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Dr. Jhuma Sadhukhan
FIChemE, CEng, CSci
115/11/2015
Dr. Elias Martinez-Hernandez University of Oxford
Diseño e Integración de procesospara biorrefinerias competitivas
15/11/2015 2
Biorefinery research - promoting international collaboration for innovative and sustainable solutions, Instituto Mexicano del Petróleo, Mexico City, Mexico, 18-22 May 2015, British Council / CONACyT funded Researcher Links Workshop
Agricultural and forestry residues and energy crops: wood, short rotation coppice, poplar, switchgrass and miscanthus.
Grass: leaves, green plant materials, grass silage, empty fruit bunch, immature cereals.
Oily crops and Jatropha.
Oily residues: waste cooking oils and animal fat.
Aquatic: algae and seaweed.
Organic residues: municipal waste, manure, and sewage.
15/11/2015 3
Biomass
15/11/2015 4
15/11/2015 5
Mexican Agricultural Residues
50km radius
Valdez Vazquez, I., J. A. Acevedo Benítez y C. Hernández Santiago. (2010) Distribution and potential
of bioenergy resources from agricultural activities in México. Renewable & Sustainable Energy
Reviews. 14(7): 2147-2153 p
• Crop diversity• “Large enough” amounts• Dispersed along vast territory• Difficult topography• Global prices (equipment, resources, logistics)
Crop PCRI Prodton10^6
/year
Res prod
ton10^3/day
Wheat 1.5 3.4 13.9
Corn 1.5 21.9 90
Sorghum 1.5 5.5 22.6
Sugarcane 0.15 50.6 20.7
CoffeeCherry(pulp)
0.24 1.5 1.0
Agave (bagasse)
0.12 1.2 0.4
Mexico biomass Sugarcane bagasse
Corn stover
Sawdust
Municipal solid waste (MSW)
Agave and tequila industry residues
Newton Research Collaboration Programme Grant of theRAEng “Economic Value Generation and Social Welfare inMexico by Waste Biorefining” by Sadhukhan is about tostart to investigate the following integrated schemesfurther – in collaboration between INIFAP, IMP, Surrey,Imperial College and Oxford.
Colaboración con Dr Jorge en Jatropha
8
Wild materials with high Oil content in 13 genotypes of J. curcas
Mainly fatty acids in J. curcas oil
%
Differences found in the
percentages of oleic and
linoleic acid according to
the origin of the seeds
Value chain creation around “piñon mexicano” (Jatropha curcas L.) – Tabasco case study, Dr Jorge Martinez-Herrera, UK-Mexico Biorefinery Research Workshop: Promoting International Collaboration for Innovative and Sustainable Solutions 18-22 May, 2015 at the Instituto Mexicano del Petróleo (IMP), in Mexico City, Mexico.
Foto: Dr. Odilón Sánchez
Use Traditional from Mexican piñón
Usado en el Totonacapan para preparar comida tradicional
Value chain creation around “piñon mexicano” (Jatropha curcas L.) – Tabasco case study, Dr Jorge Martinez-Herrera, UK-Mexico Biorefinery Research Workshop: Promoting International Collaboration for Innovative and Sustainable Solutions 18-22 May, 2015 at the Instituto Mexicano del Petróleo (IMP), in Mexico City, Mexico.
1 kg Semilla (seed)
39.1 % cascarilla 60.9 % almendra
YIELDS SEED
Value chain creation around “piñon mexicano” (Jatropha curcas L.) – Tabasco case study, Dr Jorge Martinez-Herrera, UK-Mexico Biorefinery Research Workshop: Promoting International Collaboration for Innovative and Sustainable Solutions 18-22 May, 2015 at the Instituto Mexicano del Petróleo (IMP), in Mexico City, Mexico.
1 kg Harina (flour)
42.8% Harina desgrasada 57.2% Aceite (Oil)
YIELDS
Value chain creation around “piñon mexicano” (Jatropha curcas L.) – Tabasco case study, Dr Jorge Martinez-Herrera, UK-Mexico Biorefinery Research Workshop: Promoting International Collaboration for Innovative and Sustainable Solutions 18-22 May, 2015 at the Instituto Mexicano del Petróleo (IMP), in Mexico City, Mexico.
