biohydrogen production by fermentation and bioelectrolysis · biohydrogen production by...

© University of South Wales

Biohydrogen Production by Fermentation and Bioelectrolysis

Alan Guwy University of South Wales

Sustainable Environment Research Centre

Energy and Environment Research Institute

H2FC SUPERGEN Meeting,

Newcastle University

30-31st July 2014


Introduction

Biomass to biomethane -mature technology:

• AD is widely deployed in many countries

• Germany has over 4000 AD installations

• In India at least 3 million small size digesters exist.

• China counts many thousand with implementation set to

increase significantly.

• AD industry estimated to employ ~10,000 in Germany

– worth over €1billion to the German economy.

– expected to rise to a turnover of €18 billion by 2030.


Introduction

Waste Biomass in UK:

• UK produces over 100 Mt of org. mat. p.a.

• 1.73 Million Tonnes of sewage sludge p.a. (Water UK

2007)

• 12-20 Million Tonnes of this is food waste (Defra 2009)

– 9 Mt from households,

• 90 Million Tonnes of agricultural material

– (e.g. manures and slurries)


Full Scale Biomethane Plant

Thames Waters Sewage Sludge Digesters


Biohydrogen production- Dark fermentation Theoretical:

Hexose CH3COOH (acetic acid) + 4 H2

(that is 4 mol H2/mol hexose or 0.5 m3 H2 / kg carbohydrate)

Hexose CH3CH2CH2COOH (butyric acid) + 2 H2


• A mix of acetate and butyrate is usual with H2 yields approx. 1 to 3 mol H2/mol

hexose utilised

EPSRC SUPERGEN SHEC projects EP/H019480/1 and EP/E040071/1.


Hydrogen Yields from Different Substrates

Substrate H2 Yield mol/mol hexose

H2 Yield L/kg-1 VS

Reference

Waste Activated Sludge

11.7 Li et al.

Sewage Biosolids 2.54 29.1 Massanet et al.

Potato steam peel 3.8 Mars et al.

Sugar beet extract 3.0 Panagiotopoulos et al.

Food waste 47.0 Chinellato et al.

Algae 21.9 Park et al.

Glucose 2.9 Hernández-Mendoza et al.

Kitchen waste 1.3 66.0 Chun-Feng et al.

Dark fermentation - H2 yield Theoretical:





• A mix of acetate and butyrate is usual with H2 yields approx. 1 to 2

mol H2/mol hexose utilised

Significant energy remains in acetate and butyrate


Biohydrogen Production in an Integrated

Anaerobic system-(dark fermentation)

Acetic n-Butyric Propionic Valeric

Optimised Methanogenic

Stage

Optimised Methanogenic

Stage Methane Reactor

CH4+CO2

Biomass feedstock

Hydrogen Reactor

Advanced water recycling

Soil Conditioner

H2+CO2

33% conversion 90% energy conversion (substrate)

CH4+H2

pH=5.2 pH=7.0

VFAs

Lab Bio-H2/Bio-CH4

Lab Scale:

CH4 Bioreactor

H2 Bioreactor

•Model substrates e.g. sucrose, fructose •Sewage sludge •Food industry co products e.g. wheatfeed •Rye grass •Straw

Biohydrogen Pilot Scale

Pilot scale biohydrogen and biogas plant using wheatfeed

Pilot scale biohydrogen & biomethane plant at IBERS Aberystwyth using rotated crops

H2 reactor 1.25m3

CH4 reactor 10m3


Comparison of Single and Two Stage

BioH2/BioCH4

Feed

H2

CH4

CH4

CH4

18h

20d

11.25d

19.25d

Single Stage20d HRT

Two Stage12d HRT

Two Stage20d HRT

Pretreatment: 24 h @ pH 11

Substrate Concentration 48gL-1

Hydrogen reactor pH: 5.5

Methane reactor pH: 7.0

Temperature: 35oC

Substrate

Environmental Conditions

Flour milling co-product

Experimental Design

Massanet-Nicolau, J., Dinsdale, R., Guwy, A., Shipley, G., 2013. Use of real time gas production data for more accurate comparison of continuous single-stage and two-stage fermentation. Bioresource technology 129, 561–7.


