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Fuel 84 (2005) 849857

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Predicting the heating value of sewage sludges in Thailand


from proximate and ultimate analyses
Puchong Thipkhunthoda, Vissanu Meeyoob,*, Pramoch Rangsunvigita,
Boonyarach Kitiyanana, Kitipat Siemanonda, Thirasak Rirksomboona
a
The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok 10330, Thailand
b
Center for Advanced Materials and Environmental Research, 51 Cheum Sampan Rd. Nong Chock,
Mahanakorn University of Technology, Bangkok 10530, Thailand
Received 22 July 2004; received in revised form 5 January 2005; accepted 5 January 2005
Available online 28 January 2005

Abstract
There have been various methods used for determining a heating value of solid fuel such as coal, biomass and municipal solid waste
(MSW) either by experiment using a bomb calorimeter or by modeling based on its compositions. This work proposes another aspect in
developing models to predict the heating value of sewage sludge from its proximate and ultimate analyses data. The extensive number of
samples was collected from different wastewater treatment plants in Bangkok and in the vicinity and was then analyzed for their heating
values, proximate and ultimate analyses. Based upon proximate and ultimate analyses, the models were proposed. The best results show
coefficients of determination (R2) of 0.899 and 0.905 for the models based on the proximate and ultimate analyses, respectively. The heating
values obtained from the models were in good agreement with that attained by experiment. The application of the selected models was
appreciable for the sewage sludge with ash content up to 50% (db).
q 2005 Elsevier Ltd. All rights reserved.

Keywords: Sewage sludge; Heating value; Proximate analysis; Ultimate analysis

1. Introduction Traditionally, it was disposed by depositing in the ground,


utilization in agricultural works, dumping into the sea and
The concept of converting waste to energy has drawn a incineration. With the future of disposal through the first
lot of attention from the community. It has been demon- three methods facing a ban, a growing interest is now being
strated that wastes such as municipal solid waste (MSW), directed towards incineration and other thermal sludge
plastics, agricultural waste and sewage sludge can be disposal processes [3]. These methods are found to benefit
transformed to energy or valuable chemicals. It is normally the concept of waste-to-energy. For such thermal appli-
achieved by several routes including bioconversion, incin- cations, what a crucial property of material has to be met is
eration or thermochemical conversion processes [1,2]. its energy content or heating value. It is used, as the priority,
It has been reported that the amount of sewage sludge for evaluating the potential of sewage sludge.
generated from wastewater treatment plants seems to The heating value of materials, even solid, liquid or gas, can
increase proportionally with the industrial development in be determined experimentally by a bomb calorimeter or
most countries [13]. It normally contains undesirable calculated from their compositions or some properties using a
components such as organic, inorganic, toxic substances as mathematical model. There have been many models proposed
well as pathogenic or disease-caused microorganisms. for predicting heating value of many types of materials with
various compositions [418]. Nonetheless, there have been
* Corresponding author. Tel./fax: C66 2 988 4039.
only few works contributed to sewage sludge. The objective of
E-mail address: vissanu@mut.ac.th (V. Meeyoo). this study was to develop correlations between heating value
0016-2361/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2005.01.003
850 P. Thipkhunthod et al. / Fuel 84 (2005) 849857

and sewage sludge characteristics (proximate or ultimate The first two analyses are common when dealing with
analysis) for sewage sludges produced in Thailand. MSW and lignocellulosic materials or biomass while
models based on ultimate analysis have been derived
mostly for coals and liquid fuels [13]. The physical or
2. Literature review chemical composition analysis is based on the level of
different components of the solid matrix, for instance
Regarding the empirical approaches, there are three types plastics, paper and garbage in MSW or lignin, cellulose
of models that are normally used to predict heating values and lignocellulose in biomass, etc. The proximate
based on the following analyses [10]: analysis typically involves determination of moisture,
volatile matter, fixed carbon and ash contents whereas
Physical or chemical compositions the ultimate analysis includes an assessment of the
Proximate analysis levels of carbon, hydrogen, oxygen, nitrogen and sulfur
Ultimate analysis contents.
Table 1
Summary of models used for predicting the heating value of various types of materials