15/11/2015 12
INIFAP My team
Biomass yield, characteristics
Integrated process schematics, economic
feasibility, environmental profile
15/11/2015 13
The three most important economic terms for economic comparisons between systems
15/11/2015 14
Economic Margin = Value of products – Operating cost – Capital cost
Netback (when feedstock cost is unknown) = Value of products – Operating cost w/o Cost of feedstock –Capital cost
Cost of production = Operating cost + Capital cost
Apply any of the above terms to all the life cycle stages to evaluate Life Cycle Costing (LCC) of the value chain
15/11/2015 15
COST
TIME VALUE OF MONEY
ANNUALISED CAPITAL COST
DIRECT COST OF EQUIPMENT ×ANNUALISED CAPITAL CHARGE
R
1
2
size1
size2
SIZE
SIZE
COST
COST
UPDATE WITH PLANT INDEX AND INSTALLATION FACTOR
INDIRECT CAPITAL COST
OPERATING COST
FIXED
OTHERS: R&D
VARIABLEFEEDSTOCK, UTILITY AND
ENERGY COSTS
How process integration helps in reducing costs?
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Increase resource efficiency
Heat integration, energy integration
Mass integration
High value productions
Waste and residue reduction
15/11/2015 17
p4 : Husk O 6 379831
α 0.0522 Fresh methanol Mehanol recovered
F 91.4 F 11.5 F 27.2 α 0.877 p1 : Biodiesel
VOP 50.0 Cost 372.1 Cost 372.1 F 105.3 F 100
COP 46.0 VOP 637.3 VOP 674.8
Δe 4.0 COP 592.6 COP 627.7
O 2 3863505 Δe 44.7 Δe 47.1
f1 : Seeds α 0.9478 α 0.8079
F 271.2 F 179.8 F 104.7 F 143.5 F 116.2 Oily waste
VOP 322.2 VOP 461.9 VOP 670.8 VOP 595.1 VOP 658.0 F 5.3
COP 296.3 COP 424.9 COP 619.5 COP 557.6 COP 611.8 Treatment cost 0.390
Δe 25.9 O 1 248166 Δe 37.0 Δe 51.3 O 3 5014209 Δe 37.5 O 4 1243239 Δe 46.2 O 5 49160
O 3 ' 15144819 O 4 ' -8887372
p3 : Cake p2 : Glycerol
α 0.1921 α 0.123
F 75.1 F 10.7
VOP 222.2 VOP 881.8
COP 205.2 COP 819.9
Δe 17.0 Δe 61.9
2
Oil extraction
3
Transesterification
4
Methanol recovery
5
Decantation
6
Biodiesel distillation
1
Dehusking
Mass flow rates (F) in kt year-1, VOP, COP and economic margins (∆𝒆) in $ t-1 along with allocation factors (𝜶) of the streams in a Jatropha-based biorefinery.
The methodology comes from Sadhukhan’s thesis
15/11/2015 18
The value analysis methodology is then applied to generate environmental profilesof individual products: called EVEI: Economic Value and Environmental ImpactAnalysisMartinez-Hernandez, E., Martinez-Herrera, J., Campbell, G. M., & Sadhukhan, J.(2014). Process integration, energy and GHG emission analyses of Jatropha-basedbiorefinery systems. Biomass Conversion and Biorefinery, 4(2), 105-124.
Gas and CHP
Biofuel
Chemicals, hydrogen
Polymers
Composites
Food, pharmaceutical
High value, low volume, challenging to find market
Low value, high volume, easy to find market
15/11/2015 19
Bioethanol plant configuration
Wan, Y.K., Sadhukhan, J., and Ng, D.K.S. (2015) Techno-economic evaluations for feasibility of sago biorefineries, Part 2: Integrated bioethanol production and energy systems. Chemical Engineering Research & Design, Special Issue on Biorefinery Value Chain Creation, In press.
Combined Heat and Power (CHP) system configuration
Wan, Y.K., Sadhukhan, J., and Ng, D.K.S. (2015) Techno-economic evaluations for feasibility of sago biorefineries, Part 2: Integrated bioethanol production and energy systems. Chemical Engineering Research & Design, Special Issue on Biorefinery Value Chain Creation, In press.
AD plant configuration
Wan, Y.K., Sadhukhan, J., and Ng, D.K.S. (2015) Techno-economic evaluations for feasibility of sago biorefineries, Part 2: Integrated bioethanol production and energy systems. Chemical Engineering Research & Design, Special Issue on Biorefinery Value Chain Creation, In press.
