Core-shell structured molecular sieve, its production and use

Abstract

A molecular sieve with aluminum phosphor-silicate molecular sieve kernel and Pentasil molecular sieve shell structure in proportion of 1:1-20:1 proportion and its production are disclosed. The process is carried out by mixing silicate-containing compound with aluminum-containing compound solution, agitating, adding into organic template agent to obtain mixture, mixing it with dispersed aluminum phosphor-silicate molecular sieve in proportion of SiO2:Al203:Na2O:P2O5:R:H2O=(10-500): 1(5-100): (0.1-20): (3-100): (1000-10000), crystallizing at 120-200degree, filtering, washing, drying and sintering. It can be used for light-hydrocarbon cracking reaction and has more output.

Description

technical field

[0001] The invention relates to a molecular sieve with a core-shell structure and its preparation method and application, specifically, a molecular sieve with a core-shell structure containing Pentasil molecular sieve, its preparation method and its application in the catalytic cracking process of light hydrocarbons. Background technique

[0002] The significant differences between ZSM-5 zeolite molecular sieve and other types of zeolite molecular sieves are: (1) its silicon-aluminum ratio can be changed from 10 to the maximum value, and even form all-silica zeolite; (2) it has a special three-dimensional pore structure and pore size; (3) ) has strong acidity, and the acidity is easy to adjust. Therefore, as an excellent catalytic material, ZSM-5 molecular sieve has been widely used in oil refining and chemical production, mainly for catalytic cracking, hydrocracking, isomerization, aromatics alkylation, toluene disproportionation and alkylation Catalytic re...

Examples

preparation example Construction

[0019] The preparation method of the molecular sieve provided by the present invention comprises stirring and mixing the silicon-containing compound and the acidified aluminum-containing compound solution uniformly, adding an organic template to prepare a mixture, mixing the mixture with a water-dispersed silicoaluminophosphate molecular sieve, and making the mixture The molar ratio of each substance is:

[0020] SiO 2 : Al 2 o 3 :Na 2 O:P 2 o 5 :R:H 2 O=(10~500):1:(5~100):(0.1~20):(3~100):(1000~10000), wherein R is an organic templating agent, and the amount of SAPO-11 added is based on P 2 o 5 The number of moles, and then crystallized at 120 ~ 200 ° C, filtered, washed, dried and roasted.

[0021] In the above method, the molar ratio of each substance in the mixture is preferably:

[0022] SiO 2 : Al 2 o 3 :Na 2 O:P 2 o 5 :R:H 2 O=(30-300):1:(8-90):(0.1-10):(10-80):(1000-7000). The suitable drying temperature for the molecular sieve obtained after crystalli...

example 1

[0036] Prepare molecular sieve A with core-shell structure according to the present invention.

[0037] (1) Take 10 grams of water glass (SiO 2 content is 28.8% by mass) mixed with 10 milliliters of deionized water and stirred evenly; get 0.34 gram of aluminum sulfate [Al 2 (SO 4 ) 3 18H 2 [0], 0.94 gram of concentrated sulfuric acid (purity > 95% by mass) and 15 milliliters of deionized water are mixed and stirred evenly to make a solution; the above-mentioned diluted water glass and the acidified aluminum sulfate are mixed, and 1.09 gram of ethylamine is added as a templating agent , mix and stir well to make mixture a;

[0038] (2) Get 0.24 grams of SAPO-11 molecular sieve powder and 3 milliliters of deionized water to stir and disperse evenly, add to mixture a and stir and mix evenly, and the molar ratio of each substance calculated by oxide is:

[0039] SiO 2 :Al 2 o 3 :Na 2 O:P 2 o 5 :R:H 2 O=96:1:28.3:2:50:3111, the amount of SAPO-11 was determined by P 2 o...

example 2

[0044] Prepare molecular sieve B with core-shell structure according to the present invention.

[0045] (1) Get 30 grams of water glass (SiO 2 content is 28.8% by mass) mixed with 10 milliliters of deionized water and stirred evenly; get 0.34 gram of aluminum sulfate [Al 2 (SO 4 ) 3 18H 2 [0], 0.94 gram of sulfuric acid (purity>95% quality) and 15 milliliters of deionized water are mixed and stirred; the above two mixtures are mixed with 2.50 grams of propylamine and stirred to make mixture b.

