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Anaerobic treatment of waste water derived from hydrothermal carbonization

Conference Paper · June 2012

DOI: 10.5071/20thEUBCE2012-2AO.4.3

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 20th European Biomass Conference and Exhibition, 18-22 June 2012, Milan, Italy

ANAEROBIC TREATMENT OF WASTE WATER DERIVED FROM

HYDROTHERMAL CARBONIZATION

B. Wirtha,b, J. Mummea, B. Erlachb

a)
Leibniz Institute for Agricultural Engineering, APECS Junior Research Group
b)
Technische Universität Berlin, Institute for Energy Engineering
a)
Max-Eyth-Allee 100, 14469 Potsdam, Germany, Phone: +49 331 5699900, E-Mail: bwirth@atb-potsdam.de
b)
Marchstraße 18, 10587 Berlin, Germany, Phone: +49 30 31428449, E-Mail: berit.erlach@mailbox.tu-berlin.de

ABSTRACT: Hydrothermal carbonization converts biomass into a lignite-like product which has potential
applications as a carbon-neutral power plant fuel or as a soil amendment. Since the process takes place in water it is
well suited for biomass with a high moisture content, such as organic waste. Most of the feedstock moisture,
however, leaves the HTC process as waste water highly loaded with organic and inorganic compounds. Around 10 %
of the feedstock energy is contained in the waste water, and treatment requirements may impose an additional energy
penalty and high cost. This paper analyzes the feasibility of anaerobic digestion as a treatment step. The produced
biogas can be utilized as auxiliary energy in the HTC process, thereby improving its energetic efficiency. Biogas
yield, degradability, and long-term stability of the digestion process of HTC waste water were analyzed in an
experimental set-up. The HTC liquor showed a fast degradation with 60 % of COD removed within eight days.
Methane rates were moderately high with up to 0.65 L gTOC-1. The results were then used for an economic feasibility
study of an industrial-scale HTC plant. Incorporation of an anaerobic treatment step seems viable if OLRs of
1.5 kgCOD m-3 d-1 are achievable.
Keywords: anaerobic digestion, biogas, efficiency, feasibility studies, pretreatment, waste water treatment.

1 INTRODUCTION However, the volatile organic matter is attractive as a

Hydrothermal carbonization (HTC) is an artificial
coalification process that takes place in water. Biomass is
fed into a reactor that is then heated up to temperatures
between 180 and 250 °C for 1 to 72 hours, whereas
shorter residence times of 2 to 8 hours are more
applicable for continuous operation [15]. The reaction
takes place at or above saturation pressure and is slightly
exothermic [11;16].
Besides a solid phase, HTC also produces a liquid
and a gaseous phase. The solid phase, so-called biochar
or hydrochar, is discussed as a potential soil amender, a
carbon sink, a catalyst, or as a lignite-like fuel [22]. The
gaseous phase that is formed during the reaction mainly
contains over 90 % carbon dioxide. The carbon content
of the gaseous phase, however, represents a minor loss
during the HTC process [29], while the dissolved organic
compounds can contain more than 10 % of the feedstock
energy. The liquor that remains after the reaction has a
low pH. This is caused by high amounts of volatile
organic acids. Formic acid and acetic acid show the
highest concentrations [14;17]. Other substances like
phenols, mainly originating from lignin within the raw
biomass, sugars, and polycyclic aromatic hydrocarbons
(PAHs) are also contained in the liquid phase [15;19]. All
these dissolved organic compounds can amount to a total
chemical oxygen demand (COD) of 10 to 40 g L-1 [4].
The total organic carbon (TOC) content of HTC liquor
usually ranges from 5 to 20 g L-1 [4;21]. In case of
recirculating process water, which is very likely to be
done in case of continuous operation, the TOC can
amount up to 40 g L-1 [29]. This illustrates that the
produced waste water has to be treated further.
Aerobic waste water treatment is usually associated
with a relatively high energy demand for aeration [23].
Moreover, carbon dioxide is emitted during aerobic
treatment and the energy released during the oxidation of
the organic compounds is not recovered. The organic
compounds are aerobically degradable to a high extent. A
recent study reports COD degradation rates of 50 to 62 %
by an aerobic treatment of HTC waste water [27].
substrate for anaerobic digestion. Anaerobic digestion
yields methane and can therefore be designed with a
positive energy balance. Furthermore, it could replace
part of the natural gas demand of a potential industrial-
scale HTC plant [11]. This could make the whole HTC
process economically more feasible.
Therefore, the aim of this study was to analyze the
feasibility of treating HTC waste water by anaerobic
digestion. First of all, the general feasibility of anaerobic
digestion of HTC waste water as a sole substrate was
investigated. Long-term stability of the digestion process
was determined during continuous operation. The focus
was placed on process performance and influence of
potential inhibiting substances contained in HTC liquor.
Furthermore, the influence of immobilization was
examined via a comparison of two different reactor types.
Both have been compared based on key performance
parameters used for biogas production, like specific gas
rates, and waste water treatment, like removal rates for
COD and TOC. To achieve these aims an experimental
set-up has been built up. The gained information about
methane yields and degradability of HTC waste water
was then used for an economic assessment of the impact
of anaerobic waste water treatment on the overall
economics of an industrial-scale HTC plant.
2 MATERIALS AND METHODS
2.1 Substrate properties
The HTC liquor used in this study was obtained from
a plant located at Karlsruhe, Germany. It is operated in
pilot-scale in batch mode. The batch from which the used
HTC liquor originates was produced at 220 °C with a
residence time of 6 hours. Corn silage was used as a
feedstock.
Approximately 90 L of the liquor were homogenized
and transferred into gasoline canisters with a capacity of
20 L each. One of the canisters was stored at 4 °C
whereas the remaining substrate was frozen at minus
20 °C to prevent chemical parameters from changing. A