No. Equationa Application Unit Basisb Ref. Original


Models based on proximate analysis
Eq. (1) HHV Z aK bM Refuse kJ/kg adb [7]
Eq. (2) HHV Z aFC b Biomass kJ/kg db [8]
Eq. (3) HHV Z aV C b MSW kJ/kg db [16]
Eq. (4) HHV Z aV C bF Coal/refuse kJ/kg daf [8] Goutal
Eq. (5) HHV Z aV C bF Biomass kJ/kg db [13]
Eq. (6) HHV Z aV C FC b Biomass kJ/kg db [13] Jimenez
Eq. (7) HHV Z aV C bFC c MSW kJ/kg db [16]
Eq. (8) HHV Z aV K bM Refuse kJ/kg adb [16] Liu
Eq. (9) HHV Z aV K bMC c Refuse kJ/kg adb [16] Bento
Eq. (10) HHV Z aV C FK bM MSW kJ/kg adb [10]
Eq. (11) HHV Z aV C FK bMC c Refuse kJ/kg adb [10] Bento
Eq. (12) HHV Z aV C bFK cM MSW kJ/kg adb [10]
Eq. (13) HHV Z aV C bFK cMC d MSW kJ/kg adb [10]
Models based on ultimate analysis
Eq. (14) HHV Z aCC b Biomass kJ/kg db [14] Tillman
Eq. (15) HHV Z aCC bH C cO Biomass kJ/kg db [15] Ruyter
Eq. (16) HHV Z aCC bH C cOC dS Coal/refuse kJ/kg db [16] Mott and Spooner
Eq. (17) HHV Z aCC bH C cOC d Biomass/refuse kJ/kg db [7,14] Jenkins
Eq. (18) HHV Z aCC bH C cOC dN C e MSW kJ/kg db [16]
Eq. (19) HHV Z aCC bH C cN C dSC eOC f Biomass kJ/kg db [13] Francis
Eq. (20) HHV Z aCC bH C cSC dOC eN C fAC g Coal kJ/kg db [14]
Eq. (21) HHV Z aCC bH C cSC dOC eN C fA Coal kJ/kg db [14]
Eq. (22) HHV Z aCC bH C cSC dOC NC eAC f Coal kJ/kg db [14]
Eq. (23) HHV Z aCC bH C cSC dOC NC eA Coal/refuse kJ/kg db [14,16]
Eq. (24) HHV Z aCC bH C cO2 =1  A=100C d1  A=100 Coal kJ/kg db [14]
Eq. (25) HHV Z aCC bH C cOC dO2 =1  A=100C eS Coal kJ/kg db [14]
Eq. (26) HHV Z aC=HC bOC NC cA Coal kJ/kg db [14]
Eq. (27) HHV Z 328CC 1419H C 92:8S Coal kJ/kg db [14]
Eq. (28) HHV Z 328CC 1419H C 92:8SK aOC NC bAC c Coal kJ/kg db [14]
Eq. (29) HHV Z a328CC 1419H C 92:8SC bOC NC cA Coal kJ/kg db [14]
Eq. (30) HHV Z a328CC 1419HC 92:8S  23:8N C bOC cA Coal kJ/kg db [14]
Eq. (31) HHV Z aH=1K A=100C bC=3C H K OK S=8 Coal kJ/kg db [14]
Eq. (32) HHV Z aO=1K A=100C bC=3C H K OK S=8 Coal kJ/kg db [14]
Eq. (33) HHV Z aC=1K A=100C bC=3C H K OK S=8 Coal kJ/kg db [14]
Eq. (34) HHV Z aC=1K A=100C bH=1K A=100C Coal kJ/kg db [14]
cOC N=1K A=100C dS=1K A=100C e!
C=3C H K OK S=8
Eq. (35) HHV Z 33:5CC 142:3H K 15:4OK 14:5N !10K2 Biomass MJ/kg daf [8]
Eq. (36) HHV Z 81CC 342:5HK O=8C 22:5S Coal/MSW kcal/kg daf [4,5,7,1416] Dulong
Eq. (37) HHV Z 81CK 3O=8C 171O=8C 342:5H K O=16C 25S Coal/MSW kcal/kg daf [5,7,16] Steuer
Eq. (38) HHV Z 81CK 3O=8C 342:5H C 22:55SC 171O=4 Coal/MSW kcal/kg daf [5,7,16] Scheurer-Kestner
Eq. (39) HHV Z 370:8CC 1; 112:4H K 139:1OC 317:8N C 139:1S MSW kJ/kg db [17]
a
HHV, higher heating value; a, b, c,., arbitrary constants; V, volatile matter; F, fixed carbon; M, moisture; C, carbon content; H, hydrogen content; N,
nitrogen content; S, sulfur content; O, oxygen content; A, ash content (all in percentage).
b
adb, air-dried basis; db, dry basis; daf, dry and ash-free basis.
P. Thipkhunthod et al. / Fuel 84 (2005) 849857 851

