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Preparation method of rare earth metal Ce doped H-ZSM-34 molecular sieve

A technology of rare earth metals and molecular sieves, applied in the direction of molecular sieve catalysts, molecular sieves and alkali exchange compounds, non-metallic elements, etc., can solve the problems of low propylene efficiency, easy deactivation, and short supply, and achieve high production efficiency, suitable acidity, and long life. Effect

Inactive Publication Date: 2018-10-23
HENAN NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0002] Propylene can be used to produce important chemical products such as polypropylene, propylene oxide, acetone, isopropanol, phenol, glycerin, etc. It is an indispensable chemical production raw material for the development of modern society and economy. However, the efficiency of preparing propylene is currently low, resulting in a shortage of supply. Therefore, there is a need to develop efficient methods for the production of propylene
[0003] At present, the production route of methyl halide to propylene is mature. Molecular sieve catalyst is required for the production of propylene from methyl halide. Although this method improves the yield of propylene, it is easy to deactivate due to the pore structure and acidity of the molecular sieve catalyst. Therefore, it is particularly important to prepare molecular sieve catalysts with long catalytic life, good stability and high catalytic performance.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] A preparation method of the rare earth metal Ce-doped H-ZSM-34 molecular sieve includes the following steps:

[0020] ①Add 3.5 g NaAlO 2 , 7 g NaOH, 22 g KOH, and 67.5 g of water-soluble silica gel were sequentially added to 100 ml of water, stirred for 0.5 h, and the mixture was aged for 3 days to obtain a clear seed solution (mixture A); 5.54 g NaOH, 28.85 g Water-soluble silica gel was added to 83 ml of water in sequence, stirred for 5 h, and then added in sequence of 2.71 g Al 2 (SO4) 3 ·18H 2 O and 10ml mixture A to obtain the precursor liquid;

[0021] ②After stirring the precursor fluid for 0.5 h, add Ce(NO) to the precursor fluid at the ratio of Ce / Al=0.06 3 ) 3 ·6H 2 O solid, stirred at room temperature for 13 hours, put into the kettle, crystallized at 120°C for 7 days, removed from the kettle, filtered and washed with suction, dried at 100°C, and calcined in air at 550°C for 6 hours to obtain Ce-doped Na-ZSM-34;

[0022] ③Add 2g of Ce-doped Na-ZSM-34 to 40 mL of 1mo...

Embodiment 2

[0027] A preparation method of the rare earth metal Ce-doped H-ZSM-34 molecular sieve includes the following steps:

[0028] ①Add 3.5 g Na Al O 2 , 7 g NaOH, 22 g KOH, and 67.5 g of water-soluble silica gel were added to 100 ml of water in sequence, and stirred for 0.5 h. The mixture was aged for 3 days to obtain a clear seed solution (mixture A); 5.54 g of NaOH and 28.85 g of water-soluble silica gel were sequentially added to 83 ml of water, stirred for 5 h, and then added 2.71 g of Al 2 (SO4) 3 ·18H 2 O and 10ml mixture A to obtain the precursor liquid;

[0029] ② After stirring the precursor fluid for 0.5 h, add Ce(NO) to the precursor fluid at the ratio of Ce / Al=0.07 3 ) 3 ·6H 2 O solid, stirred at room temperature for 13 hours, put into the kettle, crystallized at 120°C for 7 days, removed from the kettle, filtered and washed with suction, dried at 100°C, and calcined in air at 550°C for 6 hours to obtain Ce-doped Na-ZSM-34;

[0030] ③Add 2g of Ce-doped Na-ZSM-34 to 40 mL of 1m...

Embodiment 3

[0035] A preparation method of the rare earth metal Ce doped molecular sieve H-ZSM-35 includes the following steps:

[0036] ①Add 3.5 g Na Al O 2 , 7 g NaOH, 22 g KOH, and 67.5 g of water-soluble silica gel were sequentially added to 100 ml of water, stirred for 0.5 h, and the mixture was aged for 3 days to obtain a clear seed solution (mixture A); 5.54 g NaOH, 28.85 g Water-soluble silica gel was added to 83 ml of water in sequence, stirred for 5 h, and then added in sequence of 2.71 g Al 2 (SO4) 3 ·18H 2 O and 10ml mixture A to obtain the precursor liquid;

[0037] ②After stirring the precursor fluid for 0.5 h, add Ce(NO) to the precursor fluid at the ratio of Ce / Al=0.08 3 ) 3 ·6H 2 O solid, stirred at room temperature for 13 hours, put into the kettle, crystallized at 120°C for 7 days, removed from the kettle, filtered and washed with suction, dried at 100°C, and calcined in air at 550°C for 6 hours to obtain Ce-doped Na-ZSM-34;

[0038] ③Add 2g of Ce-doped Na-ZSM-34 to 40 mL of 1...

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Abstract

The invention discloses a preparation method of rare earth metal Ce doped H-ZSM-34 molecular sieve. The preparation method of the rare earth metal Ce doped H-ZSM-34 molecular sieve comprises the following steps: adding an aluminium source into water, continuously adding an alkali source and a silicon source, stirring and ageing to obtain a clear seed solution; successively adding sodium hydroxideand water-soluble silica gel into a certain volume of aqueous solution and stirring, successively adding aluminum sulfate crystal and a certain volume of the seed solution to obtain a precursor solution; adding a Ce(NO3)3.6H2O solid into the precursor solution; stirring at room temperature, placing into a kettle, crystallizing, taking out of the kettle, carrying out suction filtration and washing,drying, roasting in the air to obtain Ce-doped Na-ZSM-34; adding the Ce-doped Na-ZSM-34 into an ammonium nitrate solution, stirring, carrying out suction filtration and washing, and drying; repeatingammonium exchange for four times to obtain NH4-ZSM-34; and roasting in the air to obtain the rare earth metal Ce doped H-ZSM-34 molecular sieve. Conversion rate of the Ce doped H-ZSM-34 molecular sieve in chloromethane can reach 78.9%, propylene selectivity can reach 40.6%, propylene yield can reach 32%, and there is no inactivation phenomenon within 7 h. The preparation method of the invention has advantages of simple process and high production efficiency.

Description

Technical field [0001] The invention relates to the field of energy catalysis, in particular to a preparation method of a rare earth metal Ce doped H-ZSM-34 molecular sieve. Background technique [0002] Propylene can be used to produce important chemical products such as polypropylene, propylene oxide, acetone, isopropanol, phenol, and glycerin. It is an indispensable chemical production raw material for the development of modern society and economy. However, the current production efficiency of propylene is low, resulting in short supply. Therefore, it is necessary to develop an efficient method for producing propylene. [0003] At present, the production path of methyl halide to propylene is mature. The production of propylene from methyl halide requires molecular sieve catalyst. Although this method increases the yield of propylene, it is easy to deactivate due to the pore structure and acidity of the molecular sieve catalyst. Therefore, it is particularly important to prepare...

Claims

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Application Information

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IPC IPC(8): C01B39/46B01J29/50B01J29/70C07C1/26C07C11/06
CPCB01J29/505B01J29/7049B01J2229/18C01B39/46C07C1/26C07C11/06Y02P20/52
Inventor 徐霆岑诗雨杜立方刘会康
Owner HENAN NORMAL UNIV