Bioresource Technology 164 (2014) 162–169

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Characterization of biocoals and dissolved organic matter phases

obtained upon hydrothermal carbonization of brewer’s spent grain
J. Poerschmann a,⇑, B. Weiner a, H. Wedwitschka b, I. Baskyr a, R. Koehler a, F.-D. Kopinke a
a
UFZ-Helmholtz Center for Environmental Research, Department of Environmental Engineering, Permoserstr. 15, D-04318 Leipzig, Germany
b
DBFZ-Deutsches Biomasseforschungszentrum, Department of Biochemical Conversion, Torgauer Straße 116, D-04347 Leipzig, Germany

h i g h l i g h t s

 The by-product brewer’s spent grain was subjected to hydrothermal carbonization.

 Biocoal yield is high due to high carbohydrate content.
 Biocoals reveal high energy densification and high sorption capabilities.
 Biogas production from process water gives high yields.
 Phenols and fatty acids proved abundant analytes in the process water.

a r t i c l e i n f o a b s t r a c t

Article history: The wet biomass brewer’s spent grain was subjected to hydrothermal carbonization to produce biocoal.
Received 13 January 2014 Mass balance considerations indicate for about two thirds of the organic carbon of the input biomass to
Received in revised form 15 April 2014 be transferred into the biocoal. The van Krevelen plot refers to a high degree of defunctionalization with
Accepted 17 April 2014
decarboxylation prevailing over dehydration. Calorific data revealed a significant energy densification of
Available online 26 April 2014
biocoals as compared to the input substrate. Sorption coefficients of organic analytes covering a wide
range of hydrophobicities and polarities on biocoal were similar to those for dissolved humic acids. Data
Keywords:
from GC/MS analysis indicated that phenols and benzenediols along with fatty acids released from bound
Hydrothermal carbonization
Brewer’s spent grain
lipids during the hydrothermal process constituted abundant products. Our findings demonstrate that
Biocoal the brewer’s spent grain by-product is a good feedstock for hydrothermal carbonization to produce bio-
Organic carbon balance coal, the latter offering good prospects for energetic and soil-improving application fields.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction attempts have been made to use it in biotechnological processes,

Brewer’s spent grain (BSG) is the residue left after separation of
the wort during the brewing process and is available in large quan-
tities throughout the year. Its worldwide annual output amounts to
about 30 million tons, in Germany it is about 0.7 million tons as dry
mass (Schuchardt and Vorlop, 2010). The composition of this agro-
industrial co-product may vary with barley variety, time of harvest,
adjuncts added and brewing technology (Niemi et al., 2012).
The main application of BSG has been chiefly tied to animal
feeding, favorably combined with green manure or maize silage.
Shortcomings of BSG use in animal feeding are associated with
the cyclic generation peaking at summer times, as well as with
the low degradation rate of raw protein in rumen (Santos et al.,
2003). To upgrade BSG use and develop innovative value schemes,
⇑ Corresponding author. Tel.: +49 341 235 1761; fax: +49 341 235 2492.
E-mail address: juergen.poerschmann@ufz.de (J. Poerschmann).
such as cultivation of mushrooms and actinobacteria and as a
source of value-added products like ferulic and p-coumaric acids
or sugar alcohols (Faulds et al., 2004). The importance of the wet
biomass as an industrial feedstock is hampered by its chemical
deterioration and its susceptibility to microbial attacks resulting
in rapid colonization by bacteria unless it is further dried to a mois-
ture content of 10% or less.
A promising, environmentally benign approach which is pur-
sued in the framework of this contribution is to use wet BSG (dry
mass 20–25% w/w) as a feedstock for hydrothermal carbonization
(HTC). This is a process in which wet biomass is hydrothermally
converted in aqueous suspensions at moderate temperatures
(180–250 °C) and medium pressure into carbonaceous materials
(Baccile et al., 2009). The hot water serves as the solvent and reac-
tant, favoring ion chemistry while concomitantly suppressing free
radical reactions. HTC processes have the tremendous advantage
that the starting biomass does not need to be dry, thus the need