For most models, from simple to complex forms, a D3176-89, was also done for all samples providing weight
combination of proximate or ultimate analysis data is percentage of carbon, hydrogen, nitrogen, sulfur and oxygen
generally considered. Table 1 summarizes the practical (by subtraction) elements. The heating values of samples
model patterns used to predict the energy content of materials used were attained in accordance with ASTM D2015.
namely MSW, coal, refuse and biomass [48,10,1317]. The
expressions may have either variable or fixed constants. For 3.3. Heating value models
the former, they were simply assumed to be the result of a
linear combination of variables with a set of constants, i.e. Model patterns listed in Table 1 were fit with the
Eqs. (1)(23). The method of regression analysis is generally experimental data by regression analysis using all sample data
used to accomplish the most suitable values of these constants. points The method of least square, minimizing the error
All constants in the equations may change arbitrarily resulted squared, was used to evaluate the adjustable parameters for each
from the regression analysis. They may vary upon the kind or expression [19]. To select the most appropriate correlation, the
original source of materials. For the latter, Eqs. (35)(39), they coefficient of determination (R2) was mainly considered.
were derived using thermochemical concept. The total heating Models with the highest R2 were used to calculate the
value was determined from heat released by the combustion heating value and compared with the data obtained from the
reactions in correspondence to the amount of each component experiments. The validation of the selected models was
[17]. The equations are generally preferable for particular observed by an error analysis. The absolute and bias errors
materials such as MSW and coal [4,5,7,14,16,17]. It is also were considered. These quantities are defined as:
possible to use combined forms of those two types of
equations, Eqs. (24)(34). More detailed explanations on the HHVc K HHV
% absolute error Z !100%

basic assumptions for each expression were described HHV
elsewhere [48,10,1317].To select an appropriate form of  
heating value model equation, the error, simplicity, liability or HHVc K HHV
% bias error Z !100%
even versatility were considered. HHV
Other than those compositions, there are some heating
where HHVc and HHV are heating values of each data point
value models based on other properties of the materials
from calculation and experiment, respectively. Furthermore,
e.g. sponification and iodine values for predicting the
the validity of the models was also confirmed by applying to
heating value of oils, density and viscosity for predicting the
other sludge.
heating value of liquid fuels [9,11,12,18].
In this work, only models based on the proximate and
ultimate analyses were focused. The model equations
presented in Table 1 were analyzed with the aim to find 4. Results and discussion
the most appropriate form of equation for predicting heating
value of sewage sludge. 4.1. Sewage sludge characteristics

Table 2 shows the averages of sample characteristics


3. Materials and methods comparing among different sources. The results show a wide
range of the sewage sludge characteristics. The compositions
3.1. Sample preparation of sewage sludge are mainly volatile matter and ash contents
with the averages of 42.4 and 53.2% and can be as high as 60.2
Sewage sludge samples used in this study were collected and 80.3%, respectively. However, the sewage sludge contains
from 20 different wastewater treatment plants (WWTPs) in only a small amount of fixed carbon, maximum 11.8%. The
Bangkok and vicinity in accordance with the standard characteristics of the community sludge seem to cover an entire
method, ASTM D346-90. The sample sources include possible range. For example, their heating values are from less
municipal, hospital and industrial WWTPs. The sample than 4,000 kJ/kg to as high as almost 14,000 kJ/kg. However,
collection was carried out monthly over a 2-year period. The those of hospital and industrial sludge samples are between the
total number of collected samples exceeded 219 samples. average values to that on the high side. The characteristics of
The samples were naturally dried under sunlight for 12 some other sludge samples were also collected from the
days prior to characterization. literatures for comparison and given in Table 3. It was
observed that the heating values of the samples in this study
3.2. Sample characterization are lower than those reported in literatures corresponding to
the lower volatile matter and higher ash content.
Sewage sludge characteristics were analyzed according Simple correlations between the heating value of the
to ASTM D3172-89. This technique provides proximate samples and its proximate and ultimate analyses data were
analysis of the sludge, namely moisture, volatile matter, also investigated using plots exhibited in Figs. 1 and 2.
fixed carbon and ash contents. Ultimate analysis, ASTM For proximate analysis, the heating value shows a poor
852 P. Thipkhunthod et al. / Fuel 84 (2005) 849857

