SAPO-34 molecular sieve of larger specific surface area and hollow alumina-rich hierarchical pore structures and application thereof

A technology of SAPO-34 and specific surface area, which is applied in the field of molecular sieves, can solve the problems of troublesome post-processing methods, low silicon content, and limited application, and achieve the effects of reducing waste liquid pollution, high selectivity, and low solvent consumption

Active Publication Date: 2015-10-14
JILIN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The molecular sieve has low silicon content and improved MTO catalytic performance, but the post-treatment...

Method used

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  • SAPO-34 molecular sieve of larger specific surface area and hollow alumina-rich hierarchical pore structures and application thereof
  • SAPO-34 molecular sieve of larger specific surface area and hollow alumina-rich hierarchical pore structures and application thereof
  • SAPO-34 molecular sieve of larger specific surface area and hollow alumina-rich hierarchical pore structures and application thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0043] Mix and stir aluminum isopropoxide, water, triethylamine and polyethylene glycol 400 (PEG 400) thoroughly, then stir at 30°C for 5 hours to obtain a mixture; add white carbon black and phosphoric acid to the above mixture in turn, and keep stirring Treat for 2 hours to obtain the initial gel mixture of SAPO-34 molecular sieve; afterward, stir the initial gel mixture of SAPO-34 molecular sieve obtained in a water bath at 50°C for another 3 hours, and the initial gel mixture of each component in the reaction system The molar ratio is 5TEA:0.3SiO 2 : 1.0P 2 o 5 : 8Al 2 o 3 : 58.4H 2 O: 0.05PEG 400; put the initial gel mixture into a stainless steel reaction kettle with polytetrafluoroethylene lining, then put the reaction kettle in an oven, raise the temperature to 180 ° C, under autogenous pressure, under hydrothermal conditions Constant temperature (180°C) crystallization for 18 hours. Then, the solid product was separated by centrifugation, washed repeatedly with ...

Embodiment 2

[0045] Mix pseudo-boehmite, water, methanol (MeOH), triethylamine, and polyethylene glycol 2000 thoroughly and stir at 50°C for 8 hours to obtain a mixture; add active silica and phosphoric acid to the above mixture in sequence During the stirring process for 2 hours, the initial gel mixture of SAPO-34 molecular sieves was obtained; after that, the initial gel mixture of SAPO-34 molecular sieves was stirred for another 2 hours in a water bath at 80°C, and the initial gel mixture in the reaction system was The molar ratio of each component is 10TEA:0.8SiO 2 : 1.0P 2 o 5 : 4Al 2 o 3 : 200H 2 O: 40MeOH: 0.5PEG 2000; put the initial gel mixture into a stainless steel reactor with a polytetrafluoroethylene liner, then place the reactor in an oven, raise the temperature to 230 ° C, under autogenous pressure, hydrothermal conditions Crystallization at a constant temperature (230°C) for 6 hours. Then, the solid product was separated by centrifugation, washed repeatedly with deio...

Embodiment 3

[0047] Mix aluminum oxide, ethanol (EtOH), triethylamine and polyethylene glycol 1000 thoroughly and stir at 40°C for 5 hours to obtain a mixture; add ethyl silicate and phosphoric acid to the above mixture in turn, and continue stirring Treat for 5 hours to obtain the initial gel mixture of SAPO-34 molecular sieve; after that, stir the obtained initial gel mixture of SAPO-34 molecular sieve in a water bath at 60°C for another 8 hours, and the components in the initial gel mixture in the reaction system are oxidized The molar ratio of substance, triethylamine and solvent is 7TEA:0.1SiO 2 : 1.0P 2 o 5 : 8Al 2 o 3 : 20EtOH: 0.2PEG 1000; put the initial gel mixture into a stainless steel reaction kettle with polytetrafluoroethylene lining, then put the reaction kettle in an oven, heat up to 200 ° C, under autogenous pressure, under hydrothermal conditions Constant temperature (200° C.) crystallization was carried out for 20 hours. Then, the solid product is centrifuged, wash...

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Abstract

A SAPO-34 molecular sieve of a larger specific surface area and a hollow alumina-rich hierarchical pore structures and application thereof in a reaction that uses methanol to prepare low carbon olefin, belongs to the technical field of molecular sieves. The product by the invention is obtained by taking triethylamine as a template agent, adopting a traditional hydrothermal or solvothermal synthetic method, taking water or alcohol as a solvent, and introducing polyethylene glycol polymer in a high pressure reactor under an autogenous pressure through an in-situ alumina-rich method. A synthetic SAPO-34 molecular sieve sample is in a hollow and hierarchical pore structures cubic shape, the average crystal size is 5-10 [mu]m, and the mesoporou size is 2-15 nm. According to the invention, the yield of the synthetic SAPO-34 molecular sieve sample is extremely high, and can reach over 90%. The invention has extremely high selectivity of low carbon olefin in a reaction that uses methanol to prepare olefin (MTO), particularly the total yield of ethylene and propylene can reach over 85%, and the SAPO-34 molecular sieve is extremely suitable for industrial amplification application.

Description

technical field [0001] The invention belongs to the technical field of molecular sieves, and specifically relates to a SAPO-34 molecular sieve with a relatively large specific surface area and a hollow aluminum-rich hierarchical pore structure and its application in the reaction of methanol to prepare low-carbon olefins. In addition, it can also be used for various hydrocarbons species conversion, gas adsorption separation, etc. Background technique [0002] As one of the raw materials in the chemical industry, low-carbon olefins such as ethylene and propylene play a vital role in the modern chemical system. At present, petroleum cracking is the main way to obtain low-carbon olefins. However, with the decrease of cheap and easy-to-obtain oil resources, the supply of low-carbon olefins has been greatly affected, but the demand for low-carbon olefins in domestic and foreign markets continues to grow year by year. It is also the shortage of petroleum resources that forces peo...

Claims

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Application Information

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IPC IPC(8): C01B37/08C01B39/54B01J29/85C07C1/20C07C11/04C07C11/06
CPCY02P20/52Y02P30/20Y02P30/40
Inventor 于吉红王宁孙启明郭冠琦
Owner JILIN UNIV
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