CN1490085A - Zeolite catalyst for synthesis of isopropyl benzene from benzene and propylene - Google Patents
Zeolite catalyst for synthesis of isopropyl benzene from benzene and propylene Download PDFInfo
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- CN1490085A CN1490085A CNA031570674A CN03157067A CN1490085A CN 1490085 A CN1490085 A CN 1490085A CN A031570674 A CNA031570674 A CN A031570674A CN 03157067 A CN03157067 A CN 03157067A CN 1490085 A CN1490085 A CN 1490085A
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Abstract
A zeolite catalyst for synthesizing isopropylbenzene from benzene and propylene is prepared from the Na-type beta-zeolite powder containing template agent through treating in foiling aqueous solution of ammonia muriate, adding adhesive and aluminium nitrate, shaping, baking and calcining. Its advantages are low cost and energy consumption, and long service life.
Description
Technical field
The invention belongs to catalyst preparation technology, particularly a kind of new zeolite catalyzer that is used for benzene and propylene synthesizing iso-propylbenzene.
Background technology
Commercial catalysts with benzene and propylene synthesizing iso-propylbenzene can be divided into three kinds.A kind of is Fu's row Dare-Kerafyrm thatch response type catalyzer, as aluminum chloride, hydrofluoric acid, boron trifluoride and liquid acid etc.Use this class Preparation of catalysts method to be liquid phase process, full scale plant is had serious corrosive nature, cause operation and environmental problem.Second kind is the solid phosphoric acid catalyzer, and it has overcome the corrosive nature and the environmental problem of pair row Dare-Kerafyrm thatch response type catalyzer.But because of this type catalyzer can not be used for the transalkylation reaction, so the total recovery of benzene is lower.The third is the modified catalyst based on various zeolites.Because but zeolite has the characteristic of the pore passage structure and the acidity modulation of homogeneous, various countries have all developed the zeolite catalyst of number of different types in succession.
U.S.Pat.No.4,469,908 disclose the alkylation of a kind of aromatic hydrocarbons and 1-5 carbon atom alkyl reagent, and wherein catalyzer is a HZSM-12 type zeolite.U.S.Pat.No.5,081,323 discloses a kind of alkylation of aromatic hydrocarbons and the method for transfering alkylation, and wherein catalyzer is the zeolite beta catalyzer of modification.PU.S.Pat.No.5,081,323 discloses that a kind of usefulness third is rare to prepare the method for isopropyl benzene to benzene alkylation, and wherein catalyzer also is that zeolite beta improves catalyzer.The improvement ion is a basic metal, or metallic cation.EP0 521 554A2 disclose a kind of alkylating aromatic hydrocarbon catalyzer, comprise the y-type zeolite catalyzer of handling with a kind of phosphorus compound modification.
Also have lot of documents such as U.S.Pat.No.5,145,817, No.4,891,418; No.5,030,785; EPO 432 841 A1; EP0 308 097A1 etc. have described alkylating aromatic hydrocarbon and the transfering alkylation method of using various zeolite catalysts.
ZL95120165.4 discloses the method with benzene and propylene preparing isopropylbenzene.Its catalyzer is made by modification Hydrogen β zeolite, and its way is with multiple cationic exchange zeolite to be carried out acid modulation.Preparation process is complicated.Once successful in 1999 at Beijing Yan Hua company two factory's industrial experiments, be that domestic preparing isopropylbenzene uses homemade zeolite catalyst first hand.
In sum, the preparation method of zeolite catalyst is different, but different zeolites is all by following process modification: (1) is carried out high-temperature roasting to the synthetic na-pretreated zeolite and is handled removed template method; (2) na-pretreated zeolite is carried out the ammonium exchange and handle, carry out the high-temperature roasting processing again and be transformed into h-type zeolite; (3) by different method of modifying (handling and tie in advance carbon etc.) zeolite is handled again, made the catalyzer that meets certain specific reaction requirement as cationic exchange, steam-treated, ion vapour stream.
