Research Article

pubs.acs.org/journal/ascecg

Hydrothermal Carbonization of Digestate in the Presence of Zeolite:

Process Efficiency and Composite Properties
Jan Mumme,*,† Maria-Magdalena Titirici,‡ Anke Pfeiffer,§ Ulf Lüder,§ M. Toufiq Reza,∥
and Ondřej Mašek†
†
UK Biochar Centre, School of GeoSciences, University of Edinburgh, Crew Building, King’s Buildings, Edinburgh EH9 3JN, U.K.
‡
School of Engineering and Materials Science, Queen Mary University of London, Mile End Road, London E1 4NS, U.K.
§
Leibniz Institute for Agricultural Engineering Potsdam-Bornim, Max-Eyth-Allee 100, 14469 Potsdam, Germany
∥
Department of Chemical and Materials Engineering, University of Nevada, Reno, 1664 North Virginia Street, Reno, Nevada 89557,
United States
*
S Supporting Information

ABSTRACT: A systematic experimental study on hydro-

thermal carbonization (HTC) of digestate was conducted to
evaluate the catalytic impact of natural zeolite and the
properties of the produced hydrochar−zeolite composites
(HZCs). An agricultural digestate and, as reference, micro-
crystalline cellulose (MCC) were treated at HTC temperatures
of 190, 230, and 270 °C. HZCs were analyzed for their
elemental composition, NMR structural properties, thermog-
ravimetric behavior, N2 adsorption porosity, and scanning
electron microscopy morphology. The results indicate distinct
catalytic effects of zeolite on carbonization. For digestate,
catalytic effects of zeolite increased the degree of carbonization
equally to a 9−29 K higher HTC temperature. Zeolite
increased the energy and carbon recovery in solid products for digestate, whereas MCC showed a lower recovery. Interestingly,
zeolite preserved the cellulose fraction of digestate. This was attributed to physical and chemical shielding by formation of a
visible zeolite layer on organic particles. Compared to pure hydrochar, the HZCs showed less aromatic and thermally stable
carbon but higher surface area and pore volume. Potential areas of applications for the HZCs range from energetic use (e.g.,
gasification) to soil amendment and additive in bioprocesses (e.g., growing media).
KEYWORDS: Biochar, Biogas, Carbon−mineral composites, Catalysis, NMR, Proximate analysis, Porosity

■ INTRODUCTION
Hydrothermal carbonization (HTC) is not a new field of
research; it has its origin in the first decades of the twentieth
century when it was used to learn the mechanisms of natural
coalification.1 Later, hydrothermal degradation of organic
matter and synthesis of basic chemicals as well as liquid and
gaseous fuels gained scientific interest.2−4 Research activities
that focused on the solid product, termed hydrochar, began in
recent years. It was found that the process can yield nano- and
microsize carbon particles with distinct properties such as high
energetic value, high chemical and thermal stability, and
moderately high surface area and adsorption capacity.5−7
Consequently, hydrochars are discussed as solid biofuels8−11
and for various industrial, environmental, and agricultural
applications.12−15 Furthermore, integration of HTC in
bioconversions (e.g., for biogas or bioethanol production) is
assumed to considerably improve the overall energy efficiency
by making use of its organic wastes.16,17
With respect to the economic feasibility of HTC, the most
promising area of application is the treatment of high-moisture
waste biomass like sewage sludge or municipal solid waste.18
For municipal solid waste, commercial application of HTC has
already been demonstrated.19 However, when compared to
other waste treatments like anaerobic digestion, composting, or
incineration, commercial applications of HTC are still
developing. Another interesting feedstock for thermochemical
conversion is digestate. Its traditional use as soil amender and
organic fertilizer could become more and more restricted
because of environmental and economic reasons.20,21 Fur-
thermore, the feasibility of hydrothermal conversion of
digestate into hydrochar has been repeatedly demonstra-
ted.16,22,23
A known drawback of HTC are losses of carbon and energy
by the production of soluble and gaseous byproducts usually
ranging between 20 and 50%.10−12,16,23,24 In addition, several
volatile organic compounds (VOCs) contained in HTC liquids
Received: August 26, 2015
Revised: October 6, 2015

© XXXX American Chemical Society A DOI: 10.1021/acssuschemeng.5b00943

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are toxic,25,26 which increases the cost of wastewater treatment
and, in the case of a material use, of the post-treatment of
hydrochar products. Furthermore, large-scale application is also
hindered by immature HTC technology, which is still mostly
operating in batch-mode, and high costs associated with high-
temperature, high-pressure processing of heterogenic wastes.
