UK AD & Biogas 2016 _ R&I Hub 6 July

UK AD & BIOGAS
TRADESHOW
R&I HUB
6-7 JULY 2016
NEC BIRMINGHAM

© University of South Wales
Prof. Sandra Esteves
sandra.esteves@southwales.ac.uk
Optimising the AD process
UK AD & Biogas 2016, 6-7 July, Birmingham NEC

Hydrogen Energy
Biohydrogen Systems
Advanced Nanomaterials
Bio Energy Systems
Anaerobic Digestion
Waste and Wastewater Treatment
Monitoring and Control
Environmental Analysis
Bioelectrochemical Devices
The
Hydrogen
Centre
Bioplastics Production
P2G, Biogas upgrading and utilisation
LCA and economic evaluations

USW Team’s Expertise
& Facilities
• Team has numerous
decades experience
and knowledge in
bioreactor (anaerobic)
design, integration,
monitoring and control
• Novel process
development in the lab
(1-100 l), pilot (200 l -
30 m3) and full scale
(50-7000 m3)

USW Team’s Expertise
& Facilities
• Expertise in bioreactors, biochemistry,
biotechnology, microbiology,
engineering, monitoring, modelling and
control, economic and environmental
appraisals
• 450m2 lab space, 13 labs, an extensive
suite of analytical equipment -
headspace GC/FID, ion chromatography,
ICP-AES, CHNSO, TOC, TKN analysers,
GC/TCD, GC/FPD, GC/MS/MS, SEM,
NMR, SFE, GC-MIS, on-line FT-NIR,
rheometer, zeta potential analyser,
particle sizer, Ion Torrent Sequencer, RT-
PCR and DGGE
• ADM1 model, AI tools, LCA
software/databases and CFD software

Anaerobic Digestion Process
Rate limiting
Biogas

Variation in the chemical
parameters of the digester
Acetate
Propionate
Williams et al. 2013

Acetate
Propionate
Eubacteria
Methanosaetaceae
Methanobacteriales
Methanomicrobiales
Methanosarcinaceae

0
500
1000
1500
2000
2500
0.00E+00
2.00E+08
4.00E+08
6.00E+08
8.00E+08
1.00E+09
1.20E+09
0 40 80 120 160 200 240
VFAs(mg/l)
Methanosaetaceae(genecopies/ml)
Time (d)
MST
Acetate
Propionate
Methanogens and VFA residuals

0.0E+00
4.0E+10
8.0E+10
1.2E+11
1.6E+11
2.0E+11
Bacteria
0
200
400
600
800
1000
1200
3.0E+03
3.0E+04
3.0E+05
3.0E+06
3.0E+07
140 170 200 230 260 290 320
Methanogens(genecopiesml-1)
Time (days)
MMB
MBT
Propionic acid
Effect of Trace Elements on
Bacteria and Methanogens
Propionate
VFA(mg/l)

Effect of Recovered Micronutrients from Digested
Sludge on VFA production from Thermally Hydrolysed
Sewage Sludge
Digested
sewage sludge
Inoculum
N0 Reactor
NI
Reactor
Inoculum
30g/l sucrose
shock
NI-RM
Reactor
NI-CM
Reactor
TH-WAS
TH-WAS
Thermal
Treatment
Centrifuging
Supernatant
0.2 µm Filtration
RM
CM
NB: TH-WAS – Thermally hydrolysed waste activated sludge; RM – recovered micronutrients; CM – commercial micronutrients
25.11
gVFACOD
L
-1
24.03
gVFACOD
L
-119.84
gVFACOD
L
-1
16.56
gVFACOD
L
-1
Kumi et al., 2016

Comparative yield of VFA – effect of inoculum pre-
treatment, commercial micronutrients addition and
recovered microbial nutrients addition
Kumi et al., 2016
Faster hydrolysis
& acidification,
faster methane
production

Cardiff and Afan Wastewater Treatment Process
Sequencing
Batch Reactors
Storage of imported
& indigenous
sludges
Thickening of
sludges to THP
THP
Digestate Holding Tank
Digesters
Polymer injection
Polymer Mixing
Belt Press for
Digestate
Dewatering
Cause &
Effect
Each process
influences the
next ones

Archaea distribution from mcrA results for each digestate
12%
0%
26%
15%
7%
40%
Cog Moors digestate
Methanosaeta/g VS
Methanosarcina/g VS
Methanospirillium/ g VS
Methanobacterium/ g VS
Methanomicrobium/ g VS
Unknown gene copies/ g VS
97%
1%
2%
Cardiff digestate
Methanosaeta/g VS
Methanosarcina/g VS
Methanospirillium/ g VS
Methanobacterium/ g VS
Methanomicrobium/ g VS
Unknown gene copies/ g VS
Esteves et al., 2015

Characteristics of Methanosarcina
& Methanosaeta sp.
Parameter Methanosaeta Methanosarcina
μmax (d−1) 0.20 0.60
Ks (mg COD L−1) 10–50 200–280
NH4
+ (mg L−1) <3000 <7000
Na+ (mg L−1) <10,000 <18,000
pH-range 6.5–8.5 5–8
pH-shock <0.5 0.8–1
Temperature range (°C) 7–65 1–70
Acetate concentration (mg L−1) <3000 <15,000
De Vrieze et al., 2012

Further Digestion of Digestates
• Mixtures of digestates digested once again could provide ~ 20% more methane
when compared to Cambi TH – Due to populations mixtures, ammonia
reductions and significant energy remaining in the digestates
Esteves et al., 2015

