Sadhukhan J.

Biomass conversion and biorefinery process R&D

Dr Jhuma Sadhukhan

Lecturer, CES, University of Surrey

Biorefinery developments

2005-2010

Co-processing with coal

Crop based biofuel

Lignocellulosic based CHP

Co-processing with coal and carbon capture and storage

2010-2015

Bio-oil based biorefinery Bio-composites

2015-2020

Advanced biorefinery producing energy, fuels, chemicals, polymers, food additives from wastes

2020-

Sources of biomass

• Wastewater sludge

• Municipal waste / refuse derived fuel (RDF, when dehydrated)

• Industrial waste

• Forestry waste

• Agricultural waste

• Energy crops: short rotation coppice, miscanthus, switchgrass, etc.

BIREFINERY products

Chemical Composite Polymer

Liquid transportation fuel

Hydrogen Gas

Biorefinery processes

• Bio-oil (from wood) platforms.

• Bio-composite (from algae) production.

• Green diesel generation.

• Sewage sludge anaerobic digestion leading to micro and distributed generations.

• Wood, RDF and straw gasification based CHP systems.

• Transesterification catalysts.

Wood is an important feedstock for bio-oil production

Bio-oil platforms

• 25 distributed pyrolysers; 8 gasifier trains and 1 methanol or FT synthesis reactors.

Local biomass

mechanical

processing

Distributed

pyrolysers

Centralised gasifier,

oxygen supply and gas

cooling and purification

Centralised methanol synthesis

Centralised Fischer-Tropsch

liquid synthesis

Centralised bio-oil

upgrader (hydrotreating

and hydrocracking)

Refinery

Chemical production

Pulp and paper

Process Unit Technology Developer Capacity for single unit

Gasifier Shell, GE, E-Gas, Koppers Totzek, Destec, Prenflo. up to 2000 t/d of coal

Cryogenic ASU Air Products, Universal Industrial Gases, etc. 90-820 t/d of oxygen

Methanol

synthesis reactor Lurgi, ICI, Air Products, etc. 5000 t/d of methanol

FT synthesis

reactor Shell (SMDS), Sasol (ARGE), etc.

~6000 bbl/d of FT

products

Hydrocracker UOP, Exxon, Shell, etc. 35 kbbl/d of feed

FT and methanol synthesis and CHP generation platforms have been established.

• Ng K.S. and Sadhukhan J. 2011. Techno-economic performance analysis of bio-oil based Fischer-Tropsch and CHP synthesis platform. Biomass & Bioenergy, 35(7), 3218-3234.

• Sadhukhan J. and Ng K.S. 2011. Economic and European Union environmental sustainability criteria assessment of bio-oil based biofuel systems: Refinery integration cases. Industrial & Engineering Chemistry Research, 50(11), 6794-6808. IF = 2.237.

• Ng K.S. and Sadhukhan J. 2011. Process integration and economic analysis of bio-oil platform for the production of methanol and combined heat and power. Biomass & Bioenergy, 35(3), 1153-1169.

Bio-oil refining – a novel concept

Bio-oil

Syngas or CHP to export

Bio-oil

Decanter

MIEC membrane reactor

Steam(can be used for

the reboilers)

Gas

De-butaniser

Naphtha splitter

Diesel separator

Gas to refinery

Gasoline to export

Naphtha to refinery diesel pool or hydrocrackerStable bio-oil

Reboilerdistillation column

Diesel to refinery diesel pool or hydrocracker

Diesel to refinery diesel pool or hydrocracker

A distributed pyrolyser

132 t/d LHV (MJ/kg) 23.3

Fixed C and volatiles (wt%) 70

Moisture (wt%) 30

C (wt%) 56

H (wt%) 7

O (wt%) 37

W = 0.15 MW

W = 1 MW (0.65 MW for recycle gas compression; 0.35 MW for feedstock size reduction)

N2 = 1280 t/d O2 = 340 t/d

H2O = 100 t/d

340 t/d On dry basis C (wt%) 50.93

H (wt%) 6.05

O (wt%) 41.93

N (wt%) 0.17

S (wt%) 0

Ash (wt%) 0.92

+ Quench water Ash = 2.4 t/d

Air

N2 = 1280 t/d

O2 = 340 t/d

CO2 = 84.6 t/d

H2O = 16.5 t/d

Biochar production

Biochar

The bio-oil hydrodeoxygenation and decarboxylation reactions are carried out using mixed ionic electronic conducting membrane reactor

