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Fuel Vol. 75, No. 15, pp. 1715-1720, 1996 Copyright 0 1996 Elsevier Science Ltd Printed in Great Britain. All rights reserved 0016-2361/96%15.00+0.00

Heating value of biomass and biomass pyrolysis products

K. Raveendran

and Anuradda

Ganesh

Energy Systems Engineering, Department of Mechanical Engineering, Indian institute of Technology, Bombay-400 076, India. e-mail: aganesh@me.iitb.ernet.in (Received 20 January 1996; revised 75 April 7996)

Studies conducted on the heating value of various types of biomass components and their pyrolysis products such as char, liquids and gases are presented. Heating values of chars are comparable with those of lignite and coke; heating values of liquids are comparable with those of oxygenated fuels such as methanol and ethanol, which are much lower than those of petroleum fuels. Heating values of gases are comparable with those of producer gas or coal gas and are much lower than that of natural gas. It is also found that the heating values of products are functions of the initial composition of biomass; correlations are developed to express these. Also, correlations are developed which explain the influence of ash elements on heating values of the pyrolysis products and on percentage distribution of energy in the products. Copyright 0 1996
Elsevier Science Ltd. (Keywords: biomass; pyrolysis products;heating value)

There is a need for optimum utilization of pyrolysis products to make the biomass pyrolysis process an economically viable option. Figure I is a block diagram of various possible routes for deriving energy from biomass pyrolysis products. Selection of a particular utilization pattern of biomass pyrolysis products determines the overall cost of the desired fuel or energy. Knowledge of various properties of biomass pyrolysis products relevant for energy conversion is essential for identifying the optimum utilization of each product. In this context, the heating value of the pyrolysis char, liquids and gases primarily determines their utilization pattern for energy conversion. The compositions of these products also influence various other relevant properties such as volatiles in char, pH, pour point and flash point of liquids and flammability limits of gases and liquids. These properties of the pyrolysis products influence the design and/or selection of combustors for char, liquids and gases, char gasification equipment and further possible fuel upgrading processes. The results of the work carried out to determine the heating value of the products are presented here. Based on the yield, heating value and elemental composition of the products, options on the suitability of biomass for pyrolysis, carbonization, liquefaction and gasification can be identified. EXPERIMENTAL Pyrolysis experiments were conducted in a packed bed pyrolyser (PBP) at a temperature of 773 K. Various types of biomass, their isolated components and de-ashed biomass were studied. Details of biomass preparation, acid treatment to obtain de-ashed biomass and isolation

of biomass components as well as the pyrolysis method are presented in earlier paperslW3. For the sake of completeness the product yields obtained in the PBP are given in Table 1. The char and liquids and gases were collected and their heating values were measured. Heating values of chars and liquids were determined using a bomb calorimeter (model Parr-1241 EF) and those of gases by difference, using the relation

where Y is the fractional yield (daf mass basis) of each product (Table I), H is the higher heating value (MJ kg- ) and the suffixes b, c, 1 and g denote biomass, char, liquid and gas respectively. All the heating values were determined according to the ASTM standard procedure D2015-T. The chars obtained were analysed for ash according to ASTM standard method D3174. The higher heating value (HHV) was calculated on the dry, ash-free (daf) basis and throughout this paper is denoted simply heating value . The measurements were repeated until the results obtained in the last two consecutive analyses gave a reproducibility within f3%. Table 2 presents the results obtained. The total energy content in each product was obtained by multiplying each yield fraction by the corresponding heating value of that particular product:
Ei = Hi
X

Yi

where Ei is the energy content of biomass pyrolysis product i (char, liquids or gas). The percentage distribution of energy in each product

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value of biomass and biomass pyrolysis products:

K. Raveendran and A. Ganesh

Shaft power Figure 1 Various end uses of biomass pyrolysis products (ref. 1)
Table 1

Pyrolysis products distribution: PBP experimental results Product yield (wt%) Volatiles Char 29.5 20.1 27.1 17.3 19.3 31.3 12.9 27.5 24.4 13.6 11.1 41.7 20.7 Liquids 29.5 37.4 40.5 41.2 22.6 36.3 43.4 45.9 57.4 40.1 46.8 26.8 40.5 Gas 41.0 42.5 32.5 41.5 58.1 32.5 43.7 26.6 18.2 46.4 43.0 30.5 38.8

