The development history and application technology of industrial catalysts that you don’t know! Industrial catalysts

The development history and application technology of industrial catalysts that you don’t know!
Industrial catalysts
Catalysts play an extremely important role in modern chemical industry, with over 90% of chemical production processes using catalysts to accelerate reaction rates and improve production efficiency. Today, Xiaoqi will take everyone to understand the development history of industrial catalysts.
The embryonic period of industrial catalysts
The beginning of catalytic technology in industrial scale production
The development history of catalyst industry is closely related to the development and evolution of industrial catalytic processes.
In 1740, the British doctor J. Ward built a factory near London to burn sulfur and saltpeter to make sulfuric acid. Then, in 1746, the British doctor J. Robak built a lead chamber reactor. The nitrogen oxide produced by saltpeter in the production process is actually a gaseous catalyst, which is the beginning of industrial scale production using catalytic technology.
The Production of the First Industrial Catalyst
Platinum catalyst
In 1831, P. Phillips obtained a British patent for the oxidation of sulfur dioxide on platinum to sulfur trioxide. In the 1860s, a Dicken process was developed using copper chloride as a catalyst to oxidize hydrogen chloride to produce chlorine gas. In 1875, E. Jacob, a German, established the first Contact process device to produce fuming sulfuric acid in Kroyznach, and manufactured the required platinum catalyst, which was the pioneer of solid industrial catalysts. Platinum was the first industrial catalyst, and now it is still a catalytic active component in many important industrial catalysts.

In the 19th century, the product variety of the catalyst industry was limited, and manual workshops were used for production. Due to the important role of catalysts in chemical production, the manufacturing method of industrial catalysts has been regarded as a secret since their inception.
The Founding Period of Industrial Catalysts
During this period, a series of important metal catalysts were developed, with catalytic active components expanding from metals to oxides, and the scale of use of liquid acid catalysts expanded.
Basic Technology of Industrial Catalysts
Manufacturers began to use more complex formulas to develop and improve catalysts, 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, etc., becoming the fundamental technology in modern catalyst industry.
Diatomaceous earth carrier
The role and selection of catalyst carriers have also received attention, including diatomaceous earth, pumice, silica gel, alumina, etc.
In order to meet the requirements of large fixed bed reactors, forming technology has emerged in the production process, and strip and ingot catalysts have been put into use.
During this period, there was already a large production scale, but the variety was relatively single. In addition to self-produced and self used, some widely used catalysts have entered the market as commodities. At the same time, the development of industrial practice has promoted the progress of catalytic theory.
In 1925, H.S. Taylor proposed the theory of active centers, which played an important role in the development of manufacturing technology in the future.
Metal catalyst

At the beginning of the 20th century, factories were established in Britain and Germany to produce hardened oil by hydrogenation of oil and fat with nickel as catalyst. In 1913, Germany Baden Aniline Soda Ash Co., Ltd. used magnetite as raw material to produce iron series ammonia synthesis catalyst by hot melting method and adding additives.
In 1923, F. Fischer achieved success in the hydrogenation of carbon monoxide to hydrocarbons using cobalt as a catalyst.
In 1925, M. Reney of the United States obtained a patent for the manufacturing of skeletal nickel catalysts and put them into production. This is a skeleton nickel obtained by alkaline leaching of silicon from Ni-Si alloy.
In 1926, the French company used metals such as iron, tin, and molybdenum as catalysts to produce liquid fuel from coal and tar through high-pressure hydrogenation liquefaction. This method is called the Burgess process.
Iron catalyst
This stage laid the foundation for the manufacturing of metal catalysts, including the reduction technology of transition metal oxides, salts, and partial extraction technology of alloys. The material of catalysts has also expanded from platinum to cheaper metals such as iron, cobalt, and nickel.
Oxide catalyst
Given that the platinum catalyst developed in the 19th century for sulfur dioxide oxidation was prone to poisoning by arsenic in the feed gas, a process combining two catalysts emerged.
The first stage of the Mannheim plant in Germany uses low activity iron oxide as a catalyst, and the remaining sulfur dioxide is converted in the second stage using a platinum catalyst.
Vanadium oxide catalyst
At this stage, the supported vanadium oxide catalyst with high toxicity resistance was developed and used in the new Contact process sulfuric acid plant in Baden Aniline Soda Ash Company in Germany in 1913, with a service life of several to ten years.
After the 1920s, vanadium oxide catalysts quickly replaced the original platinum catalysts and became bulk commercial catalysts. The transformation of sulfuric acid catalysts has opened up broad prospects for oxide catalysts.
Liquid catalyst
In 1919, the American New Jersey Standard Oil Company developed the industrial process of producing isopropanol from propylene hydration with sulfuric acid as the catalyst. The plant was built in 1920, and by 1930, Union Carbide had built another plant for producing ethanol from ethylene hydration. These liquid catalysts are all simple chemicals.
The period of great development of industrial catalysts
At this stage, the production scale of industrial catalysts has expanded and the variety has increased. Before and after World War II, due to the need for strategic materials, the fuel and chemical industries rapidly developed and mutually promoted, and new catalytic processes continued to emerge, resulting in the rapid development of the catalyst industry.
Catalytic cracking catalyst
In the 1950s, due to the development of abundant Middle Eastern oil resources and low oil prices, petrochemical industry developed rapidly. At the same time, several important product series have gradually formed in the catalyst industry, namely petroleum refining catalysts, petrochemical catalysts, and inorganic chemical catalysts centered around ammonia synthesis. The formulation of catalysts in production is becoming increasingly complex, including polymerization catalysts made from metal organic compounds, multi-component oxide catalysts made for high selectivity, high selectivity hydrogenation catalysts, and structured molecular sieve catalysts. Due to the advancement of chemical science and technology, a rapid increase in the variety of catalyst products has emerged.

