Published: Kem. Ind. 56 (12) (2007) 633–642
Paper reference number: KUI-10/2006
Paper type: Professional paper
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Selective Oxidation of Soft Grade Carbon Blacks with Ammonium Nitrate
Oil-furnace carbon black is produced by pyrolysis of gaseous or liquid hydrocarbons or their mixtures. The oil feedstock for the production of oil-furnace carbon black is mainly composed of high-boiling aromatic hydrocarbons, which are residues of petroleum cracking, while the gaseous raw material is commonly natural gas. Most of the oil-furnace carbon black production (> 99 %) is used as a reinforcing agent in rubber compounds. Occasionally, oil-furnace carbon blacks are used in contact with other rubber compounds and fillers that have different pigments, particularly with the color white. It has been observed that frequently a migrating rubber soluble colorant would enter the white or light colored rubber composition from the adjacent carbon black filled rubber, resulting in a highly undesirable staining effect. Methods for determining non-oxidized residue on the surface of the oil-furnace carbon black include extraction of carbon black with the appropriate organic solvent, and measuring the color of the organic solvent by means of a colorimeter on 425 nm (ASTM D 1618–99). Transmittance values of 85 % or more are indicative of a practically non-staining carbon black, while transmittance values below 50 % generally lead to a carbon black with pronounced staining characteristics. Many oil-furnace carbon blacks, particularly those with a larger particle size (dp > 50 nm) which are produced by pyrolysis, have strongly adsorbed non-reacted oil on their surfaces. Upon incorporation in a rubber compound, the colored materials are gradually dissolved by the rubber matrix and migrate freely into adjacent light colored rubber compounds, causing a highly objectionable staining effect. Adjusting furnace parameters in the industrial process of producing specific soft grades of carbon black cannot obtain minimal values of toluene discoloration. The minimal value of toluene discoloration is very important in special applications. Therefore, after-treatment of the surface area is essential. Mutual oxidizing agents are ozone, air, mixture of nitric oxide and air, and nitric acid. However, treatment with highly oxidizing agents in a gaseous phase or aqueous medium may highly increase the concentration of acid oxides on the surface area of the carbon black. Acid oxides on the surface area of carbon black decrease the pH value, which is closely connected to the vulcanization of rubber compounds. Furthermore, the afore-mentioned method has other disadvantages. In the case of nitrate acid, the major disadvantage is corrosion of plant equipment. The mixture of nitrite oxide and air demands a very complicated plant, and the same procedure is very time consuming. Ozone increases the oxygen content on the surface area of the carbon black by as much as 15 %, which creates carbon dioxide and reduces utilization. Air creates thermally unstable surface area oxides, since the process demands a temperature range between 450 and 700 °C. Due to all these reasons, an oxidation method was developed of eliminating non-reacted oil from the surface area of oil-furnace carbon black, which cannot be produced with the conventional production method. An aqueous solution of salt ammonium nitrate p.a. proved to be a very good oxidizing agent. Conventional soft grades of oil-furnace carbon blacks with very high contents of non-reacted oil on their surface area, were mixed with the appropriate mass weight of ammonium nitrate p. a. (1.25 to 10.00 g L–1 NH4NO3 p. a.). The obtained homogeneous mixture was dried at temperatures from 180 to 210 °C for a period of 30 to 120 min. Namely, oil-furnace carbon blacks are first produced in a “fluffy” form with exceptionally small mass density, which is why they are very unpractical for manipulation. The “fluffy” oil-furnace carbon black must be transformed to a greater weight density and have a smaller quantity of fines as possible. However, there are many industrial processes of transforming “fluffy” carbon black into granules, and the most famous are the wet, semi-wet, and the dry process. In the oil-furnace process, the wet process of granulation is the most acceptable, in which the “fluffy” carbon black is mixed with water in an approximate ratio. After granulation, the carbon black is dried in a rotary drum at temperatures ranging between 180 to 210 °C. The period of drying is various, and depends on the production capacity and moisture fraction. The described laboratory procedure improvised successfully industrial conditions of granulating soft grade carbon black, and it is applicable to the conventional industrial method of producing soft grade oil-furnace carbon black at the Kutina plant, which is shown in Tables 1–7, and Figures 1–2.
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soft grade oil-furnace carbon-blacks, selective oxidation, ammonium nitrate p.a.