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K. H RON , P. F ILZMOSER
AND
M. T EMPL ( EDS .)
Sponsors:
data-analysis OG
ISBN: 978-3-200-03103-6
Application of chemometric analysis to determine the degree of contamination in materials obtained by thermal conversion of biomass.
M. SAJDAK and S. STELMACH
Institute for Chemical Processing of Coal, Poland, msajdak@ichpw.zabrze.pl
1 Introduction
Biomass is the oldest and most widely used renewable source of energy. It is the third largest natural energy source (European Commission, 2000). Due to a continual increase in fossil fuel prices, renewable energy sources (RES), including biomass, are expected to become the second largest source of energy for electricity generation by the end of 2035. According to a report by the International Energetic Agency (IEA, 2012), global sources of bioenergy sufficiently secure biomass and biofuel supplies for energy demand, with minimal impact on food production. An increasing demand for biomass and products of biomass conversion (torrefied or carbonised biomass) may cause an unnatural increase in the calorific value of products, which are assumed to be natural and renewable energy carriers. Biomass may be doped with fossil fuels, polymers, and wastes from the furniture industry with significant contents of resins (polyesters, alkyds, and polyuretanes) or glues (urea glues and polyvinyl acetate glues), which are not classified as biomass. Analyses of carbonised batches of these solutions would prove time- and cost-consuming, considering that 14C analysis is the best available technique for determining the origin of a sample. To fulfill current market requirements, a new combination of chemometric methods and conventional analyses of solid fuels (elementary analysis, heat of combustion, and oxide content in ashes) are suggested to simply and rapidly evaluate the purity of thermal conversion products (Sajdak, 2012, Sajdak et al., 2012). Certain methods have already been applied in the classification of various types of biomass (Guangcan Tao et al., 2012a, b). However, the use of this technique for purity control of biomass and products of biomass thermal conversion is challenging. The research presented in this paper applied a combination of principal component analysis (PCA), classification and regression trees (C&RT), and hierarchical clustering analysis (HCA). HCA enables the quantitative estimation of investigated relations, which facilitates the identification of pollutants in biomass and products of biomass thermal conversion. PCA was employed to determine the variables necessary for a clear description of the types of tested materials and to present the interactions between these variables and their groups. The C&RT method facilitated the creation of an algorithm for testing the material classifications. Regression analysis is applied to estimate the pollution content in samples with compositions that are significantly different from natural samples. The presented methodology requires continuous improvement to enhance the optimisation of the applied techniques.
2 Experimental procedure
2.1 Materials and thermal conversion method
Granules of wood biomass (pine) and polypropylene without any filler, with a radius of 4 mm and coloured with charcoal (Daplen provided by Borealis), were utilised in this research. The tested biomass was pre-dried at 80C to attain 23% water content (Wtr) and grinded to attain a granulation of <5 mm. The pure samples of biomass and various mixtures of biomass with PP (10% to 58% of PP) were subjected to a pyrolysis process. The prepared samples were pyrolysed under various thermal conditions, which are established in the central composite design by the design of experiment method (DOE, Table 1). In each test, 150 g of the sample was placed in a steel retort and pyrolysed in a nitrogen atmosphere. Figure 1 shows a schematic of the biomass thermal conversion work station. Nitrogen was purged
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through the bed from the bottom of the retort with a constant flow of 3 dm3/h. Prior to heating, the sample was washed with nitrogen for 15 min to attain a neutral atmosphere in the retort. The retort was subsequently heated at the rate of 5C/min. Once the final temperature was obtained, the sample was maintained under these conditions for 50 min and then cooled to room temperature. The basic parameters of planned and performed experiments are listed in table 1.
Table 1 Matrix of experiments for the pyrolysis of biomass and biomass-PP blends. No. 1 2 3 4 9 6 7 8 9 10 11 12 13 14 15 Temp. [C] 500 500 700 700 458 740 600 600 600 600 600 500 600 700 458 PP [%] 10 50 10 50 30 30 0 58 30 30 30 0 0 0 0
Similar research exists that focuses on biomass pyrolysis under various thermal conditions (Sowik K. et al. 2011). However, this study considered only pure biomass without the addition of other materials. All samples of carbonised biomass were investigated using the FT-IR analysis and the DRIFT method.
