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Low-silicon SAPO-34 molecular sieve as well as preparation method and application thereof

A molecular sieve and seed crystal technology, applied in molecular sieve catalysts, chemical instruments and methods, and hydrocarbon production from oxygen-containing organic compounds, can solve problems such as poor economy, environmental pollution, toxicity, etc., achieve high raw material utilization, and facilitate production and application , the effect of obvious advantages

Inactive Publication Date: 2017-03-22
CHINA UNIV OF PETROLEUM (EAST CHINA)
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For example CN102464338A discloses a kind of preparation method that adopts directing agent method to prepare small grain SAPO-34 molecular sieve, but this method is unsatisfactory in preparing low silicon SAPO-34 molecular sieve, and it must add when preparing crystallization directing agent Toxic and highly corrosive HF, so it is not suitable for large-scale industrial production
[0006] It can be seen that although some methods for preparing low-silicon SAPO-34 molecular sieves have been developed in the prior art, most of these methods have problems of poor economy and environmental pollution
Moreover, for low-silicon SAPO-34 molecular sieves, due to the influence of low silicon ratio, it is still difficult to obtain low-silicon SAPO-34 molecular sieve products with high crystallinity and small crystal grains

Method used

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  • Low-silicon SAPO-34 molecular sieve as well as preparation method and application thereof
  • Low-silicon SAPO-34 molecular sieve as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
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Embodiment 1

[0044] This embodiment provides a kind of low silicon SAPO-34 molecular sieve, the specific preparation process of this molecular sieve is:

[0045] (1) Preparation of seed crystal guide liquid

[0046] The molar ratio of the feed for the synthesis of the seed crystal guide liquid: 1.2SiO 2 : 1Al 2 o 3 : 0.8P 2 o 5 :2TEA:50H 2 O;

[0047] The specific steps are:

[0048] Mix pseudo-boehmite (68wt%), seed crystal (grain size 6 μm), and 1 / 3 deionized water, the seed crystal is 0.1wt% of the total material, stir at 0°C for 0.2h to dissolve and mix evenly; then Slowly and evenly add phosphoric acid (85wt%) dropwise, keep stirring vigorously for 1h to form a gel, add 1 / 3 deionized water dropwise, and stir for 0.2h; slowly add silica sol (40wt%) dropwise, continue stirring for 0.5h; drop evenly Add triethylamine (99wt%), keep stirring, drop the remaining deionized water, and stir vigorously for 4 hours to obtain the guide liquid gel. In the process of preparing the guide liq...

Embodiment 2

[0055] This embodiment provides a kind of low silicon SAPO-34 molecular sieve, the specific preparation process of this molecular sieve is:

[0056] (1) Preparation of seed crystal guide liquid

[0057] The molar ratio of the feed for the synthesis of the seed crystal guiding liquid: 0.9SiO 2 : 1Al 2 o 3 : 0.8P 2 o 5 :2R:50H 2 O, template R is composed of TEAOH (tetraethylammonium hydroxide) and TEA (triethylamine), the molar ratio of the two is 0.08:1;

[0058] The specific steps are:

[0059] Mix aluminum isopropoxide (99wt%), seed crystals (average grain size 8 μm), and 1 / 3 deionized water, the seed crystals are 0.1wt% of the total material, stir at 15°C for 0.2h to dissolve and mix evenly; then slowly Add phosphoric acid (85wt%) evenly dropwise, keep stirring vigorously for 1h to form a gel, add 1 / 3 deionized water dropwise, and stir for 0.2h; slowly add silica sol (40wt%), continue stirring for 0.5h; TEA (99wt%), kept stirring, added dropwise the remaining deioniz...

Embodiment 3

[0066]This embodiment provides a kind of low silicon SAPO-34 molecular sieve, the specific preparation process of this molecular sieve is:

[0067] (1) Preparation of seed crystal guide liquid

[0068] The molar ratio of the feed for the synthesis of the seed crystal guide liquid: 0.5SiO 2 : 1Al 2 o 3 : 0.8P 2 o 5 :2R:60H 2 O, the template agent R is composed of TEAOH (tetraethylammonium hydroxide) and Mor (morpholine), the molar ratio of the two is 0.15:1, the phosphorus source is composed of phosphoric acid and phosphorous acid, and the molar ratio of the two is 4: 1;

[0069] The specific steps are:

[0070] Mix pseudo-boehmite (68wt%), seed crystals (average grain size 4 μm), and 1 / 3 deionized water, the seed crystals are 0.1wt% of the total material, stir at 10°C for 0.2h to dissolve and mix evenly; then Slowly and evenly add phosphoric acid (85wt%) and phosphorous acid (80wt%) dropwise, keep stirring vigorously for 1h to form a gel, add 1 / 3 deionized water dropwi...

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Abstract

The invention provides a low-silicon SAPO-34 molecular sieve as well as a preparation method and an application thereof. The preparation method of the low-silicon SAPO-34 molecular sieve comprises steps as follows: (1), guiding lyogel is prepared from a silicon source, an aluminum source, a phosphorus source, a seed crystal, a template agent and water through stirring and mixing at the temperature of 0-20 DEG C, and a seed crystal guiding liquid is prepared after the guiding lyogel is subjected to hydrothermal crystallization; (2), initial gel of the SAPO-34 molecular sieve is prepared from the silicon source, the aluminum source, the phosphorus source, the seed crystal guiding liquid, the template agent and water through stirring and mixing at the temperature of 0-20 DEG C; the initial gel of the SAPO-34 molecular sieve is subjected to low-temperature hydrothermal crystallization and high-temperature hydrothermal crystallization sequentially and then is subjected to aftertreatment, and the low-silicon SAPO-34 molecular sieve is prepared. According to the method, an inexpensive template agent can be used less or even cannot be used, and a product meeting requirements for crystallinity and purity is obtained without prolonging of crystallization time, and the preparation method of the low-silicon SAPO-34 molecular sieve is suitable for large-scale industrial production.

Description

technical field [0001] The invention belongs to the technical field of oil refining, and in particular relates to a low-silicon SAPO-34 molecular sieve and its preparation method and application. Background technique [0002] SAPO-34 molecular sieve has a three-dimensional octanary pore structure of chabazite (CHA), the effective diameter of the pore is 0.43-0.50nm, suitable for medium-strength acidity, unique small pore structure, and has excellent catalytic performance in MTO, methanol The conversion rate is basically 100%, with good ethylene and propylene selectivity. Ethylene and propylene are important basic organic chemical raw materials in the chemical industry, and SAPO-34 molecular sieve has broad application prospects. [0003] Low-silicon SAPO-34 molecular sieve has high selectivity of low-carbon olefins in MTO catalytic reaction, especially the selectivity of ethylene, which is obviously better than ZSM-5, which promotes the industrialization of low-silicon SAPO...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/85C07C1/20C07C11/02
CPCC07C1/20C07C11/02B01J29/85
Inventor 张强马晓月李春义刘璐杨朝合
Owner CHINA UNIV OF PETROLEUM (EAST CHINA)
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