To tackle these obstacles, a range of catalysts (both
homogeneous and heterogeneous) has been investigated
including various organic acids and noble metals.27−29 A well-
known natural catalyst is the mineral zeolite, which derives its
functionality from a high specific surface area and its strong acid
sites resulting from substitution of Si by Al in its framework.30
Today, technically produced zeolites are among the most
important catalysts in chemical conversion (e.g., for catalytic
cracking, biomass conversion into chemicals, etc.). It was
shown that all of these different catalysts are capable of
catalyzing certain reactions involving HTC, e.g., use of zeolite
as sacrificial template to produce porous carbons.31 But this
faces limits with respect to energy and cost efficiency.
In light of the current state of the art, it is of high interest to
investigate to what extent natural zeolite can be used for
catalysis of HTC and production of hydrochar−zeolite
composites (HZC) with distinct properties for environmental
and other applications. Consequently, the overall aim of the
present study was to assess the effect of natural zeolite as an
alternative catalyst on the HTC process and solid product.
Individual objectives were (i) to characterize and quantify
potential catalytic effects of zeolite on HTC of digestate and
microcrystalline cellulose (MCC); (ii) to describe the impact of
zeolite on the yields and recovery rates of hydrochar, carbon,
minerals, and energy; (iii) to describe the material properties of
HZCs concerning elemental composition, chemical structure,
morphology, and porosity; and (iv) to classify the thermal
stability of carbons within the HZCs and pure hydrochars.
■
EXPERIMENTAL SECTION
Origin and Properties of Feedstocks. In this study, natural
digestate and, as reference, MCC were used as feedstock for HTC.
The digestate was obtained in dried state from an on-farm biogas plant
(Hof Karp, Rastow, Germany), which uses cow manure and maize at a
mass ratio of 4:3 as feedstock. A more detailed description of the
digestate origin can be found elsewhere.32 Before being processed, the
digestate was again dried for 24 h at 105 °C and then ground to a
particle size below 1 mm with cutting mill SM 100 from Retsch (Haan,
Germany). Industrial grade MCC (Avicel PH-101 Fluka) was obtained
from Sigma-Aldrich, Switzerland. Avicel PH 101 is a microcrystalline,
powdery material with an average particle size of 50 μm and a bulk
density of 0.28 g cm−3. The chemical properties are shown in Table 1.
Zeolite. A natural hydrated zeolite with particle size 0−100 μm
mainly composed of clinoptilolite (90−92%), cristobalite (5−7%),
feldspar (2−4%), mica (1−2%), and quartz (traces) was obtained from
Zeolithversand LTD (Germany). Based on the empirical chemical
formula Ca4K8Na8Mg4(Si40Al8)O96·24H2O provided by Zeolithver-
sand LTD, the zeolite’s crystal water (CW) amounts to a mass portion
of 10.6% of the zeolite. This was confirmed by thermogravimetric
analysis (TGA), which showed a mass loss of 11.0 ± 0.2% at 900 °C
(see Figure S1 in the Supporting Information) and is in good
agreement with data from another report.33 In consequence, it was
assumed that the whole mass loss of 11.0% represents CW and that
the eventual presence of external unbound water can be neglected.
Further material information provided by the supplier is as follows:
geometric bulk density, 1.60−1.80 kg L−1; specific weight, 2.20−2.44
kg L−1; porosity, 24−32%; effective pore size average, 0.4 nm;
compression strength, 33 MPa; thermal stability, <400 °C; acidic
stability, 79.5%; and Si/Al ratio, 4.8−5.4. According to data obtained
B DOI: 10.1021/acssuschemeng.5b00943
Research Article
from porosity measurements, the zeolite has a Brunauer−Emmett−
Teller (BET) surface area of 38.2 m2 g−1.
