Sie sind auf Seite 1von 10

Available online at www.sciencedirect.

com

ScienceDirect
Energy Procedia 114 (2017) 6057 – 6066

13th International Conference on Greenhouse Gas Control Technologies, GHGT-13, 14-18


November 2016, Lausanne, Switzerland

Reduced local emissions and long-term carbon storage through


pyrolysis of agricultural waste and application of pyrolysis char for
soil improvement
Tobias Prölla*, Rafat Al Afifa, Sebastian Schaffera, Christoph Pfeifera
a
Department of Material Sciences and Process Engineering, University of Natural Resources and Life Sciences,
Peter-Jordan-Str. 82, 1190 Vienna, Austria

Abstract

The direct storage of biologically stable pyrolysis char in soils is discussed as a low-tech below zero emission technology option
with positive side-effects. A rotary kiln pyrolysis process, which has already been successfully applied at industrial scale before,
is selected as the reference technology. Cotton stalks are considered as feed for the pyrolysis plant, representing a typical
agricultural by-product with short rotation times. The plant efficiency is calculated for the case that the thermal energy that runs
the pyrolysis process is provided by combustion of a part of the pyrolysis gas, while pyrolysis oil is provided as a product. The
remaining pyrolysis gas powers a gas engine-based combined heat and power (CHP) island. 100% of fuel power fed with the
biomass are distributed as follows (based on the lower heating value): 52% stay in the biochar, 13% in the pyrolysis oil, 10% are
converted to electric power in the CHP plant, and, finally 15% are available as heat at a temperature span between forward and
back flow of 100°C/70°C and may be used on-site for drying of agricultural products and pyrolysis feedstock. A rough
comparison of the proposed process to biomass power generation substituting coal-fired power generation shows that the net
effects on the carbon balance are comparable, but additional carbon-neutral energy streams are generated in the pyrolysis case.
© 2017
© 2017TheTheAuthors.
Authors. Published
Published by Elsevier
by Elsevier Ltd. Ltd.
This is an open access article under the CC BY-NC-ND license
Peer-review under responsibility of the organizing committee of GHGT-13.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of GHGT-13.
Keywords: Biomass, Pyrolysis, Biochar, Soil, Carbon storage, Cotton

* Corresponding author. Tel.: +43-1-47654-89311; fax: +43-1-47654-89309.


E-mail address: tobias.proell@boku.ac.at

1876-6102 © 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of GHGT-13.
doi:10.1016/j.egypro.2017.03.1742
6058 Tobias Pröll et al. / Energy Procedia 114 (2017) 6057 – 6066

