uk ad & biogas 2016 _ r&i hub 6 july

UK AD & BIOGAS TRADESHOW R&I HUB

6-7 JULY 2016NEC BIRMINGHAM

© University of South Wales

Prof. Sandra [email protected]

Optimising the AD process

UK AD & Biogas 2016, 6-7 July, Birmingham NEC

mailto:[email protected]

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


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)



• 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

http://www.google.co.uk/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&docid=DrTzSDhZo75nGM&tbnid=l15q3nyfHGyccM:&ved=0CAUQjRw&url=http://www.caer.uky.edu/services/equipmentpages/powergenequip_images.shtml&ei=6pK8Ua3CDeXz0gWuo4G4Cw&bvm=bv.47883778,d.d2k&psig=AFQjCNEe5swh0x3cy_4PFhWz4_4FMNGHKA&ust=1371399050758352

http://www.google.co.uk/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&docid=DwrduLqjgYzonM&tbnid=7OH3_8eZufJkdM:&ved=0CAUQjRw&url=http://www.easyfairs.com/events_216/lab-innovations2012_28267/lab-innovations-2012_28268/visitors_28269/exhibitor-list_28279/stand/397398/&ei=r5S8UYuEOtLs0gWv0oCgCg&bvm=bv.47883778,d.d2k&psig=AFQjCNEnA22SWtVopfhl-sUEGB8k_jJBHA&ust=1371398761123745


Acetate

Propionate

Eubacteria

Methanosaetaceae

Methanobacteriales

Methanomicrobiales

Methanosarcinaceae



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)


Methanogens and VFA residuals


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)


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


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%

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


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


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 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


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


http://gro.southwales.ac.uk/studentships/KESSII/

http://www.google.co.uk/url?sa=i&rct=j&q=&esrc=s&source=images&cd=&cad=rja&uact=8&ved=0ahUKEwjyjZ7ru9LNAhVqLsAKHZ0_BcwQjRwIBw&url=http://logok.org/corus-logo/tata-steel-logo/&psig=AFQjCNGID-5I_WuysyUKpeakiIRc-muTyw&ust=1467469447913312

http://www.wwutilities.co.uk/


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 [email protected]


http://www.insource-energy.co.uk/

https://dwrcymru-welshwater.bravosolution.co.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


DR. RAFFAELLA VILLASENIOR LECTURE, CRANFIELD UNIVERSITY

Optimising the AD process: every little helps


MARTIN RIGLEY MBE & DARREN BACONH2AD

Networking Lunch


13:15 – 14:15

PRODUCTION AND EXTRACTION OF SHORT CHAIN CARBOXYLIC ACIDS FROM THE

ANAEROBIC MIXED-CULTURE FERMENTATION OF SLAUGHTERHOUSE BLOOD

Dr Jersson Plácido, [email protected]

Dr Yue Zhang, [email protected]

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


Temperature (C)

Met

hyl V

FA Y

ield

(%)

0 5 10 15 200

10

20

30

40

50

60


Time (h)

Met

hyl V

FA Y

ield

(%)

ESTERIFICATION REACTION VOLATILE FATTY ACIDS RECOVERY

69

Waste Blood


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


Time (h)

Reco

very

%

0 0.5 1 1.5 20

102030405060708090

100


Time (h)

Reco

very

%

Waste Blood


Evaporation/Water removal

Diluted ammonium

carboxylates

Acidification

H2SO4

Esterification

Methanol

(NH4)2SO4

VFA- Methyl esters

Biomass Removal

Biomass

Water

Concentratedammonium

carboxylates

Waste Blood


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



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


http://www.acclaimimages.com/_gallery/_pages/0153-0512-0816-1002.html

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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



• 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)



• 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


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


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 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


http://www.google.co.uk/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&uact=8&ved=0CAcQjRxqFQoTCJjBmaXTusgCFUY9GgodhpgCAg&url=http://www.brightsolarpower.com.ng/solar-panels&psig=AFQjCNEntJMEQMJWV4AcqUSdgkm655syYA&ust=1444660850960082

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


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.


http://www.bpe-ds.com/

http://www2.wessexwater.co.uk/



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


~ 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 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


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



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)


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


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


http://gro.southwales.ac.uk/studentships/KESSII/

http://www.google.co.uk/url?sa=i&rct=j&q=&esrc=s&source=images&cd=&cad=rja&uact=8&ved=0ahUKEwjyjZ7ru9LNAhVqLsAKHZ0_BcwQjRwIBw&url=http://logok.org/corus-logo/tata-steel-logo/&psig=AFQjCNGID-5I_WuysyUKpeakiIRc-muTyw&ust=1467469447913312



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



http://www.insource-energy.co.uk/

https://dwrcymru-welshwater.bravosolution.co.uk/

http://www.bpe-ds.com/

http://www2.wessexwater.co.uk/


http://www.nitechsolutions.co.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


Pre-treatment


PROF. RICHARD DINSDALEUNIVERSITY 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, [email protected]


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%


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


DilemmaGrow 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 bacteria

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 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


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


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


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 detailsStephen Roe, [email protected]

07802 616188www.amt.bio