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Knowledge of Carbon Black

History of Carbon Black　

　　Carbon black is one of the petrochemical raw materials that people know earliest. Our country produced carbon black earliest in the world. Even 3,000 years ago, our ancestors mastered the technologies of manufacturing ink. The origin and development of carbon black are closely related with the formation of Chinese ancient characters and the invention of paper and printing. Carbon black was said as “soot” in ancient China. As the ancient carbon black was made from pine branches, it was also known as “pine soot”. These names have been used to the end of 19th century and gradually were replaced by the term of “carbon black” in 1892, when modern carbon black industry appeared.
　　Early application of carbon black is to manufacture ink and black pigment. The oracle-bone-inscriptions in Yin era of China were recorded in soot ink. There are a huge number of ancient bamboo-slips and wood-slips, out of which only “Shi Ji” has 130 volumes of 526, 550 characters, all written in ink. In Han dynasty, China’s first dictionary-“Shuo-Wen-Jie-Zi” was published, where “ink” was explained as “black, made from soil; as it is made from soot, it’s black; belongs to the soil category”.
Ancient Chinese carbon black manufacturing dates back to ancient times. Wei Dan (176-257AD), born in Wei dynasty, was a skilled manufacturer of ink carbon black. And Caozhi (192-232 AD) of Wei in Three Kingdoms Period had the record of “ink is from pine soot”. By the third century, in Jin dynasty, pine soot carbon black had been widely used, which also shows that China’s handicraft production of pine soot had been quite developed. Then, in the tenth century, that is the Tang dynasty, people began to burn China wood oil and other animal or plant oil in the absence of insufficient air, where the oil can not burn completely and the smoke black deposited in the ceramic bowls; then, the smoke black was collected to make quality carbon black.
　　Ancient Chinese scholars Jia Sixie, Shen Kuo, Chao Guanzhi and Song Yingxing etc summed up the practical production experience of ancient carbon black at different times in their works. In the sixth century, Jia Sixie of North Wei wrote the book “Qi Min Yao Shu”, the first historical science book in the world that recorded the performance and functions of carbon black. He described: it is so slight that it can not be exposed on screen, in case it fly away, we must be very careful.”, which is consistent with the conclusion of modern science and technology, that is, carbon black is of high decentrality, its particle size belongs to colloid category. North Song scholar Shen Kuo mentioned firstly the way of making carbon black with petroleum oil in his book “Meng Xi Bi Tan”; because he found that when people burn petroleum oil as fuel, a large amount of carbon black was produced. He wrote, “The smoke is so heavy that the curtains contact it will become black”. In addition, he made experiment in person to prove that petroleum oil produces more carbon black than burning fuel made from pine branches and Chinese wood oil, “It’s as black and lustrous as paint, even pine soot is not as good as it”. He also predicted scientifically that to make carbon black with petroleum oil would have a broad prospect, saying that “it certainly will prevail in the world”. And this scientific thesis has been confirmed by the great development of modern oil furnace carbon black. Chao Guanzhi of the Song dynasty stated his detailed narration about the pine soot manufacturing method in his book “Mo Jing” and made a production technology summery. “Tian Gong Kai Wu” of the scholar Song Ying Xing at the end of Ming dynasty systematically summed up the carbon manufacturing experience and discussed the carbon black production equipment and the factors affecting the carbon black quality. In the book, he clearly put forward that the process operation must be timely, if “too slow, the smoke will be over burned, fire burns the fuel and the quality is poor”. This shows that in that era, the importance of reaction time has been recognized on the carbon black production. Additionally, he gave a detailed introduction to the pine soot carbon black equipment: upper dome, “like the awning on the boat”, “a smock exhaust hole is opened in every certain distance”. This structure is reasonable, the awning dome is conductive to cooling and air flow; and the holes between every certain distance on one hand prevent the formation of air stagnation and dead zone, and make the wind speed decreased gradually, creating conditions for the grading settlement of various sizes of carbon black particles. The carbon black produced is divided into three classes: “carbon black on the first and second sections from the end is the final settlement of the smallest particles, and of the best quality; that on the middle section is mixed particles, that is to say, carbon black collected from the middle section is of middle quality; and those close to the furnace mouth are coarse particles for general purposes. The production principles and equipment discussed by Song Yingxing can be said to be the prototype of modern carbon black industry.