Demonstration of Ammonia Removal Benefit for Cardiff
WwTWs (thermal hydrolysed secondary sludges,
digesters at 43oc)
Tao et al, submitted

Cumulative Methane Production for Control, Zeolite and Resin
Ammonia Removal for Digesters at 43oC Treating Hydrolysed Sewage
Sludge
© University of South Wales© University of South Wales
There was a significantly
higher degradation of
proteins and carbs and
methane yields with the
sulfonic and phosphonic
acid functionalized cation
exchange resin
So the every little helps is
really 50%+ in a number of
cases

Ammonia removal using an ion exchange resin and
effect on Methanosarcinacea family (acetoclastic
methanogens)
Known to be the most
ammonia tolerant
acetate utilising
methanogens
Even these were
inhibited with
approximately 4000
mg/l ammonium, ~600
mg/l ammonia
(digesters at 43oC)

Enzyme Enhanced VFA and
Biogas Production

VFAs in Percolate
(Full Scale)
Oliveira et al. In preparation
Double solubilisation of organics to be
digested instead of composted and
available for biorefining products

0
10000
20000
30000
40000
50000
60000
70000
0 20 40 60 80
sCOD(mg/l)
Time (h)
water control
water control
0.03% Cellulase N11/12
1% Cellulase N11/12
1% Cellulase N11/12
0.3% Protease N11/11
0.3% Celluclast
Soluble COD released into the
percolate liquor

5 PhD Scholarships Related to Anaerobic
Processes and Renewable Methane Sectors
In collaboration with:
• Systems, Economic and Environmental Analysis of Treatment Options for and Valorisation of
Micro-Brewery Wastes
• Optimisation of Anaerobic Digestion Plant Design and Operations for Improved Energy
Production and Odour Management
• Production of high chain alkane gases from anaerobic biological processes
• Investigate the robustness and intensification of a novel biomethanation process for energy
recovery for the steel sector
• Enhanced green CH4 production with low cost energy storage through a real-time management
strategy for AD plants to meet variable network gas demand
http://gro.southwales.ac.uk/studentships/KESSII/
Deadlines Early August; Starting in October 2016

The sole responsibility for the content of this document lies with the authors. It does not necessarily reflect the funders opinion. Neither the authors or the funders
are responsible for any use that may be made of the information contained therein.
Acknowledgments
Dr. Tim Patterson, Dr. Julie Williams, Ivo Oliveira, Dr. James Reed, Dr. Gregg Williams, Prof. Richard Dinsdale,
Prof. Alan Guwy, Dr. Bing Tao, Dr. Phil Kumi and Dr. Des Devlin
Prof. Sandra Esteves sandra.esteves@southwales.ac.uk

The development of equipment to meet
the new research challenges of AD.
Edgar Blanco-Madrigal
Managing Director, Anaero Technology Ltd

Research and Development Manager: Interpret
and review research to apply at full-scale
• Strategy of operation: early days slurry/FW, new
feedstocks, H2S control
• Response to contingencies: drops in biogas
production, foaming, odour
• Use of digestate: agronomic value, odour,
regulation and compliance; i.e., PAS110
• Landfill gas operation and general technical
• Dilemma: No time to do research

Difficulties implementing AD academic
research in Industry
• Better performance and stability at full-scale
than in most lab tests
• No spare time to carry out research as
operational duties take priority
• Either very expensive research equipment
(GC-MS, large pilot plants with logistic
complexities), or too basic with high labour
(manual feeding and data logging, weekend
and bank holiday feeding, or affect tests)

0
200
400
600
800
1000
1200
1400
1600
1800
9/8/2015 9/13/2015 9/18/2015 9/23/2015 9/28/2015 10/3/2015 10/8/2015 10/13/2015 10/18/2015 10/23/2015
ml/hour
Hourly feed Daily feed
Feeding patterns influence the kinetics
of biogas production (higher feeding
frequency=more stable operation)

Although biogas flow rises
sharply after daily feeds, CH4%
drops. It takes hours to return
to average CH4%
Mulat, D. G., Fabian Jacobi, H., Feilberg, A., Adamsen, A. P. S., Richnow, H. H., & Nikolausz, M. (2016). Changing feeding regimes to
demonstrate flexible biogas production: Effects on process performance, microbial community structure, and methanogenesis
pathways. Applied and Environmental Microbiology, 82(2), 438–449. doi:10.1128/AEM.02320-15
Red line : feed every two
days
Blue line: feed every two
hours
Propionate and other VFAs rise
sharply with large feeds (daily),
but remain more stable for
regularly fed digesters: The
microbiology of daily fed lab
digesters and hourly fed full-scale
digesters is likely to differ.
Biogas flow and composition in daily vs hourly-
fed digesters

The idea!
• Develop a machine to feed digesters and log data
automatically to allow me to continue being a
researcher whilst being available 24/7 for
operational duties
• Machine must be capable of:
– using the same FW fed to full-scale plant (24/7)
– feed at same intervals as full-scale
– not be affected by settling in feeder tank
– real-time gas flow measurement
– eliminate opening of digesters to deliver feed

Our auto-feed lab digester concept
Feed, Mix, Heat, no O2
• Feed
– Peristaltic pumps block with minimum solids, other pumps not accurate
enough for low flows required in lab reactors (around <150ml per day for a
5litre digester).
– Single feed produces erratic biogas profile and shifts microbial populations
– There were no commercial pumps capable of accurate feeding of
heterogeneous substrates
– After several months searching found an apparently popular alternative:
enema syringes!
– But even these were too small  …………so, we designed our own

• Heat. Using water coils does
not provide flexibility in the
control of temperature for
multiple digester sets, bulky
pipework around digesters,
and can be messy.
– Electric heater jackets with
insulation = wide spectrum of
temperatures possible in a
single set. We can even
operate in pasteuriser or
enzymic hydrolysis mode.