1. Introduction

With global warming in the center of international concern and discussions, practical measures to reduce the
anthropogenic CO2 emissions are urgently needed. Besides efficiency increase and a switch to less carbon-intensive
fuels or technologies, net carbon sinks may be established in order to actively remove CO2 from the atmosphere.
Since technical CO2 capture from air is thermodynamically inefficient [1], biomass will be the key to such below
zero emission solutions. In this way, natural photosynthesis is employed to fulfil most of the capture task. Apart
from capturing gaseous CO2 along with biomass combustion as in CCS, it may be a viable option with biomass to
provide biologically stable biochar, e.g. produced by pyrolysis, for long-term storage in soils [2]. The estimated half-
live of pyrolysis char in soil has been reported to be at least 100 years but may exceed 1000 years for O:C molar
ratios lower than 0.2 [3]. This strengthens the idea to have CO2 removed from the atmosphere through
photosynthesis but to prevent the natural degradation of the biomass at least for a part of it. This will create a net
carbon sink of global potential, which is comparably easy to apply. If it will turn out, what researchers still discuss
[4-15], that biochar produced by pyrolysis can be safely and effectively used to improve the quality of soils for
agriculture, this might constitute a possibility for preserving or even creating fertile soils and economic benefit along
with the removal of carbon from the short-term cycle.
Bioenergy faces two challenges: (i) the competition on land-use for food and feed production and (ii) the
competition to fossil energy, which in most situations is available at a lower price than biomass. The first problem
could be avoided if only ligno-cellulosic residues of agricultural production and forestry would be used for energy.
In this case, still, the bioenergy system needs to take care that nutrient-cycles are closed and soil fertility is preserved
– especially if side-products are removed from the fields or forests. Thus, the efficient management of biomass is
one of the keys to achieve sustainable overall solutions. Biomass is abundantly available around the world [16].
However, these biomass resources are improperly utilized. Although 23% of the crop residues are used for forage,
4% for industrial materials, and 0.5% for biogas, large parts are used with lower efficiency or are wasted, with 37%
being directly combusted by farmers, 15% being lost during collection, and the remaining 20.5% being discarded or
directly burnt on the field [17]. An example of such an agricultural waste are the by-products of cotton.
Cotton is one of the most important textile fibers in the world, accounting for around 35% of total world fiber use
[18]. The global 2014-15 cotton production was around 29 million tons [19]. Due to this high production volume, the
amount of cotton plant residue was also high. It is estimated that, there are about 75 million tons (dry mass) of cotton
waste generated annually. Traditionally, cotton stalks must be buried or burnt to prevent them from serving as an
over-wintering site for insects such as the pink bollworm. Timely soil incorporation of this residue adds nutrients
back to the soil, increases soil organic matter content, and improves water infiltration. On the other hand, most
tillage operations employed to incorporate the residue into the soil are energy intensive. In many developing
countries where cotton is being planted, the stalks are treated as waste with just a small part of about 15% used as
fuel in traditional stoves. The bulk of the stalks are burnt on the field after the harvest [20], resulting in high
particulate and aerosol emissions and releasing the carbon as CO2 into the atmosphere. Therefore, cotton stalks
treated in the traditional way can safely be considered a negative value biomass, and improved treatment strategies
are urgently needed. A certain advantage of the traditional on-field combustion is the retention of non-volatile
nutrients on the farm-land. However, nutrients, such as potassium, may be easily leached from ash and lost into the
groundwater. Here, as well, improvement seems possible if biochar is produced from the stalks incorporating the
nutrients in a solid carbon structure.
Hence, the objective of this work is to integrate the current knowledge on the use of agricultural wastes in
distributed, small- to medium-scale, energy-autonomous pyrolysis plants in the context of net carbon sinks, energy
recovery and soil stabilizer. A high-level comparison with alternative CO2 emission reduction concepts is made.

2. Background

2.1. Rotary kiln pyrolysis of ligno-cellulosic biomass

By pyrolysis we mean a thermo-chemical conversion of an organic feedstock in the absence of free oxygen and
also, as far as possible, in absence of oxygen-donors such as steam or CO2. The process of thermal decomposition
Tobias Pröll et al. / Energy Procedia 114 (2017) 6057 – 6066 6059

starts when drying of the biomass is accomplished and temperatures start to exceed 100°C. The main parameters
determining the product distribution are temperature and heating rate. For fast or flash pyrolysis, preferably done in
fluidized bed reactors, the yield of condensable hydrocarbons (pyrolysis oil) is maximized. For slow pyrolysis,
which can be done in fixed bed or in rotary kilns, the pyrolysis oil yield is decreased whereas the pyrolysis char
yield is higher. Additional information about the particularities of different pyrolysis systems can be found
elsewhere [21]. We have chosen an indirectly heated rotary kiln slow pyrolysis process according to Fig. 1, operated
at 550°C, as the basis of the following considerations. The reasons for this decision are:

x The technology is robust and industrially proven not only for biomass but also for waste [22,23,24].
x Data are available from a test campaign in Austria using wheat straw as input biomass [23,24].
x Small to medium scale technology is readily available for distributed application in cotton-producing countries.

Fig. 1. Indirectly heated rotary kiln pyrolysis process scheme for consideration.

Halwachs et al. [23] and Kern et al. [24] report from a 3 MW test campaign that the elements chlorine and
potassium, which are critical for combustion systems, remain quantitatively in the pyrolysis char fraction. This is
important because it implies that the gas and oil fractions can be used in a versatile way for useful energy
generation. These authors [23,24] further show that about 50% of the primary fuel energy can be exported with the
gas and oil fraction while less than 50% of the primary fuel energy stays in the char fraction. The pyrolysis char,
however, if produced from low-grade biomass rich in chlorine and potassium, would be a problematic fuel for
boilers with respect to emissions and corrosion [25]. If the char is not further converted but returned to the soil, the
problematic compounds may even have positive effects as nutrients and the related carbon will not be released as
CO2. Therefore, we consider the potential application of the pyrolysis char as soil additive in the present work.

