Review Paper

Removal of wood extractives as pulp (pre‑)treatment: a technological

review
Maximilian Lehr1 · Martin Miltner1 · Anton Friedl1

Received: 19 August 2021 / Accepted: 8 November 2021

© The Author(s) 2021  OPEN

Abstract
Wood extractives usually do not exceed five percent of dry wood mass but can be a serious issue for pulping as well as for
the pulp itself. They cause contamination and damages to process equipment and negatively influence pulp quality. This
paper addresses not only the extractives-related problems but also different solutions for these issues. It is an extensive
review of different technologies for removing wood extractives, starting with methods prior to pulping. Several wood
yard operations like debarking, knot separation, and wood seasoning are known to significantly decreasing the amount
of wood extractives. Biological treatment has also been proven as a feasible method for reducing the extractives content
before pulping, but quite hard to handle. During pulping, the extractives reduction efficiency depends on the pulping
method. Mechanical pulping removes the accessory compounds of wood just slightly, but chemical pulping, on the other
hand, removes them to a large extent. Organosolv pulping even allows almost complete removal of wood extractives.
The residual extractives content can be significantly reduced by pulp bleaching. Nevertheless, different extraction-based
methods have been developed for removing wood extractives before pulping or bleaching. They range from organic-
solvent-based extractions to novel processes like supercritical fluid extractions, ionic liquids extractions, microwave
technology, and ultrasonic-assisted extraction. Although these methods deliver promising results and allow utilization
of wood extractives in most cases, they suffer from many drawbacks towards an economically viable industrial-scale
design, concluding that further research has to be done on these topics.

* Maximilian Lehr, maximilian.lehr@tuwien.ac.at | 1Institute of Chemical, Environmental and Bioscience Engineering, Technische
Universität Wien, Getreidemarkt 9/166, 1060 Vienna, Austria.

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Graphical abstract

Keywords Extractives · Pulp · Removal · Treatment · Wood

Abbreviations TCF (bleaching) Totally chlorine-free (bleaching)

ASE Accelerated solvent extraction TDS Total dissolved solids
COD Chemical oxygen demand TMP Thermomechanical pulp
CTMP Chemi-thermomechanical pulp UEA Ultrasonic-assisted extraction
CTO Crude tall oil VOC Volatile organic compounds
D (bleaching) Chlorine dioxide (bleaching) Z (bleaching) Ozone (bleaching
E (bleaching) Alkaline extraction (bleaching)
ECF (bleaching) Elemental chlorine-free (bleaching)
EDTA Ethylenediaminetetraacetic acid 1 General introduction
FT-IR Fourier-transform infrared
spectroscopy Wood has been used from prehistory on and therefore
FT-NIR Fourier-transform near-infrared rated among the oldest materials of humanity. In the
spectroscopy beginning, wood was just used as fuel wood for simple
FT-RAMAN Fourier-transform RAMAN cooking and heating purposes. Over time, wood has
spectroscopy become more important as a building material, and since
GC Gas chromatography the industrial revolution, wood has also been intensively
GWP Groundwood pulp used for different industrial purposes [1, 2]. Nowadays,
HPLC High-performance liquid there is still a broad range of wood usages even in highly
chromatography developed countries—from the initial use as fuel wood,
HW Hardwood i.e., wood pellets, through to high-performance materials
ILs Ionic liquids for various applications, like wood polymer composites
MW Microwave (WPC) as a special structural material, xylose as base chem-
O (bleaching) Oxygen (bleaching) ical and lignin as biopolymer [3–6]. One important applica-
P (bleaching) Hydrogen peroxide (bleaching) tion is wood pulp—used for paper and cardboard—with
PHWE Pressurized hot-water extraction a global production of 184 million tons in 2017, excluding
RMP Refined mechanical pulp recovered paper [7].
SC-CO2 Supercritical extraction with carbon For producing paper, wood must be defibered, which is
dioxide known as pulping. Unfortunately, this defibration is quite
SCE Supercritical extraction challenging because of the complex structure of wood
SD Standard deviation with the lignin matrix. Therefore mechanical (includ-
SW Softwood ing thermomechanical and semi-chemical) or chemical

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methods are applied [8, 9]. In mechanical pulping, on the of different technologies for removing wood extractives,
one hand, the grinding and refining processes increase from conventional pulping and bleaching processes
the temperature, which leads to softening the lignin and through different organic-solvent-based extractions to
breaking the bonds between the fibers. On the other hand, several promising novel methods, including the utilization
chemical pulping achieves defibration by removing the of extracted wood extractives.
two cellulose-fiber-surrounding components, lignin,
and hemicelluloses [10]. Besides these three main com-
ponents, wood also contains many organic compounds. 2 Introduction to wood extractives
Since those organic compounds can be extracted with
organic solvents or hot water, they are called accessory The so-called wood extractives or accessory compounds
compounds or extractives [11]. Björklund Jansson and are a mixture of many low- and high-molecular-weight
Nilvebrant [12] define wood extractives as the chemical compounds that can be extracted from wood with hot
compounds that are extractable from wood with various water and organic solvents [11, 12, 18]. In living tress,
neutral solvents. With this definition, the accessory com- wood extractives play different important roles, which is
ponents of wood can be clearly differentiated from the a reason for the complex extractive’s composition. They
major structural components (cellulose, hemicelluloses, protect living trees against biotic attacks like insects and
and lignin), because neutral solvents, in general, do not fungi, and play an important role for the metabolism of
dissolve any of the main wood components. Cellulose trees (particularly the parenchyma resin which is described
can only be dissolved by special solvents that break the later on) [11, 12, 19–21].
intermolecular hydrogen bridge bonds [13, 14]. Hemicel-
luloses must be hydrolysed under acidic (sulfite pulping) 2.1 Content and classification
or alkaline (Kraft pulping) conditions. Apart from novel
methods, in conventional pulping lignin has to be cleaved The extractives content of wood, as well as the exact
and dissolved under alkaline conditions (Kraft pulping), extractives composition, depends on various factors. On
or sulfonated first (sulfite process) to make it soluble [15]. the one hand, the extractives vary not only between the
Although wood extractives usually do not exceed five two groups, softwoods (Gymnospermae, SW) and hard-
percent of dry wood mass on average (heartwood and woods (Angiospermae, HW) but also among species and
sapwood)—except some tropical and subtropical woods, even single trees, as shown by Ekeberg et al. [22]. On the
which contain significantly higher amounts of extractives other hand, there are differences in the accessory compo-
(up to 20 wt% based on dry wood)—they can be a serious nent’s content depending on the location inside the tree
issue for pulping as well as for the pulp itself. Therefore, and the growth conditions like the geographical site, age,
the removal of these wood extractives should be consid- and cutting season [11, 21, 23, 24]. Thus, universal state-
ered as pulp (pre-)treatment—not only for avoiding any ments about the extractives content in woods are almost
problems during pulping but also for ensuring satisfying impossible.
pulp quality [11, 16, 17]. Table 1 clearly shows the broad range of extractives
After a short introduction to wood extractives, includ- contents published by different authors. Besides different
ing an overview on analytical basics, this paper describes genera and species, the determined extractives content is
the effects of wood extractives on pulp and paper quality also influenced by several other factors, i.e., the sampling
and production. The removal of wood extractives as solu- locations inside the tree, which are often not included in
tion for these problems is addressed in the main part of literature (like in the references of Table 1). One signifi-
this paper later on. Beginning with wood yard operations cant variable is the extraction itself because different sol-
and biological treatment, this paper is an extensive review vents with different polarities result in different contents

Table 1  Extractives content Wood Class Genus Extractives content in wt% on a dry Samples References
of different economically matter basis
attractive genera obtained by
various experimental works Range Mean SD

HW Beech 1.0–1.6 1.3 0.2 3 [25–27]