683
 20th European Biomass Conference and Exhibition, 18-22 June 2012, Milan, Italy
sample of the liquor was taken before transferring it into
the other storage containers. Its chemical parameters are
displayed in Tab. I.
Table I: Overview of the chemical properties of the
obtained HTC liquor used in this study.
Parameter Unit Value
PH-Value 1 3.88
Total Solids (TS) %wt 2.80
Volatile Solids (VS) %TS 79.06
Total Organic Carbon (TOC) g L-1 15.66
Chemical Oxygen Demand (COD) g L-1 41.35
Acetic Acid g L-1 5.26
Phenol Sum Parameter g L-1 0.29
Sulfur mg L-1 90.80
Phosphorus mg L-1 197.40
Ammonia Nitrogen mg kg-1 229.50
Total Kjeldahl Nitrogen (TKN) mg kg-1 685.50
The amount of acetic acid accounts for approximately
13 % of the overall TOC content and is mainly
responsible for the low pH-value. The positive phenol
sum parameter at least indicates the presence of certain
phenolic compounds that can inhibit anaerobic digestion.
Nutrients and trace elements important for the biogas
process are contained in sufficient concentrations
[10;20;28]. The most important values concerning sulfur,
phosphorus, ammonia nitrogen, and total Kjeldahl
nitrogen (TKN) concentrations can also be extracted from
Tab. I. Noticeable are very high ferrous iron concentra-
tions of 500 mg L-1. These should not act as a direct
problem to the microorganisms [10]. Nevertheless, this
value was monitored the whole time.
2.2 Experimental set-up
Two different types of biogas reactors are
investigated in this study – a continuously stirred-tank
reactor (CSTR) and an anaerobic filter (AF). The
experimental set-up built up for this study mainly
consisted of two lined glass reactors, one CSTR and one
AF, with a maximum volume of 3.8 L each. The outer
lining is perfused by water from a heat bath set at 38 °C
to maintain constant mesophilic conditions within the
reactor. Both reactors were perfused by one heat bath
consecutively.
In case of the CSTR, a shaft of a stirrer is plugged
into an immersion tube at the top of the reactor. The
bottom opening of the immersion tube maintains below
the surface of the reactor content during the whole
experiment to prevent gas leaking at the stirrer shaft. The
shaft is made of steel. The stirrer blades are made of
plastic and paddle-shaped. Each pair of paddles is locked
at the shaft – one pair near the surface but completely
immersed and another one near the bottom of the reactor.
The stirrer is propelled by an electric engine set at
50 rotations per minute (rpm).
The AF should benefit of immobilized micro-
organisms and contains 450 biofilm carriers made of
plastic. These carriers can be characterized by a high
specific surface area of 437 m2 m-3. Due to the carriers
the volume of work of the AF was always 200 mL less
compared to the CSTR. To avert floating of the biofilm
carriers a restraint sieve made of steel is mounted at the
top of the reactor. This sieve was immersed the whole
time. The fluid within the reactor is percolated by a
peristaltic pump. It is extracted from the top of the reactor
684
and pumped back into it at the bottom to ensure a regular
replacement. The pump was set to 5 rpm resulting in
approximately ten replacements of the whole reactor
content per day.
Both reactors have in common that there is another
immersion tube at the top of the reactor that is used as a
feeding tube. Additionally, there is a gas exit and a
mounted pH and temperature sensor at the top of both
reactors. The gas flows through a gas counter and is then
stored in foil bags for subsequent analysis. Gas directing
tubes are laid upwards to prevent condensate clogging the
line. All installations are fitted into stoppers and all
untapped openings are sealed by stoppers all made of
rubber. Both reactors are coated with a thin layer of
insulation to prevent the inner from light irradiation. The
complete experimental set-up is displayed in Fig. 1.
Figure 1: Schematic of the experimental set-up used in
this study (heat bath circulation not shown).
For start-up about 30 L of inoculum were obtained
from a biogas plant processing renewable raw materials
at mesophilic conditions. Most of the substrate was grass
and corn silage under the addition of solid manure. The
inoculum was extracted from the last reactor which is fed
by the separated overflow of the main digester. The
inoculum was then screened two times and diluted 1:1
with tap water. Part of the inoculum was filled into the
reactors. A sample was analyzed at the laboratory on-site
to check the condition of the inoculum. The inoculum
had a total solids (TS) content of 2.53 %wt, a volatile
solids (VS) content of 70.07 %TS (1.77 %wt), and an
overall COD of 30.54 g L-1. The ammonia nitrogen value
of the initial inoculum was within the range for biogas
production with a value of 2500 mg kg-1 [33].
2.3 Conducting the experiment
The experiment started with a start-up phase of both
reactors using dextrose monohydrate as a substrate. The
amount of organic dry matter fed was set to 1.6 grams per
day and was redistributed on two feedings per week to
result in an organic loading rate (OLR) of 0.5 gVS L-1 d-1.
Further, the process was supported by the addition of
trace elements. A fivefold concentrated solution was
diluted 1:10 and 560 µL are added two times a week
when feeding the reactors. Before adding HTC liquor for
the first time there was no feeding of the reactors for two
 20th European Biomass Conference and Exhibition, 18-22 June 2012, Milan, Italy
weeks to decrease the residual gas production of the
dextrose feeding.
The main experiment was divided into two phases of
operation. First of all there was a one-time addition of
HTC liquor to both reactors to have a first look on the
degradation speed and a potential inhibition. Based on the
results of a Hohenheim fermentation test the amount of
HTC waste water added was set to a volumetric ratio of
1:20 to prevent an overstraining. The main phase of the
experiment was following this phase – the continuous
operation of both reactors for 13 weeks. Both reactors
were fed during this continuous operation with an OLR
of 1 gCOD L-1 d-1.
Adding HTC liquor to the reactors will be referenced
as feeding in the following. Feeding became very
important during continuous operation. It had to be
conducted every day to ensure a steady amount of
substrate added to the reactors without bigger variations
of the organic load per day. Both reactors were fed with
syringes through the immersion tubes on top. The actual
feeding was conducted by removing a three-way cock
from the syringe and fitting the aperture into the opening
of the immersion tube made of silicone. The substrate
was shot into the reactor by pressing down the bung of
the syringe. Additionally, the syringe was rinsed with
reactor content and again emptied. The gas counter
reading was noted before and after feeding the reactors to
calculate the gas production without the influence of a
varying liquid volume within the reactors. The observed
degassing of carbon dioxide initially after feeding is due
to the low pH of the substrate. The gas production rates
were not corrected by this degassing due to the
assumption that with an again increasing pH the carbon
