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Method for modifying silicoaluminophosphate molecular sieve, modified molecular sieve and application thereof

A silicoaluminophosphate, molecular sieve technology, applied in molecular sieve catalyst, molecular sieve and alkali exchange phosphate, chemical instruments and methods, etc., can solve the problems of high cost, complicated operation process, etc. Effects of Reaction Stability

Active Publication Date: 2018-07-10
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] The technical problem to be solved by the present invention is the cumbersome operation process and high cost problems existing in the modification of mesoporous template agent in the prior art, and a new modification method of silicoaluminophosphate molecular sieve is provided

Method used

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  • Method for modifying silicoaluminophosphate molecular sieve, modified molecular sieve and application thereof
  • Method for modifying silicoaluminophosphate molecular sieve, modified molecular sieve and application thereof
  • Method for modifying silicoaluminophosphate molecular sieve, modified molecular sieve and application thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0033] To prepare SAPO-34 molecular sieve with hierarchical pore structure, the raw material is taken from the conventional SAPO-34 molecular sieve A prepared according to [Comparative Example 1], which only contains micropores.

[0034] Weigh 30g of molecular sieve A and place it in a 0.03M acidic solution, wherein the acidic solution is a mixed solution of nitric acid and citric acid, the ratio of the two before and after is 8:1, the amount of the solution is 0.9L, and stirred at 75°C After 3 hours, product B was obtained after filtering, washing, drying and roasting.

[0035] The XRD spectrum of B is as figure 1 shown, from figure 1 It can be seen that the synthesized molecular sieve has the characteristic diffraction peaks of SAPO-34 molecular sieve, indicating that the prepared product is pure SAPO-34 molecular sieve with a relative crystallinity of 92%.

[0036] The SEM photograph of B is as image 3 As shown, obvious pore structure appeared on the surface of molecula...

Embodiment 2

[0040] Same as [Example 1], except that the raw material used is the conventional SAPO-34 molecular sieve A roasted product prepared according to the method of [Comparative Example 1], which only contains micropores. The final obtained SAPO-34 molecular sieve with hierarchical pore structure is denoted as C.

[0041] The XRD spectrum of C is as figure 1 shown, from figure 1 It can be seen that the prepared molecular sieve has the characteristic diffraction peaks of SAPO-34 molecular sieve, indicating that the prepared product is pure SAPO-34 molecular sieve with a relative crystallinity of 90%.

[0042] SEM photographs of C with image 3 similar.

[0043] C The micropore diameter is distributed in 0.3-0.5nm, the mesopore diameter is distributed in 8-25nm, and the macropore diameter is distributed in 50-250nm; the pore volume contributed by the micropore is 0.19cm 3 / g, the pore volume contributed by mesopores is 0.20cm 3 / g, the pore volume contributed by macropores is 0....

Embodiment 3

[0046] Same as [Example 1], except that the treatment process is divided into two steps, first treat in 0.1L of 0.01M nitric acid solution for 1 hour, after filtering, washing and drying, then treat in 0.8L of 0.03M citric acid solution 2h, the obtained product is marked as D.

[0047] The XRD spectrum of D is as figure 1 shown, from figure 1 It can be seen that the synthesized molecular sieve has the characteristic diffraction peaks of SAPO-34 molecular sieve, indicating that the synthesized product is pure SAPO-34 molecular sieve with a relative crystallinity of 92%.

[0048] The SEM photograph of D with image 3 similar.

[0049] D The micropore diameter is distributed in 0.3-0.5nm, the mesopore diameter is distributed in 5-20nm, and the macropore diameter is distributed in 50-200nm; the pore volume contributed by the micropore is 0.20cm 3 / g, the pore volume contributed by mesopores is 0.21cm 3 / g, the pore volume contributed by macropores is 0.19cm 3 / g; the specifi...

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Abstract

The invention relates to a method for modifying a silicoaluminophosphate molecular sieve, a modified molecular sieve and application thereof, and aims at solving the existing problems of complicated operation process and high cost of mesoporous template agent modifying in the prior art. The method comprises the step that only the silicoaluminophosphate molecular sieve with a microporous structureis in contact with a modifier, wherein the modifier is a compound of inorganic acid and organic acid, the inorganic acid is selected from at least one of hydrochloric acid, sulphuric acid, hydrogen nitrate and phosphoric acid, the organic acid is selected from at least one of oxalic acid, acetic acid, ethanedioic acid and citric acid, and in the compound, the weight ratio of the inorganic acid tothe organic acid is (100-80):(0.1-20). By means of the method, the problems are well solved, and the method can be applied to the industrial production of the preparation of the silicoaluminophosphatemolecular sieve with a multi-stage porous structure.

Description

technical field [0001] The invention relates to a modification method of a silicon aluminum phosphate molecular sieve, a modified molecular sieve and an application thereof. Background technique [0002] In 1984, United Carbide Corporation (UCC) invented a silicoaluminophosphate molecular sieve (SAPO molecular sieve) with a pore size of about 0.4nm. SAPO molecular sieve is made of AlO 4 , SiO 4 and PO 4 The crystal network structure composed of tetrahedrons, the pores in the crystal are due to Si 4+ replace P 5+ or Al 3+ The acidity produced or replaced by metals to produce acidity. Among SAPO series molecular sieves, SAPO-34 molecular sieve is widely used in modern petroleum processing industry because of its good thermal and hydrothermal stability, moderate acidity, high specific surface area and highly ordered micropore channels. middle. The most striking thing is that the molecular sieve is used in the reaction of methanol to olefins (MTO), which can make the con...

Claims

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Application Information

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IPC IPC(8): C01B39/54B01J29/85
CPCB01J29/85C01B39/54C01P2002/72C01P2004/03C01P2004/38C01P2006/12C01P2006/14C01P2006/17
Inventor 丁佳佳刘红星陆贤管洪波张玉贤
Owner CHINA PETROLEUM & CHEM CORP
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