• Mix
– 25th of December 2012 – paint mixer. 20 paint
cans mixed by one motor. Then used pulleys with
rubber rings, then Lego provided the final idea

• No Oxygen. Opening digesters
once a day to deliver feed
marginally alters gas flow and can
affect biogas chemistry, i.e., H2S
oxidation. Our new system had to
be air-tight from feed to digestate
tank.
– The result: a system that allows
easy, precise, mass balances with
port for gas-tight access to
digester contents (i.e., to
measure pH directly, or dose
additives)

Anaero Technology auto-fed digesters
and BMP equipment: Pioneering
equipment for AD research &
innovation
(PCT patents in progress)

The impact of Auto-feed technology on AD
research
• Advance research on AD and for new product development
through precise control of research digesters. Can we
assume that the microbial composition of a digester fed
(shocked) once a day is similar to that of a digester fed
more regularly?
• Improve research on new applications. For example,
accurate feed/draw control for targeted production of
specific VFAs under tightly controlled loading conditions.
Can this be done while limited to feeding once a day?
• Save valuable researcher time. Why sacrifice valuable
research time, including weekends, feeding digesters for
the sake of it? Free up time for analytical work or research.

Auto fed CSTR Fermenter /
Anaerobic Digester Systems
Biomethane Potential /
Residual Biogas Potential Sets
Our off-the-shelf equipment for AD researchers and operators

Some of our projects
Anglian Water
NRM (PAS110 certified) Cawood Scientific Centre for Process Innovation
Marchwood Scientific, AB-En
University of
Cambridge
Collaborative projects and services: University of Cambridge,
University College London, Manchester University, Biogen, AB-
Agri, Alpheus, Anglian Water

Ongoing and future projects
• Implementation of Arduino-based gas flow monitoring:
Price of a BMP set <£10k
• Development of real-time monitoring of biogas
composition module for existing equipment. Tests taking
place summer 2016 with Cambridge University
• New compact auto-fed digesters 6x 2 litre in one water
bath
• Internet of Things preliminary work with Dr James Chong,
York University. Applying for research grant/own funds
• Development of nano-sensor real-time monitoring and
control device for full-scale applications. Applying for
research grant/own funds, PhD studentship.

Low HRT fermenter 4x10 litre feeders

Modular auto-fed 6 x 2 litre set

Arduino gas flow meter and fibre optics real-time
biogas composition sensors for precision in low
gas flow

• Auto-fed research digesters in standard or
bespoke sets (from individual digesters to
banks of 24 CSTR bioreactors)
• Biomethane potential sets with PLC controller
for up to 8 sets (8x15 reactors). Arduino-based
monitoring available
• Bespoke fermenters and Photo-bioreactors
• Collaborative research. We have 60 auto-fed CSTR
bioreactors in our Cambridge Lab available for collaborative
research with industry, academia, and other agencies, in the
UK and the EU.

Thank you for your attention
• And thank you to Peter Prior for not objecting
to me pursuing my interests in my own time

Optimising the AD process: every little helps
UK AD & BIOGAS
TRADESHOW
R&I HUB
DR. RAFFAELLA VILLA
SENIOR LECTURE, CRANFIELD UNIVERSITY

Optimising the AD process: every little helps
UK AD & BIOGAS
TRADESHOW
R&I HUB
MARTIN RIGLEY MBE &
DARREN BACON
H2AD

Networking Lunch
UK AD & BIOGAS
TRADESHOW
R&I HUB
13:15 – 14:15

PRODUCTION AND EXTRACTION OF SHORT
CHAIN CARBOXYLIC ACIDS FROM THE
ANAEROBIC MIXED-CULTURE FERMENTATION OF
SLAUGHTERHOUSE BLOOD
Dr Jersson Plácido, j.e.placidoescobar@swansea.ac.uk
Dr Yue Zhang, y.zhang@soton.ac.uk
UK AD & Biogas 2016: Producing methane or chemicals?
National Exhibition Centre (NEC), Birmingham
6th July 2016

PROTEIN WASTES
WORLDWIDE, 1 MILLION TONS OF
PROTEIN RICH WASTES
(Kovács et al. 2013).
DAIRY WASTEWATERS
SLAUGHTERHOUSE WASTES
SEA FOOD WASTES
PROTEIN RICH PLANT WASTES

SLAUGHTERHOUSE RESIDUES
40 MILLION TONS OF MEAT PER YEAR
(Marquer et al. 2014)
SOLID AND
LIQUID WASTES
Category 1
Category 2
Category 3

PROTEINS (94.4%)
LIPIDS (0.3%)
CARBOHYDRATES (5.3%)
SLAUGHTERHOUSES BLOOD TREATMENTS
ANAEROBIC DIGESTION
INOCULUM ACCLIMATION
DILUTION
CO-DIGESTION
“The introduction of energy-rich proteinaceous waste products in large quantities into the AD
process is not recommended in view of the increased risk of inhibition by NH3” (Ahring, 2003)

PREVIOUS WORK:
0
2000
4000
6000
8000
10000
12000
14000
0 50 100 150 200 250 300
Time (days)
FW1VFAprofile(mgl-1
)
A cet ic Propionic
Iso- B ut yric n- B ut yric
Iso- V aleric n- V aleric
Hexanoic Hept anoic
0
2000
4000
6000
8000
10000
0 40 80 120 160 200 240
Time (days)
TotalVFAs(mgl-1
)
BMW + gut&fat 1
BMW + gut&fat 2
BMW + blood 1
BMW + blood 2
BMW
(Zhang and Banks 2012)
FOOD WASTE DIGESTION – ACCUMULATION OF
VOLATILE FATTY ACIDS (VFA) and LONG CHAIN FATTY
ACIDS (LCFA)

