1578 Energy & Fuels 2004, 18, 1578-1583

Fast Pyrolysis of Forestry Residue and Pine. 4.

Improvement of the Product Quality by Solvent Addition
Anja Oasmaa,*,† Eeva Kuoppala,† Johan-Fredrik Selin,‡ Steven Gust,‡ and
Yrjö Solantausta†
VTT Processes, P. O. Box 1601, 02044 VTT, Biologinkuja 3-5, Espoo, Finland, and
Fortum Oyj, P.O. Box 310, 06101 Porvoo, Finland

Received March 30, 2004

Addition of alcohols was found to improve the homogeneity, decrease the viscosity and density,
lower the flash point, and increase the heating value of pyrolysis liquids. Alcohol addition also
lowered the viscosity and molecular mass increase during the aging of pyrolysis liquids. The
reduction in the viscosity change was primarily due to a stabilizing effect of alcohols on the water-
insoluble high molecular mass lignin-derived fraction. Other effects include the formation of
acetals in reactions of alcohols with aldehydes, ketones, and anhydrosugars. Low (e5 wt %) alcohol
additions prevented aging reactions by a few months, while the higher (g10 wt %) ones retarded
them by almost a year. Methanol was the most effective alcohol of those tested (methanol, ethanol,
isopropanol). By improving solubility, the alcohols also enhanced the separation of the extractive-
rich top layer in the pyrolysis of forestry residue by decreasing its volume and increasing the
concentration of extractives and solids in the top layer.

Introduction of storage. The amount of water-insoluble fraction

The advantage of pyrolysis liquids compared to pel-
lets, wood chips, or other solid biomass will be their ease
of use. All the customer has to do is to order the fuel
and perform annual maintenance. This in turn requires
that the fuel is stable. Thus, to achieve customer
acceptance, heating oils have to tolerate a storage period
of at least six months with the customer. Pyrolysis
liquids are unstable1,2 due to their high amount of
reactive oxygen-containing compounds. The instability
is seen as a viscosity increase during storage,3,4 which,
connected with the formation of water, finally leads to
the separation of a lignin-rich bottom sludge.4 The
pyrolysis liquids consist of water, acids, alcohols, alde-
hydes, ketones, carbohydrates, extractives, and de-
graded lignin.5 The main changes6 upon aging of
pyrolysis liquids take place during the first six months
* To whom correspondence should be addressed. Fax: +358-9-460
493. E-mail: anja.oasmaa@vtt.fi.
† VTT Processes.
‡ Fortum Oyj.
(1) Diebold, J. P. A Review of the Chemical and Physical Mecha-
nisms of the Storage Stability of Fast Pyrolysis Bio-oils. In Fast
Pyrolysis of Biomass: A Handbook; Bridgwater, A., Ed.; CPL Press:
Newbury, U.K., 2002; Vol. 2, pp 243-292.
(2) Oasmaa 2003: Oasmaa, A. Fuel Oil Quality Properties of Wood-
based Pyrolysis Liquids. Academic dissertation. Research Report
Series, Report: 99. Department of Chemistry, University of Jy-
väskylä: Jyväskylä, Finland, 2003; 32 pp + appendices (251 pp).
