Biomass Conversion and Biorefinery (2025) 15:1377–1391

https://doi.org/10.1007/s13399-023-05156-y

ORIGINAL ARTICLE

Influence of pulping conditions on the pulp yield and fiber properties

for pulping of spruce chips by deep eutectic solvent
Alan D. Pérez1,2 · Yagnaseni Roy1,3 · Constantijn Rip1 · Sascha R. A. Kersten1 · Boelo Schuur1

Received: 18 September 2023 / Revised: 15 November 2023 / Accepted: 16 November 2023 / Published online: 21 December 2023
© The Author(s) 2023

Abstract
The chemical pulping of wood chips using deep eutectic solvents (DES-pulping) has emerged as an alternative technology
to conventional pulping in the paper industry, allowing the production of pulp in combination with the recovery of lignin
and sugars for valorization. A challenge in the development of this technology is the understanding of how the operating
conditions influence the crucial pulp manufacturing parameters such as delignification percentage, pulp yield, and fiber
quality. This work is focused on investigating the effect of operating conditions such as cooking temperature, cooking time,
liquor-to-wood ratio, initial water content on DES, type of mixing, the addition of a pre-treatment step (pre-impregnation
of DES into the wood chips) to cooking process, and DES composition (lactic acid:choline chloride, lactic acid:sodium
chloride, and lactic acid:sodium bromide) on the cooking of wood chips by DES. A shortcut quality evaluation parameter
(Q), defined as the product of the fiber length and the degree of delignification quantified the quality of the pulping process
in a single value, shows values similar to a reference unbleached kraft pulp for cooking at 130 °C in a range of cooking times
from 3 to 4.5 h at a L/W of 10:1 by using lactic acid:choline chloride DES. More elaborate property analysis on the fibers
showed that several of the the quality-indicating properties of the fibers (coarseness, shape factor, fibril area, and crill index)
are comparable with typical sulfite pulping fibers.

Keywords DES · Spruce chips · Delignification · Fiber length · Lactic acid · Choline chloride

1 Introduction then washed and screened to remove the black liquor (the
liquor after cooking that contains solubilized and depolym-
Kraft pulping is the most widely used method for producing erized lignin and hemicellulose). The pulp is then used to
wood pulp for papermaking on an industrial scale. In this make a variety of paper products, such as office paper [1–3].
process, the wood chips are cooked at high pressure and The main advantage of the kraft pulping process is its abil-
temperature in a solution called white liquor, comprised of ity to produce strong, high-quality pulp from a wide variety
sodium hydroxide (NaOH) and sodium sulfide (­ Na2S), which of wood species. However, it also has some disadvantages,
causes the lignin and the hemicellulose to depolymerize and such as that lignin is not obtained as byproduct, but burned
dissolve, so that it can be separated from the cellulose fibers in the recovery boiler, and the high energy requirements of
[1, 2]. The resulting pulp comprised mainly of cellulose is the pulping process [2, 4]. While the energy is supplied by
burning the lignin, and in itself this is a highly integrated
process, alternative options that yield more products at low
* Boelo Schuur emissions would be desired.
[email protected]
Sulfite pulping is another industrial-scale process that
1
Sustainable Process Technology Group, Faculty of Science uses solutions of sulfite and bisulfite ions to dissolve lignin
and Technology, University of Twente, Enschede, and produce cellulose fibers from wood. This process is
The Netherlands also used to make high quality paper products (high bright-
2
Institute for Chemistry and Bioanalytics, University ness with smooth surface and resistant to wear and tear).
of Applied Sciences and Arts Northwestern Switzerland, Compared to kraft pulping, sulfite pulping has the advan-
Hofackerstrasse 30, 4132 Muttenz, Switzerland
tage of producing paper with better color and printability,
3
Centre for Sustainable Technologies, Indian Institute as well as a higher cellulose yield, while the fiber strength is
of Science (IISc), Bangalore 560012, India

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1378 Biomass Conversion and Biorefinery (2025) 15:1377–1391

a bit lower. However, sulfite pulping is more expensive and methods [15, 27]. On the other hand, it has been observed
requires more energy and wastewater treatment than kraft that delignification with DES using carboxylic acids with
pulping [3]. halide salts has a significantly faster delignification than the
These factors have led to increased interest in alterna- acid alone [28], showing that the halide anion is responsible
tive pulping methods that are environmentally friendly and for a catalytic effect [29]. Another study investigated the use
energy efficient. These include soda pulping and organosolv of DES for wood chip fractionation and found that ethylene
pulping, each with its own advantages and disadvantages. glycol:choline chloride could efficiently extract hemicellu-
Soda pulping uses sodium carbonate ­(Na2CO3) instead of loses and lignin to produce a cellulose-rich pulp, but this
sodium hydroxide (NaOH) and sodium sulfide (­ Na2S), which was not used for paper making [30]. More recent research
is used in kraft pulping to depolymerize the lignin in wood developments include use of ternary DES mixtures, although
chips. Although soda pulping has a lower environmental they usually also not aim for making paper [31–34].
impact than kraft pulping, the resulting pulp may be weaker. Only in a few studies investigating the use of deep eutec-
Organosolv pulping uses organic solvents such as ethanol tic solvents (DES) for pulping have fiber properties been
or methanol to break down the lignin in the wood chips. examined. For example, it was shown that delignification
While some authors have reported this process to produce using choline chloride-based DES can effectively delig-
a similar quality pulp with a less ­CO2 emissionscompared nify wood at lower temperatures and shorter cooking times
to kraft pulping, it is currently more expensive and energy than traditional kraft pulping [13], and the Eucalyptus fiber
intensive [1, 3]. length was not reducing much [13]. However, the fibers were
Current research is also being conducted on biorefinery already very short at the start (0.81 mm), which might be
approaches, enzymatic and mechanical pulping, and ionic due to the type of starting materials, being slabs of only
liquid (IL) delignification [2, 5–9]. Biorefinery approaches about 20 mm. We hypotize that in that work [13], the fibers
focus on the efficient conversion of lignocellulosic biomass were already damaged, so this paper does not provide rel-
into a range of bio-based products [10, 11], while enzymatic evant information for paper making. Similarly, although the
and mechanical pulping aim to reduce the use of chemicals work of Jablonski and co-workers showed importantly that
in the pulping process [1, 2, 4–6, 12]. fiber properties depend on the type of DES, they started with
Cooking of wood chips with deep eutectic solvents kraft lignin, [35], and no information on the delignification
(DESs) have been investigated as a potential pulping method of wood was gained.
alternative to conventional methods that often rely on harsh DES has been used for pulping of wood chips/slabs [13,
chemicals and high energy input [13–17]. DESs are compos- 15, 36] and also for the delignification of Asplund fibers
ite solvents comprised by hydrogen bond donors and accep- [37]. The length-weighted average fiber length of the result-
tors [15, 18] to form a mixture that shows melting at much ing DES-fibers from Eucalyptus slabs was 0.68 mm achiev-
lower temperature than would be expected at ideal behav- ing a pulping yield of 5.33% [13] while the degree of polym-
ior, for example > 50 °C lower [19], alternatively people do erization, (which is directly related with the fiber length)
consider the pure component melting points to express that of the obtained fibers in other study (that uses Eucalyptus)
DESs have a pronounced melting point depression as com- was higher than that one from kraft pulp [15]. On the other
pared to the pure components that make up the DES [15, hand, it has been shown that it is possible to obtain fibers
18, 20]. Many DESs show low toxicity, biodegradability, with lengths of about 0.6 to 0.8 mm, a lignin content of
and a relatively low cost, making them attractive alterna- about 14%, and a pulp yield of about 50% using DES for
tives to conventional and non/conventional organic solvents delignification of Asplund [37].
(e.g., ionic liquids). The cooking of wood with DES not Typical kraft pulp fibers obtained from the pulping of
only allows the delignification of the wood, preserving to spruce are much longer than other wood species while DES
a certain extent the cellulose fiber characteristics, but also pulping provides smooth delignification. However, it is well
allows the application of a biorefinery approach by valoriz- known that there are several parameters that influence the
ing the dissolved lignin and hemicellulose polymers in the paper quality. Hence, it can be expected that cooking of
DES-dark liquor (DES after cooking) [15, 17, 18, 21–23]. spruce wood chips with DES is a promising delignification
Several studies have investigated the use of DESs for del- method, but it is still unclear whether high enough quality
ignification of wood. Formic acid:benzyltriethylammonium cellulose fibers can be produced for making paper. Further
chloride [13], lactic acid:choline chloride [14, 15, 24, 25], research is needed to study the effect of operating conditions
ethylene glycol:choline chloride [16, 26], and urea:choline (cooking time, cooking temperature, type of lactic acid-
chloride [24] are some of the DESs used in these studies. based DES, type of agitation, water content, and addition of
Delignification efficiencies with DESs vary depending on a preliminary impregnation step) on the DES pulping yield,
the type of DES and conditions used, and can reach val- the pulp lignin content, fiber length, and some other fiber
ues that are comparable with conventional delignification properties. These aspects have been studied in this work.

