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UK AD & BIOGAS TRADESHOW R&I HUB
6-7 JULY 2016NEC BIRMINGHAM
© University of South Wales
Prof. Sandra Estevessandra.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 ProductionP2G, Biogas upgrading and utilisation
LCA and economic evaluations
© University of South Wales
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)
© University of South Wales
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
© University of South Wales
Variation in the chemical parameters of the digester
Acetate
Propionate
Williams et al. 2013
© University of South Wales
Acetate
Propionate
Eubacteria
Methanosaetaceae
Methanobacteriales
Methanomicrobiales
Methanosarcinaceae
Williams et al. 2013
© University of South Wales
0 40 80 120 160 200 2400.00E+00
2.00E+08
4.00E+08
6.00E+08
8.00E+08
1.00E+09
1.20E+09
0
500
1000
1500
2000
2500MSTAcetatePropionate
Time (d)
Met
hano
saet
acea
e (g
ene
copi
es /m
l)
VFA
s (m
g/l)
Williams et al. 2013
Methanogens and VFA residuals
© University of South Wales
0.0E+004.0E+108.0E+101.2E+111.6E+112.0E+11
Bac
teri
a
140 170 200 230 260 290 3203.0E+03
3.0E+04
3.0E+05
3.0E+06
3.0E+07
0
200
400
600
800
1000
1200
MMB
MBT
Time (days)
Met
hano
gens
(gen
e co
pies
ml-1
)
Effect of Trace Elements on Bacteria and Methanogens
Propionate
VFA
(mg
/ l)
Williams et al. 2013
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
-1 19.84 gVFACOD L
-1 16.56 gVFACOD L
-1
© University of South Wales
Kumi et al., 2016
Comparative yield of VFA – effect of inoculum pre-treatment, commercial micronutrients addition and
recovered microbial nutrients addition
© University of South Wales
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%
14%
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
© University of South Wales
Esteves et al., 2015
Characteristics of Methanosarcina & Methanosaeta sp.
Parameter Methanosaeta Methanosarcinaμmax (d−1) 0.20 0.60Ks (mg COD L−1) 10–50 200–280NH4
+ (mg L−1) <3000 <7000Na+ (mg L−1) <10,000 <18,000pH-range 6.5–8.5 5–8pH-shock <0.5 0.8–1Temperature 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
© University of South Wales
Esteves et al., 2015
Demonstration of Ammonia Removal Benefit for Cardiff WwTWs (thermal hydrolysed secondary sludges,
digesters at 43oc)
© University of South Wales
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
Tao et al, submitted
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)
Tao et al, submitted
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
© University of South Wales
0 10 20 30 40 50 60 70 800
10000
20000
30000
40000
50000
60000
70000water controlwater control0.03% Cellulase N11/120.03% Cellulase N11/120.03% Cellulase N11/120.1% Cellulase N11/120.1% Cellulase N11/120.1% Cellulase N11/120.3% Cellulase N11/120.3% Cellulase N11/120.3% Cellulase N11/121% Cellulase N11/121% Cellulase N11/120.3% Protease N11/110.3% Celluclast
Time (h)
sCO
D (m
g/l)
Soluble COD released into the percolate liquor
© University of South Wales
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
© University of South Wales
© University of South Wales
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.
AcknowledgmentsDr. 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
Thank you, any questions?
The development of equipment to meet the new research challenges of AD.Edgar Blanco-MadrigalManaging 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)
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 10/23/20150
200
400
600
800
1000
1200
1400
1600
1800
Hourly feed Daily feed
ml/h
our
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 daysBlue 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 conceptFeed, 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 VILLASENIOR LECTURE, CRANFIELD UNIVERSITY
Thank you, any questions?
Optimising the AD process: every little helps
UK AD & BIOGAS TRADESHOW R&I HUB
MARTIN RIGLEY MBE & DARREN BACONH2AD
Thank you, any questions?
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), Birmingham6th 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)
FW 1
VFA
pro
file
(mg
l-1) Acetic Propionic
Iso-Butyric n-ButyricIso-Valeric n-ValericHexanoic Heptanoic
0
2000
4000
6000
8000
10000
0 40 80 120 160 200 240
Time (days)
Tota
l VFA
s (m
g l-1
)
BMW + gut&fat 1BMW + gut&fat 2BMW + blood 1BMW + blood 2BMW
(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
ANAEROBICFERMENTATIO
NBIO-METHANE
MIXED FERMENTATION
ALCOHOLSPOLYMERSETHANOL
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.