HW Eucalyptus 1.4–2.5 2.2 0.5 4 [28–31]
SW Douglas fir 1.1–3.9 2.2 1.2 3 [31–33]
SW Pine 1.0–3.4 2.2 0.9 4 [34–37]
SW Spruce 1.0–4.9 3.0 1.4 4 [2, 38–40]

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and compositions of determined accessory compounds through evaporation of the volatile terpenes leaving the
[41]. Two wood-related factors important for pulping, solid resin acids (called rosin) as a hydrophobic mechani-
since they can easily be influenced, are listed by Nisula cal seal back on the tree surface [53]. Although wood does
[21]: tree age and the part of the tree. Older trees con- not contain phenol, compounds with one or more phenol
tain more extractives than younger ones; especially, the units occur in wood as structural phenolic components
extractives content of heartwood is higher in older trees (i.e., lignin) and non-structural ones [54]. The non-struc-
than in younger ones [23, 42–44]. Experiments of Miranda tural phenolic components are the phenolic extractives,
et al. [45], Morais and Pereira [46], and Tasooji et al. [47] one major group of wood extractives. They are essential
showed that heartwood, in general, contains significantly for the durability of wood since they protect the tree from
more extractives than the surrounding sapwood. Other different biotic attacks [20]. Björklund Jansson and Nilve-
parts like knots (the part of the branches inside the stem) brant [12] grouped the many different phenolic extractives
or the bark contain even more and different accessory to lignans, stilbenes, flavonoids, tannins, and tropolones.
compounds [48–50]. Björklund Jansson and Nilvebrant Since extractives are, as already mentioned, the acces-
[12] categorized the different wood extractives depending sory compounds of wood that can be extracted with hot
on the chemical composition and structure into aliphatic water or organic solvents, they can also be categorized
compounds, terpenes, and phenols (presented in Table 2), with their dissolution behavior. Depending on the solvent,
since many important properties, like dissolution behavior they can be divided into hydrophilic and lipophilic extrac-
and volatility, are similar within each of these groups. tives, which are also presented in Table 2 [55].
The aliphatic compounds and the terpenes can be The classification of wood extractives based on their
grouped to the so-called resin or pitch, including terpenes, dissolution behavior rates among the most used catego-
resin acids, fatty acids and esters, various alcohols, hydro- rization strategies, but this method also has problems.
carbons, and other neutral compounds [51]. There are sig- Both lipophilicity and hydrophilicity are just parame-
nificant differences in the resin composition depending ters—depending on various factors—not states [56, 57].
on the location of the resin inside the wood, inside paren- The polarity of solvents also depends on many parameters
chyma cells, or in resin canals. Parenchyma resin, located and is rather a spectrum than just two absolute conditions
in the parenchyma cells, serves as a reserve nutrient and “polar” and “non-polar” [58]. Therefore, the classification
therefore contains mainly fatty acids [52]. In growing trees, of the accessory compounds based on their dissolution
fatty acids mainly occur as esters (as fats when esterified behavior is just an approximate simplification. However, it
with glycerol in the form of mono-, di- and triglycerides, provides an opportunity for predicting dissolution behav-
as waxes when esterified with fatty alcohols, and as steryl iors and choosing the proper solvent(s) or mixture(s) for
esters when esterified with sterols) [12]. When cells die the extraction of the desired accessory compound(s),
during the transition from sapwood to the inner heart- rather polar solvents for hydrophilic extractives, and rather
wood or when the tree is felled, esters are enzymatically non-polar solvents for lipophilic extractives. For compar-
hydrolyzed into free fatty acids [21, 51]. The fatty acids ing determined extractives contents, a more reproduc-
in wood have lengths of 16–24 carbon atoms, with the ible way to group wood extractives is the classification
unsaturated fatty acids oleic, linoleic, and linolenic acid depending on the solvent itself, i.e. (hot-)water extractives,
(each with 18 carbon atoms) as the main components [12]. acetone extractives, or cyclohexane extractives [59, 60].
On the other hand, the resin inside resin canals, canal resin,
or oleoresin differs from the parenchyma resin in its com- 2.2 Determination and analysis
position. Oleoresin mainly consists of terpenoids, mainly
resin acids, dissolved in terpenes to ensure flowability. Wood can be analyzed for extractives directly with differ-
The function of canal resin is to seal wounds of the tree ent spectroscopy methods. This fast and non-destructive

Table 2  Classification of wood extractives based on their dissolution behavior, chemical composition, and structure ( adapted from ref. [12])
Lipophilic extractives Hydrophilic extr
Aliphatic compounds Terpenes Phenols

Free fatty acids Sterols Lignans

Esterified fatty acids (i.e., mono-, di-, triglycerides, waxes, steryl esters) Mono-, sesqui- and diterpenes Stilbenes
Fatty alcohols Terpenoids Flavanoids
Hydrocarbons Tannins
Tropolones

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measurement allows classifying and comparing wood 2.3 Effects on pulp and paper quality
species and wood treatments in terms of different wood and production
compounds, i.e., certain extractives. Wagner et al. [61] suc-
cessfully applied Fourier-transform RAMAN spectroscopy The accessory compounds are extracted from wood in
(FT-RAMAN), Fourier-transform infrared spectroscopy the papermaking process to a certain amount. Particu-
(FT-IR), and Fourier-transform near-infrared spectroscopy larly lipophilic extractives such as fatty acids and resin
(FT-NIR) for this purpose. Similar qualitative analyses were acids tend to agglomerate in the process water form-
carried out by Schnabel et al. [62] with FT-NIR for larch ing so-called pitch deposits [9, 72]. In Kraft pulping, the
wood. However, spectroscopy methods are still not the alkaline conditions enable saponification of the glycerol
right choice for quantifying wood extractives and require esters to soluble soaps. On the contrary, other lipophilic
further research [61–63]. extractives like sterols and sterol esters cannot be saponi-
The two standards T204 [59] and NREL/TP-510–42,619 fied and still form hydrophobic deposits [73]. The ratio of
[60] describe how to determine the extractives content unsaponifiable to saponifiable components is, therefore,
quantitatively. Wood shall be extracted with one or more an important indicator of pitch formation in Kraft pulp-
solvents (depending on the desired group(s) of extrac- ing. A higher ratio (for example, silver birch, which has one
tives). These solvents shall be evaporated afterward so that of the highest ratios among pulpwood species) indicates
the residue can be weighed for calculating the extractives pitch problems [74] because the deposits stick to process
content. Even though the evaporation shall be done under equipment, causing contamination and piping blockages
vacuum and low temperature, the volatile components, [75]. Pitch also sticks to different parts of the papermak-
particularly (mono)terpenes, are mostly also evaporated ing machines and stains the felts and canvas, even lead-
and therefore usually not included in the extract weight ing to major failures like web breaks of the machine [76].
[59, 60]. Due to their volatility, terpenes, in general, do Hence, pitch deposition originating from wood extractives
not play an essential role for pulps anyway. Thus, neglect- is responsible for reduced production levels, higher oper-
ing their contribution to the extractives content is mainly ating costs, and higher equipment maintenance costs of
accepted, especially when analyzing woods for (develop- papermaking processes [77]. In Kraft pulp mills, economic
ing) pulping (methods) [12]. losses due to pitch problems are assumed to account for
However, wood extractives can be quantified directly 1–2% of sales [78].
out of the extract without evaporating the solvent first Once pitch deposits become released from the equip-
with several chromatographic methods like gas chroma- ment, they contaminate the pulp in the form of dark spots,
tography (GC), high-performance liquid chromatography specks, and streaks, lowering the quality of the final prod-
(HPLC), size-exclusion chromatography, supercritical fluid uct [79, 80]. Additionally to dark spots, specks, and streaks,
chromatography, and thin-layer chromatography [64]. GC extractives are considered to have a negative influence
is the most widely used technique for analyzing the acces- on the color and bleachability of pulps [81, 82]. Also, the
sory compounds of wood with high selectivity and sensi- oxidation products of some accessory compounds, par-
tivity [65, 66], even though the derivatization prior to the ticularly polyphenols, lead to the darkening of wood and
actual measurement includes some time-consuming steps pulp when exposed to sunlight and oxygen [82]. Pereira
[67]. Nisula [21], for example, successfully quantified wood et al. [20] highlighted stilbenoids as the phenolic com-
extractives in her extensive work with long- and short-col- pounds that darken wood in the presence of sunlight,
umn gas chromatography; resin acids, fatty acids, sterols, bringing up some problems when producing paper. Wei
diterpenoids, juvabiones, lignans, stilbenes, and flavonoids et al. [83] isolated the phenolic extractives of locust wood
with long-column GC, the bigger steryl esters, triacylglyc- and observed color changes also when exposed to heat.
erols, and oligolignans with short-column GC. Poljanšek However, chromophores as the UV/VIS absorbing groups
et al. [68], on the other hand, has recommended HPLC as responsible for the color of wood cannot be attributed
the method of choice for analyzing particularly phenolic exclusively to phenolic wood extractives [84]. They also
wood compounds. For lipophilic extractives, the resolu- originate from lignin to a large extent and sometimes
tion of HPLC is unfortunately not high enough to separate even from organometallic extractive complexes [84, 85].
some individual wood extractives, particularly sterols and Especially heat- and light-induced color changes of wood
fatty acids [21]. and pulp result from complex reactions of hemicelluloses,
Although the content of lipophilic extractives in wood is lignin, and extractives [85].
in general significantly lower than the hydrophilic one [69, Besides the negative impact on color and bleachabil-
70], methods for analyzing lipophilic extractives are more ity, wood extractives are also responsible for the odor
important in pulp and paper manufacture since they cause of the pulp [86]. Ghadiriasli et al. [87] identified various
many problems like sticky deposits [55, 71]. volatile organic compounds (VOC), including terpenes

