Relationships Between Heating Value and Lignin, Moisture, Ash and Extractive Contents of Biomass Fuels

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1 ENERGY EXPLORATION & EXPLOITATION Volume 20 Number Relationships Between Heating Value and Lignin, Moisture, Ash and Extractive Contents of Biomass Fuels Ayhan Demirbas P. K. 216, TR Trabzon, Turkey ABSTRACT Various fuel characteristics, such as moisture, ash, lignin, holocellulose and extractive contents of different biomass species were determined on ash-free dry weight and extractive-free dry weight basis to find out relationship, if any, between ash and extractive content with the higher heating value. Moisture in biomass generally decreases its heating value. Ash and extractive content are two important parameters directly affecting the heating value. High ash content of a plant part makes it less desirable as fuel, whereas high extractive content adds to its desirability. Again the heat content, which is a very important factor affecting utilization of any material as a fuel, is affected by the proportion of extractives present in it. Extractives raised the higher heating values of the biomass samples. INTRODUCTION Biomass is the most abundant renewable energy resource available in the world. Biomass can be utilized by direct combustion, co-firing with coal, carbonization, liquefaction and gasification in order to obtain heat, fuels and chemicals. So far, most attention has been focussed on the various ways of steam gasifying or liquefying biomass (Wang et al., 1997). Steam gasification of biomass produces CO, which together with H 2 constitutes syngas, the feed in fuel syntheses processes. In earlier works, relationships between lignin contents and higher heating values (HHVs) of biomass, and aqueous liquefaction products of biomass have been studied and the mathematical equations have been developed to calculated the HHVs of various lignocellulosic fuels from their chemical analyses data (Demirbaș, 2001; Demirbaș, 2000a). Lignocellulosic biomass consists of three structural components: lignin, cellulose and hemicelluloses. There has been many attempts at correlating the heating value with the composition (Georing et al., 1982; Demirbaș, 1997; Demirbaș; 1998a; Demirbaș, 1998b). Formulas developed for coal, such as the Dulong equation (Perry and Chilton, 1973), typically do not do well for biomass. The increase in heat content results from a high increase in the number of carbons and hydrogens, as well as an increase in the ratio of these elements relative to oxygen. A decrease in heat content is the result of fewer hydrogen atoms (i.e., greater unsaturation) in the fuel molecule. Determination of data obtained for a great many compounds has shown that the HHV of an aliphatic hydrocarbon

2 106 Relationships Between Biomass Fuels agrees rather closely with that calculated by assuming a certain characteristic contribution from each structural unit (Morrison and Boyd, 1983). EXPERIMENTAL Moisture content was determined by drying the wood sample at 353K to constant weight. Ash content was determined by burning 1g of ground sample in a muffle furnace at 825K for 4h. Extractives were obtained by extracting the ground sample with alcohol-benzene (1/1, v/v) in a Soxhlet extractor for 18 hours (at least 15 cycles/hour). The extractive-free samples were further used for determination of lignin, by digesting with 72% sulfuric acid for 2h and holocellulose by chlorination and extraction in ethanol and ethanolamine (Kataki and Konwer, 2001). Part of the sample was ground to pass through a 0.2mm sieve and about 0.5g of ground material was pelleted and burnt in a an adiabatic oxygen bomb calorimeter according to the ASTM D2015 standard test method for determination of higher heating value (HHV). Chemical and structural analyses of the samples were carried out according to the ASTM D and ASTM D standard test methods, respectively. The other standard test methods for biomass fuel analysis are presented in Table 1. Table 1 Standard test methods of biomass fuel analyses Property Analytical method Heating value ASTM D 2015 Proximate analysis Moisture ASTM E871 Ash ASTM D1102 Volatile matter ASTM E 872 Fixed carbon by difference Ultimate elemental analysis Carbon, Hydrogen ASTM E 777 Nitrogen ASTM E 778 Oxygen by difference RESULTS AND DISCUSSION The standards measure of the energy content of a fuel is its heating value (HV), sometimes called the calorific value or heat of combustion. In fact, there are multiple values for the HV, depending on whether it measures the enthalpy of combustion, the internal energy of combustion, and whether for a fuel containing hydrogen, product water is accounted for in the vapor phase or the condensed (liquid) phase. With water in the vapor phase, the lower heating value (LHV) at constant pressure measures the enthalpy change due to combustion (Jenkins et al., 1998). The higher heating value (HHV) at constant pressure measures the enthalpy change of combustion with water condensed at initial temperature and pressure. The average ultimate and proximate including fixed carbon and volatile material