dioxide is brought back into solution. Additional
nutrients were fed by adding them directly into the
prepared syringes.
Every week the added amount of HTC liquor had to
be removed from both reactors. Liquid samples removed
from the reactors are referenced as digestate in the
following. The digestate removal was conducted via the
immersion tube on top of both reactors, too. Therefore, a
syringe with a mounted silicone tube and a plastic
extension was introduced through the feeding immersion
tube into the reactor. After submerging below the surface
the reactor content was drawn up into the syringe. The
first charge was injected back into the reactor to
homogenize the following samples. The removed reactor
content was collected in a beaker for further use. Again,
the gas counter reading was noted before and after
removing digestate from both reactors to calculate the gas
production with respect to a real production by degrading
the substrate. The amount of removed digestate was
weighed out to balance it with the amount of HTC liquor
fed during a week. The gravimetric amount of gas formed
within this week was neglected for this balance. After the
first week of continuous operation both reactor volumes
of work were decreased by 200 mL due to a very high
filling level at the end of this week. The weekly taken
liquid samples were used for the determination of
chemical parameters for process control and evaluation of
process performance.
2.4 Analytical methods
During the experiment the pH-value and the reactor
temperature are monitored online. This is done with
combined pH and temperature probes. The calibration of
the probes chosen here is a two-point calibration with
685
technical buffer solutions with pH-values of 4 and 7,
respectively.
The produced biogas flows through a volumetric gas
counter. This gas counter is a rotary drum with a specific
volume partly immersed in distilled water. Its target
volumetric flow rate is 0.5 to 50 L h-1. In the beginning
both gas counters were refilled with fresh distilled water.
Subsequently, the gas is sampled in foil bags. These
foil bags ensure no leakage of methane and carbon
dioxide. Other trace gases can diffuse through the margin
over time. After sampling enough gas the foil bag was be
connected to a gas analyzer. During continuous operation
two different gas analyzers have been applied able to
detect methane (CH4), carbon dioxide (CO2), oxygen
(O2), hydrogen sulfide (H2S), and hydrogen (H2) with
electrochemical and infrared sensors.
The COD of liquid samples was measured with test
cuvettes containing all needed reagents (potassium
dichromate, sulfuric acid, and mercury sulfate) to prevent
any interference with oxidizable inorganic compounds.
The used COD cuvettes have a measuring range of
1 to 10 g L-1. Waste water and reactor samples are diluted
1:10 to fit within this range. 500 µL of the diluted sample
are added to the cuvettes. The cuvettes are then heated for
two hours at 148 °C. Finally, the COD values are
determined spectrophotometrically. The measurement
can still interfere with ferrous iron.
TOC values were determined by the so-called non-
purgeable organic carbon method. The sample is oxidized
in a first step to release the formed CO2. In a second step
the sample is further oxidized and the remaining organic
compounds are detected subsequently. Due to the fact
that volatile organic acids can also be purged during the
first step it can be expected that the measured values are
slightly lower than the actual TOC of the sample.
COD and TOC degradation rates in this work are
calculated based on the produced gas and are then
checked with the measured values of the liquid samples.
Starting point for the calculation of a COD balance based
on the produced gas is the complete oxidation of
methane. It has a COD of 64 g mole-1. Taking into
account a molar volume of 22.414 LSTP mole-1 this results
in 350 mLSTP of methane per gram COD. Experience
shows that about 10 % of the converted COD load are
consumed by microorganisms to fuel their regeneration
and the additional formation of hydrogen sulfide [24;31].
Corrected by these 10 % approximately 315 mLSTP of
methane per gram of COD input can be expected. This
equals the maximum methane yield by COD degradation
and can therefore be used for calculating the degradation
rate of the digestion process. The proportion of carbon
dioxide within the biogas has no relevance to a COD
balance since it only consists of already oxidized carbon
and has therefore a COD of 0 g mole-1. This changes
when calculating a TOC balance. In that case, all the
carbon leaving the reactor is of relevance. Both main
components of biogas contain 12 grams of carbon per
mole. This can be again converted into a production of
approximately 1866 mLSTP of each gas compound per
gram of TOC degraded.
The determination of TS and VS contents was done
according to standard methods [8;9]. Determining values
for ammonia nitrogen and TKN was also done according
to standard methods [6;7].
Volatile fatty acids (C2-C6) are measured with a gas
chromatograph (column: FFAP, 30 m x 0.32 mm, film
thickness 0.5 µm) equipped with a flame ionization
 20th European Biomass Conference and Exhibition, 18-22 June 2012, Milan, Italy
detector. The temperatures for oven, injector, and
detector are as follows: from 80 to 210 °C at 15 °C min-1,
180 °C, and 220 °C. It additionally determines ethanol
and propanol. The measuring range is 0.1 to 8 g L-1.
Trace elements were determined via inductively
coupled plasma optical emission spectrometry (ICP-
OES). The samples are digested at 250 °C for 20 minutes
under the addition of hydrogen peroxide and concentrated
nitric acid within a microwave. Some samples were
centrifuged for 10 to 20 minutes at 5000 rpm (4240 g)
before digestion to determine the dissolved trace element
concentrations. The resulting supernatant was extracted
with 0.2 µm fiberglass syringe.
Another value for monitoring reactor performance
and stability is the ratio of total volatile fatty acids
(TVFA) and total alkalinity (TA). It can be interpreted as
an acids-to-buffer ratio. It is an indicator for the workload
of the reactor. In normal biogas plants the value should
not exceed 0.4 to prevent overacidification [13;30]. To
determine the TVFA/TA-ratio samples were diluted 1:10.
The pH-value is then decreased to 5 with 0.5 molar
sulfuric acid to determine the TA value. The pH is further
decreased to 4.4 to determine the TVFA value. Due to the
acidity of HTC waste water it is not possible to determine
the TVFA/TA-ratio for the substrate itself.
3 EXPERIMENTAL RESULTS
3.1 General feasibility of digesting HTC liquor
Gas production started nearly immediately in both
reactors after adding 5 %vol HTC liquor. Methane rates
were as high as 12 mLSTP L-1 h-1 at the very beginning.
The measured volumetric methane fraction was about
70 %vol within this phase. This is found to be due to the
solution of carbon dioxide in the distilled water within
the gas counters in the beginning. It was observed that the
gas production decreased from the very beginning and
nearly stopped after three to four days. The degradation
speed should not be limited by hydrolysis due to the fact
