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Chinese name: History of the Development of the Catalyst Industry English name: History of catalyst industry Image: KC601 methanol synthesis catalyst (high-pressure monohydric alcohol) ━━━━━━━━━━━━━━━━━━━━━━━ Incubation period (before the 20th century) Founding period (early 20th century) Metal catalysts Oxide catalysts Liquid catalysts Period of rapid development (1930s–1960s) Expansion of industrial catalyst production scale Increase in the variety of industrial catalysts Production of organometallic catalysts Development of mixed catalysts for selective oxidation Improvements in hydrogenation refining catalysts Rise of molecular sieve catalysts Formation of large-scale ammonia synthesis catalyst series Period of renewal (1970s–1980s) Emergence of highly efficient complex catalysts Industrial application of solid catalysts Industrial application of molecular sieve catalysts Industrial application of catalysts for environmental protection Industrial application of biocatalysts Development of China’s catalyst industry ━━━━━━━━━━━━━━━━━━━━━━━ From the late 19th century to the early 20th century, the use of catalytic technologies in chemical manufacturing processes increased steadily. To meet the demands for industrial catalysts, an industry that featured a wide range of products, advancing manufacturing techniques, and growing production scales and output values gradually took shape. Incubation period (before the 20th century) The history of the catalyst industry is closely related to the development and evolution of industrial catalytic processes. In 1740, the British doctor J. Ward established a factory near London to produce sulfuric acid by burning sulfur and nitrate. Later, in 1746, the British scientist J. Roback invented the lead chamber reactor; the nitrogen oxide produced during this production process acted as a gaseous catalyst, marking the beginning of industrial-scale production using catalytic technology. In 1831, P. Phillips was granted a British patent for the oxidation of sulfur dioxide to sulfur trioxide on platinum. In the 1860s, the Deacon process was developed to produce chlorine by oxidizing hydrogen chloride using copper chloride as a catalyst. In 1875, the German E. Jacob established the first contact process plant for producing sulfuric acid at Croix-Nach, where he also manufactured the platinum catalyst required for this process; this was a precursor to solid industrial catalysts. Platinum was the first industrial catalyst, and it remains today the catalytically active component in many important industrial catalysts. In the 19th century, the catalyst industry offered a limited range of products, all produced using manual workshop methods. Due to the crucial role of catalysts in chemical production, their manufacturing methods have been kept as secrets since the advent of industrial catalysts. Founding period (early 20th century) During this period, a series of important metal catalysts were developed; the catalytic active components shifted from metals to oxides, and the use of liquid acid catalysts increased. Manufacturers began to use more complex formulations to develop and improve catalysts, and by applying the principle that high dispersion can enhance catalytic activity, they devised various manufacturing techniques such as precipitation, impregnation, thermal melting, and leaching – techniques that have become the foundation of the modern catalyst industry. The role of catalyst carriers and their selection are also given importance; the selected carriers include diatomite, pumice, silica gel, alumina, etc. To meet the requirements of large fixed-bed reactors, shaping techniques have been introduced into the production process, and strip-shaped and ingot-shaped catalysts have been put into use. During this period, production scales were already relatively large, but the variety of products was limited; aside from those produced for internal use, certain widely used catalysts were available on the market as commercial products. At the same time, the development of industrial practice has driven progress in catalytic theory. In 1925, H.S. Taylor proposed the active center theory, which played an important role in the subsequent development of manufacturing technologies. Metal catalysts: At the beginning of the 20th century, factories were established in Britain and Germany to produce hardened oils through the hydrogenation of fats using nickel as a catalyst. In 1913, the Baden Aniline Soda Company in Germany used magnetite as a raw material, and