Determination of the main aliphatic carboxylic acids in kraft black liquors by high-

performance liquid chromatography-mass spectrometry

Jaana Kkl, Raimo Aln

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

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

E-mail: jaakosk@cc.jyu.fi
Tel. +358 14 260 2575
+358 40 773 8544
Fax +358 14 260 2581

Extended abstract (for a poster)

In kraft pulping, wood polysaccharides are subjected to the end-wise degradation (i.e., the
peeling reaction) under alkaline conditions with the simultaneous formation of a large
number of water/alkali-soluble hydroxy mono- and dicarboxylic acids together with
formic and acetic acids [1-3]. The versatile analysis of organic material in black liquor is
of a great importance, for example, for monitoring the progress of this delignification
process. Detailed chemical analysis of the main aliphatic acids comprises a current topic
for several reasons.

Various acid analyses have resulted in a better understanding of pulping chemistry and
have, on the other hand, been necessary for developing the isolation methods of these
aliphatic acids. For example, it has been noted [4] that there is an arithmetic correlation
between the acid formation and the degree of delignification. In addition, even small
changes in the chemical composition of black liquor remarkably influence on the burning
behavior of black liquor and the combustion properties vary more or less systematically
with the degree of delignification [5,6]. Since combustion properties are also essentially
related to the chemical composition of the acid fraction, the acids have been analyzed in
detail together with low-molecular-mass degradation fragments of lignin [7].
Consequently, the combustion behavior of black liquor can be predicted with reasonable
accuracy based on this kind of approach.

When considering the analytical methods needed to fulfill all requirements for a proper
control of delignification, it is obvious that the presently available chromatographic
methods are practically still rather complicated and time-consuming. They usually
comprise the extraction of an analyte from a sample matrix, the preparation of feasible
acid derivatives, and the separation of these derivatives by using alternative
chromatographic techniques. For this reason, in many cases, such as monitoring the kraft
process, more simple and rapid methods are clearly needed. Although numerous
straightforward methods for the determination of aliphatic carboxylic acids are used in
many applications, they are not extensively used to determine various acids formed
during wood delignification.
From the industrial point of view, the total time needed for the common gas
chromatographic (GC) analysis is too long for a proper process control. In this study, a
simple high-performance liquid chromatographic separation method with atmospheric-
pressure chemical ionization mass spectrometry (HPLC-APCI-MS) was developed and
validated to separate the most abundant low-molecular-mass aliphatic mono- and
dicarboxylic acids present in softwood (pine and spruce), hardwood (birch and aspen),
and non-wood (bamboo and wheat straw) black liquors. The method provides some
important advantages compared to the traditional GC method such as a simple sample
preparation and even two orders of magnitude faster analysis time, thus enabling almost
the real-time monitoring of these acids. In addition, it is often necessary to focus only on
changes in the total concentrations of a few acids (e.g., lactic, hydroxybutanoic, and
isosaccharinic acids). It could be concluded that this novel method has potential for
developing accurate and reproducible on-line systems.

Figure 1 shows the HPLC-MS chromatograms of the typical softwood (a) and hardwood
(b) black liquors. Main aliphatic carboxylic acids present in different black liquors have
been separated, identified, and analyzed quantitatively.

Figure 1. Selected ion monitoring chromatograms (SIM) of the acids in softwood (a) and birch (b) black
liquors: oxalic (1), glycolic (2), -glucoisosaccharinic (3), -glucoisosaccharinic (4), xyloisosaccharinic
(5), malic (6), lactic (7), 3,4-dideoxypentonic (8), 2-hydroxyglutaric (9), succinic (10), 4-hydroxybutanoic
(11), 2-hydroxybutanoic (12), glutaric (internal std) (13), 2-hydroxy-4-pentenoic (14), methylsuccinic (15),
2-hydroxy-2-methylbutanoic (16), and adipic (internal std) (17) acids.

References

[1] E. Sjstrm, Wood Chemistry, Fundamentals and Applications, Academic Press, San Diego,
USA, 1993, pp. 140-164.
[2] R. Aln, in: P. Stenius (Editor), Forest Products Chemistry, Fapet Oy, Helsinki, Finland, 2000, pp.
58-104.
[3] K. Niemel, R. Aln, in: E. Sjstrm, R. Aln (Editors), Analytical Methods in Wood Chemistry,
Pulping, and Papermaking, Springer-Verlag, Heidelberg, Germany, 1999, pp. 193-231.
[4] R. Aln, P. Hentunen, E. Sjstrm, L. Paavilainen, O. Sundstrm, J. Pulp Pap. Sci. 17 (1991) J6-
J9.
[5] T. Noopila, R. Aln, M. Hupa, J. Pulp Pap. Sci. 17 (1991) J105-J109.
[6] R. Aln, M. Hupa, T. Noopila, Holzforchung 46 (1992) 337-342.
[7] R. Aln, J. Pulp Pap. Sci. 23 (1997) J62-J66.