OUR APPROACH
Utilize anaerobic mixed culture fermentation as a method to
transform high-protein wastes such as slaughterhouse
blood into target products in concentration suitable for
extraction
POC:
Production and extraction of C3 and C4 aliphatic carboxylic acids from the
anaerobic digestion of waste blood as a model substrate

MIXED-FERMENTATION (MF) IS A FERMENTATION WHICH DOES NOT
REQUIRE STERILISATION AND UTILIZE THE SET OF MICROORGANISMS
BEST ADAPTED TO THE REQUIRED ENVIRONMENTAL CONDITIONS
ANAEROBIC
FERMENTATIONBIO-METHANE
MIXED
FERMENTATION
ALCOHOLS
POLYMERS
ETHANOL
VOLATILE FATTY ACIDS
x
MIXED-FERMENTATION
 CAN COPE WITH COMPLEX SUBSTRATES (E.G MIXED FOOD WASTE)
 CAN BE ADAPTED TO DIFFERENT TYPES OF SUBSTRATES AND PRODUCTS
 CAN BE ELICITED

Volatile fatty acids (VFA) are short chain carboxylic acids with carbon chain
between 1 and 7 carbons.
Stickland reaction

Global carboxylic acids market:
• US$ 12.14 Billions 2015
Precursors for several industries:
• Solvents
• Coatings
• Polymers
• Artificial flavours
• Scents
VFA’S MARKET
Global biogas market:
• US$ 32 Billions 2023
Combined US$ 50 billions 2023

• Chemical processes
• Oxidation
• Dehydrogenation
• Carbonylation
VFA PRODUCTION
• Biological processes
• Traditional fermentation technologies
• Mixed fermentation
Upstream process
Downstream
process
-Pre-treatment
-Fermentation
Unit operations:
-Filtration
-Centrifugation
-Liquid-liquid extraction
-Membrane technologies
-Chromatography
-Distillation
BIOLOGICAL PROCESSES

UPSTREAM PROCESS
TRADITIONAL CARBOXYLIC ACIDS PRODUCTION
COSTS:
• Upstream (sterilization, expensive substrates,
aeration, equipment costs, stability) 70-60%
MIXED FERMENTATION COSTS:
• Upstream (no sterilization, wastes as substrate,
no aeration, less equipment costs)
SUBSTRATE
Commercial freeze dried blood for black pudding (Tong master). The blood was prepared
to obtain 18% VS.
INOCULUM
Sewage sludge digestate samples from Millbrook wastewater treatment (Southampton,
United Kingdom). Before using the digestate, it was sieved (1 mm mesh) to remove large
particles
VARIABLES EVALUATED
• Reactor type (batch, fed-batch, semi-continuous)
• Methanogens inhibitor (iodoform/CHI3)
• Blood concentration (0-90%)
• Blood pretreatment (Enzymatic hydrolysis)
• Inoculum initial loading and inoculum acclimation

Chart Title
Acetic Propionic Iso-Butyric n-Butyric Iso-Valeric
n-Valeric Hexanoic Heptanoic VFA
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
100000
0 1 4 6 8 11 15 18 20 22 25 27 32 36 41
Concentration(mg/L)
Time (Days)
No-AC, No-EH, and No-IDF.
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
100000
0 1 4 6 8 11 15 18 20 22 25 27 32 36 41
Concentration(mg/L)
Time (Days)
No-AC, No-EH, and IDF.
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
100000
0 3 5 7 10 12 14 17 19 21 24 26 28 31 35 38 40 45
Concentration(mg/L)
Time (Days)
AC, EH and No-IDF.
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
100000
0 3 5 7 10 12 14 17 19 21 24 26 28 31 35 38 40 45
Concentration(mg/L)
Time (Days)
AC, No-EH, and No-IDF.
a)
c)
b)
d)
Batch Reactor

Chart Title
Acetic Propionic Iso-Butyric n-Butyric Iso-Valeric
n-Valeric Hexanoic Heptanoic VFA
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
0 5 9 14 19 23 28 33 37 42 47 51 58 63
Conentration(mg/L)
Time (Days)
IL66.6%/No-EH
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
0 5 9 14 19 23 28 33 37 42 47 51 58 63
Concentration(mg/L)
Time (Days)
IL10%/No-EH
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
0 5 9 14 19 23 28 33 37 42 47 52 56 63
Concentration(mg/L)
Time (Days)
IL66.6%/EH
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
0 5 9 14 19 23 28 33 37 42 47 51 58 63
Concentration(mg/L)
Time (Days)
IL10%/EH
a) b)
c)
d)
Semi-continuous Reactor

The recovery pathway is dependent of the process configuration, acid
structure and process economics
RECOVERY
TRADITIONAL CARBOXYLIC ACIDS
PRODUCTION COSTS:
• Downstream (product specific, well- known
methods ) 30-40%
(Straathof 2011)
MIXED FERMENTATION COSTS:
• Downstream (fermentation broth variability and
diversity)