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and degradation products from fatty acids and lignin, another important effect of wood extractives. This must
as odor-active compounds in oak wood, while Schreiner be taken into account for treating the contaminated waste
et al. [88] stated more precisely that fatty acid degrada- streams of the papermaking process, especially because
tion products represent about two third of all the odor- there is increased focus on biotechnological processes for
active compounds in pine wood. Among all fatty acid generating by-products out of waste streams like sludge
degradation products, aldehydes play an essential role as [101] or fines [102]. Also, for conventional treatment of
odor-active compounds because their odor threshold is pulp mill sludge, wood extractives shall be removed by
very low, and their smell is generally considered highly hydrothermal treatment, for example, to enhance anaero-
unpleasant [12, 89]. Aldehydes are not part of the original bic digestibility [103]. The accessory compounds of wood
wood extractives but formed through an auto-oxidation of should thus be removed already during or even prior to
unsaturated fatty acids, called lipid oxidation, catalyzed by pulping to avoid any further treatment in the papermak-
enzymes and heavy metal ions in wood [90, 91]. Although ing process.
different aldehydes are formed through these lipid oxida-
tion processes, hexanal as a linoleic acid oxidation product
accounts for most of the aldehydes content [90]. Today’s
3 Removal of wood extractives during wood
solution to deal with the odor from lipid oxidation in pulp
yard operations
and paper is using chelating agents like ethylenediami-
netetraacetic acid (EDTA) to inhibit the catalyzing effect
Regardless of any subsequent pulp pre-treatment or the
of heavy metal ions [12, 90]. However, EDTA is considered
pulping itself, there are several opportunities for removing
a risk for the aquatic ecosystem because it influences the
wood extractives at the wood yard in advance. The main
heavy metals bioavailability and remobilization processes
tasks of wood yards include debarking the logs, chipping
in the environment [92, 93]. Munn et al. [93] even con-
them (except groundwood pulping), screening the chips,
cluded in the European Union’s risk assessment report
and storing the wood [104]. The following sections explain
about EDTA that there is a need for limiting the environ-
the possible influences of these process steps on the wood
mental risks of EDTA. However, in conventional wastewater
extractives content.
treatment plants, sufficient degradation of EDTA cannot be
achieved [92]. EDTA containing process waters must there-
fore undergo special treatment before releasing them into 3.1 Removal of bark and knots
the environment, leading to higher process costs [94, 95].
Environmental legislation has led to higher wastewa- Log debarking is, in general, the first process step at
ter treatment requirements and, consequently, multiple wood yards. It removes the dirt on the logs’ outside and
reuses of process waters in the papermaking industry. ensures that the resulting pulp is free of any bark [10]. On
This system closure decreases the wastewater treatment the other hand, it is also an efficient method for reducing
costs and creates new challenges due to the accumula- the accessory compounds of the used raw material since
tion of wood extractives in process waters [67]. Naicker the content of both lipophilic and hydrophilic extractives
and Sithole [96] observed increasing extractives concen- is usually very high in the bark. Among different species,
tration and chemical oxygen demand (COD) of the pro- wood extractives account for 20–40% of the dry matter of
cess water with decreasing fresh water consumption in bark [23]. The experiments of Arisandi et al. [105] showed
their experiments. Other issues with system closure are that eucalyptus bark contains not only more extractives
corrosivity and toxicity of process waters, mainly due to than sapwood or heartwood but also more of every ana-
wood extractives, and more precisely because of phenolic lyzed group of lipophilic extractives. Salem et al. [106] con-
compounds together with resin acids [12, 97]. Krilov and firmed the findings with SW, showing that particularly fir
Gref [98] explained some corrosion effects with the abil- and spruce bark contains up to 3 times as much lipophilic
ity of some phenolic wood extractives to form iron che- extractives than the wood itself. Balaban and Uçar [107]
lates. More specifically, Hazlewood et al. [99] stated that compared the content of the accessory compounds of oak
the phenolic catechols together with resin acids highly wood with the one of the corresponding bark using differ-
increase the corrosivity of black liquor from the Kraft pro- ent polar and non-polar solvents. All the bark extracts con-
cess. On the contrary, other wood extractives like palmitic tained more extractives than the wood ones did [107]. The
acid (a saturated fatty acid) were found to decrease cor- high extractives content of bark would negatively influ-
rosivity [99]. Similar findings were published by Singh ence pulp quality and pulping; including extended cook-
and Anaya [100], who even found significant differences ing times and increased bleaching chemical consumption.
between some HW and SW species when pulping them Wood debarking prior to pulping has therefore become
with the Kraft process. Besides corrosivity, toxicity is a well-established process. Nowadays, relatively low-cost

