Advanced Technologies for Biogas Efficiency,

Sustainability and Transport

EC Marie Curie Initial Training Network
Biogas, a mixture of methane and carbon dioxide, is a source of carbon neutral
energy for electricity generation, heating and transport, which can make a significant
contribution to Europe’s climate change commitments. The ATBEST Marie Curie ITN
will tackle several key research challenges along the biogas supply chain, improving
its competitiveness with respect to fossil derived fuels.

Funding scheme: EC Framework 7, Marie Curie ITN, Contract no. 316838

Budget: € 3.86 Million
Duration: 4 Years, 1st July 2013 - 30th June 2017
Research team: 12 PhD and 2 Post Doctoral researchers

The ATBEST ITN will develop innovative research and training for the biogas
industry in Europe. It comprises eight training sites located in the UK, Ireland,
Germany and Sweden. It is a multidisciplinary collaboration between internationally-
renowned research teams and industrial partners, each with complimentary expertise
in a wide range of environmental technologies.

14 researchers have been recruited and each will participate in secondments, 3

Summer Schools and an international conference. The aim is to establish long-term
collaborations and develop structured research and training relevant to industry and
academia along the biogas supply chain: biogas production from feedstock to its
utilisation as an energy source.

Partners and Research Topics

Project Outputs
Follow the outputs of the project:
Website: www.atbest.eu Facebook: www.facebook.com/atbest.itn
Twitter: @ATBEST_ITN LinkedIn: Search for “ATBEST Biogas Network”
 Sustainability and Life Cycle Assessment of feedstock digestion systems
Markus Voelklein
Supervisor: Prof Jerry D Murphy

Bioenergy & Biofuels Research Group

Environmental Research Institute
University College Cork
Cork, Ireland

Biological methanation
Introduction Strategy Life cycle assessment
This project will assess innovative One of the major research tasks is to draw The results of the experiment are compared
biogas technologies. This will be and compare different scenarios of to a duplicate reactor without hydrogen
carried out through detailed systems innovative biomethane systems with life injection. The gained data are further
analysis including for energy and cycle assessment. subjected to life cycle assessment including
carbon balances, laboratory This biological methantion project focuses on detailed carbon and energy balances. In
assessment, cost analyses and efficient digestion systems and upgrading of addition, performance indicators of the
general life cycle analyses (LCA). biogas with external hydrogen from surplus biological methanation process will reveal the
electricity as described in the Sabatier efficiency of this upgrading system.
equation.

Multi-phase digestion
The purpose of this study is to investigate
the methane potential in a 2-phase
fermentation process based on food waste.
The first phase comprises an acidifying
hydrolytic phase, producing hydrogen and
carbon dioxide. The second phase is
dominated by the methanogenic phase,
generating higher concentrations of methane Sabatier equation:
compared to a single-phase system. 4 H2 + CO2 → CH4 + 2 H2O

Lab experiment Outlook

The evaluation of the biological methanation In a next step, the experiment will be
process is further assessed with the above gradually extended and will combine 2-phase
proposed experiment. food waste digestion and biological
methanation at lab scale. This will be carried
In addition to the daily feedstock, the
out by injecting the hydrolysis gas and
necessary quantities of hydrogen are
external hydrogen into the methane reactor
injected into a modified 5-litre lab scale
of the 2-phase system.
The main objective of this experiment is to reactor. A gas pump recirculates the
produced biogas and hydrogen mixture to In a future outlook this data will be
evaluate the performance of an innovative
enhance contact phase and retention time for implemented in a model of a full scale biogas
2-phase reactor system at high loading rates
the Sabatier reaction. The carbon dioxide is plant. In this scenario, the storage capability
(OLR) and short retention times (HRT). The
thereby upgraded to biomethane as of biogas with the associated external
efficiency of these systems is compared to a
described in the Sabatier equation. hydrogen functions as a "battery" of the
one phase reactor system subjected to the
electricity grid.
same conditions. 4 H2 + CO2 → CH4 + 2 H2O

Highlights: The final success of the upgrading process

¾ Evaluation of high OLR on SMY
is determined by a gas chromatograph. A
PLC provides the control of the experiment to
Summary
¾ Hydrolysis performance and impact of adjust the injection of hydrogen and gas ¾ Assess the biological methanation
different OLR on the hydrolysis reactor recirculation. As a consequence the methane process in lab scale
¾ Impact of trace element supplementation production almost doubles and carbon ¾ Interrogate innovative biogas
¾ Compare efficiency (carbon- and energy dioxide is successfully removed.
systems such as multi-phase
balance) of 2-phase system, 1-phase digestion and use of hydrogen to
System, BMP, Buswell upgrade biogas
¾ Evaluate sustainability and cost-
benefit of innovative biogas
systems
 Synergies from co-digestion of grass silage with other
feedstocks
Himanshu1,2,3, Padraig O’Kiely1 and Jerry Murphy2
1 - Animal & Grassland Research and Innovation Centre, Teagasc, Grange, Dunsany, Co. Meath, Ireland
2 - School of Engineering, University College Cork, Cork, Ireland
3 - Questor Centre, Queen’s University Belfast, Belfast, UK

1 5
Introduction Economic modelling of biogas yield from the co-digestion of
Ireland’s agricultural land utilization
¾ Ireland has 4.2 million hectares of agricultural. grass silage and slurry
¾ 1.7 M t of dry matter (DM) is available in excess of 8%
livestock requirements (McEniry et al., 2013). 11%
¾ This DM can be increased upto 12.2 M t Animal diet
DM/annum average by more intensive grassland Crop
management (McEniry et al., 2013). 81%

¾ 10% of the Ireland’s grassland area could fuel up Number of

to 55% of all passenger cars with compressed animals
Crops, Cereals & Horticulture Rough Grazing Grassland Time of Silage yield Slurry yield
biomethane (Wall et al, 2013).
harvest & cost & cost
¾ In 2010 there were 1. 07 M dairy cows in Ireland. During the 20 weeks winter storage period of Slurry
slurry these cows can provide 7.07 M t DS a-1 (Wall et al., 2013). management
¾ Long term mono-digestion of grass silage can suffer due to a deficiency in essential nutrients. Storage Total silage
Addition of slurry to grass silage can provide these essential nutrients. and & slurry cost Animal type
¾ Co-digestion of silage and slurry can produce synergistic effects providing higher biogas yield feeding (Cattle, Pig)
compared to mono-digestion of silage or slurry. system