ESTERIFICATION REACTION
Ammonium carboxylates
Waste Blood
Anaerobic mixed
Fermentation
Evaporation/
Water removal
Diluted
ammonium
carboxylates
Acidification
H2SO4
Esterification
Methanol
(NH4)2SO4
VFA- Methyl
esters
Biomass
Removal
Biomass
Water
Concentrated
ammonium
carboxylates
VOLATILE FATTY ACIDS RECOVERY
METHYL VFA PRICES
Methyl acetate (48-60£/L)
Methyl propionate (50-500£/L)
Methyl butyrate (50-500£/L)
Methyl iso-butyrate (100-500£/L)
Methyl iso-valerate (51-500£/L)

0
10
20
30
40
50
60
MethylVFAYield(%)
Methyl Acetate Methyl Propionate Methyl Iso-butyrate
Methyl Butyrate Methyl Iso-valerate
0
10
20
30
40
50
60
(NH4)2SO4Yield(%)

0
20
40
60
80
100
20 30 40 50 60 70
MethylVFAYield(%)
Temperature (C)
0
10
20
30
40
50
60
0 5 10 15 20
MethylVFAYield(%)
Time (h)

69
Waste Blood
Anaerobic mixed
Fermentation
Biomass
Removal
Biomass
Pertraction
system
Diluted
Ammonium
carboxylates
Water/VFA
Stripping
system
Octanol-TOA/VFA
Octanol-
TOA
Fresh stripping
solution
VFA rich stripping
solution
PERTRACTION SYSTEM

0
20
40
60
80
100
5%-1:1 10%-1:1 10%-2:1 10%-4:1 20%-1:1 20%-2:1 20%-4:1
Recovery%
Acetic Propionic Iso-Butyric n-Butyric Iso-Valeric VFA
0
20
40
60
80
100
Acidified Broth Centrifuged Broth VFA Sln pH 4.5 VFA Sln pH 7.5
Recovery%
Acetic Propionic Iso-Butyric n-Butyric Iso-Valeric Valeric VFA
30
5
1530
20 Acetic
Propionic
Iso-Butyric
n-Butyric
Iso-Valeric
VFA RECOVERY BY PERTRACTION SYSTEM
TOA/octanol experiment:
TOA/octanol experiment:
model solutions evaluating TOA concentration
in the octanol/TOA solution (5, 10 and 15%)
and the ratios of VFA to octanol/TOA (1:1, 2:1,
4:1).
Fermentation broth and pH studies

Pertraction system:
0.5x1 micromodule membrane contactor (Membrana, USA)
Centrifugation Filtration
System
equilibration
Operation for 2
hours
PERTRACTION SYSTEM

0
20
40
60
80
100
0 0.5 1 1.5 2
Recovery%
Time (h)
Acetic Propionic Iso-Butyric
n-Butyric Iso-Valeric VFA
0
20
40
60
80
100
0 6 12 18 24
Recovery%
Time (h)
Acetic Propionic Iso-Butyric n-Butyric
Iso-Valeric Valeric VFA
0
20
40
60
80
100
0 0.5 1 1.5 2
Recovery%
Time (h)
Acetic Propionic Iso-Butyric n-Butyric
Iso-Valeric Valeric VFA

Waste Blood
Anaerobic mixed
Fermentation
Evaporation/
Water removal
Diluted
ammonium
carboxylates
Acidification
H2SO4
Esterification
Methanol
(NH4)2SO4
VFA- Methyl
esters
Biomass
Removal
Biomass
Water
Concentrated
ammonium
carboxylates
Waste Blood
Anaerobic mixed
Fermentation
Biomass
Removal
Biomass
Pertraction
system
Diluted
Ammonium
carboxylates
Water/VFA
Stripping
system
Octanol-TOA/VFA
Octanol-
TOA
Fresh stripping
solution
VFA rich stripping
solution
RECOVERY
ESTERIFICATION RECOVERY
PERTRACTION SYSTEM

CONCLUSIONS
• Anaerobic mixed-culture fermentation was proved to be an effective way of transforming
slaughterhouse blood into VFA. In this process, the dominant acids were acetic, n-butyric
and iso-valeric acids.
• The batch and semi-continuous reactors generated promising results in terms of total VFA
concentration and yield.
• Integrated batch fermentation and esterification processes were proposed to be used for the
recovery of both esters (scents and fragrances) and ammonium sulphate (fertiliser).
• For semi-continuous/continuous fermentation configuration, a pertractor system was
regarded as a more suitable downstream process.
•
• The membrane extractor recovered butyric and iso-valeric acids from the fermenter effluent
in favour of acetic acid, with the residual stream rich in acetic acid returned to mix up with
dried substrate.
• These results highlighted some essential aspects for the development of a carboxylate-
platform bio-refinery from high protein wastes.

ACKNOWLEDGMENTS
the UK Biotechnology and Biological Sciences Research
Council (BBSRC) and the Anaerobic Digestion network
(ADnet) for funding this project through the proof of concept
(PoC) funding POC2014016
6th July 2016

THANKS FOR YOUR
ATTENTION
QUESTIONS
6th July 2016

Anaerobic Processes Role in the Production of Green
Methane and Chemicals
A low carbon role and with multi-sector integration potential
UK AD & Biogas 2016, 6-7 July, Birmingham NEC

UK Commitments and Targets
(by 2020)
• Climate Change Act
– Greenhouse gas emissions 34% below 1990 levels
• EU Renewable Energy Directive
– 15% of UK’s energy from renewable sources
• Power (30%); Heat (12%); and Transport fuels (10%)
• EU Landfill Directive
– Biodegradable municipal waste sent to landfill -
35% of that produced in 1995
??