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drum debarkers are among the most used technologies, the trees and continues during storage, in the shape of
reaching final bark contents below 1% [104]. chips and even entire logs, as shown in the experiments
Also, in debarked wood, the accessory compounds are of Gutiérrez et al. [117] and Silverio et al. [80]. The reaction
not evenly distributed. For example, the inner heartwood rate of all the chemical and biochemical reactions occur-
is richer in both lipophilic and hydrophilic wood extrac- ring during storage is highly dependent on environmental
tives than the outer sapwood [108, 109]. The starting conditions, i.e., temperature, UV irradiation, wind, rain, and
points of branches inside the stem referred to as knots, storage conditions like ventilation, protection with cov-
contain even more extractives than all the surrounding ers and the duration of storage [23]. The main reactions
stemwood [50]. Pohjamo et al. [110] reported significantly include oxidation of wood resin, hydrolysis of glycerides
larger quantities of the phenolic flavonoids in knots than and other esters, loss of volatile components, and micro-
in the stem of the same trees. Other hydrophilic com- bial degradation [12]. Logs and particularly wood chips
pounds like lignans can account for even 20% of the mass require well-suited storage conditions.
of the knots [111]. Willför et al. [112] analyzed knots for Otherwise, chip deterioration and wood decay due
lipophilic wood extractives and found large amounts from to sap stain and a fungal attack occur [104]. Ramnath
4.5 wt% up to 32 wt%. Besides the higher extractives con- et al. [118] even found variations in bacterial and fungal
tent, knots also differ in the mechanical properties from communities on frozen stored wood chips. They showed
wood since they are much denser and contain shorter that storing the chips at − 20 °C had similar effects on the
and stiffer fibers. As so-called reaction wood, they have decrease of lipophilic wood extractives than seasoning
to withstand higher mechanical stress [21]. They are not does. During six months of storage, 25–44% reduction of
fully cooked in chemical pulping and therefore leave the lipophilic extractives was observed [118].
digester as large and dark impurities. Subsequent pressure To summarize, wood seasoning can be applied as a
screens remove the knots (called knotting) from the pulp strategy for reducing wood extractives without a signifi-
stream [113]. However, the high extractives content of cant decrease in the quality of the wood, but wood might
knots can negatively influence the entire pulp and paper be attacked by microorganisms, resulting in chip dete-
manufacturing process, as already explained. Removing rioration and mass losses of cellulose and hemicelluloses
knots even before pulping should thus be considered. [16]. Seasoning offers no control over the microbial species
When chipping the logs, knots mainly result in over-thick growing on wood chips, leading to unpredictable wood
chips because they are adamant and rigid [114]. Based on effects, like loss of brightness or strength. Nevertheless,
this finding and the fact that knots are denser than stem- methods for controlled seasoning have been developed
wood, Eckerman and Holmbom [115] developed a method using microorganisms that effectively remove extractives
for separating knots from the oversized chip fraction. This without causing discoloration or strength loss [119]. This
method, called “ChipSep”, relies on the phenomenon that biological treatment method includes different bacteria
dried knots are heavier than water, whereas dried stem- strains and fungi, such as white-rot fungi, and is referred
wood, is lighter than water, provided that the dry matter to as biopulping. The employed microorganisms can also
content of the dried knots and stemwood is at least 85% digest lignin to a certain extent [120, 121]. Dorado et al.
(advantageously at least 87%), according to the patent of [122] proved white-rot fungi to decrease the amount of
Eckerman and Holmbom [115]. Hence, knots containing accessory wood compounds successfully. Their experi-
wood sinks in water while knots-free wood rises towards ments removed up to 51% of resin acids and up to 87% of
the water surface [115]. free fatty acids from pine wood within two weeks, while
total loss of wood mass was below 12% [122]. Similar find-
3.2 Wood storage and biological treatment ings were published by Thao et al. [123], who removed up
to 89% of fatty acids and fatty alcohols and 79% of free
Besides debarking and chipping, one primary purpose of sterols from acacia wood within 30 days by means of a
a wood yard is wood storage. Delivered logs and cut wood white-rot fungus. Košíková et al. [124] investigated four
chips are stored to ensure continuous supply of the subse- yeast strains concerning their wood extractives removal
quent pulping processes and compensate for any fluctua- behavior. They could decrease the extractives content up
tions in raw material supply [104]. Moreover, wood storage to 63% and the fatty and resin acids up to 78% within four
is even recommended to decrease the extractives content weeks. Experiments on bacterial strains done by Burnes
of the wood. During this wood seasoning, the accessory et al. [125] and Kallioinen et al. [126] showed that the total
compounds of wood are reduced through volatilization, wood extractives content can be bacterially decreased up
oxidative processes, and enzymatic hydrolysis in tree cells to 41% (the lipophilic extractives even up to 67%) within
and by microorganisms [116]. In fact, the content of wood two weeks without any visible discoloration of the wood.
extractives starts to decrease immediately after felling However, the experiments about biopulping mentioned

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above showed that microbiological treatment has to be also lipophilic extractives like fatty and resin acids [130].
carried out in a bioreactor under controlled conditions and Resin acids and phenolic compounds contribute the most
takes quite long (several weeks) compared to mechanical to the toxicity of mechanical pulping process waters [12].
or chemical pulping (minutes to hours).

4.2 Chemical pulping
4 Extractives’ removal through conventional
pulping Compared to mechanical pulping, in chemical pulping,
lignin is rather removed by degradation and dissolution
The two conventional technological principles to produce than just softened. Depending on the chemicals used
paper pulp out of wood are mechanical and chemical pro- for cooking the wood chips, there are mainly two types
cesses, differing in the yields (80–95% at mechanical pulp- of processes: the sulfite process and the sulfate or Kraft
ing comparing to 45–55% at chemical pulping), properties, process as the dominant pulping process [131]. Johansson
and economic potential [8]. et al. [132] stated as early as 1987 that most of the world’s
The defibration during pulping leads to exposure of chemical pulp is produced by the Kraft process because
the resin channels, making oleoresin accessible for disso- of several advantages, including versatility in dealing with
lution and chemical reactions. On the one hand, this can different raw materials and efficient recovery of cooking
lead to pitch problems at mechanical pulping, but on the chemicals. Sixta et al. [9] defined Kraft pulping 2006 still
other hand, it enables deresination in chemical pulping the dominating chemical pulping process with almost 90%
[12]. The parenchyma resin, on the contrary, is more dif- of the produced pulp worldwide, although sulfite pulp-
ficult to remove because the pulping liquors must diffuse ing has accounted for approximately 70% of the world’s
into the parenchyma cells, dissolve the resin or form soap dissolving pulp production [9]. Especially for dissolving
micelles with the sterols and esters and diffuse out again pulp, wood extractives are important disruptive factors
afterwards. This process is enhanced by breaking the cell since they decrease the reactivity of cellulose with car-
walls through chemical or mechanical pulping [21]. bon disulfide when producing viscose out of dissolving
pulp [133]. The accessory compounds of wood are usu-
4.1 Mechanical and semi‑chemical pulping ally mainly removed through chemical pulping but lead
to increased consumption of cooking chemicals since they
Mechanical pulping can be divided into two main catego- compete with lignin and hinder its removal [81].
ries, depending on the defibering method; groundwood The pH-flexible sulfite process uses aqueous sulfur
pulp (GWP) obtained by grinding processes and refined dioxide and a base for cooking the wood chips. The domi-
mechanical pulp (RMP) produced with refining processes nating sulfite process in Europe is the acid magnesium
[8]. In semi-chemical pulping processes, the wood under- bisulfite process [10]. While hemicelluloses are removed
goes mild chemical treatment preceded by a mechanical directly through hydrolysis during a cooking process
refining step [2]. The most important refining process is called digestion, lignin must be sulfonated by the bisulfite
thermomechanical pulping (TMP). Before refining, the ions to make it soluble in the cooking liquor [15]. In addi-
wood chips are heated with steam (to 100–130 °C) to sof- tion to hemicelluloses and lignin, most of the accessory
ten the lignin [10, 127]. The thermal treatment can also be compounds of wood are also removed through sulfite
combined with a chemical treatment to produce chemi- pulping. Unfortunately, some extractives participate
thermomechanical pulp (CTMP), representing the transi- in the sulfonation reactions, competing with lignin and
tion from mechanical to chemical pulps [2, 128]. increasing cooking liquor consumption [81]. Nevertheless,
Except for CTMP, the mechanical pulp contains most of Rodrigues et al. [133] removed with the acid sulfite pro-
the original lignin and still many accessory compounds cess nearly 85 wt% (based on initial dry wood) of acetone-
[82]. However, the high temperatures of the defibering soluble wood extractives, leaving mainly just extractives
processes lead to partial degradation of cellulose and consisting of fatty acids and sterols in the unbleached
hemicelluloses. The resulting saccharides are then dis- pulp [133]. Nevertheless, Sixta et al. [9] listed the extrac-
solved in the process water. Increased temperatures tives content of sulfite pulp and Kraft pulp for both spruce
(above approximately 160 °C) at the TMP process even and beech wood, showing that the sulfate process even
enhance these mechanisms, as shown by the work of removed about twice as much extractives as the sulfite
Schneider et al. [129]. Besides saccharides, also extractives one, independent of the wood class (SW/HW). Duan et al.
are liberated to a certain amount and released into the [134] published similar findings and attributed them to the
process water afterwards. These extracted accessory com- alkaline conditions of the Kraft process, which promote
pounds do not only include hydrophilic extractives but saponification and subsequent extractives removal.