Design of Experiment and Hydrothermal Carbonization. For
the HTC experiments, a full factorial experimental design was used
comprising two feedstocks (digestate and MCC), addition of zeolite in
a dosage of 1 g zeolite per gram of feedstock and no zeolite addition
(control), and three HTC temperatures (190, 230, and 270 °C).
Further details including the dry matter (DM)-based zeolite-to-
feedstock ratios are shown in Table 1.
The HTC experiments were carried out in a Parr 1-L 4520 Series
stirred reactor (Moline, IL, US) equipped with an external resistance
heater. For the zeolite-containing experiments, a mixture of 50 g of
feedstock, 50 g of zeolite, and 600 g of distilled water was poured into
the reactor. The feedstock-only controls were carried out with 80 g of
feedstock and 620 g of distilled water. A heating rate of 2 K min−1 was
applied to reach set temperatures of 190 °C after 80 min, 230 °C after
100 min, and 270 °C after 120 min (starting temperature, 30 °C). The
set temperature was maintained for 120 min, after that the heater was
turned off and the reactor was left for natural cooling overnight.
During the whole experiment, the stirrer was operated at 90 rpm. The
next day, the slurry was vacuum filtered (max. 100 mbar) with a filter
paper (particle retention 5−8 μm). Afterward, the solids were dried for
15 h at 105 °C and stored under dry conditions for subsequent
analyses.
Analytical Methods and Calculation Basis. Contents of DM
and organic dry matter (ODM) were determined gravimetrically by
drying the samples at 105 °C for 24 h and ashing at 550 °C for 4 h,
respectively. The elemental composition (C, H, N, and S) was
determined using a Vario EL III elemental analyzer (Elementar
Analysensysteme GmbH, Germany). The DM-based content of O was
calculated by subtracting the measured elements and ash from 100%.
For correction purposes, the zeolite’s CW is of particular interest.
Based on TGA (see Figure S1), losses of CW during drying are about
5% of initial mass (dry, without external bound water), and another
6% are lost during ashing. As described earlier, the total CW content of
zeolite was assumed to be 11% of initial dry mass. This includes the
elements H and O, which stoichiometrically represent 1.22% and
9.78% of the dry but CW-containing mass of the zeolite. The content
of H was confirmed by a measured value of 1.27% (see Table 1). All
corrections were carried out with the stoichiometric values. The
equations used to calculate and correct the HZC’s contents of DM,
ODM, ash, and C, H, N, and S elements are provided in the
Supporting Information.
13
C CP/MAS solid-state NMR was performed with a Bruker Avance
300 MHz spectrometer, operated at a magic-angle spinning (MAS)
rate of 14 kHz. For rotation, 4 mm zirconia sample holders were used.
TGA was conducted with a Mettler-Toledo TGA/DSC1 instru-
ment, equipped with an autosampler. The 7−24 mg samples of each
ground and dried material were weighed into 70 μL alumina crucibles.
The program comprised the following consecutive steps: (1)
equilibration for 2 min at 25 °C, (2) water evaporation with
temperature increased to 110 °C (heating rate 25 K min−1) and held
for 10 min, (3) pyrolysis with temperature increased to 900 °C
(heating rate 25 K min−1) and held for 10 min, and (4) oxidation
(ashing) for 30 min at 900 °C. Steps 1−3 were conducted under N2
atmosphere (flushed at 50 mL min−1), whereas step 4 was aerobic
(flushed with air at 50 mL min−1). All analyses were conducted in
triplicate.
The measurement data was pre-evaluated and converted to ASCII
format by means of Mettler-Toledo STARe evaluation software v13.
Final data assessment was performed by MS Excel 2013. This included
proximate analysis with normalization of data and attribution of mass
losses to the individual phases. Fixed carbon content was calculated on
a mass basis by subtracting moisture, volatile, and ash content from the
original mass of the sample.