EU Biogas Status, Potential and Growth
Over 17,000 AD plants across Europe
Over 300 biogas upgrading plants across Europe, over 300,000
Nm3 CH4/h
AD industry in Europe turnover ~6 billion € and ~ 70,000 jobs
By 2030, AD could provide renewable energy equivalent to
approximately 5% of EU’s current natural gas consumption
(EBA, 2016)

Unlocking new potential with R&D -
UK
ADBA, AD market report July 2015

UK Energy
Scenarios and
RE Growth

The Need to Match Renewable Electricity
Production and Demand
lost through
curtailment
Curtailment in Europe & USA is expected to be significant by 2030
& 2050
NREL, 2013© University of South Wales

Need to Match Electricity Supply and
Demand
Simulated Power Demand and Renewable Electricity Supply in Germany in
October 2050, Based on 2006 Weather
Source: Fraunhofer IWES, taken from Trost et al. (2012)

Need to Match Electricity Supply and
Demand
Electricity demand
(current pattern)
Future electricity supply
(wind-solar-biomass)
Source: Energinet.dk, Energi 2050 – Vindsporet,
January 2011

HYDROGEN ENERGY SYSTEMS
MARKET SIZE | NEW EU REPORT
Germany: 46 GW (£46bn) in 2030 | 115 – 170 GW in 2050
POWER-TO-GAS

Storage of Renewable
Electricity
• Batteries – expensive, not environ.
friendly & short life
• Pumped hydro & underground
compressed air storage are limited by
geographical factors
• Super capacitors, superconducting coils
& flywheels – short discharge period –
suitable only as emergency UPS units
Types of energy storage
plotted against the amount
of time they can be stored
for and the quantity of
energy that can be stored
(Source: Specht et al . 2009)
• Power to green gas – greatest capacity &
the only option to store electricity in order
of several TWh over a long period of time
– Sabbatier conversion using metal catalysts
– expensive, high temp requirement, low
selectivity, low yields and deactivation
– Biomethanation – low cost, low temp.,
high throughput & conversion efficiency
and resistant to contaminants

Denmark’s (100%) Renewable Energy
Strategy for 2050
Source: www.ceesa.dk/Publications

Problem: UK energy demand
Security of supply & alternative low-carbon heat solutions
• Peak gas & electric demand is x25 higher
than existing low-carbon generation
capacity (inc. nuclear)
• At peak heat demand, electrifying heat
would multiply demand by 10. In summer
it would double electricity demand
• UK legislation is aimed at reducing CO2
emissions by 80% by 2050 compared to
1990 levels
• 2016 DECC targeting heat and transport
to achieve carbon reduction targets
• Biomethane can play a role to meet
energy needs & peak demands
• The gas network is required to meet peak
heat demand – the challenge is to
decarbonise the gas supply chain

Inability to
install new RE
infrastructure
due to Grid
Restrictions

Importance and Market for
Power to Gas
• Restricted electricity network ‘Nothing is able to be
connected’ – For some regions at least
• EU 2020 Target - Share of renewable electricity in UK to
reach 30% (Target also for heat and transport fuel)
– Onshore/offshore wind capacity expected to increase to 58.5 GW
by 2035
– Curtailment could reach 2.8 TWh/a by 2020 and 50-100 TWh/a by
2050
– Monetary value of storing excess electricity could be as high as
£10bn/a by 2050
(Qadrdan et al., 2015)
• Worldwide market increasing

Power to gas conversions have the potential to transform the existing energy field by
allowing renewable energy generation systems to infiltrate the power network at a larger
extent than it is currently possible
Convert electricity into renewable heat and fuel
Electricity grid
Gas grid
electrolysis methanation
Electricity
generation
H2
H2
CH4
CH4
CH4
e-
e-
Vehicle FuelHeat
Commercial in Confidence

Biomethanation
P2G & Biogas Upgrading
Biomethanation
AERIOGEN®
Electrolysise
e-
CH4
O2
H2
CO2
CH4 + CO2
Anaerobic
Digestion
Intermittent
Renewable
Energies
Thermal &
Aerobic
Processes

Existing Commercial Technologies for Biogas
Upgrading vs. Hydrogenotrophic methanation
PSA
Water scrubbing
Organic scrubbing
Amine scrubbing
Membrane separation
Hydrogenotrophic
Methanation
AERIOGEN®
60% CH4
40% CO2
>99% CH4
Biogas
Biogas

HYDROGENOTROPHIC METHANATION
AERIOGEN® PCT filed P2G & Biogas upgrading
• AERIOGEN® has been developed at lab scale (up to 5 l) through
novel microbial community concepts, automation and control and
multiple reactor designs evaluated for increased performance and
reduced energy consumption and footprint
• Novel enriched, self sustaining and robust microbial culture
• Ex-situ process superior compared to in-situ since there are no
conflicts with organics conversions
• Designed for high rate instantaneous conversion with a small footprint
• Continuous and high rate process (>200 litre influent/litre reactor per
day) with 99.7% CH4 output
• Low temperature mesophilic and low pressure operation
• Low maintenance; no nutrient addition after start-up and no pH buffers
• Automated gas throughputs for optimal efficiency
• Automated water removal; ability to maintain culture and nutrient
levels
• Robust in terms of O2 and intermittency in gas flows

AERIOGEN® High Methane
Quality Output and Control
Over Time At Lab Scale
Biocatalyst conversion efficiency over a 6
month period has been achieved
Here various conditions were being
investigated, and response over 17 days
demonstrated at 2 litres
High input gases control allow a 99.7%
quality output and help maintain
appropriate pH

Recovery After Fasting for 45 days

Power-to-Green Methane in UK
• Feasibility study
• Production of ‘synthetic methane’ using biological
methanation and electrolytic hydrogen
• CO2 sourced from existing biogas to biomethane
upgrade facility operating at waste water treatment
plant
• H2 from rapid-response PEM electrolysis providing
grid-balancing services
• Biomethanation process AERIOGEN®
• Funded by UK Government via Innovate UK
• Project partners: ITM Power, Wessex Water, Wales &
West Utilities, University of South Wales, BPE Design
& Support Ltd.

