A Brief History Of The Development Of Titanium Dioxide Industry At Home And Abroad

- Apr 29, 2019-

Tang Zhenning, former chief engineer and senior engineer of Nanjing Titanium White Chemical Co., Ltd. He has been engaged in the production and research of titanium dioxide for more than 40 years. He used to be the director of titanium dioxide production workshop, deputy director of titanium dioxide powder factory, director of technical department and chief engineer.

Participated in the construction of the first domestic rutile titanium dioxide production workshop and was responsible for organizing and personally participating in the chemical industry's chemical fiber titanium dioxide technology research and construction and construction of the first domestic chemical fiber titanium dioxide production workshop.

He has published more than 60 papers on titanium dioxide. His main works include "Production and Environmental Management of Titanium Dioxide" (Chemical Industry Press), and participated in the compilation of "Chemical Encyclopedia" (Vol. 15 titanium dioxide).

After retirement, he also served as deputy head of the Titanium White Center and Titanium Dioxide Industry Alliance expert group of the National Chemical Productivity Promotion Center and consultants of Titanium White magazine and Jiangsu Coating Engineering Technology Center.

China's titanium dioxide industry started relatively late in 1954 ~ 1955, the unit began to research and development, 1956 public-private joint venture Shanghai Huaheng Chemical Plant and public-private joint venture Guangzhou Hezhong Chemical Plant began production of welding electrodes, enamel titanium dioxide, 2017, China's titanium dioxide Industry has gone through 62 years of history. Looking back at the early employees of the titanium dioxide industry in China, in the absence of drawings, no technical information, no foreign aid, because of the simple situation, at the time the material conditions were extremely scarce, relying on the unique intelligence, hard work and perseverance of our Chinese people. The spirit of perseverance, self-reliance and hard work have gradually established and perfected the foundation of China's titanium dioxide industry. This article is only used to commemorate the early employees and scientific research and technical personnel who struggled in the titanium dioxide industry in China, and expressed their deep respect for their hard work and outstanding contributions. 01 Development history of foreign titanium dioxide industry

In 1790, British scientist Willam Gregor and a rural missionary analyzed a black and magnetic sandstone in his hometown and found that half of it was a white metal oxide. This is human titanium. The first discovery.

In 1795, German scientist Martin Klaproth isolated a white oxide in a red Schorl ore produced in Hungary, later called rutile, exactly the same as Grieg's. It is called "titanium" (the Latin word Titans - the name of the eldest son of the Greek mythology).

Because most of these black magnetic mineral sands were found in the IMMEN mountains of Russia, they were called Ilmenite, and until now the English word for ilmenite was still Ilmenite.

In 1824, people began research on the preparation of titanium dioxide.

In 1908, the Frenchman Auguste Iacques Rossi produced some less pure titanium dioxide in a titanium ore processing company in the United States, and applied for a patent in October 1911 (US Patent US No) 118411). Their method is a process in which titanium ore is melted and fired with sodium bicarbonate or sodium carbonate, and then dissolved in dilute acid. During this period (1908 ~ 1912), Norway's Jebsen and Farup and the United States' Barton (LE Barton) also completed the preparation of titanium dioxide from ilmenite by sulfuric acid method and melting method. Research. This is the predecessor of the production of titanium dioxide by sulfuric acid method. After the preparation of titanium dioxide by sulfuric acid method, although many patents have been published, the prototype and theoretical basis of 1910 have not been shaken off.

In 1916, the Norwegian Titanium Pigment Company was established in Fredrikstad, Norway, and the world's first titanium dioxide production workshop (product of TiO 225% composite pigment) was built at 1 000 t/a. .

In 1918, the American Titanium Pigment Company was established (later acquired by the National Lead Company NL) and became a subsidiary of NL Corporation.

In 1920, Norwegian Titanium Pigment Company merged with American Titanium Pigment Company and became a subsidiary of American NL Company.

From 1921 to 1923, in the laboratory of Societe de Produits Chimiques des Terren Rares in Serquigny, France, under the leadership of Joseph Blumenfeld, the self-produced seed dilution process was successfully developed and It was called the "Brumenfield Act" and applied for a patent. Due to the large amount of sulphuric acid required for the treatment of ilmenite, the company, together with Than etMilhouse (later owned by Ronald Planck of France), used the Blumenfeld method to produce TiO2 for the first time in the world. An anatase titanium dioxide pigment having a content of 96% to 99%.

In 1925, the United States NL company completed the preparation of 100% pure titanium dioxide single crystal.