Biogas yield
2 cost
Objectives
¾ Identify the optimal growth stages of grass and legume silages and the optimal mixture with cattle
slurry for biomethane production.
6
¾ Identify the optimal slurry type and the optimal mixture with grass silages harvested at different LCA of anaerobic digester (to be built at Teagasc Grange) fed
growth stages for biomethane production. with grass silage and slurry mixture
¾ Undertake a full cost analysis of biogas/biomethane production system based on the silage and
slurry feedstock studied above.
¾ Undertake a full inventory of a farm scale anaerobic digester producing biogas from grass silage Slurry or Grass
and cattle slurry. manure

3
Co-digestion of grass and red clover silages of different growth Gathering Cut grass and
animal manure ensiling
stages with cattle slurry

Transport

Biogas Plant Digestate

CH4 Slip

Engine Fertilizer

Specific methane yields for co-

digestion. G – Grass Silage, S –
Slurry (Wall et al., 2013)
Electricity and
heat

4 7
Co-digestion of different slurry types with grass silage of References
different growth stages ¾McEniry, J.; Crosson, P.; Finnan, E.; McGee, M.; Keady, T.W.J.; O'Kiely, P. (2013) How much
grassland biomass is available in Ireland in excess of livestock requirements? Irish Journal of
Agricultural and Food Research 52
¾Wall, D.M.; O'Kiely, P.; Murphy, J.D. (2013) The potential for biomethane from grass and slurry to
satisfy renewable energy targets. Bioresource technology 149: 425-431

8
Contact Information
Himanshu
Mail Address: Teagasc (Animal & Grassland Research and Innovation Centre), Grange, Dunsany, Co.
Meath, Ireland
Email Id: [email protected]
Phone No.:+353 (0) 46 906 1112

Specific methane yields for co-

digestion. G – Grass Silage, S –
Slurry (Wall et al, 2013)
9
Acknowledgements
This work was supported by the Marie-Curie Initial Training Network ATBEST, coordinated by the
QUESTOR Centre at Queen’s University Belfast ,which received funding from the European Union’s
Seventh Framework Programme for research, technological development and demonstration under
grant agreement n. 316838
 The role of trace elements in rheology dynamics, foaming potential
and microbial population structures for efficient biogas production
Safaric L., Bastviken D., Svensson B.H., Björn A.
Department of Thematic Studies – Environmental Change, Linköping University

INTRODUCTION
In order to make anaerobic digestion (AD) more efficient, optimisation measures of the process are often needed. In this way we strive to produce as much biogas from the given
substrate as possible, while at the same time maintaining a reasonable level of process stability. One of the more promising ways to do that is by supplementation of trace elements in
the biogas reactors when necessary (Murray & Van Den Berg, 1981)
Trace elements (i.e. Co, Ni, Fe, Zn, Mo, W, Se), are needed for the growth of the microorganisms involved in biogas formation. This is mainly related to the fact that most are located in
active sites of enzymes, thus having a strong influence on their activity (Fermoso et al., 2009). As enzymatic activity is a vital part of the AD process, the supplementation of trace
elements in the biogas reactor has often proved beneficial by leading to increases in biogas production with a faster substrate turnover and lower concentrations of volatile fatty acids,
resulting in a more stable and efficient methane production (Gustavsson et al. 2013).
Additionally there are some indications in the literature that trace elements might also play an indirect role in rheology dynamics and foaming. The former can directly affect the
economics of reactor operation by influencing the energy consumption in relation to stirring and pumping of reactor fluid, as well as affecting stirring efficiency and heat exchange (Björn
et al. 2012). This can in turn increase the fluids tendency to foam, which is one of the most common and costly problems in the biogas industry today (Moeller et al., 2012). Much is still
unknown about the exact causes and mechanisms behind these processes.

HYPOTHESES & RESEARCH QUESTIONS

Our hypothesis is that, in addition to affecting the general process stability in AD, trace elements also play an important role in rheology dynamics, and through it, the foaming potential
of biogas reactor fluids. In addition, rheology shifts and foaming are complex processes that happen through cascading interactions between many components in the reactor fluid.
Based on the hypotheses the following research questions were formulated:
• Are the interactions, leading to unwanted rheology shifts and/or foaming, happening in a cascading manner? If so, can parameters for the prediction of these phenomena be
identified?
• What role do trace elements play in the interactions leading to rheology shifts/foaming?
• How are microbial community structures and activity affected by the amount of available trace elements?
• Can available trace element concentrations affect EPS production and does this lead to changes in rheological characteristics of the sludge?

EXPERIMENTAL OVERVIEW & METHODS

This research includes three phases, designed to systematically gather and analyse process
information (Image 1). The plan is to intentionally provoke process instabilities and/or failures,
while focusing on rheology shifts, foaming, and trace element concentrations/speciation. The
effect of trace element supplementation to minimise and abate these effects will also be
studied.

Phase I: Analyses of existing data

In the first, pre-experimental stage, we will analyse the existing rheological and
operational/process data of past experiments at the Department of Environmental Change in
order to determine any possible trends in the rheological behaviour of different reactor sludges.
This will help us to specify the appropriate experimental designs to be used in order to get as
much useful data from the planned experiments as possible.

Phase II: Stable reactor performance

Initially, three groups of laboratory scale CSTR reactors (5 L volume each) will be set up in
order to run the experiments. Different trace element concentrations will be maintained for each
group, ranging from low to high. We will begin by using defined substrates, allowing us to
conduct a more systematic study of the effects of e.g. proteins, lipids, and carbohydrates. This
will provide more accurate control of the experiment and a systematic overview of the related
processes. More complex substrates could then be used in the later stages.
Stable biogas production process performance at the different specified TE concentrations will
be established. Regular sampling of biogas and reactor sludge will be performed and samples
analysed for many different parameters (see Image 2).