Table 2
Characteristics of sewage sludge from different sources (average for each source)

Sourcea Proximate analysis (wt%) Ultimate analysis (wt%)b HHV


b b b (kJ/kg)
M V A F C H N S O C/H C/O
C1 6.1 53.0 38.4 8.6 31.1 4.2 3.3 1.1 24.3 7.45 1.31 13,900
C2 5.1 51.2 42.0 6.7 27.5 4.1 4.0 1.1 23.3 6.72 1.18 13,200
C3 5.4 50.0 43.0 7.0 26.4 4.1 4.3 0.9 23.7 6.46 1.13 12,600
C4 6.4 47.6 48.4 4.0 23.9 3.9 3.8 1.3 21.8 6.08 1.10 11,000
C5 3.7 42.2 51.8 6.0 20.9 3.4 3.3 0.9 21.7 6.20 0.97 10,100
C6 4.1 34.5 61.8 3.7 18.0 2.9 2.3 0.8 16.7 6.21 1.08 9400
C7 3.4 39.0 56.0 5.0 19.5 3.2 3.1 0.8 19.4 6.13 1.03 8700
C8 3.9 33.3 63.5 3.2 14.5 2.6 2.6 1.2 18.1 5.51 0.82 6900
C9 3.7 32.9 64.0 3.1 15.3 2.5 2.3 0.5 17.7 6.05 0.87 6500
C10 3.2 30.6 67.6 1.8 12.7 2.0 1.8 0.6 17.5 6.34 0.74 5700
C11 4.4 24.8 72.9 2.2 10.6 2.0 1.6 0.4 15.7 5.38 0.69 4300
C12 8.9 23.4 74.2 2.4 9.0 2.2 1.5 1.6 18.2 4.06 0.50 3500
H1 6.6 55.5 39.4 5.1 26.7 4.0 4.3 0.7 27.5 6.60 1.01 13,300
H2 5.6 52.6 40.6 6.8 29.6 4.6 5.0 1.0 21.5 6.52 1.60 12,800
H3 4.6 47.7 45.9 6.5 25.5 3.9 4.2 1.0 21.7 6.61 1.19 12,400
H4 6.9 50.4 45.7 3.9 25.0 3.8 3.7 0.8 24.3 6.62 1.04 11,100
H5 4.6 36.6 60.2 3.2 19.0 3.0 2.7 1.2 16.8 6.42 1.21 8200
I1 5.2 54.5 42.3 3.2 25.1 4.0 3.8 0.9 26.1 6.29 0.97 10,900
I2 5.0 45.6 51.6 2.8 22.6 3.2 2.9 2.0 20.3 7.01 1.13 9900
I3 4.7 38.2 58.8 3.0 18.3 3.4 1.8 1.8 18.7 5.36 1.00 9000
a
C, H and I indicate community, hospital and industrial sludges, respectively.
b
Dry basis.

correlation to moisture content (Fig. 1a). It is clear that the coefficients of determination (R2) of more than 0.880
samples that have higher volatile matter and lower ash is compiled in Table 4. For most models, they give almost
content would reasonably contain higher heating value the same coefficient. The values are in narrow ranges,
(Fig. 1b and c). The volatile matter would be the main 0.8810.901 and 0.8830.905 for models based on
component that contributes the heating value of the sewage proximate and ultimate analyses, respectively.
sludge. Meanwhile, the correlation is not quite clear in the With the reasonably high R2 of the models in Table 4,
case of fixed carbon (Fig. 1d). For ultimate analysis, the they should be applicable with an acceptable result.
carbon, hydrogen, and nitrogen contents seem to positively Nonetheless, a practical model should be in a simple form
contribute to the heating value (Fig. 2ac), whereas sulfur to avoid the complication in further mathematical analysis.
and oxygen contents give poor correlations to the heating So, simplicity of the model was also taken into account in
value (Fig. 2d and e). addition to R2 from the regression analysis. Most models in
Table 4 are a linear combination of variables except only
4.2. Heating value models Eqs. (24) and (25).
For models based on the proximate analysis, the best fit
From the regression analysis, all adjustable parameters was achieved by Eqs. (11) and (13) with the R2 of 0.901.
in each model were obtained. A list of models with According to the models, the volatile matter and fixed
Table 3
Characteristics of some other sludge samples collected from literatures

