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Preparation method and application of SAPO-34 molecular sieves with flaky morphology

A technology of SAPO-34 and molecular sieve, which is applied in the field of molecular sieves, can solve problems such as the complexity of the synthesis process, and achieve the effects of low cost, high and low carbon olefin selectivity, and reduced raw material costs

Active Publication Date: 2017-03-08
陕西煤化工技术工程中心有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] In the synthesis of the above-mentioned flaky SAPO-34 molecular sieve, due to the use of special templates, or special synthesis equipment, or the complexity of the synthesis process, there are unfavorable factors that limit the actual production and application of the product. Therefore, a simple, efficient, and low-cost method is sought. And the SAPO-34 molecular sieve with flake shape has great practical application value and prospect for the development of methanol-to-olefins technology

Method used

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  • Preparation method and application of SAPO-34 molecular sieves with flaky morphology
  • Preparation method and application of SAPO-34 molecular sieves with flaky morphology
  • Preparation method and application of SAPO-34 molecular sieves with flaky morphology

Examples

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Embodiment 1

[0037] Add water, pseudoboehmite, phosphoric acid, tetraethylammonium hydroxide, triethylamine and silica sol to the beaker in turn at room temperature, mix and stir for 3 hours, and adjust the pH of the mixture to 6.5-7 to obtain SAPO -34 molecular sieve initial gel mixture; the molar ratio of the components in this mixture is: 0.5SiO 2 : 1.3P 2 o 5 : 1.0Al 2 o 3 : 0.5TEAOH : 4.0TEA:30H 2 O: After the stirring, put the initial gel mixture into a stainless steel reaction kettle, put the reaction kettle in an oven, raise the temperature to 200°C, and crystallize at a constant temperature for 30 hours. After the crystallization is complete, take out the reactor and cool it rapidly; the solid product is separated by centrifugation, washed with deionized water until neutral, and dried to obtain the original powder of SAPO-34 molecular sieve; the original powder is calcined at 550°C for 6 hours to obtain a white tablet Shaped SAPO-34 molecular sieve (referred to as SP-1). ...

Embodiment 2

[0039] Add phosphoric acid, water, aluminum isopropoxide and activated kaolin to the beaker in turn at room temperature, mix and stir for 1 hour, then add tetraethylammonium hydroxide and diethylamine in turn, mix and stir for 0.5 hours, and adjust the mixing The pH value of the liquid is located at 5.5-6, and the initial gel mixture of SAPO-34 molecular sieve is obtained; the molar ratio of each component in the mixture is: 0.1SiO 2 : 2.0P2 o 5 : 1.0Al 2 o 3 : 2.0TEAOH : 0.05DEA : 100H 2 O: After the stirring, put the initial gel mixture into a stainless steel reaction kettle, put the reaction kettle in an oven, raise the temperature to 170°C, and crystallize at a constant temperature for 60 hours. After the crystallization is complete, take out the reaction kettle and quench it; the solid product is separated by centrifugation, washed with deionized water until neutral, and dried to obtain the original powder of SAPO-34 molecular sieve; the original powder is calcined a...

Embodiment 3

[0041] Add water, ammonium hydrogen phosphate, aluminum sol, sodium silicate, tetraethylammonium chloride and triethylamine to the beaker in turn at room temperature, mix and stir for 10 hours, and adjust the pH of the mixture to 7.5-8 to obtain SAPO -34 molecular sieve initial gel mixture; the molar ratio of each component in the mixture is: 1.2SiO 2 : 1.0P 2 o 5 : 1.0Al 2 o 3 : 0.05TEAC : 10TEA : 20H 2 O: After the stirring, put the initial gel mixture into a stainless steel reaction kettle, put the reaction kettle in an oven, raise the temperature to 220°C, and crystallize at constant temperature for 10 hours. After the crystallization is completed, take out the reaction kettle and quench it; the solid product is separated by centrifugation, washed with deionized water until neutral, and dried to obtain the raw powder of SAPO-34 molecular sieve; the raw powder is calcined at 500°C for 10 hours to obtain a white tablet Shaped SAPO-34 molecular sieve (referred to as S...

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Abstract

The invention belongs to the technical field of preparation of molecular sieves and particularly relates to synthesis of SAPO-34 molecular sieves with flaky morphology and an application of the SAPO-34 molecular sieves in preparation of methanol to olefin. The molecular sieves are subjected to one-step hydrothermal synthesis, a double-template agent is mixed with an aluminum source, a silicon source and a phosphorus source, hydrothermal crystallization is performed, and the SAPO-34 molecular sieves are prepared. The synthesized SAPO-34 product adopts the flaky morphology, the crystal size ranges from 0.5 mu m to 2 mu m, and the thickness ranges from 50 nm to 200 nm. The synthesis method is simple, other solvents, surfactants and the like do not need to be added. The prepared product has high low-carbon olefin selectivity, especially high ethylene selectivity in a methanol-to-olefin reaction.

Description

technical field [0001] The invention belongs to the technical field of molecular sieves, and in particular relates to a preparation method of a SAPO-34 molecular sieve with sheet shape and its application in methanol-to-olefins reaction. Background technique [0002] In 1984, United Carbide Corporation (UCC) developed a series of SAPO-34 molecular sieves of silicoaluminophosphate. The molecular sieve is a kind of crystalline silicoaluminophosphate, and its molecular sieve framework is made of PO 4 , AlO 4 and SiO 4 The three-dimensional skeleton structure formed by the interconnection of tetrahedrons has an ellipsoidal cage structure composed of oxygen eight-membered rings and a three-dimensional channel structure. The effective diameter of the molecular sieve aperture is kept between 0.43 and 0.50nm. Due to its good low-carbon olefin selectivity and excellent hydrothermal stability, SAPO-34 molecular sieve has become the preferred molecular sieve for the development of ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01B39/54B82Y30/00B82Y40/00
CPCB82Y30/00B82Y40/00C01B39/54C01P2002/72C01P2004/03C01P2004/20C01P2004/62C01P2004/64Y02P30/20Y02P30/40
Inventor 张世刚陈亚妮张小虎张变玲李宏伟郑鑫磊辛玉兵赵强张军民刘建斌
Owner 陕西煤化工技术工程中心有限公司
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