2.2. Biochar composition and stability

Agricultural biomass and woody biomass are widely used for the energy production in different parts of the
world [26]. Prediction of elements can help in comparing the energy content in biomass which is highly important in
selection of biomass for pyrolysis. Table 1 shows the comparison of chemical composition, proximate analysis,
ultimate analysis and calorific value of cotton stalk, wheat straw and wood. The calorific value of dry cotton stalks
is equivalent to poor quality wood, and is varying from 16.4 to 18.3 MJ/kg, furthermore, compared with the calorific
6060 Tobias Pröll et al. / Energy Procedia 114 (2017) 6057 – 6066

value of other crop residues such as wheat straw (16.4-16.8 MJ/kg), cotton stalks can be considered fuel with respect
to the specific energy content [27].

Table 1. Properties of cotton stalks, wheat straw and wood. Average values adapted from [27-30].
Biomass
Properties
Unit Basis Cotton stalks Wheat straw Wood
Ash wt% Dry 5.18 4.35 1
Proximate
Volatile matter wt% Dry 71 75.5 82
analysis
Fixed carbon wt% Dry 24 16.22 17
Carbon wt% Dry 46.07 47.82 48.8
Hydrogen wt% Dry 5.93 5.29 6
Ultimate
Nitrogen wt% Dry 1.1 0.47 0.2
analysis
Sulfur wt% Dry 0.12 0.08 0.06
Oxygen wt% Dry 41.6 41.59 45
Net calorific value (LHV) MJ/kg Dry 17.33 16.6 19.64

It is seen from Table 1 that cotton stalks reflect the typical elementary composition of lingo-cellulosic biomass
with 47.6% wt.% carbon and 42.9 wt.% oxygen. This composition is relatively similar to that of wheat straw and
wood. High carbon and oxygen content in biomass leads to more char formation as well as to a high calorific value
of the biochar product [31].
Proximate and ultimate analysis of biochar derived from cotton stalk are important for quantitative assessment of
the composition of the biochar as well as an indication of its stability. Table 2 shows data collected from the
literature. Generally, the values of each property change with pyrolysis temperature. Volatile matter (VM) contents
decreased sharply from 71 wt.% in raw cotton stalk to 13 wt.% at 400°C and to 10.1 wt.% at 550°C. Fixed carbon
(Fc) content increased significantly from 24 wt.% in raw cotton stalk to 58.7 wt.% at 400°C and to 78.4 wt.% at
550°C. Ash content also increased with pyrolysis temperatures. Ash contents at 400°C (8.4 wt.%) and 550°C (19.9
wt.%) were 1.7 and 4 times higher than that in raw cotton stalk (5 wt.%). Calorific values of the solid matter also
increased from 17.09ௗMJ/kg in raw cotton stalk to 25.3ௗMJ/kg at 400°C and 27.6ௗMJ/kg at 550°C. This observation
indicates that cotton stalk carbonization was further complete at increased pyrolysis temperatures.
Table 2. Average values of properties of raw cotton stalk and its biochar under two pyrolysis temperatures.

Adapted from [27, 32- 34]

Pyrolysis char
Properties
Unit Basis Raw cotton stalk 400°C 550°C
Ash wt% Dry 5.18 8.4 13.9
Proximate
Volatile matter wt% Dry 71 10.1 13.1
analysis
Fixed carbon wt% Dry 24 58.7 78.4
Carbon wt% Dry 46.07 59.2 71.9
Hydrogen wt% Dry 5.93 2.3 2.14
Ultimate
Nitrogen wt% Dry 1.1 1.5 1.9
analysis
Sulfur wt% Dry 0.12 - -
Oxygen wt% Dry 41.6 15.5 11.0
Net calorific value (LHV) MJ/kg Dry 17.33 25.3 26
Tobias Pröll et al. / Energy Procedia 114 (2017) 6057 – 6066 6061

Furthermore, the elemental analysis indicated that pyrolysis led to an increase in total C and total N
concentration in biochar and increasing temperature tended to further increase the total C concentration in the
biochar. Whereas, oxygen (O) contents decreased sharply from 41.6% in raw cotton stalk to 15.5% at 400°C and to
11% at 550°C. The O:C ratio ranged from 0.15 to 0.26.
Based on various literature studies reported in Table 3, there is the suggestion that the more reliable predictor of
overall stability of biochar in soils might be the O:C molar ratio. It is indicated that biochars with an O:C molar ratio
of less than 0.2 are typically the most stable, possessing an estimated half-life of more than 1000 years. Biochar with
an O:C ratio of 0.2–0.6 have intermediate half-lives (100–1000 years) and, finally, biochar with an O:C ratio of
greater than 0.6 possess a half-life in the order of 100 years. Summarizing, biochar produced via pyrolysis is stable
if applied to soil for 100 years at a minimum. Depending on the feedstock as well as on the process parameters
significantly longer half-life times can be expected. Thus, biochar can be used for soil amendment as well as for
medium to long term carbon storage.