that there can be found only minor concentrations of
complex organic matter in HTC liquor. It rather should
be dominated by acetogenesis and acetate-consuming
methanogenesis [24]. The amounts of volatile organic
acids contained in the HTC waste water should be
completely degradable within the observed short period
of time [32]. The residual production may be due to the
degradation of sugars and other more complex organic
compounds. Lower gas rates observed for the anaerobic
filter were reasoned by a slight gas leakage located at one
of the tubes. This tube was exchanged after this phase.
Based on these results the COD and TOC degradation
rates were calculated. The CSTR reached a COD removal
rate of 46.5 % after four days and 59.6 % after eight days.
The TOC removal calculated by the gas production is
significantly lower due to the solution of carbon dioxide
within the gas counter and reached values of 15.8 % after
four days and 18.8 % after eight days, respectively. The
low detected degradation rates of the AF are of course
due to the gas leakage already mentioned. The AF
showed degradation rates of only 27.1 % and 8.1 % based
on COD and TOC, respectively.
The described degradation progress is also confirmed
by the measured pH-value that is displayed in Fig. 2.
Both reactors started with an initial pH of about 7.45.
After adding the acidic HTC waste water an initial drop
in pH was observed. Both reactors nearly reached their
686
starting pH after three days. This proves the general
degradation capability of organic acids, and so HTC
liquor, of both reactors.
Figure 2: Development of the pH-value during the shock
load experiment at the very beginning of the experiment.
The results detected in case of the CSTR are
compared with results obtained by a recent study
examining the anaerobic digestion of olive mill effluent
(OME). OME is even higher contaminated with phenols
and has a COD of over 100 g L-1 leading to much longer
residence times applied. Degradation rates of 48 to 53 %
are reported in [2] after 100 days of incubation. These
values are only achieved by an initial addition of essential
nutrients. A similar degradation rate is achieved for HTC
waste water in less than 10 % of the time. The fast
degradation will benefit the economic feasibility for
industrial applications.
3.2 Long-term performance
Both reactors have been operated for 13 weeks with a
constant organic loading rate of 1 gCOD L-1 d-1. This phase
of the experiment is the most relevant one for applying
the anaerobic digestion of HTC liquor in practice.
The gas counter reading was noted every day so that
the given biogas and methane rates in Fig. 3 equal the
specific amounts per day. It has to be considered that the
target volumetric flow of the gas counter was not reached
throughout this phase which can lead to a certain error of
more than 10 %. After a short starting phase the methane
rates stabilized at a level of approximately 0.25 liters per
liter reactor volume of work and day.
Within the sixth week of operation there was a
significant decrease of gas production in both reactors.
This was assumed to be due to a lack of nutrients. Trace
elements were fed regularly from then on. Both reactors
recovered to a certain extent within one week. Another
decline a few days later could not be corrected by the
addition of trace elements. The results for nutrients
within the reactors from the laboratory that are described
more in detail in the following promoted a lack in sulfur
and phosphorus available for microorganisms. The
essential nutrient ratios were still intact whereas the
absolute amounts were too low [20;28]. For that reason
small amounts of elemental sulfur were added with no
significant influence. Afterwards, phosphoric buffer
solution (PBS) was added to increase the phosphorus
level. The addition of phosphoric acid during the last
days of operation was used to as a substitute for PBS
 20th European Biomass Conference and Exhibition, 18-22 June 2012, Milan, Italy
despite that it lowered the pH-value. Both reactors did
not fully recover until the end of the experiment as
measured by the gas production rates and the concen-
trations of available phosphorus.
Figure 3: Specific gas and methane rates during
13 weeks of continuous operation with HTC liquor as
sole substrate.
The behavior of the gas production showed less
fluctuations from day to day from the sixth week on
indicating a bottleneck in degradation. The minor
fluctuations of the AF compared to the CSTR are also
noticeable and might be favored by immobilized
microorganisms or sludge formation. The volumetric
methane fraction shows only small variations. High
volumetric fractions of nearly 70 %vol within the first
days of operation are still due to the solution of carbon
dioxide in distilled water contained in the gas counters.
The values stabilized at about 60 to 65 %vol for the whole
operation except some declines to nearly 50 %vol in
context with an overall diminishing gas production
described before. These drops are only observed for the
CSTR which reinforces the statement that the AF was
more stable. Additional measurements of hydrogen and
hydrogen sulfide in the produced biogas showed absence
within the detection limit of a few parts per million (ppm)
of both gas compounds. This is very unlikely for biogas
in practice and validates the significant lack of available
sulfur in the liquid phase but could be very advantageous
for subsequent combustion.
The pH-value was noted every day before feeding.
Both reactors showed a slight decline in pH down to
values of 7.2 to 7.3 during the first weeks of operation.
The pH-value was about 0.2 units lower at the days after
a digestate removal due to a lower actual reactor volume
of work. The stronger initial drops observed for the AF
were due to the fact that the pH-probes were mounted on
top of the reactor and feeding was also conducted at the
top. The drop in gas production shown before coincides
with a drop in pH below the important value of 7. The
characteristic drops in pH after digestate removal also
vanished from then on confirming the assumed
bottleneck in degradation. The decreasing pH during the
last days of operation was due to the addition of
phosphoric acid. Again it can be noted that the AF
showed a more stable operation with pH-values of over 7
during the whole experiment whereas the CSTR showed
fluctuating values between 6.7 and 7.
As it could be supposed the ammonia nitrogen and
687
TKN values decreased over time within the digestate and
are likely to approach the values of the fed substrate
asymptotically. After 13 weeks, the TKN values were
still 14 and 4 % higher at the CSTR and AF, respectively,
compared to the initial value of the HTC liquor. The
concentration of ammonia nitrogen in both reactors was
still nearly twice as high compared to the HTC waste
water. The CSTR showed higher TKN concentrations
compared to the AF. It was also observed that the VS
concentration of AF samples was always 5 to 10
percentage points lower than that of the CSTR. Due to
the fact that samples extracted from the CSTR are more
representative for the whole reactor in comparison with
