Key Engineering Materials Submitted: 2018-08-30

ISSN: 1662-9795, Vol. 800, pp 256-260 Revised: 2019-01-09

doi:10.4028/www.scientific.net/KEM.800.256 Accepted: 2019-01-09
© 2019 Trans Tech Publications Ltd, Switzerland Online: 2019-04-30

Desorption of Phenols from Anion Exchange Resins after the

Separation of Wood Pyrolysis Products
Kristine Meile1,a , Nadezda Iljina1,2,b* and Aivars Zhurinsh1,c
1
Latvian State Institute of Wood Chemistry, Dzerbenes 27, Riga, LV-1006, Latvia
2
University of Latvia, Jelgavas 1, Riga, LV-1004, Latvia
a
kristine.meile@inbox.lv, bn.iljina17@gmail.com, caivarsz@edi.lv

Keywords: added value chemicals, column chromatography, fast pyrolysis, polymeric adsorbents.

Abstract. Replacing fossil resources with biomass for the production of chemicals is another step
closer to a sustainable bio-economy. To make the production of biomass based chemicals
economically feasible, several valuable products need to be obtained from a single feedstock in a
bio-refinery. In our work the pyrolysis products obtained from wood are explored with a focus on
the separation of particular groups of added value chemicals. Anion exchange resins can be used to
separate carbohydrates from phenolics, by adsorbing the latter onto the resin, but further desorption
is needed to obtain concentrated fractions of phenol derivatives.

Introduction
In order to establish a global bio-economy, very efficient methods that use renewable resources
need to be devised. Biomass, including wood, is a traditional source of heat, energy and materials.
Since biomass is the only carbon based renewable resource, it would be rational to process biomass
into value added chemicals to replace fossil resources in the chemical industry. In order to decrease
the current high price of biomass based chemicals, a bio-refinery strategy needs to be employed, to
obtain several valuable products from a single feedstock.
For now the most successful bio-refinery examples are pulp and paper mills [1], but the potential
of lignocellulosic biomass bio-refineries go beyond that. Since the pyrolysis process is considered
to be inexpensive and easy to up-scale [2], a lot of effort is invested into the optimization of pre-
treatment and pyrolysis conditions as part of a bio-refinery concept [3]. Depending on the pre-
treatment procedure, the presence of catalysts and the pyrolysis conditions, hundreds of various
products can be obtained from wood. The main two groups of pyrolysis products of lignocellulosic
feedstock are carbohydrate derivatives and phenolics [4], also other low molecular weight
compounds. Carbohydrates are the thermochemical degradation products of holocellulose, among
which levoglucosenone, levoglucosan, galactose, 1,6-anhydro-β-D-glucofuranose and other
anhydrosugars are most often produced [5,6]. The phenolic fraction is formed by the pyrolysis of
lignin and consists of numerous individual compounds at low concentrations [7].
Because of the complex composition of the pyrolysis products, downstream processing, i. e.
separation and purification, is often the most challenging step for obtaining marketable end
products. Keeping in mind the main two groups of pyrolysis products – phenolics and
carbohydrates – the authors of this paper are investigating the possibilities of separating the
condensable pyrolysis products by column chromatography with anion exchange resins as the
stationary phase. This approach has been previously reported by our group [8], and similarly by
other researchers [4] for the separation of levoglucosan. In this paper we are refocusing on
separating the phenolics as by-products of anhydrosugars.
Several resins have been mentioned in literature for adsorbing phenols from various wood
related matrices – SP207 and XAD4 for the heavy fraction of red oak bio-oil [4], as well as for
eucalyptus bark extract. XAD16N and SP700 were tested for bark extract [9]. XAD and SP type
resins belong to neutral polymeric adsorbents with varying pore size, particle diameter and other
characteristics. The sorption of phenols is said to be improved by weaker polarity, lower pore
diameters and larger specific surface areas [10]. However, functionalized strongly basic anion

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 Key Engineering Materials Vol. 800 257

exchange resins have also been described, such as, Monosphere 550a OH for kraft black
liquor [11].
Phenol derivatives with biomass origin as a group can be used for textile dyes [12] or to some
extent in phenol-aldehyde resins [13]. An even more appealing approach would be to obtain
individual phenolics as valuable fine chemicals. The aim of this study was to evaluate the
possibilities of separating phenol derivatives from wood pyrolysis products.