through a thermal melting process along with the addition of additives, produced iron-based catalysts for ammonia synthesis. In 1923, F. Fischer succeeded in producing hydrocarbons through the hydrogenation of carbon monoxide using cobalt as a catalyst. In 1925, M. Reaney in the United States obtained a patent for the production of skeletal nickel catalysts, which were then put into production (see figure). This is a type of skeletal nickel obtained by removing silicon from Ni-Si alloys using alkalis. In 1926, the Farben Company used metals such as iron, tin, and molybdenum as catalysts to produce liquid fuels from coal and tar through high-pressure hydrogenation liquefaction; this method is known as the Burgess process. This stage laid the foundation for the basic technologies in manufacturing metal catalysts, including reduction techniques for transition metal oxides and salts, as well as partial extraction techniques for alloys. The materials used for catalysts also expanded from platinum to cheaper metals such as iron, cobalt, and nickel. Oxide catalysts: Given that the platinum catalysts developed in the 19th century for the oxidation of sulfur dioxide were prone to being poisoned by arsenic in the feed gas, a process using two types of catalysts in combination was developed. In the Mannheim plant in Germany, the first stage uses iron oxide with lower activity as a catalyst, while the remaining sulfur dioxide is converted in the second stage using a platinum catalyst. During this phase, load-type vanadium oxide catalysts with high resistance to poisoning were developed, and in 1913 they were used in new contact process sulfuric acid plants by the Baden Aniline Soda Company in Germany, where their service life could last from several years to a decade. After the 1920s, vanadium oxide catalysts rapidly replaced the previous platinum catalysts and became widely used commercial catalysts. This advancement in sulfuric acid production catalysts has opened up broad prospects for oxide catalysts. Liquid catalysts: In 1919, Standard Oil of New Jersey in the United States developed an industrial process for producing isopropyl alcohol from propylene via hydration, using sulfuric acid as a catalyst. A plant was built in 1920, and by 1930, Union Carbonide Company in the U.S. constructed a plant for producing ethanol from ethylene via hydration. These liquid catalysts are all simple chemicals. Period of Rapid Development (1930s–1960s) During this phase, the production scale of industrial catalysts increased, and the variety of such catalysts expanded. Around the time of World War II, due to the demand for strategic materials, the fuel industry and the chemical industry developed rapidly and promoted each other; new catalytic processes kept emerging, and accordingly the catalyst industry also grew swiftly. Firstly, due to the high demand for liquid fuels, a large amount of catalysts are used in the petroleum refining industry, which has driven an increase in the scale of catalyst production and technological advancements. The rise of moving bed and fluidized bed reactors has spurred the catalyst industry to develop new shaping methods, including production techniques for pellets and microspheres. At the same time, as processes for producing synthetic materials and their monomers emerged one after another, the variety of industrial catalysts increased rapidly. During this period, large factories for the production and sale of industrial catalysts began to appear, with some of them already starting to produce a variety of products. The expansion of the production scale of industrial catalysts played an important role in the development of the synthetic fuel and petroleum industries during this period. Following the Burgess process, in 1933 in Germany, the Ruhr Chemical Company utilized Fischer’s research findings to establish plants for producing hydrocarbons from syngas using coal as a raw material. It also produced the required cobalt-based catalysts, with diatomite serving as the carrier. This industrial process for hydrocarbon production is known as the Fischer-Tropsch process, or simply FTS synthesis. It was widely used in Germany during World War II, and plants were built in South Africa in the 1940s. In 1936, E.J. Hudley developed an acid-treated bentonite catalyst for use in fixed-bed petroleum catalytic cracking processes to produce gasoline with an octane rating of 80, which was a major achievement in the modern petroleum refining industry. In 1942, the Davidson Chemical Division of the American company Grace introduced microspherical