3 ENERGY EXPLORATION & EXPLOITATION Volume 20 Number contents analyses results are given in Table 2. Table 3 shows the average structural, extractive and ash content analyses results and HHVs. Table 2 Average proximate and ultimate analyses results (wt. % dry basis) Sample C H O N Fixed carbon Volatile material Spruce trunkwood Spruce trunk bark Beech trunk wood Beech trunk bark Ailanthus trunk wood Sunflower shell Almond shell Hazelnut shell Olive husk Hazelnut kernel husk Walnut shell The HHVs of extractive-free samples reflect the HHV of lignin relative to cellulose and hemicelluloses. It was reported that (Demirbas, 2001), cellulose and hemicelluloses (holocellulose) have a HHV of MJ/kg, whereas lignin has a HHV of to MT/kg. As discussed by Baker (1982), HHVs reported for a given species reflect only the samples tested and not the entire population of the species. The HHV of a lignocellulosic fuel is a function of its lignin content. Using linear regression analysis, it can be compared the HHVs with the chemical composition data. In general, the HHVs of lignocellulosic fuels increase with increase of their lignin contents and the HHV is highly correlated with lignin content. For the model including the lignin content, the regression equation is HHV (LC) , (1) where HHV is the higher heating value of fuel sample (MJ/kg)) and LC is lignin content (wt % daf and extractive-free sample basis). For the wood samples, the regression equation is HHV = (LC) (2) For the non-wood biomass samples, the regression equation is HHV = (L) (3)

4 108 Relationships Between Biomass Fuels For Eqn (1), correlation coefficient (r) is The HHVs calculated with Eqn (1) showed a mean difference of %. For Eqns (2 and 3), r is and , and mean difference is and % respectively. There are no direct relations between HHV and the holocellulose of the lignocellulosic fuels, but there are good relations between the lignin contents and the determined HHVs of the wood samples (Demirbaș, 2001b). The plots of HHVs of biomass samples versus percentages of carbon + hydrogen, lignin, and fixed carbon are given in Figure 1. The HHV (MJ/kg) of the biomass fuels as a function of fixed carbon content (FCC, wt%) was calculated from Equation (4): HHV= (FCC) (4) Figure 1. Plots of HHVs of biomass samples versus percentages of carbon + hydrogen, lignin, and fixed carbonas seen from Figure 1, HHV increases as increase (C + H) contents of the samples.

5 ENERGY EXPLORATION & EXPLOITATION Volume 20 Number The differential higher heating values (ÆHHVs in MJ/kg) of various biomass species vs percent extractive content are given in Figure 2. The HHVs of the extractive-free samples were found to be lower than those of the unextracted samples which indicate a likely positive contribution of extractives towards the increase of HHV. The ÆHHV (MJ/kg) of the biomass samples as a function of extractive content (EC, wt%) can be calculated from Equation 5: ÆHHV = (EC) (EC) (5) For Eqn (5), in a square of the correlation coefficient (r 2 ) was Apart from physiological differences that might cause variation in moisture content in different plant parts, seasonal changes and geographic location also contribute towards the difference in moisture content among different species and their plant parts (Diaz and Golueke, 1981). Moisture in biomass generally decreases its heating value. Figure 2. Plot of increase of higher heating values of various biomass species versus Percentage of extractive content