VOLATILE FATTY ACIDS
Stickland reaction
Global carboxylic acids market:• US$ 12.14 Billions 2015• US$ 18.49 Billions 2023
Precursors for several industries:• Solvents• Coatings• Polymers• Artificial flavours• Scents
VFA’S MARKET
Global biogas market:• US$ 19.5 Billions 2015• 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
VOLATILE FATTY ACIDS UPSTREAM PROCESSTRADITIONAL 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)
SUBSTRATECommercial 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 HexanoicHeptanoic VFA
0 1 4 6 8 11 15 18 20 22 25 27 32 36 410
100002000030000400005000060000700008000090000
100000
No-AC, No-EH, and No-IDF.
Time (Days)
Conc
entr
ation
(mg/
L)
0 1 4 6 8 11 15 18 20 22 25 27 32 36 410
100002000030000400005000060000700008000090000
100000
No-AC, No-EH, and IDF.
Time (Days)
Conc
entr
ation
(mg/
L)
0 3 5 7 10 12 14 17 19 21 24 26 28 31 35 38 40 450
10000
20000
30000
40000
50000
60000
70000
80000
90000
100000 AC, EH and No-IDF.
Time (Days)
Conc
entr
ation
(mg/
L)
0 3 5 7 10 12 14 17 19 21 24 26 28 31 35 38 40 450
10000
20000
30000
40000
50000
60000
70000
80000
90000
100000 AC, No-EH, and No-IDF.
Time (Days)
Conc
entr
ation
(mg/
L)a)
c)
b)
d)Batch Reactor
Chart Title
Acetic Propionic Iso-Butyric n-Butyric Iso-Valeric n-Valeric HexanoicHeptanoic VFA
0100002000030000400005000060000700008000090000
IL66.6%/No-EH
Time (Days)
Cone
ntra
tion
(mg/
L)
0100002000030000400005000060000700008000090000
IL10%/No-EH
Time (Days)
Conc
entr
ation
(mg/
L)
0 5 9 14 19 23 28 33 37 42 47 52 56 630
100002000030000400005000060000700008000090000
IL66.6%/EH
Time (Days)
Conc
entr
ation
(mg/
L)
0100002000030000400005000060000700008000090000
IL10%/EH
Time (Days)
Conc
entr
ation
(mg/
L)a) b)
c) d)Semi-continuous Reactor
The recovery pathway is dependent of the process configuration, acid structure and process economics
VOLATILE FATTY ACIDS RECOVERYTRADITIONAL 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 mixedFermentation
Evaporation/Water removal
Diluted ammonium
carboxylates
Acidification
H2SO4
Esterification
Methanol
(NH4)2SO4
VFA- Methyl esters
Biomass Removal
Biomass
Water
Concentratedammonium
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)
50%-1.5-2.5
50%-1.5-5
50%-2.5-2.5
50%-2.5-5
80%-1.5-2.5
80%-1.5-5
80-2.5-2.5
80%-2.5-5
0
10
20
30
40
50
60
Methyl Acetate Methyl Propionate Methyl Iso-butyrateMethyl Butyrate Methyl Iso-valerate
Met
hyl
VFA
Yiel
d (%
)
80%-2.5-2.5
80%-2.5-5
80%-1.5-2.5
80%-1.5-5
50%-2.5-2.5
50%-2.5-5
50%-1.5-2.5
50%-1.5-5
0
10
20
30
40
50
60
(NH4
)2SO
4 Yi
eld
(%)
ESTERIFICATION REACTION VOLATILE FATTY ACIDS RECOVERY
20 25 30 35 40 45 50 55 60 65 700
102030405060708090
Methyl Acetate Methyl Propionate Methyl Iso-butyrateMethyl Butyrate Methyl Iso-valerate
Temperature (C)
Met
hyl V
FA Y
ield
(%)
0 5 10 15 200
10
20
30
40
50
60
Methyl Acetate Methyl Propionate Methyl Iso-butyrateMethyl Butyrate Methyl Iso-valerate
Time (h)
Met
hyl V
FA Y
ield
(%)
ESTERIFICATION REACTION VOLATILE FATTY ACIDS RECOVERY
69
Waste Blood
Anaerobic mixedFermentation
Biomass Removal
Biomass
Pertraction system
Diluted Ammonium
carboxylates
Water/VFA
Strippingsystem
Octanol-TOA/VFA
Octanol-TOA
Fresh stripping solution
VFA rich stripping solution
PERTRACTION SYSTEMVOLATILE FATTY ACIDS RECOVERY
5%-1:1 10%-1:1 10%-2:1 10%-4:1 20%-1:1 20%-2:1 20%-4:10
20
40
60
80
100
Acetic Propionic Iso-Butyricn-Butyric Iso-Valeric VFA
Reco
very
%
Acidified Broth Centrifuged Broth
VFA Sln pH 4.5 VFA Sln pH 7.50
20
40
60