synthetic silicoalumina cracking catalysts for use in fluidized beds, which soon became the most produced type in the catalyst industry. Increase in the variety of industrial catalysts: Initially, various catalysts were developed for producing chemicals from coal via acetylene, among which those needed for synthesizing synthetic rubber were developed earliest. During the technical development of synthesizing the rubber monomer 2-chloro-1,3-butadiene from acetylene in 1931–1932, vinyl acetylene was produced from acetylene using copper(I) chloride as a catalyst. In the 1940s, industrial processes for synthesizing styrene-butadiene rubber, nitrile rubber, and butyl rubber were developed respectively using lithium, aluminum, and peroxides as catalysts; all of these reactions were carried out in a liquid phase. To obtain the relevant monomers, many solid catalysts have also been developed. During World War II, Cr-Al-O catalysts for the production of butadiene via butane dehydrogenation were developed and put into use in the mid-1940s. During the same period, iron oxide-based catalysts for the dehydrogenation of ethylbenzene to produce styrene were developed. After the production process for polyamide fibers (nylon 66) was established in the second half of the 1930s, solid nickel catalysts for the hydrogenation of benzene to produce cyclohexane were developed in the 1940s, as well as cobalt-based catalysts for the liquid-phase oxidation of cyclohexane to produce **(alcohols)**. During this period, cobalt-based complex catalysts for the carbonylation of olefins were also developed. At this stage, the production and use of solid acid catalysts contributed to the development of the theory of solid acid catalysts. To obtain the aromatic raw materials needed for the production of TNT, Standard Oil of America developed hydroreforming technology in 1939 and produced the required platinum oxide-alumina and chromium oxide-alumina catalysts. In 1949, the American company Universal Oil Products developed a platinum reforming technique based on fixed-bed operation with semi-regenerative cycling for long-term use, to produce catalysts containing platinum and alumina. In this catalyst, alumina serves not only as a support but also as a solid acid, which is one of the active components, making it the first important bifunctional catalyst. In the 1950s, thanks to the development of abundant oil resources in the Middle East and low oil prices, the petrochemical industry developed rapidly. Meanwhile, several important product series have gradually emerged in the catalyst industry, namely petroleum refining catalysts, petrochemical catalysts, and inorganic chemical catalysts centered on ammonia synthesis. In catalyst production, the formulations are becoming increasingly complex. These catalysts include polymerization catalysts made from metal-organic compounds, multicomponent oxide catalysts developed to achieve high selectivity, highly selective hydrogenation catalysts, and structurally ordered molecular sieve catalysts. Due to advancements in chemical science and technology, there has been a rapid increase in the variety of catalyst products. Production of organometallic catalysts: Most homogeneous catalysts used in the past were acids, bases, or simple metal salts. In 1953, K. Ziegler in West Germany developed a catalyst (C2H5)3Al-TiCl4 that enabled the polymerization of ethylene at atmospheric pressure, and it was put into use in 1955. In 1954, G. Natta in Italy developed the (C2H5)3Al-TiCl3 system for the isotactic polymerization of propylene, and a plant was built in Italy and brought into operation in 1957. Since this complex homogeneous catalyst became available on the market as a commercial product, the catalyst industry has begun producing certain organometallic compounds. Currently, in the catalyst industry, polymerization catalysts have become an important production sector. Development of mixed catalysts for selective oxidation. Selective oxidation is one of the important methods for producing organic chemicals. The vanadium oxide and molybdenum oxide catalysts that have been developed so far do not exhibit ideal selectivity; as a result, there has been significant effort to develop highly selective oxidation catalysts suitable for large-scale production. In 1960, the industrial process for synthesizing acrylonitrile through the ammoxidation of propylene, developed by Ohio Standard Oil Company, was put into operation. It used a complex bismuth-molybdenum-phosphorus-oxygen/silica catalyst, which later evolved into a catalyst in which