Ref. Sample Proximate analysis (wt%) Ultimate analysis (wt%) Heating value
a a a a a a a a a a (kJ/kg)
M V A F C H N S O C/H C/O
[2] S1 5.2 60.7 29.5 9.8 35.7 5.2 3.5 0.7 25.4 6.87 1.41 16,600
[20] S2 5.0 72.5 16.0 11.5 45.9 6.3 5.1 0.6 26.9 7.29 1.71 20,900
[21] S3 11.8 60.6 26.6 12.8 39.5 6.2 3.9 1.5 25.5 6.38 1.55 17,100
[22] S4 4.3 59.3 31.0 9.7 38.1 5.2 4.5 0.9 20.3 7.33 1.88 16,800
S5 3.9 58.5 30.8 10.7 38.3 5.1 3.7 0.7 21.4 7.48 1.79 16,600
S6 8.5 50.8 43.3 5.9 30.1 4.1 3.8 0.9 17.8 7.31 1.69 13,300
[23] S7 78.1 60.7 36.9 2.4 37.3 5.8 5.5 0.8 13.7 6.43 2.72 16,600
[24] S8 55.9 40.3 3.8 29.0 4.4 3.2 0.5 22.6 6.56 1.28 12,800
S9 49.6 44.0 6.4 25.5 3.7 2.4 0.6 23.8 6.88 1.07 12,600
S10 71.0 21.2 7.8 40.0 6.0 7.0 0.7 25.1 6.69 1.59 18,400
a
Dry basis.
P. Thipkhunthod et al. / Fuel 84 (2005) 849857 853

Fig. 1. (ad) Correlation between the heating value of sewage sludge and its proximate analysis data.

carbon contribute positively to the resulting heating value For models based on the ultimate analysis, Eqs. (19)(21)
whereas the moisture content more or less has the negative give the same highest R2 of 0.905. All models are a linear
effect. However, for practical applications, it is important combination of ultimate analysis data. Three models give
to note that the moisture content rarely presents in the the same coefficients even though they have somewhat
expression except for only some applications such as different numbers of variables. However, they have the
refuse and MSW in which the moisture contents can be as same contexts in the parameters contributing to the heating
high as 50% [16,18]. Depending on the method or even value. That is, the carbon, sulfur and oxygen contents
the conditions of preparation, the final moisture content contribute positively to the heating value while the
can be arbitrarily varied. Eventually, it may cause a hydrogen, nitrogen and ash contents have negative effects.
significant error in heating value determination by using The difference between Eqs. (20) and (21) is only whether it
mathematical models. The explanation is confirmed by has the residual constants or not. However, it was proved to
considering the moisture content in the sludge, which have no significant effect on the final heating value
shows a poor correlation to its heating value (Fig. 1a). calculation. Results from Eq. (19) are comparable to that
Therefore, in order to eliminate the effect of moisture on from Eqs. (20) and (21). As these equations are in a simple
the determination of heating value, the term M should not linear combination of variable form, these three equations
be present in the equation, leading to Eq. (7). From the were selected as the best model from the ultimate analysis
regression analysis, it gives R2 of 0.899. This shows an data. Fig. 4 exhibits the plots between the heating values
acceptable level of correlation, which is not much different from the experiment and calculation by Eq. (19) (Eqs. (20)
from that of Eq. (13). To sum up, the best universal and (21) give a similar result).
correlation to represent the heating value of sewage sludge
in terms of proximate analysis data would be Eq. (7). 4.3. Validation of the models
Fig. 3 shows the plots of heating values from experiment
and calculation by Eq. (7). The results show fairly small The validation of the models was discussed in two
discrepancies between the calculated and experimental aspects, the error of the models and its application. For
values. error analysis purpose, the statistical approach was taken.
854 P. Thipkhunthod et al. / Fuel 84 (2005) 849857

Fig. 2. (ae) Correlation between the heating value of sewage sludge and its ultimate analysis data.