(3) Czernik, S. Storage of Biomass Pyrolysis Oils. In Proceedings of
Specialist Workshop on Biomass Pyrolysis Oil Properties and Combus-
tion; Estes Park, CO, Sept 26-28, 1994; NREL Paper No. CP-430-
7215, pp 67-76.
(4) Oasmaa, A.; Leppämäki, E.; Koponen, P.; Levander, J.; Tapola,
E. Physical Characterisation of Biomass-Based Pyrolysis Liquids.
Application of Standard Fuel Oil Analyses; VTT Publication 306;
VTT: Espoo, Finland, 1997; 46 pp + appendices (30 pp).
(5) Oasmaa, A.; Kuoppala, E.; Solantausta, Y. Fast Pyrolysis of
Forestry Residue. 2. Physicochemical Composition of Product Liquid.
Energy Fuels 2003, 17 (2), 433-443.
increases mainly due to polymerization and condensa-
tion reactions.6 This causes an increase in the average
molecular mass of the liquid and in viscosity.3 The water
content increases due to condensation reactions. The
decrease in volatile aldehydes and ketones raises the
flash and pour points of the liquid.6 An increase in water
decreases the heating value.6
Polar solvents have been used to homogenize pyrolysis
liquids4,7 and to reduce the increase in their viscosity.8,9
Quantitative data is reported on the effects of water,10,11
methanol8,12 and furfural.13 The addition of solvents,
(6) Oasmaa, A.; Kuoppala, E. Fast Pyrolysis of Forestry Residue. 3.
Storage Stability of Liquid Fuel. Energy Fuels 2003, 17 (3), 1075-
1084.
(7) Oasmaa, A.; Kytö, M.; Sipilä, K. Pyrolysis Liquid Combustion
Tests in an Industrial Boiler. In Progress in Thermochemical Biomass
Conversion; Bridgwater, A. V., Ed.; Blackwell Science, U.K., 2001; Vol.
2, 1468-1481.
(8) Diebold, J. P.; Czernik, S. Additives to Lower and Stabilize the
Viscosity of Pyrolysis Oils during Storage. Energy Fuels 1997, 11,
1081-1091
(9) Czernik, S.; Maggi, R.; Peacocke, G. V. C. Review of Methods
for Upgrading Biomass-derived Fast Pyrolysis Oils. In Fast Pyrolysis
of Biomass: A Handbook; Bridgwater, A., Ed.; CPL Press: Newbury,
U.K., 2002; Vol. 2, p 424.
(10) Solantausta, Y.; Diebold, J.; Elliott, D. C.; Bridgwater, T.;
Beckman, D. Assessment of Liquefaction and Pyrolysis Systems. VTT
Research Notes 1573; VTT: Espoo, Finland, 1994.
(11) Tiplady, I. R.; Peacocke, G. V. C.; Bridgwater, A. V. Physical
Properties of Fast Pyrolysis Liquids from the Union Fenosa Pilot Plant.
In Proceedings of the Second EC/Canada Workshop on Thermal
Biomass Processing; Bridgwater, A. V., Hogan, E., Eds.; CPL Scientific
Information Services, Ltd.: Newbury, U.K., 1996; pp 164-174.
(12) Casanova, J. Comparative Study of Various Physical and
Chemical Aspects of Pyrolysis Bio-Oils Versus Conventional Fuels
Regarding Their Use in Engines. In Proceedings of Specialist Workshop
on Biomass Pyrolysis Oil Properties and Combustion; Estes Park, CO,
Sept 26-28, 1994, NREL CP-430-7215, pp 343-354.
(13) Salvi, G.; Salvi, G., Jr. Pyrolytic Products Utilization Assessment
Study, Commission of European Communities, Contract No. EN3B-
0191-1(CH), 1991.