http://dx.doi.org/10.1016/j.biortech.2014.04.052
0960-8524/Ó 2014 Elsevier Ltd. All rights reserved.
 J. Poerschmann et al. / Bioresource Technology 164 (2014) 162–169
for energy-intensive removal of water is eliminated. A wide array
of natural raw biomasses as well as agricultural and municipal
waste products including liquid manure, sewage sludge, maize
grist, molasses, and sugar beet residues have been subjected to
HTC (Funke and Ziegler, 2009).
The HTC process is characterized by a combined hydrolysis–
deoxygenation–polymerization mechanism (Titirici and
Antonietti, 2010). As a result of hydrothermal treatment of bio-
masses, an aqueous phase is generated next to the water-insoluble
biocoal. The biocoal can be used to enhance soil fertility (Steinbeiss
et al., 2009), for energetic purposes and/or to produce tailor-made
sorbents and catalysts with defined functionalization and pore
structure (Titirici and Antonietti, 2010). In contrast to biocoal,
the dissolved organic matter (DOM) in the process water is basi-
cally an unwanted side-product.
Herein, the suitability of BSG as an input substrate to produce
valuable biocoal is addressed including the following objectives:
(i) To determine the mass balance of the organic carbon (OC)-
fraction of the biomass at different operating temperatures.
In an ideal scenario, the OC-fraction is overwhelmingly con-
verted into biocoal with a minor DOM content and negligible
formation of gases (chiefly CO2).
(ii) To determine the mass balance of other elements including
nitrogen, phosphorous, and heavy metals.
(iii) To study the degree of defunctionalization of biomass com-
partments on hydrothermal treatment. Clearly, high defunc-
tionalization of biomass compartments (cellulose,
hemicellulose, lignin, proteins) results in high calorific value
of the biocoals in view of a potential energy source.
(iv) To study the sorption capability of biocoals in the face of
their potential application as sorbent in wastewater
treatment.
(v) To characterize low molecular weight organic components
(MW 6 300 Da) in the process water in the light of prospec-
tive obtaining of value-added products (e.g. levulinic acid)
and as a source of biogas when applying a cascadic use of
the process water rich in DOM.
BSG was already used as input substrate for HTC (Heilmann
et al., 2011). The focus of that contribution was the mechanism
of coal formation and characterization of the biocoal by micros-
copy rather than addressing the objectives listed above. Our contri-
bution is aimed at supplementing the findings published by
Heilmann et al. rather than compete with them. The combined
data (meaning: our data and Heilman’s data) are expected to foster
the field of utilizing BSG as a substrate for HTC.
2. Methods
2.1. Hydrothermal carbonization of BSG
BSG was delivered by Reudnitzer Brewery Leipzig, Germany,
and stored at 4 °C until use. The hydrothermal process was per-
formed in an autoclave with a capacity of 200 mL (Roth; Karlsruhe,
Germany) filled with 50 g BSG (23.5% w/w dry mass) and 50 mL of
distilled water. The dilution proved beneficial for further
handling of product fractions resulting from the HTC-process.
The HTC parameters were chosen according to findings from
previous HTC experiments with a wide array of biomasses
(Poerschmann et al., 2013): operating temperature of 200 and
240 °C, reaction time of 14 h, and 80 lg mL1 of citric acid as
catalyst. The pH of the slurry obtained after carbonization was
2.8, that of the native slurry was 7.0. The shift indicates the
formation of carboxylic acids. The HTC slurry was allowed to pass
163
through a filter paper (Whatman filter paper, Grade 595, 150 lm
thickness). After phase separation, process waters were evaporated
to dryness and biocoals were dried, both at 105 °C (4 h), for elemental
analysis, ash determination, and X-ray fluorescence spectroscopy.
2.2. Elemental analysis, X-ray fluorescence, bulk parameters
An elemental analyzer LECO model CHN 932 (Moenchenglad-
bach, Germany) was used to determine C, H, N and S in the input
substrate, the biocoal and the lyophilized process water. The oxy-
gen concentration was calculated from the difference between the
ash-free dry mass and the combined mass of the elements
measured. Elemental composition was determined in duplicate.
The averaged data were reported herein. BSG compartments were
isolated according to a scheme developed for maize plants to
quantify rhizodeposition based on Sparling et al. (1982). Briefly,
lipids were extracted with a chloroform/methanol solvent mixture
(1:1, v/v), soluble carbohydrates with hot water, delignified
holocellulose by refluxing the residue with sodium hypochlorite
solution, and cellulose by 24% potassium hydroxide solution.
X-ray fluorescence measurements were performed using a
WDXRF-spectrometer S4 PIONEER (Bruker-AXS, Bremen, Germany),
equipped with a 4 kW-Rh X-ray tube (75 lm Be window) and a
60 kV generator.
Total organic carbon (TOC) in filtered aqueous solutions was
analyzed by a TOC analyzer (Shimadzu, Duisburg, Germany).
Determination of the Chemical Oxygen Demand (COD) was carried
out by a micro-method with chromo-sulfuric acid (cuvette test kit
LCK014 from HACH LANGE GmbH, Duesseldorf, Germany). The bio-
chemical oxygen demand (BOD) was measured manometrically
with a WTW BOD analyzer OxiTopÒ IS 6 (Weilheim, Germany).
The samples were dried at 105 °C prior to analysis. The ash fraction
was determined by a burning process at 550 °C. The specific sur-
face area was determined by BET analysis using a Belsorp Mini
(Microtrac, Meerbusch, Germany) with multipoint adsorption iso-
therms of nitrogen at 77 K.
2.3. Exhaustive extraction of HTC matrices
Five hundred mg aliquots of the slurry lyophilizate, the DOM
lyophilizate resulting from HTC at 200 °C, and the lyophilized
BSG substrate were each subjected to exhaustive pressurized
solvent extraction. The lyophilizates were spiked with internal
standards before freeze drying. Internal standards included [2H2]-
palmitic acid, [2H4]-lactic acid, [2H6]-phenol, [2H4]-hydroquinone,
and [2H10]-phenanthrene in acetone to give a final concentration
of 1000 lg g1 each ([2H10]-phenanthrene: 10 lg g1) referred to
BSG as dry matter (DM). Standards were purchased from Ehren-
storfer (Augsburg, Germany); all solvents from Aldrich (Munich,
Germany). Labeled palmitic acid was used to quantify long-chain
monocarboxylic acids, whereas lactic acid served for quantifying
short-chain dicarboxylic acids and short-chain hydroxyl acids.
Labeled phenol and hydroquinone served for quantification of phe-
nols and benzenediols, respectively. Hydrophobic analytes were
calibrated against labeled phenanthrene. The experimental extrac-
tion details were the following: extraction device ASE 300 (Ther-
moFisher, Dreieich, Germany), 11 mL cell cartridges filled with
inert Hydromatrix to capacity, benzene/acetone/methanol
(2:1:0.5, v/v/v) solvent mixture. Two 10 min cycles at a tempera-
ture of 100 °C and 12 MPa pressure were applied to each sample.
Solvents were sparged with helium to prevent oxidative cleavage
of susceptible analytes including linolenic acid (18:3xccc) during
