In the late 19th and early 20th centuries, the technology of using catalysts in the chemical industry gradually emerged. In order to meet the requirements of industrial catalysts, a catalyst industry with a wide variety of products, advanced manufacturing technology, and increasing production scale and output value was gradually formed.

(1) Early catalyst applications

Sulfuric acid production: According to records, the earliest industrial grade catalysts were applied in the mid-18th century. At that time, British doctors John Ward and Joseph Roback used lead chamber reactors for sulfuric acid production, in which nitrogen oxides produced from saltpeter were used as gaseous catalysts. This process marked the beginning of the application of catalytic technology in industrial scale production.

Platinum catalyst patent: Furthermore, in 1831, Phillips obtained a patent for the oxidation of sulfur dioxide to sulfur trioxide on platinum, representing the first industrial application of platinum catalysts and greatly promoting the industrial production of sulfuric acid.

(2) Early types of catalysts

Gaseous catalyst: As mentioned earlier, nitrogen oxide used in sulfuric acid production is a typical example of early gaseous catalysts, which effectively promote the progress of chemical reactions.

Solid state catalyst: In 1875, E. Jacob of Germany established the first contact method device for producing fuming sulfuric acid and manufactured the required platinum catalyst, marking the birth of solid industrial catalysts. Platinum is not only the first widely used industrial catalyst, but it is also widely used as a catalytic active component in various important industrial catalysts to this day.

(3) Early important chemical catalytic processes

Dickon process: In the 1860s, the Dickon process was developed using copper chloride as a catalyst to oxidize hydrogen chloride to produce chlorine gas. This process was an important breakthrough in chemical production during that era.

Contact method device: The contact method device established in 1875 not only demonstrated the important role of platinum catalysts in the production of fuming sulfuric acid, but also demonstrated the potential application of solid catalysts in chemical production.

Early catalyst varieties were limited, and production was mainly carried out in manual workshops. Due to the importance of catalysts in chemical production, their manufacturing methods are considered trade secrets. The production method during this period, although simple, played an important role in maintaining the stability and reliability of catalyst quality.

2. Foundation period

The initial formation of the chemical industry.

Catalytic theory: The development of industrial practice has promoted the research of catalytic theory. In 1925, Taylor proposed the theory of active centers, which provided a theoretical basis for the advancement of manufacturing technology in the future.

Overall, the foundational period of catalysts laid the foundation for modern catalyst industry and scientific research. The technological progress and theoretical exploration in this stage not only enhance the application effectiveness and economy of catalysts in industrial production, but also provide important theoretical and technical support for the development of more complex and efficient catalysts in the future.

(1) Expansion of production scale

The development of synthetic fuels and petroleum industry: Before and after World War II, due to the high demand for strategic materials, especially liquid fuels, the production scale of catalysts rapidly expanded. For example, the Fischer Tropsch synthesis plant established in Germany used cobalt supported catalysts to convert coal into hydrocarbons, a process that was widely adopted during wartime.

The promotion of petroleum refining industry: In the 1950s, due to the development of Middle Eastern oil resources and low oil prices, the petrochemical industry developed rapidly, and the use of catalysts increased significantly. The microsphere shaped synthetic silicon aluminum cracking catalyst launched by Grace Corporation in the United States quickly became the most widely produced variety.

(2) Technological progress

Innovation in catalyst forming methods: With the rise of moving bed and fluidized bed reactors, the catalyst industry has established new forming methods, including the production technology of small balls and microspheres.

Multi variety production: During this period, large factories producing and selling industrial catalysts emerged, and some factories began to produce multiple varieties to meet the needs of different industrial applications.

(3) Significant increase in variety

Production of organometallic catalysts: In 1953, Ziegler developed the atmospheric pressure ethylene polymerization catalyst (C2H5) 3Al-TiCl4, marking the entry of organometallic catalysts into the market and becoming an important product line.

The rise of molecular sieve catalysts: In the mid-1950s, Union Carbide Corporation of the United States produced X-type and Y-shaped crystalline aluminosilicate molecular sieves with uniform pore size, pioneering the development of molecular sieve catalysts.

(4) Catalytic process update

Selective oxidation mixed catalyst: A mixed catalyst for selective oxidation has been developed, such as the Wacker method palladium chloride copper oxide catalyst for direct oxidation of ethylene to acetaldehyde.