Porosity and surface analyses were conducted for HZCs as well as
for raw digestate and raw zeolite by using a QuadraSorb SIMP analyzer
(Quantachrome Instruments, US). The specific surface area was
measured based on N2 adsorption and multipoint BET method
according to ISO Standard 9277. Barrett−Joyner−Halenda (BJH),
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Table 1. Process Conditions, Composition of Solid Product and Yieldsa

composition, yield, and energy content of hydrochar and HZC
recovery (% initial
process conditions elements (%DM) amount) HHV
b c d
sample dig. (gDM) zeo. (gDM) temp (°C) C (%ODM) H O ash (%DM) DM ODM ash XZeo J/kgDM J/kgODM
zeolitee N.A. N.A. N.A. N.A. 1.27 9.77 88.96 N.A. N.A. N.A. N.A. N.A. N.A.
dig. N.A. N.A. N.A. 47.60 (53.15) 7.07 32.62 10.45 N.A. N.A. N.A. N.A. 21.8 24.4
MCC N.A. N.A. N.A. 43.67 (43.67) 6.70 49.63 N.D. N.A. N.A. N.A. N.A. 18.4 18.4
D-190 74.08 0 190 51.12 (55.87) 6.11 32.05 8.51 70.5 72.1 57.4 N.A. 21.7 23.8
D-230 74.08 0 230 61.68 (73.30) 5.43 13.94 15.85 45.7 43.0 69.4 N.A. 26.4 31.4
D-270 74.08 0 270 62.74 (74.95) 5.55 12.27 16.29 42.1 39.3 65.6 N.A. 27.2 32.5
DZ-190 46.30 50 190 22.06 (61.84) 3.08 16.05 57.88 78.7 65.2 88.9 0.59 9.5 26.4
DZ-230 46.30 50 230 22.89 (75.20) 2.90 10.56 62.58 73.7 52.1 90.1 0.63 10.3 33.1
DZ-270 46.30 50 270 21.28 (77.69) 2.57 9.63 65.33 71.3 45.3 90.9 0.66 9.4 33.6
C-190 76.60 0 190 42.40 (42.40) 6.85 50.58 N.D. 95.8 95.8 N.A. N.A. 18.1 18.1
C-230 76.60 0 230 70.68 (70.68) 4.35 24.84 N.D. 47.8 47.8 N.A. N.A. 26.6 26.6
C-270 76.60 0 270 70.88 (70.88) 4.24 24.72 N.D. 46.2 46.2 N.A. N.A. 26.5 26.5
CZ-190 47.88 50 190 24.64 (48.29) 4.23 27.40 43.59 93.4 97.4 89.6 0.49 10.6 20.9
CZ-230 47.88 50 230 21.77 (71.00) 2.22 14.24 61.71 68.8 43.2 93.4 0.69 8.4 26.9
CZ-270 47.88 50 270 20.40 (68.41) 2.18 14.88 62.46 63.0 38.4 86.5 0.70 7.8 25.7
a
N.A., not available or not applicable; N.D., not detected. bCalculated by subtracting percentage of C, H, N, S, and ash from 100%. Calculation for
HZC with corrected ash content by eq 13 in Supporting Information. cValues for HZC corrected by eq 8 in Supporting Information. dXZeo: dry
matter (DM) portion of zeolite within composites calculated by eq 9 in Supporting Information. eFor zeolite: H and O represent CW. H was
measured by elemental analysis, ash by TGA, and O was assumed to be the remainder of 100%.

Horvath−Kawazoe (HK), and non-local density functional theory
(NLDFT) methods were used to determine the volume of meso- and
micropores according to DIN Standard 66134 and DIN Standard
66135, respectively. Scanning electron microscopy (SEM) imaging was
performed on a Cambridge S200 scanning electron microscope at an
accelerating voltage of 20 kV at a distance of 18 mm.
higher temperatures led to an increased ratio of zeolite within
the HZCs.
Impact of HTC Temperature and Zeolite on the
Degree of Carbonization. The impact of HTC temperature
and presence of zeolite was evaluated based on the shifts in

■
terms of the O/C versus H/C atomic ratio in the Van Krevelen
diagram (Figure 1).
RESULTS AND DISCUSSION
Solid Product Yield and Elemental Composition. All
individual HTC experiments with pure feedstock and with
addition of zeolite resulted in solid product as expected. Thus,
all process and material data were considered suitable for
subsequent analyses and assessment. Elemental composition of
the solid products, the recovery of DM, ODM, and ash as well
as the estimated fraction of zeolite within the hydrochar−
zeolite composites are shown in Table 1 along with the HTC
process conditions.
