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Superacid-coated HZSM-5 molecular sieve catalyst and preparation method and application thereof

A technology of molecular sieve and super acid, which is applied in the direction of molecular sieve catalyst, molecular sieve catalyst, catalyst, etc., can solve the problems of destroying the pore structure of HZSM-5 molecular sieve, the decrease of the utilization rate of acid sites in the pore, and the insignificant suppression of surface carbon, so as to improve the work Stability, easy large-scale preparation, and the effect of improving catalytic activity

Active Publication Date: 2016-11-09
TIANJIN UNIV
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  • Claims
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Problems solved by technology

In the actual application process, there is such a problem: when the HZSM-5 molecular sieve is working in a high temperature environment, carbon deposits will occur on the surface, resulting in blockage of the pores, and a decrease in the utilization rate of the acid sites inside the channels, making the catalytic rapid decrease in activity
However, these modification treatments have their own shortcomings, especially in the suppression of surface carbon deposition.
In addition, these modification methods often destroy the unique pore structure of the HZSM-5 molecular sieve, resulting in a decrease in the selectivity of the target product, and some modification processes are too complicated

Method used

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  • Superacid-coated HZSM-5 molecular sieve catalyst and preparation method and application thereof

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preparation example Construction

[0022] The preparation method of catalyst of the present invention is as follows:

[0023] In order to prepare the superacid-coated HZSM-5 molecular sieve catalyst, firstly, by adjusting the raw material formula in the chemical liquid phase deposition method, a layer of TiO with controllable quality is deposited on the outer surface of the HZSM-5 molecular sieve grain. 2 or ZrO 2 . Vulcanization is then accomplished in a sulfur-containing solution (sulfuric acid, ammonium sulfate, persulfuric acid, or an aqueous ammonium persulfate solution). By adjusting the concentration of sulfur-containing solution and the time of vulcanization, the TiO 2 and ZrO 2 Different degrees of super-acidification, and then on the outer surface of the HZSM-5 molecular sieve, a layer of adjustable super-acid shell is formed to realize the improvement of the catalytic activity of the HZSM-5 molecular sieve and inhibit the formation of carbon on the surface.

[0024] As mentioned above, the presen...

Embodiment 1

[0026] Example 1: TiO 2 ·H 2 SO 4 Preparation of wrapped HZSM-5

[0027] Dissolve 0.15 g of tetrabutyl titanate in 125 mL of absolute ethanol, add 5 g of commercial HZSM-5 molecular sieves into the solution, and heat and stir for about 1 hour. Next, the solution was filtered, dried, and calcined at 550° C. for 3 hours. Take 100 mL of 10 wt % ammonium sulfate aqueous solution, and add the calcined sample into the solution, and then stir at room temperature for about 8 hours. Next, the solution was filtered, dried, and calcined at 550°C for 3 hours to obtain TiO 2 ·H 2 SO 4 Wrap HZSM-5 catalyst (sample 1).

Embodiment 2

[0028] Example 2: ZrO 2 ·H 2 SO 4Preparation of wrapped HZSM-5

[0029] Under the condition of protective gas, the air was isolated, 0.30 g of zirconium butoxide was dissolved in 125 mL of absolute ethanol, 5 g of commercial HZSM-5 molecular sieves were added to the solution, and stirred for about 1 hour. Next, the solution was filtered, dried, and calcined at 550° C. for 3 hours. Take 100 mL of 2 wt% sulfuric acid aqueous solution, and add the calcined sample into the solution, and then stir at room temperature for about 1 hour. Next, filter, dry the solution, and then calcinate at 550°C for 3 hours to obtain ZrO 2 ·H 2 SO 4 Wrap HZSM-5 catalyst (sample 2).

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Abstract

The invention belongs to the technical field of catalysts, and particularly discloses a superacid-coated HZSM-5 molecular sieve catalyst. The catalyst is prepared through the step that the surface of an HZSM-5 molecular sieve is coated with one of superacids including TiO2.H2SO4, ZrO2.H2SO4, TiO2.H2S2O8 and ZrO2.H2S2O8 or a composition of TiO2.H2SO4, ZrO2.H2SO4, TiO2.H2S2O8 and ZrO2.H2S2O8. The invention further discloses a preparation method of the superacid-coated HZSM-5 molecular sieve catalyst and application of the superacid-coated HZSM-5 molecular sieve catalyst in a technology for preparing low carbon olefin from naphtha through catalytic cracking.

Description

technical field [0001] The invention belongs to the technical field of catalysts, and in particular relates to a preparation method of a superacid-wrapped HZSM-5 molecular sieve catalyst and its application in the process of preparing light olefins by catalytic cracking of naphtha. Background technique [0002] Light olefins, represented by ethylene and propylene, are important basic raw materials in the petrochemical industry. With the rapid development of the global economy, the demand for ethylene and propylene is increasing, and its production capacity is far from meeting the needs of the international market. This imbalance of supply and demand directly restricts the rational development of related derivatives and downstream products. Therefore, vigorously developing new processes for preparing low-carbon olefins with low energy consumption and using new resources, increasing the production capacity of ethylene and propylene, so as to meet the production needs of the m...

Claims

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Application Information

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IPC IPC(8): B01J29/40C07C4/06C07C11/02C07C11/06
CPCY02P20/52B01J29/405B01J2229/26B01J2229/37C07C4/06C07C2529/40C07C11/02C07C11/06
Inventor 刘国柱侯旭邱园张香文王莅
Owner TIANJIN UNIV
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