H2O

O2-

2h+

H2

MIEC Oxygen selective

membrane

(at high temperature and pressure)

(at lower pressure)

Overall electrochemical reaction:

H2O → H2 + O2- + 2 protons

The MIEC membrane reactor

H2O

O2-

2h+

H2

MIEC Oxygen selective membrane

Catalytic partial oxidation

Syngas

Bio-oil

Hydroprocessingfor fuel or hydro-de-oxygenation for chemical production

Bio-oilBio-oil

H2O

H2

O2-

2h+

Biofuel or chemical

Gasoline meets product spec and diesel can be co-processed

CHEMICAL COMPONENTS GASOLINE DIESEL

N-HEPTANE 47.8 0.5

ISOBUTANE 2.4 0.0

2,5-XYLENOL 2.0 12.8

1-TRANS-3,5-TRIMETHYLCYCLOHEXANE 17.0 5.8

3,3,5-TRIMETHYLHEPTANE 4.2 2.8

N-PROPYLCYCLOHEXANE 9.7 6.9

1,2,3-TRIMETHYLBENZENE 0.7 1.0

N-BUTYLCYCLOHEXANE 0.2 0.4

1,2-DIMETHYL-3-ETHYLBENZENE 0.8 2.7

CIS-DECALIN 1.4 5.1

1-TRIDECENE 1.2 14.4

1,2,4-TRIETHYLBENZENE 0.7 5.3

BICYCLOHEXYL 0.0 0.5

DIPHENYL 0.3 7.3

DIAMANTANE 0.9 14.3

PHENANTHRENE 0.0 10.2

CHRYSENE 0.0 3.9

P-XYLENE 10.6 1.8

1-TRANS-3,5-TRIMETHYLCYCLOHEXANE 0.0 4.4

PROPERTY GASOLINE DIESEL Refinery hydrocracker feed

Flowrate, weight % of bio-oil 2.12 36.68

Specific gravity 0.737 0.873 0.87-0.97

API gravity 60.6 30.6 14-30

Volumetric average boiling point oC 115 225 200-450

Reid vapour pressure bar 1.1 0.1

Flash point oC -38 47 50-150

Aniline point oC 45 28 25-65

Cetane number oC 26 29 29-32

Bio-oil

Syngas or CHP to export

Bio-oil

Decanter

MIEC membrane reactor

Steam(can be used for

the reboilers)

Gas

De-butaniser

Naphtha splitter

Diesel separator

Gas to refinery

Gasoline to export

Naphtha to refinery diesel pool or hydrocrackerStable bio-oil

Reboilerdistillation column

Diesel to refinery diesel pool or hydrocracker

Diesel to refinery diesel pool or hydrocracker

Chemicals can be produced from bio-oil using MIEC membrane reactor

Guaiacol(C7H8O2)

Catechol(C6H6O)

Phenol(C6H6O)

Cyclohexanone(C6H12O)

Cyclohexanol(C6H10O)

Cyclohexene(C6H10)

Cyclohexane(C6H12)

Benzene(C6H6)

Anisole(C6H5(OCH3))

Cresol(C7H8O)

Toluene(C7H8)

O-Methylanisol(C8H8O)

2,6 Xylenol(C8H10O)

Benzofuran(C8H6O)

Dihydrobenzofuran(C8H8O)

2-Ethylphenol(C8H10O)

Ethylbenzene(C8H10)

Ethylcyclyhexane(C8H16)

Methylcyclyhexane(C7H14)

Ethylcyclyhexene(C8H14)

Novel contributions

• Reaction mechanistic studies of bio-oil hydrotreating and hydrocracking to control product properties from co-processing

• Membrane based multi-functional reactors used to increase efficiency

0.01

0.10

1.00

10.00

100.00

1000.00

10000.00

0.10 0.20 0.30 0.40 0.60

% of biofuel blending

kg

/t o

f h

yd

rocra

cker

feed

Carbon dioxideemission saving

Crude oil saving

Diesel yield loss

Gasoline yieldloss

Land use,hector/ ton ofbio-oil

Hectare/t bio-oil

Bio-composite production: green building – A bioreactor?