Materials and Methods

Materials. Lewatit VPOC 1024 strongly basic anion exchange resin (SBA) was used in its native
Cl form, and also in OH- form after conditioning with 1.5 % NaOH solution. All reagents
-

(NaOH ≥ 98 %, NaCl ≥ 99.5 %, acetic acid ≥ 99.8 %, methanol ≥ 99.9 %, ethanol ≥ 95 %) were
purchased from Sigma-Aldrich and used without further purification.
Samples. The condensable pyrolysis products were obtained at Latvian State Institute of Wood
Chemistry. Birch (Betula pendula) chips were treated with diluted sulfuric acid (2 % of oven dry
wood mass) and washed with diluted water. The obtained lignocellulose was ground to particle size
< 2 mm. The lignocellulose was pyrolysed in a superheated steam (380–420 °C) flow in an
entrained flow thermoreactor, after which the char was separated in a cyclone, but the liquid
products in a condenser. The condensates were filtered through a Whatman 597 paper filter before
separation with the anion exchange resins.
Sorbtion Kinetics. The resin was placed in a beaker and conditioned with deionized water for
1 h; then the resin was washed with five portions of 50 mL deionized water and dried at room
temperature until a constant mass was reached. 20 g of the dried resin was weighed with precision
of ± 0.001 g in a conical flask with a stopper. 40 mL of pyrolysis condensate was added to the resin
and stirred. 0.1 mL of the condensate was sampled after 2 min, 5 min, 10 min, 20 min, 30 min,
45 min, 60 min, 90 min, 120 min, 180 min and 240 min. 5 mL of deionized water was added to the
taken sample and UV absorption (A) was measured with a Perkin Elmer Lambda 25 UV/VIS
spectrometer at 275 nm wavelength in a 1 cm cuvette. Afterwards the phenol-saturated resin was
washed with deionized water and dried at room temperature to use in desorption experiments. 3 g of
the saturated resin was weighed into six conical flasks, and 30 mL of different regeneration
solutions were added in each flask: methanol, ethanol, water/acetic acid mixture (75:25 v/v),
methanol/acetic acid mixture (75:25 v/v), 1.5 % NaOH and 1.5 % NaCl solutions in water. The
mixtures were stirred, and 0.1 mL samples of the solutions were taken for spectrometric analysis as
described before. The adsorption and desorption kinetics were depicted in graphs with UV
absorption as a function of time.
Composition of the Desorption Solvents. 3 g of saturated resins were weighed with precision
± 0.001 g in seven conical flasks, and 30 mL of the regeneration solvents were added. After stirring
for 1 h, 1 mL of each solvent was diluted three times with acetonitrile/water (50:50 v/v) mixture for
analysis with UHPLC as described in the next section. The experiments were performed in
triplicate.
Ultra-High Performance Liquid Chromatography Analysis. Waters Acquity UPLC system
with a CSH Phenyl-Hexyl column was used (1.7 μm, 2.1×100 mm) at gradient conditions (0.1 %
formic acid in water/ acetonitrile 90:10 to 10:90 in 8 min with flow rate 0.4 mL/min). HPLC grade
acetonitrile, formic acid and Millipore Type 1 water were used. All solutions were filtered through
Kinesis syringe filters (nylon, 0.22 μm pore size) before injection. Waters photodiode array detector
was used for quantitative analysis of the phenols (at 275 nm wavelength) and Waters quadrupole
mass spectrometer was used for qualitative analysis (positive ESI with 12 V cone voltage).

Results and Discussion

First of all, the adsorption rate of phenols from the condensable wood pyrolysis products onto
two types of strongly basic anion exchange resins was investigated and the results show (Fig. 1) that
258 Materials Science and Applied Chemistry II

the adsorption in both cases was completed almost instantaneously – in 2 min or less, followed by a
stable equilibrium. However, the resin in OH- form was more efficient in removing phenols from
the condensate. According to the UV absorption measurements at 275 nm wavelength, the SBA
resin in Cl- form removed 33.6 ± 0.2 % of the phenolics, while the resin in OH- form removed
60.4 ± 0.2 %. It is mentioned in literature that Dowex XZ (strong anion exchange resin) reaches the
balance by absorbing 65 % of phenols, similarly to that obtained with the OH- form [14]. Yet, a
more detailed analysis of the pyrolysis condensate using UHPLC-UV/MS before and after treatment
with the resins showed that there also were some furan derivatives (furfural, 5-
hydroxymethylfurfural) present in the condensate. These components were not adsorbed with either
of the resins, and so contributed to the total UV absorption value at 275 nm. Specific quantitative
UHPLC-UV/MS analysis showed that both resin forms completely adsorbed phenolcarboxylic
acids – vanillic acid and syringic acid, but only the OH- form resin could separate other phenols,
such as vanillin and syringaldehyde by more than 90 %. The Cl- form resin achieved only 20–30 %
separation of the phenols without carboxylic groups.