10.1021/ef040038n CCC: $27.50 © 2004 American Chemical Society

Published on Web 08/31/2004
Fast Pyrolysis of Forestry Residue and Pine
Scheme 1. Esterification of Aldehydes and Ketones15
Scheme 2. Hemiacetal and Acetal Formation from
Aldehydes and Ketones15
Scheme 3. Acetal Formation from Monosaccharides15
especially methanol, showed a significant effect on the
stabilization. The rate of viscosity increase for the liquid
with 10 wt % of methanol was almost 20 times less than
for the liquid without additives.8 It has been postu-
lated8,14 that solvent addition can impact the liquid
viscosity by three mechanisms:
(1) physical dilution without affecting the chemical
reaction rates,
(2) reducing the reaction rate by molecular dilution
or by changing the liquid microstructure, and
(3) chemical reactions between the solvent and the
liquid components that prevent further chain growth.
The chemical reactions1,8 that have been suggested
to occur between the pyrolysis liquid compounds and
methanol or ethanol include esterification (Scheme 1)
and acetalization (Schemes 2 and 3).15 Acetals serve as
protecting groups for aldehydes and ketones.15 Consid-
ering the simplicity, the low cost of some solvents, and
their beneficial effects on the liquid properties, alcohol
addition has been suggested to be the most practical
approach for pyrolysis liquid quality upgrading.14 In the
present study, confirmation of the suggested reactions
as well as new data on the effect of alcohol addition on
physicochemical changes of softwood liquids during
storage are presented. This is the fourth part of a series
of publications that have focused on fuel oil properties
of fast pyrolysis liquids of forestry residue: optimization
of separation of extractives,16 physicochemical proper-
ties,5 and storage stability.6
(14) Oasmaa, A.; Czernik, S. Fuel Oil Quality of Biomass Pyrolysis
Oils - State of the Art for the End Users. Energy Fuels 1999, 13 (4),
914-921.
(15) McMurry, J. Fundamentals of Organic Chemistry. Brooks/Cole
Publishing Co.: Pacific Grove, Albany, 1998; pp 566 + appendices.
(16) Oasmaa, A.; Kuoppala, E.; Gust, S.; Solantausta, Y. Fast
Pyrolysis of Forestry Residue. 1. Effect of Extractives on Phase
Separation of Pyrolysis Liquids. Energy Fuels 2003, 17 (1), 1-12.
Energy & Fuels, Vol. 18, No. 5, 2004 1579
Table 1. Properties of Alcohols Compared to Those of
Pyrolysis Liquids
pyrolysis liquid methanol ethanol isopropanol
water, wt % 20-30 max 0.05 max 6 max 0.1
viscosity at 20 °C, 100-200 0.75 1.5 2.8
cSt
LHV, MJ/kg 13-18 19.9 26.6 28.7
density at 20 °C, 1.10-1.30 0.791 0.800 0.785
kg/dm3
boiling point, °C - 64.6 78.0 82.2
flash point, °C 40-110 11 12 12
pour point, °C 27 DNAb -111a -89.5
a Freezing point. b DNA ) data not available.
Experimental Section
Liquid Production. Pyrolysis was carried out by employ-
ing a 20 kg/h capacity process development unit (PDU) at
VTT.16,17 This transport bed reactor was initially designed and
delivered by Ensyn Technology in 1995, and it has been
subsequently modified by VTT. The ground, sieved (<3 mm),
and dried (moisture 4-11 wt %) feedstock was fed to the
reactor. The pyrolysis temperature was about 520 °C, and
residence time for pyrolysis vapors was 1-2 s. The product
vapors were condensed in liquid scrubbers. Liquid yields
(organics and water) from forestry residue ranged from 61 to
64 wt % for dry feed and from 68 to 75 wt % for pine sawdust.17
Forestry residue and pine produced an extractive-rich top
layer, the amount of which varied from 1 to 25 wt %, depending
mainly on the content of extractives in the feedstock. The
extractive-rich top phase was separated from the bottom phase
after 24 h of standing at 35 °C.16
Solvent Addition and Liquid Storage. Solvent (Table 1)
was added either to the whole product liquid just after
condensation or to the bottom phase of the liquid after
separation of the top phase.
Pyrolysis liquids were stored in closed bottles at room
temperature. In addition, accelerated aging tests (stability
tests) were carried out for studying the storage stability of the
liquids. In the test, pyrolysis liquid was kept at fixed temper-
ature for a certain time, and the increases in viscosity and
water content were measured. The conditions of the stability
test were 24 h at 80 °C, and 6 h at 80 °C. The temperature of
the viscosity measurement was 40 °C. It has been presented
earlier6 that the chemical changes in the stability test at 80
°C for 6/24 h correlated roughly with the changes in 3-4
months/1 year storage at room temperature.
Liquid Analyses. Physical characterization of liquid prod-
ucts was carried out by employing modified standard and new
methods.4,18 Chemical characterization was performed using
the solvent extraction scheme5 based on water extraction. With
the method, the following water-soluble fractions6 were ob-
tained: carboxylic acids and alcohols, ether-solubles (mainly
aldehydes, ketones, and lignin monomers), water, and ether-
insolubles (mainly anhydrosugars, anhydrooligomers, hydroxy
acids C < 10). The water-insoluble fraction consisted of
dichloromethane-soluble [low molecular mass (LMM) lignin
material, extractives] and dichloromethane-insoluble [high
molecular mass (HMM) lignin material, solids] substances. Of
volatile acids, only the main compounds,5 acetic and formic
acids (about 90% of volatile acids), were quantified by using a
capillary electrophoresis technique.
(17) Solantausta, Y.; Oasmaa, A.; Sipilä, K. Fast Pyrolysis of
Forestry Residues. In Pyrolysis and Gasification of Biomass and
WastesThe Future for Pyrolysis and Gasification of Biomass and
Waste: Status, Opportunities and Policies for Europe; Strasbourg, FR,
30 Sept-1 Oct, 2002. Bridgwater, A. V., Ed.; CPL Press: Newbury,
U.K., 2003; pp 271-276.
(18) Oasmaa, A.; Peacocke, C. A Guide to Physical Property Char-
acterisation of Biomass-Derived Fast Pyrolysis Liquids; VTT Publica-
tion 450; VTT: Espoo, Finland, 2001; 65 pp + appendices (34 pp).
1580 Energy & Fuels, Vol. 18, No. 5, 2004 Oasmaa et al.