80
100
Acetic Propionic Iso-Butyric n-ButyricIso-Valeric Valeric VFA
Reco
very
%
305
1530
20 AceticPropionicIso-Butyricn-ButyricIso-Valeric
VFA RECOVERY BY PERTRACTION SYSTEMTOA/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
equilibrationOperation for
2 hours
PERTRACTION SYSTEMVOLATILE FATTY ACIDS RECOVERY
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 20
102030405060708090
100
Acetic Propionic Iso-Butyric n-ButyricIso-Valeric VFA
Time (h)
Reco
very
%
0 6 12 18 240
20
40
60
80
100
Acetic Propionic Iso-Butyric n-ButyricIso-Valeric Valeric VFA
Time (h)
Reco
very
%
0 0.5 1 1.5 20
102030405060708090
100
Acetic Propionic Iso-Butyric n-ButyricIso-Valeric Valeric VFA
Time (h)
Reco
very
%
Waste Blood
Anaerobic mixedFermentation
Evaporation/Water removal
Diluted ammonium
carboxylates
Acidification
H2SO4
Esterification
Methanol
(NH4)2SO4
VFA- Methyl esters
Biomass Removal
Biomass
Water
Concentratedammonium
carboxylates
Waste Blood
Anaerobic mixedFermentation
Biomass Removal
Biomass
Pertraction system
Diluted Ammonium
carboxylates
Water/VFA
Strippingsystem
Octanol-TOA/VFA
Octanol-TOA
Fresh stripping solution
VFA rich stripping solution
VOLATILE FATTY ACIDS 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
UK AD & Biogas 2016: Producing methane or chemicals?National Exhibition Centre (NEC), Birmingham6th July 2016
THANKS FOR YOUR ATTENTION
QUESTIONSUK AD & Biogas 2016: Producing methane or chemicals?National Exhibition Centre (NEC), Birmingham6th July 2016
© University of South Wales
Prof. Sandra Esteves sandra.esteves@southwales.ac.uk
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
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 ProductionP2G, Biogas upgrading and utilisation
LCA and economic evaluations
© University of South Wales
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)
© University of South Wales
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
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 EuropeOver 300 biogas upgrading plants across Europe, over 300,000
Nm3 CH4/hAD 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
EU 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
© University of South Wales
Denmark’s (100%) Renewable Energy Strategy for 2050
Source: www.ceesa.dk/Publications
Problem: UK energy demandSecurity 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
© University of South Wales
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
© University of South Wales
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 methanationElectricity generation
H2
H2
CH4
CH4
CH4
e-
e-
Vehicle FuelHeat
Commercial in Confidence
Biomethanation P2G & Biogas Upgrading
BiomethanationAERIOGEN®
Electrolysis
e e-
CH4
O2
H2
CO2
CH4 + CO2
Anaerobic Digestion
Intermittent Renewable
Energies
Thermal &Aerobic
Processes
© University of South Wales
Existing Commercial Technologies for Biogas Upgrading vs. Hydrogenotrophic methanation
PSAWater scrubbing
Organic scrubbingAmine scrubbing
Membrane separation
Hydrogenotrophic MethanationAERIOGEN®
60% CH4
40% CO2
>99% CH4Bi
ogas
Biog
as © University of South Wales
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
© University of South Wales
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
© University of South Wales
High input gases control allow a 99.7% quality output and help maintain appropriate pH
Recovery After Fasting for 45 days
© University of South Wales
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.