Table 3. Sum oxygen to carbon (O:C) ratio of the biochar.mary of the residency times of biochar in various studies along
with corresponding
Production notes O:C ratio of biochar Estimated half-life (years) Ref.
Laboratory oven (pyrolysis) 0.32–0.72 100–500 [35]
Chronosequence (natural C) black 0.7 10s (decades) [36]
Laboratory oven (pyrolysis) 0.008 51,000 [37]
Laboratory oven (pyrolysis) 0.01 1400 [37]
Laboratory oven (pyrolysis) 0.18–0.23 40 [38]
(limited O2 environment) 0.16 80 [38]
Laboratory oven (pyrolysis) 0.008 51,000 [39]
Laboratory oven (pyrolysis) 0.008 51,000 [39]
Laboratory oven (pyrolysis) 0.099–0.60 100–110,000 [40]
Historic charcoal blast furnaces 0.06 1000 [41]
Kiln 0.23 600 [42]

3. Process model

The equation-oriented steady state simulation environment IPSEpro is used for the calculation of mass and
energy balances of the process. A previously developed model library [43] has been used and partly extended to
cover the particular streams of the pyrolysis plant. All unit models strictly fulfill mass and energy balances, the latter
employ the conventional enthalpy concept. Organic streams or loadings, such as the feed biomass, the pyrolysis char
and the pyrolysis oil, are modelled as a matrix consisting of C, H, O, N, S and Cl and the empirical formula by Boie
[44] is used to assign the chemical energy content to these streams.
The graphical representation of the simulated process is shown in Fig. 2. Biomass containing inorganic ash and
free water is fed to the pyrolysis drum, where the thermal decomposition takes place. Coarse char with a loading of
inorganic ash is removed at the end of the drum and a raw gas stream is generated which is sent to a cyclone
separator for better dust removal. The product gas is quenched in the pyrolysis oil separator generating a mixture of
condensate and organic phase, which can be partially separated in a phase separation tank. The relatively clean off-
gas after the scrubber is moderately compressed and then partially used for heating the pyrolysis drum. Heat
integration in the form of an air preheater and a fuel gas preheater reduces the pyrolysis gas requirement for the
heating jacket. The remaining pyrolysis gas, which is the larger part, is used in a gas engine for combined heat and
power generation.
It is clear that the process is relatively complex for small scale decentralized application and, likely,
simplifications will need to be made in order to optimize economic figures. One could, for instance, avoid pyrolysis
oil condensation and the gas engine and run a gas-fired Rankine cycle plant or, in an even more simple approach,
6062 Tobias Pröll et al. / Energy Procedia 114 (2017) 6057 – 6066

avoid electricity generation and provide only heat from simple combustion of the hot volatile fraction. The process
presented here, however, shows a theoretical possibility for polygeneration of the different possible products.

Airgasengine AMB

Pyrolysisgas
Gasengine
Exhaust
Fuelpreheater gasfan
G
Chimney
Airpreheater
Airheating jacket AMB Pyrolysisgasfan
WAT
District heat
WAT 70/95°C
Pyrolysisoil
scrubber ORG Org.solvent
Biomass fuel pyr. ORG
startup
WAT

Cooling cycle
Raw gas WAT
35/50°C

Pyrolysisdrum
ORG Pyrolysisoil
Coarse Char WAT Condensate
char fines

ORG Pyrolysischar

Fig. 2. Indirectly heated rotary kiln pyrolysis process scheme for consideration.