In 1930, Meklenberg used alkaline neutralization and seeding, and made a major reform of the hydrolysis process of sulfuric acid process, which made the sulfuric acid process more perfect. Until now, the hydrolysis process of the sulfuric acid titanium dioxide plant in the world has adopted both methods without exception.

The Blumenfeld Act was later widely transferred around the world, and many factories were established around the world, one of which was owned by DuPont, and the National Lead Company (NL) used the technology in Germany, the United Kingdom, Japan, etc. Established a series of joint ventures, which were later in Germany's Kronos (now translated as Connors), the British BTP (later changed to the titanium dioxide group under ICI), Japan's titanium industry company Wait. The Titanium Dioxide Group was once the world's second-largest producer of titanium dioxide after DuPont. The US SCM (later for Merrill Lynch) purchased NL's US factory, and Larpote in the UK and Australia. The factory has become the world's third largest producer of titanium dioxide. This is the pattern of the world's major titanium dioxide producers in the 1990s. After 2000, several foreign titanium dioxide merchants have undergone several mergers and acquisitions to form the current pattern. The top five producers are DuPont (Kemo) and Huntsman. Cristal, Connors, Teno, everyone is familiar, this article is not covered here.

In the case of chlorination, in the Czech Republic, from 1930 to 1937, the rutile-type titanium dioxide was first produced in the laboratory by the external seed hydrolysis method and the titanium tetrachloride heating method, and it was not continued because of the Second World War, followed by In 1940, Pittsburgh Flat Glass Company (PPG) also produced rutile titanium dioxide from titanium tetrachloride solution, which was officially sold in the US market in 1941.

The successful development of rutile titanium dioxide has made the titanium dioxide industry a huge development. It grew at an average rate of 12% per year from 1934 to 1959 (World Titanium Dioxide Production Capacity: 225,000 t/a in 1934 and 516,000 in 1940) t/a, 655,000 t/a in 1950, 1.518 t/a in 1965, 2.5 million t/a in 1976).

In 1948, DuPont began research on chlorination production technology, established a 35 t/d pilot plant in Aichmore, Delaware, and built a 10 in 1954 in New Johnsonville, Tennessee. The 10,000 t/a factory has been optimized for 5 years to produce high quality chlorinated titanium dioxide. However, this method can only produce rutile type and cannot produce anatase type. Since 1967, DuPont has started large-scale industrial production of chlorinated titanium dioxide.

In 1975, DuPont successfully produced anatase titanium dioxide by chlorination and realized the production of titanium tetrachloride by chlorination of ilmenite. DuPont’s major breakthrough in chlorination technology made it quickly replaced. NL is the largest producer of titanium dioxide in the United States and the world's largest producer of titanium dioxide.

In 1951, Quebec Iron and Titanium Metallurgical Company (QIT) developed acid-soluble titanium slag with TiO2 content of 70%-85%, which provided high-quality raw materials for reducing the waste by-product of sulfuric acid.

In the 1950s, inorganic surface treatment agents were widely used in foreign titanium white industries to improve their weather resistance. In the 1960s, organic surface treatment agents were used to improve their dispersion properties.

02 China's titanium white industry with 63 years of history

China's titanium dioxide industry is relatively young, and some units began to contact titanium dioxide research from 1954 to 1955.

In 1956, the public-private joint venture Shanghai Huaheng Chemical Plant (later Shanghai Titanium Dioxide Factory) began to produce non-pigment-grade titanium dioxide for welding electrodes and enamel by sulfuric acid method, followed by public-private joint venture Guangzhou Hezhong Chemical Plant (later Guangzhou Titanium Dioxide Factory). A similar process was used to produce a similar product, which was a full 40 years behind the world's first titanium dioxide factory built in Norway in 1916.

In 1957, the Tianjin Chemical Industry Research Institute of the Ministry of Chemical Industry began to organize the research and development of the production process of pigment-grade anatase titanium dioxide.

In 1958, under the situation of industrial leapfrogging in the industry, Tianjin, Jinan, Liaoyang, Wuxi and other places have successively built a small non-pigment-grade small titanium dioxide factory.

From 1962 to 1963, the Tianjin Chemical Industry Research Institute's pigment-grade anatase titanium dioxide expansion test results were industrially scaled up trial production at Shanghai Huaheng Chemical Plant and Tianjin Tonghua Chemical Plant, and passed the Ministry of Chemical Industry and Shanghai Chemical Industry Bureau. The identification of the organization laid the foundation for the production of anatase titanium dioxide in China.

