, the deposition that makes carbon is 0.2～5% by weight percentage.
5, produce ethylbenzene Preparation of catalysts method according to the described benzene alkylation with ethylene that is used for of claim 4, the mixture that it is characterized in that benzene and ethene when pre-carbon distribution is handled is with molar ratio computing benzene: ethene is 0.2～0.95.
6, produce ethylbenzene Preparation of catalysts method according to the described benzene alkylation with ethylene that is used for of claim 5, the mixture that it is characterized in that benzene and ethene when pre-carbon distribution is handled is with molar ratio computing benzene: ethene is 0.6～0.8.
CN99113574A 1999-03-30 1999-03-30 Catalyst for producing ethylbenzene and its preparation method Expired - Lifetime CN1110364C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100532506C (en) * 2001-11-16 2009-08-26 弗纳技术股份有限公司 Alkylation catalyst carried on silica
CN101993331A (en) * 2009-08-31 2011-03-30 中国石油化工股份有限公司上海石油化工研究院 Method for preparing ethylbenzene by alkylating pure ethylene or dry gas and benzene
CN104726131A (en) * 2015-03-17 2015-06-24 东南大学 Device and method for increasing hydrocarbon productivity employing catalyst and pre-deposit carbon
CN107537549A (en) * 2017-08-24 2018-01-05 中国烟草总公司郑州烟草研究院 A kind of zeolite molecular sieve catalyst and its application

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100532506C (en) * 2001-11-16 2009-08-26 弗纳技术股份有限公司 Alkylation catalyst carried on silica
CN101993331A (en) * 2009-08-31 2011-03-30 中国石油化工股份有限公司上海石油化工研究院 Method for preparing ethylbenzene by alkylating pure ethylene or dry gas and benzene
CN101993331B (en) * 2009-08-31 2013-06-05 中国石油化工股份有限公司 Method for preparing ethylbenzene by alkylating pure ethylene or dry gas and benzene
CN104726131A (en) * 2015-03-17 2015-06-24 东南大学 Device and method for increasing hydrocarbon productivity employing catalyst and pre-deposit carbon
CN104726131B (en) * 2015-03-17 2016-06-08 东南大学 The pre-carbon distribution of a kind of catalyst increases the apparatus and method of hydro carbons productivity
CN107537549A (en) * 2017-08-24 2018-01-05 中国烟草总公司郑州烟草研究院 A kind of zeolite molecular sieve catalyst and its application

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