Different sorts zeolite, different ingredients, different preparation method all can obtain the catalyzer of different performance.So the development research of zeolite catalyst is very active, the kind of catalyzer is very numerous and diverse.There is short shortcoming of life-span in domestic existing preparing isopropylbenzene technology industrial catalyst, further develops better new catalyst, and be crucial the work-ing life that prolongs catalyzer.
Summary of the invention
The purpose of this invention is to provide a kind of new zeolite catalyzer that is used for benzene and propylene synthesizing iso-propylbenzene, it is characterized in that: the described preparation process that is used for the zeolite catalyst of synthesizing iso-propylbenzene is:
(1) zeolite treatment: with concentration is the ammonia chloride water solution of 0.5N-5N (volumetric molar concentration), under boiling state, handle without the sodium type β zeolite that contains template of any processing 1-6 hour, be washed till no chlorion with deionized water, repeat 1-5 time again after the filtration, behind the sample filtering in 120 ℃ of dryings; The silica alumina ratio that this sodium type β zeolite that contains template is a zeolite is 15-30, and degree of crystallinity is greater than 90%.
(2) moulding
Forming method 1: be that the zeolite of 70-90% and the thin aluminium stone class tamanori (as the SB adhesive powder) of plan that weight ratio is 10-30% be the main body powder with the weight ratio, add after day mountain valley with clumps of trees and bamboo powder of weight ratio 0.5-2%, mix.The aluminum salt solution of volumetric molar concentration 0-5N that adds weight ratio and be 0-10% is in above-mentioned mixed powder, the rare nitric acid that adds the 3-10% weight concentration again is in powder, moulding after mixing, at room temperature slowly be heated to 120 ℃, smoked 2-30 hour, cooling be placed in the stoving oven 150 ℃-750 ℃ roasting 15-120 hour.
Forming method 2: with the unit weight zeolite is the main body powder, adds the sky mountain valley with clumps of trees and bamboo powder of 0.5-5% weight ratio, mixes.With weight concentration is that the 5-25% silicon oxide aqueous solution is made tamanori, adding the silicon oxide amount is the 10-20% of zeolite weight, the aluminium salt that adds weight ratio and be 0-10% is in above-mentioned solution, moulding after mixing with powder again, at room temperature slowly be heated to 120 ℃, smoked 2-30 hour, cooling be placed in the stoving oven 150 ℃-750 ℃ roasting 15-120 hour.
Forming method 3: be that the zeolite of 70-90% and the thin aluminium stone class tamanori of plan that weight ratio is 10-30% are the main body powder with the weight ratio, the sky mountain valley with clumps of trees and bamboo powder that adds the 0.5-5% weight ratio mixes, the silicon oxide aqueous solution with weight concentration 5-25% is another kind of tamanori, the aluminium salt and an amount of concentrated nitric acid that add the 0.5-5% weight ratio are made into mixing solutions in the above-mentioned aqueous solution, the amount that adds silicon oxide is the 5-20% of above-mentioned zeolite weight, afterwards mixed powder and mixing solutions are mixed, moulding at room temperature slowly is heated to 120 ℃ and smoked 2-30 hour.Cooling be placed in the roasting kiln 250 ℃-750 ℃ roasting 15-120 hour.
The thin aluminium stone class tamanori of described plan is the SB adhesive powder.
Described zeolite is the β zeolite after (1) zeolite treatment, and its silica alumina ratio is 15-30, and degree of crystallinity is greater than 90%.