IUK / BBSRC Industrial Biotechnology Catalyst
Feasibility of an Innovative reactor for enhanced
C1 gas bioconversion for energy production and
storage
Start Date: January 2016
Evaluate potential for improvement of gas /
liquid transfer in novel reactor
Production of green methane
Production of carboxylic acids
AERIOGEN® Technology Development

What about GREEN Chemical
Platforms?

Chemicals from Methane: Acetic Acid
Acetic Acid Production Route:
Price of Acetic Acid
Variable, but can be sold for $500-1300 per
metric tonne
Acetic Acid End-uses
Adhesives, coatings, inks, resins, dyes, paints and
pharmaceuticals. It can also be further converted into
other chemicals e.g. vinyl acetate, acetic anhydride,
cellulose acetate, terephthalic acid and polyvinyl chloride
Annual Global Production of Acetic Acid
10.7 million tonnes (34th highest production volume chemical)
CH4
2H2 + CO
CH3OHCH3COOH
Steam Reforming
+ H2O
Methane
Synthesis
Gas
Methanol
Acetic Acid
Methanol
Carbonylation
+ CO
CH4
Biomethane
Biohydrogen
Acetic Acid
2H2+ CO
CH3COOH CH3OH
Chemicals from Biomethane: Acetic Acid
Products from
anaerobic
fermentations

Chemicals from Methane: Urea
Urea Production Route:
CH4
2H2 + CO
NH3(NH2)2CO
Steam
Reforming
+ H2O
Methane Synthesis Gas
AmmoniaUrea
H2 + CO2
Water Gas Shift
Reaction
+ H2O
+ N2
Haber
Process
+ CO2
Hydrogen and
Carbon Dioxide
End-uses of Urea
91% of urea is used for the production of solid nitrogen-based
fertilisers. Non-fertiliser uses include the production of urea-
formaldehyde resins, melamine, animal feed and numerous
environmental applications
Annual Global Production of Urea
120 million tonnes (18th highest production volume chemical)
Chemicals from Biomethane: Urea
CH4
Biohydrogen and
carbon dioxide
2H2+ CO
Products from
anaerobic
fermentations
H2+ CO2
Biomethane
NH3
Ammonia
(NH2)2CO
Price of Urea
$300-500 per metric tonne

Enzyme Enhanced VFA,
Biohydrogen and Biogas
Production

~ 1/3 of the initial VS converted to VFAs
in a matter of a couple of days and the
rest can be produced in another
fermentation
Jobling-Purser et al., submitted
Experiments
Volatile Fatty Acids from Food
Wastes

Kumi et al., to be submitted
Volatile Fatty Acids from
Badmington Grass

Comparative yield of VFA from thermally hydrolysed
secondary sludges
Effect of inoculum pre-treatment, commercial micronutrients addition and recovered
microbial nutrients addition
Kumi et al., 2016
Faster hydrolysis and acid phase, faster methane
production

Production of Volatile Fatty Acids
from H2 and CO2
Mixed culture
0
2000
4000
6000
8000
10000
12000
14000
16000
0 5 10 15 20
AceticAcid(mg/l)
Days

Chain of Processes for
Valorisation of Sewage
Sludge
Tao et al., 2016

Volatile Fatty Acids Concentration
for Energy Storage, Chemical and
Biopolymer Production
• The max VFA concentration was defined
in this case for polymer production,
higher concentrations can be achieved
• Sterile stream of VFA for energy
storage, chemical and polymer
production was demonstrated
• The concentrating efficiency showed
that over 92% of the MF recovered VFAs
were concentrated (and there is the
potential to reutilise all the organic
stream)
• Polymer accumulation was improved by
nearly 7 times
• Struvite production for the agriculture
sector
Tao et al., 2016

PHA Concentration/Yield from
Digestates as Nutrient Media
NM – nutrient media (peptone and
meat extract)
D1 - digestates from animal slurries
D2 – digestates from food wastes
and wheat feed
0
3
6
9
12
15
0 20 40 60
NM D1 D2
Time (h)PHA(g/l)
PHA Yields and % CDW:
NM - 0.21 g PHA/ g VFA (28 h); 78 % CDW
D2 - 0.48 g PHA/ g VFA (43 h); 90% CDW
Passanha et al. (2013)

 Polyhydroxyalkanoates (PHA) accumulate as intracellular carbon and energy
reserve naturally within a variety of gram positive and gram negative bacteria.
 General principle for PHA accumulation = Excess carbon + Nutrient deficiency.
 PHAs are thermoplastic polyesters with melting point 50-180ºC. UV stable, low
permeation of water and good barrier properties
 Properties can be tailored to resemble elastic rubber (long side chains) or hard
crystalline plastic (short side chains)
Polyhydroxyalkanoates
O
O
O
OO
O
OO
O
O O
O
O
O
O
Polyhydroxybutyrate
(PHB)
Brittle
PHBcoPHV
Hard/flexible
Medium chain length
Polyhydroxyalkanoate
(mclPHA)
Thermoplastic Elastomer

Anaerobic Biodegradability of
Polymers
-100
0
100
200
300
400
500
600
0 10 20 30 40 50 60 70
MethaneyieldmlCH4/gVSadded
Days