This information was used to indicate the performance of the experimental values, which can be noticed from the
the models based upon the following criteria [16]: high range of error. Even for Eqs. (7) and (19), the absolute
error can be as high as 65%. To explain the cause of error
the average absolute and bias errors should be or from the models, lets consider the plots between the
close to zero, bias error and ash content of sewage sludge. As shown in
the range should be smallest, and Figs. 5 and 6, the plots indicate the increase in the error
the standard deviation should be smallest. with the higher ash content in the sewage sludge. Similarly,
this trend was also observed for other models. It infers that
The results of statistical evaluations are given in ash components would have a significant effect on the error
Table 4. For most models, they show small discrepancies in the determination of heating value.
between the calculated and experimental values. The On the other hand, this confirms the inapplicability of
averages and standard deviations of error are 11.4 and some equations for sewage sludge, especially popular
13.5%, respectively. Nonetheless, there are some expressions such as Dulong, Steuer, and Scheurer-Kestner
calculated data points showing big difference from equations. In such models, the organic materials were
P. Thipkhunthod et al. / Fuel 84 (2005) 849857 855

Table 4
Models achieved from regression analysis and relative error generated when applying to the experimental data

No. Equationa R2 % Relative error


Avg. abs. Avg. bias Mini- Maxi- SD
error error mum mum
Models based on proximate analysis
Eq. (6) HHV Z 259:83V C FK 2454:76 0.899 9.1 2.1 K38.7 66.6 10.5
Eq. (7) HHV Z 255:75V C 283:88FK 2386:38 0.899 9.1 2.1 K38.3 64.5 10.3
Eq. (11) HHV Z 278:07V C FK 50:44MK 2875:52b 0.901 8.9 1.8 K38.8 64.1 9.8
Eq. (12) HHV Z 219:98V C 327:44FK 68:39M b 0.881 11.4 4.9 K37.3 99.4 13.5
Eq. (13) HHV Z 276:04V C 289:70FK 51:45MK 2847:53b 0.901 8.9 1.8 K39.1 65.5 9.9
Models based on ultimate analysis
Eq. (15) HHV Z 491:2CK 911:9H C 117:7O 0.891 10.8 K3.9 K66.9 29.1 11.6
Eq. (16) HHV Z 492:5CK 926:0H C 117:6OC 19:3S 0.891 10.8 K3.9 K66.7 29.1 11.6
Eq. (17) HHV Z 414:8CK 184:1H C 178:9OK 2159:5 0.904 9.3 K2.1 K60.2 32.5 10.2
Eq. (18) HHV Z 425:9CK 69:8H C 181:7OK 180:5N K 2277:0 0.904 9.3 K2.1 K62.1 32.0 10.2
Eq. (19) HHV Z 430:2CK 186:7H K 127:4N C 178:6SC 184:2OK 2379:9 0.905 9.3 K2.1 K64.8 32.4 10.4
Eq. (20) HHV Z 406:4CK 210:6H C 154:7SC 160:3OK 151:3N K 23:8AC :0034 0.905 9.3 K2.1 K64.8 32.4 10.4
Eq. (21) HHV Z 406:4CK 210:5H C 154:8SC 160:4OK 151:2N K 23:8A 0.905 9.3 K2.1 K64.8 32.4 10.4
Eq. (22) HHV Z 395:9CK 447:1H C 255:5SC 154:3OC NK 18:1AK 21:7 0.903 9.3 K2.1 K63.0 33.3 10.6
Eq. (23) HHV Z 395:6CK 446:0H C 254:5SC 154:0OC NK 21:9A 0.903 9.3 K2.1 K63.0 33.3 10.6
Eq. (24) HHV Z 134:3CK 1; 502:1HK 2:7O2 =1K A=100C 29; 132:81K A=100 0.893 10.4 K3.6 K67.4 30.1 11.5
Eq. (25) HHV Z 279:8CK 849:1H C 724:9OK 9:2O2 =1K A=100K 118:5S 0.902 9.6 K3.1 K61.4 32.0 9.7
Eq. (28) HHV Z 328CC 1; 419H C 92:8SC 276:7OC NC 110:4AK 14; 278:3 0.883 10.2 K2.4 K89.4 34.0 13.4
Eq. (29) HHV Z 661:00:328CC 1:419H C 0:0928SC 146:5OC NK 31:4A 0.890 9.9 K2.4 K87.8 34.1 13.2
Eq. (30) HHV Z 683:80:328CC 1:419HC 0:0928SK 0:0238N C 154:6OK 33:1A 0.892 9.9 K2.4 K89.9 34.0 13.4
a
Dry basis and unit of kJ/kg unless otherwise stated.
b
Air-dried basis.