Performance of Hydrogen Bioreactor

Pro

duction R

ate

(cm

3m

in-1

)

Time (Days)

Yie

ld (

L k

g-1

VS

Fed)

0

5

10

15

0

4

8

12

0 10 20 30

Production rate (cm3 min-1)

Yield (L Kg-1 VS)

Production Rate

YieldH

2 P

rod

uct

ion

Rat

e (c

m3 m

in-1

)

H2 Y

ield

(L

kg-1

VS

Fed

)

Time (Days)



VFA Concentration in Hydrogen Bioreactor

0

2000

4000

6000

0 10 20 30

acetic

Propionic

n-butyric

n-valeric

Time (Days)

VFA

Co

nce

ntr

atio

n (

mg

L-1)

0

2000

4000

6000

0 10 20 30

acetic

Propionic

n-butyric

n-valeric

Time (Days)

VFA

Co

nce

ntr

atio

n (

mg

L-1)

0

2000

4000

6000

0 10 20 30

acetic

Propionic

n-butyric

n-valeric

Time (Days)

VFA

Co

nce

ntr

atio

n (

mg

L-1)

0

2000

4000

6000

0 10 20 30

acetic

Propionic

n-butyric

n-valeric

Time (Days)

VFA

Co

nce

ntr

atio

n (

mg

L-1)

0

2000

4000

6000

0 10 20 30

acetic

Propionic

n-butyric

n-valeric

Time (Days)

VFA

Co

nce

ntr

atio

n (

mg

L-1)



Performance of Methane Bioreactors

0

150

300

450

0

10

20

30

0 10 20 30

Production RateYield

CH

4 P

rod

uctio

n R

ate

(cm

3 m

in-1

)

CH

4 Y

ield

(L k

g-1

VS

Fe

d)

Time (Days)

0

150

300

450

0

10

20

30

0 10 20 30

0

150

300

450

0

10

20

30

0 10 20 30

0

150

300

450

0

10

20

30

0 10 20 30

1 stage – 20 day HRT 2 stage – 12 day HRT 2 stage – 20 day HRT

Feedstock

Effluent

(Reduction percentages are in parentheses)

Single-stage

20 day HRT

Two-stage

12 day HRT

Two-stage

20 day HRT

CH4 Yield 261.14 306.09 (17.5) 359.65 (37.7)

Volatile Solids (g L-1) 48.02 15.97 (66.7) 15.9 (66.9) 13.56 (71.8)

COD (g L-1) 58.61 21.65 (63.1) 22.76 (61.2) 18.49 (68.5)

Carbohydrate (g L-1) 26.24 3.37 (87.2) 5.58 (78.7) 4.6 (82.5)

VFA (mg L-1) 572 287 237 243



Two stage fermentation research

Robust comparison of single and two stage

demonstrated:

• 38% increase in energy yields

• Greater stability even at lower retention times

• Retention times as low as 12 days possible while

still obtaining 18% increase in energy yields



Two Stage Fermentation of Grass

Comparison of single and two stage

BioH2/BioCH4 of grass demonstrated:

• Yields and efficiency were again higher in

two stage

• 13% increase in Energy yields

• The difference was less pronounced than

with wheat feed (38% increase)

• Substrate digestibility may be the

determining factor (solids residuals higher in

effluent of wheat feed experiments) 0

2

4

6

8

10

12

14

Single Stage20 day

Two Stage12 day

Two Stage20 day

Ener

gy y

ield

fro

m b

ioga

s(M

J kg

-1V

S)En

ergy

yie

ld f

rom

bio

gas

(MJ

kg-1

VS)

10.36 10.27

(-0.8%)

11.74

(+13.3%)