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In Kraft pulping, lignin is depolymerized by cooking aims to minimize mass loss, lignin of mechanical pulps is
wood chips with an alkaline cooking liquor consisting of rather just brightened than removed compared to chemi-
caustic soda and sodium sulfide. The resulting phenolic cal pulps. This so-called lignin-preserving bleaching is
fragments are then dissolved into the cooking liquor [135]. accomplished commercially, primarily with hydrogen
For producing dissolving pulp, hemicelluloses have to be peroxide and/or sodium dithionate [142].
removed from wood by prehydrolysis prior to pulping. The Alkaline hydrogen peroxide bleaching as lignin-
prehydrolysis can be done with diluted acid (acid-prehy- preserving bleaching method decreases the lipophilic
drolysis) or just hot water, called autohydrolysis because extractives content of TMP just slightly [143]. Ekman and
wood typically releases acetic acid through autohydrolysis Holmbom [144] examined alkaline peroxide bleaching
[136]. Although autohydrolysis is technically a hot-water of mechanical pulps with spruce groundwood. Hydro-
extraction, Da Silva Morais et al. [137] and Li et al. [138] philic extractives were oxidized almost wholly, whereas
found an increased extractive content, especially at more resin acids were just partly oxidized and fatty acids even
severe prehydrolysis conditions. Da Silva Morais et al. [137] unaffected [144]. As already mentioned, chemical pulp-
explained that phenomenon with the partial degrada- ing typically eliminates far more wood extractives than
tion of some macromolecules (mainly hemicelluloses) at mechanical pulping, showed by Rodrigues et al. [133],
high prehydrolysis temperatures. Therefore, the macro- with a removal rate of 85 wt% (based on initial dry wood)
molecules are mobilized, meaning that the degradation acetone-soluble wood extractives through the acid sulfite
products can easily be extracted in the case of subse- process. With subsequent E–O–P bleaching, they removed
quent extractions. When determining the extractives con- further 11 wt%, leaving just four wt% of the initial extrac-
tent gravimetrically by evaporating the solvent from the tives in the bleached pulp, mainly consisting of fatty acids
extract, the degradation products are then distorting the and sterols [133]. España Orozco et al. [145] achieved com-
extractives content. As already mentioned, experiments parable results with oxygen-reinforced alkaline extraction
showed, that the sulfate process removes about twice as of mixed HW sulfite pulp, followed by Z and P bleaching.
many extractives as the sulfite one due to saponification. They decreased the gravimetric acetone extract of pulp by
The alkaline black liquor converts resin and fatty acids into 68% through the TCF bleaching sequence, with oxygen-
soluble sodium soaps [12]. However, Dunlop-Jones et al. reinforced alkaline extraction as the most effective stage,
[139] published that in typical Kraft pulping, only half of leaving mainly just sterols and sterol esters in the pulp. For
the potentially saponifiable wood resin was saponified lipophilic extractives (determined by GC–FID), the highest
in the digester. Moreover, Shin et al. [140] found sterols, drop was observed after Z bleaching (− 38%). Freire et al.
steryl esters, and fatty acids as the main compounds in [146] and Gutiérrez et al. [147] compared different bleach-
residual Kraft pulp extractives. Therefore, there is a need ing sequences with eucalyptus Kraft pulp. They observed
to further eliminate the remaining accessory wood com- that unsaturated sterols and fatty acids were extensively
pounds through pulp bleaching, for example, removing degraded during D and Z bleaching but only partially
the unsaturated fatty acids by oxygen delignification [140]. degraded during O and P bleaching. The wood extractives
removed during bleaching are not only degraded and oxi-
4.3 Pulp bleaching dized but also dissolved to a certain extent into bleaching
and washing liquids, as shown through analysis of pitch
Extended cooking for removing color in pulp originating deposits in bleaching stages by Del Rio et al. [75] and eval-
from lignin, extractives and other colored impurities would uation of precipitated extractives on bleached Kraft pulp
significantly decrease pulp quality due to enhanced cel- by Koljonen et al. [148]. For avoiding such problems dur-
lulose degradation [141]. Thus, pulp bleaching has been ing bleaching, the extractives content can be reduced by
developed, which is defined by Sixta et al. [141] as a chemi- extrations before bleaching or even before pulping which
cal process for removing the color sources in pulps, has is explained in the following chapter.
been introduced. To quantify the results of these bleaching
processes, brightness has been established as an indica-
tion of the pulp’s whiteness [10]. Starting with chlorine 5 Alternative methods for pulping
as the main bleaching agent, in the 1980s, so-called ele- and removing extractives
mental chlorine-free (ECF) bleaching processes have been
developed to substitute chlorine with chlorine dioxide Currently, high-purity cellulose fibers are commercially
(D). The recent development is the totally chlorine-free produced from wood with the sulfite or the Kraft process.
(TCF) bleaching process, applying oxygen (O), hydrogen These pulping methods are considered cellulose-first
peroxide (P) and/or ozone (Z) as bleaching agents, and an strategies since fractionation of biomass usually targets
alkaline extraction stage (E) [141]. Since mechanical pulp high-quality cellulose. The resulting lignin has different

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properties than the native one (i.e., it is less reactive) and a vapor bypass in the middle. There are many siphon cycles
is mainly burned for energy recovery instead of using as a within the entire extraction period, with fresh solvent for
by-product [149]. The approach for using all the compo- each cycle [59, 60]. The long period for complete extrac-
nents of the biomass feedstock as products are so-called tion can be compensated with high pressures. National
lignocellulose biorefineries. Besides pulping, lignocellu- Renewable Energy Laboratory [60] describes a method to
lose biorefineries also include separation and purification use a speed extractor with high pressures, which allows
processes, which contrasts the increased revenue streams quantitatively extracting the wood in a few minutes. This
with the high capital and operating costs of up to 20–50% method is called accelerated solvent extraction (ASE).
of the total capital and operating costs of biorefineries Table 3 compares the ASE with the traditional Soxhlet
[150]. However, there is growing interest in organosolv extraction, as well as different solvents.
pulping processes using organic solvents instead of inor- Vek et al. [156] showed that with the same solvent(s),
ganic pulping liquors. The recovery of satisfying by-prod- ASE yields comparable amounts of extractives but takes
ucts is easier than in the Kraft process [151]. just 10–20% of the time of Soxhlet extraction. The rea-
son for the difference in extraction time is that Soxhlet
5.1 Organosolv pulping and extraction with organic extraction is carried out under atmospheric pressure and
solvents temperatures between 7 °C and 10 °C below the boiling
point of the solvent compared to temperatures above the
Kleinert and Tayenthal [152] successfully carried out boiling point and pressures higher than 100 bar at the
experiments as early as 1931 for fractionating different speed extraction [158, 160]. The solvent itself, on the con-
woods with aqueous ethanol. This so-called organosolv trary, can have a significant influence on the determined
pulping uses—as already mentioned—organic solvents. extractives content. It can be seen in Table 3 that solely
It is a two-stage process where hydrolysis degrades hemi- extracting with non-polar solvents like Cyclohexane is
celluloses, and lignin is dissolved into the organic solvent not appropriate for quantitatively removing wood extrac-
to a certain extent depending on the pulping conditions tives. Non-polar solvents mainly extract lipophilic acces-
[153]. Johansson et al. [132] showed that the organosolv sory compounds of wood, which are less in amount than
process has considerable potential in terms of delignifi- the hydrophilic ones, as already mentioned. To enhance
cation selectivity. Compared to pulps produced through the quantitative removal of wood extractives, non-polar
conventional pulping, organosolv SW pulps can have solvents should be mixed with miscible polar solvents, or
higher yields at equal kappa numbers, which indicates a subsequent extraction with a polar solvent should be
the lignin content of the pulp [132]. Good delignification added [69, 156, 159]. Moodley [157] and Schwanninger
of the organosolv process was also proved by the experi- and Hinterstoisser [160] could increase the amount of
ments of Botello et al. [28] and Kirci and Akgül [154]. They extracted material up to 150% with a hot-water extrac-
concluded that organosolv pulping could be a suitable tion in addition to the organic solvent extraction step.
alternative for producing dissolving pulps with very high On the other hand, one must be aware of autohydroly-
cellulose contents. Moreover, organosolv pulps can have sis occurring during hot-water extraction, dissolving
better optical and strength properties than conventional considerable amounts of wood compounds that are not
Kraft pulp [155]. wood extractives by definition, i.e., hemicellulose degra-
Another advantage of the organosolv process is the dation products [161]. Krogell et al. [162] and Song et al.
effective removal of extractives from wood. As already [163] removed considerable amounts of hemicelluloses
described, the accessory compounds of wood can be from the wood meal by pressurized hot-water extraction
extracted with (aqueous solutions of ) organic solvents. (PHWE) within 20 min. Increasing the wood particle size
This is even considered as the method of choice for the significantly decreased the amount of total dissolved sol-
exclusive extraction of accessory wood compounds. The ids (TDS) [162, 163]. The influencing factor particle size
two most commonly used standards, T204 [59] and NREL/ was also investigated by Bertaud et al. [158] at extractions
TP-510–42,619 [60], for quantitatively determining the of coarse-crushed wood and groundwood with acetone
wood extractives content, are based on a mild extrac- and cyclohexane and significantly influenced the extrac-
tion with organic solvents through a Soxhlet apparatus. tion behavior. A lower particle size led to sharply higher
According to the standards, the wood shall be extracted amounts of extracted wood extractives [158]. In terms
with organic solvents at ambient pressure and low tem- of process design for an industrial application of organic
peratures (below the solvent’s boiling point) for a long solvent extraction for removing wood extractives, dif-
period (up to 24 h). The extraction works automatically in ferent extraction methods and conditions should thus
a closed loop with a boiler on the bottom, a condenser on be compared using the actual wood particle size of the
the top, and the extraction thimble with a siphon as well as process later on. Thurbide and Hughes [164] carried out