Biomass Coir pith Corn cob Groundnut shell Rice husk Subabul wood De-ashed biomass Coir pith Corn cob Groundnut shell Rice husk Subabul wood Components Cellulose Lignin Xylan

70.5 79.9 72.9 82.7 80.7 68.7 87.0 72.5 75.6 86.5 88.9 58.3 79.3

can be calculated from the relation


%Ei=

where %Ei is the percentage distribution of energy in product i. The percentage distribution of energy of products obtained from de-ashed biomass was obtained by taking the heating value of de-ashed biomass to be the same as that of untreated biomass, as no major change is expected in heating value of the biomass during deashing. RESULTS The heating values obtained for cellulose, lignin and xylan components and their pyrolysis products are also presented in Table 2. It can be seen that xylan has the highest heating value, followed by lignin. Among the

c>
g

components studied, cellulose has the lowest heating value. Though the heating values of the components per se vary, yet the heating values of their pyrolysis chars are almost the same at -33 MJ kg- . However, the heating values of their liquids and gases are quite different. For all three components studied, the heating values of the chars are the highest, followed by those of the liquids, and the heating values of the gases are the lowest. It is clear that among the liquids obtained from the components, lignin pyrolysis liquids have the highest heating value; among the gases obtained from the components, xylan gases have the highest heating value. The percentage distribution of energy in the component pyrolysis products is presented in Table 2. As can be seen, cellulose holds the most energy (~65%) in its liquids fraction, lignin holds -58% of its energy in its char fraction, and xylan holds the most energy (-48%) in the gas fraction. Thus the higher the lignin content of the biomass, the higher should be the fraction of energy held in its char product. Correspondingly, the higher the cellulose content of the biomass, the higher should be the energy content of its liquid product, and the higher the xylan (or hemicellulose) content of the biomass, the higher should be the fraction of energy held in its gas fraction. These results explain the trends in heating values and distribution of energy of biomass pyrolysis products. It is also observable quite logically (Table 2) that the percentage distribution of the energy of biomass in its products lies between the maximum and minimum values for the components. As can be seen from Table 2, the heating values of liquids vary narrowly from ~22 to 25 MJ kg-1 and those of the gases are the lowest and vary from 5 to 16 MJ kg- . Hence, it is necessary to upgrade both gases and liquids to produce substitutes for fossil fuel. It is useful to compare the percentage distribution of energy in the products presented in Table 2 in identifying the

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value of biomass and biomass pyrolysis products:

K. Raveendran

and A. Ganesh

Table 2

Higher heating value (MJ kg- daf) of biomass and component pyrolysis products Higher heating value Biomass Char Liquids Gasa Char Energy distribution (%) Liquids Gas

Biomass Coir pith Corn cob Groundnut shell Rice husk Wood De-ashed biomass Coir pith Corn cob Groundnut shell Rice husk Wood Components Cellulose Lignin Xylan 11.7 24.1 30.4 32.4 33.3 32.3 16.2 28.7 22.5 01.3 08.2 37.6 30.8 57.7 22.0 64.6 31.9 30.0 04.5 10.4 48.0 26.2 26.4 29.8 31.0 24.2 22.3 24.2 21.8 19.5 28.5 9.9 5.0 6.2 6.6 11.3 42.1 21.2 41.2 37.9 16.5 41.4 65.2 50.5 56.1 57.3 16.6 13.7 08.3 06.0 26.2 19.5 16.1 19.8 20.0 20.0 25.0 28.6 27.4 44.2 24.1 18.7 23.8 23.6 22.5 24.9 16.1 05.2 10.0 07.4 16.6 37.9 35.6 37.5 38.3 23.4 28.3 49.4 44.7 46.2 28.3 33.9 15.0 17.9 15.5 48.3

a Gas yield and heating value obtained by difference

Rice husk char (high ash content)

40 Biomass chars (0) Char coal Lignite char Cellulose char Xylan char Xylan Corn cob char G. nut shell char Coir oith char Wood char

Fossil fuels (m) Anthracite coal Coke Graphite (pure) Bituminous coal Biomass liquids (0) Brown coal Lignite Lignin Rice husk liquids Methanol (m) Ethanol (?? )

