Pyrolysis Reactions The sequence and rate at which pyrolysis reactions occur and the factors that influence

the rate are described by the kinetics of the reaction. The kinetics of fast pyrolysis reactions are characterized by Equation 1, (Equation 1) where Wt is the particle weight after reaction time (in grams), t is the pyrolysis time (in seconds), Ko is the frequency factor (in seconds), W is the ultimate particle weight (in grams), R is the universal gas constant (in Joule per grams Kelvin), E is the activation energy (in Joule per grams), and T is the temperature (in degrees Kelvin). The reported value of E varies substantially (ranging from 40 to 250 kJ/mole) depending on the operating conditions and the type of material used. Factors that affect the kinetics of pyrolysis reactions include the heat rate (length of heating and intensity), the prevailing temperature, pressure, the presence of ambient atmosphere, the existence of catalysts, and the chemical composition of the fuel (e.g., the biomass resource). Pyrolysis reactions occur over a range of temperatures, and products formed earlier in the process tend to undergo further transformations in a series of consecutive reactions. Control of these factors determines the yield and mix of products formed. Figure 1 presents a schematic of pyrolysis reactions. During pyrolysis, two main types of reactions occurdehydration reactions and fragmentation reactions.

Dehydration reactions occur under conditions of slow heat rates, low temperatures (< 310 C), and long residence times. During these reactions, the molecular weight of the fuel is reduced (in part due to the elimination of water) and char and water vapor are formed. As the heat rate and temperature increase, free radicals and low molecular weight (< 105) volatile compounds such as hydrogen (H2), carbon monoxide (CO), and carbon dioxide (CO 2), are formed. Increasing temperatures reduce char formation and alter the chemical composition of the char. Conversion of non-aromatic hydrocarbons to aromatic hydrocarbons (i.e., carbon compounds that are unsaturated (contain few hydrogen compounds) and that show low reactivity) occurs at temperatures between 300 and 400 C. Dehydration reactions are typical of slow pyrolysis. Fragmentation reactions occur at > 310 C. During these reactions, the fuel is de-polymerized to form levoglucosan (an anhydrosugar derived from cellulose) and tar. The tars undergo secondary reactions depending on heat rate, temperature, and pressure which affects the residence time of compounds. Under conditions of medium temperatures (200 to 600 C), high pressure, and long residence times, the volatile compounds and light tars are recombined to form stable secondary tars. Under conditions of rapid heat rates, high temperature, and low pressure, tars vaporize and produce transient oxygenated fragments which are further cracked to yield olefins (alkenesorganic chemicals characterized by double bonds between carbon atoms), CO, N2, and other hydrocarbons such as acetol, furfural, and unsaturated aldehydes. If

high temperatures are maintained for an extended period of time (long residence times), the olefins are converted to permanent hydrocarbon gases (e.g., C2H6, C3H6), condensable aromatic vapors (e.g., benzenoid and non-benzenoid hydrocarbons), and carbon black (mixture of partially burned hydrocarbons). Rapid quenching of intermediate products (i.e., short residence times) is needed to recover the ethylene-rich gases (olefins) used to produce alcohols, gasoline, and bio-oil. Fragmentation reactions are typical of fast pyrolysis. Ambient atmosphere affects the heat rate and the nature of the secondary reactions and may be a vacuum, an inert surrounding, or a reactive surrounding. In a vacuum, primary products are rapidly removed in the gas phase and are unavailable for further reactions. Water or steam speeds up the breakdown of molecules (hydrothermolysis) and may be catalyzed by acid or alkali reagents. The presence of inorganic salts and acid catalysts can lower the process temperature, increase char formation, and alter char properties. The chemical and physical properties of the fuel are key variables in the pyrolysis kinetics and thus significantly affect the yields and product mix. The heat rate is a function of the fuel size and type of pyrolysis equipment. Heat rates are lower for large particle sizes which favors the formation of char and higher for small particles which favors the formation of tars and liquids. Pyrolysis of Biomass Resources All biomass resources are composed primarily of cellulose (typically 30 to 40 percent of dry weight), hemicellulose (25 to 30 percent of dry weight), and lignin (12 to 30 percent of dry weight), but the percent of each compound differs significantly among biomass resources. This heterogeneity creates variability in the yields of pyrolysis products. Cellulose is converted to char and gases (CO, CO 2, H2O) at low temperatures (< 300oC), and to volatile compounds (tar and organic liquids, predominantly levoglucosan) at high temperatures (> 300oC) (Funakuzuri, 1986). The yield of light hydrocarbons (i.e., C1 - C4) is negligible below 500C but increases substantially at high temperatures (Scott et al., 1988). At temperatures above 600C, tar yields drop, gas yields increase, and the pyrolysis of cellulose is complete (Hajaligol, 1982; Bradbury, 1979; Funazukuri, 1986; and Piskorz, 1986). Hemicellulose is the most reactive component of biomass and decomposes between 200 and 260oC (Koufopanos, 1989). The decomposition of hemicellulose is postulated to occur in two stepsthe breakdown of the polymer into water soluble fragments followed by conversion to monomeric units and decomposition into volatile compounds (Soltes and Elder, 1981). Hemicelluloses produce more gases and less tar than cellulose, and no levoglucosan. They also produce more methanol and acetic acid than cellulose. Lignin is a highly linked, amorphous, high molecular weight phenolic compound which serves as cement between plant cells and is the least reactive component of biomass. The time required to pyrolyze biomass resources is controlled by the rate of pyrolysis of lignin under operating conditions. Decomposition of lignin occurs between 280C and 500C, although some physical and/or chemical changes (e.g., depolymerization, loss of some methanol) may occur at lower temperatures (Koufopanos, 1989). At slow heating rates, lignin loses only about half of its weight at temperatures below 800C (Wenzel, 1970). Pyrolysis of