It was found that at higher temperature, as expected, the
ODM-based carbon content increased, while the amount of
oxygen declined. At 190 °C, carbonization of the MCC was not
detected, which is in accordance with earlier findings.22
Interestingly, only little changes occurred between 230 and
270 °C in the pure hydrochars. An earlier study on HTC of Figure 1. Van Krevelen diagram showing chemical changes of
digestate showed a more pronounced change between these digestate (D) and cellulose (C) by HTC temperature and zeolite (Z).
temperatures,22 probably reflecting a different composition of
both digestates.
Naturally, the addition of zeolite increased the ash content This graphical evaluation confirms the earlier described
and reduced the concentration of all other compounds. At strong changes between 190 and 230 °C. At 190 °C, the
higher temperatures, the recovery of solid matter declined influence of the zeolite is clearly visible. Between 230 and 270
moderately for DM and strongly for ODM. This can be °C, the impact of temperature and zeolite was considerably
attributed to a stronger conversion of organic matter into lower. MCC treated at 190 °C was found to be chemically
volatile compounds (e.g., CO2, acids, aldehydes, etc.) that are stable, but some hydration of MCC might have taken place.34
lost to the liquid or gas phase.12,13,26 There is no clear trend for For quantification of the catalyzing effect of zeolite, an
the recovery of mineral compounds, which might indicate estimation of temperature replacement was carried out based
antagonistic dissolving and precipitation mechanisms during on changes in the carbon content (wC) of the ODM (see Table
HTC. Because of disproportionate losses of organic matter, 1). Because of insufficient data for MCC, evaluation of the
C DOI: 10.1021/acssuschemeng.5b00943
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catalyzing effect was limited to digestate. A simple regression
model
wC = a + b·ϑp + c·tr (1)
was used to describe the influence of HTC temperature (ϑp)
and time (tr) on wC. Using cofactors reported earlier for HTC
of digestate (a = −38.4, b = 0.21, c = 0.54)22 revealed a
relatively good fit (R2 = 0.81). Fitting of the present study’s
measurement results reduced the sum of least-squares only
slightly from 44.3 to 41.5. Thus, further evaluation was carried
out with the original cofactors, which assumes an average
carbon increase of 0.21%ODM per K. Considering the differences
in the carbon content of digestate-only and zeolite-added HTC
products at 190 °C (ΔwC = 6%ODM), 230 °C (ΔwC =
1.9%ODM), and 270 °C (ΔwC = 2.7%ODM), a temperature
replacement by zeolite of 28.4, 9.0, and 13.1 K, respectively,
was found. The average temperature replacement for the whole
investigated temperature range of 190−270 °C was 16.8 K.
Certainly, these results provide only a rough orientation.
Further investigations are necessary to reveal the underlying
catalytic mechanisms and to determine the mass-specific effects
of the zeolites.
13
C CP/MAS Solid-State NMR Investigations. Figure 2
shows the 13C CP/MAS solid-state NMR spectra of digestate in
raw, carbonized, and HZC state in the area of the chemical
shifts between 0 and 250 ppm.
Figure 2. NMR spectra of raw digestate, hydrochar derived from
digestate treated at 230 °C (D-230), and hydrochar−zeolite composite
from digestate and zeolite treated at 230 °C (DZ-230).