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Biomass Conversion and Biorefinery (2025) 15:1377–1391 1379

2 Materials and methods flask (typically 450 g of aqueous LA). Afterward, the HBA
was added in a specific HBD:HBA mass ratio (10:1 unless
2.1 Materials mentioned otherwise, referred to as the weight of the aque-
ous LA) to the same flask. Then, the DES (HBD + HBA)
Lactic acid (90% aqueous solution) was purchased from was stirred with a magnetic stirring plate (Salmenkipp,
VWR Chemicals, and pure lactic acid crystals were kindly at 360 rpm) for 1 h at room temperature. After stirring,
donated by Corbion. Choline chloride (> 98%, solid phase), LA:ChCl DES produces a single liquid phase, while in the
anhydrous sodium chloride (ACS reagent ≥ 99%, solid LA:NaCl and LA:NaBr DESs, a fraction of the salt replacing
phase), sodium bromide (BioUltra ≥ 99.5%, solid phase), the HBA remains solid.
and sulfuric acid (95–98 ACS reagent) were purchased from
Sigma Aldrich. Ethanol (100%) was purchased by Boom 2.3 DES‑pulping of wood (spruce) chips
B.V. Wood chips (spruce) were supplied by Sappi Austria
Produktions-GmbH & Co. KG. Moisture content in wood The DES-pulping of spruce chips consists of a cooking
chips was quantified by weighing its mass on a wet basis and stage followed by separation of DES-dark liquor from
a dry basis (after oven drying) in triplicate. Mondi AG, Aus- cooked solid material (including a pre-washing of cooked
tria, supplied flash dried kraft pulp made of Norway spruce solids with an ethanol solution), then is followed by a dis-
and Scotts pine in approximate ratio of 3:1. This sample, integration step (to liberate the delignified fibers) and then
serving as reference, had a kappa number of approximately a screening stage to wash out the remaining DES-dark liq-
45 (acid-insoluble lignin content of 9%). uor entrapped in the solid cooked material and separate the
undercooked wood chips, pulp, and fines using size-specific
sieves (Fig. 1).
2.2 Preparation of DES For cooking, 450 g of DES is added to the 1-L round-
bottomed flask placed in the cooking setup (see Fig. 2,
Lactic acid (LA) was used as the hydrogen bond donor description in Sect. 2.3.1). Afterwards, the heating man-
(HBD) compound of the DES, whereas choline chlo- tle, water flow (in the condenser), and stirring are turned
ride (ChCl) was used as the main hydrogen bond accep- on. Temperature is set to the cooking temperature (typi-
tor (HBA). Sodium bromide (NaBr) and sodium chloride cally 130 °C), and the stirring is set at 360 rpm. Once the
(NaCl) also were investigated as alternative salts to the HBA cooking temperature is reached, 45 g (dry basis) of wood
compound. The HBD compound was added to a 1-L glass chips are added into the round-bottom flask to achieve a

Fig. 1  Stages of the DES-pulping process at lab-scale. The red cate the disintegration step, and the blue dashed lines indicate the
dashed lines indicate the cooking step. The green dashed lines indi- washing and screening step
cate the first wash and separation step. The yellow dashed lines indi-

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1380 Biomass Conversion and Biorefinery (2025) 15:1377–1391

Fig. 2  Cooking setups used in

this work. Left side mechanical
stirring setup, right side rotary
evaporator setup

liquor-to-wood (L/W) mass ratio of 10:1, and the timer 2.3.1 Variations in cooking setups and conditions
is started to measure the cooking time of the experiment
(which usually was 3 h). Two different setups were used to investigate the effect of
After cooking, the solid material and the DES dark-liquor the operating conditions on the delignification of the wood
were separated from each other by a 53-µm sieve, while 1 L chips. The first setup is a 1-L round-bottom flask with a
of a 50 wt% aqueous ethanol solution was used to wash the 4-neck lid equipped with a heating mantle (Electrothermal),
remaining DES dark-liquor from the solid cooked material and mechanical stirring. An open condenser was applied
(green dashed line stage in Fig. 1). for reflux of the produced vapor and a thermocouple. The
The cooked solid material from the sieve and 4 L of hot motor was coupled to an impeller (half-moon style) within
water (50–60 °C) were collected in a bucket while stirring the round-bottom flask, and the thermocouple is set to a PID
with a crossed blade radial impeller and a IKA power con- for temperature control with the heating mantle. The second
trol for 5 min at 275 ± 15 rpm (yellow dashed line stage setup comprised a rotary evaporator (Heidolph VV2000)
in Fig. 1). Next, the screening step was carried out using equipped with an oil bath, 1-L round-bottom flask, and a
three different sieves (2.8 mm, 200, and 53 µm) to separate condenser. The main difference was thus that in the first
the undercooked wood chips, pulp (cellulose fibers), and setup, mechanical stirring with an impeller was applied, and
fines (smaller cooked solid material of 200 µm) as is shown in the second setup, no internal stirring was done, but the
in Fig. 1. In the first stage of screening, a 2.8-mm sieve whole vessel was rotated to induce mixing of the liquid.
was used to separate the undercooked wood chips from the The temperature for delignification was controlled by the
smaller cooked wood material (pulp and fines). The washing oil bath, while the 360-rpm rotation of the flask induced
liquid containing the solids from the first screening stage the mixing of the DES and the wood chips, and a condenser
were poured through a 200-µm sieve to separate the pulp without receiving flask was applied to reflux the produced
from the liquid and the smaller cooked wood material using vapor during cooking.
about 8–10 L of hot water (50–60 °C). The pH of the col- All cooking experiments were performed at atmospheric
lected washing liquid was measured with pH indicator paper. pressure, and the effect of the cooking temperature on delig-
When the pH of the washing liquid was stable (indicating nification and fiber length was investigated at 90, 110, 125,
6–7 pH), the pulp washing was stopped. The collected wash- and 130 °C (fixing the liquor-to-wood ratio at 10:1 and 3 h
ing liquid was then poured through the 53-μm sieve and of cooking). In another series of experiments, the cooking
washed with a maximum of 2 L of hot water (no more water time was investigated at 2, 2.5, 3, 3.5, 4, and 4.5 h (fixing the
is required to achieve a pH of the washing liquid of approxi- liquor-to-wood ratio at 10:1 and the cooking temperature at
mately 6–7), resulting in no more than 12 L of hot water 125 °C). Four levels of the liquor-to-wood ratio (5:1, 10:1,
being used in total for the screening step. 15:1, and 20:1) were investigated at 130 °C during 4.5 h
Undercooked wood chips (cooked solid wood material of cooking. The impact of the initial water content on the
above 2.8 mm), pulp (cooked solid wood material between DES was studied at 2.4, 7.05, and 10.48 wt%. The water
2.8 mm and 200 µm), and fines (cooked solid wood material content on the DES was measured by Karl-fisher method
between 200 and 53 µm) were collected in separate glass once it was prepared. Experimentally, for an initial water
bottles and oven-dried at 105 °C for at least 48 h for dry content on the DES higher than 13 wt%, it was not possi-
basis yields quantification. ble to reach a temperature higher than 130 °C in the batch

