阅读说明：本技术 利用复合储氢材料对一氧化碳加氢制备低碳烯烃的方法 (Method for preparing low-carbon olefin by hydrogenation of carbon monoxide by using composite hydrogen storage material ) 是由 陈海鹏 刘金强 李佳奇 王远洁 舍晨星 李晓楠 张岩 马宁宁 于 2019-09-30 设计创作，主要内容包括：本发明涉及利用复合储氢材料对一氧化碳加氢制备低碳烯烃的方法,属于化工技术领域,所述方法是首先将镁铝合金粉和氧化铈粉置于球磨罐中,在氧化锆研磨介质、氩气气氛下球磨活化减小颗粒尺寸；然后打开球磨罐,以铁球替换部分氧化锆磨球,在氢气气氛下球磨活化得到复合储氢材料；将所得复合储氢材料放入固定床反应器中,通入合成气,提高压强并加热反应器,一氧化碳和氢气在储氢材料作用下生成低碳烯烃。本发明加氢方法的复合储氢材料原料成本低、反应活性高、使用条件温和以及低碳烯烃的选择性高。(The invention relates to a method for preparing low-carbon olefin by hydrogenation of carbon monoxide by using a composite hydrogen storage material, which belongs to the technical field of chemical industry, and the method comprises the steps of firstly placing magnesium-aluminum alloy powder and cerium oxide powder in a ball milling tank, and carrying out ball milling activation under the atmosphere of zirconia grinding medium and argon to reduce the particle size; then opening the ball milling tank, replacing part of zirconia grinding balls with iron balls, and carrying out ball milling activation in a hydrogen atmosphere to obtain a composite hydrogen storage material; and (3) putting the obtained composite hydrogen storage material into a fixed bed reactor, introducing synthesis gas, increasing the pressure and heating the reactor, so that carbon monoxide and hydrogen generate low-carbon olefin under the action of the hydrogen storage material. The composite hydrogen storage material prepared by the hydrogenation method has the advantages of low raw material cost, high reaction activity, mild use conditions and high selectivity of low-carbon olefin.)

1. The method for preparing the low-carbon olefin by hydrogenating the carbon monoxide by using the composite hydrogen storage material is characterized by comprising the following steps of: the method comprises the following steps:

placing magnesium-aluminum alloy powder and cerium oxide powder in a ball milling tank, adding zirconia grinding balls as grinding media, introducing argon, and carrying out ball milling under the argon atmosphere;

step two, opening the ball milling tank after ball milling is finished, replacing part of zirconia grinding balls with iron balls, introducing hydrogen, and performing ball milling activation in hydrogen atmosphere to obtain a composite hydrogen storage material;

and step three, putting the composite hydrogen storage material obtained in the step two into a fixed bed reactor, introducing synthesis gas with a lower hydrogen-carbon ratio, heating for reaction, and generating low-carbon olefin from carbon monoxide and hydrogen under the action of the hydrogen storage material.

2. The method for preparing the low-carbon olefin by hydrogenating the carbon monoxide by using the composite hydrogen storage material according to claim 1, wherein the method comprises the following steps: in the first step, the mass ratio of the magnesium-aluminum alloy powder to the cerium oxide powder is 8:2, and the ball milling time in the argon atmosphere is 3-5 h.

3. The method for preparing the low-carbon olefin by hydrogenating the carbon monoxide by using the composite hydrogen storage material according to claim 1, wherein the method comprises the following steps: the diameters of the zirconia grinding balls in the step one are respectively 3mm, 6mm, 10mm and 20mm, and the number of the zirconia grinding balls with the diameters of 3mm, 6mm, 10mm and 20mm is respectively 1000, 300, 30 and 2.

4. The method for preparing low carbon olefin by hydrogenation of carbon monoxide through the composite hydrogen storage material as claimed in claim 1, wherein in the second step, the iron balls are used to replace part of the zirconia grinding balls, 15 ~ 30 zirconia grinding balls with the diameter of 10mm are replaced by 15 ~ 30 iron balls with the diameter of 10 mm.

5. The method for preparing low-carbon olefin by hydrogenating carbon monoxide through the composite hydrogen storage material according to claim 1, wherein the ball milling activation is performed in the second step under a hydrogen atmosphere, the hydrogen pressure in a ball milling tank is 1 ~ 2MPa, and the activation time is 3 ~ 5 h.

6. The method for preparing the low-carbon olefin by hydrogenating the carbon monoxide by using the composite hydrogen storage material as claimed in claim 1, wherein the hydrogen-carbon ratio of the synthesis gas in the step three is 1:4 ~ 1:10, the reaction pressure is 1 ~ 2MPa, and the reaction temperature is 280 ~ 350 ℃.

Technical Field

The invention belongs to the technical field of chemical industry, and particularly relates to a method for preparing low-carbon olefin by hydrogenating carbon monoxide by using a composite hydrogen storage material.