the AF samples it was assumed that there have to be
some compounds that precipitate in the AF.
This led to the idea that some precipitation reactions
could also cause the lack of nutrients discussed before.
That called to mind the very high ferrous iron (Fe)
concentration of the obtained HTC liquor. A sample of
the waste water was analyzed as received, filtered, and
filtered with a subsequent centrifugation and underwent a
trace element analysis via ICP-OES. It was observed that
the ferrous iron concentration remained unaltered but the
concentrations of essential nutrients like sulfur and
phosphorus diminished. The sulfur concentration
decreased by 10 % whereas the phosphorus concentration
diminished by more than 30 % mainly due to the removal
of smaller char particles. These particles could be
assumed as nonbiodegradable for anaerobic micro-
organisms.
It was hypothesized that at a low pH the majority of
the nutrients remains dissolved whereas at neutral pH-
values within the reactors the ferrous iron starts to
precipitate both nutrients to form insoluble iron(II)
sulfide (FeS) and iron(II) phosphate (Fe3(PO4)2). The FeS
could also account for the strong black tinge of the
obtained HTC liquor. The precipitation was validated by
the results of an analysis of the precipitated sludge at the
bottom of the AF at the end of the experiment. Very high
concentrations of over 300 mg L-1 of sulfur and
phosphorus combined with a higher TS concentration
were observed. The high ferrous iron concentrations of
the HTC waste water is partly due to the fact that it was
stored within gasoline canisters that started to corrode
during storage. Nevertheless, the initial ferrous iron
concentration accounted for two thirds of the measured
value of 700 mg L-1 of the HTC liquor at the end of the
experiment. The origin of ferrous iron remains unclear,
since the feedstock biomass most likely did not have a
high Fe content. The observed corrosion of the gasoline
canisters indicates that an acid proof handling of samples
should be applied in the whole storage and transport
chain. Furthermore, all parts within an HTC plant that are
in contact with the acidic waste water should be made of
stainless steel although this increases the capital
investment. In contrast, this additional investment can
save maintenance costs and can prevent a complete
downtime of a plant.
Analysis of the concentrations of all three involved
elements during the whole experiment in Fig. 4 reveals a
significant increase of ferrous iron contained in both
reactors. The subsequent precipitation of sulfur and
phosphorus was validated by significantly lower
concentrations within the AF digestate compared to the
CSTR samples which were up to three times less. Some
intermediate samples have been centrifuged before trace
element analysis. These samples proved a significant lack
 20th European Biomass Conference and Exhibition, 18-22 June 2012, Milan, Italy
of sulfur and phosphorus with concentrations beneath
25 and 10 mg L-1, respectively. After adding the missing
elements a significant decrease in ferrous iron was
observed. This proved the forced precipitation of
available ferrous iron by the added nutrients. The added
amounts of nutrients have still not been enough to fully
recover the reactors into ranges of adequate
concentrations of sulfur and phosphorus until the end of
continuous operation.
Figure 4: Development of the concentrations of ferrous
iron, sulfur, and phosphorus within both reactors during
13 weeks of continuous operation.
The precipitation of sulfur also could have been
forced by the so-called bacterial anaerobic corrosion of
metal installation parts within biogas reactors [18]. In a
wet environment bacteria are able to corrode metal parts
by removing the thin protective coating of molecular
hydrogen. Part of the ferrous iron is subsequently
precipitated with hydrogen sulfide to form the water
insoluble FeS. Possibly affected could be the stirrer shaft
in the CSTR and the restraint sieve in the AF, both made
of steel. Nevertheless, both installations showed no clear
signs of corrosion at the end of the experiment.
During the last weeks of continuous operation when
adding phosphoric acid to the feeding syringes it was
observed that the black tinge of the substrate vanished to
a certain extent. This can be explained by the solution of
residual FeS due to a lower pH. It illustrates again the
complex reactions within both reactors. Nutrient
requirements for digesting HTC waste water could be fit
by co-digesting another substrate. Agricultural residues
like slurry are very rich in nutrients. A recent study
examined the improvement by co-digesting OME
compared with its digestion as a sole substrate. The use
of laying hen litter as a co-substrate increased biogas
688
production by 90 % compared to the sole digestion of
OME [2].
Substances like phenols, furfural, and PAHs are very
likely formed during the production of hydrochar. Small
amounts of these substances can also be found in HTC
liquor and may be harmful for the microbiological
community involved in anaerobic digestion. For the
calculation of the maximum concentration within the
process liquor it was assumed that the compounds are not
degradable. They only enter the reactor via feeding and
leave it via digestate removal. There was no obvious
inhibition within the first five weeks of operation. From
then on, a potential inhibition is superimposed by the
nutrient problematic described before. An inhibition by
concentrations of approximately 50 % of the initial
concentration seems very unlikely and is backed by these
observations. Higher concentrations could lead to a
partial inhibition of the process and therefore lead to
decreasing gas rates. It is very unlikely that the biogas
process is grinded to a halt by concentrations of over
90 % of the initial value due to the fact that the gas
production never stopped during the whole experiment.
Inhibiting substances could also be removed by
chemical pre-treatment [1]. Within this study the phenol
removal efficiency of aluminum and iron salts added to
raw OME rich in phenols with concentrations of up to
10 g L-1 was examined. After acid cracking and adding
these salts the concentrations of phenol diminished by up
to 50 %. All treatments improved the anaerobic degrada-
bility of OME [1]. This could also be an interesting
option as a pre-processing step for HTC waste water.
Calculating the average specific methane yields per
gram of COD or TOC fed yields different results with
respect to the considered period of time. Due to the
inhibition already described the gas production during the
first five weeks of operation should be more
representative compared to the residual continuous
operation. For that reason the average methane yields
displayed in Tab. II are calculated for the first five weeks
of operation and the whole 13 weeks duration.
The degradation rates of COD and TOC are
calculated based on the measured gas volume and its
composition on a weekly basis and are also averaged for
the beginning five week period and the whole
experiment. The results are also displayed in Tab. II.
These results were checked with the results of the