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Biomass Conversion and Biorefinery (2025) 15:1377–1391 1381

cooking at atmospheric pressure while using the reflux con- Valmet Fiber Image Analyzer (Valmet FS5). All samples
denser because of the vapor–liquid equilibrium limitations. were analyzed in Duplo. The length-weighted average of
In the mentioned experiments, LA:ChCl was applied in a the fiber on the pulp, the coarseness, fiber shape, fibril area/
10:1 mass ratio. perimeter, and crill index are reported in this work.
The impact of changing the DES composition was inves-
tigated using sodium chloride and sodium bromide (within 2.6 Definitions
a DES with LA) in mass ratios of LA:NaCl of 100:1, 10:1,
and 5:1 and LA:NaBr of 10:1 at 130 °C, 4 h of cooking, and The performance of the delignification process was quan-
a L/W ratio of 10:1. For all experiments mentioned so far, tified in all experiments by measuring the percentage of
the setup with mechanical stirring was used. undercooked wood chips (UC), the pulp yield, and the per-
The influence of the mechanical stirrer or the absence of centage of fines of the screened solid material after the DES-
that was studied for a range of conditions using the rotary cooking as follows:
evaporator setup (RE), using a varying L/W ratio at 130 °C,
during 4 h of cooking. Additionally, the impact of an impreg- UWC (wt%) =
Mass of UWC (dry basis)
× 100%
nation step (previous to the DES-cooking) was investigated. Initial wood chips mass (dry basis)
The wood chips were left in the DES at room temperature
overnight before cooking. Then, the DES-cooking was per- Pulp yield (wt%) =
Mass of pulp (dry basis)
× 100%
formed at two different cooking times (2 and 3 h) in the RE Initial wood chips mass (dry basis)
setup at a L/W ratio of 10:1, and 130 °C.
Mass of f ines (dry basis)
Fines (wt%) = × 100%
2.4 Lignin content quantification Initial wood chips mass (dry basis)

The lignin content (LC) on the spruce chips (after milling) On the other hand, the solids yield (ratio of solids after
and on all achieved pulps were experimentally quantified cooking compared to the amount of wood chips before
using the Klason method. Extractives and ashes were not cooking, all on dry basis) and wood conversion (amount of
quantified. Therefore, the reported LC in this work is the wood chips that is converted in pulp, fines, or dissolved com-
sum of acid-insoluble lignin (AIL), extractives, and ashes, pounds in DES) were also used to compare results (defined
unlike some other reports, where pulp is extensive washed below).
with solvents before AIL quantification [38]. The LC quan- Solids yield (wt%) = UWC + Pulp yield + Fines
tification method was described elsewhere [37]. In this
method, 300 ± 10 mg material was impregnated with 3 mL (
Mass of UWC (dry basis)
)
of sulfuric acid (72 wt%) in a pressure tube at 30 °C, stirring Wood conversion (wt%) = 1−
Initial wood chips mass (dry basis)
× 100%

the mixture every 10 min for 1 h. Then, 84 mL of milli-

Q water was added to the pressure tube. The pressure tube The degree of delignification (DD) as well as the normal-
was closed and placed in an autoclave for 1 h at 121 °C for ized fiber length (NFL) were calculated similar as they were
hydrolysis. After hydrolysis, the tube was cooled down in defined elsewhere [37]:
a water bath till it reached room temperature. Afterwards, LCwood − LCpulp
the hydrolyzed material was poured into a filter paper in a DD(−) =
Buchner funnel setup. The material over the filter was rinsed LCwood
with 100 ± 10 mL of milli-Q water. Then, the filter with the
solid materials was placed in an aluminum tray and dried FLpulp
NFL(−) =
in an oven at 105 °C. After drying, the solid material was FLref
weighed, and the lignin content was calculated as the per-
centage of dried solids related to the initial weight of the For calculation of the DD, the lignin content ­(LCwood) in
pulp sample. the milled wood (from spruce chips) and the lignin content
on the achieved pulp ­(LCpulp) was used.
2.5 Pulp fiber analysis For comparison purposes, the fiber length was normal-
ized to the length of the reference fiber from the Kraft
The fiber length of the achieved pulps and a benchmark pulp (2.349 mm). The lowest normalized fiber length was
pulp (unbleached Kraft pulp) was measured by Sappi (Aus- achieved at the lowest value for which fibers were still
tria) using an L&W Fiber tester Plus, at the French Pulp considered as pulp fibers, which is 0.2 mm. At this length,
and Paper Research & Technical Center (CTP, France) in ­NFLmin = 0.2/2.349 = 0.08. Particles with sizes smaller than
a MorFi analyzer, and at Mondi GmbH (Austria) with a 0.2 mm are defined as fines. The maximum value of the NFL

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1382 Biomass Conversion and Biorefinery (2025) 15:1377–1391