The sole responsibility for the content of this document lies with the authors. It does not necessarily reflect the funders opinion. Neither the authors or the funders
are responsible for any use that may be made of the information contained therein.
Acknowledgments
Dr. Tim Patterson, Dr. Julie Williams, Ivo Oliveira, Dr. James Reed, Savvas Savvas, Dr. Gregg Williams, Prof.
Richard Dinsdale, Prof. Alan Guwy, Dr. Alex Chong, Pearl Passanha, Dr. Gopal Kedia, Dr. Bing Tao, Dr. Phil Kumi
and Dr. Des Devlin

ACADEMIC EXPERTISE FOR BUSINESS (A4B)
Collaborative Industrial Research Project
SuPERPHA – Systems and Product Engineering Research for
Polyhydroalkanoates (PHA)
July 2013 – Dec 2014 (£1.2M)
University of South Wales (lead)
Partners:
Swansea and Bangor Universities
Aber Instruments Ltd.
Axium Process Ltd.
Excelsior Technologies Ltd.
FRE-Energy Ltd.
Kautex-Textron Ltd.
Loowatt
NCH
Nextek Ltd.
Scitech Adhesives systems Ltd.
(Supported by BASF)
Thames Water
Waitrose
Welsh Water

Pre-treatment
UK AD & BIOGAS
TRADESHOW
R&I HUB
PROF. RICHARD DINSDALE
UNIVERSITY OF SOUTH WALES

Making Waves in the World of Liquid Thermal Processing
Innovative AD pre-treatment
Unlocking the potential of microwaves
Originated by: Stephen Roe, CEO
stephen@amt.bio

Contents
• Background
• Imperatives for the industry
• Innovation for AD
• Programme of work
• How to accelerate results

Background
Signing of the Paris Climate agreement: Imperative
the world acts on decarbonising
Withdrawal of subsidies. Threatens expansion and
markedly increases the payback period for new
installations.
ADBA Research and Innovation Forum in York (April
2016):
“Challenge to increase biogas
yields by 30%

Food vs Energy Crops
“Global rush to energy crops threatens to
bring food shortages and increase poverty,
says UN”
Courtesy: The Guardian, 2007
We can do better and find abundant
feedstocks waiting needing R&D to solve
process problems

Dilemma
Grow the industry globally

Dilemma
Reduce food competition

Dilemma
Succeed without FIT

The need
30% more CH4

Innovation for AD
100s of technical papers describe positive impact of
microwave pre-treatment on biomass feedstocks in
laboaratories
Most conclude with:
“ …the global outlook is positive for the use of MW irradiation
for the pretreatment of lignocellulosic biomass, sludge or
biodiesel feedstock.”

Innovation for AD
To overcome the limitations for scaling up MW-assisted
technology for pretreatment, development of a
continuous process offers numerous advantages, but
still poses several challenges that require detailed
investigation especially when working with high
temperature and high pressure”
Armando T. Quitain, Mitsuru Sasaki and Motonobu Goto,
Chapter 6
• AMT technology overcome these
limitations
• Continuous microwave pre-treatment is
now available at industrial-scale

Microwave Volumetric Heating
AMT’s design of microwave system
heats flowing liquids to a uniform
and precise temperature within ±1°C
without hot or cold spots
The entire volume of the flowing
liquid is heated
This is called Microwave Volumetric
Heating

Profound impacts of MVH
# 1.Cell lysis provides access to contents for AD
bacteriaProcessintensification: Microwave
Solvent-free
extraction
Anaerobic digestion is accelerated because the cell wall
has been destroyed allowing the AD bacteria to act much
more quickly

Profound impacts of MVH
#2. Rapid bacteria kill, no competition for AD bacteria
AMT sterilises the feedstock eliminating bacteria that would
otherwise compete with the anaerobic bacteria, allowing them to
grow more quickly
It also complies with EU Animal by Products Regulations
Vegetative cells
E coli in PBS
Listeria in PBSMVH appears to kill microbes 10°-12°C lower than
conventional and almost instantaneously
Test results from
independent research

Programme of work underway
Testing on large range of
feedstocks
Process parameters
optimised for maximum BMP
No capacity limitations,
system can be extended
Energy recuperation to
maximise efficiency
Temperature
Pressure
Cellulosic
Protein rich
Feedstock T°C P bar Time sec
2nd sludge
ABP cat 2
Mixed food
& veg
Cellulosic
Rice straw

Early results are transformational
• Generates 30% more total biogas
• Retention time reduced by 50%
• Total 60% more biogas from
same facility
• Equipment payback in <2 years
and in some cases <1 year
Data is for animal by-products category 2 specifically
AMT’s pre-treatment technology directly addresses the stated need of the
industry for 30% more methane to make installed AD plants more profitable
after removal of feed-in-tarrifs

How to accelerate results and benefits
for the industry
Enter into discussions with AMT
Contribute to research programme
AMT will pre-treat your feedstocks
Get involved, get ahead, take the lead

Contact details
Stephen Roe, CEO
stephen@amt.bio
07802 616188
www.amt.bio

Thank you, any questions?
UK AD & BIOGAS
TRADESHOW
R&I HUB

UK AD & Biogas 2016 _ R&I Hub 6 July

Recommended

Recommended

More Related Content

What's hot

What's hot (20)

Viewers also liked

Viewers also liked (20)

Similar to UK AD & Biogas 2016 _ R&I Hub 6 July

Similar to UK AD & Biogas 2016 _ R&I Hub 6 July (20)

Recently uploaded

Recently uploaded (20)

UK AD & Biogas 2016 _ R&I Hub 6 July