4. Results and discussion

4.1. General aspects and input quantities

Biomass with a dry composition according to the cotton stalks reported in Table 1 have been used in the
simulation assuming a water content of the material of 9% based on total wet mass. Product distribution and
composition out of the pyrolyzer are assumed to correspond to the measurements obtained with wheat straw at
550°C reported by Halwachs et al. and Kern et al. [23,24]. The oil separator is operated at 40°C. Air and fuel for the
pyrolyser heating jacket are preheated to 500°C and 450°C, respectively. The gas engine electric efficiency is
assumed to be 35% including the generator. District heat at a temperature level of 70/95°C is generated from
consecutive gas engine cooling and exhaust gas cooling. The exhaust gas temperature in the chimney is 134°C.

4.2. Energy balance

The energy balance of the process is shown in Fig. 3. The values are normalized to the energy flow with the input
biomass, which is assessed based on the lower heating value. It can be seen that about half of the energy provided
with the raw biomass stays in the pyrolysis char while about 12% are lost to the environment. The rest, which
amounts to about 36% of the fuel power input, is distributed on exported pyrolysis oil, electricity and low
temperature heat. Pyrolysis oil could potentially be sent to larger, centralized stations and converted with increased
efficiency. A stream which is not shown in the energy flow diagram is the condensate stream from the phase
separation. This stream, according to the definition of the lower heating value, ports a negative energy content and is
compensated with the heat loss to the environment form the oil scrubber recycle cooler, which in reality is larger
than shown in Fig. 3.
Tobias Pröll et al. / Energy Procedia 114 (2017) 6057 – 6066 6063

Fig. 3. Energy flow diagram of the investigated process.

4.3. Carbon balance

Figure 4 shows the carbon balance of the process with the marginal carbon flow with CO2 in ambient air
neglected. The numbers are normalized to the carbon flow with the biomass input to the plant. About 54% of the
primary carbon input are expected to stay with the char while the rest will be released to the atmosphere after
conversion of the volatile pyrolysis fractions. If we assume that the cotton stalks make up for about 70% of the total
biomass in the cotton crop, the system can provide about 35% of the originally captured CO2 as potentially long-
lasting char for disposal on the field. Moreover, the inorganic nutrients contained in the pyrolyser feed are expected
to be kept almost completely in the agricultural system.

Exhaust gas pyrolyzer heating 9 Chimney


Pyrolysis gas pyrolyzer heating
26 35
Gas engine
9
Oil scrubber 26
Pyrolyzer
Biomass Pyrolysis oil
46
11

Pyrolysis char
100

54
All values refer to carbon in raw biomass = 100

Fig. 4. Carbon flow diagram of the investigated process.

4.4. Comparison to alternative CO2 emission reduction options

An important question with respect to the greenhouse gas emission reduction effects is, how the investigated
biochar storage compares to other options. While a comparison of CO2 emission avoidance costs goes beyond the
focus of the present study, we try to provide a high-level comparison to biomass combustion for electricity
generation substituting a state-of-the art coal-fired power plant.
If the waste biomass would be used in small- to medium-scale plants to produce electricity, coal-fired production
could be potentially substituted. Also in this case, carbon would stay in the ground. Due to several limitations in
6064 Tobias Pröll et al. / Energy Procedia 114 (2017) 6057 – 6066

terms of plant size and biomass combustion particularities, we can realistically assume an electric efficiency of 30%
for electricity generation from biomass residues, while electricity generation from hard coal can reach 45% electric
efficiency in state-of-the-art coal-fired power plants. We further assume a carbon content in the hardcoal of 90 wt.%
and a lower heating value (LHV) of the coal of 35 MJ/kg (9.72 kWh/kg of coal). The raw biomass contains 9 wt.%
of water and its LHV is 15.5 MJ/kg (4.32 kWh/kg of wet biomass). This corresponds to the dry cotton stalks LHV
reported in Table 1. Carbon in biomass is considered to have just been separated from the atmosphere, i.e. CO2
emitted from biomass is not counted, but avoided fossil CO2 emissions from coal are counted as well as sequestered
carbon from biomass. These assumptions are justified if agricultural biomass residues are used which otherwise
would be subject to a quick decay with release of the carbon as CO2. The assumptions are not valid in the same way
for woody biomass from trees with a relevant half-life in the natural cycle. The results of the high-level comparison
are summarized in Table 4 taking 1 MWh of biomass fuel power input as the basis.