that could be obtained was 2.8/2.349 = 1.19, correspond- is most likely correlated with the larger fraction of the wood
ing to the size of the sieve used during the screening of the that ends up as pulp fraction. At low reaction temperature,
cooked material. hardly any pulp is formed, and only smaller fibers close to
As a quick measure of the quality of fibers in terms of the surface of the wood chips are liberated. These surface
the DD and NFL, the quality parameter Q was introduced fibers are expected to be shorter since the wood, thus the
recently [37] as follows: fibers, are cut to form chips. At the higher temperatures, the
delignification is much more significant, resulting in larger
Q = DD × NFL
fibers also being liberated from deeper in the matrix of the
Naturally, during the delignification process, the value of chip. Some aspects of the pulping process that have impor-
DD will increase, while NFL will decrease. Ideally, DD can tant influences on the delignification include the following
increase without too much fiber length loss. However, for steps: the penetration of the DES into the internal structure
comparison purposes, the DD, NFL, and finally the Q value of wood through the lumen. Then, once the DES is in con-
of kraft pulp are calculated as benchmarks. tact with the internal cell walls, the cleavage of ether bonds
Next to the DD and the NFL, several other fiber quality in cellulose, and between lignin and cellulose, as well as in
parameters have been measured during the fiber analyses lignin (such as the characteristic β-O-4 ether bonds) takes
(L&W Fiber tester Plus). These include courseness (how place if enough energy is provided. Afterwards, the liberated
much mass per length of fiber), shape factor (how much the lignin polymers are solubilized into the DES and transported
fiber it is bent), crill index (the amount of fiber fragments from the DES in the lumen to the DES in the bulk of the
that can interact with other fibers), fibril area, and fibril liquid phase [39, 40].
perimeter (fibrils are small particles, distinguish between The sequence of these steps is affected by temperature,
fibrils and fibers). as high temperature decreases the viscosity of the DES and
consequently promotes its penetration into the internal wood
structure. Also, the high temperature provides more energy
for the cleavage of the ether [29, 41]. In addition, the solu-
3 Results and discussion bility of solutes into liquids increases with the increase of
the temperature. In this case, the derived lignin polymers
3.1 Impact of DES‑cooking operating conditions solubilize better into the DES at a high temperature.
on the spruce chips delignification Since more bonds are cleaved and the mass transport is
improved at high temperature (130 °C), as compared to the
The impact of cooking temperature, cooking time, liquor-to- low temperature (90 °C), more fibers are liberated from the
wood (L/W) ratio, and initial water content on the perfor- wood matrix. Thus giving a higher pulp yield. Besides, the
mance of the DES-cooking of spruce chips was investigated lignin content of the fibers and thus pulp decreases because
using lactic acid:choline chloride DES at a mass ratio of 10:1 of the increased reaction rate at higher temperatures. The
in the mechanical stirring (MS) setup. The results are dis- quality parameter Q that relates the degree of delignification
played in Fig. 3, and include the percentage of undercooked and the normalized fiber length is displayed in Fig. 4.
wood chips (UWC), the pulp yield, the percentage of fines, Next to the reaction rates and mass transfer, one addi-
the lignin content (LC), and the fiber length on the pulp. For tional aspect might influence the fiber length, which is the
comparison, the lignin content on the raw material (spruce beating of the wood by the impeller. In the DES-cooking
chips) was measured experimentally, giving a 29.05 ± 0.05 at 90 and 110 °C, a very high lignin content (25.5 and 21.5
wt%. Two batches of spruce chips were used, the first one wt%) is combined with a low pulp yield (2.20 and 5.61 wt%,
with a water content of 31.5 ± 0.2 wt% and the second batch respectively), which hardly would not lead to liberation of
with 35.2 ± 0.4 wt%. fibers, and the short fiber length (0.624 and 0.772 mm)
In Figure 3(i), it is observed that with an increase in the achieved might be due to another fiber liberation mechanism,
cooking temperature (from 90 to 130 °C), both the under- i.e., some of the fibers were liberated due to the beating of
cooked wood chips percentage and the lignin content on the the impeller with the spruce chips during stirring. To evalu-
pulp decrease, while the pulp yield increases. While these ate this hypothesis, also experiments were done using the
trends are well in line with expectations due to higher reac- rotatory-evaporator setup, these results are shown in Fig. 5.
tion rates at higher temperatures, examining the fiber length Figure 3(ii) shows the effect of the cooking time on the
as function of reaction temperature shows that the fiber DES-cooking of spruce chips in a L/W ratio of 10:1 and a
length is increasing with increasing reaction temperature, cooking temperature of 125 °C. At short cooking times, it
and this is a bit more complex to explain. At higher tempera- was observed that delignification of the wood allows only the
tures, the breakdown reactions of the cellulose are expected liberation of small fibers (0.996 and 1.263 mm at 2 and 2.5 h
to be more predominant. However, the fiber length increase of cooking) and thus yielding only small amounts of pulp

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Biomass Conversion and Biorefinery (2025) 15:1377–1391 1383

Fig. 3  The percentage of fines, pulp yield, undercooked wood chips, L/W ratio of 10:1 and 125 °C; the L/W (iii) at 130 °C during 4.5 h;
pulp fiber length, and LC studied as function of the temperature (i) and the initial water content in the DES (iv) at L/W of 10:1, 130 °C
at L/W ratio of 10:1 during 3 h of cooking; the cooking time (ii) at during 3 h

(8.81 and 12.20 wt% at 2 and 2.5 h of cooking) with the wood and higher than 53 µm). Then, the fines remain degrad-
chips remaining almost intact (89.79 wt% of the wood chips ing until producing oligomers and subproducts. Also, the
is undercooked at 2 h of cooking). Apparently, the contact derived lignin polymers that come from the cleavage of their
time of the DES with the wood chips is too short to cleave a ether bonds are solubilized into the DES and may continue
significant amount of the ether bonds in the lignin. In addition, depolymerizing and repolymerizing.
since the lumen of the internal wood structure fills gradually, Thus, with increasing cooking time the pulp yield
and no pressure is applied, the time of contact of the DES and increases, the UWC percentage decreases, and the sol-
the internal wood walls is not uniform over the whole chip. ids yield (UWC + pulp + fines) decreases as is shown in
Over the cooking time, several continuous and succes- Fig. 3(ii). At 2.5 h of cooking, the solids yield is 84.95 wt%,
sively processes occur. Fibers are liberated from the wood while at 4 h of cooking is 66.21 wt%. The solids yield in the
due to the cleavage of the β-O-4 bonds. Liberation of the experiment at a cooking time of 2 h was 101.43 wt%. This
fibers from the wood matrix makes them more accessible to result suggests there is DES entrapped in the UWC after the
the DES, which leads to their delignification and degrada- washing step. Elisabet Brännvall et al. showed [42] that a
tion. A previous work [37] that investigated DES-cooking portion of the DES-dark liquor (with significant lignin con-
of Asplund fibers (instead wood chips) showed how fast the tent) remains entrapped within the wood chips after cooking
shortening of Asplund occurs (reduction of 53.67% of its in kraft pulping. Hence, the UWC of this set of experiments
length after 30 min of cooking) at the same conditions of this was rinsed again. They were put in a bucket with hot water
work. Due to the shortening of the cellulose fiber, the fibers (4 L) overnight, and then they were poured over a sieve of
become in fines (particles with a size smaller than 200 µm 53 µm, and 3 L more of hot water was used to rinse it. Then,

