Char oxidation

Further evidence pointing in the same direction was provided by Pierce, Wiley and Smith, who found that on steam activation of a particular char at 900°C the saturation uptake increased three-fold, yet the isotherm was still of Type I. They argued that even if the width of the pores was only two molecular diameters before activation, it would increase, by removal of oxides, during the activation so that the second Type I isotherm would correspond to pores more than two molecular diameters wide. (The alternative explanation, that activation produced new pores of the same width as the old, seems unlikely.)... 

Activated carbons are made by first preparing a carbonaceous char with low surface area followed by controlled oxidation in air, carbon dioxide, or steam. The pore-size distributions of the resulting products are highly dependent on both the raw materials and the conditions used in their manufacture, as maybe seen in Figure 7 (42). 

Antimony Oxide as a Primary Flame Retardant. Antimony oxide behaves as a condensed-phase flame retardant in cellulosic materials (2). It can be appHed by impregnating a fabric with a soluble antimony salt followed by a second treatment that precipitates antimony oxide in the fibers. When the treated fabric is exposed to a flame, the oxide reacts with the hydroxyl groups of the cellulose (qv) causing them to decompose endothermically. The decomposition products, water and char, cool the flame reactions while slowing the production and volatilization of flammable decomposition products (see Flaa retardants for textiles). 

In polymers such as polystyrene that do not readily undergo charring, phosphoms-based flame retardants tend to be less effective, and such polymers are often flame retarded by antimony—halogen combinations (see Styrene). However, even in such noncharring polymers, phosphoms additives exhibit some activity that suggests at least one other mode of action. Phosphoms compounds may produce a barrier layer of polyphosphoric acid on the burning polymer (4,5). Phosphoms-based flame retardants are more effective in styrenic polymers blended with a char-forming polymer such as polyphenylene oxide or polycarbonate. 

Mechanisms and Rates of Combustion. AH soHd fuels and wastes bum according to a general global mechanism (Fig. 2). The soHd particle is first heated. FoHowing heating, the particle dries as the moisture bound in the pore stmcture and on the surface of the particle evaporates. Only after moisture evolution does pyrolysis initiate to any great extent. The pyrolysis process is foHowed by char oxidation, which completes the process. 

Fig. 3. Schematic of the sequential nature of waste fuel combustion (1). A, particle heating and drying B, soHd particle pyrolysis and C, char oxidation. A...

Formation of Airborne Emissions. Airborne emissions are formed from combustion of waste fuels as a function of certain physical and chemical reactions and mechanisms. In grate-fired systems, particulate emissions result from particles being swept through the furnace and boiler in the gaseous combustion products, and from incomplete oxidation of the soHd particles, with consequent char carryover. If pile burning is used, eg, the mass bum units employed for unprocessed MSW, typically only 20—25% of the unbumed soHds and inerts exit the combustion system as flyash. If spreader-stoker technologies are employed, between 75 and 90% of the unbumed soHds and inerts may exit the combustion system in the form of flyash. 

Rea.ctlons, When free (R-R, R -tartaric acid (4) is heated above its melting point, amorphous anhydrides are formed which, on boiling with water, regenerate the acid. Further heating causes simultaneous formation of pymvic acid, CH COCOOH pyrotartaric acid, HOOCCH2CH(CH2)COOH and, finally, a black, charred residue. In the presence of a ferrous salt and hydrogen peroxide, dihydroxymaleic acid [526-84-1] (7) is formed. Nitrating the acid yields a dinitro ester which, on hydrolysis, is converted to dihydroxytartaric acid [617 8-1] (8), which upon further oxidation yields tartronic acid [80-69-3] (9). 

Oxidizing Properties. Nitric acid is a powerful oxidizing agent (electron acceptor) that reacts violentiy with many organic materials (eg, turpentine, charcoal, and charred sawdust) (19,20). The concentrated acid may react explosively with ethanol (qv). Such oxidizing properties have had military appHcation nitric acid is used with certain organics, eg, furfuryl alcohol and aniline, as rocket propellant (see Explosives AND PROPELLANTS). 

Other techniques include oxidative, steam atmosphere (33), and molten salt (34) pyrolyses. In a partial-air atmosphere, mbber pyrolysis is an exothermic reaction. The reaction rate and ratio of pyrolytic filler to ok products are controlled by the oxygen flow rate. Pyrolysis in a steam atmosphere gives a cleaner char with a greater surface area than char pyroly2ed in an inert atmosphere however, the physical properties of the cured compounded mbber are inferior. Because of the greater surface area, this pyrolytic filler could be used as activated carbon, but production costs are prohibitive. Molten salt baths produce pyroly2ed char and ok products from tine chips. The product characteristics and quantities depend on the salt used. Recovery of char from the molten salt is difficult. 

Solutions of these fire retardant formulations are impregnated into wood under fliU cell pressure treatment to obtain dry chemical retentions of 65 to 95 kg/m this type of treatment greatly reduces flame-spread and afterglow. These effects are the result of changed thermal decomposition reactions that favor production of carbon dioxide and water (vapor) as opposed to more flammable components (55). Char oxidation (glowing or smoldering) is also inhibited. 

The process for the thermal activation of other carbonaceous materials is modified according to the precursor. For example, the production of activated carbon from coconut shell does not require the stages involving briquetting, oxidation, and devolatilization. To obtain a high activity product, however, it is important that the coconut shell is charred slowly prior to activation of the char. In some processes, the precursor or product is acid-washed to obtain a final product with a low ash content (23,25). 

The largest consumer of coke is the iron and steel industry. In the United States, ca 600 kg of coke is used to produce a metric ton of steel. Japanese equipment and practice reduce the requirement to 400—450 kg. Coke is also used to gas from the char in one vessel. The reducing gas converts iron oxide to iron in the upper two stages of a second vessel. Steam is converted to hydrogen and reoxidizes the iron in two stages in the lower half of the vessel. 

The stmcture of residual char particles after devolatilization depends on the nature of the coal and the pyrolysis conditions such as heating rate, peak temperature, soak time at the peak temperature, gaseous environment, and the pressure of the system (72). The oxidation rate of the chat is primarily influenced by the physical and chemical nature of the chat, the rate of diffusion and the nature of the reactant and product gases, and the temperature and pressure of the operating system. The physical and chemical characteristics that influence the rate of oxidation ate chemical stmctural variations, such as the... 

---