Phase III: Induced process instability

During this phase we will provoke the processes and induce unstable reactor performance. The
potential provocation categories aimed at are presented in Table 1.
The provoking methods will be carried out by gradually changing the relevant parameters in
order to evaluate their critical levels at the onset of process instability. The concomitant levels
of TE bioavailability, rheology and foaming potential, as well as the status of the microbial
community will be determined. The provocative changes will then be continued until we reach Image 1: Project design
system failure in all reactors in one form or the other (extensive foaming / acidification /
extreme rheology shifts).
Table 1: Process provocation categories
Category Name Description

I. Reactor overload OLR increase and/or HRT decrease

II. Surface activity provocation Increase of surface active agent content of substrate

III. Rheological change provocation Increase of viscosity-increasing substance content of substrate

IV. Inhibitory agent overdose Increase in inhibitory agent content of substrate

V. Substrate degradability increase Increase in easily degradable portion of substrate

VI. Substrate degradability decrease Increase in difficult to degrade portion of substrate

VII. pH modulation Increase and/or decrease of pH

REFERENCES
Björn, A., Karlsson, A., Shakeri Yekta, S., Danielsson, Å., Ejlertsson, J., Svensson, B.H. 2012. Rheological characteristics of reactor liquid from 12 full-scale
biogas reactors. International Conference on Applied Energy (ICAE 2012), in Suzhou, China, 5– 8 July 2012.
Fermoso F.G., Bartacek J., Jansen S., Lens P.N.L. 2009. Metal supplementation to UASB bioreactors: from cell-metal interactions to full-scale application.
Science of the Total Environment; 407: 3652-3667
Gustavsson J., Shakeri Yekta S., Karlsson A., Skyllberg U., Svensson B.H. 2013. Potential bioavailability and chemical forms of Co and Ni in the biogas
process – an evaluation based on sequential and acid volatile sulfide extractions. Engineering in life sciences. 13: 572-579
Moeller L., Goersch K., Neuhaus J., Zehnsdorf A., Mueller R.A. 2012. Comparative review of foam formation in biogas plants and ruminant bloat. Energy, Image 2: Parameters to be monitored
Sustainability and Society; 2, 12: 1-9
Murray W.D., Van Den Berg L. 1981. Effects of nickel, cobalt and molybdenum on performance of methanogenic fixed-film reactors. Applied and Environmental
Microbiology; 42, 3: 502-505
Development of macroalgae as a substrate
for biogas production
Ometto Francesco*, Berg Andreas and Ejlertsson Jörgen

Aim and Deliverables

To develop technical and logistical guidelines for biogas production from marine macroalgae
addressing topics of harvesting, storage and processing.
The potential methane content of different algae species from the North Sea will be
determined and linked to their specific growth stage. In addition, the feasibility of a full scale
system for cultivation and anaerobic digestion (AD) of macroalgae will be investigated to
guarantee the sustainability and the economics of the system.

What is the methane potential of macroalgae?

Tab.1 – Algae elemental composition. All data reported in term of mg/kg TS. Algae
Biochemical Methane Potential (BMP) are collected from the wild environment by SINTEF, Norway.
300 The methane content of Aelaria Ascophyllum Fucus Laminaria Saccharina
macroalgae varies between esculenta nodosum vesciculosus digitata latissima
250 Al 50 < 50 140 < 50 63
algae species and it Sb < 1.00 < 1.00 < 0.99 < 1.00 < 0.99
depends on the chemical As 70 23 36 86 68
200 Ba 7.8 6.8 13 18 14
composition, the growth
ml/gVSadd

Pb 1.1 < 0.5 < 0.5 < 0.5 < 0.5

B 110 120 180 110 120
150 environment condition and P 3100 520 890 2600 2400
the algae age. The project Fe < 150 < 150 260 190 230
100 Cd 2.7 0.14 0.86 1.0 0.91
is currently investigating the Ca 22000 12000 14000 18000 16000

50
impact of seasonal K
Cu
20000
< 2.5
14000
3.1
21000
5.5
76000
< 2.5
64000
3.0
variation of five different Cr < 2.5 < 2.5 4.3 < 2.5 < 2.5
Mg 5600 8900 7300 8000 8200
0 algae species to identify the Mn 3.1 10 80 3.8 4.4
Ascophyllum Aelaria Laminaria Saccharina optimal biomass depending Na 22000 32000 28000 44000 48000
nodosum esculenta digitata latissima Ni < 2.5 < 2.5 6.9 < 2.5 < 2.5
Fig.1 - The BMP is performed in 320ml bottles maintained at
on the harvesting period. S 6200 32000 28000 14000 11000
Ti < 5.0 < 5.0 8.1 < 5.0 < 5.0
37
C for 60 days. F. vesciculosus not available.
Zn 36 49 41 63 38

Mesophilic or Thermophilic digestion condition?

1. BIOMASS 2. PRE-PROCESSING 3. DIGESTION 4. PERFORMANCE
Cultivated S. latissima Algae are blended to 5L reactors SLR 2.1 gVS/L with a HRT 19d
harvested in June 2014 homogeneous mixture at 37



 The substrate composition changes every 3HRT
from 100% wwt sludge to 80:20 (sludge:algae),
50:50 and 20:80.

Daily Biogas production

Biogas composition
Solids content
Conductivity
Viscosity
VFA
pH

How to guarantee a positive energy and economic balance?

An integrated biorefinary solutions is the only feasible alternative to maintain positive
energetic and economic balance while cultivated algae for biofuels production. The project will
perform a full scale energy/costs analysis to identify the optimal flowsheet configuration. This
will help companies to develop and design efficient integrated AD plants.
*[email protected]
Scandinavian Biogas Fuels AB, Linköping University, Dep. of Thematic Studies (TEMA-M) 58183, Linköping – Sweden
 Joanna Grebosz, Mike Larkin, Chris Allen, Leonid Kulakov; Queen’s University
Belfast, School of Biological Sciences
97 Lisburn Road, Belfast BT9 7BL , E-mail address: [email protected]