In a word, ancient Chinese people have accumulated rich experience in carbon black production technology and made outstanding contributions to the world civilization.
According to the historical document of Japan and the Occidental countries, the carbon black manufacturing method abroad is introduced to Japan and the oriental countries from China, and then spread to Greece, Rome and Europe finally. Since the 16th century, Germany, France and the United Kingdom began to make soot with coal tar, animal oil and natural resins etc as raw materials. In 1864, American began to burn artificial gas and use stone plate as the collecting surface, then scratch it and get the quality soot. This method is almost similar with that of the ancient China.
　　Until 1872, mass production of carbon industry appeared for the first time in the world and there was the term “Carbon Black” at the same time, this is the beginning of modern carbon black industry. Americans invented gas channel carbon black manufacturing method in 1892; carbon black produced was mainly used as coloring agent. Then in 1912, the British people Mottee found the carbon black has strengthening function to rubber, especially can improve tyre’s wear resistance significantly, and the demand of carbon black increases rapidly. Thermal black and furnace black appeared in 1920s, they also use gas as raw materials, can give rubber lower modulus, low heat and low strengthening performance, having been widely used in tyres.
　　During the first half of the 20th century, most carbon black was made from natural gas. Most oil and gas wells are far away from the industrial cities, before the building of long-distance gas pipe lines; natural gas almost has no other uses. Therefore, natural gas’ price is very low and used to produce carbon black. For example, in the south of Texas of the United States, origin place of natural gas, several channel carbon black plants had been established one after another. Almost all the carbon black the world needed in that era was supplied by this region’s carbon black manufacturers, namely Cabot, Colombia and other companies today.
　　With the development of natural gas industry and the application of long-distance high-pressure gas transmission, the use of natural gas is ever-increasing and its price rose, too. This has promoted the scientific workers to develop new carbon black materials and new manufacturing methods. By the 1930s, American people R.D Snow began to study high efficient carbon black manufacturing methods and later J.C Krejci devoted to studying the manufacturing of carbon black with liquid hydrocarbon and successfully developed oil-furnace process. In 1943, during the Second World War, carbon black produced with the oil-furnace method was quite applicable to synthetic rubber; with the rapid development of synthetic rubber industry, the demand of oil-furnace carbon black grew rapidly, and all kinds of properties of oil-furnace carbon black came out in progression. Since 1944, high abrasion furnace black (HAF), intermediate super abrasion furnace black (ISAF), general purpose furnace black (GPF) and fast extrusion furnace black (FEF) had been developed one after another. At the same time, natural gas prices rose, the cost of production of carbon black substantially increased. Environmental pollution was serious, and in many fields, oil furnace carbon black can replace the channel carbon black, which consumes more energy and polluted air more seriously. Therefore, demand of oil furnace carbon black increased constantly, while the channel carbon black’ output declined sharply. By the middle of 1960s, almost no channel carbon black was produced. In the 1970s, new oil-furnace carbon black production techniques came out and grew very rapidly to replace the traditional oil-furnace carbon black production technology. The total output of carbon black over the world was 170Kt in 1930; in 1997, it was up to 6,600Kt and will continue to develop.
Our ancestors had ever made an outstanding contribution to the carbon black manufacture. However, in the semi-feudal and semi-colonial old China, there had been no its own carbon black industry. Before the liberation, the carbon black’ output in Fushun and Anshan etc, northeast of China was only 252Kt; then, when new China was founded, the Party and government attached great importance to the development of China’s national carbon black industry. Relying on our own strength, our carbon black industry is quickly established and developed. Sichuan Longchang and Liaoning Fushun, the two carbon black plants were listed as the key construction projects in the First Five-year Plan of China.
　　China’s carbon black industry has experienced for nearly half a century since the early 1950s. In 1998, the total national carbon black’s output was 570kt, ranking third in the world; the products can not only meet the basic needs of domestic rubber industry and other industries, but also have been exported to Japan, Western Europe and Southeast Asia. Since reform and opening up, by promoting the application of domestic developed technologies and introducing foreign advanced technologies, we increased our carbon black’s varieties, improved the quality, reduced the energy consumption, and enhanced the environmental protection at the same time, as well as narrowed the gap between the foreign production technologies.