Figure 1. Effect of 5 wt % isopropanol (IPA) addition on the amount and composition of phases of a brown forestry residue
liquid.

Figure 2. Effect of isopropanol (IPA) addition on the homogeneity of a forestry residue liquid. Microscopic images.

Results and Discussion
Effect of Alcohol Addition on the Top Phase.
Extractive-rich feedstocks, like forestry residue and
pine, produced a separate top phase of 1-25 wt % of
the total liquid product, which depended mainly on the
total extractive content of the product liquid. The
formation of a top phase also separated the main portion
of the solids into the top phase. The bottom phase
resembled the normal bark-free wood pyrolysis liquid.
The addition of alcohol into pyrolysis liquids enhanced
the solubility of poorly water-soluble compound groups,
like lignin dimers and extractives, into the matrix. This
reduced the amount of top phase (Figure 1). However,
the concentration of extractives both in the top and
bottom phases increased (Figure 1). The concentration
of extractives in the top phase increased from ∼20 wt
% to >50 wt %. In addition, the solid content of the top
phase increased.
After the water content of the top phase decreased to
about 6-7 wt %, no further reduction of the top phase
in any pyrolysis liquid was achieved by further alcohol
additions. This water content was typically achieved by
5 wt % alcohol addition. There was no significant
difference between ethanol (EtOH) and isopropanol
(IPA) in this respect.
Effect of Alcohol Addition on Physicochemical
Properties of Pyrolysis Liquids. Addition of alcohol
(Table 1) improved the homogeneity/solubility of hydro-
phobic compounds (Figure 2) of the liquid; decreased its
Fast Pyrolysis of Forestry Residue and Pine
Figure 3. Effect of alcohol addition on viscosity of a brown
forestry residue pyrolysis liquid (bottom phase): [, methanol;
0, ethanol; 4, IPA.
Figure 4. Effect of solvent addition on the flash point of a
brown forestry residue pyrolysis liquid (bottom phase): [,
methanol; 0, ethanol; 4, IPA.
Figure 5. Effect of solvent addition on lower heating value
(LHV) of a brown forestry residue pyrolysis liquid: [, metha-
nol; 0, ethanol; 4, IPA.
viscosity (Figure 3), density, and flash point (Figure 4);
and increased its heating value (Figure 5).
Homogeneity/Solubility. Alcohols are known4 to be
efficient solvents for pyrolysis liquids. Figure 2 shows
how another liquid phase (extractive material) dissolves
in the pyrolysis liquid matrix. The amount of alcohol
addition required for the dissolution of the extractives
varied depending on the chemical composition of the
pyrolysis liquid. As presented previously,6,19 the polar
pyrolysis liquid compounds, like acids and alcohols,
dissolved the hydrophobic lignin-derived and extractive
material in the polar pyrolysis liquid matrix. If the ratio
of hydrophobic to hydrophilic material increased sig-
nificantly, the hydrophobic material, like lignin, sepa-
rated out of the matrix. In aging, the increase in
molecular mass of the liquid caused the separation of
(19) Radlein, D. The Production of Chemicals from Fast Pyrolysis
Bio-Oils. In Fast Pyrolysis of Biomass: A Handbook; Bridgwater, A.,
Ed.; CPL Press: Newbury, U.K., 1999; Vol. 1, pp 164-188.
Energy & Fuels, Vol. 18, No. 5, 2004 1581
Figure 6. Effect of alcohol on viscosity increase with room-
temperature storage: 9, pine; 0, pine + 5 wt % EtOH; [,
brown forestry residue (BFR); ], BFR + 5 wt % IPA; /, BFR
+ 10 wt % IPA.
Figure 7. Viscosity increase (aging test for 6 h at 80 °C, which
correlates to 3-4 months storage at room temperature6) versus
added alcohol: [, methanol; 0, ethanol; 4, IPA.
the lignin-derived material as a heavy bottom sludge.4,18
Addition of alcohols prevented the phase separation
longer. In the pyrolysis of forestry residue with a high
extractive content, this phenomenon was seen as a
separation of an extractive-rich top phase.16
Viscosity. Alcohol addition decreased the viscosity of
the liquid (Figure 3) depending on the viscosity of the
added solvent (Table 1). Pyrolysis liquids are typically
Newtonian ones.16,18 The extractive-rich viscous top
phase of forestry residue liquid caused a slight non-
Newtonian behavior19 at lower temperatures, but the
behavior disappeared when heated, as the extractives
melted.16
Density. Addition of alcohol into pyrolysis liquid
decreased expectedly its density. The difference between
the samples was marginal due to minor differences in
the densities of the alcohols (Table 1).
Flash Point. Addition of alcohols (Table 1) into
pyrolysis liquids had a beneficial effect on the pour
point, but it also decreased the flash point (Figure 4) of
the liquid. The relative change in the flash point
diminished when the amount of added alcohol was
increased.
Chemical legislation in Finland limits the flash point
of a flammable liquid to 21 and 55 °C. In transportation
legislation the limit is 62 °C. The flash point of pyrolysis
liquids typically falls into this category,4,18 if the product
has been condensed at low temperature. The flash point
of forestry residue liquids is lower than that of pine
sawdust pyrolysis liquids, due to a larger amount of
volatile compounds in the forestry residue feedstock
(spruce, needles, bark). The flash point of pyrolysis
1582 Energy & Fuels, Vol. 18, No. 5, 2004 Oasmaa et al.