lignin yields more char and tar than cellulose (Soltes and Elder, 1981). For wood, the decomposition of the major components occurs separately and sequentially with the hemicellulose decomposing first and the lignin last. Up to 200C, moisture is removed, volatile products such as acetic acid and formic acid are released, and noncondensable gases such as CO and CO2 are produced. Between 200 and 280C, further decomposition of the char and wood occur resulting in the release of pyroligneous acids, water and non-condensable gases. Separation of tar occurs. Between 280 and 500C, release of combustible volatile products (CO, CH4, H2, formaldehyde, formic acid, methanol, and acetic acid) occurs. Char formation decreases and the carbon content of the char increases. Condensable tar is released. Above 500C, carbonization is complete. Secondary reactions begin if the materials are not removed from the reaction zone as quickly as they form. When cooled, some volatile compounds produced during the pyrolysis of biomass resources condense to form a liquid called bio-oil. Bio-oil consists of 20-25% water, 25-30% pyrolytic lignin, 5-12% organic acids, 5-10% non-polar hydrocarbons, 5-10% anhydrosugars, and 10-25% other oxygenated compounds. Due to large amounts of oxygenated compounds, bio-oil is polar and does not mix readily with hydrocarbons (such as petroleum-derived fuels). It contains less nitrogen than petroleum, and almost no metal or sulfur. Bio-oil is acidic (pH of 2 to 4) due to the creation of organic acids (e.g., formic and acetic acid) when biomass degrades and is corrosive to most metals except stainless steel. Hydrophilic bio-oils contain 15 to 35 percent water by weight which can not be removed by conventional methods like distillation. High water content decreases its viscosity which aids in transport, pumping and atomization, improves stability, and lowers the combustion temperature which reduces NOx emissions. Some additional water can be added, but only up to a point before phase separation occurs which prevents bio-oils from being dissolved in water. Bio-oil is relatively unstable compared to fossil fuels due to the presence of more polymeric compounds. Table 1 summarizes select properties of bio-oil derived from the pyrolysis of wood.

A number of studies have examined factors that affect the kinetics of biomass pyrolysis reactions. Studies that have examined temperature and heat rate interactions include Scott, 1988 (maple wood); Aarsen, 1985 (wood); Ayllon, 2006 (meat and bone meal); Koufapanos, 1989 (sawdust); Nunn, 1985 (wood and cellulose); Utioh, 1989 (wheat grain); Sadakata, 1987. These studies indicate that temperature is more important than rate of heating with respect to the mix of products, and that at any given temperature and heat rate, bio-oil and char are the dominant products. Bio-oil yields increase up to temperatures between 550C and 680C and then decline. As temperatures increase, char production decreases (to a steady level above 650C) and the carbon content of the char increases. Hydrocarbon gas yields (e.g., C 2H6, C3H6) increase up to about 660C and then decline, probably due to thermal cracking. The time required to obtain a given conversion level decreases with increasing temperature. Biomass weight loss is higher at lower pressures (Ward and Braslaw, 1985). At any given temperature, char residues increase pressure. Cellulose displays the strongest pressure

dependency and lignin the lowest--the pressure effect is observable at temperatures above 350C. The higher pressure increases the residence time of the volatile compounds resulting in higher yields of low molecular weight gases and lower yields of tar and liquid products (Blackadder and Rensfelt, 1985). The presence of inorganic materials (either as additives or as the natural ash content of the biomass resource) affects the mix of pyrolysis products. The impacts are measured using thermogavimetry (TG), thermal evolution analysis (TEA), and differential thermal analysis (DTA). Alkaline compounds have a more pronounced effect than do acidic compounds. Alkaline catalysts increase gas yields and char production and decrease tar yields; reduce the decomposition temperature; increase weight loss; and increase reaction rates (Utioh, 1989; Roberts, 1970; Tsuchiya and Sumi, 1970). Acid catalysts cause transglycosylation reactions in small quantities, and dehydration of the anhydrosugars in larger quantities. Acidic catalysts enhance the condensation of intermediate compounds and affect char oxidation. Inorganic salts reduce CO, H 2, and hydrocarbon gases, but increase CO 2; decrease tar; increase water yields; and increase char yields (Nasser, 1986). The presence of catalysts are most significant for wood and cellulose pyrolysis but negligible for lignin pyrolysis (Nassar and MacKay, 1986).
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