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Modified zeolite catalyst for methanol dehydration to propylene and preparation method thereof

A zeolite catalyst and methanol dehydration technology, which is applied in the industrial field, can solve the problems of poor stability and easy fluctuation of product yield, and achieve the effects of long stable period, slow decay of methanol conversion rate and good catalytic activity

Inactive Publication Date: 2016-03-30
INNOVATIVE COAL CHEMICAL DESIGN INSTITUTE (SHANGHAI) CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The ZSM-5 zeolite catalyst prepared by binderless technology shows the advantages of high propylene selectivity and high propylene / ethylene ratio in the MTP reaction [patent disclosure CN101269340A], but the continuous catalytic reaction product yield is easy to fluctuate, Poor stability

Method used

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  • Modified zeolite catalyst for methanol dehydration to propylene and preparation method thereof
  • Modified zeolite catalyst for methanol dehydration to propylene and preparation method thereof
  • Modified zeolite catalyst for methanol dehydration to propylene and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1-9

[0040] Embodiment 1-9: the preparation of aluminum salt working solution

[0041] The typical raw materials, proportions and preparation conditions used to prepare the aluminum salt working solution are shown in Table 1 below.

[0042] Table 1. Preparation of aluminum salt working solution

[0043]

[0044] The preparation process is as follows:

[0045] Taking Example 1 as an example, weigh 17.1 grams of anhydrous aluminum sulfate, put it into a beaker, add an appropriate amount of water to dissolve it, pour it into a 1L volumetric flask after completely dissolving, and set the volume to 1L.

Embodiment 10-18

[0046] Examples 10-18: Catalyst Hydrothermal Modification

[0047] The typical conditions of hydrothermal modification with aluminum salt solution are shown in Table 2 below:

[0048] Table 2. Catalyst hydrothermal modification

[0049] Example

working solution

solid to liquid mass ratio

10

Example 1

1:10

11

Example 2

1:5

12

Example 2

1:3

13

Example 3

1:2

14

Example 5

1:5

15

Example 7

1:8

16

Example 7

1:10

17

Example 9

1:2

18

Example 9

1:5

[0050] The preparation process is as follows:

[0051] Taking Example 12 as an example, weigh 100 grams of dry ZSM-5 zeolite powder (Shanghai Fuxu Molecular Sieve Co., Ltd.), transfer it into a beaker, weigh 300 grams of the working solution prepared in Example 2 and pour it into the above beaker, stir well and wait for use.

Embodiment 19

[0052] Embodiment 19: Catalyst preparation completes and performance analysis

[0053] Transfer the mixture obtained in Example 12 into a 500mL autoclave, seal it and heat it in an oven at 180°C for 24 hours. ℃ for 5 hours in a muffle furnace to obtain the prepared catalyst.

[0054] The physical and chemical properties and catalytic performance of the prepared catalyst were analyzed, the results are as follows:

[0055] figure 1 is the XRD spectrum of the catalyst. It can be seen that the catalyst is a typical MFI structure type molecular sieve with high crystallinity, and its SiO 2 / Al 2 o 3 The ratio (SAR) was 120.5. There is no obvious characteristic diffraction peak of alumina, indicating that the aluminum salt exists in the zeolite material in a highly dispersed state after high-temperature calcination, and no other crystal structure is formed.

[0056] 27 The results of AlNMR analysis show that the coordination state of Al is mainly four-coordinated, with a sm...

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Abstract

The invention discloses a modified ZSM-5 zeolite catalyst for a catalytic reaction for preparing propylene through methanol as well as a preparation method of the catalyst. The catalyst is formed by introducing controllable acid site through aluminum atom hybrid modification by taking all-silicon ZSM-5 zeolite as the basis. The catalyst is moderate in acidity and is particularly favorable for methanol conversion, and the propylene is produced at high selectivity. The catalyst is high in catalytic activity, the reaction conversion rate is high, and the stable period is long. The 30-100 mass percent of methanol serves as a reaction raw material, the one-way service life is longer than 80 hours, the selectivity of the propylene is more than 48 percent, the regeneration method is simple, and the regeneration performance is well restored.

Description

technical field [0001] The invention relates to the industrial field, in particular to a catalyst for producing propylene by dehydration of methanol and a preparation method thereof. Background technique [0002] Zeolite molecular sieve is a kind of inorganic aluminosilicate crystal, which contains regular and orderly arranged molecular-sized pores (ca. 0.3-1.5nm) in the framework. It is used in industrial processes such as catalysis, adsorption separation and ion exchange. [0003] The ZSM-5 zeolite (MFI type) molecular sieve reported by Mobil in 1972 [US Patent No. 3702886, 1972] has a two-dimensional ten-membered ring channel (a ten-membered ring straight channel with a pore size of 0.54nm×0.56nm and ten-membered Ring sinusoidal channel, the pore diameter is 0.51nm×0.54nm), is the most widely used catalytic material so far, and is widely used in oil refining processes such as petroleum fluid catalytic cracking (FCC), hydrocracking and refining. There are also many impor...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/40C07C11/06C07C1/24
CPCY02P20/52
Inventor 潘凡峰汪雍陈玉忠
Owner INNOVATIVE COAL CHEMICAL DESIGN INSTITUTE (SHANGHAI) CO LTD
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