Introduction Methods
Biogas, due to its high content of methane (60-70%) might be
a good source of environmental-friendly renewable energy
(Yadvika et al. 2004; Berglund and Bӧrjesson 2006). Collection of a
454-
sample – high
Biogas production is conducted by complex microbial DNA extraction – pyrosequencing qPCR optimization
methane-yielded
Power Soil DNA (bacterial and (optimized qPCR
two-stage pilot-
community characterized by some relationships amongst it scale mesophilic
Isolation Kit
(Thermo
archaeal 16S
investigation) and
for mcrA_1035F
and mcrA_1538R
anaerobic digester
that influence methane yields in anaerobic digesters (Yadvika (AFBI,
Scientific) processing results
in QIIME
primers)
Hillsborough)
et al. 2004). The microbial community structure can be
changed by high amounts of some compounds produced
during the process, for instance – hydrogen. Low hydrogen
concentrations can be maintained by hydrogenotrophic
methanogens (considered as methanogens causing low
methane yields) and connected with the promotion of for
example hydrogen-producing bacteria activity (Weiland 2010; Results
Li et al. 2011; Ziganshin et al. 2011). 454-pyrosequencing of the sample revealed that the most
The hypothesis of the project is the assumption that some kind abundant group of bacteria was Firmicutes (especially order
of syntrophy exists between particular candidate division Clostridiales). The most dominant Archaea were
hydrogen-producing bacteria and hydrogenotrophic Euryarchaeota (especially order Methanosarcinales). More
methanogens whose activity are connected with low methane detailed results are showed below.
yields. Thus, the candidate division bacteria could act as a Optimisation of some qPCRs are conducting resulting in
biomarker of low methane production in anaerobic digesters. optimised reaction with mcrA_1035F and mcrA_1538R
archaeal primers.
H2 and ammonia H2S

1 2
Mono- and oligomers
Polymers (lipids,
(long chain fatty Short-chain volatile
proteins, Volatile fatty acids
acids, sugars, amino fatty acids
polysaccharides)
acids)

H2 and CO2 Acetate

Legend: Legend:

k_Bacteria;p_Bacteroidetes k_Archaea;p_Crenarchaeota;c_MCG;o_pGrfC26;f_;g_
k_Bacteria;p_Proteobacteria k_Archaea;p_Euryarchaeota;c_Methanobacteria;o_Methanoba
4 cteriales;f_Methanobacteriaceae;g_Methanobacterium
k_Bacteria;p_Firmicutes
k_Archaea;p_Euryarchaeota;c_Methanobacteria;o_Methanoba
k_Bacteria;p_Fibrobacteres cteriales;f_Methanobacteriaceae;g_Methanobrevibacter
Biogas – mainly k_Bacteria;p_WWE1 k_Archaea;p_Euryarchaeota;c_Methanomicrobia;o_Methanosa
methane
rcinales;f_Methanosarcinaceae;g_Methanosarcina

Fig. 2. The chart showing the Fig. 3. Pie chart indicating the proportion
Fig. 1. Diagram showing the biogas production process. Designation: 1 – hydrolysis, 2 – acidogenesis, 3 – abundancy of bacteria phyla in the between different species of Archaea in the
acetogenesis, 4 - methanogenesis AFBI’s sample sample from AFBI

Aims
Conclusions
The results indicate that the most abundant Archaea in the
The investigation of possible syntrophy digester is Methanosarcina which is classified as aceticlastic
between candidate division hydrogen- methanogen group. The predominance of such
producing bacteria and hydrogenotrophic
methanogens and its influence on methane
methanogens with simultaneous absence of particular
yields by using metagenomic tools candidate division bacteria in the digester characterized by
high methane production is in agreement with our
hypothesis. In contrast, hydrogenotrophic methanogens
predominance with the presence of particular candidate
The study on the possible shifts in division hydrogen-producing bacteria would be connected
microbial community as a result of various
with non-optimal digester performance. However, the
The development of robust reactor performance – especially in terms
of feedstock hypothesis still needs confirmation by investigating samples
metagenomic technique (targeting from other reactors.
the biomarker – candidate division
bacteria) to monitor methane
yields in anaerobic digesters

References:
Berglund M, Bӧrjesson P (2006) Assessment of energy performance in the life-cycle of biogas production. Biomass Bioenergy 30:254-266
Li Y, Park SY, Zhu J (2011) Solid-state anaerobic digestion for methane production from organic waste. Renew Sust Energ Rev 15:821-826
Weiland P (2010) Biogas production: current state and perspectives. Appl Microbiol Biotechnol 85:849-860
Yadvika, Santosh, Sreekrishnan TR, Kohli S, Rana V (2004) Enhancement of biogas production from solid substrates using different techniques – a review. Bioresour Technol 95:1-10
VZiganshin AM, Schmidt T, Scholwin F, Il’inskaya ON, Harms H, Kleinsteuber S (2011) Bacteria and archaea involved in anaerobic digestion of distillers grains with solubles. Appl Microbiol Biotechnol 89:2039-2052

Acknowledgements:
The study is supported by a grant from the European Union within ATBEST project.
Analysis of anaerobic fermentation process by online
spectroscopic UV/Vis, NIR and MIR-measurement
Eccleston, Robin*; Wolf, Christian; Bongards, Michael.
Cologne University of Applied Sciences, Institute for Automation & Industrial IT, Steinmüllerallee 1, 51643 Gummersbach, Germany
*[email protected]

Introduction
The aim of this project is to develop an innovative online-measurement system for biogas plants. The system will use a new min-
iaturised MIR spectroscopic sensor, and will perform online measurements of anaerobic digester substrates and methane con-
centration in biogas. Machine learning methods will be applied to the measured spectral data to estimate the concentrations of
process parameters (NH4-N, VFAs, etc.) from the measurements. The information about concentrations can then be used to
control substrate flow into the digester to maintain stable operating conditions whilst also allowing optimisation of the levels of bi-
ogas produced. A further benefit is that the analysis will be performed automatically which will return results significantly faster
and cheaper than a laboratory analysis.

Testing To Date PIR Fibres

Figure 1 shows the previous system as used for testing [1]. As Significant attenuation occurs during transmission of the
numbered in the figure, the components are as follows: light in the PIR fibres, as can be seen in Figure 2. During
1.Diamond tipped ATR probe mounted in the Knick Ceramat® previous testing, due to constraints on the equipment loca-
housing. tion, it was necessary to have a fibre length of 6m. Reduc-
2.Nicolet™ iS™5 spectrometer used to perform spectroscopic ing this fibre length will improve the SNR and hence meas-
measurements connected by PIR fibre to ATR probe. urement quality. A new spectrometer is being developed
3.Laptop to control the spectrometer and Unical® system. with a smaller footprint which will allow more flexibility and
4.Knick Unical® 9000 system for probe cleaning. shorter fibres, and reduced optical signal attenuation.