The preparation method who the invention has the beneficial effects as follows 1. new catalysts is succinct, and with the stripper plate agent, take off ammonium and the sinter molding process is once finished simultaneously, the less energy consumption cost is low, is easy to industrialization; 2. new catalyst has the specified proportion of specific B acid, strong B acid amount and these two kinds of acid, and micropore has specific distribution; 3. new catalyst is applicable to bubbling bed process (gas-liquid solid state reaction) and liquid phase method technology (liquid and solid phase reaction), and the accelerated life of new catalyst is 3-4 a times of commercial catalysts, and other technical indicator all reaches requirement, has long work-ing life
Embodiment
The present invention is the new zeolite catalyzer that is used for benzene and propylene synthesizing iso-propylbenzene.The described preparation process that is used for the zeolite catalyst of synthesizing iso-propylbenzene is:
(1) zeolite treatment: with concentration is the ammonia chloride water solution of 0.5N-5N (volumetric molar concentration), under boiling state, handle without the sodium type β zeolite that contains template of any processing 1-6 hour, be washed till no chlorion with deionized water, repeat 1-5 time again after the filtration, behind the sample filtering in 120 ℃ of dryings; The silica alumina ratio that this sodium type β zeolite that contains template is a zeolite is 15-30, and degree of crystallinity is greater than 90%.
(2) moulding
Forming method 1: be that the zeolite of 70-90% and the thin aluminium stone class tamanori (as the SB adhesive powder) of plan that weight ratio is 10-30% be the main body powder with the weight ratio, add after day mountain valley with clumps of trees and bamboo powder of weight ratio 0.5-2%, mix.The aluminum salt solution of volumetric molar concentration 0-5N that adds weight ratio and be 0-10% is in above-mentioned mixed powder, the rare nitric acid that adds the 3-10% weight concentration again is in powder, moulding after mixing, at room temperature slowly be heated to 120 ℃, smoked 2-30 hour, cooling be placed in the stoving oven 150 ℃-750 ℃ roasting 15-120 hour.
Forming method 2: with the unit weight zeolite is the main body powder, adds the sky mountain valley with clumps of trees and bamboo powder of 0.5-5% weight ratio, mixes.With weight concentration is that the 5-25% silicon oxide aqueous solution is made tamanori, adding the silicon oxide amount is the 10-20% of zeolite weight, the aluminium salt that adds weight ratio and be 0-10% is in above-mentioned solution, moulding after mixing with powder again, at room temperature slowly be heated to 120 ℃, smoked 2-30 hour, cooling be placed in the stoving oven 150 ℃-750 ℃ roasting 15-120 hour.
Forming method 3: be that the zeolite of 70-90% and the thin aluminium stone class tamanori of plan that weight ratio is 10-30% are the main body powder with the weight ratio, the sky mountain valley with clumps of trees and bamboo powder that adds the 0.5-5% weight ratio mixes, the silicon oxide aqueous solution with weight concentration 5-25% is another kind of tamanori, the aluminium salt and an amount of concentrated nitric acid that add the 0.5-5% weight ratio are made into mixing solutions in the above-mentioned aqueous solution, the amount that adds silicon oxide is the 5-20% of above-mentioned zeolite weight, afterwards mixed powder and mixing solutions are mixed, moulding at room temperature slowly is heated to 120 ℃ and smoked 2-30 hour.Cooling be placed in the roasting kiln 250 ℃-750 ℃ roasting 15-120 hour.
Described aluminium salt comprises: aluminum nitrate, Tai-Ace S 150.
Described zeolite is the β zeolite after (1) zeolite treatment, and its silica alumina ratio is 15-30, and degree of crystallinity is greater than 90%
Used sodium type β zeolite and the SB adhesive powder (intending thin aluminium stone class tamanori) that contains template all bought from catalyzer subsidiary factory of Fushun No.3 Petroleum Factory in following examples.
Embodiment 1
100 grams are contained the sodium type β zeolite of template, carry out following processing:
1. under stirring or boiling condition, handled 6 hours with the aqueous ammonium chloride solution of 500 milliliters of 0.7N.
2. cooled and filtered goes out zeolite, is washed till no chlorion with deionized water.
3. repeat 1-2 once, 120 ℃ of oven dry down.
4. use the SB adhesive powder, mix with zeolite by 15% weight ratio.
5. the aluminium that adds 5% weight ratio mixes moulding afterwards again with above-mentioned powder in weight concentration 7% dilute nitric acid solution.