Reference: Arup

Application of algal photobioreactor in built environment

• Algal PBR is an important mechanism to convert solar heat into space heating or geothermally storing heat.

• The PBR can produce bio-gas for gas grid and community generations.

• The PBR can also be used for biodiesel production

Epoxy Resin (ER) plant chemical and energy requirements

Oil extraction Epoxidation Curing Epoxy resin

Soya paste

or Algae paste

Hexane to feedstock

weight ratio to be

maintained at 10-14.4

(soya oil and algal oil

respectively)

Only 4% of hexane is

consumed.

Steam: 0.46 times the

weight of feedstock

Electricity: 1.3 MJ times

the weight of feedstock

Formic acid: 0.224

times the weight of

oil

Hydrogen peroxide

(50% by weight):

0.635 times the

weight of oil

Phthalic anhydride

4.75 and 4.35 times

the weight of soya

and algal oils,

respectively

Triethanolamine

0.02 times the

weight of oil

Extracted oil Epoxidised oil

ER plant yields

Soya paste

362 kg

> Soya oil

175 kg

> Epoxidised oil

175 kg

> Epoxy resin

1000 kg

Algae paste

435 kg

> Algal oil

188 kg

> Epoxidised oil

188 kg

> Epoxy resin

1000 kg

Comparison of avoided emissions between soya and algal based epoxy resin production plants

Soya based system provides greater avoided impact potentials.

Avoided impact Avoided impact Avoided impact

due to soya paste use due to algae paste use by algal system

Acidification potential kg SO2 equivalent 2.9336 0.6528 -2.2808

Eutrophication Potential kg phosphate equivalent 0.7191 2.6218 1.9027

Freshwater aquatic ecotoxicity potential kg DCB equivalent 35.69 4.10 -31.59

Global warming potential (GWP 100 years) kg CO2 equivalent 987.00 816.20 -170.80

Human toxicity potential kg DCB equivalent 167.09 21.08 -146.02

Marine aquatic ecotoxicity potential kg DCB equivalent 313678 22458.07 -291220.28

Photochemical ozone creation potential kg ethene equivalent 0.4345 0.0777 -0.3568

Terrestric ecotoxicity potential kg DCB equivalent 5.0546 0.4190 -4.6356

Abiotic depletion potential kg Sb equivalent 5.1542 0.6788 -4.4754

Land use impact of soya based system is greater, 1623.5 m2 compared to (145) m2 for algal system.

Reference

• Sadhukhan J., Martinez-Hernandez E. and Ng K.S. 2013. Biorefineries and chemical processes: Design, integration and sustainability analysis. Wiley-Blackwell, UK, First advanced level Engineering text book in the field in preparation.

Green diesel generation

Seed

processing

Biodiesel production

Anaerobic

digestion and

biogas-to-power

Green diesel

production

IBGCC-H2

Seeds

Biodiesel

Green diesel

Waste water

Oily Waste

Cake

Methanol

H2

Steam

Optional uses of Jatropha by-products

Utility integration

Oil

Jatropha cultivation

IBGCC-CH3OH

CO2

Flue gas

Flue gas

1

2

4

3

5

2

4

3

Glycerol

4

1 2 3

Ash,

Purge

Acid gas

Acid gas

Ash,

Purge

Shells

5

5

Net power

Net power

Heat and

Power

Heat

Power

Sludge

Husk

For animal

feed

As fuel

As fuel

As fertiliser

Net power

As fuel

Propane fuel mix

Biogas leakage

(2%)