Internet

Router Router

Raspberry Pi

Spectrometer

Figure 1: Measurement system fitted to digester. Figure 2: PIR Fibre Attenuation [2]. Figure 3: System Block Diagram.

Software Development
Software has been written to control the new miniaturised spectrometer over USB. The software has
been tested on a Raspberry Pi and runs a web server to deliver the data over a network connection.
Figure 3 shows how the system will work. The custom software to control the Unical® system was in-
complete and had some issues, which are currently being addressed. The Raspberry Pi and NIR
spectrometer used for testing can be see in Figure 4. Figure 4: Raspberry Pi
and NIR Spectrometer.
Upcoming work Expected results
Delivery of the hardware is expected in December, and once The measurements with the new hardware will vary com-
obtained the immediate tasks are follows: pared to the previous results. The SNR is expected to vary
x Take substrate sample from digester. due to multiple reasons.
x Create multiple spiked samples. x The sensor’s SNR will be different from the iS™5.
x Perform laboratory analysis on samples. x The fibre length will be reduced which will increase the
x Perform spectral measurements on samples. optical signal magnitude reaching the sensor and im-
x Reduce data dimensionality. prove the optical SNR.
x Apply machine learning methods on subset of data for train- x The overall measurement SNR will also depend on the
ing purposes. number of scans.
x Apply methods to remaining data and analyse results.

References
1. M. Bongards, O. Trauer, S. Janz, V. Artyushenko, and J. Mannhardt, INNO-MIR Biogas - Entwicklung und Automatisierung eines innovativen MIR-Online Messsystems für Biogasanla-
gen, tech. rep., Cologne University of Applied Sciences, Gummersbach, 2013.
2. Art Photonics, Polycrystalline IR-Fiber Cables art photonics - Broad Spectra Optical Fiber Solutions from UV to Mid-IR, 2014.
Combined H2S and CO2 Removal Processes For
Upgrading Biogas
Keren Jenifer Rajavelu1,2; Martin Denecke1
1Department of Urban Waste and Water Management, University of Duisburg Essen, Germany
2QUESTOR Centre, Queen’s University Belfast, United Kingdom

Abstract Background and Research Aims

Biogas produced from anaerobic digestion is a renewable • Development of energy efficient, scalable processes for hydrogen sulphide
energy resource. Typical biogas composition is 50-60 % (H2S) removal in biogas using naturally occurring bacteria.
methane (CH4), 30-45 % Carbon dioxide (CO2), moisture
and traces of hydrogen sulphide (H2S). However, presence • Test the Bioreactor (Bio trickling filter) for optimized bacterial activity.
of CO2 and H2S greatly affects CH4 content and purity of
biogas. In this work, a method using bottom ash for removal • Development of energy efficient, scalable processes for carbon dioxide
of CO2 and biological Desulphurization of H2S using sulphur removal in biogas using bottom ash.
Oxidizing bacteria (SOB) will be studied. The technical
feasibility of employing combined removal process will be • Combination and optimization and interaction of combined process.
investigated.

Experimental Process and Results

Hydrogen Sulphide removal (Biological oxidation) Carbon dioxide Removal (Carbonation reaction)
The main principle involved:
The main reaction principle involved:
1) CO2 + H2O H2CO3
H2S + ½ O2 Sº + H2O
2) H2CO3 + Ca(OH)2 CaCO3 + 2H2O

• Operating parameters such as CO2

Fig:1 Elemental Sulphur deposition on a Thiobacilli pressure, ash humidity, temperature L/S
bacterial cell ratio will be studied.
• Various microbiological studies were performed before
the start up of the reactor.
• Lab scale reactor will be designed and
• Two different activated sludge SOB 1 and SOB 2 (as developed based on resulting carbonation
shown in graph) were initially inoculated into the efficiency. Fig:2 Bottom ash from
thiosulphate and basal medium (for enriching sulphur MSW plant
oxidising bacteria).

• SOB bacteria showing higher efficiency has been

selected for further processes for H2S removal in bio
trickling filter.
• Figure 4 shows the comparative sulphate ion production
at 144 hrs (6 days) at 30 0C.
Process layout
• SOB2 has high sulphate production though SOB1
produced significantly higher sulphate even after 40 hrs.

• The selected sludge sample has been acclimatized to the

reactor for H2S removal.

Fig:4 Comparative Sulphate ion production ( mg/l) of different

Fig:3 Biotrickling filter set up with a aeration unit for desulphurization of Biogas
Sulphur oxidizing bacteria in different medium at various pH
(to be integrated and coupled with CO2 removal using bottom ash)

Acknowledgments
I would like to thank Dr. Martin Denecke, Dr. Michael Eisinger, Simon Murray, and ATBEST project committee.
 Novel technologies for integrated biogas separation and compression

ESR:4.2: Jing-xiao Liang (Leanne) QUB

Supervisor: Pro. David Rooney Dr. Geoffrey McCullough Dr. Beatrice Smith

Aqueous alkanolamine solutions are widely used for the removal of acid gases Theoretical Analysis
such as CO2 and H2S from biogas. Methyldiethanolamine (MDEA) is one of the
Donaldson and Nguyen (1980) proposed the following reaction mechanism for
industrially important alkanolamines used for this purpose. MDEA is characterized
the reaction of CO2 with MDEA:
by a slow reaction rate with CO2 compared with primary and secondary amines.
R3N + CO + H2O = HCO3- + R3NH+ (1)
To improve the CO2 absorption rates
This reaction mechanism is essentially a base catalysis of the CO2 hydration
of tertiary amines, small amounts of
reaction and it can be divided into two steps: First, MDEA combines with CO2
absorption activators (cyclical amines
in a liquid film to form an unstable weakly boned CO2-nitrogen atom complex
in most cases) can be added to the
as follows:
tertiary amines in order to reach
R3N + CO2 = R3NCOO (2)
sufficient absorption performances
Then the hydrolytic reaction of R3NCOO takes place in the liquid phase in
the absorption capacities of the
equilibrium as follows:
solutions remaining high.
R3NCOO + H2O = R3NH+ + HCO3- (3)
CO 2 Regeneration experiments㻌 below is experimental apparatus for regeneration, Because of the concentration of MDEA in bulk phase is high, the
the whole regeneration experiment was accomplished at atmospheric pressure. concentration of MDEA in liquid film is nearly equal to that of bulk phase if the
1. Two condensers were placed over the partial pressure of CO2 is not very high and the conversion of MDEA is not
bottle to minimize the evaporation loss of large. The reaction with respect to MDEA can be regarded as pseudo-first-
water
order and the reaction rate can be expressed as
2. The released gas was eventually led to a
rm= k2Cam(PCO2 – PCO2*) (4)
suction bottle in which saturated calcium
am = methyldiethanolamine * = equilibrium at the interface
hydroxide was applied to detect CO2
3. The flow rate of the released gas was
next step: continuous in-line measurement
measured using a soap-film meter
4. Before the soap-film meter, the gas
temperature was measured, thus the
amount of released gas could be
calculated as the amount of water in the
gas being excluded