Figure 8. Aging of brown (stored) forestry residue liquid with various amounts of ethanol.

Table 2. Change in Alcohols during Aging of a Brown Forestry Residue Liquid

fresh liquid, wt % aged (24 h at 80 °Ca) liquid, wt % change, wt %
water MeOH EtOH IPA water MeOH EtOH IPA water MeOH EtOH IPA
BFRb 26.7 1.04 0 0 28 0.82 0 0 28 -27 0 0
BFR + 5 wt % EtOH 25.5 0.94 4.88 0 26.5 0.81 3.98 0 26 -16 -23 0
BFR + 10 wt % EtOH 24.3 0.91 9.34 0 25.4 0.77 7.73 0 25 -18 -21 0
BFR + 5 wt % IPA 25.5 0.94 0 5.19 26.6 0.75 0 4.44 26 -25 0 -17
BFR + 10 wt % IPA 24.3 0.89 0 10.3 25.4 0.71 0 8.74 25 -25 0 -18
a Correlates with changes upon 1 year of storage at 20 °C.6 b Brown forestry residue.

liquid can be affected both by feedstock choice and by

changing the liquid condensation conditions.5
Heating Value. Addition of alcohols increased the
heating value of pyrolysis liquid (Figure 5), which can
also be noticed by arithmetic calculations. The amount
of the increase depended on the heating value of added
alcohol (Table 1). With forestry residue liquids, the
solvents also improved the solubility of high energy
value16 extractives in pyrolysis liquids from the top
phase to the bottom phase (Figure 1), which caused an
additional increase in the heating value.
Effect of Alcohol Amount on Aging. Addition of
alcohol diminished the increase in viscosity of pyrolysis
liquids (Figure 6). Methanol was the most efficient agent
for decreasing aging, even though the differences be-
tween the used alcohols were small (Figure 7).
Figure 9. Change in ether-solubles (ESs, dry matter) with
There were some differences in chemical changes
and without alcohol during storage for pine pyrolysis liquids:
during the storage of pyrolysis liquids with or without6 [, pine 1; ], pine 1 + 5 wt % IPA; 9, pine 2; 0, pine 2 + 5 wt
alcohol addition (Figure 8). Addition of 2 wt % alcohol % EtOH.
did not have any significant effect on stability improve-
ment, but addition of 5 wt % alcohol prevented or Chemical Changes in Water-Soluble Fraction
retarded the aging reactions by a few months, especially during Storage. Acids. There was no significant
the reactions of water-soluble compound groups. With change in the amount of the main acids, acetic and
5 wt % alcohol addition, after 3-4 months storage the
formic acids, during 4-month storage of pyrolysis liquids
changes were fast, and within 6-7 months they reached
with or without6 alcohol addition.
the same level as without alcohol addition. Addition of
10 wt % alcohol prevented clearly the aging reactions Alcohols. The amount of alcohol in pyrolysis liquids
(Figure 8). The efficiency of alcohols decreased in the is very low (<1 wt %), but upon alcohol addition the
following order: methanol, ethanol, isopropanol. Diebold reactivity of this group was clearly seen. The amount
and Czernik8 drew a similar conclusion: a decrease in of alcohols decreased approximately by 20% (Table 2)
efficiency in the order methanol, acetone, methanol- during 1 year storage. The consumption of ethanol was
acetone (1:1), ethanol, methyl isobutyl ketone-methanol higher than that of isopropanol during storage. Because
(1:1), ethyl acetate. acids do not react, the decrease in alcohols may be
Fast Pyrolysis of Forestry Residue and Pine
Figure 10. Effect of alcohol type on chemical changes (%) in
the water-insoluble fraction: [, methanol; 9, ethanol; 2, IPA.
Figure 11. The correlation of viscosity with water-insolubles
of fresh and aged liquids with alcohol additions: 0, fresh
liquid; 9, aged liquid.
attributed to reaction of alcohols with aldehydes and/
or ketones to form acetals. These reactions are catalyzed