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As the L/W ratio increases from 5:1 to 20:1, the pulp yield
increases from 7.77 to 39.44 wt%, while the percentage of
UWC decreases from 93.22 to 18.7 wt%. The L/W ratio
mainly affects the mass transfer process. A high L/W ratio
provides a higher volume of DES as compared to the wood
chips. Therefore, the lignin molecules dissolved into the
DES after cleavage of the β-O-4 ether bonds will be more
diluted at a high L/W ratio than at low L/W ratio, providing
a higher driving force for lignin transport from the internal
wood structure towards the bulk of the DES in the reactor.
Besides, also the lignin content on the pulp is reduced due to
the higher driving force as the L/W ratio increases. The most
significant impact of the L/W was achieved between the L/W
ratio of 5:1 and 10:1. However, it should be considered that
in industrial processing conditions in scaled-up processes,
Fig. 4  Quantification of the quality of the achieved fibers through the mass-transfer conditions are better due to static pressure, and
parameter Q for the DES-pulps achieved at the operational conditions most likely lower L/W ratios are sufficient, while operation
investigated. Cooking temperature (red squares) at L/W ratio of 10:1
under flow conditions and recycling of solvent may also be
during 3 h of cooking. Cooking time (blue triangles) at L/W ratio of
10:1 and 125 °C. L/W ratio (black circles) at 130 °C during 4.5 h. considered.
Water content on the prepared DES (green diamonds) at L/W of 10:1, The fiber length was considerably affected by increasing
130 °C during 3 h. The Q value for unbleached kraft pulp (black star) the L/W ratio from 5:1 to 10:1. It was reduced from 1.967
was calculated to compare with the achieved pulps
to 1.141 mm. A high L/W ratio promotes dilution of the
solubilized lignin in the DES-dark liquor, making the DES
the washed UWC were oven-dried for 48 h, where its weight more available to interact with both, the solubilized lignin
remained constant. After the re-washing and drying steps, and the cellulose fiber, resulting in smaller fibers.. Further-
the UWC percentage was reduced from 89.79 wt% (no re- more, it should be considered that the mechanical impact of
washed) to 82.14 wt%. This result proves that there is DES the beating of the impeller with the wood chips and fibers is
dark-liquor entrapped in the UWC, which overestimates the another cause of the shortening. This source of shortening
reported values of the percentage of UWC (and subsequently is evaluated and discussed in Fig. 5(ii).
the wood conversion and solid yield) in this work. The initial water content on DES does not affect the fiber
Prolonged cooking time, such as 3.5 or 4.5 h, allows the length achieved after cooking (Fig. 3(iv)). The fiber length
liberation of long fibers (1.716 and 2.267 mm, respectively). remains around 1.5 mm (in a DES-cooking at 130 °C with
At these cooking time, the DES penetrates to a greater a L/W ratio of 10:1 during 3 h) in the range of initial water
extend into the internal wood structure promoting contact content on the DES investigated, 2.4 to 10.48 wt%. For an
with the wood walls for reactive cleavage of lignin ether increasing initial water content from 2.4 to 10.48 wt%, it was
bonds. observed that the pulp yield increases with 3.46 wt%, while
The lignin content on the achieved pulps remains near 12 the percentage of UWC decreases with 25.1 wt%. Although
wt% for every cooking time evaluated. Meaning an actual the conversion of wood increases from 41.01 to 66.11 wt%,
amount of about 8.6 wt% due to not extracting extractives the pulp yield increased by 3.46%. It indicates 21.64 wt%
prior; in separate Soxhlet experiment, 3.44 wt% extractives of the pulp has dissolved into the DES (as derived polymers
were removed. However, it was observed that pulp yield from degradation of lignin, hemicellulose, and cellulose).
increased with cooking time. There is not a songle to explain Furthermore, the fact that the wood conversion increases in
why the LC does not drop below 12 wt%, but the inter- a higher proportion than pulp yield suggests that the pres-
play between delignification, fiber release, and degradation ence of water into the DES significantly promotes the cleav-
may help to explain this effect. The more fiber released, the age of β-O-4 bonds of lignin. Further increasing the initial
higher the lignin content in the DES-dark liquor. The DES water content is of limited interest, because adding water
then interacts with the solubilized polymers of lignin (depo- will increase the vapor pressure significantly at operational
lymerizing and polymerizing them), and this reduces the temperatures, and one of the benefits of using DES instead
availability of DES to interact with the cellulose of the fiber of aqueous media, such as sulfite or sulfide as in current
to degrade it (and thus avoiding significant fiber shortening). industrial processes, is the low vapor pressure.
The increment of the L/W ratio impacts the delignifica- The presence of water in the DES provides lower vis-
tion of the wood chips positively, as is shown in Fig. 3(iii). cosity of the DES as compared with the DES without any

13
Biomass Conversion and Biorefinery (2025) 15:1377–1391 1385

Fig. 5  The effect of the salts within the DES with LA (i) in the setup to cooking, on the percentage of fines, pulp yield, undercook wood
with mechanical stirring, the type of mixing (ii) provided by mechan- chips, and fiber length (on pulp). The following conditions were
ical stirring (MS) or Rotatory flask in a Rotary-evaporator (RE), the fixed, at least in the plot it is indicated the contrary: 4 h of cooking, a
L/W ratio (iii), and the addition of a previous impregnation stage (iv) L/W ratio of 10:1, 130 °C in the RE setup. *Indicates 3 h of cooking

water content. Therefore, the penetration rate of DES and operating conditions evaluated on the properties of the
water mixture into the wood chip is promoted. Water is pulp achieved. The Q parameter of the unbleached Kraft
involved in several reactions during the cooking process. pulp (KP) was included in Fig. 4 as a benchmark (Q = 0.56
Esterification of the OH group of the ChCl with the lac- and pulp yield = 50 wt%).
tic acid may occur [43]. However, because the water is Since a cooking temperature (red squares in Fig. 4) lower
already present in the DES, the forward reaction of the than 110 °C does not provide enough energy for delignifi-
esterification (hydrolysis) is less favored as esterifica- cation and fiber liberation, low values of the Q parameter
tions are equilibrium reactions where water is produced. and pulp yield are achieved (lower than 0.1 and 10 wt%,
Hydrolysis of dimers or trimers of the LA may also occur respectively). On the other hand, although the Q parame-
because of the initial water content on the DES during ter remains around 0.4 for a cooking temperature between
cooking [44]. Both hydrolysis reactions avoid the con- 125 and 130 °C, the pulp yield significantly increases from
sumption of the ChCl and LA molecules on side reac- 22.21 to 45.82 wt% in the same range of temperatures. The
tions, leading to these molecules of DES be available for increase in the cooking temperature of 5 °C allowed increas-
delignification during cooking. Hence, both pulp yield and ing the pulp yield 23.61 wt% without a detrimental effect on
LC are promoted at a higher water content on the DES. the quality parameter of the cellulose fiber.
In Fig. 4, the Q parameter vs the pulp yield is The cooking time (blue triangles in Fig. 4) also provides
shown to understand the impact among the different significant changes in both Q and pulp yield. It was possible