The spectrum of the raw digestate indicates a strong
presence of cellulose with typical signals at 104.8 ppm (C-1),
74.2 ppm (C-2, C-3, and C-5), 83.3 and 88.1 ppm (C-4), and
64.3 ppm (C-6) as reported earlier.35−37 The presence of
hemicellulose is suggested by acetate group peaks at 21.3 ppm
for methyl carbons and 172.8 ppm for carboxyl carbons,36,38
D DOI: 10.1021/acssuschemeng.5b00943
Research Article
while lignin is indicated by various peaks from oxygen-bound
aromatic carbons at 146.7 and 153.1 ppm from phenolic groups
and aromatic ethers.39 The peak at 55.9 ppm indicates methyl
carbons in methoxyl groups of lignin.36,38,39
HTC of pure digestate for 2 h at 230 °C (D-230) removed
all signs of cellulose from the spectrum. Meanwhile, signals
indicating guaiacyl and syringyl residues in lignin at 55.3 ppm
(methoxyl groups), 133.0 ppm (propyl-bound aromatic
carbon), and 146.8 (carbon bound to C3/C5) became more
pronounced. This suggests the complete conversion of cellulose
at 230 °C, while lignin remained largely intact. These
observations correspond well with a previous NMR study on
HTC-treated digestate especially at a temperature of 260 °C.38
Surprisingly, the NMR spectrum of the zeolite-containing
composite (DZ-230) differs considerably from that of the pure
hydrochar, despite the same digestate and same HTC
conditions being applied. Most noticeable is the clear presence
of the cellulose peaks, especially at 104.5 and 74.6 ppm, as
already described for raw digestate. Interestingly, the differently
shaped C-4 signals of cellulose at 89 ppm (crystalline regions)
and 84 ppm (amorphous regions) suggest a stronger
degradation of amorphous cellulose. Furthermore, the typical
lignin signals found in D-230 (e.g., 55.8, 133.0, and 147.0 ppm)
are also present in DZ-230. A signal at 176.2 ppm not observed
for D-230 could be associated with carboxyl carbons of
lignin.36,38
These findings suggest a stabilizing effect of zeolite on the
digestate’s cellulose. This agrees with both SEM analysis, which
shows formation of a zeolite layer on organic plant tissues, and
TGA, which revealed a higher ratio of volatile to fixed carbon
for the DZ-230 sample. According to Van Krevelen analysis,
however, D-230 and DZ-230 reached almost an identical level
of carbonization, which appears contradictory. A possible
explanation might be a relatively low content of cellulose in
DZ-230 and a disproportionately high degree of decarbox-
ylation and dehydration of other organic compounds. Besides a
shielding effect, also some buffering can be expected from
zeolite potentially suppressing the hydrolysis step. However,
the almost identical final pH values of the HTC liquors from D-
230 (pH 4.49) and DZ-230 (pH 4.54) do not support a major
impact from buffering. Furthermore, according to a previous
HTC study showing little degradation of digestate-cellulose at
220 °C after 2 h but strong degradation at 220 °C after 6 h,38
the 230 °C used in this study can be assumed to be the
threshold temperature for the hydrolysis of digestate-cellulose.
A compound of the digestate that completely vanished in D-
230 and DZ-230 was hemicellulose, as can be assumed from the
lack of acetate bands at 21.0 and 172 ppm. Hemicellulose is
well-known for its low thermal stability40 and was previously
reported to disappear already at 180 °C in HTC.38 The
aliphatic band of the digestate’s NMR spectrum at 30−35 ppm
sustained the HTC process in both products and became even
more pronounced. The same effect for pure digestate-derived
hydrochars was previously reported.38
In contrast to DZ-230, the MCC-derived CZ-230 composite
shows no typical cellulose peaks and only small differences with
the spectra of C-230 (Figure 3). Hydrothermal decomposition
of MCC at temperatures above 200 °C is in accordance with
previous studies.37,41
Element and Energy Recovery in Solid Products. The
recovery of the elements and chemical energy was calculated for
the feedstocks (i.e., digestate and cellulose) entering the HTC
process and the solid phase leaving the process. Contributions
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Figure 3. NMR spectra of hydrochar derived from microcrystalline
cellulose treated at 230 °C (C-230) and hydrochar−zeolite composite
from microcrystalline cellulose and zeolite treated at 230 °C (CZ-
230).
of the zeolite’s CW to the contents and recovery of H and O
were corrected using eqs 11 and 12 in the Supporting
Information. The results are shown in Figure 4.
The recovery of C, H, and O was found to decrease at higher
HTC temperatures, which is in good agreement with previous
studies12,16,22,23 and can be attributed to an intensified
production of CO2 and VOCs. For digestate and zeolite
processed at 190 °C, the recovery of carbon, hydrogen, and
energy was determined to be above 100%. Because the cellulose
was found to be relatively stable at 190 °C, very high recovery
rates can be expected. The exceedance of 100% might be
Figure 4. Recovery of carbon (a), hydrogen (b), oxygen (c), nitrogen (d), sulfur (e), and chemical energy (f) by the solid HTC products from
digestate and microcrystalline cellulose at three different temperatures with addition of zeolite (+Z) and without zeolite (−Z).