oxides of seven metal elements—bismuth, molybdenum, phosphorus, iron, cobalt, nickel, and potassium—were supported on silica. In the 1960s, vanadium-phosphorus-oxygen catalysts for the oxidation of butylene to maleic anhydride, vanadium-titanium-oxygen catalysts for the oxidation of o-xylene to phthalic anhydride, and copper chloride catalysts for the oxychlorination of ethylene were also developed; all of these are solid-supported catalysts. In terms of production methods, due to the widespread use of the impregnation method, the production of carriers with various properties has also become an important aspect of this industry, including alumina of different grades, silica gel, and certain carriers with low specific surface areas. As fluidized bed reaction technology was transferred from the petroleum refining industry to chemical production, modern catalyst manufacturers have also begun to use spray drying technology to produce microspherical chemical catalysts. The most important achievement in homogeneous catalytic selective oxidation was the commissioning in 1960 of a large-scale plant for the direct oxidation of ethylene to acetaldehyde. This method of producing acetaldehyde using a palladium chloride-copper oxide catalyst is known as the Wacker process. Improvements in hydrorefining catalysts: To develop the petrochemical industry, a large number of catalysts for the hydrorefining of petroleum cracking fractions have been developed, many of which are improvements based on metal hydrogenation catalysts from previous eras. In addition, nickel-sulfur catalysts and cobalt-molybdenum-sulfur catalysts for the hydrogenation dehydrogenation of pyrolysis gasoline, as well as palladium catalysts for the low-temperature liquid-phase hydrogenation removal of alkynes and dienes, have also been developed. The rise of molecular sieve catalysts: In the mid-1950s, Union Carbide Corporation was the first to produce X-type and Y-type molecular sieves. These are crystalline silicoaluminates with uniform pore sizes; their pore dimensions are on the order of molecular sizes, allowing them to filter molecules. The molecular sieve produced by the ion exchange method in 1960 had enhanced structural stability. In 1962, small-particle molecular sieve catalysts for oil cracking were put into use in moving-bed reactors, and in 1964, the XZ-15 microsphere molecular sieve was used in fluidized-bed reactors, lifting the oil refining industry to a new level. Since the emergence of molecular sieves, in 1964, Union Oil Company and Esso Standard Oil Company introduced metal-supported molecular sieve cracking catalysts. Taking advantage of the shape selectivity of molecular sieves, building on the achievements made in the petroleum refining industry in the 1960s, many important catalytic processes based on molecular sieve catalysts were developed in the chemical industry after the 1970s. Another achievement of catalysts in the petroleum refining industry during this period was the platinum-rhodium/alumina bimetallic reforming catalyst, which appeared in 1967. The development of large-scale ammonia synthesis catalyst series: Starting from the 1960s, in the ammonia synthesis industry, the feedstock for hydrogen production from hydrocarbons shifted from coal to naphtha and natural gas. In 1962, the American company Kellogg and the British company ICI developed supported nickel catalysts catalyzed by alkalis or alkaline earth metals, which could operate under pressure (3.3 MPa) without carbon deposition, thereby contributing to energy savings in large ammonia plants. Hydrocarbon steam reforming catalysts, hydrodesulfurization catalysts, high-temperature shift catalysts, low-temperature shift catalysts, ammonia synthesis catalysts, methanation catalysts, and others constitute the range of catalysts used in ammonia synthesis plants. (See color illustration) The period of transition (1970s–1980s) During this stage, highly efficient complexing catalysts were introduced one after another ； Catalysts for low-pressure operations have been developed to save energy ； The shapes of solid catalysts are becoming increasingly diverse ； New types of molecular sieve catalysts have emerged ； Begin large-scale production of environmental protection catalysts ； Biocatalysts are gaining attention. Major catalyst manufacturers have been strengthening their research and development departments in order to cope with the increasingly shortening cycle of catalyst upgrades, striving to stay ahead; they have also enhanced their advisory services for customers, giving rise to multinational