extraction. Clean-up of the combined extracts was performed by
SPE using DSC-diol cartridges (spacer bonded 2,3-dihydroxyprop-
oxypropyl; Supelco, Munich, Germany) with chloroform/acetone
(1:1, v/v) as eluent. Purified extracts were dried over anhydrous
164 J. Poerschmann et al. / Bioresource Technology 164 (2014) 162–169
sodium sulfate, then concentrated in a rotary evaporator to a final
volume of 100 lL. Derivatization of volume-reduced extracts
involved a silylation with BSTFA (N,O-bis-(trimethylsilyl) trifluoro-
acetamide, Sigma Aldrich) to produce TMS (trimethylsilyl) ethers,
as well as a combined transmethylation with boron trifluoride
(14% w/w in methanol; Sigma Aldrich Munich, Germany) to pro-
duce non-polar methyl esters of mono- and dicarboxylic acids fol-
lowed by silylation with BSTFA. Structural assignments were
confirmed by using silyl ethers produced with isotopically labeled
BSTFA-d9 (Ehrenstorfer). Saponification of solvent extracts origi-
nating from both the lyophilized process water and the BSG sub-
strate was performed with 3 N methanolic sodium hydroxide
solution.
2.4. Sorption of organic compounds on HTC coal
Sorption coefficients on HTC coal (200 °C) were determined by
Solid Phase Microextraction (SPME) at pH  4. This method was
elaborated and validated in our institute to overcome shortcom-
ings in the traditional determination of sorption coefficients in
both particulate and dissolved sorbents (Kopinke et al., 2002).
The basic idea of using the SPME analytical technique to study
sorption phenomena is that only the freely dissolved fraction of
the target analytes is sampled by the SPME-fiber. By contrast, the
analyte fraction bound to both dissolved and solid sorbents is not
enriched onto the fiber coating. Experimental details to conduct
these experiments are given in the Supplementary information
section (S-1 and S-2) as well as in a recent publication
(Poerschmann and Schultze-Nobre, 2014). Solutions contained
100 lg mL1 sodium azide to inhibit microbial activity. Likewise,
5 mM calcium chloride was used to maintain relatively constant
ionic strength.
2.5. GC/MS analysis
A thin-film capillary column (30 m  0.25 mm) coated with
0.25 lm non-polar DB-1 MS stationary phase was used (Agilent
Technologies, Waldbronn, Germany). The linear temperature pro-
gram was as follows: initial temperature 40 °C, 10 °C min1 to a
final temperature of 300 °C. Data acquisition was performed using
HP 5973B MSD in full scan mode.
2.6. Biochemical methane potential test
The biochemical methane potential test was carried out accord-
ing to guidelines defined in VDI (2006). The potential methane pro-
duction was obtained from the incubation of triplicate anaerobic
batch cultures containing both the substrate and a methanogenic
inoculum at a predetermined substrate/inoculum ratio. Incubation
took place in glass culture bottles at mesophilic conditions (38 °C)
over 30–45 days. The biogas volume was measured using the Eudi-
ometer technology (Janzon et al., 2014). The methane content was
determined with the Geotech GA2000 Landfill Gas Analyzer (War-
wickshire, UK). The pH was measured at the beginning and at the
end of the experiment. The test is stopped when the daily biogas
production does not exceed 1% of the total accumulated biogas vol-
ume. The methanogenic inoculum was a mixture of sewage sludge
from a wastewater treatment plant and of digested effluent from
an agricultural biogas plant. To monitor the inoculum perfor-
mance, each test run included triplicate control cultures containing
inoculum and microcrystalline cellulose. The required inoculum
performance was achieved when the inoculum converted at least
70% of the reference cellulose to biogas during the incubation per-
iod as defined by the American Society for Testing and Material
standard (ASTM, 2007).
3. Results and discussion
3.1. Mass balance of BSG during hydrothermal treatment
3.1.1. Total mass balance and carbon, nitrogen balance
Table 1 provides information on physico-chemical characteris-
tics of native BSG, which are comparable to those previously
reported for BSG covering different origins (Santos et al., 2003;
Mussatto et al., 2008).
Table 2 lists data from gravimetric and elemental analysis along
with COD and BOD5 data for BSG and the hydrothermally con-
verted products. BSG gave a high yield of black-colored carbona-
ceous precipitates as a result of the hydrothermal treatment
(51.1% and 47.5%, see Table 2). This finding is in line with the high
content of carbohydrates in BSG (see Table 1). Carbohydrates are
known as good substrates for HTC to form biocoal (Funke and
Ziegler, 2009). Table 2 also shows that two thirds of the feed-
stock-organic carbon (OC) was fixed inside the biocoal network
(67.5% – 200 °C, 67.6% – 240 °C). Increased HTC-temperatures
resulted in lower coal mass yields but higher OC- content, which
is in line with previous findings obtained with other biomasses
(Funke and Ziegler, 2011; Parshetti et al., 2013). The high yield
and the high carbon content of the biocoal points to a good suit-
ability of BSG to the HTC process and is expected to be beneficial
for a prospective energetic application. The high similarity
between the OC- fraction retained in the biocoal at both 200 °C
and 240 °C favors low operating temperatures of 200 °C in the
face of a linear dependence between energy demand (synonymous
with costs) and HTC temperature.
Compared to the biocoal, a significantly lower fraction of the
substrate OC was converted into the (basically undesirable)
DOM-product stream (18.9% at 200 °C, 17.3% at 240 °C). The loss
of substrate OC (13.6% – 200 °C, 15.1% – 240 °C) was mainly related
to gas formation, as well as to experimental shortcomings (e.g.
droplet and spill losses, losses by phase separation). Results from
headspace analyses (not detailed here) showed that carbon dioxide
constituted the most abundant gas with minor abundances of car-
bon monoxide, methane, ammonia, sulfur dioxide, methanethiol,
dimethyl sulfide, and i-butanal (less than 15% combined). Carbon
dioxide arises from decarboxylation reactions, it may also originate
from the breakdown product formic acid (Lu et al., 2014). As a
rough estimate, the combined fraction of gases referred to the sub-
strate dry mass across a multitude of biomasses and HTC process
parameters amounts to 9% (Funke and Ziegler, 2009).
Table 1
Chemical characteristics of BSG.
Analysis Result
Dry matter content (DM) (g kg1) 235
pH of suspension 6.9
Ash (%-w/w DM) 4.5
Organic carbon (%-w/w DM) 51.3
Elemental ratio C/N (g g1) 13
COD (g O2 L1) 262
BOD5 (g O2 L1) 153
Cellulose (%-w/w DM) 18.5
Hemicellulose (%-w/w DM) 26.5
Soluble sugars (%-w/w DM) 1.0
Proteins (%-w/w DM)a 21.5
Total lipids (%-w/w DM)b 7.3
Klason-lignin (%-w/w DM)c 19.1
a
Protein fraction for the BSG as dry matter was calculated by multiplying the
total nitrogen (standard method ASTM D-5291) value by a factor of 6.25.
b
Determined by Folch-extraction using chloroform/methanol (1:1, v/v).
c
Determined gravimetrically (after drying at 105 °C) after lipid extraction and
carbohydrate removal.
 J. Poerschmann et al. / Bioresource Technology 164 (2014) 162–169 165