E DOI: 10.1021/acssuschemeng.5b00943
Research Article
explained by organic residues from former experiments inside
the HTC reactor in combination with the zeolite’s high
sorption capacity, the lack of absorbable intermediates from the
cellulose, and relative low amount of biomass feedstock (50 g)
compared to zeolite-free trials (80 g). At higher temperatures,
however, the presence of zeolite reduced the recovery of
cellulose-C. Interestingly, the opposite effect was observed for
digestate-C, leading to the assumption that zeolite affects the
HTC process at different stages. On an overall basis, it
apparently catalyzed the hydrolysis of cellulose, whereas HTC
of digestate was disproportionately amplified in the con-
densation step. The same tendency, but less pronounced, was
also found for H and O. The recovery of O shows strong
changes between 190 and 230 °C, while the effect of zeolite is
limited to 190 °C.
Because of the zeolite’s sorption capacity, the recovery of N
and S was in almost any case higher when zeolite was present.
Interestingly, the zeolite-based recovery of N increased at
higher temperatures. The recovery of energy was calculated
based on the higher heating value (HHV) by the equation
HHV = 336 ·C + 1418·H − 153·O + 0.72· O2 (2)
suggested by Mott and Spooner,42 which was applied
previously for hydrochar.22 The results are in good agreement
with other studies.22,23,43,44 With respect to zeolite, the results
are in line with the aforementioned statement concerning the
contrary effects of zeolite in HTC with cellulose and digestate.
Clearly, zeolite is capable of both increasing and decreasing the
energy recovery by solid products depending on the feedstock.
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Proximate Analysis. Proximate analysis data obtained by
TGA, shown in Figure 5, and shown in detail in Supporting
Figure 5. Proximate analysis components (a) and ODM-basis fixed
carbon (b) of digestate (D), zeolite (Z), and microcrystalline cellulose
(C) derived hydrochar and hydrochar−zeolite composites (DZ and
CZ). Values shown are means of triplicate analysis. Fixed carbon
values are shown with standard deviations. Different letters indicate
significantly different means according to Tukey’s posthoc test.
Figure 6. Morphologic properties of digestate (D), zeolite (Z), digestate-derived hydrochar−zeolite composites (+Z) and pure hydrochars (−Z) in
terms of BET surface area (a), BJH mesopore volume (b), HK micropore volume (c), and meso-to-micropore ratio (d).
F DOI: 10.1021/acssuschemeng.5b00943
Research Article
Information (Figure S2 for digestate and Figure S3 for
microcrystalline cellulose), show expected trends of increasing
fixed carbon and decreasing volatile matter content with
increasing treatment temperature for both MCC and digestate
in the absence of zeolite. This behavior confirms the results of
earlier studies, in which hydrochars from municipal solid
waste,8 sewage sludge,43 and miscanthus45 were investigated by
proximate analysis.
It can be noted, however, that no further progress was found
between 230 and 270 °C. As discussed earlier, MCC was
chemically stable at 190 °C. The very small amount of fixed
carbon corresponds well with the absence of any carbonization
(see Figure 1).
Not surprisingly, the composites possess a much larger
fraction of ash, as they were produced with 1:1 ratio of biomass
and zeolite. Higher HTC temperatures generally increased the
ash content of the composites as larger parts of organic matter
are converted into volatile compounds present in dissolved or
gaseous form. Interestingly, despite an observed catalytic effect
of zeolite, the composites’ content of fixed carbon was in all
cases significantly lower than that in pure hydrochars. In
contrast to the hydrochar, however, the content of fixed carbon
in the digestate-derived composites was significantly higher at
HTC temperature of 270 °C compared to 230 °C. These two
findings are in accordance with the different molecular
structures of hydrochar and composite revealed by NMR.
Another potential reason for the relatively low amount of
fixed carbon measured for the composites could be the release
of vapor from the zeolite’s CW during TGA (see Figure S1).