6. sample is placed baking oven, slowly heat up only 120 ℃, smoked 10 hours from room temperature.
7. again sample is placed horse expense stove, 500 ℃ of roastings 80 hours.
The principal character of embodiment 1 new catalyst is: the sour amount of B 0.64 mmole/gram, strong B acid amount 0.24 mmole/gram, micropore size distribution 56% (0.3-0.6nm), 23% (0.6-0.8nm), 21% (0.8-1.0nm).The benzene and the third rare alkylated reaction benzene transformation efficiency are 22.4%, and the isopropyl benzene selectivity is 96.1%.
Benzene and third rare alkylated reaction accelerated life experiment (gas-liquid solid state reaction) are 300 hours, are 80 hours with the fast aging life-span experiment of industrial catalyst under the condition (ZL95120165.4, down with).
Benzene and third rare alkylated reaction accelerated life experiment (liquid and solid phase reaction) are 696 hours, are 168 hours with the fast aging life-span experiment of industrial catalyst under the condition (ZL95120165.4).
Embodiment 2
1-3 is with embodiment 1.
4. mix by weight 3.5% adding field mountain valley with clumps of trees and bamboo powder and zeolite.
5. be tamanori with the weight ratio 18% silicon oxide aqueous solution, add 15% silicon oxide of zeolite weight.
6. the aluminum nitrate that adds 5% weight ratio dissolves in above-mentioned solution, moulding after mixing with above-mentioned powder again.
7. sample is placed baking oven, slowly heat up only 120 ℃, smoked 7 hours from room temperature.
8. again sample is placed horse expense stove, 650 ℃ of roastings 75 hours.
The principal character of embodiment 2 new catalysts is: the sour amount of B 0.62 mmole/gram, strong B acid amount 0.27 mmole/gram, micropore size distribution 55% (0.3-0.6nm), 23% (0.6-0.8nm), 22% (0.8-1.0nm).The benzene and the third rare alkylated reaction benzene transformation efficiency are 22.2%, and the isopropyl benzene selectivity is 96.0%.
Benzene and third rare alkylated reaction accelerated life experiment (gas-liquid solid state reaction) are 290 hours, are 80 hours with industrial catalyst accelerated life experiment under the condition.
Embodiment 3
1-3 is with embodiment 1.
4. add the SB adhesive powder by 18% weight ratio, mix with zeolite after adding the field mountain valley with clumps of trees and bamboo powder of weight ratio 4% again
5. be another kind of tamanori with 20% (weight concentration) silicon oxide aqueous solution, add-on is the 5-20% of zeolite weight, adds the aluminium salt of 6% (weight) concentrated nitric acid and 3.5% (weight) again in this solution, forms mixing solutions.
6. moulding after mixing with 4 gained powders.
7. sample is placed baking oven, slowly heat up only 120 ℃, smoked 10 hours from room temperature.
8. again sample is placed horse expense stove, 450 ℃ of roastings 100 hours.
Repeat the 6-7 among the embodiment 1.
The principal character of embodiment 3 new catalysts is: the sour amount of B 0.61 mmole/gram, strong B acid amount 0.22 mmole/gram, micropore size distribution 54% (0.3-0.6nm), 22% (0.6-0.8nm), 23% (0.8-1.0nm).The benzene and the third rare alkylated reaction benzene transformation efficiency are 21.8%, and the isopropyl benzene selectivity is 95.2%.
Benzene and third rare alkylated reaction accelerated life experiment (gas-liquid solid state reaction) are 284 hours, are 80 hours with industrial catalyst accelerated life experiment under the condition.