In 1966, the Tianjin Chemical Research Institute of the Ministry of Chemical Industry began research on the production of rutile titanium dioxide by the sulfuric acid process. In 1968, a 300 t/a rutile titanium dioxide pilot plant was built at the Nanjing Grease Chemical Plant, which was subsequently expanded to 1,000. t/a, put into production in 1970, the product was successfully applied in Tianjin Paint Factory and expanded to a scale of 3 000 t/a.

In 1972, the Coatings Industry Research Institute of the Ministry of Chemical Industry and the Third Design Institute of the Ministry of Chemical Industry, as well as the Nanjing Grease Chemical Plant and the Zhenjiang Titanium Dioxide Factory, conducted a small test of the carbon monoxide internal heating method in the Shanghai Titanium Dioxide Factory. As a result, a pilot plant was built in the Xiamen Electrochemical Plant in Fujian Province. Then, from 1973 to 1974, the Institute of Nonferrous Metals Research of the Ministry of Metallurgy and the Institute of Chemical Metallurgy of the Chinese Academy of Sciences established a 30 kW and 40 kW plasma torch in the chlorinated titanium dioxide in the Tianjin Chemical Plant and the Zunyi Ferroalloy Plant in Guizhou. The test device, the test device of the above two places all produced chlorinated rutile titanium dioxide. After the technology is not mature, the equipment material can not be solved, and it has not been put into industrial production.

In 1975, in order to cooperate with several sets of large-scale chemical fiber equipment introduced in China, the Ministry of Chemical Industry provided titanium dioxide for chemical fiber, and organized chemical fiber titanium dioxide in the Nanjing Oil Chemical Plant. It was led by Nanjing University and participated in Shanghai Titanium Dioxide Factory and Shanghai Dongsheng. Titanium dioxide factory, Zhenjiang, Jinan and other units. Under the leadership of Master Wu Jiansheng, the third design institute of the Ministry of Chemical Industry, more than ten engineers and technicians, in the titanium dioxide workshop of the Nanjing Grease Chemical Plant, to operate on-site, collecting test engineering data and process data, based on this data in Nanjing oleochemical industry. A 1 000 t/a full-process chemical fiber titanium dioxide workshop (which can produce anatase 2 000 t/a) has been built in the plant. The project includes three waste treatments (acidification tail gas, calcined tail gas, waste acid concentration, sewage treatment). Public works (substation, water plant, railway special line, part of office and living facilities), the project design was awarded in the Ministry of Chemical Industry and the Ministry of Environmental Protection.

1976-1977, six new test results of the sulfuric acid method of the Institute of Coatings Industry of the Ministry of Chemical Industry: modified polyacrylamide flocculant (previously used iron sulfide + cerium oxide inorganic precipitant in China), trivalent titanium bleaching Prior to this, the domestic use of zinc powder or aluminum powder bleaching, titanium tetrachloride seed crystal, rutile calcined seed crystal, hydrocyclone classifier and silicon, aluminum coating technology in the Nanjing oil chemical plant for industrial trials, until now 6 The results of the test were not used except for the supply of titanium tetrachloride seeds due to the supply, storage and transportation of raw materials. The other five test results are still in use in the domestic titanium dioxide industry.

In order to cooperate with the comprehensive utilization of Panzhihua titanium mine, the Ministry of Chemical Industry organized a research project by the Coatings Industry Research Institute of the Ministry of Chemical Industry in 1979, and successfully carried out industrial trials of producing rutile titanium dioxide from Panzhihua high-sulfur ilmenite in Zhenjiang Titanium Dioxide Factory. It has also passed the appraisal organized by the Science and Technology Bureau of the Ministry of Chemical Industry, and accumulated practical experience for the large-scale use of rock climbing in China's titanium dioxide industry.

In the mid-1980s, with the overheating of the domestic economy, many small titanium dioxide factories were built throughout the country. According to statistics, there are 108, mainly concentrated in Henan, Guangxi, and Jiangsu provinces. Most of these small titanium dioxide factories are township enterprises and factories. The scale is small, the technology and equipment are backward, the product quality is poor, and the “three wastes” are seriously polluted, which also causes a short supply of short-term domestic titanium ore supply.

In order to restrict the township enterprises that do not have the production conditions, the Ministry of Chemical Industry formulated the national industrial policy for the construction of titanium dioxide factories below 3 500 t/a, and introduced the titanium dioxide production license system in 1991. .