Flue

gas

IBGCC: Integrated Biomass Gasification

and Combined Cycle

BIGCC system

CATHODE

SOFC

ANODE

Power

Superheater +

Direct quench

Steam

Air

Combined heat

and power

Waste heat

boiler

* Waste heat

into hot water

Waste water

treatment

Absorption based co-

capture

Interconnected

gasifier

Clean syngas BFW

Sludge to char

combustor Agricultural and

forestry residues

Char

Steam

gasifier

Hot gas

clean-up

Gas cooler / clean syngas

heater

Char

combustor

To SOFC

Air preheater

From air

preheater

Gas

Hot

syngas

*

Ash

Sewage sludge anaerobic digestion leading to micro and distributed generations

Primary settler

Waste water

Secondary

settler

Activated

sludge

aeration

Primary sludge

Activated sludge

Biogas

Digested matter

Water to river

or reserve

Gas grid

Agricultural application

Anaerobic

digestion

Clean-up,

Storage

Distributed, micro generationsCHP System boundary

for LCA

Biogas constituents t d-1

CH4 11.21CO2 10.9

Digested matter t d-1

C2.25H5.39N0.24Cl0.002O 46.44Sulphur recovered 0.64Ash 23.8Metals 48.96 kg d-1

Primary sludge t d-1

Fixed C 4.2Volatile C 18.3H 3.3O 15.0N 3.6S 0.6Ash 15.0

Activated sludge t d-1

Fixed C 4.8Volatile C 11.6H 2.2O 9.2N 3.2S 0.04Cl 0.16Ash 8.8

Cradle to grave systemAvoided emissions by

GWP, kg CO2-Eq.

AP, kg SO2-Eq.

POCP, kg Ethylene-Eq.

Biogas grid, per MJ 0.0793 4.47×10-5 6.59×10-6

Biogas – PEMFC, per MJ 0.1200 7.57×10-5 1.11×10-5

Biogas – SOFC, per MJ 0.0951 5.18×10-5 7.65×10-6

Biogas – SOFC-GT, per MJ 0.0916 4.59×10-5 7.20×10-6

Biogas – Micro GT, per MJ 0.0982 4.26×10-5 7.64×10-6

DM, per kg 0.44-0.77 0.01186 0.00093

Wood, RDF and straw (fluid bed) gasification based CHP systems (IGCC) Air separation

unit

Gasification

unit

Biomass pellet

/ chip slurry

Gas cooler

HT WGS

LT WGS

Gas condenser

Selexol GT

combustor

Air

compressor Expander

HRSG Exhaust

condenser

Ash

Dry exhaust gas

To ETP

To ETP

1

2 3 4 5 6 7

8

9 10

11

12 13

BFW return after purge

BFW return

after purge

VHP steam HP steam MP steam

Condensate / BFW return

BFW

BFW

BFW

Steam turbine: back pressure /

condensing turbine

Levelised Cost of Electricity (12-17 £ per MWh) : Wood > Straw > RDF Greenhouse gas emission reduction compared to natural gas (25 – 26 kg CO2 eq. / MJ) : Wood > Straw > RDF Land use transformation is 1897 m2 / PJ (straw); 970 m2 / PJ (wood). However, aquatic toxicities are more for wastes. Biomass > Water emission causing aquatic toxicity (Aquatic toxicity due to water emission: Nickel > Mercury > Cadmium > Copper > Arsenic) > More energy input for water purification > Some water would actually be depleted to an extent beyond recovery

References • Martinez-Hernandez, Elias; Ibrahim, Muhammad H.; Leach, Matthew; Sinclair, Phillip;

Campbell , Grant M.; Sadhukhan, Jhuma. Sustainability analysis of UK whole wheat bioethanol and CHP systems. Biomass and Bioenergy 2013, In Press.

• Martinez-Hernandez, Elias; Martinez-Herrera, Jorge; Campbell, Grant M.; Sadhukhan, Jhuma. Jatropha-based integrated biorefineries for efficient and sustainable biofuel production. Presented at the 1st Iberoamerican Congress on Biorefineries, 24 – 26 October, 2012. Los Cabos, Baja California, México. ISBN 978-607-441-200-0.

• Zhao Y., Sadhukhan J., Brandon N.P. and Shah N. 2011. Thermodynamic modelling and optimization analysis of coal syngas fuelled SOFC-GT hybrid systems. Journal of Power Sources, 196(22), 9516-9527.