Water vapor is an oxidant and could therefore have caused
partial gasification. As described earlier, the zeolite possesses
about 11% of CW, and TGA showed a mass loss of 6% during
pyrolysis (see Figure S1). However, taking the similar TGA
curves of C-190 and CZ-190 (see Figure S3b) and the similar
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering
ODM-based carbon contents (Table 1) into account, the
present study’s result do not support such effects. Nevertheless,
for clarification, additional TGA analyses were conducted with
a 1:2 (w/w) mixture of raw digestate and zeolite as well as
mixtures of D-230 with zeolite in mass-ratios of 1:0.125, 1:0.5,
and 1:2 (see curves in Figure S4). The measured amounts of
fixed carbon were 19.2%ODM for the digestate-zeolite mixture
(raw digestate, 17.5%ODM) and 35.5−39.1%ODM for the D-230-
zeolite mixture (only D-230, 41.9%ODM). Consequently, an
oxidation effect from CW, if any, was assumed to be negligible,
probably because of the N2 flushing and the vast portion of CW
being released already at lower temperature before pyrolysis
starts (Figure S2b).
Surface Area, Porosity, and SEM Investigation on
Digestate-Derived HZCs. For the pure digestate-derived
hydrochars without zeolite, N2 adsorption technique revealed
the highest surface area (7.3 m2 g−1) and total volume of
mesopores (0.056 mL g−1) and micropores (2.6 μL g−1) for the
190 °C treatment (Figure 6).
At 230 and 270 °C, produced hydrochars had a surface area
(1.3−1.9 m2 g−1), mesopore volume (0.006−0.010 mL g−1),
and micropore volume (0.4−0.7 μL g−1) similar to fresh
digestate (1.2 m 2 g −1 , 0.008 mL g −1 , and 0.4 μL g −1 ,
respectively). These results agree well with an earlier study in
which digestate-derived hydrochars at 190 °C also had the
highest surface area (12 m2 g−1), which declined considerably at
230 and 270 °C.22 The addition of zeolite increased and
stabilized the porosity and surface area considerably. By taking
into account the mass fraction of zeolite XZeo (see Table 1),
theoretical values based on pure zeolite and pure hydrochars
can be calculated for the HZC. With respect to surface area, the
theoretical values (24−26 m2 g−1) are considerably higher than
the measured values. This is also true for the micropore volume
(theoretical value, 14−15 μL g−1). The calculated mesopore
volume (0.13−0.15 mL g−1), however, is close to the measured
values. Thus, it can be assumed that the zeolite’s micropores are
blocked by HTC products, whereas the mesopores are largely
preserved. Interestingly, despite having a low meso-to-micro-
pore ratio of 5, zeolite in consequence stabilizes a high ratio of
23−26 throughout the temperature range. This behavior is also
reflected in the pore size distribution shown in the Supporting
Information (Figure S5).
Scanning electron microscopy pictures reveal an amorphous
shape of the digestate-derived HZC particles, which are usually
smaller than 100 μm (Figure S6). In addition, all HZCs
produced at 190, 230, and 270 °C show structures that are
typical for plant tissues. At 190 and 230 °C, these structures
comprise delicate cell and fiber structures <10 μm, whereas at
270 °C only larger tissue features were preserved (>100 μm).
Certainly, this structures can be attributed to the biomass (i.e.,
cow manure and maize silage) used to produce the digestate for
this study. The surface of these amorphous particles and plant
tissues comprise small features <5 μm. Some of these show a
crystalline structure, which can be assumed to be the zeolite’s
main compound clinoptilolite, when compared with previously
reported morphologic properties of clinoptilolite.46 Other <5
μm structures have an amorphous shape and might indicate
carbonic structures formed in HTC. The presence of nano- and
microscale carbon features in HTC-treated digestate has been
reported earlier.22 The same group found that the surfaces of
carbon products become smoother at higher HTC temper-
atures. Clearly, the SEM pictures obtained in this study show
that HZCs differ considerably from hydrochars.
G DOI: 10.1021/acssuschemeng.5b00943
Research Article
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.5b00943.
TGA measurement curves, calculation basis for HZC
composition, N2 adsorption and pore size distribution
data, and SEM pictures (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*Phone: +44-131-650-5401. E-mail: jan.mumme@ed.ac.uk.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The research conducted by the authors was supported by grants
from a Marie Curie fellowship of J.M. (Grant 661323). M.T.R.
acknowledges Western Sun Grant Initiatives, United States
(Grant C0432G-C) for providing his funding. The authors
express their gratitude to Laureen Herklotz for chemical
analyses at ATB Potsdam.
■
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