Table 2
Mass balances after hydrothermal treatment of BSG.

COD BOD5 BOD5/ DMMatrix/DMBSG VStand.,biogas/mODM OCDM HDM NDM SDM ODM AshDM DBE
(g L1) (g L1) COD (%, w/w) (mL g1)a (%, w/w) (%, w/w) (%, w/w) (%, w/w) (%, w/w) (%, w/w)
BSG- 262 153 0.58 100 51.3 6.71 4.07 0.45 32.9 4.5 4.67
Educt (2.27)d
b
200 °C- 60.8 47.1 0.77 21.2 479 45.7 6.65 8.55 0.80 29.2 8.7 2.30
DOM (18.9%)c (21%) (44%) (37%) (19%) (40%) (1.26)
200 °C- 51.1b 67.8 6.74 4.18 0.35 15.1 5.6 9.14
biocoal (67.5%)c (52%) (49%) (39%) (23%) (64%) (9.68)
Loss (%) 28 13.6 27 7 24 58 0
240 °C- 64.2 51.1 0.80 18.8b 654 47.2 6.48 8.15 0.75 28.9 8.6 5.02
DOM (17.3%)c (18%) (37%) (32%) (16%) (37%) (2.78)
b
240 °C- 47.5 72.9 6.41 3.93 0.34 10.5 6.3 11.73
biocoal (67.6%)c (45%) (46%) (36%) (15%) (67%) (17.85)
Loss (%) 34 15.1 37 17 32 69 0
a
Standard volume of biogas referred to organic dry mass.
b
Mass yield as (non-diluted) DM-dry matter (105 °C), DMBSG = 23.5% w/w; DMBSG, DMDOM, and DMBiocoal are each referred to DMBSG (%, w/w).
c
In parentheses: % carbon recovered in the biocoal, i.e. OCDOM referred to OCBSG, OCCoal referred to OCBSG (%, w/w), correspondingly for HDM, NDM, SDM, ODM, AshDM each
referred to the element’s content in dry BSG.
d
In parentheses: DBE/oxygen.