presumed to combust with oxygen gas and yield certain The combustion heat may compensate for breaking this kind
compounds such as CO2 and H2O. Heat released (or heating of sorption bonding, resulting in lower final heating value.
value) is then determined by thermochemical and stoichio- The net heating value is eventually decreased.
metric calculations. These equations are generally useful in However, for a certain application such as incineration,
most cases [4,5,7,9,14,16,17]. However, they may not be pyrolysis and gasification as focused in this work, the
applicable for the case of sewage sludge. Although it is not characteristics of the materials are also necessarily con-
reported here, using such equations usually overestimates sidered rather than only their heating value. Here, the
the heating value of sewage sludge [14]. It is possibly due to proximate analysis plays an important role in the sludge
complex sorption of organic contents on ash components. evaluation. Normally, the more volatile matter or the less

Fig. 3. Comparison between the heating values of sewage sludge calculated Fig. 4. Comparison between the heating values of sewage sludge calculated
from Eq. (7) and experimental value. from Eq. (19) and experimental value.
856 P. Thipkhunthod et al. / Fuel 84 (2005) 849857

Table 5
Calculated heating values of sewage sludge from literatures

Sample Experimental Eq. (7) Eq. (19)


heating valuea
Heating % Error Heating % Error
valuea valuea
S1 16,600 15,900 K3.9 16,400 K1.2
S2 20,900 19,400 K7.1 20,600 K1.4
S3 17,100 16,700 K2.3 17,900 4.4
S4 16,800 15,500 K7.4 16,400 K2.4
S5 16,600 15,600 K5.7 16,700 1.0
S6 13,300 12,300 K8.0 12,800 K4.4
S7 16,600 13,800 K16.8 14,500 K12.4
S8 12,800 13,000 1.6 13,100 2.4
S9 12,600 12,100 K4.1 12,100 K4.5
Fig. 5. Plots between bias errors generated by the model based on proximate S10 18,400 18,000 K2.5 17,500 K4.9
analysis (Eq. (7)) and ash content in the sewage sludge.
a
kJ/kg.
ash content, the more heating value. It is not beneficial to
deal with sludge containing high ash content or low heating heating value than those of the samples in this study. The
value. models also give good result in the determination of heating
Therefore, after the observation from this study, the value even though its characteristics are sometimes outside
limitation of the model may be mentioned because of two the range used in this study. The models can be extrapolated
reasons: to predict the heating value of the sludge with the higher
heating value than that of sample used in this study.
the error arises when models are applied to high ash
content sludge, which also contain low heating value,
and 5. Conclusions
it is unlikely to deal with sewage sludge samples with
low heating value as they are not attractive for With the extensive number of sample data point, the
underlined applications. models predicting the heating value of sewage sludge based
on the proximate and ultimate analyses were created. The
As seen in Figs. 5 and 6, it is reasonable to limit the calculated heating values using the selected correlations
application of the model for samples having the ash content show good agreement with experimental values. The error
less than 50%. The selected models then were reanalyzed analysis confirmed the validity and applicability of the
with this specific range of data. From Eqs. (7) and (19), the models to sewage sludge data both in this work and
averages of the absolute error were reduced to 5.9 and 6.4%, literatures. The application of models however limited to
respectively. In addition, the averages of bias error were 1.2 sewage sludge with the ash content of less than 50%. In the
and 1.1% for both equations. Other statistical values are also case of proximate analysis, such a simple procedure may
improved. have a particular interest in contexts where relatively
Finally, the validity of the heating value models was also sophisticated equipments for experimental determination of
proved by applying to some other sludge samples. The heating values or ultimate analysis are not available.
results are given in Table 5. This sludge has slightly higher Nonetheless, the ultimate analysis data is required for
some applications. This allows the model based on ultimate
analysis to work instead.

Acknowledgements

This work was supported by the Thailand Research Fund


(under Waste-to-Energy project and Royal Golden Jubilee
PhD Program: Grant 0051/45) and by the Ratchadapisake-
somphot Fund of Chulalongkorn University.

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