companies that deal in catalysts. An important feature is: the emergence of highly efficient complexing catalysts. In the 1960s, cobalt complexes were used as catalysts in the process of methanol carbonylation to produce acetic acid, but the operating pressure was very high and the selectivity was poor. Around 1970, the low-pressure methanol carbonylation process developed by Monsanto was introduced, using rhodium complex catalysts with high selectivity. Later, rhodium complex catalysts modified with phosphine ligands were developed for the hydroformylation of propylene to butyraldehyde. Compared with traditional cobalt complex catalysts, this catalyst exhibits high selectivity for n-aldehydes and operates at low pressures; it was widely used by Union Carbide in the United States after 1975. Rhodium complex catalysts are used. The process of producing chiral amino acids through the hydrogenation of α-aminoacrylic acid emerged in the 1970s. These catalysts are all used in homogeneous catalytic systems. About a century after platinum and palladium, rhodium became another precious metal element used in the catalyst industry, and rhodium catalysts will play an important role in the development of carbon-1 chemistry. Rhodium complex catalysts for the direct synthesis of ethylene glycol from carbon monoxide and hydrogen are under development. Another major advancement in complex catalysts was the development of highly efficient olefin polymerization catalysts in the 1970s. These were supported complex catalysts formed by a titanium tetrachloride-alkyl aluminum system loaded on a magnesium chloride carrier; they exhibited extremely high efficiency, with one gram of titanium enabling the production of dozens to nearly a million grams of polymer. As a result, there was no need to separate the catalyst from the product, which helped reduce energy consumption during the production process. Industrial applications of solid catalysts: In 1966, the British company Brunel Chemical Industries developed a catalyst for the low-pressure synthesis of methanol. This catalyst, based on copper-zinc-aluminum-oxygen, replaced the zinc-chromium-aluminum-oxygen catalyst used in previous high-pressure processes, reducing the process pressure from 24–30 MPa to 5–10 MPa. This allowed the process to operate within the pressure range typical of modern hydrocarbon steam reforming processes for hydrogen production, thereby achieving energy savings. This catalyst was put into use in the 1970s. To achieve the goals of increasing production capacity and saving energy, the shapes of solid catalysts have become increasingly diverse since the 1970s. Examples include trilobal and tetralobal catalysts used in hydrorefining, honeycomb catalysts for vehicle exhaust purification, as well as spherical and radial catalysts used in ammonia synthesis. There are also some new designs regarding the distribution of catalytically active components within the catalyst; for example, in the palladium/alumina catalysts used for the first-stage hydrorefining of cracked gasoline, the active components are concentrated in the near-surface layer. Industrial applications of molecular sieve catalysts: Following catalysts used in petroleum refining, molecular sieve catalysts have also become an important type of catalyst in the petrochemical industry. In the early 1970s, molecular sieve catalysts for xylene isomerization were introduced, replacing the previously used platinum/alumina catalysts ； A mordenite (M-silica gel) catalyst for toluene disproportionation was developed. In 1974, Mobil Oil developed the ZSM-5 type molecular sieve for selective reforming, which allows n-paraffins to be cracked without affecting aromatics. At the end of the 1970s, ZSM-5 molecular sieve catalysts were developed for the alkylation of benzene to produce ethylbenzene, replacing the previously used aluminum trichloride. In the early 1980s, ZSM-5 molecular sieve catalysts for synthesizing gasoline from methanol were developed. Molecular sieve catalysts will play an important role in developing resources and advancing carbon-one chemistry. Industrial applications of catalysts for environmental protection: In 1975, the American company DuPont produced catalysts for purifying automobile exhaust gases, using platinum as the catalyst; a large amount of platinum was required for this purpose. In 1979, platinum used in these applications accounted for 57% of the total platinum consumption in the United States, amounting to 23.33 tons (750,000 troy ounces). Currently, environmental catalysts, along with chemical