The high recoveries of substrate-nitrogen in biocoals (49% and
46%) provided strong indication that proteins contributed to bio-
coal formation, e.g. by Maillard reactions. Since HTC biocoal
decreases rapidly in the soil (50% in 100 days regardless of soil
type) (Malghani et al., 2013), the bioavailability of the released
organic nitrogen is expected to be high, which favors the applica-
tion for soil improvement.
There was a good agreement between gravimetric data on the
one hand and spectroscopic data on the other hand concerning
the distribution of the ash fraction between process water and bio-
coal (compare 64% ash recovery in biocoal at 200 °C obtained by
incineration in Table 2 with 70% obtained by X-ray fluorescence
in Table 3; analogously for 240 °C: 67% versus 75%).
3.2. Extent of carbonization/defunctionalization

The loss of oxygen – calculated on an ash-free basis – and

3.1.2. Balance of inorganics
hydrogen was each higher than the loss of OC (58% and 69% for
Balances of individual inorganic cations along with Si, P, and S
oxygen, 27% and 37% for hydrogen, see Table 2). Oxygen and
from the input substrate to HTC matrices were studied by X-ray
hydrogen contents in either biocoal or DOM decreased with
fluorescence spectroscopy (Table 3). Inorganics are necessary for
increasing operation temperature due to more defunctionalization
the metabolic pathways of plants and can occur in the form of salts
(mainly dehydration), and aromatization reactions. The high
or bound to organic structures. The enrichment of calcium in the
hydrophobicity of both biocoals became already evident when sol-
biocoal was consistent with a previous study (Santos et al.,
vent extraction experiments have been performed at earlier stages
2003). Bivalent calcium constitutes the most abundant cation in
of this project: Both biocoals partitioned into organic solvents such
the input substrate, with the overwhelming majority being trans-
as benzene and chloroform, whereas the input BSG substrate
ferred into the biocoal (85% at 200 °C and 92% at 240 °C). As with
proved immiscible with organic solvents as expected. This hydro-
the fraction of OC, the mass fraction of the mineral matrix which
phobic feature favors a prospective application of the biocoal as a
was fixed inside the biocoal amounted to about two thirds (70%
sorbent for wastewater treatment.
at 200 °C, 75% at 240 °C, see Table 3, last column). The residual
According to the elemental composition of the educt and the
minerals (30% at 200 °C, 25% at 240 °C) remained dissolved in the
product streams, stoichiometric equations to characterize the
process water. The high recovery of phosphorous in the biocoals
HTC process can be derived. Hypothetical molecular formulas are
– consistent with the findings from a previous study (Stemann
C305H479N22S1O149 for BSG, C520H620N27S1O87 and C152H266N24S1O73
et al., 2013) – may refer to a potential application as a fertilizer
for the biocoal and the DOM formed at 200 °C, respectively, as well
in case of its P-availability. Unfortunately, phytotoxic elements
as C571H609N26S1O61 and C171H282N25S1O77 for the biocoal and the
including copper and zinc were overwhelmingly transferred into
DOM formed at 240 °C, respectively. Given an operating tempera-
the biocoal as well, which may hamper the potential application
ture at 200 °C, the formal stoichiometry is as follows:
as soil additive. However, the release of (potentially) phytotoxic
elements from biocoal-amendments in soil into their soluble form
needs to be clarified. As expected, potassium showed high ten- 50 C305 H479 N22 S1 O149 ! 20 C520 H620 N27 S1 O87 þ 22 C152 H266 N24 S1 O73
dency to transfer into the aqueous product stream (the same was þ1356 CO2 þ 105 CO þ 45 CH4 þ 2711 H2 O ð1Þ
expected to occur with monovalent sodium, whose concentrations þ32 NH3 þ 50 SO2
were however very low; see Table 3).

Table 3
Concentrations of inorganic elements in the input BSG-substrate and HTC-biocoals (concentration data given in lg g1 DM).

