CN1114493C - Catalyst and process for prodn. of alkyl benzene - Google Patents

Catalyst and process for prodn. of alkyl benzene Download PDF

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Publication number
CN1114493C
CN1114493C CN99113813A CN99113813A CN1114493C CN 1114493 C CN1114493 C CN 1114493C CN 99113813 A CN99113813 A CN 99113813A CN 99113813 A CN99113813 A CN 99113813A CN 1114493 C CN1114493 C CN 1114493C
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catalyst
zeolite
propylene
reaction
benzene
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CN1287885A (en
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方永成
周斌
戴德斌
江桂秀
熊瑾�
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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

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Abstract

The present invention relates to a catalyst and a method thereof for producing alkyl benzene. The method mainly overcomes the defects that the existing catalysts have poor stability, short regeneration period and low air speed for usage. The present invention uses a technology in which catalysts for platinum are loaded on zeolites and react under the conditions of liquid phase, the reaction temperature interval from 150 to 250 DEG C, and the reaction pressure range from 0.7 to 4.0MPa, so that the problems are well solved. Therefore, the present invention can be used in producing alkylbenzene.

Description

Be used to produce the catalyst and the method thereof of alkylbenzene
The present invention relates to the method that is used to produce the catalyst of alkylbenzene and adopts this Catalyst Production alkylbenzene, more particularly, the present invention relates to the zeolite catalyst of carried metal palladium and adopt it to produce the method for alkylbenzene.
Isopropylbenzene is a kind of important Organic Chemicals, belongs to the substituted arene compound.It is a main intermediate compound of producing phenol, acetone and AMS, also is simultaneously the auxiliary element as aviation gasoline, to increase the octane number of gasoline.The catalyst of propylene and benzene synthesizing iso-propylbenzene has multiple, traditional catalyst that crystallization and noncrystalline silica, boron fluoride, aluminium oxide and phosphoric acid, alchlor and solid phosphoric acid catalyst are arranged.All there are shortcomings such as seriously corroded, equipment investment is big, the three wastes are many in these conventional catalyst technologies.In recent years, deep day by day along with molecular sieve research, people are conceived to develop the new technology that zeolite catalyst is produced isopropylbenzene.Reported the new technology of utilizing the y-type zeolite molecular sieve to produce isopropylbenzene among the patent documentation EP0272830.This patented technology has overcome the deficiency of using traditional catalyst to exist, but also there is the poor stability of catalyst in it, the regeneration period short (just needed in 700 hours for example driving regeneration); Reaction velocity is low (for example in propylene air speed 0.10hr only -1), shortcoming such as plant capacity is low.
One of purpose of the present invention is the shortcoming that has poor catalyst stability in the above-mentioned document in order to overcome, and a kind of new catalyst that is used to produce alkylbenzene is provided, and this catalyst has the characteristics of good stability.
Two of purpose of the present invention is short in order to overcome in the above-mentioned document regeneration period, and the shortcoming that reaction velocity is low provides a kind of new method that is used to produce alkylbenzene, and this method has production capacity and can improve, the characteristics that the catalyst regeneration cycle is long.
One of purpose of the present invention is to realize by following technical scheme: a kind of catalyst that is used to produce alkylbenzene, form by following component:
A) silica alumina ratio is 2～20 zeolite and is stated from the zeolite;
B) be 0.008～0.045% Metal Palladium by weight percentage.
The silica alumina ratio of technique scheme mesolite is 2～8, and zeolite is Y zeolite, β zeolite, modenite or ZSM-5 zeolite, and its preferred version is the Y zeolite, and alkylbenzene is ethylbenzene or isopropylbenzene.
Two of purpose of the present invention is to realize by following technical scheme: a kind of method that is used to produce alkylbenzene, with propylene or ethene and benzene is raw material, in reaction temperature is 150～250 ℃, reaction pressure is 0.7～4.0MPa, benzene/olefin molar ratio is that liquid phase is synthetic under 4～20 conditions, and catalyst system therefor is made up of following component:
A) silica alumina ratio is 2～20 zeolite and is stated from the zeolite;
B) be 0.008～0.045% Metal Palladium by weight percentage.
The reaction temperature preferred version is 180～210 ℃ in the technique scheme, and the reaction pressure preferred version is 2.0～3.5MPa.
Catalyst of the present invention can prepare as follows:
A) with silica alumina ratio be 2～20 zeolite with acid, ammonium salt exchange, make the content of sodium metal ion in zeolitic frameworks below 0.1% (weight), then oven dry;
B) impregnating metal palladium on zeolite.
The acid and the ammonium salt that are used to handle zeolite can be acid commonly used and ammonium salt, for example hydrochloric acid, nitric acid or phosphoric acid etc., and ammonium chloride, ammonium sulfate or ammonium phosphate etc.
Method of the present invention is carried out in the fixed bed mode usually.
The present invention is 0.008～0.045% Metal Palladium by weight percentage by load on zeolite, suppressed the carbon distribution that reaction mass generates at the catalyst surface dehydrocyclization effectively, thereby improved the reaction stability of catalyst, prolonged the regeneration period of catalyst.Use catalyst of the present invention that the hydrogenation reaction of raw material olefin does not take place in course of reaction in addition, by using two the technical scheme that realizes purpose, making reaction mass is 2.0 hours in weight liquid air speed -1Reaction is 1000 hours under the condition, uses Y or β zeolite, does not detect propylene or ethene in its product, and activity of such catalysts, selectivity do not descend, and have obtained effect preferably.The reaction mechanism inventor of the present invention still is difficult to get across at present.
The invention will be further elaborated below by embodiment.
[embodiment 1]
Getting 100 gram silica alumina ratios is 5.0 NaY type zeolite powder, with the hydrochloric acid exchange, with the ammonium chloride exchange, makes the Na in the zeolite again +Ion concentration is less than 0.1% (weight).Will be through the zeolite PdCl of above-mentioned processing 2Solution impregnation makes that Metal Palladium content is 0.003% (weight) in the catalyst, after oven dry, the roasting, grinds evenly.Is that 90: 10 amount is mediated with the zeolite of carried metal palladium and aluminium oxide with weight ratio, and pressure forming is the shape of 1.6 millimeters of φ.
[embodiment 2]
Getting 100 gram silica alumina ratios is 5.0 NaY type zeolite powder, with the hydrochloric acid exchange, with the ammonium chloride exchange, makes the Na in the zeolite again +Ion concentration is less than 0.1% (weight).Will be through the zeolite PdCl of above-mentioned processing 2Solution impregnation makes that Metal Palladium content is 0.02% (weight) in the catalyst, after oven dry, the roasting, grinds evenly.Is that 90: 10 amount is mediated with the zeolite of carried metal palladium and aluminium oxide with weight ratio, and pressure forming is the shape of 1.6 millimeters of φ.
[embodiment 3]
Getting 100 gram silica alumina ratios is 5.0 NaY type zeolite powder, with the hydrochloric acid exchange, with the ammonium chloride exchange, makes the Na in the zeolite again +Ion concentration is less than 0.1% (weight).Will be through the zeolite PdCl of above-mentioned processing 2Solution impregnation makes that Metal Palladium content is 0.008% (weight) in the catalyst, after oven dry, the roasting, grinds evenly.Is that 90: 10 amount is mediated with the zeolite of carried metal palladium and aluminium oxide with weight ratio, and pressure forming is the shape of 1.6 millimeters of φ.
[embodiment 4]
Getting 100 gram silica alumina ratios is 5.0 NaY type zeolite powder, with the hydrochloric acid exchange, with the ammonium chloride exchange, makes the Na in the zeolite again +Ion concentration is less than 0.1% (weight).Will be through the zeolite PdCl of above-mentioned processing 2Solution impregnation makes that Metal Palladium content is 0.045% (weight) in the catalyst, after oven dry, the roasting, grinds evenly.The zeolite and the aluminium oxide of carried metal palladium are mediated with 90: 10 amount of weight ratio, and pressure forming is the shape of 1.6 millimeters of φ.
[embodiment 5]