Background

Generally, when the carbonaceous material is not completely combusted, toxic and harmful carbon monoxide gas is generated. In the industrial processes of iron making, coking, casting, calcining, garbage disposal and the like, carbon monoxide gas is generated. Carbon monoxide and hydrogen in the coal-based synthesis gas can be used for synthesizing high value-added products such as methanol, ethanol, ethylene glycol, low-carbon olefin, oil products and the like, wherein the low-carbon olefin is an important chemical raw material. Currently, the methanol route is mainly adopted for industrially converting synthesis gas into low-carbon olefins, i.e. carbon monoxide is firstly hydrogenated to prepare methanol, and then the methanol is converted into the low-carbon olefins. The process has high energy consumption, serious pollution and insignificant economic benefit. The one-step method for preparing the low-carbon olefin from the carbon monoxide is beneficial to shortening the process flow, reducing the equipment investment and improving the economic benefit. At present, the preparation of low-carbon olefin from carbon monoxide by a one-step method is still a bottleneck problem in the coal chemical industry. The development and development of new and highly efficient catalysts is an important approach to solving this problem.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention aims to provide a method for preparing low-carbon olefin by hydrogenating carbon monoxide by using a composite hydrogen storage material. The method uses the composite hydrogen storage material to hydrogenate the carbon monoxide, and the composite hydrogen storage material is prepared by a mechanochemical method, so that the preparation method is simple and has strong repeatability. The obtained product low-carbon olefin has high selectivity.

In order to achieve the purpose, the invention adopts the specific scheme that:

the method for preparing the low-carbon olefin by hydrogenating the carbon monoxide by using the composite hydrogen storage material comprises the following steps:

placing magnesium-aluminum alloy powder and cerium oxide powder in a ball milling tank, adding zirconia grinding balls as grinding media, introducing argon, and carrying out ball milling under the argon atmosphere;

step two, opening the ball milling tank after ball milling is finished, replacing part of zirconia grinding balls with iron balls, introducing hydrogen, and performing ball milling activation in hydrogen atmosphere to obtain a composite hydrogen storage material;

and step three, putting the composite hydrogen storage material obtained in the step two into a fixed bed reactor, introducing synthesis gas with a lower hydrogen-carbon ratio, heating for reaction, and generating low-carbon olefin from carbon monoxide and hydrogen under the action of the hydrogen storage material.

As a further optimization of the scheme, in the step one, the mass ratio of the magnesium-aluminum alloy powder to the cerium oxide powder is 8:2, and the ball milling time in the argon atmosphere is 3-5 h.

As a further optimization of the scheme, the diameters of the zirconia grinding balls in the step one are respectively 3mm, 6mm, 10mm and 20mm, and the numbers of the zirconia grinding balls with the diameters of 3mm, 6mm, 10mm and 20mm are respectively 1000, 300, 30 and 2.

As a further optimization of the scheme, in the step two, replacing part of the zirconia grinding balls with the iron balls is to replace 15 ~ 30 zirconia grinding balls with the diameter of 10mm with 15 ~ 30 iron balls with the diameter of 10 mm.

As a further optimization of the scheme, in the second step, ball milling activation is performed in a hydrogen atmosphere, the hydrogen pressure in a ball milling tank is 1 ~ 2MPa, and the activation time is 3 ~ 5 h.

As a further optimization of the scheme, the hydrogen-carbon ratio of the synthesis gas in the step three is 1:4 ~ 1:10, the reaction pressure is 1 ~ 2MPa, and the reaction temperature is 280 ~ 350 ℃.

The method for preparing the low-carbon olefin by hydrogenating the carbon monoxide by using the composite hydrogen storage material adopts a mechanochemical method to cause material particles to generate a large amount of defects and reduce reaction potential barrier, thereby compounding the cerium oxide and the hydrogen storage material and doping iron elements on the surface of the hydrogen storage material. During the hydrogenation of carbon monoxide, the hydrogen storage components (magnesium, aluminum and iron) in the composite hydrogen storage material can activate hydrogen to be hydrogen ions with negative valence, and the cerium oxide component activates the hydrogen to be hydrogen ions with positive valence. The negative hydrogen ions attack the carbon sites of carbon monoxide and the positive hydrogen ions attack the oxygen sites of carbon monoxide. Under the condition of low hydrogen partial pressure, the carbon chain is increased to generate low-carbon olefin.

The invention has the beneficial effects that:

1. the method for preparing the low-carbon olefin by hydrogenating the carbon monoxide by using the composite hydrogen storage material is simple in preparation method and strong in repeatability, and the composite hydrogen storage material is prepared by adopting a mechanochemical method. The used raw materials are cheap and easy to obtain, and have strong market competitiveness;

2. according to the method for preparing the low-carbon olefin by hydrogenating the carbon monoxide by using the composite hydrogen storage material, the hydrogenation method is a one-step hydrogenation method, the obtained product low-carbon olefin has high economic value, the process flow is simple, the reaction conditions are mild, the low-carbon olefin selectivity is high, and the economic benefit is obvious.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.