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Catalytic cracking catalyst promoter containing beta-zeolite and application thereof

A catalytic cracking, catalyst technology

Active Publication Date: 2013-12-18
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In the 1960s and 1970s, Heden and others synthesized NaY zeolite for the first time by in situ crystallization method, which is not yet mature.

Method used

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  • Catalytic cracking catalyst promoter containing beta-zeolite and application thereof
  • Catalytic cracking catalyst promoter containing beta-zeolite and application thereof
  • Catalytic cracking catalyst promoter containing beta-zeolite and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] Preparation of in-situ crystallized microspherical β zeolite. Calculated according to the mass percentage of the feed amount in the whole prepared microsphere mixture, 50wt% of commercially available kaolin (see Table 1 for composition), 10wt% of silica sol (with SiO 2 Calculate), 38wt% of distilled water and 2wt% of β molecular sieve seed crystals are mixed uniformly, spray molded on a small spray device, and calcined at 900°C for 4 hours. In turn, 72 grams of tetraethylammonium hydroxide solution (containing 25% by weight of TEAOH), 34 grams of calcined kaolin microspheres, and 200 grams of water glass (containing 28.08% by weight of SiO 2 , 8.83wt% Na 2 O), 72 grams of sulfuric acid solution (containing 25.48wt% sulfuric acid) was put into a stainless steel reactor and stirred for 2 hours to prepare a mixture gel. The molar ratio of each component in the gel based on its oxide is: SiO 2 / Al 2 O 3 =8.60; TEAOH / SiO 2 =0.10; Na 2 O / SiO 2 =0.08; H 2 O / SiO 2 =10.77; OH - / S...

Embodiment 2

[0048] Preparation of in-situ crystallized microspherical β zeolite. (1) Calculated according to the mass percentage of the feed amount in the whole prepared microsphere mixture, 35wt% of commercially available kaolin (see Table 1 for composition), 40wt% of distilled water, 10wt% of β molecular sieve seed crystals and 15wt% of water glass (Calculated as SiO2) mix uniformly, spray molding, and fire at 600°C for 8 hours. (2) Put 143 grams of tetraethylammonium hydroxide solution (containing 25wt% TEAOH), 30 grams of kaolin microspheres, 3.1 grams of NaOH (solid reagent), and 54 grams of coarse-pored silica gel in step (1) into the stainless steel reactor. After stirring for 2 hours, the mixture gel was prepared. The molar ratio of each component in the gel based on its oxide is: SiO 2 / Al 2 O 3 =8.57; TEAOH / SiO 2 =0.23; Na 2 O / SiO 2 =0.035; H 2 O / SiO 2 =5.73; OH - / SiO 2 =0.30. After sealing, the temperature was raised to 150°C for constant temperature crystallization for 96 ho...

Embodiment 3

[0050] Preparation of in-situ crystallized β zeolite catalyst promoter. Take 100g of the in-situ crystallized microspherical β zeolite prepared in Example 1 (relative crystallinity is 33%), add 500g of water, 10.67g of ammonium chloride, 5ml of 1:1 hydrochloric acid, and perform primary ammonium ion exchange at 90°C , Time is 1h; exchange the sample obtained by suction filtration; then add 500g of water and 5.33g of ammonium chloride to the filter cake, and carry out the second ammonium ion exchange at 90℃; finally, the obtained sample is dried and demoulded, The conditions are: heating from room temperature to 450°C for 1 hour and constant temperature for 1 hour; heating to 550°C for 2 hours and constant temperature for 2 hours to obtain modified samples. The modified sample was aged at 800°C for 3 hours to obtain in-situ crystallized β zeolite catalyst promoter. The relative crystallinity of the sample measured by XRD was 31%.

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Abstract

The invention relates to a beta-zeolite catalyst promoter suitable for catalytic cracking reaction and capable of increasing liquid yield, reducing coke and increasing yield of propylene. Kaolin microballoon in-situ crystallization beta-zeolite is subjected to modification, demoulding and ageing for preparation of the catalyst promoter, which is applied to catalytic cracking reactions. The in-situ crystallization microballoon beta-zeolite catalyst promoter can substitute 2-50 wt% of a base catalyst. Compared with a beta-zeolite catalyst promoter prepared by a binder method, the in-situ crystallization beta-zeolite catalyst promoter has stronger capability in propylene yield increase, coking resistance and liquid yield increase.

Description

Technical field [0001] The invention belongs to the preparation field of zeolite catalysts. The in-situ crystallized microspherical β zeolite is used to prepare catalytic cracking catalyst promoter. Background technique [0002] The preparation methods of catalytic cracking catalysts are generally divided into two types: binder method and in-situ crystallization method. Binder-type catalysts are made into microsphere catalysts by bonding zeolite and matrix with a binder. This method is mature and has been widely used. The in-situ crystallization process is to first roast the kaolin to generate active SiO 2 And A1 2 O 3 , And inactive spinel and a small amount of mullite, and then use roasted kaolin as raw material to synthesize zeolite under alkaline conditions. Among them, the active part is used for crystallization to form zeolite, and the non-active part can be used as the substrate of the catalyst, which has the effect of enhancing the stability of the catalyst (in-situ cr...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/06C10G11/05
Inventor 庞新梅申宝剑张美英郭巧霞朱珊张伟沈虹佟雪芳朴佳锐王骞朱晓晓
Owner PETROCHINA CO LTD