In order to quickly get rid of the backward appearance of China's titanium dioxide industry, in formulating the "seventh five-year" plan, the Ministry of Chemical Industry proposed the "sulfuric acid method and the chlorination method" on the basis of summarizing the production and construction work of titanium dioxide in China at that time; The development strategy of both the basic construction and the technological transformation; the introduction of technology and domestic technology development, the planned production, construction and scientific research projects of titanium dioxide, a batch of 10,000-ton titanium dioxide plants began to be built, and the introduction of technology Conducted in an orderly manner.

In the late 1980s, the Ministry of Chemical Industry organized relevant enterprises to go abroad for inspections and chose to introduce technology. Among them, the 404 factory of the Ministry of Nuclear Industry introduced the technology and engineering technology of the Czech Boley Color Titanium Dioxide through a consultancy company in Yugoslavia. The technology of the Rhone-Poulec plant was completed in 1993 with a 15,000 t/a sulfuric acid titanium dioxide plant; Sichuan Chongqing Dagang Titanium Dioxide Co., Ltd. introduced the technology and equipment of the Polish Politz titanium dioxide plant (original Germany) Kronos's technology) built a 15,000 t/a titanium dioxide factory in 1995; Liaoning Jinzhou Ferroalloy Factory, through a technology consulting company opened in the United States, found some Americans who worked at DuPont. Provided a part of the information on the production technology of titanium chloride white powder and purchased some key equipment abroad. In 1994, China built the first 15,000 t/a plant of the chlorination method. At the same time, Guangzhou Titanium Dioxide Factory provided the rutile titanium dioxide technology through the introduction of the retired technicians from the original Australian Laport company, and purchased some production equipment and analytical instruments, which were designed by Guangzhou Chemical Industry Bureau in Guangzhou Titanium Powder Factory. The enamel titanium dioxide production line was transformed into a production workshop for producing rutile titanium dioxide, which was later referred to by the industry as “Guangzhou Titanium Technology” or “Australian Technology”. On this basis, the Ministry of Chemical Industry has organized six factories including Hunan Zhuzhou Titanium Dioxide Factory, Shanghai Titanium Dioxide Factory, Nanjing Grease Chemical Plant, Zhenjiang Titanium Dioxide Factory, Jinan Yuxing Chemical Plant and Liaoyang Metallurgical Chemical Plant. ". Later, Jinan Yuxing Chemical Plant introduced a 15,000 t/a titanium dioxide factory through the same channel and introduced Czech technology. The main difference from the 404 factory was the hydrolysis of its own seed dilution method to external crystal. A micropressure hydrolysis method.

The digestion and absorption of the above introduced projects, especially the successful introduction of the complete set of technical devices introduced by the 404 plant, the 渝Titanium and the Jinan Yuxing, have greatly promoted and demonstrated the technological progress and large-scale installation of the titanium dioxide industry in China. effect.

In the past 63 years, China's titanium dioxide industry has grown from scratch, from small to large. From 1993, 51 titanium dioxide factories produced an annual output of 133,500 tons, with a production capacity of 175,000 t/a, and by 2018, the actual production of 39 full-process production enterprises. It has an export volume of 9.8403 million tons and a production capacity of 9.8 million tons. It has a production capacity of more than 3.4 million tons. It has been the world's number one producer for 11 consecutive years and has become a net exporter of titanium dioxide. Before the 1990s, there was no 10,000-ton enterprise in China. By 2016, the total output of Henan Longyi Lilian was 588,000 t/a, the first in Asia and the fourth in the world. Before the 1990s, only one titanium dioxide factory in Nanjing produced a small amount of rutile. Type Titanium Dioxide, by 2018, China's rutile titanium dioxide production reached as high as 22.928 million tons, accounting for 77.61% of the national total output; before the 1990s, there was no chlorinated titanium dioxide factory in China, and there were 4 chlorinated by 2018. The Titanium Dioxide Factory started production with a production capacity of 210,000 t/a and an actual output of 134,000 t/a.

The great development achievements of China's titanium dioxide industry over the years should be attributed to the country's reform and opening up policy and the attention and support of leaders at all levels. It is also the result of hard work and hard work of the employees and engineering technicians in the titanium dioxide industry.

At present, China is already a veritable producer of titanium dioxide in the world, but it is not a strong country. We still have a certain gap with foreign large companies in terms of product quality, product structure and control management, and the gap in chlorination production technology is even greater. In the future, we must strive to improve product quality and development of special varieties while building energy-saving emission reduction, clean and civilized production, create independent brands, continue to explore the international market, continue the chlorination method, and master the true key technologies. On the basis of the domestic promotion of the chlorination process, the old sulfuric acid law enterprises vigorously promote the joint production law route to achieve sustainable development of the industry, and soon become the world's largest producer and strong country of titanium dioxide.