This apparatus including an absorption column under elevated pressure and a

regeneration column under normal pressure is established to mimic the industrial
installation of CO2 removal both of the columns were in adiabatic state.


3
CO2 was passed through absorption
(

9

column from its bottom, and tail gas was

emitted at the top The rich solution that

3  Wiped-film evaporator
was drawn from the bottom of the
absorption column was flashed and then A single analyzer is now capable of measuring

( (
allowed to flow into regeneration column, a wider selection of gas components utilizing
,



3
(
 where it was stripped by a reboiler. The many different types of sensor technology.
(

(

CO2 from the stripper was metered and Non-dispersive infrared (NDIR) modules are
Diagram of the experimental apparatus: purged. The lean solution drawn from the available to measure gas such as CO, CO2, NO,
1.CO2 steel bomb 2.absorption column 3. pump 4.surge tank
5.reboiler6.Wet flow meter 7.flash valve 8.regeneration regeneration column was sent back to the N2O, CH4, SO2 and others
column 9.condenser
absorption column with a metering pump

HORIBA gas analyzer

Permanent gases such as CO, CO2, O2, N2, and
methane are common analysis in refinery gases,
natural gas, fuel cell gases, and many other
industrial processes. Understanding the
concentration of these components can be very
important for controlling manufacturing
processes, and impact the quality and
commercial value of end products

Agilent Technologies GC
Surplus electricity to biogas via hydrogen
Nikoletta Giantsiou, M.Sc.
University of Duisburg – Essen, Faculty of Engineering, Urban Water and Waste Management, Essen, Germany
Research Supervisor: Prof. Dr. – Ing. R. Widmann, Dr. – Ing. T. Mietzel, Dr. – Ing. S. Schmuck
E-mail: [email protected]

Aim and Objectives

To develop a technical solution of converting surplus wind energy or other fluctuating source into a
storable gas such as methane, CH4. The conversion of electricity to methane will be evaluated. By
using the bio – Sabatier reaction H2 and CO2 can lead to CH4 production. Lab scale reactors for this
conversion will be implemented. The continuous operation of this configuration will result in an
efficiency calculation. In addition, H2 consumption from hydrogenotrophic archaea will be optimised.

Task & methodology

on going
Task 1
Background • Possibilities of biological and chemical bio – Sabatier reaction K
Đ K
research • Minimal chemicals and energy demand Đ
ŝŽƌĞĂĐƚŽƌ

on going
Task 2
Lab scale
• Continuous stirred reactor - plexiglas double jacket reactor
reactor - possibility of recirculation streams
design • ~ 10 L working volume
- parameters on line control

Task 3 recently started

Operation
• Continuous operation - continuous operation at 37º C
and - operation without H2 injection
• Batch tests
monitoring - operation with H2 injection

starting January 2015

Task 4
Efficiency • Calculation of efficiency Evaluation of the systems’ stability under
analysis • Biogas yield different operational conditions

starting November 2015

Task 5
Large – scale
- scale up the optimal configuration
reactor • Design of a full – scale reactor - energy and costs analysis

Outcome
The expected outcome of this project is to implement an efficient process for converting the
excessive renewable energy into CH4. This process will result in decreased biogas upgrading costs
and the possible use of biogas as an alternative to natural gas. The main benefit will be the use of
the existing infrastructure system for storing electricity.
ESR 5.2
Micro-reforming of biogas for micro-combined heat and power generation
Fabio De Rosa
School of Chemistry and Chemical Engineering, David Keir Building, Queen’s University Belfast
Centre for Theory and Application of Catalysis (CenTACat)
Belfast BT7 5AG, e-mail: [email protected], phone; +44(0)28 9097 4462
Supervisors : Professor David Rooney, Dr Beatrice Smyth, Dr Geoffrey McCullough, Dr Alex Goguet
Reforming of Biogas: optimal conditions through thermodynamics and MCDM analysis
1. Introduction 2.2 – Multi-Criteria Decision-Making (MCDM) techniques
One of the ways to exploit biogas is by thermo-chemical conversion The entropy method can be used to determine the objective weights of criteria for MCDM
into syngas (CO+H2) through reforming (Table 1). In turn syngas is problems (1). If the data distribution is narrow the entropy is small, the considered criterion
used as starting material to synthesize liquid fuels or to produce provides more useful information and the corresponding weight should be set high,
hydrogen (Fig.1). compared to another criterion with a broader distribution.
TOPSIS stands for Technique for Order Preference by
Similarity to the Ideal Solution Method. It needs informa-
tion about the relative importance of the criteria consi-
dered in the selection process and is used to find the clo-
sest alternative to the positive-ideal solution (PIS) and the
farthest from the negative-ideal solution (NIS). The PIS
maximizes all the benefit criteria (minimizing cost
criteria) (Fig. 4).The solutions are ranked according to the
Figure 4 – TOPSIS method
closeness to the PIS (C*) (2).

