A method for modifying molecular sieves used in methanol-to-gasoline reaction

A methanol-to-gasoline and treatment method technology, applied in the field of methanol-to-gasoline catalysts, can solve problems such as high silicon content, low aluminum content, and limited effect, achieve good micropore structure, protect pore structure, and promote desiliconization Effect

Active Publication Date: 2017-05-31
HUANENG CLEAN ENERGY RES INST
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] Chinese patent CN102513142B "A Preparation Method of Methanol-to-Gasoline Catalyst" adopts acid treatment and hydrothermal treatment to remove the aluminum on the molecular sieve skeleton and increase the silicon-aluminum ratio, which can improve the selectivity of gasoline, but because ZSM-5 itself is a silicon For molecular sieves with higher content and less aluminum content, a large number of aluminum atoms on the skeleton will be removed to destroy the pore structure of the molecular sieve, which will inevitably affect the long-term activity of the molecular sieve
[0005] Chinese patent CN103506150A "Catalyst for methanol to gasoline through water vapor modification and its preparation method and application" mentioned that the use of hydrothermal treatment to remove the amorphous aluminum on the molecular sieve can dredge the pores and The effect of increasing the specific surface area, but the effect is limited compared with the new alkaline treatment

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] A method for modifying molecular sieves for methanol-to-gasoline, comprising the following steps:

[0024] Step 1, the Na of 10g molecular sieve and 500ml 0.5mol / L 2 CO 3 The solution was mixed and stirred at room temperature for 30 minutes;

[0025] Step 2. Transfer the mixture of Step 1 into an autoclave with a polytetrafluoroethylene liner, add 10 g of n-butylamine, seal the container, and heat and stir at 140° C. for 4 hours;

[0026] Step 3. Cool the mixture in Step 2 to room temperature, vacuum filter, wash with deionized water until neutral, and dry at 110°C overnight;

[0027] Step 4. Mix the solid powder obtained in Step 3 with 500ml of 0.5mol / L hydrochloric acid solution, stir at room temperature for 30min, place in a polytetrafluoroethylene-lined autoclave, heat and stir at 140°C for 4h;

[0028] Step 5. Cool the mixture in Step 4 to room temperature, vacuum filter, wash with deionized water until neutral, dry at 110°C overnight, and place in a muffle furn...

Embodiment 2

[0031] Step 1, the Na of 10g molecular sieve and 500ml 0.5mol / L 2 CO 3 The solution was mixed and stirred at room temperature for 30 minutes;

[0032] Step 2. Transfer the mixture of Step 1 into an autoclave with a polytetrafluoroethylene liner, add 10 g of ethylenediamine, seal the container, and heat and stir at 140 ° C for 4 hours;

[0033] Step 3. Cool the mixture in Step 2 to room temperature, vacuum filter, wash with deionized water until neutral, and dry at 110°C overnight;

[0034] Step 4. Mix the solid powder obtained in Step 3 with 500ml of 0.5mol / L hydrochloric acid solution, stir at room temperature for 30min, place in a polytetrafluoroethylene-lined autoclave, heat and stir at 140°C for 4h;

[0035] Step 5. Cool the mixture in Step 4 to room temperature, vacuum filter, wash with deionized water until neutral, dry at 110°C overnight, and place in a muffle furnace for calcination at a high temperature of 400°C to obtain modified molecular sieve 2.

[0036] The ac...

Embodiment 3

[0038] Step 1, the Na of 10g molecular sieve and 500ml 0.5mol / L 2 CO 3 The solution was mixed and stirred at room temperature for 30 minutes;

[0039] Step 2. Transfer the mixture of Step 1 into an autoclave with a polytetrafluoroethylene liner, add 10 g of tetrapropylammonium hydroxide, seal the container, and heat and stir at 140 ° C for 4 hours;

[0040] Step 3. Cool the mixture in Step 2 to room temperature, vacuum filter, wash with deionized water until neutral, and dry at 110°C overnight;

[0041] Step 4. Mix the solid powder obtained in Step 3 with 500ml of 0.5mol / L hydrochloric acid solution, stir at room temperature for 30min, place in a polytetrafluoroethylene-lined autoclave, heat and stir at 140°C for 4h;

[0042] Step 5. Cool the mixture in Step 4 to room temperature, vacuum filter, wash with deionized water until neutral, dry at 110°C overnight, and place in a muffle furnace for calcination at a high temperature of 400°C to obtain modified molecular sieve 3.

...

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PUM

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Abstract

The invention discloses a modification treatment method of a molecular sieve for methanol to gasoline reaction. The method comprises the following steps: mixing and stirring the molecular sieve for methanol to gasoline reaction with an aqueous alkali to obtain a mixture, wherein the aqueous alkali is selected from one or more of Li2CO3, Na2CO3 and K2CO3; transferring the obtained mixture into a high pressure kettle with a polytetrafluoroethylene lining, adding organic amine, sealing, heating and stirring, and then cooling to room temperature, vacuum-filtering, washing to neutral through deionized water, drying at 110 DEG C, passing the night to obtain solid powder; mixing and stirring the obtained solid powder and an acid solution, placing in the high pressure kettle with the polytetrafluoroethylene lining, heating and stirring, and then cooling to room temperature, vacuum-filtering, washing to neutral through the deionized water, drying at 110 DEG C, passing the night, placing in a muffle furnace, calcining at high temperature of 400 DEG C to obtain the modified molecular sieve. Through the adoption of the method disclosed by the invention, the activity, the selectivity and the thermal stability of the molecular sieve are improved.

Description

technical field [0001] The invention belongs to the technical field of methanol-to-gasoline catalysts, in particular to a method for modifying molecular sieves used in methanol-to-gasoline reactions. Background technique [0002] my country is short of oil resources, and the proven oil reserves only account for 1.4% of the world's reserves. However, in recent years, the rapid development of the national economy has increased the demand for energy, and the dependence on oil imports has also increased year by year. my country's energy structure is "rich in coal, low in oil, and short of gas". The reserve, output and consumption of coal resources have reached 12.6%, 35.3% and 34.4% of the world's total. Therefore, vigorously developing the clean transformation and utilization of coal resources has become The current research hotspot and the way out to solve the future energy crisis. [0003] Coal gasification to methanol process is a relatively mature process in the coal chemic...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/26C10G3/00
CPCY02P30/20
Inventor 王晓龙蒋彪郜时旺肖天存许世森
Owner HUANENG CLEAN ENERGY RES INST
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