Circular economy
15/11/2015 23
LCA
SLCALCC
X
BIOETHANOL PLANT
AD PLANT
CHP PLANT
BIOMASS
NUTRIENT
BIOFUELBIOENERGY
BIOCHEMICALBIOMATERIAL
Conversion rate for pre-treatment, enzymatic hydrolysis and fermentation processes (NREL/TP-5100-47764)
Pre-treatment Enzymatic Hydrolysis Fermentation
Conversion Rate (%) Conversion Rate (%) Conversion Rate (%)
Cellulose to Glucolig 0.3 Cellulose to Glucolig 4.0 Glucose to Ethanol 95.0
Cellulose to Cellobiose 0.0 Cellulose to Cellobiose 1.2 Glucose to Zymo (cell mass) 2.0
Cellulose to Glucose 9.9 Cellulose to Glucose 90.0 Glucose to Glycerol 0.4
Cellulose to HMF 0.3 Cellobiose to Glucose 100.0 Glucose to Succinic Acid 0.6
Xylan to Oligomer 2.4 Glucose to Acetic Acid 0.0
Xylan to Xylan 90.0 Glucose to Lactic Acid 0.0
Xylan to Furfural 5.0 Xylose to Ethanol 85.0
Xylan to Tar 0.0 Xylose to Zymo 1.9
Mannan to Oligomer 2.4 Xylose to Glycerol 0.3
Mannan to Mannose 90.0 Xylose to Xylitol 4.6
Mannan to HMF 5.0 Xylose to Succinic Acid 0.9
Galactan to Oligomer 2.4 Xylose to Acetic Acid 0.0
Galactan to Galactose 90.0 Xylose to Lactic Acid 0.0
Galactan to HMF 5.0 Arabinose to Ethanol 85.0
Arabinan to Oligomer 2.4 Arabinose to Zymo 1.9
Arabinan to Arabinose 90.0 Arabinose to Glycerol 0.3
Arabinan to Furfural 5.0 Arabinose to Succinic Acid 1.5
Arabinan to Tar 0.0
Acetate to Oligomer 0.0
Acetate to Acetic Acid 100.0
Furfural to Tar 100.0
HMF to Tar 100.0
Lignin to soluble lignin 5.0
Biomass composition
15/11/2015 25
Composition (%, dry basis)
Starch
Fibre
Bark
Starch 73.7 52 -
Soluble dietary fibres 3.3 - -
Insoluble dietary fibers 4.0 - -
Cellulose - 16 23.1
Hemicellulose - 9.8 17.31
Lignin - 5.2 18
Moisture 16.1 15.6
2.76
Acetate - 1.4
38.83
Ash 0.2 - -
Protein 2.4 - -
Lipids 0.3 - -
Product yields
Starch Fibre Bark Fibre + Bark
Feed Amount (ton/d , dry basis) 12 6.458 10.202 16.660
Produced ethanol (ton/d) 4.171 2.008 2.745 4.750
Yield 0.35 0.31 0.27 0.28
Generated Lignin to CHP system (ton/d) 6.338 3.220 4.136 7.647
Generated biogas (ton/d) 3.718 1.856 2.444 4.398
Generated energy (kW) 1303 657 852 1559
Total generated VHP steam (kg/s) 0.41 0.22 0.29 0.53
Required LP steam (kg/s) 0.18 0.09 0.12 0.22
Required HP steam (kg/s) 0.04 0.02 0.04 0.06
Generated Electricity (kW) 217 116.63 136.4 252
Electricity consumption (kW) 156.43 84.18 133.00 217.19
- Ethanol Production 95.84 51.57 81.48 133.06
- WWTP 42.44 22.84 36.08 58.92
- Storage and Utilities 18.15 9.77 15.44 25.21
Electricity to grid (kW) 60.56 32.44 3.40 35.30
Required make up water / ethanol
produced (ton/ton.d) 4.50
4.34
5.97
4.60
Economics
Produce Enzyme On-site
Raw material Fibre + Bark
Scenario c/w Labour w/o Labour
Total capital cost (million $) 6.929 6.929
Feedstock handling (million $) 0.580 0.580
Pre-treatment (million $) 1.310 1.310
Hydrolysis and fermentation (million $) 0.733 0.733
Cellulase enzyme production (million $) 0.021 0.021
Ethanol recovery (distillation) (million $) 0.769 0.769
WWTP (million $) 1.412 1.412
Storage System (million $) 0.230 0.230
Utilities system (million $) 0.368 0.368
CHP system (million $) 1.506 1.506
Total Operating Cost (million $/year) 0.601 0.122
Revenue (million $/year) 1.175 1.175
Profit (million $/year) 0.574 1.053
Payback Period (year) 12.06 6.58
28
Lignocellulose (e.g. straw, wood, etc.)
Size reductionSteam
pretreatment(solid state)
FermentationDistillation, dehydration
Ethanol
Enzyme production
Yeast propagation
Fractionation e.g. modified pulping /
organosolv, acid hydrolysis, etc.
