PREDICTION OF THE COMBUSTION BEHAVIOR OF BLACK

LIQUOR BY INFRARED SPECTROSCOPY

Jarmo Louhelainen, Raimo Aln and Hannu Pakkanen

University of Jyvskyl, Department of Chemistry, Laboratory of Applied Chemistry,

P.O. Box 35, FIN-40014 University of Jyvskyl, Finland

ABSTRACT

Combustion behavior (swelling during combustion and combustion time) of the kraft
black liquors varies significantly between pulp mills and also time-dependent
variations within a mill occur. In addition, due to the different raw materials and
pulping conditions, some further variations in these combustion properties are
typically observed. Therefore, by means of the proper process control and
optimization, it would be beneficial if these characteristic changes could be rapidly
detected from black liquor prior to its combustion in the recovery boiler. In this paper,
the possibility of applying infrared spectroscopy (utilizing mid-infrared range, MIR)
to predict the combustion behavior of softwood black liquor was studied.

INTRODUCTION

FTIR spectroscopy has been shown to be a versatile method for indicating different
chemical bonds and thus different functional groups in wood and pulp samples [1-4].
For this reason, with respect to the topics related to chemical pulping, there are
several FTIR-based techniques for measuring, for example, the kappa number of pulp
and, on the other hand, the contents of lignin and carbohydrates in wood and pulp.
Since there exist correlations between the chemical composition and the combustion
properties of black liquor [5-8], it could be further concluded that correlations
between these properties and, for example, easily detectable FTIR data offer an
interesting possibility of developing a proper method for characterizing also the
combustion behavior of black liquor.

The purpose of this study was to find out one suitable way to predict the combustion
behavior of black liquor with different chemical compositions. In this study, FTIR
spectroscopy, as a rapid analysis technique, was selected to obtain composition data
on industrial softwood black liquors.

EXPERIMENTAL

The black liquors studied comprised of industrial softwood black liquor from kraft
pulping treated with different conditions [9]. The single black liquor droplet
combustion technique developed by Hupa and coworkers [10] was applied in
combustion experiments. In this study, the overall duration of the combustion stages
of black liquor is expressed for each liquor as a term combustion time, which is
obtained as a sum of the combustion times separately determined for the
devolatilization and char burning stages.

The FTIR measurements were performed in each case from a thin pellet prepared
from a homogenized mixture of oven-dried black liquor and KBr (about 200 mg, mass
proportion 1:40, respectively). The analysis was carried out with a Nicolet Magna-IR
550 Series II FTIR spectrometer in the wavenumber range 4004000 cm-1. In each
measurement 128 scans were accumulated at 4 cm-1 resolution. To obtain the
background contribution, the KBr spectrum was measured for automatic background
subtraction. In addition, the absorbance peaks of water (i.e., air humidity) and CO2
were eliminated by subtracting these peaks from the spectra of the sample mixtures.

Multivariate calibration models were calculated using partial least squares (PLS)
method. A range of spectral processing methods was used prior to the regressions,
such as mean centering and multiplicative signal correction.

RESULTS AND DISCUSSION

The organic substance groups of black liquor (polysaccharides, aliphatic carboxylic

acids, and lignin) absorb infrared light mainly in the wavenumber range 8001600
cm-1. Each different bond within these organic constituents has their absorption bands
at characteristic wavenumber, but these absorption bands strongly overlap in the
infrared spectrum of black liquor. For this reason, we selected a wide range of
wavenumbers 8601530 cm-1 from infrared absorption spectra to create useful PLS
calibration models.

As can be seen from Figure 1, black liquor swelling and combustion time were
predicted with reasonable accuracy by the PLS calibration models. For evaluating the
calibration models, residuals (measured-predicted values) were divided by root mean
square error of the calibration (RMSEC) values shown in the Figure 1 to obtain
standardized residuals (). Since almost all the data were within the 95 % confidence
level equivalent to 2 (Figure 2), the calibrations seemed to be reasonable. When
considering the quality of the calibrations made, it should be pointed out that the
reference data (measured values) were based on the measurements with some
variations as well.

50 1.05
Predicted combustion time, s/mg

Corr. Coeff.: 0.937 RMSEC: 2.06 Corr. Coeff.: 0.896 RMSEC: 0.0184
45
Predicted swelling, cm /g

1
3

40
0.95
35

0.9
30

25 0.85
25 30 35 40 45 50 0.85 0.9 0.95 1 1.05
3
Measured swelling, cm /g Measured combustion time, s/mg

Figure 1. Predicted swelling (left) and combustion time (right) vs. respective
measured data of the black liquor dry solids.
 3 3

Standardized residuals,
Standardized residuals, 2

1 1

0 0

-1 -1

-2 -2

-3
-3
0.85 0.95 1.05
25 50
3
Measured swelling, cm /g Measured combustion time, s/mg

Figure 2. Standardized residuals for PLS calibration of the black liquor swelling (left)
and combustion time (right).

CONCLUSIONS

The results clearly showed that the FTIR spectroscopic data on black liquor combined
with multivariate PLS calibration seems to be a potential tool for predicting rapidly
the combustion behavior of black liquor. These results also confirmed the earlier
findings of the correlations between the organic material and combustion properties of
black liquor. In addition, it was concluded that this kind of approach offers a suitable
way of developing online measurements for this purpose.

ACKNOWLEDGEMENTS

Financial support from the Academy of Finland (project numbers 201352 and 210321)
is gratefully acknowledged.

REFERENCES

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