Two Stage Dark Fermentation with

Steam Methane Reformer

CH4

Reactor

H2+CO2

VFAs

Biomass

Remove CO2

H2

reactor

H2+CO2

CH4

Reactor

H2+CO2

Biomass

Remove CO2

PEMFC

To Land

H2

reactor

Steam Methane Reforming

MFC

reactor

e-

Using Biogas from BioH2/BioCH4

i-V Plot of SOFC

operating at 850°C on

•H2 (2 cm3 min-1)

•and simulated biogas

(CH4:CO2 1:0.5 cm3 min-1)

Similar power output for hydrogen and simulated biogas

Laycock et al., Dalton Transactions, 2011 40 (20), pp. 5494-5504,.


Biomethane emissions from AD and BioH2/BioCH4

Problem

• 75 or 21 depending on a 20 or 100 year time frames for methane

compared to 0 primary GWP or 5.6 secondary GWP for hydrogen.

• In full scale plants up to 15% of the produced methane can escape,

either from the plant, the liquid residues from the facility, the gas

cleanup process or from the end use technology selected.

Research Challenge

• Evaluate/design a novel biological process that can convert

biomass to hydrogen rather than biomethane or a mix of hydrogen

or methane.

• Get closer to the theoretical yield of 12 mol H2 / mol


Integrating Biohydrogen Fermentation with

Bioelectrolysis

Alan Guwy, Richard Dinsdale, Iano Premier and Jaime Massanet-Nicolau

Integrated Biological Hydrogen Production Options

Guwy, A.J., Dinsdale, R.M., Kim, J.R., Massanet-Nicolau, J., Premier, G., 2011. Fermentative biohydrogen production systems integration. Bioresource Technology 102 (18), 8534–8542. Premier, G.C., Kim, J.R., Massanet-Nicolau, J., Kyazze, G., Esteves, S.R.R., Penumathsa, B.K.V., Rodríguez, J., Maddy, J., Dinsdale, R.M., Guwy, A.J., 2013. Integration of biohydrogen, biomethane and bioelectrochemical systems. Renewable Energy 49 (2013), 188–192.

Reduced ProductsNaOH, Clean H2O

HOCl, H2O2 etc

H2 + CO2

e- + H+ + CO2

Hydrogen fermentation

Methanefermentation

Photo fermentation

MFC

MEC

CH4 + CO2

H2 + CO2

H2 + CO2Biomass

e-

BES e-

Flexible Funding

Dark fermentation BioH2/ Microbial Electrolysis Cells (MEC)

H2+CO2

+

H2 reactor

MEC

H2+CO2

To Land

Acetate Biomass

Remove CO2

PEMFC

Fermentation + microbial catalysed electrolysis

C6H12O6 + 2H2O 2CH3COOH + 2CO2 + 4H2

CH3COOH + 2H2O 2CO2 + 4H2

Using Acetate

Theoretically 12 mol H2 / mol


REALITY CHECK-VFAs other than Acetate

are produced in hydrogen fermentation

0

2000

4000

6000

0 10 20 30

acetic

Propionic

n-butyric

n-valeric

Time (Days)

VFA

Co

nce

ntr

atio

n (

mg

L-1)

0

2000

4000

6000

0 10 20 30

acetic

Propionic

n-butyric

n-valeric

Time (Days)

VFA

Co

nce

ntr

atio

n (

mg

L-1)

0

2000

4000

6000

0 10 20 30

acetic

Propionic

n-butyric

n-valeric

Time (Days)

VFA

Co

nce

ntr

atio

n (

mg

L-1)

0

2000

4000

6000

0 10 20 30

acetic

Propionic

n-butyric

n-valeric

Time (Days)

VFA

Co

nce

ntr

atio

n (

mg

L-1)

0

2000

4000

6000

0 10 20 30

acetic

Propionic

n-butyric

n-valeric

Time (Days)

VFA

Co

nce

ntr

atio

n (

mg

L-1)