Lignin platform
C6, C5 platform
Solid / liquid separation of
stillage
Combustion
Solid
Air cathode in MFC: WaterOr, Anaerobic cathode in MEC: HydrogenOr, Anaerobic biocathode in MEC: Biofuel
(glutamate, propionate, butanol, etc.)
Energy
Electricity generated in MFCOrVoltage applied in MEC
Bioanode:Glu CO2 / Acetate + 24H+ + 24e-
e- e-
H+
CO2 / Acetate / H2
21
1
Liquid
15/11/2015
Integrated flowsheet example (1)
Reference: Sadhukhan, J.,Lloyd, J., Scott, K., Premier,G.C., Yu, E., Curtis, T., and Head,I. (2015). A Critical Review ofIntegration Analysis ofMicrobial Electrosynthesis(MES) Systems with WasteBiorefineries for theProduction of Biofuel andChemical from Reuse of CO2.Renewable & Sustainable EnergyReviews, Submitted.
29
Oily residues
Sulphuric acid and methanol
Dilute acid esterification
TransesterificationMethanol Waste oil
Glycerol refining
Biodiesel refining
Glycerol Biodiesel
Stillage Electricity generated in MFCOrVoltage applied in MEC
Bioanode:Glycerol Ethanol + CO2 + 2H+ + 2e-
Ethanol
e- e-
H+
Air cathode in MFC: WaterOr, Anaerobic cathode in MEC: HydrogenOr, Anaerobic biocathode in MEC: Biofuel or Chemical
Substrate for biocathode shown in Figure 1
15/11/2015
Integrated flowsheet example (2)
Reference: Sadhukhan, J., Lloyd, J., Scott, K.,Premier, G.C., Yu, E., Curtis, T., and Head, I. (2015).A Critical Review of Integration Analysis ofMicrobial Electrosynthesis (MES) Systems withWaste Biorefineries for the Production of Biofueland Chemical from Reuse of CO2. Renewable &Sustainable Energy Reviews, Submitted.
ANODE
CATHODE
Anode substrate: Organic waste/ wastewaters / lignocellulosic wastes and their hydrolysates/stillage from biodiesel and bioethanol plants / glycerol from biodiesel plant
H2 and CO2 / carbonic acid / pyruvate / formate / fatty acids
e-e-
External Voltage Supply
H+
H+
Bio
ele
ctro
che
mic
al
ox
idat
ion
Cat
alyt
ic e
lect
ro-h
ydro
ge
nat
ion
, h
ydro
de
ox
yge
nat
ion
re
du
ctio
n
reac
tio
ns
CO2 reuse in Chemical / Bioplastic / Biofuel production
Biofuel / Bioplastic / Chemical
Cathode substrates 1: Anode Effluents (pyruvate / organic acids)
Gaseous products (e.g. hydrogen, methane)
H+
H+
H+
H+
H+
H+
H+
H+
H+
H+
Cathode substrates 2: Other Wastes (Wastewaters / hydroxy acids, glucose, etc. from lignocellulose wastes
PR
OT
ON
EX
CH
AN
GE
ME
MB
RA
NE
Reference: Sadhukhan, J., Lloyd, J., Scott, K., Premier, G.C., Yu, E., Curtis, T., and Head, I. (2015). A Critical Reviewof Integration Analysis of Microbial Electrosynthesis (MES) Systems with Waste Biorefineries for the Productionof Biofuel and Chemical from Reuse of CO2. Renewable & Sustainable Energy Reviews, Submitted.
Reference: Sadhukhan, J., Lloyd, J., Scott, K., Premier, G.C., Yu, E., Curtis, T., and Head, I. (2015). A Critical Reviewof Integration Analysis of Microbial Electrosynthesis (MES) Systems with Waste Biorefineries for the Productionof Biofuel and Chemical from Reuse of CO2. Renewable & Sustainable Energy Reviews, Submitted.