Figure 1 Diagram of the experimental stand for biomass thermal conversion testing
Blank
Central
Regular experiment
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Figure 2 Example spectrogram of the analysed char from the biomass and polypropylene
xi j
aij b j sj
(1)
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aij bj sj
initial value of the parameter, average value of the parameter, and standard deviation of the jth parameter.
Figure 3 presents the results of the spectral data normalisation process that was performed according to equation (1). After normalisation of the spectral data of the carbonised samples (figure 3a), a new data set was obtained (figure 3b) that can be subsequently normalised and analysed. The normalised data set was subjected to cluster analysis and principal component analysis.
Figure 3 Spectra of the investigated materials (bio-char) before (a) and after (b) the normalisation process
After pre-preparation, the data set was subjected to cluster analysis (CA) and principal component analysis . Cluster analysis is an exploratory multivariate method that can be used to describe the relationships among variables. For the hierarchical clustering analysis (HCA), Ward's method was employed to obtain the cluster plots. This method, which is considered extremely efficient, utilises an analysis-of-variance approach to evaluate the distance between clusters and minimises the sum of squares (SS) among clusters. The Euclidean distance, which was chosen for the analysis in this study, is expressed as
d ij
x
m k 1
ik
x jk
(2)
where m number of variables dij Euclidean distance between objects i and j, xik value of the variable i, xjk value of the variable j Wards method differs from other binding methods in the use of a variance analysis to estimate the distance between clusters. This method minimises the deviation in the sum of squares (SS) between arbitrary clusters.
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Direct analysis of large data sets (e.g., spectral data) is challenging. Therefore, a simpler interpretation of the data from the cluster analysis is presented in dendrograms rather than in tables, as shown in figure 4.
Principal component analysis is another technique employed in this research. It is an efficient tool for the analysis of multidimensional data because it defines the support vectors from the covariance matrix of original variables. Facilitates the discovery of relationships between the test variables and the materials (samples) and reduces the matrix dimension (reduction of variable number is significant in the subsequent analysis). A characteristic feature of PCA is the ability to determine dominant components (specific value) in decreasing order from information conveyed by subsequent variables. In some cases, a new variable may become a specific physical or chemical interpretation during PCA (Tao at al., 2012 a, b). Principal component analysis is primarily applied for the following reasons: Data space reduction (fewer variables), Transformation of input variables into new variablesprincipal components, and Graphical presentation of multidimensional data on a 3D surface without significant loss of information. Data obtained from principal component analysis were applied as input values in the mathematical model evaluation, which was based on classification and regression trees and constructed to estimate the polymer content in the biomass pyrolysis. The primary objective of the C&RT method is a gradual division of test arguments (samples) into homogeneous subsets, until homogeneity is attained based on assignment to the correct class. A set of rules based on the if formula is created, which enables the subdivision of arguments into groups, depending on subsequent qualitative and quantitative parameters. In the C&RT method, a decisive formula may be presented graphically in the form of a decisive tree. The tree resembles a graph that is comprised of a mother root from which a minimum of two paths to nodes emerges. The tree resembles a graph that consists of a root node and a minimum of two branches, which emerge from the root node and lead to inferior nodes (child nodes). Each node corresponds to a class
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description, and each branch corresponds to a decision rule, i.e., a condition that is related to arguments from an entry data set and describes the case in which each branch is chosen. Child nodes become parent nodes during successive splitting of the data set. Each division is performed for separate features (parameters). In a common algorithm, the conditions on the branches of each node must be complementary, such that one possible path is provided downward when walking the tree. Nodes that do not contain any child nodes are known as leaf nodes, outer nodes or terminal nodes; they represent the final classes. In a formal approach, a tree is a graph without cycles (loops), which displays only one path between two different nodes. The main advantages of C&RT are as follows: Ability to present arbitrarily complex problems. Resistance to unusual feature values. Resistance to a large number of features that do not influence the outgoing variable. The main disadvantages of C&RT are as follows: Large size of the trees, because the algorithm tests only one feature at a time. Each node corresponds to a proper class and each class is defined by a function (decisive parameter). In subsequent division, a child node becomes a parent node, which undergoes splitting.