13
1386 Biomass Conversion and Biorefinery (2025) 15:1377–1391

to achieve a value of Q of 0.63 (at 4.5 h of cooking) which is into the DES) is comparable in the DES-cooking among the
higher than the value achieved for the unbleached KP. Nev- LA:NaCl ratios.
ertheless, the pulp yield is 38.89 wt% at the highest cooking Comparing the results achieved by using LA:NaCl with
time, while for the unbleached KP is around 50 wt%. At those achieved using LA:ChCl (both at 10:1 ratio and the
4.5 h of cooking, the fiber length and the LC (2.267 mm, and same conditions), it was observed that reaction rates by
7.66 wt%) are slightly lower than those in the unbleached KP using NaCl are faster than by using LA:ChCl. Using NaCl
(2.349 mm and 9 wt%). provides a higher wood conversion (76.87 wt%), pulp yield
Unlike the cooking temperature and time, the L/W ratio (33.83 wt%), fines (5.36 wt%), and a lower LC (6 wt%). This
(black circles in Fig. 4) has a negligible impact on the Q indicates faster rate of the cleavage of the β-O-4 bonds of
parameter. The Q parameter remains around 0.35 for the lignin as compared to the results achieved with ChCl (55.89,
L/W ratio from 5:1 to 20:1, while the pulp yield increases 29.44, 1.71, and 8.95 wt%, respectively). The lower fiber
from 7.77 wt% (at a L/W ratio of 5:1) to 39.44 wt% (at a length (1.145 mm) obtained after the DES-cooking with
L/W ratio of 20:1). On the other hand, the initial water con- NaCl than the fiber length (1.557 mm) achieved with ChCl,
tent on the DES slightly affects both the Q parameter and suggests a faster cellulose degradation by using NaCl. Pre-
the pulp yield. vious research showed that in a DES containing LA, the
The operating conditions that provide similar values of sodium provides higher wood conversion than the anion
the pulp yield and Q parameter as the unbleached KP were choline with chloride [28], which agrees with the results
at 130 °C (at a L/W ratio of 10:1 and 3 h of cooking) and at in this work.
4.5 h of cooking time (at a L/W ratio of 10:1 and 125 °C). The DES-cooking of spruce chips using LA:NaBr pro-
vides even faster reaction rates than using LA:NaCl or
3.2 Further improvements on DES‑cooking LA:ChCl. Despite the solids yield after cooking was simi-
for spruce chips delignification lar by using NaBr or NaCl (62 wt%), the wood conversion
(72.32 wt%) and the LC (4.95 wt%) were slightly lower
After knowing the effect of the operating conditions of DES- when is used NaBr than using NaCl (76.87 wt% and 6.07
cooking on the spruce chips delignification, several trials wt%, respectively). It indicates that the reaction rate of lignin
were made looking to improve the quality of the pulp and cleavage is faster by using LA:NaBr than using LA:NaCl,
get additional insights into the DES-cooking of spruce chips. due to the cooking time was 3 h in the DES-cooking with
For that set of experiments, the cooking temperature was set LA:NaBr as compare to 4 h of cooking with LA:NaCl. Simi-
at 130 °C, the L/W ratio at 10:1, and the cooking time at 4 h. larly, the fiber length was 1.056 mm using LA:NaBr, while
Two alternatives for choline chloride, sodium chloride it was 1.145 mm using LA:NaCl (Fig. 5(i)). Considering the
(NaCl) and sodium bromide (NaBr), were used to produce difference of 1 h in the cooking time implies that the cellu-
DES mixtures with LA. The impact of each mixture on the lose degradation rate is faster using LA:NaBr than LA:NaCl.
DES-cooking of spruce chips is evaluated and compared The fact that the wood conversion (60.88 wt%) and LC
with the LA:ChCl DES (Fig. 5 (i)). The DES-cooking at (8.95 wt%) are lower using ChCl than using NaBr, while
three LA:NaCl ratios (100:1, 10:1, and 5:1) produced a the fiber length (1.464 mm) is higher using ChCl than using
similar amount of pulp (around 32 wt%). However, it was NaBr (72.32%, 4.95%, and 1.056 mm, respectively), at the
observed that the higher the amount of NaCl, the faster the same operating conditions of DES-cooking (and LA:HBA
delignification and cellulose degradation rate resulting in ratio of 10:1), implies that both the lignin cleavage and the
a lower amount of UWC. The wood conversion increased cellulose degradation rates are faster in the DES-cooking
from 65.08 wt% at 100:1 LA:NaCl ratio to 91.45 wt% at with NaBr than NaCl.
5:1 LA:NaCl ratio, whereas the fiber length decreased from Although both DESs, LA:NaCl and LA:NaBr (at ratio
1.743 to 0.765 mm, respectively. The high wood conversion of 10:1), provide faster delignification than LA:ChCl, these
(which means low UWC percentage) is related to the rate of DESs have a detrimental impact on the fiber length because
the cleavage lignin bonds, while both the shortening of the cellulose degradation is also faster using these DESs. How-
cellulose fibers and the increase of the amount of fines are ever, when a low amount of NaCl is used in the LA:NaCl
related to the cellulose degradation rate. On the other hand, DES (such as 100:1 ratio), similar wood conversion and pulp
both the LC and the pulp yield remained constant at the three yield among the DESs evaluated are achieved. In contrast,
LA:NaCl ratios evaluated. The pulp yield remains around 32 a slightly higher fiber length is provided by using LA:NaCl
wt%, while the LC is about 6 wt%. It suggests that, although than using LA:ChCl.
the reaction rate (delignification and cellulose degradation) As was mentioned before, it is suspected that the beating
changes depending on the LA:NaCl ratio used, the inter- of the impeller during the stirring in the DES-cooking breaks
play between the conversion of wood chips into pulp and down the wood chips and the produced fibers. Pérez et al.
the conversion of pulp into fines (and dissolved compounds [37], showed this detrimental impact on the DES-cooking

13
Biomass Conversion and Biorefinery (2025) 15:1377–1391 1387

of Asplund fibers, comparing the results using two setups, DES-delignification only. In the RE setup, it was observed
the mechanical stirring (MS) setup and the rotary-evaporator that the fiber length slightly increases as the L/W ratio rises.
setup (RE). In this work, both setups were used to prove and At the L/W ratio of 23:1, it was possible to achieve cellulose
quantify the impact of the MS on the DES-cooking of spruce fibers with low LC (9.93 wt%), and a pulp yield (47.58 wt%),
chips, and the results are shown in Fig. 4(ii). The experi- and fiber length (2.344 mm) comparable to the unbleached
ments were performed at two levels of the L/W ratio (10:1 Kraft pulp (5 wt%, 50 wt%, and 2.349 mm, respectively).
and 23:1). At a 10:1 L/W ratio, the percentage of UWC, the An additional variable investigated in this work was the
pulp yield, and amount of fines (around 45 wt%, 29 wt%, and effect of the impregnation step previous to the DES-cooking
1 wt%, respectively) were similar for both setups. However, in the RE setup. The wood chips were in contact with the
the achieved fiber length using the RE setup was 2.152 mm, DES (at L/W ratio of 10:1) overnight at room temperature
while in the MS setup was 1.557 mm, supporting the det- to allow full penetration of the DES into the internal wood
rimental effect that the MS has on the fiber length during structure without reaction. The experiments were performed
DES-cooking. Similar results were obtained at a L/W ratio at 130 °C with LA:ChCl (10:1) DES at 2 and 3 h of cooking,
of 23:1, where the fiber length was 2.344 mm in the RE comparing to the DES-cooking experimental results at the
setup, whereas it was 0.719 mm in the MS setup. The short- same conditions and setup without the impregnation step
ening of the cellulose fiber has a bigger impact at the L/W (Fig. 5(iv)). It was observed that in 2 h of cooking with
ratio of 23:1 than in the L/W of 10:1. impregnation, similar results are achieved (in terms of UWC,
Additionally, at the L/W ratio of 23:1, the percentage of pulp yield, fines, and fiber length) as compared to 3 h of
UWC (5.1 wt%), the pulp yield (47.85 wt%), and the LC cooking without impregnation. However, the LC (13.3 wt%)
(9.93 wt%) were higher in the RE setup, than in the MS obtained in the pulp from the DES-cooking with the previ-
setup (3.93 wt%, 35.05 wt%, and 3.77 wt%, respectively). It ous impregnation of the spruce chips is lower than the LC
is because the impeller breaks down small pieces of the wood (21.31 wt%) in the process without impregnation. For 3 h
chips and weakens and breaks down the liberated cellulose of cooking with impregnation, a slightly higher pulp yield
fibers. Hence, in the MS setup, the shrinking of the spruce (32.47 wt%), lower LC (12.73 wt%), and slightly higher
chips and the shortening of the cellulose fiber are both due fiber length (2.260 mm) are achieved as compared with 4 h
to the delignification and cellulose degradation as well the of cooking without impregnation (29.35 wt%, 16.23 wt%,
fiber breaking by the impeller. This effect is magnified when and 2.152 mm). The addition of an impregnation step to the
the L/W ratio is 23:1 because, in this condition, there is more DES-cooking of the wood chips is advantageous because it
distance among the wood chips than at a 10:1 ratio. A higher reduces the cooking time and allows a higher delignifica-
free space between the chips allows the impeller to drag the tion without detrimental impact on the fiber length. It allows
chips more easily and, consequently, beat them. On the con- achieving fiber with higher length as compared to the pro-
trary, when the L/W ratio is 10:1, the free space among wood cess without impregnation.
chips is reduced, and the wood chips move like one solid In the DES-cooking without the previous impregnation
body, where only the wood chips near the impeller are beaten. step, the DES penetration into the internal wood structure
Another interesting result to notice from Fig. 5(ii) is the occurs simultaneously with the delignification of wood, and
opposite trends in the fiber length between both setups when at atmospheric pressure, the impregnation might be slow.
the L/W varies. In Fig. 3(iii) and Fig. 5(ii), the fiber length In the DES-cooking with impregnation step, the internal
decreases as the L/W increases (from 10:1 to 23:1) in the structure of wood appears better filled with cooking liquor
MS setup, while in the RE setup (Fig. 5(ii)), it seems like before the delignification begins. When penetration of DES
the fiber length is slightly increasing as the L/W rises. Con- into the internal wood structure happens simultaneously
firming this trend in the RE setup, the DES-cooking was with delignification, the contact time of the DES with the
performed at L/W ratios of 10:1, 15:1, and 23:1 at 130 °C internal wood walls differs from the point of penetration
during 4 h of cooking (Fig. 5(iii)). The trends in UWC, towards the most internal point of the wood. The contact
pulp yield, fines, and LC were similar using both setups. time will be higher at the initial penetration point compared
However, it was proven that the trend of the fiber length to most internal wood point. It leads to the delignification
achieved in the MS setup is opposite to the one achieved in occurring progressively in the wood lumen direction where
the RE setup. When the MS setup is used, the conversion the DES is penetrating. Therefore, the wood section near
of wood is favored by the breakdown of the wood chips, the penetration point has a higher delignification and sub-
leading the broken pieces of the wood chips to increase the sequent higher degradation of the released fibers than the
area of contact between the DES and the wood, and conse- most internal section of the wood chip. On the other hand,
quently speeding up the delignification rate. Nevertheless, in when the lumen is filled to a larger extent with DES before
the DES-cooking using the RE setup, there was no breaking cooking, the delignification occurs more homogenously
down of wood chips, allowing to observe the effect of the in the longitudinal direction of the lumen, providing more

