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Method for improving B acid content of ZSM-5 molecular sieve and realizing yield increase of light olefin

A technology of ZSM-5 and molecular sieve, which is applied in molecular sieve catalysts, chemical instruments and methods, hydrocarbon cracking and hydrocarbon production, etc., can solve the problem of low activity, achieve the effect of simple steps, improve overall reactivity, and increase yield

Active Publication Date: 2011-07-06
CHINA UNIV OF PETROLEUM (BEIJING)
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Gallium and chromium-modified ZSM-5 by impregnation showed better selectivity to lower olefins than unmodified ZSM-5, but lower activity than copper-modified samples by ion-exchange

Method used

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  • Method for improving B acid content of ZSM-5 molecular sieve and realizing yield increase of light olefin
  • Method for improving B acid content of ZSM-5 molecular sieve and realizing yield increase of light olefin
  • Method for improving B acid content of ZSM-5 molecular sieve and realizing yield increase of light olefin

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Take by weighing 29.1 grams of dried HZSM-5 molecular sieves (silicon-aluminum ratio 30-40), measure its water absorption; weigh Fe(NO 3 ) 3 .9H 2 O 3.31 g, Ti(SO 4 ) 2 2.35 grams, dissolved in an appropriate volume of distilled water to prepare a ferric nitrate / titanium sulfate mixed impregnation solution, slowly pour the mixed impregnation solution into the dried HZSM-5 molecular sieve, and keep stirring to achieve equal volume impregnation; stand for 12 hours Then put it into an oven at 120°C for 6 hours and bake it in a muffle furnace at 540°C for 4 hours to obtain the modified molecular sieve Fe-Ti / ZSM-5.

[0054] The ZSM-5 before modification and the Fe-Ti / ZSM-5 after modification were tabletted, ground and sieved to obtain catalysts ZSM-5 and Fe-Ti / ZSM-5 with spherical particles respectively.

[0055] The above-mentioned ZSM-5 and Fe-Ti / ZSM-5 catalysts were used to determine the amount of acid by pyridine adsorption-desorption infrared spectroscopy, and the ...

Embodiment 2

[0057] Take by weighing two parts of dried HZSM-5 molecular sieves 29.1 grams (silicon-aluminum ratio 30-40) respectively, measure its water absorption; Weigh Fe(NO 3 ) 3 .9H 2 O 3.31 g, Ti(SO 4 ) 2 2.35 grams were respectively dissolved in an appropriate volume of distilled water to prepare ferric nitrate and titanium sulfate impregnating solutions, and the impregnating solutions were slowly poured into the above-mentioned dried HZSM-5 molecular sieves, stirring continuously to realize equal volume impregnation; After standing for 12 hours, put it into an oven at 120°C for 6 hours and bake it in a muffle furnace at 540°C for 4 hours to obtain modified molecular sieves Fe / ZSM-5 and Ti / ZSM-5.

[0058] Prepare catalyst Fe / ZSM-5 and Ti / ZSM-5 according to the method for embodiment 1, and adopt n-propylamine temperature-programmed decomposition method to measure wherein B acid content, the results are shown in Table 2.

[0059] Table 1 Comparison of acidity between ZSM-5 and F...

Embodiment 3

[0064] Take the dried HZSM-5 molecular sieve (silicon-aluminum ratio is 29.7 grams, measure its water absorption; weigh Fe(NO 3 ) 3 .9H 2 O 0.66 g, Ti(SO 4 ) 2 4.23 grams, dissolved in an appropriate volume of distilled water to prepare a ferric nitrate / titanium sulfate mixed impregnation solution, and slowly pour the mixed impregnation solution into the dried HZSM-5 molecular sieve, stirring constantly, and impregnating with equal volume; After 12 hours, put into 120 DEG C of oven and dry for 6 hours; Roast in 540 DEG C of muffle furnaces for 4 hours, obtain the catalyst Fe-Ti / ZSM-5 (Fe / Ti mass ratio of spherical particle by tableting, grinding, sieving then =0.11), after being diluted with 60% quartz sand, the catalyst Fe-Ti / ZSM-5-A1 was obtained. The catalyst was evaluated using n-decene as raw material, and the results are shown in Table 3.

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Abstract

The invention relates to a method for improving the B acid content of ZSM-5 molecular sieves and realizing the yield increase of light olefins. Both iron and titanium used for ZSM-5 molecular sieves are modified to obtain a weight ratio of the iron and titanium elements in a modified molecular sieve of 0.3-3:1; the obtained catalyst are evaluated respectively by n-decane, isopropyl benzene, and Daqing heavy oil, and the B acid content in the ZSM-5 molecular sieve catalyst is demonstrated to be significantly increased after iron / titanium bimetallic modification; therefore the catalysis reactivity of the molecular sieve is improved, which represents that the conversion of long-chain alkanes and aromatic hydrocarbons with long-chain alkyl side chains such as isopropyl benzene can be effectively promoted so as to realize the effect of a significant increase of the yield of light olefins; and the invention has a positive significance on the research of preparing light olefins by the catalytic cracking of heavy oil raw materials.

Description

technical field [0001] The invention relates to a method for providing a modified ZSM-5 molecular sieve with enhanced B acid content through metal modification, and a method for using the modified molecular sieve to catalytically crack hydrocarbon raw materials to increase the production of low-carbon olefins, and belongs to the technical field of catalysts. Background technique [0002] Light olefins, especially ethylene and propylene, are very important basic chemical raw materials. At present, there is a huge demand for light oil in the world, and light oil is increasingly scarce as a raw material for the production of low-carbon olefins. Therefore, the technology of direct catalytic cracking of heavy oil as raw material to produce low-carbon olefins has been paid more and more attention, and catalysts play a very important role in these processes. Therefore, the research on low-carbon olefin selective catalysts, especially molecular sieve catalysts, has received extensiv...

Claims

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Application Information

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IPC IPC(8): B01J29/46C10G11/05C07C4/06C07C11/04C07C11/06
CPCY02P20/52
Inventor 申宝剑李贤丰沈文郭巧霞
Owner CHINA UNIV OF PETROLEUM (BEIJING)
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