Remove product inhibition to increase H2 yield

Theoretical:





• A mix of acetate and butyrate is usual with H2 yields approx. 1 to 2

mol H2/mol hexose utilised

H2+CO2

+

MEC

H2+CO2

To Land

Remove CO2 PEMFC

H2

- +

Higher Substrate Strength

>[Ac/Bu]

+ + + + + + + + + + + + + + + + + + + +

AC

/Bu

Na+

+ + + + + + + + + + + + + + + + + + +

H2O

H2O

e-

H+ OH-

H2O

H+

O2

High rate BioH2 Reactor Integrated with Electro-dialysis

Power source

H2+CO2

MEC

H2+CO2

Remove CO2 PEMFC

Increasing H2 yields from biohydrogen systems: •Development of high rate biohydrogen reactor to increase substrate loading •Increase the AC/Bu loading to the tubular MEC using electro-dialysis


Main Objectives

•Design and investigate a fully integrated fermentation and bioelectrolysis biohydrogen production process. •Evaluate the use of electro-dialysis membrane extraction systems to maximise the hydrogen from a novel tubular microbial electrolysis cells and fermentation stage through the control of intermediates, acetate and butyrate. •To increase the overall hydrogen yield from the biohydrogen process from 2-3 mol H2 mol-1 hexose utilised to greater than 7 mol H2 mol-1 hexose on substrate concentrations and loading rates which are commercially viable.

Flexible Funding

Integrating Biohydrogen Fermentation with

Bioelectrolysis

26

High Rate Biohydrogen fermenters built and commissioned

27

Photograph of laboratory set-up.

Key: (1) power supply; (2) concentrate circuit reservoir; (3) diluate circuit reservoir; (4) three peristaltic pumps; (5) two magnetic stirrers; (6) CED stack; (7) gas bag; (8) electrode rinse reservoir. Yellow dotted line – concentrate circuit; blue dotted line – diluate circuit; red dotted line – electrode rinse circuit. The red wire emanating from (1) connects the positive terminal of (1) to the anode of (6). The blue wire emanating from (1) connects the negative terminal of (1) to the cathode of (6).

Conventional electro dialysis of VFA typically present in fermentation systems

Idealised, diagram of a typical CED stack with 4 AEMs, 5 CEMs, and 4 cell pairs.

PhD StudentRhys Jones

28

0.00

200.00

400.00

600.00

800.00

1000.00

1200.00

0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00

Co

nce

ntr

atio

n (

mg∙l

-1)

Time (minutes)

Acetic Acid (Concentrate)

Propionic Acid (Concentrate)

i-Butyric Acid (Concentrate)

n-Butyric Acid (Concentrate)

i-Valeric Acid (Concentrate)

n-Valeric Acid (Concentrate)

Acetic Acid (Diluate)

Propionic Acid (Diluate)

i-Butyric Acid (Diluate)

n-Butyric Acid (Diluate)

i-Valeric Acid (Diluate)

n-Valeric Acid (Diluate)

Changes in VFA concentration in concentrate and diluate streams during CED Degrees of dilution: 95% AA removal; 95% PA removal; 94% iBA removal; 93% nBA removal;

92% iVA removal; 92% nVA removal; 93% total VFA removal. Reduction in VFA

concentrations: 848 mg∙l-1 AA; 964 mg∙l-1 PA; 996 mg∙l-1 iBA; 958 mg∙l-1 nBA; 920 mg∙l-1 iVA;

782 mg∙l-1 nVA; 5,468 mg∙l-1 total VFA.

Conventional electrodialysis of VFA typically present in fermentation systems

MFC and MEC

MedRed

Medo

x

Ac-

CO2

H+

Ac-

Ac-

CO2

e-

e-

e-

CO2 H+

H+

H+

H+

O2

O2

H2O

H2O

e-

e-

e-

Anode Chamber

Cathode Chamber

Anode Cathode Ion

Exchange Membrane

MedRed

Medo

x

Ac-

CO2

H+

Ac-

Ac-

CO2

e-

e-

e-

CO2 H+

H+

H+

H+

O2

O2

H2O

H2O

e-

e-

e-

Anode Chamber

Cathode Chamber

Schematic of a typical microbial fuel cell (MFC).