3 – Analysis and results

The analytical steps are shown in Figure 5. The processes in Table 3 were
studied and a sensitivity analysis on the feeds was carried out. Methane
Figure 1 – Biogas exploitation roadmap steam reforming was taken as the reference process.
In the big scenario of biogas exploitation in Figure 1 problems arise during the Criteria’s weights relative to the Table 3– Processes under exam

comparison of the reforming processes due to the different characteristics of each 960 x 8 matrix calculated
one of them and to the complicated relationships between the criteria of interest. according to the entropy method
The comparison should are shown in Figure 6 (a),
Table 1 – Biogas reforming technologies
be made using industrial whereas the final ranking
standard processes as according to the C* value
reference (e.g. methane calculated through the TOPSIS
steam reforming). is reported in Figure 6 (b).
Biogas can be an effective
methane substitute for
reforming processes, giving
comparable values of C*
2. Methodology even at lower
temperatures (highlighted
2.1 – Thermodynamic simulations
area in Fig. 6(b)).
Several thermodynamic simulations of biogas reforming processes were run using
the commercial software ASPEN Plus by AspenTech (Fig.2) in order to obtain data
for the criteria in Table 2.
Table 2 – Relevant criteria Figure 5 – Analytical steps
S: separator; (a) (b)
H: heat exchanger;
M: mixer;
R: reactor

Figure 2 – ASPEN Plus simulation

Each process was simulated at P=1 bar Figure 6 – Final results for the processes under exam: weights for the criteria (a) and C* ranking (b)

and divided in 30 “sub-processes” here

called alternatives, according to the
operative temperature, which ranges from 4. Conclusions and future works
200 to 1200˚C (ΔT≈35˚C). Results are Conclusions:
available both in graphs and 30x8 matrixes - The proposed method is rational and straightforward;
(Alternatives x Criteria) (Fig.3). - Multiple criteria can be taken into consideration in the assessment of
the effectiveness of the process, rather than η alone;
- Biogas can be employed as a methane/natural gas substitute for
reforming processes over an effective range of operating conditions.
Interestingly biogas results in slightly higher overall-performances than
methane.
Future work:
- Add more cases to the sensitivity analysis on the feeds;
- Add more criteria to the method (e.g. economical);
- Set-up an experimental rig for simulated biogas tri-reforming (on
going);
Figure 3 – Example of ASPEN Plus simulation results: methane steam reforming at P=1 bar and CH4/CO2/H2O/O2=1/0/1/0
- Validate experimentally the data from thermodynamic simulations plus
Trade-offs between cost (T, yCH4, yCO2, yCOKE, Heat) and benefit criteria (yCO, yH2, η) MCDM analysis;
were found using two multi-criteria decision-making (MCDM) techniques in series: the - Apply the method to the other processes reported in Figure 1 in order to
entropy method and TOPSIS. have an overall assessment of biogas exploitation techniques.
References : 1 - Shannon, C.E. A mathematical theory of communication. Bell Syst. Tech. J. 1948, 27, 379–423
2 - Xiangxin Li,Kongsen Wang,Liwen Liu,Jing Xin, Hongrui Yang,Chengyao Gao, Application of the Entropy Weight and TOPSIS Method in Safety Evaluation of Coal Mines, Procedia Engineering 26 (2011) 2085 – 2091
M.Sc. Christian Jenne
University Duisburg-Essen (UDE), Facility of Engineering
Institute of Product Engineering, Transport Systems and Logistics Department
Keetmannstraße 3-9, 47058 Duisburg, Germany
E-Mail: [email protected] Phone: 0049 - 203 379 7044
Research supervisor: Prof. Dr.-Ing Bernd Noche

ESR Project 5.3 “Biogas distribution concepts

for the transportation sector”
Raw biogas

Dehumidifying
of biogas

Desulphurisation of Biogas

Natural gas Fuel for

Transportation Electricity Heat
Network sector

Private Commercial Fleets & Remote rail Commercial Domestic Distric heating
transportation transportation Taxis network CHP units CHP units networks
sector sector >50kW <10kW

• It is very difficult to compare CNG/CBG, LPG, LNG with diesel fuel due to the fact that some fuel types are measured in
weight (kilogrammes) and others are measured in liquid volume (litres). CNG/CBG prices are often given in gaseous metric
volumes (m3) which makes it even more difficult to compare like for like.
• The second significant point to be considered should be, that fuel consumption might be higher but the purchase price is
significantly lower. Therefore, the difference in fuel price does not represent a complete saving analysis.
• Energy heat values; known as calorific values; are also very much dependant on temperature and pressure to achieve the
right measurements and volumes. A comparison chart on the right illustrates the most common fuel types in Germany given
as caloric values, compositions and price indications.

Fuel Source Fuel Price Calorific values Combination level

Minimum methane
CNG/CBG (High gas) 1,105 €/kg ̴ 14 kWh/kg
concentration of 97%
Minimum methane
CNG (Low gas) 0,983 €/kg 10 - 11.5 kWh/kg • CNG – Compressed Natural Gas
concentration of 80%

Diesel 1,354 €/Litre 9.86 kWh/Litre

Assumption with 5% • CBG – Compressed Biomethane Gas
biofuel mix
Assumption with 5% • LPG – Liquefied Petroleum Gas
Petrol 1,545 €/Litre 8.77 kWh/Litre
biofuel mix
60/40
• LNG – Liquefied Natural Gas
LPG (Autogas) 0,830 €/Litre 6.6 kWh/Litre
butane/propane fuel mix
LNG (-162㼻C @ Minimum methane
1,08 €/kg 15 kWh/kg
atmospheric pressure) concentration of 99%

(Table 1: Own table comparison and price research in Germany, July 2014)
 Applications of Biogas in Chemical Energy Storage and Liquid
Fuel Production
Rawan Hakawati - ESR 5.4
Supervisors: Prof.David Rooney, Dr.Geoffrey McCullough, Dr.Beatrice Smyth

1. Introduction 4. Biogas to Energy Routes

BG : Biogas
ATR FT
Various options for AD feedstock in N Ireland were investigated as well as the possible routes DR : Dry Reforming
DR FT FC SR:Steam Reforming
from biogas to energy production. General Energy assessment is performed in each case which FC Tri-R: Tri Reforming
will set the basis for the extensive analysis of Liquid Fuel Production in future work.
ATR : Auto thermal reforming
Before choosing relevant feedstock, a quick environmental overview was conducted for N ATR FT
FT : Fischer Tropsch
Ireland. The Green House Gas Emissions for the years 1990-2010 are presented in Table 1. SR FT FC CHP: Combined Heat and Power
Emissions presented in the year of 2010 show a total of 20,460 ktCO2eq with 26% contribution FC FC : PEM Fuel Cell CHP
BG
from Agriculture, 21% from Transport, 19% from Energy Supply and 19% from Residential ATR FT EL : Electrolysis
Sector Tri-R FT SAB : Sabatier
FC LIQ : Liquefaction
FC
Table 1 1990-2010 Northern Ireland GHG Emission Inventory (ktCO2e) ICE : Internal Combustion Engine