K Ca Na Mg Si Al Fe P S Mn Cu Zn R (Xi⁄Ci)a
BSG 650 5750 <300 1180 6480 <200 165 5260 3540 69 23 144 23.2
Biocoal at 200 °C 180 9565 <300 1520 5580 <200 275 8130 2770 70 40 245 19.7
Recovery in biocoal (%) 14 85 66 44 86 79 40 52 90 86 70b
Biocoal at 240 °C 165 11020 <300 1910 7230 <200 320 9200 3210 87 49 245 26.9
Recovery in biocoal (%) 12 92 77 53 93 83 43 60 105 82 75b
a
In mg g1 DM, Xi corresponds to individual cation recovery.
b
Ash (in % w/w) recovered in biocoal referred to the concentration of ashBSG = 23.2 mg g1 DM.
166 J. Poerschmann et al. / Bioresource Technology 164 (2014) 162–169
Herein, it is assumed that gaseous carbon was located to 93% in
CO2, 7% in CO, and 3% in CH4. Furthermore, nitrogen was assumed
to be transferred into NH3, and sulfur into SO2, which is a valid
assumption considering that these gases were detected by head-
space analysis detailed in a previous paper (Poerschmann et al.,
2013).
The balance of Eq. (1) is complete except for oxygen. The same
holds true when considering the stoichiometry at an operating
temperature of 240 °C. The difference between oxygen located in
the end-products and oxygen in the feedstock amounts to 7.0%
(referred to CO2; left side of Eq. (1): 7450 oxygen atoms, right side
of Eq. (1): 6534). Tentative hydrogen formation as indicated in
Escala et al. (2013), tentative oxygen losses in the form of ash dur-
ing the HTC process, as well as the (error-prone) indirect calcula-
tion of oxygen (see Table 2) could explain oxygen imbalances.
The defunctionalization processes can be illustrated by a van
Krevelen plot, in which dehydration and decarboxylation trajecto-
ries are depicted (see Fig. 1). Positions of biocoals in the van Krev-
elen plot in comparison to the position of the input substrate
provide strong evidence that decarboxylation prevails over dehy-
dration (oxygen is depleted to a higher degree than hydrogen).
Fig. 1 arranges the native feedstock along with HTC matrices of
BSG into elemental composition of common biological molecules,
with carbohydrates being outside the scale due to very high O/C-
ratios. The stoichiometric ranges to depict boundaries in the van
Krevelen diagram were taken from Ohno et al. (2010) and refer-
ences cited therein. As can be seen in Fig. 1, the H/C and the O/C
atomic ratios of both biocoals resemble the corresponding elemen-
tal composition of lignite. However, H/C ratios of both biocoals are
significantly higher as compared to condensed aromatic structures
including anthracite which refers to an incomplete coalification
process. Differences in O/C elemental ratios between air-dried
and 105 °C-dried biocoals turned out to be minor (less than 7%).
This finding refers to low amounts of biocoal-adsorbed water,
which improves their calorific values (see chapter 3.4.). Elemental
compositions of input BSG and DOM originating from HTC were
similar, resembling those of humic and fulvic acids.
The position of BSG coals in the van Krevelen plot is close to
those of anaerobically digested maize silage once carbonized under
harsh conditions (operating temperature P230 °C, operating time
P6 h) (Mumme et al., 2011). A modified two-dimensional van
Krevelen plot in which the y-axis is based on N/C elemental ratio
instead of H/C as well as a 3D version are depicted in the Supple-
mentary information section (Fig. S-4.1 and S-4.2).
In addition to elemental ratios addressed in Fig. 1, further (aver-
aged) parameters to categorize HTC biocoals may be applied,
2.0 H/C
Lipids
DOM 200
1.6 DOM 240
BSG
Coal 200
1.2
Humic
Lig- acids
Fulvic
Coal 240 nite acids
0.8
0.4
Condensed aromatics
0.1 0.2 0.3 0.4 0.5 0.6
O/C
Fig. 1. van Krevelen diagram of BSG feedstock and HTC products along with
common biological molecules.
which have been primarily developed to characterize the global
carbon cycle. Among them are the double bond equivalents
(DBE) and the aromaticity index (AI). DBE-values describing the
degree of unsaturation (number of p-bonds) were calculated based
on the number of atoms (C, H, O, N, S) and their prevailing cova-
lences according to a previous study (Zhang et al., 2013). Data in
Table 2 (last row) reveal a high number of aromatic or condensed
aromatic structures in both HTC coals. The DBE to oxygen ratio –
inversely related to the abundance of C@O bonds – points to a
low number of carboxyl and carbonyl moieties in the HTC-coals.
The AI-values, which consider the contribution of heteroatoms
towards degree of unsaturation, were also calculated according
to a previous study (Zhang et al., 2013): AI = 0.53 for coal-200 °C
and AI = 0.62 for coal-240 °C. Aromaticity indices for the input sub-
strate as well as both DOM phases proved close to zero, which indi-
cates a similarity between the number of heteroatoms and the
number of p-bonds. Generally, the AI-values are used to differenti-
ate between non-aromatic (AI 6 0.5), aromatic (AI > 0.5), and con-
densed aromatic (AI P 0.67) compounds. (The DBE/C-ratio of
benzene is 0.67, i.e. higher values must involve condensed ring
systems.)
3.3. Biogas formation from aqueous HTC phases
The basic idea to combine HTC and anaerobic digestion has
been suggested by several groups (Mumme et al., 2011;
Poerschmann et al., 2013; Oliveira et al., 2013). Both BSG process
waters (pH  2.8) are characterized by high concentrations of dis-
solved organic carbon (DOC  14 g L1). Further on, high BOD5/
COD-ratios of both aqueous HTC phases (0.77 and 0.80, see Table 2)
suggest a good biological degradability. The BOD5/COD-ratios are
significantly higher in comparison to that of the BSG substrate
(0.58) due to the breakdown of macromolecules, in particular lig-
nin, into smaller units during the hydrothermal treatment.
Biogas formation was performed as described by Schmidt et al.
(2013). The inoculum performance test according to ASTM (2007)
revealed cellulose conversion of 82%, thus being beyond the
required 70%. The pH-value measured before and after the experi-
ment were 7.7 and 7.8, respectively. The formation of biogas
dependent on the time of the anaerobic experiment is depicted
in the Supplementary information section (Fig. S-5.1). The biogas
formation amounted to 479 mL (200 °C) and 654 mL (240 °C) stan-
dard volume of biogas referred to 1 g ODM (organic dry matter),
which translates into 287 mL g1 ODM and 405 mL g1 ODM meth-
ane, respectively. Clearly, the methane yield was higher with the
DOM-phase originating from the higher processing temperature
at 240 °C. According to our experience, anaerobic digestion of
low value (waste) biomass feedstocks such as maize silage results
in methane yields of 75–250 mL methane referred to 1 g ODM. For
reasons of comparison, lipids give a methane yield of 780 mL g1
ODM, proteins 470 mL g1 ODM, and carbohydrates 390 mL g1
ODM (see Schmidt et al. (2013) and references cited therein). In
conclusion, DOM in process waters from HTC of BSG proved a very
good substrate (or co-substrate) for biogas generation. Due to the
very high concentration of DOC (about 14 g L1) in the process
water, the solubilized methane fraction in water (20 mg L1 at
20 °C taken as average from several databases) does not constitute
a lost methane resource.
3.4. Energetic considerations of BSG biocoal
To describe the energy content of biocoals, higher heating val-
0.7
ues (HHV) expressing the enthalpy of complete combustion
(including the heat of condensation of the water formed) proved
a valuable parameter. Over the last decades, calculation of caloric
data made huge progress, so that pre-calculated data are very
 J. Poerschmann et al. / Bioresource Technology 164 (2014) 162–169 167