catalysts (catalysts used in processes such as the production of synthetic materials, organic synthesis, and ammonia synthesis), and petroleum refining catalysts, are considered the three major fields within the catalyst industry. Industrial applications of biocatalysts: The use of biochemical methods in the chemical industry is increasing. In the mid-1960s, progress in enzyme immobilization technology was rapid. In 1969, immobilized enzymes for the cleavage of acetyl-DL-amino acids were put into use. After the 1970s, various immobilized enzymes for large-scale applications were developed. Glucose isomerase for producing high-fructose syrup was developed in 1973 and was soon used on a large scale. In 1985, acrylonitrile hydrolyase was put into industrial use. The development of biocatalysts will bring about significant changes in chemical industry production. In addition, catalysts for the energy industry have also been developed, such as platinum supported on carbon or nickel in fuel cells to facilitate the combination of hydrogen and oxygen. The development of China’s catalyst industry: The first catalyst production facility was the Catalyst Department of Yongli Tungsten Factory, which was renamed the Catalyst Plant of Nanjing Chemical Industry Company in 1959. Production of AI-type synthetic ammonia catalysts, C-2-type high-temperature carbon monoxide conversion catalysts, and Type VI vanadium catalysts for sulfur dioxide oxidation began in 1950, and subsequently, the production of various catalysts required for the synthetic ammonia industry was gradually established. In the 1980s, China began producing supported nickel catalysts for natural gas and light oil steam reforming. By 1984, more than 40 companies were producing catalysts for the sulfuric acid, nitric acid, and synthetic ammonia industries. To develop the fuel chemical industry, in the early 1950s, the Third Petroleum Plant began producing molybdenum sulfide-clay, tungsten sulfide-active carbon, tungsten sulfide-clay, as well as pure tungsten sulfide and molybdenum sulfide catalysts for shale oil hydrogenation. Plant No. 6 for petroleum began producing cobalt-based catalysts for Fischer-Tropsch synthesis, and starting in 1960, it began producing phosphate-diatomite catalysts for polymerization. In the early 1960s, China discovered abundant oil resources and began to develop the industrial production of petroleum refining catalysts. At that time, petroleum cracking catalysts were first produced at the Lanzhou Refinery, and in 1964, the small-ball silica-alumina catalyst plant was built and put into operation. In the 1970s, China began producing rare earth-X type molecular sieves and rare earth-Y type molecular sieves. At the catalyst factory of Changling Refinery in the late 1970s, rare-earth Y-type molecular sieves on silica-alumina supports produced by the co-agglomeration method were introduced into production; later, high bulk density and wear-resistant semi-synthetic rare-earth Y-type molecular sieves were manufactured at the catalyst factory of Qilu Petrochemical Company. China began developing reforming catalysts in the 1960s; in the mid-1960s, the Third Petroleum Plant started producing platinum catalysts. In the 1970s, bimetallic platinum-rhodium catalysts as well as multimetallic reforming catalysts were produced successively. In terms of hydrorefining, the Third Oil Plant began producing molybdenum-cobalt and molybdenum-nickel reforming pre-hydrogenation catalysts in the 1960s. Mo-Co-Ni low-pressure pre-hydrogenation catalysts were produced starting in the 1970s, while trilobal hydrofining catalysts were produced starting in the 1980s. To develop the organic chemistry industry, from the late 1950s to the early 1960s, iron-based catalysts for the dehydrogenation of ethylbenzene, mercury chloride/activated carbon catalysts for the production of vinyl chloride from acetylene and hydrogen chloride, vanadium oxide catalysts for the oxidation of naphthalene to phthalic anhydride in fluidized beds, and skeleton nickel catalysts for hydrogenation were begun to be manufactured. In the mid-1960s, to meet the needs of China’s petrochemical industry, the number of newly developed catalyst types increased rapidly. By the 1980s, a variety of selective hydrogenation catalysts for refining olefins had been produced, as well as microspherical oxide catalysts for the ammoxidation of propylene, supported metal catalysts for the oxidation of ethylene to vinyl acetate, high-efficiency olefin polymerization catalysts, and honeycomb catalysts for treating industrial waste gases.