35 zi -Y 2 z 1 30 3

3
= 25

20 t 15 t

Biomass (0) -Y Corn cob

Peat Wood Cellulose liquids-

Cellulose iolid fuels Liquid fuels

Figure 2

Comparison of heating values of pyrolysis products with those of fossil fuels

appropriate biomass for a desired product distribution. The influence of ash on the heating values of the pyrolysis products has previously been reported2. DISCUSSION
Comparison with fossil fuels

chars compare well with those of lignite and coke. The heating values of biomass pyrolysis liquids are on the low side compared with those of methanol and ethanol, and they are also much lower than for petroleum fuels. The heating values of biomass pyrolysis gases are also much lower than those of natural gas, but are comparable with those of blast furnace gas and producer gas. Correlations for heating value As has been discussed, the heating values of biomass

It is useful to compare the heating values of biomass pyrolysis products with those of fossil fuels4-6 as shown in Figure 2. As can be seen, the heating values of biomass

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value of biomass

and biomass

pyrolysis

products:

K. Raveendran

and A. Ganesh

pyrolysis products are mainly a function of the initial composition of the biomass. All five components of biomass were considered for correlation development. Certainly all the components of biomass contribute to the heating value of the product; however, heating values of the products can be obtained with the critical components alone, as can be seen in the correlations obtained. The following correlations have been developed to express the influence of each of the components on the heating values of the products: H = 34 o1xo.l9x-o.l8xo,l4 s, ; SE = 0.06, R2 = 0.99
c 1 a

Correlations for energy contents of products

As has been discussed above, it is useful to have correlations as a function of the initial composition of biomass to obtain the energy content of each of the products. Total energy content of a product is obtained by multiplying the heating value by the corresponding product yield. On a similar basis to that for heating values, correlations have been developed for energy content: OjoR 7 SE = 0.02, R2 = 0.99 a c = 57 g4X;0.4sX0.26X;js4. (4)
%E, = 907 tj()x2.52x;0.63x0.42.
c a

(1) HI = 91 6&. 8Xp.25-J-O.O3.


c a 7

SE = 0.04, R2 = 0.96
(2)

SE = 0.02, R2 = 0.99 (5)

H g

= 0 96X-2.53X . c

1.7SX-0.61. I a >

SE = 0.11, R2 = 0.99
(3)

O,~E = 0 21~-3.~~1.57~-0.88. 1 a 1 g . c

SE = 0.12, R2 = 0.99 (6)

where H,, Hi and Hg are the higher heating values of biomass pyrolysis char, liquids and gas respectively, and X,, Xr, Xsi and X, are the initial fractions of cellulose, lignin, silica, and silica-free ash, respectively, in the biomass. SE is the standard error, R is the correlation coefficient and R2 is the coefficient of determination. It can be seen from Figure 3 that the calculated and experimental heating values of biomass pyrolysis products match very well. It can further be accordingly seen from Equation (1) that the heating values of chars are mainly a function of the lignin and ash contents, whereas the heating values of liquids and gases are functions of the cellulose, lignin and silica-free ash

where %E,, %El and %Eg are the energy contents of biomass pyrolysis char, liquids and gases, respectively. As can be seen from the above equations, the R2 values obtained are very high and therefore these correlations can be used to calculate the energy content of each of the products from a knowledge of the cellulose, lignin, silica-free ash and silica contents of the biomass.
Influence of de-ashing

On de-ashing, the heating values of the biomass pyrolysis liquids increase and those of the gases decrease2. Hence it may be suggested that de-ashing is favourable for liquids production but not when gases are the desired product. In the particular cases of coir pith or

55 Liquids

55 Gases 45
/ OCP WDO

3:

3:

202: 50 Char

23

30

35 Distribution of energy - calculated (a) 30 Liquids

2:

20 Gases

1 1;-i 1:/
CP
20 20 Figure 3 30

40

50

'515

20

2s

30

Oo

10

15

20

Heating value - calculated (Ml/kg) Heating values of pyrolysis products: calculated vs. experimental

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value of biomass and biomass pyrolysis products:

K. Raveendran

and A. Ganesh

groundnut shell, de-ashing is favourable also for char production. The influence of ash elements on heating values of biomass pyrolysis products can be explained as follows: On de-ashing, it has been found that the rate of release of volatiles increases3; consequently, the residence time available for volatiles inside the biomass particle decreases. The reduced residence time allows volatiles to escape, by reason of which the condensation or cracking of volatiles decreases. This results in more higher-molecular-weight species being accumulated in the liquids. As a result, the heating value of the liquids increase. Consequently, the concentration of hydrocarbons (lower molecular weight) in the gases falls, resulting in a reduced heating value. In the absence of ash elements, there is no catalytic action on secondary cracking of volatiles, thereby resulting in an increased fraction of high-molecularweight volatiles collected in the liquids fraction. This results in increased heating value of the liquids and reduced heating value of the gas besides reduced heating value of the char. In the absence of ash elements, the catalytic effect on the secondary char gasification reactions, which is reported to increase combustible gases such as CO and HZ, is eliminated. Therefore the heating value of the gas decreases.
Correlations for i&ewe of de-ashing

this effect: char: A&(, = -7.16XK - 253.71Xz, + 0.87X1 - 18.89; (7)

SE = 3.15, R* = 0.99 liquids: AH,/, =-11.52&-264.68&,-0.53X,+239.97X,,; SE = 12.11, R2 = 0.81 gases: AH& = 29.52XK - 103.11Xz, - 2.06X1 + 17.26; SE = 0.47, R* = 1.0

(8)

(9)

where AH&, AH,/, and AH& are the percentage changes due to de-ashing in the heating values of char, liquids and gas, respectively, and X,, Xz, and X,, are the fractions of K, Zn and Mg in the biomas; char: A%,!& = 37.64XK + 311.51Xz, + 3.47X, - 199.08; SE = 5.47, R= = 0.99 liquids: A%E,jd = -80.72X, -157.62Xz,-0.93X~+911.90X~p; (11) SE = 16.06, R* = 0.95 gases: SE = 2.37, R2 = 0.997 (10)

A%,?,& = 34.71X, - 599.19X,, - 2.53X, + 17.11; (12) where A%&/,+ A%E,ld and A%,!?& are the percentage changes due to de-ashing in the percentage distribution of energy in char, liquids and gas, respectively. Figure 4 compares the calculated and experimental changes in heating values due to de-ashing; it can be seen

The change in heating values of the products due to de-ashing can be explained based on the elemental composition of the ash. Ash elements influence the product yields through the catalytic action of certain elements (potassium and zinc)*13.The catalytic action of these elements also alters the heating values of the products. Correlations have been developed to explain

CP

0 -7f70 -60 -50 -40 -30 -20 -10 Change in distribution of energy due to deashing - calculated (5%)

-10 -

-20 -

i/l
CP RH

-3OC

WD Gases -20 10 0

GS -40 -30 Change in heating value due to deashing - calculated (46) Figure 4 Percentage change in heating values of products due to de-ashing: calculated vs. experimental

1 -4o-

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value of biomass and biomass pyrolysis products:

K. Raveendran

and A. Ganesh

that the calculated and the experimental values match very well. Equations (7)-(12) show the influence of ash elements K, Zn and Mg in combination with lignin present in biomass on the heating values of the products. It can pertinently be noted that these correlations are similar to the correlation developed to explain the change in product yield due to de-ashing. CONCLUSIONS 1. Heating values of biomass pyrolysis products are functions of the initial composition of the biomass feed; this has been explained through the correlations developed. 2. Heating values of biomass are comparable with those of peat, and those of biomass chars with those of solid fossil fuels (ranging from lignite to anthracite). 3. Heating values of biomass pyrolysis liquids are comparable with those of ethanol and methanol.

4. Heating values of biomass pyrolysis gases are comparable with those of producer gas or coal gas. 5. Correlations have been developed to explain the influence of ash elements on heating values of the products and on percentage distribution of energy in the products.

REFERENCES
1 Raveendran, K. Studies on influence of biomass composition on pyrolysis , Ph.D. Thesis, Indian Institute of Technology, Bombay, 1995 Raveendran, K., Ganesh, A. and Khilar, K. C. Fuel 1995,74,1812 Raveendran, K., Ganesh, A. and Khilar, K. C. Fuel 1996,75,987 Sharma, S. P. and Mohan, C. M. Fuels and Combustion , TataMcGraw-Hill, New Delhi, 1980 Sarkar, S. Fuels and Combustion , Orient Longman, Bombay, 1990 Harker, J. H., and Backhurst, J. R. Energy and Fuels , Academic Press, London, 1980

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