Fig. 1. The relative concentration of phenols in pyrolysis condensates, while being removed by strongly
basic anion exchange resins (SBA) in Cl- and OH- form.
Since the anion exchange resin in OH- form demonstrated superior phenol removal from the
pyrolysis condensates, further desorption experiments were carried out using only the saturated
resin in OH- form. Three water solutions with different additives were tested – NaCl (salt), NaOH
(base) and acetic acid. Furthermore, organic desorption solvents were used – methanol and ethanol,
and also a methanol/acetic acid mixture. It could be observed (Fig. 2) that desorption in the solvents
without acid was faster to reach equilibration: at 10 min or even 5 min in case of the NaOH
solution, while desorption in the solvents containing acetic acid only reached equilibrium after
30 min.

Fig. 2. Desorption of phenols from the anion exchange resin in OH- form with different desorption solutions.
 Key Engineering Materials Vol. 800 259

Very moderate desorption of phenols was achieved by using organic solvents without any
additives, but the addition of acetic acid to methanol increased the desorption efficiency more than
five times. However, the highest concentration of phenols was obtained by desorption with a
mixture of water/acetic acid. The aqueous solution of NaCl in water was more efficient than NaOH,
which is due to the higher affinity of the Cl- ion. Even though NaCl solution showed promising
desorption results, this solvent was not further considered because of the difficulties to remove the
desorbed phenols from the salt. For a comparison, it should also be noted that desorption of phenol
with NaOH solution in water is considered to be a commercially effective method [15]. It has been
shown that NaOH manages to desorb up to 60 % of phenols from various polymeric resins [16].
Seven desorption solvents (Fig. 3) were compared in terms of selectivity: 1) acetic acid and
water mixture AA/H2O (25:75); 2) acetic acid, water and methanol mixture AA/H2O/MeOH
(20:20:60); 3) acetic acid and methanol mixture AA/MeOH (25:75); 4) acetic acid and ethanol
mixture AA/EtOH (25:75); 5) water and methanol mixture H2O/MeOH (25:75); 6) methanol
MeOH; 7) water H2O. The main observation was that the acidic desorption solvents were
significantly more efficient for the desorption of phenolcarboxylic acids, since the concentrations of
vanillic and syringic acids in the first four solvents was more than two times higher than in
H2O/MeOH and more than ten times higher compared to the two pure solvents (MeOH and H2O).
On the other hand, the desorption of vanillin was the same in all solvents, but the concentration of
syringaldehyde in all regenerants was below the limit of detection. Taking into consideration these
differences, it is possible to design a strategy to consecutively desorb phenols without carboxylic
groups with acid-free solvents, and then to desorb the phenolcarboxylic acids with a solvent that
contains acid.

Fig. 3. The concentration of syringic acid, vanillic acid and vanillin in different desorption solvents.

Conclusions
Anion exchange resins can be used to separate wood pyrolysis products into two major fractions,
because carbohydrates and furans are not adsorbed on the resins, while phenolics are strongly
adsorbed and can be consecutively desorbed with chosen desorption solvents. The SBA resin in
OH- form demonstrated sufficient phenol adsorption by removing approximately 90 % of phenols
from the pyrolysis products. Desorption of phenols from the resin was influenced by various
changes in the regeneration solutions, such as, acidity and different anions. This proves that the
overall sorption of phenols on the anion exchange resins is a combination of several retention
mechanisms, including ion exchange and hydrophilic-hydrophobic interactions. Because of the
selectivity differences of the evaluated desorption solvents, there is a potential to separate the
phenol fraction into phenolcarboxylic acids and phenols with other functionalities.
260 Materials Science and Applied Chemistry II

Acknowledgement
This research was supported by the ERDF project No. 1.1.1.1/16/A/010 “Developing an
innovative technology for producing levoglucosenone from lignocellulose”.

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