similar to data determined experimentally by calorimetry.
A multitude of approximations was established (see Buckley
(1991) and references cited therein). Nowadays, an empirical
unified correlation based on elemental compositions (Channiwala
and Parikh, 2002) is widely used to pre-calculate HHV data for
fuel-like substances devoid of water (see Eq. (2)).
HHVðkJ=kgÞ ¼ 349:1  C þ 1178:3  H þ 100:5  S  103:4  O
 15:1  N  21:1  Ash
with C, H, S, O, N, and Ash representing the mass percentages on dry
basis.
Table 4 lists calculated HHV data for the BSG substrate and HTC
matrices of BSG along with data for selected biopolymers and char-
acteristic low molecular weight compounds representing typical
HTC intermediates according to Channiwala’s approach. Due to
decarboxylation, dehydration and condensation reactions, both
HTC coals showed distinctively higher HHV values compared to
the input feedstock and the aqueous HTC phase. The energy densi-
fication of the coalification process as expressed by the HHVBiocoal/
HHVFeedstock ratio amounted to 1.35 for the 200 °C-biocoal and 1.43
for the 240 °C-biocoal (Table 4). Obviously, energy densification is
due to mass decrease as a result of deoxygenization. Hence, the
higher the operating HTC temperature, the higher the calorific
value of the coal. However, higher operating temperatures entail
higher heat consumption and higher pressures associated with
the need to use more robust autoclaves (i.e. higher costs, higher
explosion risk).
Calorific data of both biocoals were slightly higher than those of
brown coal and lignin, and significantly higher than those of carbo-
hydrates, but lower compared to those of anthracite and lipids (tri-
palmitin considered synonymous for acylglycerines here).
Experimental literature data available for BSG derived biocoal-
200 °C (29.6 MJ kg1) and input feedstock (20.1 MJ kg1)
(Heilmann et al., 2011) coincide with our calculations shown in
Table 4. The calorific values calculated for both aqueous product
streams (20.5 and 20.9 MJ kg1) agreed well with experimental
data gathered for process waters from mixed municipal waste
and paper waste (Berge et al., 2011).
3.5. Sorption coefficients of organic compounds onto HTC coal (200 °C)
The sorption capability of HTC coals constitutes an important
feature regarding the potential application as sorbent for waste-
water treatment or their utilization for soil improvement. Fig. 2
Table 4
Calorific data according to Channiwala for BSG, HTC-product streams and selected
organic compounds.
depicts sorption coefficients referred to OC (KOC) for selected sol-
utes in relation to their hydrophobicities, expressed by their oct-
anol–water (KOW) coefficients. The chosen solutes cover a wide
range of hydrophobicities and polarities. Data for hydrophobic
PAHs naphthalene through phenanthrene revealed a strong
Log KOC – Log KOW correlation (dashed line in Fig. 2). Sorption
coefficients of PAHs were very similar to those measured on
coal-derived dissolved humic acids supplied by Roth and Aldrich
ð2Þ (Kopinke et al., 2002). In contrast to that, sorption coefficients
(mg kg1/L mg1) for granular activated carbon are higher by
orders of magnitude (see Supplementary information section
S-3). The specific surface area of both biocoals determined by
the BET-method (200 °C: 1.5 m2 g1, 240 °C: 2.2 m2 g1) turned
out lower by orders of magnitude compared to those of activated
carbons and pyrogenic charcoals, but was similar to those
determined for HTC biocoals produced from poultry litter
(2.0–8.7 m2 g1) (Sun et al., 2011). Thus, microporosity is not
intensely developed in BSG derived biocoals. The sorption coeffi-
cients of functionalized organic solutes were higher compared to
the arbitrary ‘‘PAH-line’’, mainly driven by non-specific hydro-
phobic interactions. This deviation mirrors the contribution of
specific interactions, the most important of which are based on
hydrogen bond polarity. Clearly, H-bonding acceptor or donor
parameters of PAHs are close to zero. The highest deviations
from the hydrophobic line were found for N-aromatics including
nitrobenzene, skatol, and aniline. The latter is not addressed in
Fig. 2 due to its very low hydrophobicity (Log KOW = 0.96) and
its protonation at pH  4.
It should be noted that the SPME-based protocol applied to
determine sorption coefficients (‘‘one point measurement’’ rather
than measurement of isotherms) does not allow assessing linearity
versus non-linearity of sorption isotherms. In a former contribu-
tion (Sun et al., 2011) the Freundlich exponent was 0.75–0.91 for
phenanthrene sorption on HTC biocoal produced from poultry lit-
ter at 250 °C for 20 h. The nonlinearity of the isotherms for Bisphe-
nol A and 17a-ethinyl estradiol turned out even higher. This
nonlinearity may be referred to surface-related adsorption or pre-
ferred sorption sites (e.g. nanovoids) located inside the condensed
aromatic network.
In summary, application of BSG derived biocoals to prevent
leaching of organic compounds and to improve soil characteristics
is feasible. Their application to bind inorganic species such as
highly mobile U(VI)-, Cr(VI)- and As(V)-species seems more
straightforward due to the high density of hydrophilic groups as
shown above.

Matrixa HHVChanniwala (MJ kg1 ‘‘fuel’’) 5.0 Log KOC

Fluorene

BSG-substrate 22.3
DOM at 200 °C 20.5 (17)b 4.5
Phenanthrene

(62)b
ß-HCH

Biocoal at 200 °C 29.9

DOM at 240 °C 20.9 (16)b
4.0
Naphthol-1

(62)b
Lindane

Biocoal at 240 °C 31.8

2,3,5-TM-Phenol

Acenaphthene

Brown coal (C120H128O32S1) 28.5

p-Chlorophenol

Anthrazite (C63H24O1) 36.5 3.5

200°C
Skatol
Nitrobenzene

3,5-Xylenol

Trichloro-Benzene

Cellobiose (C12H22O11) 16.9 240°C

Glucose (C6H12O6) 16.3 3.0 PAH-200°C
TeM-Phenol

Lignin (average C26H46O10) 28.3 PAH-240°C

p-Cresol

Naphthalene

Tripalmitin (C51H98O6) 39.5

Phenol

2.5
Phenol (C6H6O1) 32.5
Benzenediol (C6H6O2) 26.3
Furfural (C5H4O2) 23.3 2.0
Benzoic acid (C7H6O2) 27.1 Log KOW
1.5
a
Carbon used in Eq. (2) to calculate HHV-data: organic carbon (inorganic carbon 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
not considered).
b
Data in parentheses: energetic retention efficiency (mBiocoal  HHVBiocoal)/ Fig. 2. Sorption of selected organic compounds on HTC coals versus hydrophobicity
(mFeedstock  HHVFeedstock), or (mDOM  HHVDOM)/(mFeedstock  HHVFeedstock), each in %. (TM – trimethyl, TeM – tetramethyl).
168 J. Poerschmann et al. / Bioresource Technology 164 (2014) 162–169