Claims (4)
1. new zeolite catalyzer that is used for benzene and propylene synthesizing iso-propylbenzene, it is characterized in that: the described preparation process that is used for the zeolite catalyst of synthesizing iso-propylbenzene is:
(1) zeolite treatment: with concentration is the ammonia chloride water solution of 0.5N-5N (volumetric molar concentration), under boiling state, handle without the sodium type β zeolite that contains template of any processing 1-6 hour, be washed till no chlorion with deionized water, repeat 1-5 time again after the filtration, behind the sample filtering in 120 ℃ of dryings; The silica alumina ratio that this sodium type β zeolite that contains template is a zeolite is 15-30, and degree of crystallinity is greater than 90%;
(2) moulding
Forming method 1: be that the zeolite of 70-90% and the thin aluminium stone class tamanori (as the SB adhesive powder) of plan that weight ratio is 10-30% are the main body powder with the weight ratio, add after the sky mountain valley with clumps of trees and bamboo powder of weight ratio 0.5-2%, mix, the aluminum salt solution of volumetric molar concentration 0-5N that adds weight ratio and be 0-10% is in above-mentioned mixed powder, the rare nitric acid that adds the 3-10% weight concentration again is in powder, moulding after mixing, at room temperature slowly be heated to 120 ℃, smoked 2-30 hour, cooling be placed in the stoving oven 150 ℃-750 ℃ roasting 15-120 hour;
Forming method 2: with the unit weight zeolite is the main body powder, the sky mountain valley with clumps of trees and bamboo powder that adds the 0.5-5% weight ratio, mix, with weight concentration is that the 5-25% silicon oxide aqueous solution is made tamanori, and adding the silicon oxide amount is the 10-20% of zeolite weight, and the aluminium salt that adds weight ratio and be 0-10% is in above-mentioned solution, moulding after mixing with powder again, at room temperature slowly be heated to 120 ℃, smoked 2-30 hour, cooling be placed in the stoving oven 150 ℃-750 ℃ roasting 15-120 hour;
Forming method 3: be that the zeolite of 70-90% and the thin aluminium stone class tamanori of plan that weight ratio is 10-30% are the main body powder with the weight ratio, the sky mountain valley with clumps of trees and bamboo powder that adds the 0.5-5% weight ratio mixes, the silicon oxide aqueous solution with weight concentration 5-25% is another kind of tamanori, the aluminium salt and an amount of concentrated nitric acid that add the 0.5-5% weight ratio are made into mixing solutions in the above-mentioned aqueous solution, the amount that adds silicon oxide is the 5-20% of above-mentioned zeolite weight, afterwards mixed powder and mixing solutions are mixed, moulding, at room temperature slowly be heated to 120 ℃ and smoked 2-30 hour, cooling be placed in the roasting kiln 250 ℃-750 ℃ roasting 15-120 hour.
2. according to the described new zeolite catalyzer that is used for benzene and propylene synthesizing iso-propylbenzene of claim 1, it is characterized in that: the thin aluminium stone class tamanori of described plan is the SB adhesive powder.
3. according to the described new zeolite catalyzer that is used for benzene and propylene synthesizing iso-propylbenzene of claim 1, it is characterized in that: described zeolite is the β zeolite after (1) zeolite treatment, and its silica alumina ratio is 15-30, and degree of crystallinity is greater than 90%.
4. according to the described new zeolite catalyzer that is used for benzene and propylene synthesizing iso-propylbenzene of claim 1, it is characterized in that: described aluminium salt comprises: aluminum nitrate and Tai-Ace S 150.
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| CNB031570674A CN1234457C (en) | 2003-09-12 | 2003-09-12 | Zeolite catalyst for synthesis of isopropyl benzene from benzene and propylene |
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| CNB031570674A CN1234457C (en) | 2003-09-12 | 2003-09-12 | Zeolite catalyst for synthesis of isopropyl benzene from benzene and propylene |
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| CN1490085A true CN1490085A (en) | 2004-04-21 |
| CN1234457C CN1234457C (en) | 2006-01-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453178C (en) * | 2006-03-27 | 2009-01-21 | 中国石油化工股份有限公司 | Catalyst for synthesizing iso-propylbenzene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453178C (en) * | 2006-03-27 | 2009-01-21 | 中国石油化工股份有限公司 | Catalyst for synthesizing iso-propylbenzene |
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