ZSM-5 and ZSM-11 eutectic zeolite molecular sieve and preparation method and application thereof

A technology of ZSM-11 and ZSM-5, which is applied in ZSM-5 and ZSM-11 eutectic zeolite molecular sieves and their preparation and application fields, can solve problems that have not been reported, and achieve good economical and technical properties, good reaction performance, and improved The effect of raw material adaptability

Active Publication Date: 2015-05-20
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the direct hydrothermal synthesis of ZSM-5 / ZSM-11 eutectic molecular sieves with high crystallinity has not been reported so far.
The application of ZSM-5 / ZSM-11 eutectic molecular sieve synthesized by direct method in the technology of methanol to propylene has not been reported yet.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Put 0.48g of aluminum sulfate crystals with a content of 99.9%, 3g of sodium hydroxide, 1g of ZSM-5 molecular sieve crystal seeds, and 30g of deionized water into the reaction kettle, and stir until uniform at room temperature to obtain the working solution 1.

[0038] Add 4.2g of tetrabutylammonium bromide (99.8wt%, the same below), 3.4g of sodium hydroxide and 10g of deionized water into a beaker, mix until uniform, and obtain working solution 2. Under constant stirring, add working solution 2 to working solution 1 until the mixture is uniform. After half an hour, under constant stirring, add 30g of silica sol (SiO 2 40%,Na 2 O0.4%,H 2 O59.6%), continue to stir at room temperature for 2 hours until the mixture is uniform. Put the reactor into an oven at 110°C for 48 hours of crystallization, and then continue to place it in an oven at 180°C for 12 hours of crystallization. The material after the crystallization reaction is rapidly cooled to room temperature, the s...

Embodiment 2

[0040] Synthetic raw material is constant according to example 1, and ZSM-5 seed crystal addition amount is increased to 2g, and organic template is tetrabutyl ammonium hydroxide, and crystallization condition is constant. The material after the crystallization reaction is rapidly cooled to room temperature, the solid and the mother liquor are separated, washed with deionized water to a pH of 8-9, and dried at 100° C. for 10 hours to obtain a molecular sieve powder. After the final product is tested by X-ray diffraction, the mass fraction of ZSM-5 in the ZSM-5 / ZSM-11 eutectic molecular sieve is about 50%, and the particle size is about 1-2 μm.

Embodiment 3

[0042] Synthetic raw materials are kept unchanged according to Example 1, the addition amount of ZSM-5 seed crystals is increased to 3g, the aluminum source is aluminum hydroxide, and the crystallization conditions are unchanged. The material after the crystallization reaction is rapidly cooled to room temperature, the solid and the mother liquor are separated, washed with deionized water to a pH of 8-9, and dried at 100° C. for 10 hours to obtain a molecular sieve powder. After the final product is tested by X-ray diffraction, the mass fraction of ZSM-5 in the ZSM-5 / ZSM-11 eutectic molecular sieve is about 70%, and the particle size is about 3-5 μm.

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Abstract

The invention relates to a ZSM-5 and ZSM-11 eutectic zeolite molecular sieve and a preparation method and application thereof. The preparation method of the ZSM-5 and ZSM-11 eutectic zeolite molecular sieve comprises the following steps of: adding an aluminum source, a part of alkali and a seed crystal to deionized water, and mixing at 0-30 DEG C to obtain a working solution 1; mixing an organic template agent, the part of alkali and the deionized water to obtain a working solution 2; adding the working solution 2 to the working solution 1 to prepare a mixed glue; adding a silicon source to the mixed glue; placing a reaction kettle into a drying box at 110-140 DEG C, crystallizing for 12-36 hours, and crystallizing in a drying box at 160-180 DEG C for 12-36 hours; cooling a material subjected to crystallizing reaction to room temperature, separating a solid and a mother solution, washing by using the deionized water till the pH value is 8-9, and drying at 100 DEG C for 10 hours. The ZSM-5 and ZSM-11 eutectic zeolite molecular sieve disclosed by the invention can be used for preparing propylene by catalyzing methanol and / or dimethyl ether, wherein the conversion rate of methanol is 100%, the yield of low-carbon olefin is kept as 55%-58%, the yield of propylene is 48%, the P / E ratio is 9, and the life of a catalyst is more than 500 hours.

Description

technical field [0001] The invention relates to a ZSM-5 and ZSM-11 eutectic zeolite molecular sieve and its preparation method and application. The invention provides a one-step method for synthesizing eutectic zeolite with both ZSM-5 and ZSM-11 structures. Background technique [0002] With the continuous increase of demand for propylene in various economic and social fields and the continuous reduction of oil and gas resources, it is urgent to open up new non-petroleum-based propylene production routes. In recent years, the methanol to propylene (MTP) process has The sources of raw materials (which can be produced from coal, natural gas, and biomass) and high propylene yields have attracted more and more attention, and are considered to be an important way for propylene production in the post-oil and gas era. At present, HZSM-5 molecular sieve has become the preferred catalyst for MTP process because of its high propylene selectivity and good anti-coking deactivation perf...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/80C07C11/06C07C1/20
CPCY02P20/52
Inventor 展江宏徐新良巩雁军徐亚荣裴蓓聂宏元龚涛贺春梅杨亚敏
Owner PETROCHINA CO LTD
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