3.6. Organic compounds in HTC process water Clearly, pyrazines – known to be Maillard products formed during
roasting - originated from proteins, which are hydrolyzed during
Selected analytes representing significant compound classes HTC. Likewise, their sorption potential is low.
in both the non-treated BSG feedstock and HTC matrices (at
operating temperature of 200 °C) are listed in Table 5. A more
4. Conclusions
detailed component analysis of the HTC process water compris-
ing a multitude of fatty acids, phenolic acids, short-chain
BSG as an important side product of brewing processes proved
mono- and dicarboxylic acids, alkylphenols, cyclic ketones,
an appropriate substrate for wet hydrothermal carbonization. Pro-
N- and S-functionalized organic compounds will be given in a
spective application fields of the biocoal include soil improvement
forthcoming contribution.
and sorbent uses, the latter being more significant for functional-
The fatty acid pattern was characterized by high abundances of
ized, hydrophilic organic compounds as well as inorganic species.
palmitic acid, oleic acid (18:1x9c), and linoleic acid (18:2x6, 9 cc),
The aqueous product stream turned out a very good substrate for
their combined concentration in lipids as released by alkaline
biogas production. Alternatively, it might be subjected to subse-
saponification amounting to approximately 2.7% (w/w) referred
quent wet oxidation to significantly reduce the DOC fraction along
to dry mass of BSG. The combined concentration of C12–C30 ali-
with improving the energy autarchy of the HTC process. Calorific
phatic monocarboxylic acids amounted to approximately 4.2%,
considerations revealed a similarity of HHV data for HTC coals
which coincides well with the total lipid content of 7.3% (Table 1).
and lignite.
The largest fraction of fatty acids was bound in lipids including
triacylglycerines, with less than 10% of total fatty acids being pres-
ent in their free state (for palmitic acid: compare 1050 lg g1 in Acknowledgements
BSG versus 16,100 lg g1 in saponified BSG). Hydrolysis as a result
of the hydrothermal treatment proved quantitative: saponification We thankfully acknowledge the work of A. Raemmler (X-ray
of DOM did not result in an increase of fatty acid concentrations. fluorescence spectroscopy), D. Sonntag (elemental analysis) and
However, lipids do not significantly contribute to biocoal forma- B. Forkert (BET analysis). Furthermore, we thank the Federal Min-
tion as it was already reported by Heilmann et al. (2011). As a istry of Education and Research of Germany for financial support in
rough estimate, about 40% of fatty acids survived the HTC process the framework of the International Water Research Alliance
under the applied, moderate conditions (200 °C, 16 h). In line with Saxony (IWAS) project.
sorption data presented in Section 3.5., the major fraction of the
released fatty acids turned out to be sorbed onto biocoal particles.
Only a small fraction was present in the aqueous phase, either Appendix A. Supplementary data
sorbed onto DOM macromolecules or freely dissolved. Phenols
including lignin-originating surrogates as well as benzenediols in Supplementary data associated with this article can be found, in
their free state were basically absent in the input substrate. Phenol the online version, at http://dx.doi.org/10.1016/j.biortech.2014.04.
along with (alkylated) phenols and (alkylated) benzenediols may 052.
have different sources as a result of hydrothermal treatment
(Poerschmann et al., 2013), the most important of which are carbo- References
hydrates (Sevilla and Fuertes, 2009). Hemicellulose as a source
which is reported to be hydrolyzed at temperatures starting from ASTM D5210-92 (American Society for Testing and Materials), 2007. Standard test
method for determining the anaerobic biodegradation.
180 °C is of greater significance compared to cellulose, because Baccile, N., Laurent, G., Babonneau, F., Fayon, F., Titirici, M.-M., Antonietti, M., 2009.
the hydrolysis onset of the latter is at 200 °C (Peterson et al., Structural characterization of hydrothermal carbon spheres by advanced solid-
2008). Clearly, guaiacol and syringol formation during HTC induced state MAS 13C NMR investigations. J. Phys. Chem. C 113, 9644–9654.
Berge, N.D., Ro, K.S., Mao, J., Flora, J.R.V., Chappell, M.A., Bae, S., 2011. Hydrothermal
hydrolysis originates from lignin. All phenols listed in Table 5 share carbonization of municipal waste streams. Environ. Sci. Technol. 45, 5696–
the common characteristic of not being significantly sorbed onto 5703.
the particulate biocoal. Analogously to phenols, cyclopentenones Buckley, T.J., 1991. Calculation of higher heating values of biomass materials and
waste components from elemental analyses. Resour. Conserv. Recyc. 5, 329–
(predominantly C2-cyclopenten-1-ones) arise from carbohydrates.
341.
Channiwala, S.A., Parikh, P.P., 2002. A unified correlation for estimating HHV of
solid, liquid and gaseous fuels. Fuel 81, 1051–1063.
Table 5 Escala, M., Zumbuehl, T., Koller, C., Junge, R., Krebs, R., 2013. Hydrothermal
Concentration of selected analytes in the BSG-substrate and in HTC-product streams carbonization as an energy-efficient alternative to established drying
at 200 °C (in lg g1 DM BSG). technologies for sewage sludge: a feasibility study on a laboratory scale.
Energy Fuel 27, 454–460.
Analyte BSGa BSG saponifieda HTC-slurrya DOMa Faulds, C.B., Mandalari, G., LoCurto, R., Bisignano, G., Waldron, K.W., 2004.
Arabinoxylan and mono- and dimeric ferulic acid release from brewer’s grain
Palmitic acid 1050 16,100 5900 350 and wheat bran by feruloyl esterases and glycosyl hydrolases from Humicola
Oleic acid 330 3700 1200 55 insolens. Appl. Microbiol. Biotechnol. 64, 644–650.
Linoleic acid 570 7300 3150 130 Funke, A., Ziegler, F., 2009. Hydrothermal carbonization of biomass: a summary and
Phenol 19 11 210 170 discussion of chemical mechanisms for process engineering. Biofuels Bioprod.
R Benzenediolsb 3 nnc 345 285 Bioref. 4, 160–177.
Guaiacol nn nn 460 340 Funke, A., Ziegler, F., 2011. Heat of reaction measurements for hydrothermal
Syringol nn nn 390 245 carbonization of biomass. Bioresour. Technol. 102, 7595–7598.
R Cyclopentenonesb nn nn 35 30 Heilmann, S.M., Jader, L.R., Sadowsky, M.J., Schendel, F.J., Keitz v., M.G., Valenta, K.J.,
R Pyrazinesb nn nn 110 85 2011. Hydrothermal carbonization of distiller’s grains. Biomass Bioenergy 35,
2526–2533.
a
Shorthand designation of preparation (see chapter 2): (i) BSG: lyophilizate Janzon, R., Schuett, F., Oldenburg, S., Fischer, E., Koerner, I., Saake, B., 2014. Steam
subjected to: exhaustive solvent extraction; (ii) BSG saponified: lyophilizate pretreatment of spruce forest residues: optimal conditions for biogas
refluxed with 3 N methanolic KOH, filtrate lyophilized then exhaustively extracted, production and enzymatic hydrolysis. Carbohydr. Polym. 100, 202–210.
Kopinke, F.-D., Georgi, A., Mackenzie, K., Kumke, M.U., 2002. Sorption and chemical
(iii) HTC-slurry: exhaustive solvent extraction of slurry lyophilizate, (iv) DOM:
reactions of polycyclic aromatic hydrocarbons with dissolved refractory organic
exhaustive solvent extraction of DOM-lyophilizate (DOM obtained after coal
substances and related model polymers. In: Frimmel, F.H. et al. (Eds.),
filtration).
b
Refractory Organic Substances in the Environment. Wiley-CH.
Analytes include methylated and C2-alkylated surrogates. Lu, X., Flora, J.R.V., Berge, N.D., 2014. Influence of process water quality on
c
Below detection limit. hydrothermal carbonization of cellulose. Bioresour. Technol. 154, 229–239.
 J. Poerschmann et al. / Bioresource Technology 164 (2014) 162–169
Malghani, S., Gleixner, G., Trumbore, S.E., 2013. Chars produced by slow pyrolysis
and hydrothermal carbonization vary in carbon sequestration potential and
greenhouse gases emission. Soil Biol. Biochem. 62, 137–146.
Mumme, J., Eckervogt, L., Pielert, J., Diakité, M., Rupp, F., Kern, J., 2011.
Hydrothermal carbonization of anaerobically digested maize silage. Bioresour.
Technol. 102, 9255–9260.
Mussatto, S.I., Fernandes, M., Milagres, A.M.F., Roberto, I.C., 2008. Effect of
hemicellulose and lignin on enzymatic hydrolysis of cellulose from brewer’s
spent grain. Enzyme Microb. Technol. 43, 124–129.
Niemi, P., Tamminen, T., Smeds, A., Viljanen, K., Ohra-aho, T., Holopainen-Mantila,
U., Faulds, C.B., Poutanen, K., Buchert, J., 2012. Characterization of lipids and
lignans in brewer’s spent grain and its enzymatically extracted fraction. J. Agric.
Food Chem. 60, 9910–9917.
Ohno, T., He, Z., Sleighter, R.L., Honeycutt, C.W., Hatcher, P.G., 2010. Ultrahigh
resolution mass spectrometry and indicator species analysis to identify marker
components of soil- and plant biomass-derived organic matter fractions.
Environ. Sci. Technol. 44, 8594–8600.
Oliveira, I., Bloehse, D., Ramke, H.G., 2013. Hydrothermal carbonization of
agricultural residues. Bioresour. Technol. 142, 138–146.
Parshetti, G.K., Hoekman, S.K., Balasubramanian, R., 2013. Chemical, structural and
combustion characteristics of carbonaceous products obtained by hydrothermal
carbonization of palm empty fruit bunches. Bioresour. Technol. 135, 683–689.
Peterson, A.A., Vogel, F., Lachance, R.P., Froeling, M., Antal Jr., M.J., Tester, J.W., 2008.
Thermochemical biofuel production in hydrothermal media: a review of sub-
and supercritical water technologies. Energy Environ. Sci. 1, 32–65.
Poerschmann, J., Schultze-Nobre, L., 2014. Sorption determination of phenols and
polycyclic aromatic hydrocarbons in a multiphase constructed wetland system
by solid phase microextraction. Sci. Total Environ. 482–483, 234–240.
Poerschmann, J., Baskyr, I., Weiner, B., Koehler, R., Wedwitschka, H., Kopinke, F.D.,
2013. Hydrothermal carbonization of olive mill wastewater. Bioresour. Technol.
133, 581–588.
169
Santos, M., Jiménez, J.J., Bartolomé, B., Gómez-Cordovés, C., 2003. Variability of
brewer’s spent grain within a brewery. Food Chem. 80, 17–21.
Schmidt, T., Proeter, J., Scholwin, F., Nelles, M., 2013. Anaerobic digestion of grain
stillage at high organic loading rates in three different reactor systems. Biomass
Bioenergy 55, 285–290.
Schuchardt, F., Vorlop, K.-D., 2010. Estimation of the carbon amount in biomass
residues in Germany for hydrothermal carbonization (HTC) and disposal of HTC
coal to the soil. Agric. Forestry Res. 60, 205–212.
Sevilla, M., Fuertes, A.B., 2009. Chemical and structural properties of carbonaceous
products obtained by hydrothermal carbonization of saccharides. Chem. Eur. J.
15, 4195–4203.
Sparling, G.P., Cheshire, M.V., Mundie, C.M., 1982. Effect of barley plants on the
decomposition of 14C-labelled soil organic matter. J. Soil Sci. 33, 89–100.
Steinbeiss, S., Gleixner, G., Antonietti, M., 2009. Effect of biochar amendment on soil
carbon balance and soil microbial activity. Soil Biol. Biochem. 41, 1301–1310.
Stemann, J., Putschew, A., Ziegler, F., 2013. Hydrothermal carbonization: process
water characterization and effects of water recirculation. Bioresour. Technol.
143, 139–146.
Sun, K., Ro, K., Guo, M., Novak, J., Mashayekhi, H., Xing, B., 2011. Sorption of
bisphenol A, 17a-ethinyl estradiol and phenanthrene on thermally and
hydrothermally produced biochars. Bioresour. Technol. 102, 5757–5763.
Titirici, M.-M., Antonietti, M., 2010. Chemistry and materials options of sustainable
carbon materials made by hydrothermal carbonization. Chem. Soc. Rev. 39,
103–116.
VDI (Verein Deutscher Ingenieure) 4630, 2006. Fermentation of organic materials –
characterization of the substrate, sampling, collecting of material data.
Fermentation tests. Beuth Publ., Berlin.
Zhang, Z., Cao, X., Liang, P., Liu, Y., 2013. Adsorption of uranium from aqueous
solution using biochar produced by hydrothermal carbonization. J. Radioanal.
Nucl. Chem. 295, 1201–1208.