chemical analysis of the digestate leading to an average
accordance of 95 to 100 % in the COD balance and only
75 to 85 % in the TOC balance, respectively. The TOC
value of the liquid digestate was always lower than
expected. This cannot be justified only by a varying
solution of carbon dioxide and indicates that carbon
dioxide was eventually leaking through some of the
silicone hoses over time. The fact that the calculated
TOC accordance reached its top values when the pH-
value was low reinforces this assumption. The amounts
of formic acid and acetic acid that are purged without
detection during the TOC measurement further lower the
obtained values. Overall, the TOC degradation rates can
be expected to be slightly higher. The degradation rates
for COD and TOC show a similar trend for both reactors.
They also correlate with the observed gas rates described
before due to their calculation basis. Again, the CSTR
showed greater extremes whereas the AF was more stable
during the whole operation.
Results for the continuous operation of an anaerobic
sludge blanket reactor with OME indicated COD
 20th European Biomass Conference and Exhibition, 18-22 June 2012, Milan, Italy
degradation rates of up to 90 % within 10 days. The pH
of the substrate was adjusted to a neutral level. The study
further reports achieved OLRs of over 20 kgCOD m-3 d-1
indicating the advantage of immobilized microorganisms
when handling highly contaminated substrates [3].
Table II: Calculated methane yields in LSTP gCOD/TOC-1
and COD and TOC degradation rates based on the
measured gas volume and its composition on a weekly
basis. The results are averaged for the first five weeks of
operation and compared with averaged values for the
whole duration of continuous operation.
Measurement Unit CSTR AF
Averaged Methane Yield
COD (5 weeks) LSTP g-1 0.236 0.219
COD (13 weeks) LSTP g-1 0.191 0.194
TOC (5 weeks) LSTP g-1 0.624 0.577
TOC (13 weeks) LSTP g-1 0.505 0.511
Averaged Degradation Rate
COD (5 weeks) % 74.96 69.37
COD (13 weeks) % 60.68 61.42
TOC (5 weeks) % 53.84 48.94
TOC (13 weeks) % 46.26 43.71
Coincidentally with the diminished degradation
capability the concentrations of volatile organic acids
increased significantly, especially within the CSTR. The
concentration of propanoic acid intermittently reached an
apprehensive value of 0.7 g L-1 at the CSTR. This
development was also observed via the TVFA/TA-ratio.
The ratio reached values of over 1.2 at the CSTR. The
increase was mainly due to an increasing TVFA value.
The AF hereby proved its stability with significantly
lower levels of volatile organic acids in the digestate. The
TVFA/TA-ratio at the AF did not even extent a value of
0.4 during the whole experiment.
The conducted experiments could be further
optimized. Starting with the applied measurement, a
mounted probe measuring the redox potential could
indicate changes within the reactors faster. This is due to
the fact that the pH-value reacts with a certain time lag.
The anaerobic filter should also be complemented by a
discharge system for settled sludge to prevent any
clogging. An automated feeding system would facilitate
feeding and subsequently would homogenize the daily
load. An adequate feeding system has to be capable to
handle very small volumetric flows to be applied to this
experimental set-up.
4 ECONOMIC FEASIBILITY ANALYSIS
The feasibility analysis conducted here is intended to
analyze the impact of an anaerobic waste water treatment
on an industrial-scale HTC plant. A plant design of an
industrial-scale HTC plant and the related investment and
operation cost estimates are described in [12;34]. The
HTC plant comprises pressurization and preheating of the
biomass slurry, a continuous HTC reactor, de-
pressurization, cooling, dewatering and drying of the
hydrochar to a moisture content of 10 %, and internal
heat recovery. Mass and energy balances were calculated
with the chemical engineering flowsheeting software
AspenPlus. As the thermal energy recovered from the
product and waste streams and from the exothermic HTC
689
reaction is not sufficient for the pre-heating of the
biomass slurry and the drying, some additional steam is
generated by a natural gas fired boiler [11;33]. Per MJ of
produced hydrochar, the HTC plant consumes 69 to 93 kJ
of natural gas depending on the feedstock. In this study,
an anaerobic digestion module is added to the described
plant design, and the produced biogas is utilized to
replace natural gas for the boiler.
The total capital investment (TCI) of the complete
anaerobic digestion as part of the plant comprises the
bare module costs (CBM) plus off-site costs (OFSC), fees
and contingencies (15 % of CBM), working capital, and
first start-up costs. The only bare module that needs to be
added to an already existing HTC plant is the digester
itself. Specific costs of 250 € m-3 are assumed for a
completely equipped CSTR including stirrer, electric
engine, heat insulation, and gas storage within the top of
the reactor [10]. This value can of course vary according
to the size of the reactor and its installations but is
assumed to be constant here. The OFSC are calculated
via percental shares on the purchased-equipment-cost
(PEC). The ratio of PEC to CBM is set to 2.88. The
OFSC consist of costs for land (2 % of PEC), ancillary
buildings (20 % of PEC), site development (5 % of PEC),
and utilities (10 % of PEC).
No additional labor is assumed as well as an
overnight construction. Fixed operating and maintenance
costs (OMC) are calculated as 2 % of CBM. Variable
OMC only consist of the consumption of electricity for
stirrers and pumps. The electricity demand is estimated to
7.5 % of the electricity that a CHP with an electric
efficiency of 37.5 % would produce by the combustion of
the produced biogas [5], corresponding to 1124 kJ m-3
methane. The specific price for electricity is set to
22.22 € GJHHV-1. Heating of the digester is unnecessary.
The HTC waste water leaves the HTC process at over
90 °C, and since there is no need for low temperature
heat in the HTC process, its residual heat is discharged to
the environment via coolers. Therefore, the effluent
temperature after cooling can be adapted to the
requirements of the digester.
Savings in terms of natural gas consumption are
calculated with a natural gas price of 6.31 € GJHHV-1.
Additional savings because of a less intense aerobic
waste water treatment are not included in this feasibility
analysis.
The investment annuity is calculated with an
economic plant life n of 15 years and an interest rate ieff
of 7 % per year. Recovery values for land and working
capital are considered. Constant monetary values are used
with real escalation rates rn of 0.5 % per year for natural
gas and electricity excluding general inflation. Annual
carrying charges are calculated as an investment annuity
with a capital recovery factor (CRF) determined by
Eq. (1) plus annual taxes and insurances (1 % of TCI).
The annual levelized costs for auxiliary energy and
operation and maintenance are calculated with the
constant escalation levelization factor (CELF) as defined
in Eq. (2) and (3).
ieff  1  ieff 
n
CRF  (1)
1  i 
eff
n
1
 
