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Integral supported carbon molecular sieve catalyst, preparing method and applications thereof

A carbon molecular sieve, integrated technology, applied in the field of methanol dehydration to dimethyl ether synthesis, can solve the problems of complex equipment, large bed temperature difference, low space velocity, etc., and achieves reduction of growth times, high production efficiency, and good low temperature activity. Effect

Inactive Publication Date: 2008-07-23
ENERGY RES INST OF SHANDONG ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, all of these catalysts are granular. In the process of dehydration of fixed bed methanol to synthesize dimethyl ether, it is difficult to remove the heat of reaction in time, the generated water cannot be separated from the surface of the catalyst in time, the space velocity is low, and the bed temperature difference is large. and other problems seriously affect the service life of the catalyst and the single-pass conversion rate of the reaction.
Patents CN2723451Y, CN2928846Y, CN2900523Y, etc. solve the above problems by improving the reaction equipment, and have achieved certain effects, but there are weaknesses such as long process flow, complicated equipment, and large investment.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Example 1: (1) The monolithic honeycomb cordierite substrate used in the experiment has a pore density of 400 cpsi. After the substrate is cut and ground into a cylindrical sample of φ7mm×20mm (0.505g), it is washed with deionized water and dried. (2) Vacuum impregnation of Fe(NO 3 ) 3 The solution was put into a carbon nanotube growth device after drying, reduced by flowing a hydrogen-nitrogen mixed gas at 500°C for 2 hours, directly raising the temperature to 750°C and passing through acetylene for 30 minutes, and switching to nitrogen to cool down to room temperature. The cordierite carrier with the crude product of carbon nanotubes was put into 30% HNO3 solution and boiled for 1.0 h, washed and dried with deionized water, and the loading capacity of carbon nanotubes was 15%. (3) Place the acid-treated CNT / cordierite in the pre-dispersed 1.0% HZSM-5 molecular sieve suspension by ultrasonic wave, take it out after 30 seconds, blow off the residual liquid in the hole,...

Embodiment 2~3

[0022] Embodiments 2-3: The preparation method of the catalyst is the same as that of Embodiment 1, except that the growth time of carbon nanotubes is adjusted to 10-30 minutes, and other synthesis conditions remain unchanged. The conversion of methanol and the selectivity of DME are shown in Table 2. When the loading of carbon nanotubes is in the range of 8% to 16%, the loading of carbon nanotubes has little effect on the conversion of methanol and the selectivity of DME.

Embodiment 4~5

[0023] Embodiments 4-5: The preparation method of the catalyst is the same as that of Embodiment 1, except that the growth temperature of carbon nanotubes is adjusted to 700-800° C., the growth time is fixed at 10 min, and other synthesis conditions remain unchanged. Methanol conversion rate and dimethyl ether selectivity are shown in Table 2. The acetylene cracking temperature has a great influence on the growth of carbon nanotubes. If it is lower than 700°C, what is obtained is basically carbon deposition, which cannot promote methanol conversion.

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PUM

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Abstract

A catalyst for an integrated supported carbon modular sieve comprises an integrated beehive cordierite, a carbon-nano tube and an HZSM-5 modular sieve, wherein the carbon-nano tube takes 7-20 proportions, HZSM-5 takes 10-30 proportions, and cordierite tales 60-80 proportions. The preparation method is that: carbon-nano tube is produced in situ on the integrated beehive cordierite by using chemical vapor deposition firstly, and the carbon-nano tube is taken as carrier, then the ZSM-5 modular sieve is developed on the carrier by using a secondary growth method. The catalyst for an integrated supported carbon-modular sieve can be used for the gas-phase synthesis of dimethyl ether DME by the dehydration of methanol.

Description

technical field [0001] The invention belongs to a novel synthesis technology of methanol dehydration to dimethyl ether, in particular to the preparation of an integral supported carbon molecular sieve catalyst and its application in methanol dehydration to dimethyl ether. Background technique [0002] At present, the production methods of methanol dehydration to dimethyl ether are mainly as follows: [0003] A. Methanol liquid phase dehydration method. Traditional liquid-phase dehydration of methanol to produce dimethyl ether is to form methyl bisulfate first in the presence of concentrated sulfuric acid, and then generate dimethyl ether. Although the reaction conditions of this process are mild (130-160°C), the single-pass conversion rate of methanol is high (>80 %), good selectivity (>98%), but the process equipment is corroded, the intermediate product is toxic, the residual liquid in the kettle and the waste water seriously pollute the environment, and it has tend...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/40B01J21/18B01J21/16C07C43/04C07C41/09
Inventor 王建梅蔡飞鹏王波许敏孙立
Owner ENERGY RES INST OF SHANDONG ACAD OF SCI
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