by acids (5-7 wt % volatile carboxylic acids in pyrolysis
liquids), and their formation could explain the stability
improvement by alcohol addition. Water is formed in
the reaction, which was also observed with pyrolysis
liquid.
Aldehydes and Ketones. Without any alcohol addition
the ether-soluble fraction (aldehydes, ketones, lignin
monomers) decreased steadily during aging.6 With
alcohol addition the reactivity of this fraction was
similar within the first 2-3 months of storage. However,
after that the alcohols seemed to protect aldehydes and
ketones toward further reactions (Figure 9), probably
due to acetal formation.
Anhydrosugars. Addition of alcohol stabilized little the
aging of the sugar fraction (anhydrosugars, anhydro-
oligomers), perhaps through acetal formation.
Chemical Changes in Water-Insoluble Fraction
during Storage. During the first six months of storage,
alcohols were found to retard significantly the increase
Energy & Fuels, Vol. 18, No. 5, 2004 1583
in the water-insoluble fraction of pine and forestry
residue pyrolysis liquids. An alcohol addition of 5 wt %
retarded the increase in water-insolubles by about 6
months. The major factor affecting changes in water-
insolubles was the HMM lignin fraction of water-
insolubles. After 6 months the water-insoluble fraction
started to increase and reached the same level as
without the alcohol addition. An addition of 10 wt %
alcohol retarded the changes in water-insolubles by
almost 1 year. Methanol reduced the change in water-
insolubles (Figure 10) best. Ethanol was more effective
than IPA. Increasing amounts of alcohols retarded the
aging reactions (Figure 10).
Correlations of Changes in Physical Properties
with Chemical Changes in the Liquid. Viscosity. As
earlier6 presented with pyrolysis liquids without any
alcohol additions, viscosity correlates with water-in-
solubles (Figure 11) also when alcohol is added to the
product liquid.
Conclusions
Addition of alcohols improved the homogeneity and
physical dilution of pyrolysis liquids through enhancing
the solubility of the hydrophobic compounds, which were
high molecular mass lignin and extractives. Other
beneficial effects of alcohols to the fuel oil quality of
pyrolysis liquids were the decrease in viscosity and
density and the increase in heating value. A disadvan-
tage was the decrease of flash point.
By improving the solubility of hydrophobic com-
pounds, alcohols also enhanced the separation of extrac-
tive-rich top layer in pyrolysis of forestry residue by
decreasing its volume and increasing the concentration
of extractives and solids in the top layer.
Alcohol addition decreased significantly the viscosity
and molecular mass increase during aging of softwood
pyrolysis liquids. The change in viscosity correlated well
with the change in the water-insoluble lignin-derived
fraction. With low (e5 wt %) alcohol additions, the aging
reactions were prevented for a few months. With higher
(g10 wt %) alcohol additions, the aging reactions were
retarded for almost 1 year. Methanol was the most
effective of the alcohols tested (methanol, ethanol,
isopropanol). Acetal formation of alcohols with alde-
hydes, ketones, and sugars was observed.
Acknowledgment. The work was funded by Tekes
under contract 40921/99, Fortum Oyj and by EU Con-
tract ERK5-CT1999-00011. Jukka-Pekka Nieminen and
Tuula Koskelo from Fortum are acknowledged for
valuable discussions. At VTT, Sirkka-Liisa Huru, Sirpa
Lehtinen, Jaana Korhonen, and Mirja Muhola are
acknowledged for the skillful analytical work, as are
those at Fortum Sirpa Hägg.
EF040038N