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Preparation method and applications of modified ZSM-5 molecular sieve for high-selective preparation of propylene from methanol and dimethyl ether

A ZSM-5, high-selectivity technology, applied in molecular sieve catalysts, chemical instruments and methods, chemical/physical processes, etc., can solve problems such as poor stability and easy carbon deposition, and achieve extended catalytic life, simple operation, and controllability strong effect

Inactive Publication Date: 2013-12-04
巩雁军 +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

It mainly solves the problem that ZSM-5 molecular sieves in other technologies are easy to accumulate carbon on the outer surface in the high-selectivity reaction of methanol / dimethyl ether to propylene, which leads to poor stability.

Method used

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  • Preparation method and applications of modified ZSM-5 molecular sieve for high-selective preparation of propylene from methanol and dimethyl ether
  • Preparation method and applications of modified ZSM-5 molecular sieve for high-selective preparation of propylene from methanol and dimethyl ether
  • Preparation method and applications of modified ZSM-5 molecular sieve for high-selective preparation of propylene from methanol and dimethyl ether

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1-10

[0021] The silicon-aluminum ratio is (SiO 2 / Al 2 o 3 ) is 100, and the ZSM-5 molecular sieve with a grain size of about 200 nanometers is calcined at 500° C. for 5 hours. Then exchange with 1 mol / l ammonium chloride or ammonium nitrate at 90°C for 2 hours. After washing, filtering and drying, use 0.1, 0.2, 0.5, 0.8, 1.0 mol / L ammonium fluorosilicate solution to reflux at 30°C, 60°C, 90°C for 2 hours or 6 hours, then wash with deionized water, filter and dry Afterwards, they were calcined at 500°C for 5 hours to obtain a series of modified HZSM-5 catalysts.

Embodiment 11

[0023] The modified catalyst modified in Example 1-10 was pressed into tablets, sieved into 20-40 meshes, and the reaction temperature was 470°C, normal pressure, methanol partial pressure was 50kPa, and methanol space velocity was 3. Carry out methanol-to-propylene reaction Evaluation, the results of the reaction are listed in Table 1.

[0024] Table 1 Methanol to propylene reaction performance of modified ZSM-5 zeolite catalyst

[0025]

[0026]

[0027] a The reaction time to maintain the conversion rate of methanol above 90%.

Embodiment 12-20

[0029] The silicon-aluminum ratio is (SiO 2 / Al 2 o 3 ) is 60, 200, 300, 500, and the grain size is about 1000 nanometers

[0030] Baking at 500°C for 5 hours. Then, it was exchanged with 1.0 mol / liter hydrochloric acid at 90° C. for 2 hours. After washing, filtering and drying, reflux with 0.1, 0.2, 0.5, 0.8, 1.0 mol / liter ammonium fluorosilicate solution at 30°C, 60°C, and 90°C for 6 hours, then wash with deionized water, filter and dry to obtain a series of modified products. Sexual ZSM-5 catalyst.

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Abstract

The invention provides a preparation method and applications of modified ZSM-5 molecular sieve for high-elective preparation of propylene from methanol and dimethyl ether, and mainly solves the problem of bad stability, which is caused by low propylene selectivity and easy carbon deposition, of ZSM-5 molecular sieve in the high-selective preparation of propylene from methanol and dimethyl ether. The preparation method comprises following steps: burning ZSM-5 molecular sieve original powder with a silicon / aluminum ratio in the range of 20 to 1000 and an average particle size in the range of 60 to 5000 nanometers to remove the organic template agent, then exchanging for 3 to 10 hours at the temperature of 20 to 100 DEG C in an ammonium chloride solution or an ammonium nitrate solution with a concentration of 0.1 to 5.0 mol / L, processing the obtained ammonium molecular sieves with different concentration (0.1 to 5.0 mol / L) ammonium fluosilicate solutions at the temperature of 20 to 100 DEG C for 1 to 48 hours, then fully washing with deionized water, filtering, drying for 12 hours at the temperature of 30 to 150 DEG C, and finally burning for 3 to 10 hours at the temperature of 300 to 550 DEG C so as to obtain series modified HZSM-5 molecular sieves. The processing method of ZSM-5 molecular sieve is simple and easy to operate. The modified HZSM-5 molecular sieve catalyst has high propylene selectivity and stability in the selective preparation of propylene from methanol and dimethyl ether.

Description

technical field [0001] The invention belongs to the field of molecular sieve material preparation and catalyst technology, and in particular relates to a preparation method and application of a modified ZSM-5 zeolite catalyst for methanol / dimethyl ether to propylene (MTP). Background technique [0002] Propylene, as one of the basic organic chemical raw materials with the largest demand and widest application in petrochemical industry, plays an important role in the modern petrochemical industry. It is not only the monomer of polypropylene, but also can be derived from various organic intermediates. At present, the main sources of propylene production are light hydrocarbon cracking and catalytic cracking processes. However, due to the increasing shortage of global oil resources and the high price of crude oil, the traditional production route of propylene will have to be adjusted to the direction of diversification of raw material sources. Among them, the production of prop...

Claims

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Application Information

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IPC IPC(8): B01J29/40C07C11/06C07C1/20
CPCY02P20/52
Inventor 巩雁军窦涛胡思张卿张兰兰刘远帅杨飞鹰孙晶
Owner 巩雁军
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