The Foundation Period of the Development History of Catalyst Industry (Early 20th Century)

During this period, a series of important metal catalysts were prepared, and the catalytic active components expanded from metals to oxides, and the use scale of liquid acid catalysts expanded. Manufacturers began to develop and improve catalysts with more complex formulations, and applied the principle that high dispersion can improve catalytic activity to design related manufacturing technologies, such as precipitation method, impregnation method, hot melt method, leaching method and so on. Become the basic technology of modern catalyst industry. The function and selection of catalyst carriers have also been paid attention to. The selected carriers include diatomite, pumice, silica gel, alumina, etc. In order to meet the requirements of large-scale fixed-bed reactors, molding technology has appeared in the production process, and strip and ingot catalysts have been put into use. During this period, there has been a large production scale, but the varieties are relatively single. In addition to self-production, some widely used catalysts also enter the market as commodities. At the same time, the development of industrial practice has promoted the progress of catalytic theory. 1925, H.S. Taylor put forward the theory of active center, which played an important role in the development of manufacturing technology in the future. Metal Catalyst In the early 20th century, Britain and Germany set up factories to produce hardened oil by hydrogenation of oils and fats with nickel as catalyst. 19 13 Germany baden aniline soda company used magnetite as raw material to produce iron-based ammonia synthesis catalyst by hot melting method with additives. 1923 F. Fischer successfully hydrogenated carbon monoxide into hydrocarbons with cobalt as catalyst. 1925, American M. Raney company obtained the patent for manufacturing skeleton nickel catalyst and put it into production.

This is a kind of skeleton nickel obtained by desilication of nickel-silicon alloy by alkali leaching. 1926 French companies use iron, tin, molybdenum and other metals as catalysts, and coal and tar as raw materials to produce liquid fuel through high-pressure hydrogenation liquefaction. This method is called Burgess method. At this stage, the basic technology of manufacturing metal catalysts was laid, including the reduction technology of transition metal oxides and salts and the partial extraction technology of alloys. The materials of catalysts also expanded from platinum to cheaper metals such as iron, cobalt and nickel. With the increasing variety of industrial catalysts, a variety of catalysts for the production of chemicals from acetylene with coal as resource were first developed, among which the catalyst for the production of synthetic rubber was the earliest. 193 1 ~ 1932 in the technical development of synthesizing rubber monomer 2- chloro-1, 3- butadiene from acetylene, vinyl acetylene was produced under the action of cuprous chloride catalyst. In the 1940s, the industries of synthesizing styrene-butadiene rubber, nitrile-butadiene rubber and butyl rubber with lithium, aluminum and peroxide as catalysts appeared one after another, and all these reactions appeared. In order to obtain related monomers, many solid catalysts have also appeared. Cr-Al-O catalyst for dehydrogenation of butane to butadiene appeared during World War II and was put into use in the mid-1940s. At the same time, an iron oxide catalyst for dehydrogenation of ethylbenzene to styrene was developed. After the production route of polyamide fiber (nylon 66) was established in the second half of 1930s, in order to obtain a large number of monomers, solid nickel catalyst for hydrogenation of benzene to cyclohexane was produced in the 1940s, and cobalt catalyst for liquid phase oxidation of cyclohexane to cyclohexanone (alcohol) was developed. During this period, cobalt-based composite catalysts for the synthesis of olefins by carbonyl group have also been developed.

At this stage, the production and use of solid acid catalyst promoted the development of solid acid catalyst theory. In order to obtain the aromatic raw materials of TNT explosives, Standard Oil Company of the United States developed the hydrogenation reforming technology in 1939, and produced the required platinum oxide-alumina and chromium oxide-alumina catalysts. From 65438 to 0949, Global Oil Company developed a platinum reforming technology with long-term operation and semi-regenerative fixed bed operation to produce catalysts containing platinum and alumina. Among these catalysts, alumina is both a carrier and a solid acid as one of the active components, and it is the first important bifunctional catalyst.

In 1950s, the petrochemical industry developed rapidly due to the exploitation of abundant oil resources in the Middle East and low oil prices. At the same time, the catalyst industry has gradually formed several important product series, namely, petroleum refining catalyst, petrochemical catalyst and catalyst for inorganic chemical industry centered on synthetic ammonia. The formula of catalyst is becoming more and more complicated. These catalysts include polymerization catalysts made of organometallic compounds, multicomponent oxide catalysts for high selectivity, hydrogenation catalysts with high selectivity and molecular sieve catalysts with regular structures. Due to the progress of chemical science and technology, the types of catalyst products have increased rapidly. Industrial application of biocatalysts The process of using biochemical methods in the chemical industry is increasing. In the mid-1960s, the technology of enzyme immobilization developed rapidly. In 1969, the immobilized enzyme for resolving acetyl -DL- amino acids was put into use. After 1970s, various immobilized enzymes were made into large-scale applications. Glucose isomerase made from 1973 was used to produce high fructose corn syrup, and it was used on a large scale soon. Acrylonitrile hydrolase was put into industrial use from 65438 to 0985. The development of biocatalysts will cause great changes in chemical industry production.

In addition, catalysts for energy industry, such as platinum supported on carbon or nickel in fuel cells, have been developed to promote the combination of hydrogen and oxygen.