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Table 3  Lab scale extractions of groundwood with different methods and solvents
Wood genus Extraction 1 Extraction 2 Amount of Reference
extracted extrac-
Method Solvent(s) Time in min Method Solvent(s) Time in min tives in wt%

Beech1 Soxhlet Cyclohexane 240 – – – 1.0 [156]

Beech1 Soxhlet Cyclohexane 240 Soxhlet Methanol 360 5.7 [156]
Beech1 ASE Cyclohexane 15 – – - 1.0 [156]
Beech1 ASE Cyclohexane 15 ASE Methanol 15 5.3 [156]
Eucalyptus2 Soxhlet Acetone 240–300 – – – 3.1 [157]
Eucalyptus2 Hot-water Water 180 – – – 4.6 [157]
Eucalyptus2 Hot-water Water 180 Soxhlet Acetone 240–300 5.2 [157]
Eucalyptus2 Hot-water Water 180 Soxhlet Ethanol/Toluene 240–300 6.7 [157]
(1/2)
Eucalyptus3 Soxhlet Acetone 240–300 – – – 2.2 [157]
Eucalyptus3 Hot-water Water 180 – – – 4.8 [157]
Eucalyptus3 Hot-water Water 180 Soxhlet Acetone 240–300 5.4 [157]
Eucalyptus3 Hot-water Water 180 Soxhlet Ethanol/Toluene 240–300 5.4 [157]
(1/2)
Fir4 Soxhlet Acetone 360 Soxhlet Acetone/Cyclohex- 480 4.9 [158]
ane (1/9)
Fir4 ASE n-Hexane 20 ASE Acetone/Water 20 5.9 [158]
(95/5)
Pine5 Soxhlet Acetone 360 Soxhlet Acetone/Cyclohex- 480 5.7 [158]
ane (1/9)
Pine5 ASE n-Hexane 20 ASE Acetone/Water 20 9.5 [158]
(95/5)
Pine6 Soxhlet Cyclohexane 360 – – – 4.1 [159]
Pine6 Soxhlet Cyclohexane 360 Soxhlet EtOH 360 4.8 [159]
Pine6 Soxhlet Acetone 480 – – – 4.6 [159]
Pine6 Soxhlet Cyclohexane/EtOH 360 – – – 4.6 [159]
(2:1 v/v)
Pine6 Soxhlet Cyclohexane/EtOH 360 Soxhlet EtOH 360 4.8 [159]
(2:1 v/v)
Spruce7 Soxhlet Acetone 360 Soxhlet Acetone/Cyclohex- 480 4.8 [158]
ane (1/9)
Spruce7 ASE n-Hexane 20 ASE Acetone/Water 20 6.9 [158]
(95/5)
Spruce7 Soxhlet Benzene/EtOH 540 – – – 2.3 [160]
(2:1 v/v) + EtOH
(abs.) + EtOH (95
vol%)
Spruce7 Soxhlet Benzene/EtOH 540 Hot-water Water 180 4.2 [160]
(2:1 v/v) + EtOH
(abs.) + EtOH (95
vol%)

Description: The amount of extracted wood extractives in wt% is based on initial dry wood
1
Fagus sylvatica L.; 2Eucalyptus grandis; 3Eucalyptus nitens; 4Abies alba; 5Pinus pinaster; 6Pinus nigra; 7Picea abies

experiments comparing Soxhlet extraction and ASE with Soxhlet extraction is just a lab-scale method because of
TMP instead of wood meal as the standards T204 [59] and the long extraction period and the high energy demand
NREL/TP-510–42,619 [60] require. The obtained extractives for recycling the vast amount of organic solvent needed.
content was quite similar, meaning that even at industrial Nevertheless, organic solvent extraction, in general,
wood particle sizes like TMP, long extraction times can be would technically be an interesting technology for remov-
compensated by high temperatures and pressures and ing wood extractives as pulp (pre-)treatment as well as
vice versa [164]. for pulping itself. Shin et al. [165], for example, could