Getting 100 gram silica alumina ratios is 14.0 the former powder of zeolite beta, with the hydrochloric acid exchange, with the ammonium chloride exchange, makes the Na in the zeolite again +Ion concentration is less than 0.1% (weight).Will be through the zeolite PdCl of above-mentioned processing 2Solution impregnation makes that Metal Palladium content is 0.035% (weight) in the catalyst, after oven dry, the roasting, grinds evenly.The zeolite and the aluminium oxide of carried metal palladium are mediated with 90: 10 amount of weight ratio, and pressure forming is the shape of 1.6 millimeters of φ.
[embodiment 6]
Getting 100 gram silica alumina ratios is 20.0 ZSM-type zeolite powder, with the hydrochloric acid exchange, with the ammonium chloride exchange, makes the Na in the zeolite again +Ion concentration is less than 0.1% (weight).Will be through the zeolite PdCl of above-mentioned processing 2Solution impregnation makes that Metal Palladium content is 0.03% (weight) in the catalyst, after oven dry, the roasting, grinds evenly.The zeolite and the aluminium oxide of carried metal palladium are mediated with 90: 10 amount of weight ratio, and pressure forming is the shape of 1.6 millimeters of φ.
[embodiment 7]
Catalyst 21 grams of getting embodiment 1 place fixed bed reactors, under 210 ℃, 2.6MPa condition, benzene and propylene are reacted by beds, wherein the benzene inlet amount is 702 Grams Per Hours, the propylene feed amount is 42 Grams Per Hours, is 2.0 hours with propylene calculated weight liquid air speed -1This reaction was investigated through 1000 hours, did not detect propylene in the product, and activity of such catalysts, selectivity do not descend.Selectivity is 97.5% (calculating with propyl group).
[embodiment 8]
Catalyst 21 grams of getting embodiment 2 place fixed bed reactors, under 200 ℃, 2.6MPa condition, benzene and propylene are reacted by beds, wherein the benzene inlet amount is 585 Grams Per Hours, the propylene feed amount is 42 Grams Per Hours, is 2.0 hours with propylene calculated weight liquid air speed -1This reaction was investigated through 1000 hours, did not detect propylene in the product, and activity of such catalysts, selectivity do not descend.Selectivity is 98.0% (calculating with propyl group).
[embodiment 9]
Catalyst 21 grams of getting embodiment 3 place fixed bed reactors, under 205 ℃, 2.6MPa condition, benzene and propylene are reacted by beds, wherein the benzene inlet amount is 670 Grams Per Hours, the propylene feed amount is 42 Grams Per Hours, is 2.0 hours with propylene calculated weight liquid air speed -1This reaction was investigated through 1000 hours, did not detect propylene in the product, and activity of such catalysts, selectivity do not descend.Selectivity is 97.7% (calculating with propyl group).
[embodiment 10]
Catalyst 21 grams of getting embodiment 4 place fixed bed reactors, under 195 ℃, 2.6MPa condition, benzene and propylene are reacted by beds, wherein the benzene inlet amount is 468 Grams Per Hours, the propylene feed amount is 42 Grams Per Hours, is 2.0 hours with propylene calculated weight liquid air speed -1This reaction was investigated through 1000 hours, did not detect propylene in the product, and activity of such catalysts, selectivity do not descend.Selectivity is 98.0% (calculating with propyl group).
[embodiment 11]
Catalyst 21 grams of getting embodiment 5 place fixed bed reactors, under 215 ℃, 2.6MPa condition, benzene and propylene are reacted by beds, wherein the benzene inlet amount is 702 Grams Per Hours, the propylene feed amount is 42 Grams Per Hours, is 2.0 hours with propylene calculated weight liquid air speed -1This reaction was investigated through 1000 hours, did not detect propylene in the product, and activity of such catalysts, selectivity do not descend.Selectivity is 96.0% (calculating with propyl group).
[embodiment 12]
Catalyst 84 grams of getting embodiment 6 place fixed bed reactors, under 215 ℃, 2.6MPa condition, benzene and propylene are reacted by beds, wherein the benzene inlet amount is 702 Grams Per Hours, the propylene feed amount is 42 Grams Per Hours, is 2.0 hours with propylene calculated weight liquid air speed -1This reaction was investigated through 45 hours, did not detect propylene in the product, and activity of such catalysts, selectivity do not descend.Selectivity is 95.0% (calculating with propyl group).
[embodiment 13]
Catalyst 21 gram of getting embodiment 4 places fixed bed reactors, under 250 ℃, 4.0MPa condition, benzene and ethene is reacted by beds, and wherein the benzene inlet amount is 400 Grams Per Hours, is 0.5 hour with ethene calculated weight liquid air speed -1This reaction was investigated through 1000 hours, did not detect ethene in the product, and activity of such catalysts, selectivity do not descend.Selectivity is 90.0% (calculating with ethyl).