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1388 Biomass Conversion and Biorefinery (2025) 15:1377–1391

homogeneous liberation of fibers from the whole internal of 0.66 was achieved, slightly higher than the Q parameter
wood structure simultaneously. (0.57) of the unbleached Kraft pulp at similar pulp yield
Since the penetration has a beneficial impact on the DES- (47.84 wt% and 50 wt%, respectively).
cooking, it could be considered to include in the industrial The value of the Q parameter at 3 h of cooking with
sized process. Alternatively, to improve DES-penetration impregnation (green diamonds) is 0.54, which is near the
into the internal wood structure, using a pressurized reactor value of the benchmark, the unbleached Kraft pulp (0.56).
to allow faster penetration of the DES may be considered. However, the pulp yield is still lower, at 32 wt%, as com-
The effects of the salt in the DES with LA, the kind of mix- pared to 50 wt% in the KP (Fig. 6). Nevertheless, it is possi-
ing, the L/W ratio (using the RE setup), and the addition of the ble to improve the Q parameter and the pulp yield by increas-
impregnation step on the DES-cooking of spruce chips were also ing the cooking time, as shown in Fig. 4 (blue triangles).
quantified in terms of the quality (Q) parameter as is shown in
Fig. 6. It was observed that when the type of salt was varied at 3.3 Effect of the DES‑cooking on the fiber
otherwise constant conditions, the Q parameter varies while the properties
yield remained similar. Also changing the LA:salt ratio in a series
with NaCl experiments influenced on the Q parameter but kept In addition, the effect of the evaluated operating conditions on
similar pulp yields. The pulp yields did vary significantlywith the fiber properties of the obtained pulp, coarseness, shape, fibril
variations in the operating conditions. The operating conditions area/perimeter, and crill index is shown in Fig. 7 and compared
of the DES-cooking on all trials for evaluating the effect of the to unbleached softwood KP and spruce/beech sulfite pulp.
salt remained fixed, and the pulp yield slightly varied (from 30 to The coarseness of the fibers obtained at the investigated liq-
34 wt%), as is showed in the red squares of Fig. 6. uor to wood ratios (5, 10, 15, and 20) has an average value of
The type of mixing (MS or RE) showed a negligible 221.68 +  − 31.52 g/m, which is slightly higher than the value
impact on the Q parameter (around 0.4) and pulp yield of KP and sulfite pulp (Fig. 7i). Since the coarseness is the
(approximately 29 wt%) at a L/W ratio of 10:1 at the experi- mass per fiber length, it can be assumed that the higher value
mental conditions tested (blue triangles in Fig. 5). On the of coarseness in the DES pulp fibers is due to the higher LC of
other hand, at a L/W ratio of 23:1, a detrimental impact these fibers (Fig. 3(iii)) compared to KP and sulfite pulp.
on the Q parameter (0.27) and pulp yield (35.5 wt%) was The shape factor is a measure of how much the fiber
observed in the MS setup, while its effect on both Q (0.66) is bent (i.e., a shape factor of 90% indicates the fiber is
and pulp yield (47.85 wt%) was significantly better at the fairly straight). Fibers from KP and sulfite pulp are more
same L/W ratio in the RE setup. Additionally, it is observed curled than the resulting fibers from DES pulp (Fig. 7(ii),
the higher the L/W ratio is (using the RE setup), the higher Figure S1(ii) and Figure S2(ii)). However, the shape factor
the pulp yield and Q parameter (black circles in Fig. 5) will of the fibers obtained at a cooking temperature of 90 °C
be. Even at a 23:1 L/W ratio, a value of the Q parameter is comparable to the shape factor of both KP and sulfite
pulp fibers. Furthermore, the cooking time did not affect
the shape factor of the resulting fibers (Figure S2(ii)). For
this parameter, important information is that at larger scale
productions, typically lower shape factors are obtained than
with laboratory experimentation due to processing of the
fibers, such as pumping in industrial operation that may
damage the fibers.
The fibril area/perimeter of the resulting DES pulp fibers
decreased with increasing temperature and liquor/wood ratio
(Figure S1(iii) and Fig. 7(iii)). In addition, the fibril perimeter
of the DES pulp fiber was always higher than that of the KP and
sulfite pulp fibers, while the fibril area of the DES pulp fiber
was comparable to that of the KP and sulfite pulp fibers in all
ranges of temperatures and liquor/wood ratios studied (except
for the lowest temperature and liquor/wood ratio). On the other
hand, the fibril perimeter was not affected at cooking times of
2 to 4 h, where it remained close to a value of 4%. However, it
Fig. 6  Quality of the pulp (trough the Q parameter) obtained for the decreased dramatically to a value of 2.9 at a cooking time of
different salts evaluated (red squares), the type of mixing (blue trian- 4.5 h. Despite this decrease in fibril perimeter in the DES pulp
gles), the L/W ratio (black circles), and the pulping with an impreg-
nation step (green diamonds). The Q value for unbleached kraft pulp fiber, the values of this fiber property always remained higher
(black star) was calculated to compare with the achieved pulps than those of the KP and sulfite pulp fibers (Figure S2(iii)).