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significantly decrease the chromophore groups of aspen As it can be seen in Table 4, supercritical extraction and
Kraft pulp just by extracting the pulp with organic sol- steam explosion can yield significantly more extractives
vents to remove residual extractives. Baptista et al. [166] than a Soxhlet extraction. Still, one should be aware that
extracted wood with organic solvents even prior to Kraft SCE and especially steam explosion degrades hemicellu-
cooking. The results showed better bleachability and less loses to a certain extent [170]. This means that the extrac-
chlorine dioxide consumption to reach the same bright- tives content gravimetrically determined by evaporating
ness levels when bleaching the pulp [166]. the solvent from the extract can incorrectly be too high
Despite all the advantages of extracting wood with because the evaporation residue contains extractives
organic solvents and aqueous solutions of organic sol- and hemicellulose degradation products. Nevertheless,
vents, like good pulp properties and superior capabilities Demirbaş [175], for example, extracted four times more
of removing lignin as well as extractives (depending on the extractives and ten times more amount of fatty acids with
process conditions), it is unfortunately not an economic SCE than the Soxhlet extractions. The big advantage of
pulp (pre-)treatment method [167]. Notably, organic sol- steam explosion is the lower capital costs and the higher
vent recycling has a significant impact on the energy con- energy efficiency, which makes it suitable for lab-scale and
sumption of the process, as it remains one of the main commercialized applications from an economical point of
challenges towards an economically viable design [168, view [176]. Despite the benefits of SC–CO2 as low solvent
169]. costs and low temperatures, the exceptionally high pres-
sure of up to several hundred bars is a barrier for upscaling
this process to an industrial scale [177].
5.2 Novel extraction and fractionation methods One relatively new approach to overcome the disad-
vantages of using volatile organic solvents, or applying
In the organosolv process, as already mentioned, not only high pressures for SCE or steam explosion, for example, are
the accessory compounds of wood are extracted, but also ionic liquids (ILs) which are also considered to have lower
lignin and hemicelluloses by breaking down the internal environmental impacts [178]. ILs are salts and therefore
bonds. The lignin obtained as a by-product of this process composed of anions and cations. The properties resulting
is characterized by high purity and quality [170]. On the from this composition are thermal stability, remarkable
other hand, organic solvents are associated with flam- solvating ability, nonvolatility, and near-zero vapor pres-
mability, volatility, toxicity, environmental hazards, and sure [179]. Especially in biorefineries, ILs were proven to
increased costs [171, 172]. Thus, extensive research has be an effective solvent for fractionating wood and even
been done to develop various (pre-)treatment processes dissolving entire wood particulates after an autohydrolysis
with different methods and solvents, particularly environ- step, as shown by Deb et al. [180]. On the other hand, Papa
mentally friendly or green solvents [172, 173]. et al. [181] could extract significant amounts of the ter-
One alternative method with green solvents is super- pene α-pinene from pine wood applying IL treatment, and
critical extraction (SCE), more precisely, the extraction with Kilulya et al. [182] demonstrated the removal of lipophilic
supercritical fluids. The advantages of using supercritical wood extractives from dissolving pulp with ILs in amounts
fluids are the low viscosity, high diffusivity, high dissolving comparable to other extraction technologies. Additionally,
power, and low surface tension, leading to higher solvent ILs exhibit favorable behavior when producing food sup-
mass transfer when penetrating cell wall layers. Typical plements or drugs out of wood, i.e., antioxidants. Pinkert
SCE solvents are water, carbon dioxide, and mixtures with et al. [183] successfully applied food-additive-derived ILs
organic co-solvents [171]. Supercritical extraction with car- for extracting wood lignin without dissolving or degrading
bon dioxide (SC-CO2) has become an established technol- cellulose. However, the drawback was the requirement of
ogy since ­CO2 is non-toxic, non-flammable, and recyclable. recycling the ILs more than 100 times for an economically
Furthermore, carbon dioxide is considered non-polar and feasible process [183]. The reason are high costs for ILs due
dissolves lipophilic compounds, i.e., resin and fatty acids to synthesis, purification, and downstream processing pro-
[158]. Another alternative process is steam explosion, cedures, which are currently the limiting factors for using
which is technically the treatment of wood through hot ILs at a large scale [179]. Other disadvantages of ILs are
steam under pressure with a subsequent pressure drop to poor biodegradability and biocompatibility, and usually,
atmospheric pressure. This leads to the destruction of cell fossil resources are needed to produce ILs [184]. In 2007,
wall layers and easier solubilization of wood compounds Fukaya et al. [185] developed so-called “Bio-ILs” completely
[174]. Table 4 compares different supercritical extractions derived from biomaterials to overcome these problems.
and steam explosion treatments with Soxhlet as the refer- However, Yiin et al. [184] concludes that further research
ence method for quantitatively extracting the accessory has to be done on Bio-ILs, because studies are still limited
wood compounds. in 2021.

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 SN Applied Sciences

Table 4  Groundwood extraction results of SCE and steam explosion compared to Soxhlet extraction
Wood genus Extraction 1 Extraction 2 Amount of Reference
extractives in
Method Solvent(s) Temp. in °C Pressure in bar Time in min Method Solvent(s) Temp. in °C Pressure in bar Time in min wt%

Fir1 Soxhlet Acetone N/A N/A 360 Soxhlet Acetone/ N/A N/A 480 4.9 [158]
Cyclohexane
(2021) 3:886

(1/9)
Fir1 SCE CO2 60 200 90 – – – – – 4.8 [158]
Fir1 SCE CO2 60 300 90 – – – – – 5.7 [158]
Spruce2 Soxhlet Acetone N/A N/A 360 Soxhlet Acetone/ N/A N/A 480 4.8 [158]
Cyclohexane
(1/9)
Spruce2 SCE CO2 60 200 90 – – – – – 6.0 [158]
Spruce2 SCE CO2 60 300 90 – – – – – 5.8 [158]
Pine3 Soxhlet Acetone N/A N/A 360 Soxhlet Acetone/ N/A N/A 480 5.7 [158]
Cyclohexane
(1/9)
Pine3 SCE CO2 60 200 90 – – – – – 7.4 [158]
Pine3 SCE CO2 60 300 90 – – – – – 8.5 [158]
Juniper4 SCE CO2/EtOH (8/2 120 250 60 – – – – – 3.2 [174]
v/v)
Juniper4 Soxhlet EtOH/Water N/A N/A 240 SCE CO2/EtOH (8/2 120 250 60 4.1 [174]
(95/5) v/v)
Juniper4 Steam explo- Water 235 32 3 SCE CO2/EtOH (8/2 120 250 60 5.9 [174]
sion v/v)
| https://doi.org/10.1007/s42452-021-04873-1

Beech5 Soxhlet Acetone N/A N/A 1080 – – – – – 2.5 [175]

Beech5 SCE Acetone 240 60–65 30 – – – – – 9.6 [175]

Description: The amount of extracted wood extractives in wt% is based on initial dry wood
1
Abies alba; 2Picea abies; 3Pinus pinaster; 4Juniperus communis L.; 5Fagus orientalis

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One of the drawbacks of all the treatment methods and antioxidant activity. Additionally, the extract exhibited
mentioned above is the heat transfer resistance limiting antibacterial behavior against different bacterial strains,
the process efficiency. Microwave (MW) technology, which i.e., Escherichia coli, suggesting the usage to control plant
has received increased attention in recent years, can over- and human pathogens [195]. Hosseini Hashemi and Jahan
come this limitation because MWs penetrate materials and Latibari [196] found that walnut-heartwood-extractives-
deliver energy throughout the material volume. Therefore, coated poplar wood had significantly less mass loss after
this so-called in-core volumetric heating generates heat exposing it to white-rot fungus than untreated poplar
directly inside the volume instead of heat transfer through wood. Belt [197] observed pine knot extract to have a sig-
conduction and convection when conventionally heating nificant antifungal character, but suggested more study
from outside [186]. The advantages are enhancement of before approving pine extractives as preservative chemi-
reaction rate, reduction of the reaction time, increased cals. However, wood extractives have enormous potential
product yield, and less formation of by-products, provided in wood protection because they have many different anti-
that the solvent and/or the biomass are high-microwave- microbial properties, are renewable, and are less eco-toxic
absorption materials [187]. For example, Xu et al. [188] than chemical biocides [198].
proved MW technology as an efficient method by liquefy- Pine extractives have been used by humans for hun-
ing about 75% of the initial wood in methanol at 180 °C in dreds of years for paintings and coatings, particularly for
just 15 min. However, applying microwave extraction can caulking seams of wooden ships [199]. Since distilling
lead to local overheating since composition, geometry, wood extractives, the two resulting products, turpentine
and size affect microwave power distribution, making it and rosin, have served as important platform chemicals.
challenging to up-scaling the process [171]. Today, the overwhelming predominance of petroleum-
Another novel method applying high-energy radiation based chemicals has led to much less usage of wood
is ultrasonic-assisted extraction (UEA) [189]. The principle extractives than their potential would be. Nevertheless,
behind UAE is disrupting the solid structure with ultrasonic the rising demand for renewable materials and chemicals
waves [190]. In detail, the ultrasonic waves degrade cell increases interest in wood extractives [200].
walls and rupture bonds between lignin, hemicelluloses, Currently, wood extractives resulting from thermome-
and cellulose [171]. He et al. [191] proved the ultrasound- chanical pulping are wasted because today’s approaches
induced mechanical damage of wood structure in his work for managing them with additives during pulping do not
and observed a significant reduction of wood extractives. allow efficient recovery [201]. In Kraft pulping of SW, on
Wang et al. [192] could increase the extraction efficiency the other hand, the volatile accessory compounds of wood
even by factor 2.6 when extracting hemicellulosic and can be isolated, yielding approximately 10 kg/ton of pulp.
phenolic compounds from bamboo wood with water. These volatile extractives mainly consist of monoterpenes
Similar findings were published by Sillero et al. [193], who and are distilled for removing impurities. The resulting
successfully increased the extraction of phenolic wood fraction is called turpentine, with the major constituent
extractives from different HW species with intensified UEA. α-pinene. Turpentine is mainly used for producing chemi-
Although UEA has been successfully proved as an effective cals, fragrances, and flavors. The non-volatile accessory
extraction method, much more research has to be carried compounds of wood, mainly soaps of resin acids and fatty
out for using UEA in large industrial-scale processes, i.e., acids, are separated from the cooking liquor after the Kraft
optimization in terms of ultrasound power input and fre- cooking process. The addition of sulfuric acid liberates the
quency [189]. free fatty acids, giving crude tall oil (CTO) with a yield of
up to 50 kg/ton of pulp [202]. The CTO production in 2018
was about 2.5 million metric tons worldwide. From that
6 Utilization of wood extractives amount, globally, two million metric tons were refined,
while the rest was used for heat and power generation
When applying extractive methods as pulp (pre-)treat- [203]. The distillation products of CTO are 30–50% pitch,
ment, the accessory compounds of wood cannot only be 30–50% fatty acids, and 15–35% resin acids [204]. In the
removed but also isolated as side products since they have rosin fraction (colophony), Holmbom [205] found 62–80%
many interesting properties. of the resin acids from the crude tall oil feed.
Wood extractives play an essential role in protecting liv- From a product point of view, CTO products can be
ing trees against fungal attacks and other pests like insects divided into chemical intermediates, biodiesel, and tall oil
[19]. Especially phenolic extractives and resin acids act as pitch. Pitch is currently just used for heat and power gen-
natural fungicides of trees [12, 194]. The extract of Delonix eration, whereas the chemical intermediates, rich in resin
regia (also known as flame tree or flamboyant) in the study acids, are used as adhesives and in paintings and printing
of Salem et al. [195] showed inhibition of fungal growth inks [203]. The fatty acids of tall oil can be converted into