Table 4. Comparison of pyrolysis char storage in soils to biomass-fired electricity generation.

a) Biomass power plant b) Pyrolysis char storage

1 MWh biomass 1 MWh biomass


Kel (biomass power plant) = 30% LHV (raw biomass) = 4.32 kWh/kg
300 kWh electricity 232 kg raw biomass

Kel (coal-fired power plant) = 45% Biomass water content = 9 wt.%


211 kg dry biomass
667 kWh coal input for equal electric output
46.1 wt.% C in dry biomass (Table 1)
LHV (coal) = 9.72 kWh/kg
97 kg carbon in biomass feed
69 kg hardcoal
54 kg C in char for sequestration
90 wt.% carbon in hardcoal per 100 kg C in biomass feed (Fig. 4)
62 kg carbon 52 kg carbon sequestered
3.67 kg CO2 / kg C 3.67 kg CO2 / kg C
227 kg CO2 avoided per MWh raw biomass 192 kg CO2 removed per MWh raw biomass

It is evident that the net effect on the CO2 concentration of the atmosphere is comparable around 200 kg CO2 per
MWh biomass fuel power. In the biomass power plant case (Table 4a), the effect is due to avoided fossil fuel
emissions while in the pyrolysis char storage case (Table 4b), the effect is due to storage of atmospheric CO2 from
biomass. The slightly higher effect for the power plant case might suggest this option is the better one. However,
one needs to consider the additional energy output of the pyrolysis plant according to Fig. 3 (electricity, pyrolysis oil
and district heat), which is available on top of the effect derived in Table 4. Further, this comparison neglects any
challenges regarding biomass boiler operation, biomass transport and sustainability with respect to nutrients in the
agricultural system. For the pyrolysis plant option, a potential challenge is in the proper handling of the condensate
stream leaving the oil separator, which is expected to contain aromatic hydrocarbons. As mentioned earlier, more
detailed evaluations may show that simpler schemes without oil separation and gas engine are advantageous with
respect to economics. It is important to note that such a simplification of the process would not change the figures of
the comparison in Table 4.

5. Conclusion

If net CO2 sinks are to be implemented as climate change mitigation or climate repair strategy, it is advantageous
to base the primary CO2 capture from ambient air on natural photosynthesis, i.e. to eliminate carbon contained in
biomass from the natural carbon cycle. This can be done by separating CO2 from bioenergy applications and store
the CO2 in suitable geological sites. Another option, which requires less energy and avoids the concerns associated
Tobias Pröll et al. / Energy Procedia 114 (2017) 6057 – 6066 6065

with CO2 storage sites, is the sequestration of black carbon from biomass. Since pyrolysis char shows sufficiently
low oxygen/carbon ratios to assume half-lives of the charcoal in soil in the order of 1000 years, it seems viable to
convert biomass residues into biologically stable pyrolysis char and use this char in agricultural soils where it may
serve as buffer for water and nutrients. If this is done, the net climate effects are comparable with the use of biomass
for electricity generation substituting coal.
Reliable long-term studies are required with respect to the effects of pyrolysis char addition to agricultural soils
on the soil quality and area yield. If advantages can be generated for agricultural production, there could be a chance
to establish sustainable net carbon sinks with positive side-effects on soil fertility, welfare and development.