Improvement of Hydrorefining Catalysts: In response to the needs of the petrochemical industry, improvements have been made to metal hydrogenation catalysts, such as nickel sulfur catalysts and cobalt molybdenum sulfur catalysts.

(5) Formation of Synthetic Ammonia Catalyst Series

Development of large-scale synthetic ammonia catalysts: Since the 1960s, the raw materials in the synthetic ammonia industry have shifted from coal to naphtha and natural gas, and supported nickel catalysts using alkali or alkaline earth metals have been developed, promoting the formation and development of a series of large-scale synthetic ammonia catalysts.

In short, during this period of great development, the catalyst industry has achieved a leap from quantitative expansion to qualitative advancement. Not only has the production scale and variety been greatly improved, but manufacturing technology and application scope have also made significant progress. The development during this period laid a solid foundation for further innovation in catalyst technology.

(1) Types of catalysts

Molecular sieve catalysts: Molecular sieve catalysts have been widely used during this period, especially in petroleum refining and chemical production.

Solid catalysts: Solid catalysts such as synthetic silicon aluminum cracking catalysts play an important role in petroleum refining, improving refining efficiency.

Automotive exhaust purification catalysts: The demand for environmental protection has driven research on catalysts that reduce harmful emissions, such as honeycomb catalysts used for automotive exhaust treatment.

(2) Manufacturing Technology

Molding technology: With the popularity of mobile bed and fluidized bed reactors, the molding technology of catalysts is constantly innovating, producing catalysts in the shape of small balls and microspheres to meet new demands.

Dispersing active ingredients: The technology of highly dispersing active ingredients has been further applied, improving the activity and stability of catalysts.

(3) Surface and Interface Chemistry Research

Integration of theory and experiment: In the modern era, catalyst research has begun to closely integrate theory and experiment, and deepen the understanding of catalytic processes through advanced characterization methods.

In situ dynamic characterization technology: Developed in-situ dynamic and high-resolution characterization methods, providing new experimental methods for catalyst design and performance optimization.

(4) Environmental Protection and Sustainable Development

Environmentally friendly catalysts: A series of catalysts have been developed for environmental protection, such as those used for exhaust gas treatment and reducing greenhouse gas emissions.

Renewable resource utilization: Emphasize the efficient utilization of renewable resources and carbon dioxide resources, and develop relevant catalytic conversion technologies.

Overall, the modernization period of catalysts is not only reflected in the innovation of catalyst types and technologies, but also in the emphasis on environmental protection and sustainable development. The technological progress during this period has made significant contributions to the country’s economic development and environmental protection. With the advancement of technology, the catalyst industry will continue to move towards a more efficient and environmentally friendly development direction.

In China, the catalyst industry has developed and grown with the rise of industries such as fertilizers, oil refining, and petrochemicals. Before 1950, all catalysts needed for China’s chemical production were purchased from abroad. At that time, Yongli Chemical Industry Company, the largest chemical enterprise in China, was unable to import vanadium catalysts for sulfuric acid production and faced a crisis of complete shutdown. Therefore, Yu Zuxi, a technician at Yongli Mining Plant, devoted himself to the research of vanadium catalysts and successfully trial produced vanadium oxide catalysts on September 26, 1950, ending the history of China’s inability to produce catalysts.

Subsequently, China’s catalyst industry continued to develop. At present, some factories produce catalysts such as steam reforming, low-temperature transformation, medium temperature transformation, methanation, and ammonia synthesis used in the fertilizer industry; Microsphere molecular sieve cracking catalysts, small ball silicon aluminum cracking catalysts, bimetallic reforming catalysts, various hydroprocessing catalysts, hydrocracking catalysts, and composite catalysts in the refining industry have been widely produced; Catalysts used in the petrochemical industry, such as cracking gas hydrogenation to remove alkynes, selective hydrogenation of cracking gasoline, xylene isomerization, and toluene disproportionation, have also been put into production; In addition, various catalysts such as ammoniation oxidation of propylene, oxidation of ethylene to produce ethylene oxide, and polymerization of ethylene and propylene are also produced. Part of China’s catalyst factories are affiliated with fertilizer plants, refineries, and petrochemical plants, producing catalysts that are supplied nationwide and undertaking the large-scale trial production of new catalysts; There is also a batch of factories specializing in the production of alumina carriers, silica carriers, activated carbon carriers, and molecular sieves.

Article source: www.xianjichina.com

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