H2

CO2

Schematic of a typical microbial electrolysis cell (MEC).


Microbial Electrolysis Cell (MEC)-Functionality

Biofilm Electrode

Microorganisms

e-

e-

e-

e-

H2

H+

H+

H+ H+

Membrane

2HCO3-

H2 H2

H2 H2 Anode Cathode

Acetate & Butyrate From dark fermentation

Vapplied 118 mV (lower than water electrolysis = 1230 mV (pH7)

Kim, J.R., J. Rodríguez, F.R. Hawkes, R.M. Dinsdale, A.J. Guwy, G.C. Premier. 2011. Increasing power recovery and organic removal efficiency using extended longitudinal tubular microbial fuel cell (MFC) reactors. Energy and Environmental Sciences. Energy & Environmental Science. 4(2): 459 – 465.

Ion exchange Membrane

Cathode

Hydrogel

Plastic tube shell

Anode

Flow path

Figure: Schematic of a typical microbial fuel cell (MFC).

MedRed

Medo

x

Ac-

CO2

H+

Ac-

Ac-

CO2

e-

e-

e-

CO2 H+

H+

H+

H+

O2

O2

H2O

H2O

e-

e-

e-

Anode Chamber

Cathode Chamber

Anode Cathode Ion

Exchange Membrane

MedRed

Medo

x

Ac-

CO2

H+

Ac-

Ac-

CO2

e-

e-

e-

CO2 H+

H+

H+

H+

O2

O2

H2O

H2O

e-

e-

e-

Anode Chamber

Cathode Chamber

MFC work at USW-led by Iano Premier


• Modularization and optimisation

• Moved from

• annular flow path to helical

• Batch to continuous

• ~6W/m3 to ~30W/m3 (projected)

Kim et al (2009), J.Power Sources;

Kim et al (2010), Bioresource Tech.;

Kim et al (2011), AMB;

Kim et al (2011), EES

Michie et al (2011), EES

Michie et al (2011), AMB

Premier et al (2011), J. Power Sources

Guwy et al (2011), Bioresource Tech.

Kim et al (2012), J. Power Sources

Boghani et al (2013), J. Power Sources

Boghani et al (2013), Bioresource Tech.

Michie et al (2013), Wat, ci. And Tech.

Kaur et al (2013), Biosensors bioelectronics

Premier et al (2013), Renewable Energy

Fradler et al (2014), Biochemical Eng. J.

Fradler et al (In Press), Process biochemistry

Fradler et al (In Press), Water Research

Kaur et al (In press), Sensors and Actuators B

Monolithic carbon foam

electrode

•Increasing flowrate

•Not much mixing

•Shear does exist

Carbon fiber veil and former

•Increasing flowrate

•Better mixing with velocity

mW

Flowrate

3D arrow plots showing fluid particle velocities (with arrows showing velocity field direction and their tone indicates magnitude); zoomed in on helical flow path MMCC (a) – (c); and LVSF (a) – (c). Inlet velocities and flow rates:

(a, d) Vin = 1.67e-9 m3 s-1 [0.1 mL min-1], (b, e) 3.33e-8 m3 s-1 [2 mL min-1], (c, f) 1.25e-7 m3 s-1 [7.5 mL min-1].

Kim J.R., Boghani H.C., Amini N., Aguey-Zinsou K.-F., Michie I., Dinsdale R.M., Guwy A.J., Guo Z.X. and Premier G.C.,. Journal of Power Sources, 213, 382-390 (2012).