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SN Applied Sciences (2021) 3:886 | https://doi.org/10.1007/s42452-021-04873-1 Review Paper

biodiesel by esterification with the challenge of remov- seasoning after chipping can also reduce the accessory
ing the remaining sulfur [206]. However, tall oil biodiesel compounds even prior to pulping. Still, it requires well-
is one way to add more value to CTO. In Finland, the first suited storage conditions and long storage times for signif-
industrial-scale CTO biodiesel plant worldwide produced icantly lowering the extractives content. Otherwise, wood
more than 100,000 tons of biodiesel per year, already in decay and/or fungal attack might lead to quality losses.
2015 [207, 208]. On the other hand, several studies proved different fungi
and bacterial strains to effectively decrease the extractives
content by more than 60% [124] without decreasing wood
7 Concluding remarks and outlook quality. However, the main drawback for an industrial-scale
use is the requirement of controlled conditions in a bio-
Wood extractives are still a big issue for the pulp and paper reactor for several weeks required for such a biological
industry. They lower pulp quality and cause many prob- treatment.
lems for the pulping process itself due to the formation of Conventional pulping also removes wood extractives to
sticky deposits. Some established process steps already a certain extent. At mechanical pulping, just a small part
decrease the extractives content to a certain extent, i.e., of hydrophilic and lipophilic wood extractives are released
debarking, chemical pulping, and bleaching. Addition- into the process water, but Rodrigues et al. [133], for exam-
ally, many alternative technologies for reducing accessory ple, could remove in their work nearly 85 wt% (based on
wood compounds have been developed to replace or sup- initial dry wood) of acetone-soluble wood extractives by
plement the conventional process steps, as shown in Fig. 1. the acid sulfite process. Kraft pulping was found to remove
Wood debarking as a well-established technology is even more extractives than the sulfite process does. Fur-
a very effective method to reduce the wood extractives thermore, pulp bleaching plays an important role in
content. In bark, wood extractives account for 20–40% decreasing the amount of accessory wood compounds.
[23] of the dry matter compared to less than in wood. With the right choice of pulping stages, the residual
Research about the extractives content of different wood extractives content can be lowered significantly, leaving
parts showed that besides bark, also knots contain large mainly just sterols and sterol esters in the bleached pulp.
amounts of extractives from 4.5 wt% up to 32 wt% [112]. Additionally, a number of organic-solvent-based
Knots are also denser and stronger than heart- and sap- pulping and extraction methods have been developed
wood, which allows rejecting knot-containing chips. Wood to remove the accessory compounds from wood and

Fig. 1  Overview of established

and alternative methods for Wood yard operaons
removing wood extractives Debarking Knot removal Wood seasoning
at pulp production. Descrip-
tion: Blue solid-line frames
are established conventional
Biological treatment
processes, green double-line
frames are novel alternative Fungal treatment Treatment with bacteria strains
methods. Solid lines inside
the frames separate differ-
ent options at the respective
Chemical Mechanical and Alternave
process stage; dashed lines
indicate possible combinations pulping semi-chemical pulping
of different methods Kra process Organosolv
TMP GW
MW technology and UAE

(incl. pre-hydrolysis) pulping

Sulfite process CTMP
Novel
Extracon fraconaon
Extracon with organic solvents methods,
MW, UAE

i.e. SCE, steam

Novel extracon methods, i.e. SCE,
explosion, ILs
steam explosion, ILs

Pulp bleaching
Oxygen Hydrogen peroxide Ozone Alkaline extracon

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Review Paper SN Applied Sciences (2021) 3:886 | https://doi.org/10.1007/s42452-021-04873-1

pulps. The extraction with organic solvents, as one of Author contributions ML carried out the literature research and
the most used extraction techniques for woody biomass, drafted the work, MM and AF provided literature, and substantively
revised the work. All authors read and approved the final manuscript.
even allows quantitatively removing wood extractives
and is therefore also the method of choice for determin- Funding The authors declare that no funds, grants, or other support
ing the extractives content. However, the typical organic were received during the preparation of this manuscript.
solvents like ethanol, acetone, or cyclohexane are quite
volatile and highly flammable. This has led—together Declarations
with economic challenges for solvent recycling—to the
development of novel extraction methods, ranging from Conflict of interest The authors declare that they have no competing
alternative solvents like supercritical fluids or ILs through interests.
MW technology as an alternative heating method to UAE Consent for publication All the references used for the tables in this
for enhancing the extraction by mechanically damaging work are provided in or below the tables. Figure 1, as well as the
cell wall structures. All these extraction-based methods graphical abstract, were created by the authors.
are not only technically suitable for removing wood
extractives but can also be used as an alternative pulp- Open Access This article is licensed under a Creative Commons Attri-
ing method for wood fractionation and delignification, bution 4.0 International License, which permits use, sharing, adap-
as proved by many studies. Moreover, the extraction- tation, distribution and reproduction in any medium or format, as
long as you give appropriate credit to the original author(s) and the
based removal of wood extractives allows using the source, provide a link to the Creative Commons licence, and indicate
extracted accessory compounds of wood, i.e., as natu- if changes were made. The images or other third party material in this
ral biocides or platform chemicals. However, further article are included in the article’s Creative Commons licence, unless
research is required to overcome the problems of novel indicated otherwise in a credit line to the material. If material is not
included in the article’s Creative Commons licence and your intended
extraction methods which are currently hindering the use is not permitted by statutory regulation or exceeds the permitted
application for removing wood extractives on an indus- use, you will need to obtain permission directly from the copyright
trial scale. On the one hand, there is a need for better holder. To view a copy of this licence, visit http://​creat​iveco​mmons.​
synthesis and recycling processes to reduce operating org/​licen​ses/​by/4.​0/.
costs (ILs). On the other hand, there are several technical
issues, like high pressures (SCE) and irradiation power
input and distribution for large geometries (MW tech- References
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