[0046] (2) Get the SAPO-11 molecular sieve of 1.2 grams and mix with 6 milliliters of deionized water and stir and disperse evenly, join in the mixture b and stir and mix evenly, the molar ratio of described each material is calculated by oxide is:

[0047] SiO 2 :Al 2 o 3 :Na 2 O:P 2 o 5 :R:H 2 O=288:1:85.2:10:85:5560, the addition amount of SAPO-11 is expressed by P 2 o 5 In terms of moles, Al in SAPO-11 2 o 3 Al with aluminum sulfate 2 o 3 The molar ratio is 10:1. ...

technical field

[0001] The invention relates to a molecular sieve with a core-shell structure and its preparation method and application, specifically, a molecular sieve with a core-shell structure containing Pentasil molecular sieve, its preparation method and its application in the catalytic cracking process of light hydrocarbons. Background technique

[0002] The significant differences between ZSM-5 zeolite molecular sieve and other types of zeolite molecular sieves are: (1) its silicon-aluminum ratio can be changed from 10 to the maximum value, and even form all-silica zeolite; (2) it has a special three-dimensional pore structure and pore size; (3) ) has strong acidity, and the acidity is easy to adjust. Therefore, as an excellent catalytic material, ZSM-5 molecular sieve has been widely used in oil refining and chemical production, mainly for catalytic cracking, hydrocracking, isomerization, aromatics alkylation, toluene disproportionation and alkylation Catalytic re...

Examples

preparation example Construction

[0019] The preparation method of the molecular sieve provided by the present invention comprises stirring and mixing the silicon-containing compound and the acidified aluminum-containing compound solution uniformly, adding an organic template to prepare a mixture, mixing the mixture with a water-dispersed silicoaluminophosphate molecular sieve, and making the mixture The molar ratio of each substance is:

[0020] SiO 2 : Al 2 o 3 :Na 2 O:P 2 o 5 :R:H 2 O=(10~500):1:(5~100):(0.1~20):(3~100):(1000~10000), wherein R is an organic templating agent, and the amount of SAPO-11 added is based on P 2 o 5 The number of moles, and then crystallized at 120 ~ 200 ° C, filtered, washed, dried and roasted.

[0021] In the above method, the molar ratio of each substance in the mixture is preferably:

[0022] SiO 2 : Al 2 o 3 :Na 2 O:P 2 o 5 :R:H 2 O=(30-300):1:(8-90):(0.1-10):(10-80):(1000-7000). The suitable drying temperature for the molecular sieve obtained after crystalli...

example 1

[0036] Prepare molecular sieve A with core-shell structure according to the present invention.

[0037] (1) Take 10 grams of water glass (SiO 2 content is 28.8% by mass) mixed with 10 milliliters of deionized water and stirred evenly; get 0.34 gram of aluminum sulfate [Al 2 (SO 4 ) 3 18H 2 [0], 0.94 gram of concentrated sulfuric acid (purity > 95% by mass) and 15 milliliters of deionized water are mixed and stirred evenly to make a solution; the above-mentioned diluted water glass and the acidified aluminum sulfate are mixed, and 1.09 gram of ethylamine is added as a templating agent , mix and stir well to make mixture a;

[0038] (2) Get 0.24 grams of SAPO-11 molecular sieve powder and 3 milliliters of deionized water to stir and disperse evenly, add to mixture a and stir and mix evenly, and the molar ratio of each substance calculated by oxide is:

[0039] SiO 2 :Al 2 o 3 :Na 2 O:P 2 o 5 :R:H 2 O=96:1:28.3:2:50:3111, the amount of SAPO-11 was determined by P 2 o...

example 2

[0044] Prepare molecular sieve B with core-shell structure according to the present invention.

[0045] (1) Get 30 grams of water glass (SiO 2 content is 28.8% by mass) mixed with 10 milliliters of deionized water and stirred evenly; get 0.34 gram of aluminum sulfate [Al 2 (SO 4 ) 3 18H 2 [0], 0.94 gram of sulfuric acid (purity>95% quality) and 15 milliliters of deionized water are mixed and stirred; the above two mixtures are mixed with 2.50 grams of propylamine and stirred to make mixture b.

[0046] (2) Get the SAPO-11 molecular sieve of 1.2 grams and mix with 6 milliliters of deionized water and stir and disperse evenly, join in the mixture b and stir and mix evenly, the molar ratio of described each material is calculated by oxide is:

[0047] SiO 2 :Al 2 o 3 :Na 2 O:P 2 o 5 :R:H 2 O=288:1:85.2:10:85:5560, the addition amount of SAPO-11 is expressed by P 2 o 5 In terms of moles, Al in SAPO-11 2 o 3 Al with aluminum sulfate 2 o 3 The molar ratio is 10:1. ...

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