References

[1] Brandani S. Carbon Dioxide Capture from Air: a Simple Analysis. Energy&Environment 2012;23:319-28.
[2] Fowles M. Black carbon sequestration as an alternative to bioenergy. Biomass&Bioenergy 2007;31:426-32.
[3] Spokas KA. Review of the stability of biochar in soils: predictability of O:C molar ratios. Carbon Management 2010;1(2):289–303.
[4] Atkinson CJ, Fitzgerald JD, Hipps NA. Potential mechanisms for achieving agricultural benefits from biochar application to temperate soils: a
review. Plant and Soil 2010;337(1-2):1-18.
[5] Abel S, Peters A, Trinks S, Schonsky H, Facklam M, Wessolek G. Impact of biochar and hydrochar addition on water retention and water
repellency of sandy soil. Geoderma 2013;202:183-91.
[6] Ameloot N, Graber ER, Verheijen FGA, Neve S. Interactions between biochar stability and soil organisms: review and research needs.
Journal of Soil Science 2013;64(4):379-90.
[7] Bell MJ, Worrall F. Charcoal addition to soils in NE England: a carbon sink with environmental co-benefits? Science of the Total
Environment 2011;409(9):1704-14.
[8] Blackwell P, Krull E, Butler G, Herbert A, Solaiman Z. Effect of banded biochar on dryland wheat production and fertiliser use in south-
western Australia: an agronomic and economic perspective. Soil Research 2010;48(7):531-45.
[9] Busch D, Stark A, Kammann CI, Glaser B. Genotoxic and phytotoxic risk assessment of fresh and treated hydrochar from hydrothermal
carbonization compared to biochar from pyrolysis. Ecotoxicology and environmental safety 2013;97:59-66.
[10] Hua L, Chen Y, Wu W. Impacts upon soil quality and plant growth of bamboo charcoal addition to composted sludge. Environmental
Technology 2012;33(1):61-8.
[11] Jeffery S, Verheijen FGA, van der Velde M, Bastos AC. A quantitative review of the effects of biochar application to soils on crop
productivity using meta-analysis. Agriculture, Ecosystems & Environment 2011;144(1).175–87.
[12] Jones DL, Murphy DV, Khalid M, Ahmad W, Edwards-Jones G, DeLuca TH. Short-term biochar-induced increase in soil CO2 release is
both biotically and abiotically mediated. Soil Biology and Biochemistry 2011;43(8):1723-31.
[13] Laird D, Fleming P, Wang B, Horton R, Karlen D. Biochar impact on nutrient leaching from a Midwestern agricultural soil. Geoderma
2010;158(3-4);436-42.
[14] Spokas KA, Reicosky DC. Impacts of Sixteen Different Biochars on Soil Greenhouse Gas Production. Annals of Environmental Science
2009;3:179-93.
[15] Verheijen FGA, Graber ER, Ameloot N, Bastos AC, Sohi S, Knicker H. Biochars in soils: new insights and emerging research needs.
European Journal of Soil Science 2014;65(1):22-7.
[16] Ramage J, Scurlock J. Biomass. In: Boyle G, editor. Renewable Energy-Power for a Sustainable Future. Oxford, UK: Oxford University
Press; 1996.
[17] Liu H, Jiang GM, Zhuang HY, Wang KJ. Distribution, utilization structure and potential of biomass resources in rural China: with special
references of crop residues Renew. Sustainable Energy Rev. 2008;12:1402-18.
[18] Campiche J, Boyd S, Huffman M. The Economic Outlook For U.S. Cotton 2016. National Cotton Council of America; 2016.
www.cotton.org (last viewed October 2016).
[19] Johnson J, MacDonald S, Meyer L, Norrington B, Skelly C. The world and United States cotton outlook. Agricultural Outlook Forum. U.S.
Department of Agriculture; 2014. www.usda.gov.
[20] Gurjar RM, Shaikh AJ, Balasubramanya RH, Sreenivasan S. Composite boards from cotton stalks. Central Institute for Cotton Research,
Regional Station, Coimbatore, Tamil Nadu-641 003; December 15-22, 2007.
[21] Bridgwater AV. Pyrolysis – state of the art.In: Success & Visions for Bioenergy: Thermal Processing of Biomass for Bioenergy, Biofuels
and Bioproducts. Bridgwater AV, editor. Newbury, Berks, UK: CPL Press; 2007.
[22] Meier M, Schmid K, Heger S. Pyrolyseverfahren in Burgau – eine Betrachtung aus Sicht der Überwachungsbehörde. In: Thomé-
Kozmiensky KJ, Beckmann M, editors. Energie aus Abfall, Vol. 11. Nietwerder, Germany: TK Verlag; 2014 (in German). p. 780-795.
[23] Halwachs M, Kampichler G, Kern S, Pröll T, Hofbauer H. Rotary kiln pyrolysis - a comprehensive approach of operating a 3 MW pilot plant
over a period of two years. In: Bridgwater AV, editor. Proceedings of the bioten conference on biomass, bioenergy and biofuels 2010.
Newbury: CPL Press, 2011.
[24] Kern S, Halwachs M, Kampichler G, Pfeifer C, Pröll T, Hofbauer H. Rotary kiln pyrolysis of straw and fermentation residues in a 3 MW
pilot plant - Influence of pyrolysis temperature on pyrolysis product performance. Journal of Analytical and Applied Pyrolysis 2012;97:1-10.
[25] Khan AA, de Jong W, Jansens PJ, Spliethoff, H. Biomass combustion in fluidized bed boilers: Potential problems and remedies. Fuel
Processing Technology 2009;90(1):21-50.
6066 Tobias Pröll et al. / Energy Procedia 114 (2017) 6057 – 6066