13
Biomass Conversion and Biorefinery (2025) 15:1377–1391 1389

Fig. 7  Impact of the liquor 300 100

to wood ratio on the coarse-

Coarseness [g/m]

Shape factor [%]

ness, shape factor, fibril area/
perimeter, and crill index of 200
the obtained pulp fibers after
DES-pulping. DES-cooking 50
was performed at 130 °C during
4.5 h 100

0 0
5 10 15 20 KP ulfite 5 10 15 20 KP ulfite
S S
L/W ratio L/W ratio

10 1.5
Fibril Area

Crill Inderx [-]

Fibril Perimeter
1
[%]

5
0.5

0 0
5 10 15 20 KP ulfite 5 10 15 20 KP ulfite
S S
L/W ratio L/W ratio

The crill index tells us how many fragments are present in industry, with some of the parameters such as the crill
the pulp that can interact with other fibers to make the sur- factor even slightly higher. The cooking time and the
face more binding. A higher crill factor would result in bet- cooking temperature were the operating conditions that
ter bonding in the sheet, which would have a positive effect provide the most significant changes on the pulp yield
on the paper properties. The crill index of DES pulp fibers and quality of the achieved cellulose fibers. On the
was always slightly higher than that of KP and sulfite pulp other hand, addition of an impregnation step before the
(Fig. 7(iv), Figure S1(iv), and Figure S2(iv)). However, it was cooking resulted beneficial in terms of the pulp yield
found that the crill index of DES pulp decreased with increas- and quality of the fibers.
ing cooking temperature and liquor to wood ratio. On the other Fibers from DES pulp showed a slightly higher crill index,
hand, the crill index of the DES pulp fibers was not affected by shape factor, and fibril perimeter than the reference kraft and
the increase in cooking time (from 2 to 4.5 h). sulfite pulps, indicating that DES pulp has the potential to pro-
Based on these results, indicating that fiber properties com- duce higher quality paper than kraft and sulfite. However, in
parable to sulfite pulp can be achieved, and for some param- the case of shape factor, it is known that laboratory produced
eters even KP, it is suggested that DES-based pulping is further pulps will always have a higher shape factor (straighter fib-
researched on larger scale in pilot facilities, so that larger por- ers) than industrially produced pulps, as the pulp is pumped
tions of fibers can be applied in paper sheet making and next to through several stages on an industrial scale (the more you
the fiber parameters, also qualitative and quantitative analysis pump the fibers, the more they are bent). On the other hand,
of the final paper quality can be performed. the DES pulp fibers showed a higher coarseness value than the
KP and sulfite pulp fibers, which may not necessarily have a
positive effect on further products such as office paper, as this
4 Conclusions higher coarseness value may be due to the higher lignin content
in the DES pulp fiber. Therefore, additional properties of DES
Delignif ication of spr uce chips by using lactic pulp fibers and above all paper sheets made from these fibers
acid:choline chloride deep eutectic solvent is a promis- should be investigated to better understand the strength of DES
ing technology to achieve pulp with fibers of a qual- pulp and compare it to the values of the KP and sulfite pulp
ity that approaches the current standards in the paper fibers and paper sheets made from them.

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1390 Biomass Conversion and Biorefinery (2025) 15:1377–1391

Supplementary Information The online version contains supplemen- 4. Cheremisinoff NP, Rosenfeld PE (2010) Sources of air emissions
tary material available at https://​doi.​org/1​ 0.​1007/s​ 13399-​023-0​ 5156-y. from pulp and paper mills. In: Handbook of pollution prevention
and cleaner production. pp 179–259
Acknowledgements The authors thank Mondi AG Austria for the 5. Bajpai P (2012) Environmentally benign approaches for pulp
kraft pulp sample. Thanks to CTP, Mondi, and Sappi for fiber analy- bleaching. Elsevier
sis. Thanks also go to Heribert Winter and Vincent Philippi (Sappi), 6. Mongkhonsiri G, Gani R, Malakul P, Assabumrungrat S (2018)
Thomas Tripolt (Mondi), François Cottin, and Michel Petit-Conil (CTP) Integration of the biorefinery concept for the development of sus-
for the fiber analyses. Leo Arpa is acknowledged for his expert advice. tainable processes for pulp and paper industry. Comput Chem Eng
119:70–84. https://​doi.​org/​10.​1016/j.​compc​hemeng.​2018.​07.​019
Author contribution Alan Perez:investigation, methodology, data 7. Usmani Z, Sharma M, Gupta P et al (2020) Ionic liquid based pre-
analysis, writing—original draft. treatment of lignocellulosic biomass for enhanced bioconversion.
Yagnaseni Roy:investigation, methodology, data analysis. Bioresour Technol 304:123003. https://d​ oi.o​ rg/1​ 0.1​ 016/j.b​ iorte​ ch.​
Constantijn Rip:investigation, methodology, data analysis, writ- 2020.​123003
ing—review and editing. 8. Zhang J, Zou D, Singh S, Cheng G (2021) Recent developments in
Sascha R.A. Kersten:methodology, project administration, ionic liquid pretreatment of lignocellulosic biomass for enhanced
supervision. bioconversion. Sustain Energy Fuels 5:1655–1667. https://d​ oi.o​ rg/​
Boelo Schuur:supervision, project administration, funding acquisi- 10.​1039/​d0se0​1802c
tion, writing—review and editing, methodology. 9. Wang Y, Kim KH, Jeong K et al (2021) Sustainable biorefin-
ery processes using renewable deep eutectic solvents. Curr Opin
Funding This project received funding from TKI E&I with the sup- Green Sustain Chem 27:100396. https://​doi.​org/​10.​1016/j.​cogsc.​
plementary grant “TKI-Toeslag” for Topconsortia for Knowledge and 2020.​100396
Innovation (TKI’s) of the Dutch Ministry of Economic Affairs and Cli- 10. Smit AT, Van Zomeren A, Dussan K et al (2022) Biomass pre-
mate Policy. The authors would like to thank the members of the ISPT extraction as a versatile strategy to improve biorefinery feedstock
“Deep Eutectic Solvents in the pulp and paper industry” consortium flexibility, sugar yields, and lignin purity. ACS Sustain Chem Eng.
for their financial and in kind contributions. This cluster consists of https://​doi.​org/​10.​1021/​acssu​schem​eng.​2c008​38
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the corresponding author. pulping technology for eucalyptus slabs using a deep eutectic sol-
vent. Green Chem. https://​doi.​org/​10.​1039/​D3GC0​0589E
Declarations 14. Soleimanzadeh H, Salari D, Olad A, Ostadrahimi A (2023) Opti-
mization of delignification and cellulose isolation process from
Ethical approval Not applicable. natural cotton pods and preparation of its nanofibers with choline
chloride – lactic acid eutectic solvents. Biomass Convers Biore-
Competing interests The authors declare no competing interests. finery. https://​doi.​org/​10.​1007/​s13399-​023-​04141-9
15. Cui J, Chen R, Lei L, Hou Y (2022) Green wood pulping pro-
cesses with high pulp yield and lignin recovery yield by deep
Open Access This article is licensed under a Creative Commons Attri- eutectic solvent and its aqueous solutions. Biomass Convers
bution 4.0 International License, which permits use, sharing, adapta- Biorefinery. https://​doi.​org/​10.​1007/​s13399-​022-​03498-7
tion, distribution and reproduction in any medium or format, as long 16. Jablonsky M, Haz A, Majova V (2019) Assessing the opportuni-
as you give appropriate credit to the original author(s) and the source, ties for applying deep eutectic solvents for fractionation of beech
provide a link to the Creative Commons licence, and indicate if changes wood and wheat straw. Cellulose 26:7675–7684. https://​doi.​org/​
were made. The images or other third party material in this article are 10.​1007/​s10570-​019-​02629-0
included in the article’s Creative Commons licence, unless indicated 17. Loow YL, New EK, Yang GH et al (2017) Potential use of deep
otherwise in a credit line to the material. If material is not included in eutectic solvents to facilitate lignocellulosic biomass utilization
the article’s Creative Commons licence and your intended use is not and conversion. Cellulose 24:3591–3618. https://d​ oi.o​ rg/1​ 0.1​ 007/​
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