Method for preparing low-carbon olefin through methanol dehydration

A technology for methanol dehydration and carbon olefins, which is applied to chemical instruments and methods, hydrocarbon production from oxygen-containing organic compounds, ethylene production, etc. The effect of tight bonding between grains and increasing carbon capacity

Active Publication Date: 2013-12-18
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0017] The technical problem to be solved by the present invention is the problem of high catalyst use temperature and low yield of low-carbon olefins in the prior art, and a new method for producing low-carbon olefins by methanol dehydration is provided

Method used

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  • Method for preparing low-carbon olefin through methanol dehydration
  • Method for preparing low-carbon olefin through methanol dehydration
  • Method for preparing low-carbon olefin through methanol dehydration

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Take 60 grams of ZSM-5 molecular sieve with a silicon-aluminum ratio (molecular ratio, the same below) of 30, add 40 grams of silica sol with a weight percentage of 40%, mix and stir evenly, and then add 1 mol / liter of sodium bicarbonate The solution is 10 ml, mixed and stirred evenly, and then the agent bar is formed, and the formed catalyst is dried at 80°C for 3 hours, and then put into an autoclave containing water at the bottom of the liner. The catalyst and liquid water are not in contact. Take it out after crystallization at 180°C for 60 hours, then wash it twice, put it in an oven for drying at 120°C for 3 hours, put it in a muffle furnace and bake it at 400°C for 2 hours, and then bake it at 550°C for 3 hours to obtain non-sticky Binder ZSM-5 catalyst. The XRD spectrum of the prepared catalyst shows a pure ZSM-5 phase. The scanning electron microscope picture of the prepared catalyst shows pure ZSM-5 grains, almost no binder in the amorphous state, and the con...

Embodiment 2

[0032] According to the method of Chinese patent CN101428233A, the ZSM-5 / beta zeolite mixed crystal molecular sieve with a silicon-aluminum ratio of 40 is prepared. Take 60 grams of ZSM-5 / beta zeolite, add 40 grams of silica sol with a weight percentage of 40%, mix and stir evenly, then add 20 milliliters of 1 mol / liter ammonium citrate solution, mix and stir evenly, and then dispense Forming, the forming catalyst is dried at 80°C for 3 hours, and then put into an autoclave containing water at the bottom of the liner. The catalyst and liquid water are not in contact. After the autoclave is sealed, put it into an oven, take it out after crystallization at 165°C for 80 hours, and then wash it with water. 2 times, put it in an oven for 3 hours at 120°C, put it into a muffle furnace and bake it at 400°C for 2 hours, and then at 550°C for 3 hours to prepare a binder-free ZSM-5 / β zeolite catalyst as shown in the table 1. The crushing strength of the test catalyst sample was 160 New...

Embodiment 3～16

[0034] Take mordenite with a silicon-aluminum ratio of 20, 60 grams of Y zeolite with a silicon-aluminum ratio of 10, MCM-22 molecular sieve with a silicon-aluminum ratio of 40, ZSM-5 / mordenite symbiotic molecular sieve with a silicon-aluminum ratio of 20, and silicon-aluminum ratio ZSM-5 / beta zeolite / Y zeolite symbiotic molecular sieve with a ratio of 40, ZSM-5 / Y zeolite / mordenite symbiotic molecular sieve with a silicon-aluminum ratio of 20, ZSM-23 with a silicon-aluminum ratio of 20, and a silicon-aluminum ratio of 30 ZSM-11, MCM-49 with a silicon-aluminum ratio of 40, MCM-56 with a silicon-aluminum ratio of 60, ZSM-5 / Y symbiotic molecular sieves with a silicon-aluminum ratio of 20, MCM-22 / mordenite with a silicon-aluminum ratio of 40 , the ZSM-5 / Magadiite that the silicon-aluminum ratio is 200, the ZSM-5 / beta zeolite / mordenite that the silicon-aluminum ratio is 30, raw material proportioning is such as table 1, according to the method for embodiment 1, obtains binderless mo...

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Abstract

The invention relates to a method for preparing low-carbon olefin through methanol dehydration, and mainly solves the problems that the activity of a catalyst and the yield of the low-carbon olefin are low in the conventional technology for preparing the low-carbon olefin through catalytic pyrolysis. In the invention, methanol which is taken as a raw material is contacted with an adhesive-free molecular sieve catalyst through a catalyst bed to generate the low-carbon olefin under the conditions that the reaction temperature is 400 to 600 DEG C, the gauge pressure of the reaction is 0.001 to 0.5MPa, the weight space velocity of the reaction is 0.1 to 4h<-1> and the weight ratio of water to methanol is (0.1-3):1, wherein the pore volume, the average aperture and porosity of the adhesive-free molecular sieve catalyst are tested by mercury porosimetry, the pore volume is 0.31 to 0.5ml / g, the average aperture is 71 to 100nm, and the porosity is 31 to 40 percent. Through the technical scheme, the problems are better solved. The method can be used for the industrial production of the low-carbon olefin through methanol dehydration.

Description

technical field [0001] The invention relates to a method for preparing low-carbon olefins by dehydrating methanol. technical background [0002] As the leader of the petrochemical industry, the low-carbon olefin industry plays a pivotal role in the development of the national economy. With the development of society, the market demand for low-carbon olefins in my country has increased sharply, and the import volume of low-carbon olefins and their downstream products has increased year by year, and the market share of domestic products is less than half. At present, the world produces more than 100 million tons of ethylene per year, mainly using naphtha (or ethane) as raw material and using steam pyrolysis technology (at a temperature of about 800°C) to produce, and its output exceeds 90% of the total output. However, steam cracking requires high reaction temperature, high energy consumption, expensive high-temperature-resistant alloy steel molecular sieve, short operation p...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C1/24C07C1/20C07C11/04C07C11/06B01J29/40B01J29/80B01J29/18B01J29/08B01J29/70
CPCY02P20/52Y02P30/20Y02P30/40
Inventor 马广伟张惠明
Owner CHINA PETROLEUM & CHEM CORP
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