　　China carbon black industry’s over 40 years of development experienced the following stages: 1949-1957, period of economic recovery and establishment of China’s carbon black industry, during which, 11 carbon black plants had been established successively, and channel, mixed gas, roller and spray carbon black etc had been produced; national total carbon black output increased from 252t to 8679t, with an annual average growth rate of 55.6%; at the same time, a number of talents had been nurtured; all had laid a solid foundation for the development of China’s carbon black industry.

　　1958-1960, Great Leap Forward period, during which oil-furnace high abrasion furnace black and gas furnace semi-reinforcing furnace black were successfully developed in succession; a large number of indigenous carbon black plants had been established; output of carbon black soared to 62000t, but because of the poor quality, the supply exceeded demand. After adjustment in 1962, the output fell to 24, 281t. On this basis, the average annual growth rate was still as high as 22.8%. Among the numerous new carbon black development plants, seven have become the main enterprises today.
　　1961-1966, period of adjustment and consolidation, in 1962, China’s national economy began to be adjusted. Former Chemical Industry Ministry reorganized the carbon black enterprises in the whole country, formulated carbon black ministerial standard, carried out interfactory emulations and organized meeting aiming at improving carbon black quality. Productive output increased steadily, and reached 51416t by 1966, with an annual average growth rate of 20.6%. In this period, acetylene black, general purpose furnace black and intermediate super abrasion furnace black had been successfully developed; in addition, five new carbon black factories put into production, and China’s first and sole carbon black industry research and design unit was prepared to construct.
　　1967-1976, Cultural Revolution period, because of technical progress and the affection of the turmoil to other industries, supply of resources of natural gas and oil was relative surplus, therefore, carbon black industry still maintained a relatively high developing speed, and its output reached 90,317t by 1970, with an annual average growth rate of 15.1%. However, the slow development of rubber industry resulted to the over-supply of carbon black, and the carbon black output was only about 100kt during 1971 to 1975; until 1976, it rose to 123, 763t; so in the period of 1971 to 1976, the average growth rate of carbon black was only 5.4%. In the aspect of technology, people used tail gas to heat the boiler, used pulse type bag filter and produced roller high pigment carbon black etc. Six new carbon black plants were founded in this period.
During 1977-1979, former Ministry of Chemical Industry strengthened management over the carbon black enterprises across the country. The allocation of 100, 000t of heavy oil coupled with the successful application of ethylene bottom oil solved the difficulties of industry-wide shortage of base oil, thereby enabling the rapid growth of carbon black output. By 1979, the output was 188, 364t, with an average annual growth rate of 15%, carbon black became oversupplied products again; and in 1981, the productive output fell to 154, 500t. Technology developed rapidly during this period, oil-gas channel new technique carbon black had been initially developed; tail gas power generation devices had been put into production. Through adjustment and reorganization, the enterprises became strong and created good conditions for the development of carbon black industry in 1980s.
　　From 1980 to now, it’s the period of reform and opening up. Since 1982, China’s carbon black output has increased steadily, in 1989, the output is 306t and in 1998, the output became 570t, with the average growth rate of 7.2%. Technologies have achieved rapid development, having promoted the overall improvement of quality of the carbon black industry. And the oil-oil channel new technique carbon black independently developed by China was widely used. There have been 12 sets of 10, 000 tons of large new technique carbon black production devices. Due to certain reasons, varieties of rubber carbon black increased from 1 to 25, and the quality improved significantly, while the average oil of every ton of carbon black (for example, N330) reduced from 2.74t to 2.14t. Generally, the enterprises have improved the temperature of air pre-heating, adopted high-efficient bag filters and researched matching filter bags. The promotion and application of a large number of new technologies and facilities, such as tail gas power generation, wet granulation, particle disintegrators and microcomputer controlled production etc have made the whole carbon black industry step on a new stage. At the same time, special carbon blacks, such as pigment carbon black, conductive carbon black and carbon black for various special purposes have speeded up development to adapt the ever-increasing demand of printing ink, paint, plastics and leather and other industries.