k  1 kn
CELF   CRF (2)
1 k
 20th European Biomass Conference and Exhibition, 18-22 June 2012, Milan, Italy

values represent the overall additional expenses. The

1  rn values for an OLR of 1 come close to the estimated bare
k (3)
module costs of an aerobic waste water treatment of
1  ieff
182 or 230 k€, respectively.
For an estimation of the economic feasibility it does
To balance potential savings and additional expenses not matter whether the calculated volumes have to be
the framework parameters are extracted from the design divided onto more than one digester. This is due to the
with a plant capacity of 11.15 MWHHV of biomass as assumption of constant specific costs.
received at 7000 full-load operating hours per year [34].
The design offers the possibility to process two different Table IV: Results of the dimensioning of the digesters
feedstocks – wood chips from short-rotation forestry with for both feedstocks at different organic loading rates
a water content of 50 % and municipal organic waste (OLRs) and the resulting overall levelized costs (only
with a water content of 70 %. These feedstocks amount to expenses).
28,000 or 60,000 tons per year, respectively. The
framework parameters required for this study comprise
Parameter Unit Wood Chips
the mass flow of waste water leaving the HTC plant and
its TOC content as well as the natural gas consumption of OLR kgCOD m-3 d-3 1 2 3
the plant. Natural gas is modeled as pure methane with an Digester Volume m3 3328 1664 1109
HHV of 55.53 MJ kg-1. The TOC value of the waste Investment Costs k€ 1091 546 365
water is converted into a COD value by a conversion Levelized Costs k€ a-1 152 78 54
factor of 2.65. This is due to a more reliable COD Organic Waste
balance compared to a TOC balance. The parameters are OLR kgCOD m-3 d-3 1 2 3
displayed in Tab. III. The amount of hydrochar produced Digester Volume m3 5098 2549 1699
by each plant is also listed to calculate savings or Investment Costs k€ 1672 837 559
expenses on a specific basis for a better comparison. Levelized Costs k€ a-1 233 120 83
It needs to be pointed out that there is quite a high
uncertainty regarding gas yields and degradation of the The levelized costs are balanced with the additional
waste water. Firstly, the waste water used in the income generated by the additional investment. The COD
experiments is derived from a different HTC feedstock degradation rate is varied between 0 and 100 % within
than used in the simulation of the industrial-scale plant, the calculation resulting into an increasing amount of
and was produced in a batch HTC process rather than a methane produced. This is done to obtain a value for a
continuous process. Secondly, the TOC of the waste minimum degradation rate from which on the earnings
water in the simulation is based on results from outweigh the expenses for the additional investment. This
laboratory experiments and modeling assumptions point will be called break-even point in the following.
regarding a continuous process. Waste water composition Fig. 5 gives an overview of the conducted sensitivity
and gas yields from its anaerobic digestion may vary analysis for the OLR and COD degradation rate for both
significantly with feedstock and operating parameters of feedstocks.
the HTC.

Table III: Framework parameters of a design of an

industrial-scale HTC plant processing wood chips or
municipal organic waste used for the economic feasibility
analysis within this study.