Claims (8)

1、一种用于生产烷基苯的催化剂，由以下组份组成：1. A catalyst for the production of alkylbenzenes, consisting of the following components: a)硅铝摩尔比为2～20的沸石和载于沸石上的；a) zeolites with a molar ratio of silicon to aluminum of 2 to 20 and those carried on zeolites; b)以重量百分比计为0.008～0.045％的金属钯。b) 0.008-0.045% metal palladium by weight percentage. 2、根据权利要求1所述用于生产烷基苯的催化剂，其特征在于沸石的硅铝摩尔比为2～8。2. The catalyst for producing alkylbenzene according to claim 1, characterized in that the molar ratio of silicon to aluminum of the zeolite is 2-8. 3、根据权利要求1所述用于生产烷基苯的催化剂，其特征在于沸石为Y沸石、β沸石、丝光沸石或ZSM-5沸石。3. The catalyst for producing alkylbenzene according to claim 1, characterized in that the zeolite is Y zeolite, beta zeolite, mordenite or ZSM-5 zeolite. 4、根据权利要求3所述用于生产烷基苯的催化剂，其特征在于沸石为Y沸石。4. The catalyst for the production of alkylbenzenes according to claim 3, characterized in that the zeolite is Y zeolite. 5、根据权利要求1、2、3或4所述用于生产烷基苯的催化剂，其特征在于烷基苯为乙苯或异丙苯。5. The catalyst for producing alkylbenzene according to claim 1, 2, 3 or 4, characterized in that the alkylbenzene is ethylbenzene or cumene. 6、一种用于生产烷基苯的方法，以丙烯或乙烯和苯为原料，在反应温度为150～250℃，反应压力为0.7～4.0MPa，苯/烯烃摩尔比为4～20条件下液相合成，其特征在于所用催化剂由以下组份组成：6. A method for producing alkylbenzene, using propylene or ethylene and benzene as raw materials, under the conditions of a reaction temperature of 150-250°C, a reaction pressure of 0.7-4.0MPa, and a benzene/olefin molar ratio of 4-20 Liquid phase synthesis, characterized in that the catalyst used consists of the following components: a)硅铝摩尔比为2～20的沸石和载于沸石上的；a) zeolites with a molar ratio of silicon to aluminum of 2 to 20 and those carried on zeolites; b)以重量百分比计为0.008～0.045％的金属钯。b) 0.008-0.045% metal palladium by weight percentage. 7、根据权利要求6所述用于生产烷基苯的方法，其特征在于反应温度为180～210℃。7. The method for producing alkylbenzene according to claim 6, characterized in that the reaction temperature is 180-210°C. 8、根据权利要求6所述用于生产烷基苯的方法，其特征在于反应压力为2.0～3.5MPa。8. The method for producing alkylbenzene according to claim 6, characterized in that the reaction pressure is 2.0-3.5 MPa.
CN99113813A 1999-06-24 1999-06-24 Catalyst and process for prodn. of alkyl benzene Expired - Fee Related CN1114493C (en)

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CN111330631B (en) * 2020-04-08 2022-09-16 中国石油大学(华东) Preparation method of modified molecular sieve loaded Pd catalyst and application of modified molecular sieve loaded Pd catalyst in synthesis of dimethyl carbonate by gas phase method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62246532A (en) * 1986-04-16 1987-10-27 Maruzen Petrochem Co Ltd Alkylation of phenol
CN1155531A (en) * 1996-01-25 1997-07-30 中国石油化工总公司 Process for preparation of alkyl benzene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62246532A (en) * 1986-04-16 1987-10-27 Maruzen Petrochem Co Ltd Alkylation of phenol
CN1155531A (en) * 1996-01-25 1997-07-30 中国石油化工总公司 Process for preparation of alkyl benzene

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