阅读说明：本技术 一种甲醛与乙炔反应合成1 ,4-丁炔二醇的催化剂 (Catalyst for synthesizing 1, 4-butynediol by reacting formaldehyde with acetylene ) 是由 邓少亮 周焕文 李鼎 于 2019-11-27 设计创作，主要内容包括：一种甲醛与乙炔反应合成1,4-丁炔二醇的催化剂,其属于催化剂制备的技术领域。该催化剂以微米级α-氧化铝为载体,其特征在于采用质量百分比含量为20％～70％的氧化铝为载体,以沉积沉淀、浸渍、共混焙烧等方法把氧化铜和氧化铋负载到载体上,使催化剂颗粒具有蛋壳型结构,载体处于核心,活性组分氧化铜、氧化铋包裹在载体外表面。催化剂含有质量20％～65％氧化铜、2％～10％氧化铋。这样制备的催化剂避免了现有1,4-丁二醇生产过程中炔化工段炔化催化剂采用硅酸镁负载铜铋在使用过程中存在硅、镁流失的问题,可较少了工业装置废水的排放量80%以上,同时催化剂具有活性好、选择性高的特点。(The catalyst uses micron-sized α -alumina as a carrier, and is characterized in that the alumina with the mass percentage content of 20-70% is used as the carrier, copper oxide and bismuth oxide are loaded on the carrier by methods of deposition, precipitation, impregnation, blending roasting and the like, so that catalyst particles have an eggshell type structure, the carrier is positioned at the core, and active components of the copper oxide and the bismuth oxide are coated on the outer surface of the carrier.)

1. A catalyst for synthesizing 1, 4-butynediol by reacting formaldehyde and acetylene is characterized in that micron-sized α -alumina is used as a carrier, copper oxide and bismuth oxide are loaded on the carrier by deposition, precipitation, impregnation, blending and roasting, catalyst particles have an eggshell structure, the carrier is positioned at a core, and active components of copper oxide and bismuth oxide are coated on the outer surface of the carrier, wherein the catalyst adopts 20-70% by mass of alumina as the carrier, and contains 20-65% by mass of copper oxide and 2-10% by mass of bismuth oxide.

2. The catalyst for synthesizing 1, 4-butynediol by reacting formaldehyde with acetylene according to claim 1, wherein: the particle diameter of the catalyst is 0.5-100 μm.

3. The catalyst for synthesizing 1, 4-butynediol by reacting formaldehyde with acetylene according to claim 1, wherein: the diameter of the carrier particles is 0.2-50 mu m, and the specific surface area is less than 50m²/g。

4. The catalyst for synthesizing 1, 4-butynediol through the reaction of formaldehyde and acetylene according to claim 1, wherein the carrier is α -alumina, and the content of α crystalline phase in the alumina is more than 30%.

Technical Field

The invention belongs to the technical field of catalysts, and particularly relates to a novel ethynylation catalyst for synthesizing 1, 4-butynediol.

Background

The domestic and foreign production process for producing 1, 4-butynediol by alkynal method includes Invida process, I.S.P process and domestic three-dimensional process, etc., the Invida process adopts basic copper bismuth carbonate without carrier as catalyst precondition, and other processes adopt magnesium silicate carrier loaded copper bismuth oxide silicon magnesium copper bismuth catalyst, such as CN107952443A, CN103638937A and CN102950014A, etc. all containing SiO₂The catalyst has SiO in the using process₂Loss problem of SiO in the reaction mass₂Raney nickel has a toxic effect on a subsequent 1, 4-butynediol hydrogenation catalyst and needs to be removed by an ion exchange method. The ion exchange process using resin produces a large amount of waste water which is difficult to treat, and the production process consumes a large amount of acid and alkali to clean the resin.

At present, all the catalysts applied in industry are copper bismuth magnesium silicon catalysts, and in order to thoroughly solve the problems of environmental protection wastewater and acid and alkali consumption, a carrier which does not run off in the using process of the catalyst is needed to be adopted to prepare the catalyst. Meanwhile, the catalyst carrier needs to meet the requirement of industrial catalyst mass production.

Disclosure of Invention

The invention relates to a catalyst for synthesizing 1, 4-butynediol by reacting formaldehyde and acetylene, which takes micron-sized α -alumina as a carrier and is characterized in that 20-70% of alumina by mass percent is taken as the carrier, copper oxide and bismuth oxide are loaded on the carrier by methods of deposition, precipitation, impregnation, blending roasting and the like, so that catalyst particles have an eggshell type structure, the carrier is positioned at the core, and active components of copper oxide and bismuth oxide are coated on the outer surface of the carrier, wherein the catalyst contains 20-65% of copper oxide and 2-10% of bismuth oxide by mass.

The granularity of the adopted catalyst carrier is directly 0.2-50 mu m, and the specific surface area is less than 50m²(ii) in terms of/g. The diameter of the prepared catalyst particles is 0.5-100 mu m, and the specific surface area is 10-100m²/g，

The α -alumina of the carrier has a α crystalline phase content of greater than 30%.

The above catalyst preparation methods include catalyst preparation methods such as a precipitation method, an impregnation method, a solid mixing and roasting method, and the like, but are not limited to the above preparation methods.

The catalyst particle structure is in an eggshell shape, the carrier is positioned in the core, and the active components of copper oxide and bismuth oxide are coated on the outer surface of the carrier.

Selecting specially treated Al₂O₃As a catalyst carrier, the carrier basically does not run off within the pH value range of 2-8, and can completely meet the requirement of using the catalyst within the pH value range of 5-6.

The invention has the beneficial effects that:

the activity of the alkynylation catalyst prepared by adopting the α -alumina carrier meets the requirement of industrial products, the aluminum ion content and the silicon content in reaction liquid after reaction are lower than the values of the existing industrial catalyst, which shows that the alkynylation catalyst prepared by adopting the α -alumina carrier can meet the industrial requirement in the aspect of ion loss, particularly the silicon content is obviously reduced, the deionization working section after alkynylation can be completely saved by adopting the catalyst by adopting an industrial device, and the generation of industrial wastewater can be obviously reduced.

Drawings

FIG. 1 is a structural diagram of copper oxide crystal peaks of a catalyst analyzed by an X-ray diffractometer (XRD).

Fig. 2 is a microscopic view of the catalyst.

Detailed Description