HTC plant design

Parameter Unit Wood Organic
Chips Waste
Waste Water kg h-1 2141 6706
TOC g L-1 20.4 10.0
COD g L-1 54.0 26.4
kW 965 1272
Natural Gas Demand m3 h-1 45.0 59.4
kJ MJchar-1 69.0 92.9
Produced Hydrochar tTS a-1 9797 12947

The digester volume was calculated for varying

organic loading rates of 1 to 3 kgCOD m-3 d-1. A higher
OLR leads to a smaller digester volume and can therefore
favor the feasibility. The volume can be calculated by the
volumetric flow of waste water (its density is assumed to
be 1 kg L-1) and its COD. The value is further multiplied
with an overdesign factor of 1.2 to ensure a constant
working capability. Depending on the digester volume
the calculated electricity consumption can amount up to
8 W m-3. The results of the dimensioning of the digesters
for both feedstocks at different OLRs and the resulting
overall levelized costs are summarized in Tab. IV. These
Figure 5: Results of the economic feasibility analysis of
the additional investment for different organic loading
rates (OLRs) and a varying COD degradation rate for
both examined feedstocks.
It can be seen that at an OLR of 1 no breaking-even is
achievable without taking into account additional savings
at the aerobic treatment step. The break-even points move

690
 20th European Biomass Conference and Exhibition, 18-22 June 2012, Milan, Italy
as expected to lower degradation rates with higher OLRs.
Higher OLRs will nevertheless lead to decreasing
degradation rates due to a shorter residence time of the
substrate. The course in case of organic waste as
feedstock is slightly steeper due to a higher overall mass
flow of organics and higher initial investment costs.
Noticeable, the break-even points do not differ between
the feedstocks at a given OLR. This is due to the rigid
calculation method applied here. CSTRs found in
practice are mostly operated with an OLR below 4 [26].
Even higher OLRs can be achieved with anaerobic filters
working already for several years. OLRs of up to
32 kgVS m-3 d-1 are reported [3]. Nevertheless, such high
values seem unachievable using HTC waste water as a
substrate for anaerobic digestion without adjusting the pH
of the inlet stream. This may be due to a constantly low
pH-value within the digester.
The amount of natural gas that could be replaced and
the share of the energy content of the produced biogas on
the energy content of the feedstock and on the produced
char are summarized in Tab. V.
Table V: Summary of the amount of natural gas that
could be replaced and the share of the energy content of
the produced biogas on the energy content of the
feedstock and on the produced char for different COD
degradation rates.
Parameter Unit Wood Chips
COD Degradation % 60 80 100
Natural Gas Replaced % 42.1 58.2 74.4
Share on the Feedstock % 1.9 2.6 3.3
Share on the Char % 2.1 2.9 3.7
Organic Waste
COD Degradation % 60 80 100
Natural Gas Replaced % 56.4 75.2 94.0
Share on the Feedstock % 3.3 4.4 5.6
Share on the Char % 3.8 5.0 6.3
Even at unachievable 100 % of COD degradation
only part of the natural gas can be replaced. The share of
the produced gas on the feedstock can nearly be
construed as an increase of the energetic efficiency based
on HHV of the whole plant in the same order.
Nevertheless, the results of the feasibility analysis
prove an economical advantage in including the
anaerobic digestion. A digester can easily be integrated
into an industrial-scale HTC plant. The HTC waste water
leaving the HTC process itself can be fitted to the
demands of the digester regarding temperature.
Additionally, only a small amount of auxiliary electricity
needs to be applied. In case of a CSTR energy is needed
for propelling the stirrer. An AF could work without
auxiliary energy if the input stream provides a hydraulic
mixing within the reactor. The examined feedstocks do
not allow a complete replacement of the natural gas
demand of the HTC plant. It depends on the share of
biogas on the total energy demand whether the design of
the steam producing boiler has to be changed. This
consequently could increase the total capital investment.
Using fresh biomass as a feedstock for HTC and
subsequently using the waste water as a substrate for
anaerobic digestion is not the only possibility to connect
both techniques. Another interesting way of incorporating
both techniques would be the digestion of fresh biomass
with a subsequent carbonization of solid digestate [25].
691
Furthermore, the anaerobic step would allow the co-
digestion of the produced waste water. The solid biomass
could increase the stability of the degradation of the
waste water and offers other advantages.
A subsequent aerobic waste water treatment still
seems to be required to fulfill effluent restrictions.
Depending on the residual amount of COD some physical
filtering techniques could do the rest. Upcoming research
should also focus on an optimum in the overall cleaning
capability of both treatment steps together like in modern
sewage treatment plants.
5 CONCLUSIONS
The experiment conducted here indicates the
feasibility of an anaerobic treatment of waste water
derived from hydrothermal carbonization (HTC).
The one-time addition of HTC liquor at the very
beginning proved its fast degradability within eight days.
Nevertheless, only 60 % of the COD fed was degraded.
The continuous operation of both reactors for 13 weeks
with an OLR of 1 gCOD L-1 d-1 showed only minor
difficulties. These difficulties have been connected to an
atypical high ferrous iron content of the obtained HTC
liquor. This led to a precipitation of essential nutrients
like sulfur and phosphorus. The gas production rates
decreased due to the consequent lack of those nutrients.
Despite that, TOC-specific methane rates were
moderately high with values of up to 0.65 LSTP gTOC-1.
The produced biogas showed volumetric methane
fractions of up to 70 %vol and no traces of hydrogen and
hydrogen sulfide within the detection limit. Feeding of
the HTC liquor was always followed by an initial drop of
the pH-value and a degassing of carbon dioxide. The AF
proved to be more stable during the whole operation
compared to the CSTR. A lasting intrinsic inhibition by
process intermediates was not observed.
The results of the economic feasibility analysis
indicate that the addition of an anaerobic treatment step
to an industrial-scale HTC plant is economically feasible
for COD degradation rates of 80 % and OLRs of at least
1.5 kgCOD m-3 d-1. Higher OLRs lead to an increased
feasibility. A subsequent aerobic treatment step still
seems to be necessary. Savings in energy requirement
and investment for the aerobic treatment are not
considered here and may further improve the economic
viability of the anaerobic digestion step.
6 ACKNOWLEDGEMENTS
This work is funded by the German Federal Ministry
of Education and Research (BMBF) in cooperation with
Project Agency Jülich (PtJ).
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