Anode Systems for Tubular Microbial Fuel Cells (MFC)

Current (mA)

0 5 10 15 20 25 30 35

Po

we

r (W

/m3)

4

6

8

10

12

14

16

18

20

22

MFC 1

MFC 2

MFC 3

MFC 4

Current (mA)

0 5 10 15 20 25 30 35

Po

we

r (W

/m3)

4

6

8

10

12

14

16

18

20

22

MFC 1

MFC 2

MFC 3

MFC 4

MFC 5

34 © University of South Wales

Scaled-up tube MFC

The scaled-up tube is shown in the photo.

Total size:

Length = 1.2 m

Diameter = 55 mm (external)

Empty bed volume = 1.42 L

Power from individual MFCs in the reactor > 5.7 mW and rising. Total power from the tube = 28.5 mW (20 W/m3).

Internal resistance of individual MFCs in the tube is around 10 Ω – 15 Ω.

Projected power from MFC 1 = 33.2 W/m3 at higher flow rate and from MFC 5 = 39.2 W/m3.

Flow rate = 3 mL/min; Temperature = 20 ± 2 °C; Feed = 10 mM acetate


Challenges for MECs

Low CE (substrate to electrons)

•Competing biological pathways-Methanogenesis

•Utilisation of both acetate & butyrate from dark biohydrogen

fermentation stage

•Maximise substrate availability to biofilm

Poor cathodic H2 efficiency (electrons to H2)

•H2 diffusion to anode (worse at low current densities)

•Efficient evolution of hydrogen from the cathode chamber

MEC 2

MEC 1

Acetate 20mM

Butyrate 20mM

Operated for 1 weeks in MEC mode

MEC 2

MEC 1

Acetate 10mM & Butyrate 10mM


Acetate mM & Butyrate 10mM

MEC 2

MEC 1 Acetate 5, 10,20 mM

Butyrate 5,10,20 mM



Enrichment Strategy-MEC Operational Parameters

MFC 2

MFC 1 Acetate 20 mM

Butyrate 20 mM

Operated for 9 weeks in MFC mode

Two 0.34L anode MEC cells operated for o 14 weeks at 30oC ,a 850 mv applied voltage across 1 ohm resistor

(to allow on-line monitoring of the cell potential difference) o The anode chamber was maintained at pH 6-7 and the cathode

chamber at pH 5.3.


Hydrogen Production from MEC Using Acetate and Butyrate

Acetate (ac) and butyrate (bu) concentrations (mML-1

)

20 10 5 10ac and 10bu 20(change)

Ga

s p

rod

uctio

n (

cm

3 L

-1day

-1)

0

50

100

150

200

250

300

Hydrogen production for MEC AC

Methane production for MEC AC

Hydrogen production for MEC BU

Methane production for MEC BU

MEC 1

MEC 2

New Biohydrogen Task approved by IEA-HIA ExCo

Subtask 1: Basic research on biohydrogen production

• Subtask 1.1: Biohydrogen production by dark fermentation and bioelectrolysis

• Subtask 1.2: Light-driven biohydrogen production

• Subtask 1.3: Enzymatic and bio-inspired molecular systems

Subtask 2: Applied research on biohydrogen production

• Subtask 2.1: Development and integration of biohydrogen fermentation systems for enhanced energy production

• Subtask 2.2: Feasibility of biohydrogen energy systems

• Subtask 2.3: Biohydrogen’s role in future sustainable communities

Proposal: The new task will run from 2014 to 2017 with a focus on two main subtasks that reflect current and planned R&D activities world wide

H Y D R O G E N I M P L E M E N T I N G A G R E E M E N T

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Acknowledgements Co-worke

Professor Richard Dinsdale

Professor Iano Premier

Dr Jaime Massanet-Nicolau

Dr Hitesh Bogani

Dr Iain Michie

Dr Jun Rae Kim

Rhys Jones

Arsensy Popov

Gary Shipley

41

ERDF H2 Wales project EPSRC SUPERGEN SHEC projects EP/H019480/1 and EP/E040071/1.

http://www.carbontrust.co.uk/

http://www.premierfoods.co.uk/

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