• Ng K.S., Lopez Y., Campbell G.M. and Sadhukhan J. 2010. Heat integration and analysis of decarbonised IGCC sites. Chemical Engineering Research and Design, 88(2), 170-188. Winner of the IChemE Junior Moulton medal for the best publication by IChemE, 2011.

• Sadhukhan J., Zhao Y., Leach M., Brandon N.P. and Shah N., 2010. Energy integration and analysis of solid oxide fuel cell based micro-CHP and other renewable systems using biomass waste derived syngas. Industrial & Engineering Chemistry Research, 49(22), 11506-11516.

• Sadhukhan J., Zhao Y., Shah N. and Brandon N.P. 2010. Performance analysis of integrated biomass gasification fuel cell (BGFC) and biomass gasification combined cycle (BGCC) systems. Chemical Engineering Science, 65(6), 1942-1954.

• Sadhukhan J., Ng K.S., Shah, N. and Simons, H.J. 2009, Heat integration strategy for economic production of CHP from biomass waste. Energy & Fuels, 23 (10), 5106-5120.

Biodiesel catalysts: hydrotalcites

Catalyst composition

Nominal Mg:Al

ratio

Surface area

(m2/g)

Activity/mmolmin-

1.g(cat)

-1

Glyceryl

Tributyrate

Conversion %

Mg0.81Al 1:1 166.4±8.3 0.004 42.4

Mg1.38Al 2:1 121.9±6.1 0.01 49.2

Mg1.82Al 3:1 92.5±4.6 0.024 55.3

Mg2.93Al 4:1 104.1±5.2 0.025 74.8

Mg4.05Al 6:1 130.1±6.2 0.03 >97%

Biodiesel catalysts: Polystyrene beads and silica precursor

RSO3H-SBA-15-(6nm) MM-SBA15-1-(5nm) MM-SBA15-4-(4nm)

Ester (mmol) Ester (mmol) Ester (mmol)

0 0 0

0.7 0.1 0.7

0.5 0.26 0.9

0.8 0.45 1.6

1.1 0.97 2.7

1.7 2.1 4.3

2.3 3.37 5.5

9.2

k=0.6447 k=0.4791 k=1.4353

Palmitic acid esterification with MeOH (C16) Reaction

temperature=50C

y = 0.6447x

y = 0.4791x

y = 1.4353x

0

0.5

1

1.5

2

2.5

3

0 0.5 1 1.5 2

Est

er p

rod

. (m

mol)

Time (h)

Templating routes to prepare meso-structured oxides

N

H

H

NH

H

N

H H

NHH

N HHN HH

N

H

H

N

H

H

NH

H

NHH

N

H H

N

H

H

N

H

H

N

H

H

NH

H

N HH

Surfactantmicelle

Silicate-surfactant mesostructure

(EtO)4Si

Hexagonalarray

Templateextraction

MesostructuredSilica

Al or Si

alkoxide

Template

extraction

Mesoporous

Al2O3 or SiO2 Surfactant

Micelle

Liquid

crystal array

Templated

meso-structure

Routes to prepare mesoporous solid acids and bases.

References

• Thomas J. Davison , Chinedu Okoli , Karen Wilson , Adam F. Lee , Adam Harvey , Julia Woodford and Jhuma Sadhukhan. Multiscale modelling of heterogeneously catalysed transesterification reaction process: an overview. RSC Adv., 2013, DOI: 10.1039/C2RA23371A

• Kapil A., Lee A.F., Wilson K. and Sadhukhan J. 2011. Kinetic modelling studies of heterogeneously catalyzed biodiesel synthesis reactions. Industrial & Engineering Chemistry Research, Special Issue, 50(9), 4818-4830.

• Kapil A., Bhat S.A. and Sadhukhan J. 2010. Dynamic simulation of sorption enhanced simulated moving bed reaction processes for high purity biodiesel production. Industrial & Engineering Chemistry Research, 49(5), 2326-2335.

• Kapil A., Bhat S.A. and Sadhukhan J. 2008. Multi-scale characterisation framework for sorption enhanced reactions processes. AIChE J, 54(4), 1025-1036.

Acknowledgement

• EPSRC

• Industrial collaborators (Arup, Thames Water, NPL, MW Kellogg Ltd., BP, etc.)

• Academic colleagues

• Students