Anode substrate: Organic waste/ wastewaters
H2 and CO2 / carbonic acid / pyruvate / formate / fatty acids
e- e-
External voltage applied
H+
An
od
e c
ham
be
r:
Bio
ele
ctro
che
mic
al
ox
idat
ion
Cat
ho
de
ch
amb
er:
𝑴++𝒆−→𝑴
CO2 reuse in reactions
MetalBiofuel or Chemical or Polymer (Optional)
Gaseous products (e.g. hydrogen, methane)
Cathode substrate: Wastewaters containing metal contaminants
PR
OT
ON
EX
CH
AN
GE
ME
MB
RA
NE
H+
Proton exchange membrane (optional)
CxHyOz + (2x-z)H2O →(y+4x-2z)H+ + xCO2 + (y+4x-2z) e-
BES performance in CO2 reduction and bulk recovery
Database created for decision making software 63 anodic and 72 cathodic reactions of metabolism and 9
metabolic pathways have been collated for assessing technical feasibility based on thermodynamic spontaneity of resource recovery from waste substrates and combinations of anodic and cathodic reactions using MES
The database (spreadsheet) as supplementary information available with: Sadhukhan, J., Lloyd, J., Scott, K., Premier, G.C., Yu, E., Curtis, T., and Head, I. (2015). A Critical Review of Integration Analysis of Microbial Electrosynthesis (MES) Systems with Waste Biorefineries for the Production of Biofuel and Chemical from Reuse of CO2. Renewable & Sustainable Energy Reviews, Submitted.
15/11/2015 33
15/11/2015 34
Analysis method
3515/11/2015
LCA
SLCALCC
X
Life Cycle Sustainability Assessment (LCSA) combines Life Cycle Assessment (LCA)
Life Cycle Costing (LCC)social Life Cycle Assessment (sLCA)
Strategy for bioproduct and bioprocess development from ideas to market: Utilisation of predictive power
15/11/2015 36
Societal needs and market
demands for products
Availability of waste
resources and infrastructures
Health, environment
and job creation
Policy incentives
Project definition: Characterise waste
substrates and identify pathways to products
Identify appropriate gut communities
responsible for rapid rates of microbial
bioconversion in nature
Hypothesise metabolic pathways; Metabolic
flux analysis for targeting products
thermodynamic optimisationEconomics
Design options and regions for
operability
Process Integration and
flowsheet synthesis, industrial symbiosis
Process simulation and dynamics
Control experimentation
Economics and sustainability
Piloting, demonstration and
fully operational symbiotically
integrated process plant
15/11/2015 37
Surrey’s strategy to resource recovery from waste streams
• Waste flows and characteristics: Environmental Data Centre on Waste, EUROSTAT; DEFRA’s database on UK’s waste for each county; biomass data from INIFAP
• Waste prevention: Apply Process Integration and Intensification and Green Chemistry Principles and ‘plug-and-play’ technologies
• Resource Recovery: Metals and minerals• Resource Recovery: Biofuels, chemicals, nutrients and fibre• Product logistics• Apply LCA, LCC and SLCA to the same system boundary to maximise
the benefits of trade-off analyses and select the best integrated design
15/11/2015 38
15/11/2015 39
Building block C No. NREL BREW Building block C No. NREL BREW
Syngas (H2 + CO) C1 Aspartic acid C4
Ethanol C2 Arabinitol C5 Acetic acid C2 Furfural C5 Lactic acid C3 Glutamic acid C5 Glycerol C3 Itaconic acid C5 Malonic acid C3 Levulonic acid C5 Serine C3 Xylitol C5 Propionic acid C3 Xylonic acid C5 3-Hydroxypropionic acid C3 Glucaric and Gluconic acid C6 1,3-propanediol C3 1-butanol C6
Acrylic acid C3 1,4-butanediol C6 Acrylamide C4 Sorbitol C6
Acetoin C4 Adipic acid C6
3-Hydroxybutryolactone C4 Citric acid C6
Malic acid C4 Caprolactam C6
Theonine C4 Lysine C6
Succinic acid C4 Fat and oil derivatives >C6
Fumaric acid C4 Polyhydroxyalkanoates (PHA) >C6
Oil refinery Biorefinery
Mature process technology (e.g. thermal and catalytic cracking, reforming, hydrotreatment)
Mature and innovative process technology (e.g. fractionation, pyrolysis, fermentation, anaerobic digestion, MBT and bioseparations)
Use of every crude oil fraction Use of every biomass fraction and components Process flexibility and product diversification
Process flexibility and product diversification
Co-production of valuable chemical building blocks
Co-production of valuable and highly functionalised chemical building blocks
Cogeneration of heat and power Cogeneration of heat and power Process integration Process integration and design for sustainability Economy of scale Scale according to biomass logistics but must be maximised
to benefit from economy of scale
15/11/2015 40
Publications/know-how reciprocal
Experimental analysis without global contexts and viability has little/no impactModelling analysis without experimental validation has little/no impactTeam cooperative papers are more cited and carry more credibility than individually written onesSurrey runs LCA module with hands-on experience in modelling with LCA software and LCC, SLCA and LCSA know-how
Acknowledgements:[email protected]@surrey.ac.ukNATURAL ENVIRONMENT RESEARCH COUNCIL, UK
4115/11/2015