© University of South Wales
© University of South Wales
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 AcidVariable, but can be sold for $500-1300 per metric tonne
Acetic Acid End-usesAdhesives, 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)
CH42H2 + CO
CH3OHCH3COOH
Steam Reforming
+ H2O
Methane
Synthesis Gas
Methanol
Acetic AcidMethanol
Carbonylation
+ CO
CH4
Biomethane
Biohydrogen
Acetic Acid
2H2+ CO
CH3COOH CH3OH
Chemicals from Biomethane: Acetic Acid
Products from anaerobic
fermentations
Chemicals from Methane: UreaUrea Production Route:
CH42H2 + CO
NH3(NH2)2CO
Steam Reforming
+ H2O
Methane Synthesis Gas
AmmoniaUrea
H2 + CO2Water Gas Shift
Reaction
+ H2O
+ N2
Haber Process
+ CO2
Hydrogen and Carbon Dioxide
End-uses of Urea91% 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 Urea120 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
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
© University of South Wales
~ 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
© University of South Wales
Kumi et al., to be submitted
Volatile Fatty Acids from Badmington Grass
© University of South Wales
Comparative yield of VFA from thermally hydrolysed secondary sludges
Effect of inoculum pre-treatment, commercial micronutrients addition and recovered microbial nutrients addition
© University of South Wales
Kumi et al., 2016
Faster hydrolysis and acid phase, faster methane production
Production of Volatile Fatty Acids from H2 and CO2
Mixed culture
© University of South Wales
0 2 4 6 8 10 12 14 16 180
2000
4000
6000
8000
10000
12000
14000
16000
Ace
tic A
cid
(mg/
l)
Days
Chain of Processes for Valorisation of Sewage
Sludge
Tao et al., 2016
© University of South Wales
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
• VFA concentration
Tao et al., 2016
© University of South Wales
© University of South Wales
PHA Concentration/Yield from Digestates as Nutrient Media
NM – nutrient media (peptone and meat extract)D1 - digestates from animal slurriesD2 – digestates from food wastes and wheat feed
0 10 20 30 40 50 600369
1215
NM D1 D2
Time (h)
PHA
(g/l
)PHA Yields and % CDW:
NM - 0.21 g PHA/ g VFA (28 h); 78 % CDWD2 - 0.48 g PHA/ g VFA (43 h); 90% CDW
Passanha et al. (2013)
© University of South Wales
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
OO
OOO
OOO
OO O
OO
OO
Polyhydroxybutyrate(PHB)
Brittle
PHBcoPHV
Hard/flexible
Medium chain lengthPolyhydroxyalkanoate
(mclPHA)Thermoplastic Elastomer
Anaerobic Biodegradability of Polymers
0 10 20 30 40 50 60 70
-100
0
100
200
300
400
500
600
Met
hane
yie
ld m
l CH
4 / g
VS
adde
d
Days
© University of South Wales
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
© University of South Wales
© University of South Wales
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.
AcknowledgmentsDr. 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
Prof. Sandra Esteves sandra.esteves@southwales.ac.uk
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 UniversitiesAber Instruments Ltd.Axium Process Ltd.Excelsior Technologies Ltd.FRE-Energy Ltd.Kautex-Textron Ltd.Loowatt
NCHNextek Ltd.Scitech Adhesives systems Ltd. (Supported by BASF)Thames WaterWaitrose Welsh Water
© University of South Wales
Thank you, any questions?
Pre-treatment
UK AD & BIOGAS TRADESHOW R&I HUB
PROF. RICHARD DINSDALEUNIVERSITY OF SOUTH WALES
Thank you, any questions?
Making Waves in the World of Liquid Thermal Processing
Innovative AD pre-treatment
Unlocking the potential of microwaves
Originated by: Stephen Roe, CEOstephen@amt.bio
Making Waves in the World of Liquid Thermal Processing
Contents
• Background
• Imperatives for the industry
• Innovation for AD
• Programme of work
• How to accelerate results
BackgroundSigning 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%
Making Waves in the World of Liquid Thermal Processing
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
Making Waves in the World of Liquid Thermal Processing
DilemmaGrow the industry globally
Making Waves in the World of Liquid Thermal Processing
Dilemma
Reduce food competition
Making Waves in the World of Liquid Thermal Processing
Dilemma
Succeed without FIT
Making Waves in the World of Liquid Thermal Processing
The need
30% more CH4
Making Waves in the World of Liquid Thermal Processing
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.”
Making Waves in the World of Liquid Thermal Processing
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
Making Waves in the World of Liquid Thermal Processing
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
Making Waves in the World of Liquid Thermal Processing
Profound impacts of MVH
# 1.Cell lysis provides access to contents for AD bacteria
Anaerobic digestion is accelerated because the cell wall has been destroyed allowing the AD bacteria to act much
more quickly
Making Waves in the World of Liquid Thermal Processing
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 quicklyIt also complies with EU Animal by Products Regulations
MVH appears to kill microbes 10°-12°C lower than conventional and almost instantaneously
Test results from independent research
Making Waves in the World of Liquid Thermal Processing
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
Pre
ssur
e
Cellulosic
Protein rich
Feedstock T°C P bar Time sec
2nd sludge
ABP cat 2
Mixed food & veg
Cellulosic
Rice straw
Making Waves in the World of Liquid Thermal Processing
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 yearData 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
Making Waves in the World of Liquid Thermal Processing
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
Making Waves in the World of Liquid Thermal Processing
Contact detailsStephen Roe, CEOstephen@amt.bio
07802 616188www.amt.bio
Thank you, any questions?
UK AD & BIOGAS TRADESHOW R&I HUB
Recommended