6 110 Relationships Between Biomass Fuels Ash and extractive content are two important parameters directly affecting the heating value. High ash content of a plant part makes it less desirable as fuel, whereas high extractive content adds to its desirability (Table 3). Again the heat content, which is a very important factor affecting utilization of any material as a fuel, is affected by the proportion of extractives present in it. Table 3 Average structural, extractive and ash content analyses results and HHVs (wt % dry basis) Sample Holocellulose Lignin Extractives a Ash HHV b HHV C Spruce trunk wood Sprucetrunkbark Beechtrunkwood Beech trunk bark Ailanthus trunk wood Sunflower shell Almond shell Hazelnut shell Olive husk Hazelnut kernel husk Walnut shell a Alcohol/Benzene (1/1, vlv) extractives b HHV: Higher Heating Value on ash free basis (MJ/kg) c HHV: Higher Heating Value on extractive free basis (MJ/kg) For the samples tested in this study, the mean difference in HHVs of the softwoods, hardwoods, and non-wood biomass fuels was primarily caused by their difference in lignin contents. There are many different types of lignins and extractives in structures of different species of lignocellulosic materials. The lignins from grasses, softwoods, and hardwoods differ somewhat in composition, chiefly in methoxyl substitution and the degree of carbon-carbon linkage between phenyl groups. The aromatic and phenolic character is apparent in conifer (softwood and spruce wood) lignin, as is the covalent carbon-carbon bonding that prevents reversion to monomers by mild processing. In conifers the precursors is principally coniferyl alcohol (3-methoxy-4- hydroxycinnamyl alcohol) that yields the so-called guaiacyl lignin. CONCLUSION Fuel value of biomass is greatly dependent on its heating value and is generally believed to be one of the parameters to compare one fuel with another. Moisture in biomass generally decreases its heating value. Ash and extractive content are two important parameters directly affecting the heating value. High ash content of a plant part makes it less desirable as fuel, whereas high extractive content adds to its desirability.

7 ENERGY EXPLORATION & EXPLOITATION Volume 20 Number There are no direct relations between HHV and the holocellulose of the lignocellulosic fuels, but there are good relations between the lignin contents and determined HHVs of the lignocellulosic fuel samples. Thus the HHVs of the renewable natural fuels can be calculated by using the lignin content obtained from simple chemical analysis. The experimental determination of HHV requires special instrumentation, whereas chemical analysis data can be obtained relatively easily by available laboratory equipment. BIBLIOGRAPHY Baker, A. J. (1982). Wood Fuel Properties and Fuel Products from Woods, in Proc. Fuelwood Management and Utilisation Seminar, Michigan State Univ., East Lansing, MI. Demirbaș, A. (1997). Calculation of higher heating values of biomass fuels, Fuel, Vol. 76, pp Demirbaș, A. (1998a). Fuel properties and calculation of higher heating values of vegetable oils, Fuel, Vol. 77, pp Demirbaș, A. (1998b). Determination of combustion heat of fuels by using noncalorimetric experimental data, Energy Education Science and Technology, Vol. 1, pp Demirbaș, A. (2000a). Effect of lignin content on aqueous liquefaction products of biomass, Energy Conversion and Management, Vol. 41, pp Demirbaș, A. (2001). Relationships between lignin contents and heating values of biomass, Energy Conversion and Management, Vol. 42, pp Diaz, L. F. and C. G. Golueke. (1981). Residues and Wastes. in: Sofer SS, Zabrosky OR, editors. Biomass conversion process for energy and fuels, New York: Plenum Press, pp Goering, E., W. Schwab, J. Daugherty, H. Pryde, and J. Heakin. (1982). Fuel properties of eleven vegetable oils, Transactions of the American Society of Agricultural Engineers, Vol. 25, pp Jenkins, B. M., L. L. Baxter, T. R. Miles, Jr., and T. R. Miles. (1998). Combustion properties of Biomass, Fuel Processing Technology, Vol. 54, pp Kataki, R. and D. Konwer. (2001). Fuelwood characteristics of some indigenous woody species of north-east India, Biomass & Bioenergy, Vol. 20, pp Morrison, R. T. and R. N. Boyd. (1983). Organic Chemistry, 4 th edn. Allyn and Bacon Inc., Singapore. Perry, S. W. and C. N. Chilton. (1973). Chemical Engineers Handbook, 5th ed. McGraw-Hill, New York. Wang D, Czernik S, Montane D, Mann M, Chornet E. (1997). Biomass to hydrogen via fast pyrolysis and catalytic steam reforming of the pyrolysis oil or its fractions, Industrial Engineering and Chemical Research, Vol. 36, pp

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