NR800-A-002

http://www.yokogawa.com/us
Pulp and Paper Applications
Industry: Pulp and Paper
Product: NR800


INFORMATION
On-line measurements in the pulp and paper industry are
among the most difficult challenges of process analytical
chemistry. Pulp and paper production streams are typically
very high in both dissolved and suspended solid material.
The samples are often optically opaque or nearly so. Sample
conditioning systems are prone to plugging and corrosion.
On-line titrators tend to be very troublesome due to the
problems with handling the streams, dispensing measured
amounts of sample, reagent consumption and disposal of the
titrated wastes. Here we report on the application of the
InfraSpec NR800 FT-NIR analyzer to the determination of
alkali salts in various Kraft process streams.

KRAFT PROCESS
Although there are a number of different processes for
making pulp and paper from wood, the Kraft or sulfate
process of chemical pulping is the most common. Wood
chips are fed into a solution of Sodium Hydroxide and
Sodium Sulfide at high temperature in a digester which
breaks the lignin chemical bonds which bind the cellulose
fibers together. After cooking, the fiber or pulp is then
separated by screening and/or filtering from the undigested
wood chips and washed. Additional steps to remove residual
lignin are often employed in modern plants. The pulp is then
bleached to whiten the fibers, formed into a sheet, dried and
rolled.



Figure 1: Simplifies schematic of pulp and paper mill




Chemical reprocessing in the Kraft process is illustrated in Fig. 2

Figure 2: Chemical reprocessing block flow diagram

MEASUREMENT of ALKALI
The spectra of white liquor and green liquor are shown in
Fig.3. Changes in the absorbance spectra are related to
changes in the hydrogen bonding of water caused by the
concentration of the various alkali salts dissolved in the
water.








Figure 3: Spectrum of Green Liquor


All Rights Reserved, Copyright 2008, Yokogawa Corporation of America




NR800-A-002
http://www.yokogawa.com/us
Pulp and Paper Applications
PLS calibration models were created for NaOH, Na
2
S and
Na
2
CO
3
concentrations and are shown in Figures 4-6.
Correlations for all 3 calibrations are 0.97 or greater and the
Standard Error of the Prediction (SEP) is approximately 1 g/L
for all 3 calibrations.

A key point to be noted is that these spectra and calibrations
were made at a fixed temperature. One issue that must be
addressed in this application of FTNIR is the change in the
spectrum of water caused by temperature. Figure 7 shows
the spectrum of water at various temperatures. The change
in the spectrum due to temperature change is great
compared to the change in spectrum caused by the alkali
concentration.





Figure 4: Predicted vs. Measured Plot for NaOH (g/L)


Figure 5: Predicted vs. Measured Plot for Na
2
CO
3
(g/L)



Figure 6: Predicted vs. Measured Plot for Na
2
S (g/L)

There are basically three ways to deal with the effects of
temperature on the spectra such that it does not affect the
measurement. The first, and most obvious is to control the
sample temperature using a sample conditioning system.
Figure 8 shows such a system for white liquor, green liquor
and black liquor. Note the provisions for flushing the system
with water and with Hydrochloric Acid to remove deposits.
This approach has the advantage of being the most precise,
but is also usually the most expensive.




Figure 8: System for Pulp and Paper Liquors


Another approach is to create the calibration at a constant
and convenient temperature, then to measure the effect of
temperature on the output of the calibration model.
Temperature changes in the sample often apply a linear bias
to the output that can be compensated by a temperature
measurement and a factor applied to the analyzer output.

The third approach is to include the variations in temperature
into the calibration model. One of the advantages of Partial
Least Squares (PLS) calibration models is that they separate
effects that are not correlated with the measurement. To do
this, the set of samples used to make the calibration model
(typically 30-50 samples) must have spectra taken over the
entire range of temperatures likely to be seen. This need not
be done systematically, that is, by varying the temperature of
each sample by set amounts. The spectral scans can be
taken at random temperatures, provided the range of
temperatures covers the range likely to be observed in the
process. This approach is referred to as making the model
robust to temperature effects.

Figure 9: Temperature compensated FT-NIR measurement


Figure 10: Robust Calibration Model


All Rights Reserved, Copyright 2008, Yokogawa Corporation of America



Figure 11 shows an on-line trend graph of FT-NIR measurements on green liquor. Figure 12 shows the measurement of effective
alkali in black liquor.

Figure 11: On-Line Measurement of Alkali in Green Liquor



Figure 12: On-Line Measurement of Effective Alkali in Black Liquor


All Rights Reserved, Copyright 2008, Yokogawa Corporation of America




NR800-A-002
http://www.yokogawa.com/us
Pulp and Paper Applications
Other Applications of FT-NIR and Paper Process
Measurements of kappa number in black liquor have been
reportedi. Near infrared spectral measurements have been
used to predict pulp yield ii. In-situ ATR probes have been
used on spent liquorsiii. Andersson and Wilsoniv report
excellent measurements of effective alkali (EA), lignin, Xylan,
total organic material, Cellulose and Glucomannan among
other parameters in black liquor by NIR.

Clearly, we have only begun to scratch the surface of
applications for NIR in the pulp and paper industry. Given the
capital-intensive nature of the industry, and the size of the
facilities, the economic justifications will be found for new
and creative applications of NIR technology over the next
several years.





i R. E. Hodges, Applications of near infrared spectroscopy in the pulp and paper industry, PhD thesis, Auburn University, Auburn
Alabama, US, 1997.

ii T. Lindgren and U. Edlun, Prediction of lignin content and pulp yield, Nor. Pulp Pap. Res. J., 13(1):78-80, 1998.

iii V.M. Saucedo and G.A. Krishnagopalan, Applications of in-situ near-infrared analysis for the measurement of cooking liquor
components during kraft pulping, J. pulp Paper Sci., 26(1):25-30, 2000.

iv N. Andersson and D. I. Wilson, http://www.ee.kau.se/forskning/ModSim/nir_tappi.pdf