ICE
SR :CH4+H2O = CO+3H2
LIQ DR :CH4+CO2=2CO+2H2
EL+SAB
TRI-R :SR+DR+TOx+POx
ICE
POx :CH4+0.5O2՜CO+2H2
TOx :CH4+2O2՜CO2+2H2O
SAB :CO2+4H2՜CH4+2H2O

5. Biogas to Energy Assessment

*The values are adopted from the "Report to the Department for Energy and Climate Change, The Scottish Government, The Welsh Government and The Northern
Ireland Department of Environment. On August 2012." Process Energy Ratio E
Syngas TRI-R 0.82
2. Road-Map DR(ATR) 0.84
Agricultural Feedstock can be classified into: SR(ATR) 0.77
TRI-R(ATR) 0.77
Anaerobic SR 0.83
Wet Biomass Biogas
Digestion
DR 0.90
Biochemical Processing Process Energy Ratio E
DR(ATR)+FC 0.58
Gasification Syngas
SR(ATR)+FC 0.57
Dry biomass BioGas
TRI(ATR)+FC 0.53
Pyrolysis Syngas
CHP
1 Kmol/s TRI-R+FC 0.56
Thermo-chemical Processing
CH4/CO2=1.5 SR+FC 0.62
BG+ICE 0.90
3. Methodology and Results 0.59
DR+FC
Multi-criteria decision-making (MCDM) was used to asses the feedstock available in NI for AD. EL+SAB+ICE 0.53 (NG=0.26, W=0.18, C=0.16)
It is useful for ranking and selecting purposes of the available alternatives when multiple
criteria have to be considered simultaneously. An MCDM problem can be expressed in a Process Energy Ratio E
matrix format with possible alternatives; the decision maker has to choose criteria on which DR(ATR)+FT 0.82
the assessment will be based. Weights corresponding to each criteria are generated according TRI-R+FT 0.55
to a method knows as the “Entropy Method”. Then, the ranking is done according to the TRI(ATR)+FT 0.80
“Topsis Method”. Liquid Fuel
SR(ATR)+FT 0.84
Table 2 MCDM for feedstock selection in NI
SR+FT 0.65
Feedstock CH4 yield **Availability *Opportunity Biogas Calorific value
(m3/t VS) (t/year) cost (£/t) production (MJ/mn3) EL+SAB+LIQ 0.44 (NG=0.22, W=0.16, C=0.13)
(mn3/kg VS) DR+FT 0.77
Manure 175.5 10,800,000 0 0.4 23.28 Assumptions:
Food waste 415 188,000 45 0.55 25.1 ே௘௧ ௘௡௘௥௚௬ ௢௨௧ ௅ு௏೚ೠ೟ ௠ሶ ೚ೠ೟ ିொሶ ೔೙
• ‡”‰› ܴܽ‫  ݋݅ݐ‬ൌ ൌ
Grass silage 412 1,901,250 25.67 0.56 20.7 ஻௜௢௚௔௦ ௘௡௘௥௚௬ ௜௡ ௅ு௏೔೙ ௠ሶ ೔೙

Biogas CO & H2
Sewage 175 39,000 0 1 15 ܳሶ ௜௡ ൌ –Š‡ ‡‡”‰› •——’Ž‹‡† –‘ –Š‡ ”‡ƒ…–‘” (KJ/s) Reactor
*Opportunity cost: What the product will be sold for on the open market or transferred into other enterprise. These are based on various contributions
but will vary considerably according to local outlets • LHV- Lower Heating Value KJ/kmol
** Availability: values were taken from Do Bio energy Report: Quantification of Feedstocks for Anaerobic Digestion Group Report A Northern Ireland Case
Study Appendix 3.1, Biogas Action Plan for Northern Ireland
• ݉ሶ ௜௡ = molar flow rate entering the reactor kmol/sec (of calorific
Table 3 Weights Generated by the Entropy Method value) = ‫ܪܥ‬ ሶ ସ
೔೙ ܳሶ ௜௡
C1 C2 C3 C4 C5 • ݉ሶ ௢௨௧ = molar flow rate leaving the reactor kmol/sec (of calorific
CH4 yield Availability (t/year) Opportunity cost Biogas Calorific value
3
value) = ‫ܱܥ‬ሶ ௢௨௧ + ‫ܪ‬ሶ ଶ೚ೠ೟
(m /t VS) (£/t) production (MJ/m3)
(mn3/kg VS • Operating Temperature and Pressure in
NB: Numbers may not sum exactly due to rounding
w Reforming Processes: T=1073 K & P=1 bar
0.041 0.429 0.499 0.029 0.002
• Operating Temperature and Pressure
Table 4 Feedstock Ranking based on Topsis
Anaerobic Digestion of single substrates known as in FT Processes= T= 573 K & P=20 bar
mono- digestion has some disadvantages that are Feedstock Ranking
linked to the substrate properties. Manure 1
6. Future Work
1. Animal manures have high N concentrations that
Sewage 2
The rig is currently under construction.
can inhibit methanogens and also have low organic
It will be extensively used for Fischer-
loads. Sludge Tropsch experiments will be carried out
2. Sewage sludge is also characterized with low organic
on synthetic syngas to test the production
loads Grass Silage 3
of liquid fuel at different operating
3. Crops and agro-industrial wastes are seasonal and conditions.
Food Waste 4
thus might lack N. These problems can be solved by
the addition of a co-substrate.
Developing strategies to facilitate integration of biogas
into the existing gas infrastructure
Laura Gil Carrera & Ian Kilgallon

Significant Indigenous Renewable Natural Gas Resources

Biogas Potential- 2014 Waste Sources
Resources
Waste:
Over 8% of Irish Gas Demand
Some 2st Generation sources also viable – such as
grass from marginal land, and excess silage.

Future & more substantive resources

3rd Generation.
Algae (Micro & Macro)
eGas / P2G

The Future Gas Market

Innovation/Collaboration – Commercial Demonstrations

1st Direct Biogas Grid Injection Facility Mobile/Aggregator Solution

Demonstrator for development of commercial market arrangements Getting off-grid biogas production to market