Organic metal catalysts
(C2H5) 3Al TiCl4 catalyst
Most of the homogeneous catalysts used in the past were acids, bases, or simple metal salts. In 1953, K. Ziegler of Federal Germany developed a catalyst (C2H5) 3Al-TiCl4 for ethylene polymerization under atmospheric pressure, which was put into use in 1955; In 1954, G. Nata of Italy developed the (C2H5) 3Al-TiCl3 system for propylene isotactic polymerization, and in 1957, a factory was built and put into use in Italy. Since this complex homogeneous catalyst entered the market as a commodity, the catalyst industry has begun to produce certain organometallic compounds. At present, catalysts for polymerization have become an important production department in the catalyst industry.
Selective catalyst
Activated alumina microsphere
In terms of production methods, due to the widespread use of impregnation, the production of various carriers with different properties has also become an important part of the industry, including different grades of alumina, silica gel, and certain low specific surface area carriers. Since the fluidized bed reaction technology has been transplanted from petroleum refining industry to chemical production, modern catalyst plants have also begun to use spray drying technology to produce microsphere chemical catalysts. The most important achievement in homogeneous catalytic selective oxidation was the production of a large-scale unit for direct oxidation of ethylene to acetaldehyde in 1960. The method of using palladium chloride copper oxide catalyst to produce acetaldehyde is called the Wacker method.
Hydrorefining catalyst
Cobalt molybdenum catalyst
In order to develop petrochemical industry, a large number of catalysts have emerged for the hydrofining of petroleum cracking fractions, many of which have been improved based on metal hydrogenation catalysts from a previous period. In addition, nickel sulfur catalysts and cobalt molybdenum sulfur catalysts have been developed for the hydrogenation and dehydrogenation of cracked gasoline, as well as palladium catalysts for the low-temperature hydrogenation and dehydrogenation of acetylene and dienes in the liquid phase of hydrocarbons.
Molecular sieve catalyst
Molecular sieve catalyst
By utilizing the shape selectivity of molecular sieves, following the achievements made in the refining industry in the 1960s, many important catalytic processes based on molecular sieve catalysts have been developed in the chemical industry since the 1970s.
Large ammonia synthesis catalyst series
Nickel catalyst
Since the 1960s, the raw materials for hydrogen production from hydrocarbons in the synthetic ammonia industry have shifted from coal to naphtha and natural gas. In 1962, Kellogg Corporation in the United States and ICI in the UK developed supported nickel catalysts using alkali or alkaline earth metal as catalysts, which can operate under pressurized conditions (3.3MPa) without coking, which is beneficial for energy conservation in large ammonia plants. A series of catalysts for synthetic ammonia plants are composed of hydrocarbon steam conversion catalysts, hydrodesulfurization catalysts, high-temperature shift catalysts, low-temperature shift catalysts, ammonia synthesis catalysts, methanation catalysts, etc.
Industrial catalytic upgrading period
At this stage, high-efficiency chelating catalysts were successively introduced; Catalysts for low-pressure operations have been developed to save energy; The shapes of solid catalysts are becoming increasingly diverse; The emergence of new molecular sieve catalysts; Start large-scale production of environmental protection catalysts; Biocatalysts are receiving attention.
Efficient complexing catalyst
Rhodium catalyst
After platinum and palladium, it has been about a century since rhodium became another precious metal element used in the catalyst industry. In the development of carbon chemistry, rhodium catalysts will have significant significance.
Another significant development of complex catalysts is the efficient olefin polymerization catalyst developed in the 1970s, which is a supported complex catalyst formed by the titanium tetrachloride alkyl aluminum system supported on magnesium chloride support. Its efficiency is extremely high, and one gram of titanium can produce tens to nearly one million grams of polymer. Therefore, there is no need to separate the catalyst from the product, which can save energy consumption in the production process.

Industrial Application of Solid Catalysts
Honeycomb shaped wire carrier
In order to achieve the goals of increasing production load and saving energy, solid catalyst designs have become increasingly diverse since the 1970s, with the emergence of catalysts such as trilobal and quadrilateral catalysts used in hydrofining, honeycomb catalysts used in automotive exhaust purification, and spherical and spoke catalysts used in ammonia synthesis. There are also some new designs for the distribution of catalytic active components in the catalyst, such as the palladium/alumina catalyst used for the primary hydrogenation of cracked gasoline, which concentrates the active components on the near outer surface.
Industrial Application of Molecular Sieve Catalysts
ZSM-5 molecular sieve catalyst
In the late 1970s, a ZSM-5 molecular sieve catalyst was developed for the alkylation of benzene to ethylbenzene, replacing the previous aluminum trichloride. In the early 1980s, a ZSM-5 molecular sieve catalyst was developed for synthesizing gasoline from methanol. Molecular sieve catalysts will play an important role in the development of resources and carbon chemistry.
Industrial Application of Environmental Protection Catalysts
At present, environmentally friendly catalysts, along with chemical catalysts (including catalysts used in production processes such as synthetic materials, organic synthesis, and ammonia synthesis), and petroleum refining catalysts, are listed as the three major fields in the catalyst industry.
Industrial application of biocatalysts
The use of biochemical methods in the chemical industry is increasing. After the 1970s, a variety of large-scale applications of immobilized enzyme were made. The development of biocatalysts will cause significant changes in chemical industry production.