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The polymer applied in the subsequently described research (Borealis Daplen) undergoes depolimerisation (thermal decomposition) at approximately 400C. Elemental analysis was performed by direct method using Macro Cube CHNS, O, and a Cl elemental analyser provided by Elementar Analsensysteme GmbH (high-temperature pyrolysis), and oxygen detection was performed by the NDIR method (Muzyka R., et al., 2013). When the cluster analysis was completed, the obtained data were subjected to chemometric analysisprincipal component analysis. As a result, a new data set with fewer variables was established; the trees basic variables constituted the main components. The first (PC 1) and third (PC 3) components allow descriptions of the given data set with respect to the pyrolysis conditions in which the samples were processed. The second component (PC 2) refers to the PP content in the copyrolysis with biomass (figure 6). The new data set from the PCA was used as the input data in the analysis based on classification and regression trees.
Figure 6 The projection of samples on the space defined by the tree s principal factors
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The data set obtained using the main component method during the analysis of examined materials are presented in table 2
Table 2 Results of principal component analysis.
No 1 2 3 4 5 6 7 8 9 10 11 12 13
PC 0 0,58 0,53 0,41 0,72 0,82 0,80 0,84 0,63 0,76 0,86 0,54 0,63 0,45
PC 1 0,79 0,75 0,90 -0,29 0,28 0,39 0,25 -0,13 -0,20 0,21 0,80 -0,14 0,87
PC 2 -0,06 0,16 -0,07 0,44 0,49 0,42 0,46 0,04 0,60 0,45 0,05 0,06 -0,02
PC 3 -0,11 0,27 0,16 -0,34 0,09 0,08 0,01 -0,77 -0,04 -0,08 0,12 -0,75 0,17
Temp. [C] 500,00 500,00 500,00 700,00 600,00 700,00 600,00 740,00 600,00 600,00 458,00 740,00 458,00
PP [%] 10,00 50,00 0,00 10,00 0,00 0,00 30,00 30,00 58,00 30,00 30,00 30,00 0,00
The new data set (table 2) from the PCA was employed as input data in the analysis based on classification and regression trees. Using this method, the predictive C&RT model was constructed to estimate the PP content added to pyrolysed biomass, as presented in figure 7.
Although it can be used to estimate the PP content in a sample of carbonised biomass, the presented model is a preliminary model due to the small amount of input data employed during its
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creation. Therefore, the model was not subjected to cross-check validation and is considered a model suitable for the initiation of new research. As a result of this research, a procedure pattern was formulated for these types of analyses. The procedure algorithm is shown in figure 8.
4 Conclusion
This paper presents the results of research on the application of chemometric methods, which can be employed to determine the presence and quantity of polymeric materials carbonised with biomass in pyrolytic processes. The cluster analysis employed in the research allowed the creation if three well-defined groups of biomass, which were carbonised at temperatures of 500C, 600C and 750C. The results exhibit 100% agreement with the initial assumptions. The Euclidean distance was used to describe the similarities between the tested materials, which demonstrated the potential of the new method as a quantitative analysis of the PP content in carbonised biomass. The research results indicate the potential of its application to construct a complete analytical procedure. In the future, this procedure will facilitate the identification of pollutions in carbonised biomass that is available on the market. The presented data are preliminary data. However, based on this research, a direction for subsequent analyses in this field has been defined.
5 Acknowledgments
These studies were funded under the budget of research task No. 4 "Development of integrated technology of fuels and energy from biomass, agricultural waste, and others as part of the strategic program of research and development: Advanced technology of obtaining energy" provided by the NCBiR.
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6 References
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