[26] Manoj T, Sahu JN, Ganesan P. Effect of process parameters on production of biochar from biomass waste through pyrolysis: A review,
Renewable and Sustainable Energy Reviews 2016;55:467-81.
[27] Phyllis2 - Database for biomass and waste – ECN. https://www.ecn.nl/phyllis2
[28] Ahmed FA, Abdel-Moein NM, Mohamed AS, Ahmed SE. Biochemical studies on some cotton by products Part I – Chemical constituents
and cellulose extraction of Egyptian cotton stalks. Journal of American Science 2010;6(12):1306-13.
[29] Ertas M, Acemioglu B, Alma MH, Usta M. Removal of methylene blue from aqueous solution using cotton stalk, cotton waste and cotton
dust. J. Hazardous Mater. 2010;183:421-7.
[30] Xing X, Li H, Ma P, Sun Y, Hu Y, Li T. Thermal Behaviour of Corn/Cotton Stalk Blends during Co-pyrolysis. Energy Procedia 2015;66:
297-300.
[31] Obernberger I, Thek G. Physical characterisation and chemical composition of densified biomass fuels with regard to their combustion
behaviour. Bio- mass Bioenergy 2004;27(6):653–69.
[32] Yang H, Sheng K. Characterization of biochar properties affected by different pyrolysis temperatures using visible-near-infrared
spectroscopy. International Scholarly Research Network ISRN Spectroscopy 2012;Article ID 712837, 7 pages doi:10.5402/2012/712837.
[33] Yang F, LEE XQ, Wang B. Characterization of biochars produced from seven biomasses grown in three different climate zones. Chin. J.
Geochem. 2015;34(4):592-600.
[34] Venkatesh Govindarajan, Gopinath K.A., Minakshi Grover, Sasikala ch (213) Biochar Production Technology for Conversion of Cotton
Stalk Bioresidue into Biochar and its Characterization for Soil Amendment Qualities, Indian Journal of Dryland Agriculture Research and
Development 2013;28(1):48-57.
[35] Baldock JA, Smernik RJ. Chemical composition and bioavailability of thermally, altered Pinus resinosa (Red Pine) wood. Org. Geochem.
2002;33(9),1093-109.
[36] Nguyen BT, Lehmann J. Black carbon decomposition under varying water regimes. Org. Geochem. 2009;40(8):846–53.
[37] Novak JM, Busscher WJ, Watts DW, Laird DA, Ahmedna MA, Niandou MAS. Short-term CO2 mineralization after additions of biochar
and switchgrass to a Typic Kandiudult. Geoderma 2010;154(3-4):281–8.
[38] Hamer U, Marschner B, Brodowski S, Amelung W. Interactive priming of black carbon and glucose mineralisation. Org. Geochem.
2004;35(7):823–30.
[39] Novak JM, Busscher WJ, Watts DW, Laird DA, Ahmedna MA, Niandou MAS. Short-term CO2 mineralization after additions of biochar
and switchgrass to a Typic Kandiudult. Geoderma 2010;154(3-4):281-8.
[40] Zimmerman AR. Abiotic and Microbial Oxidation of Laboratory-Produced Black Carbon (Biochar). Environ. Sci. Tech. 2010;44(4):1295-
301.
[41] Cheng CH, Lehmann J, Thies JE, Burton SD, Engelhard MH. Oxidation of black carbon by biotic and abiotic processes. Org. Geochem.
2006;37(11):1477-88.
[42] Major J, Lehmann J, Rondon M, Goodale C. Fate of soil-applied black carbon: downward migration, leaching and soil respiration. Global
Chang. Biol. 2010;16(4):1366-1379.
[43] Pröll T, Hofbauer H. Development and Application of a Simulation Tool for Biomass Gasification Based Processes. International Journal of
Chemical Reactor Engineering 2008;6:A89. Available at: http://www.bepress.com/ijcre/vol6/A89
[44] Boie, W. Vom Brennstoff zum Rauchgas - Feuerungstechnisches Rechnen mit Brennstoffkenngrößen und seine Vereinfachung mit Mitteln
der Statistik. Leipzig: Teubner, 1957 (written in German).