A kind of modification method of Y-type molecular sieve

A molecular sieve and modification technology, applied in the direction of crystalline aluminosilicate zeolite, octahedral crystalline aluminosilicate zeolite, etc., can solve the problem of not meeting the requirements of high stability and high number of acid centers at the same time, affecting cracking activity or selectivity , reducing the total acid content of molecular sieves, etc., to achieve the effects of increasing the number of acid centers, moderately adjusting cracking activity, and high skeleton silicon-aluminum ratio

Active Publication Date: 2018-09-28
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, it is unavoidable that during the ultra-stabilization process, due to the dealumination of the skeleton, the Si-O-Al bonding structure is reduced, resulting in the loss of the B acid center, and because the charges in the Si-O-Si structure are balanced, there is no acidity. , thus leading to a decrease in the total acid content of the molecular sieve, affecting the cracking activity or selectivity
Therefore, the ultra-stabilization process cannot meet the requirements of high stability and high number of acid sites at the same time.

Method used

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  • A kind of modification method of Y-type molecular sieve

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Comparison scheme
Effect test

Embodiment 1

[0022] Mix 25.8g of industrial NaY molecular sieve (90% crystallinity, 77.5% solid content, 2.65 skeleton silicon-aluminum atomic ratio, Sinopec Changling Catalyst Factory) with water, add 200g of glycerol, heat up to 160°C for 2 hours, and wait for After it was cooled to room temperature, it was mixed with 40g TPAOH solution (mass fraction 25wt%), then the temperature was raised to 60°C and 64mL water glass solution (SiO 2 Content 250g / L, modulus 3.3), after stirring, add 29mL sodium metaaluminate (Al 2 o 3 Content 190g / L) and continue aging for 2h. The aged slurry was crystallized at 100°C for 20 hours, filtered, washed and dried, and calcined at 600°C for 4 hours to obtain the molecular sieve of the present invention, which is designated as GYD-1. The XRD spectrum confirmed that the obtained molecular sieve had the structural characteristics of Y-type molecular sieve.

Embodiment 2

[0024] Mix 25.8g of industrial NaY molecular sieve (same as above) with water, add 120g of glycerol, raise the temperature to 130°C for activation treatment for 6h, wait for it to cool to room temperature, mix with 16g of TPAOH solution, then add 24mL of water glass solution at 40°C After stirring, 13 mL of sodium metaaluminate was added and the temperature was raised to 70° C. for aging for 2 h. The aged slurry was crystallized at 120°C for 10h, filtered, washed and dried, and then calcined at 600°C for 2h to obtain the molecular sieve of the present invention which is designated as GYD-2. The XRD spectrum confirmed that the obtained molecular sieve had the structural characteristics of Y-type molecular sieve.

Embodiment 3

[0026] Mix 25.8g of industrial NaY molecular sieve (same as above) with water, add 160g of propylene glycol, heat up to 180°C for activation treatment for 4h, and after cooling to room temperature, mix with 56g of TEAOH solution (mass fraction 25wt%), then heat up to 50°C and Add 34g tetraethoxy silicon, add 53mL aluminum sulfate solution (Al 2 o 3 Content 90g / L) and continue to heat up to 70°C for aging for 2h. The aged slurry was crystallized at 120°C for 15 hours, filtered, washed and dried, and then calcined at 550°C for 6 hours to obtain the molecular sieve of the present invention, which is designated as GYD-3. The XRD spectrum confirmed that the obtained molecular sieve had the structural characteristics of Y-type molecular sieve.

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Abstract

The invention provides a Y type molecular sieve modification method. The Y type molecular sieve modification method is characterized by comprising the steps that (1) a NaY molecular sieve is activated for 1-10 h through polyhydroxy alcohol at 80-200 DEG C to obtain slurry A, wherein the alcohol-sieve weight ratio is (1-20):1; (2) the slurry A is cooled and mixed with organic alkali to obtain slurry B, wherein the alkali-sieve weight ratio is (0.1-1):1; (3) a silicon source and an aluminum source are sequentially added into the slurry B, and the mixture is aged to obtain slurry C, wherein the weight ratio of the silicon source (in terms of SiO2) to the NaY molecular sieve is (0.1-1):1, and the weight ratio of the aluminum source (in terms of Al2O3) to the silicon source (in terms of the SiO2) is (0.3-0.5):1; and (4) the slurry C is subjected to hydrothermal crystallization, and a product is recovered. By adoption of the Y type molecular sieve modification method, the silicon-aluminum ratio of a molecular sieve skeleton can be remarkably increased, meanwhile, the acid site number of the molecular sieve is increased, and the cracking activity of the molecular sieve is improved.

Description

technical field [0001] The invention relates to a method for modifying a Y-type molecular sieve. Background technique [0002] Breck successfully synthesized Y-type molecular sieve in the 1960s. After half a century of research and development, Y-type molecular sieve has been widely used in modern industry. Y-type molecular sieve is a kind of aluminosilicate with faujasite structure (FAU), which is a very important kind of microporous catalytic material, with uniform pore structure, high thermal and hydrothermal stability and strong It is acidic and has high catalytic activity, so it is widely used in petroleum refining and petroleum processing, especially in catalytic cracking and hydrocracking, and has become an extremely important cracking active component in cracking agents. [0003] In the catalytic cracking reaction process, according to the carbon ion reaction mechanism, the molecular sieve should have a strong B acid center to ensure a high cracking activity. For t...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C01B39/24
Inventor 郑金玉罗丁王成强罗一斌
Owner CHINA PETROLEUM & CHEM CORP
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