biomasa a partir de catálisis enzimáticas_mercedes ballesteros

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BIOFUELS FROM ENZYMATIC BIOFUELS FROM ENZYMATIC CATALYSTCATALYST

CATALYSIS FOR ENERGY: NEW CHALLENGES FOR A SUSTAINABLE CATALYSIS FOR ENERGY: NEW CHALLENGES FOR A SUSTAINABLE ENERGETIC DEVELOPMENTENERGETIC DEVELOPMENT

M. BallesterosHead of Biofuels Unit

CIEMAT

Santander, 19th august 2010

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They can be used pure or blending with fossil fuels

Bioethanol: sugars, starch, cellulose

Biodiesel: vegetable oils or animal fats

Biogas: Biomass

Biometanol: Biomass

Biodimetylether: Biomass

BioETBE and BioMTBE

Synthetic biofuels

Biohydrogen: a partir de biomasa

Pure Plant Oil

BIOFUELS

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BIODIESEL

- From vegetable oils - To be used in diesel engines

.

BIOETHANOL and its derivative (ETBE)

- From sugar-rich feedsotcks - To be used in Otto engines

MAIN BIOFUELS

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American Standard for Testing and Materials (ASTM):

a fuel comprised of mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal fats, designated B100, and meeting the requirements of ASTM D 6751 to be use for transport or heating

BIODIESEL DEFINITION

European Directive 2003/30/CE

Biodiesel is a methyl-ester produced from vegetable or animal oil, of diesel quality to be used as biofuel in internal combustion engines

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Vegetable oils

Used vegetable oils

Animal fats

Microalgae

FEEDSTOCKS FOR BIODIESEL PRODUCTION

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*BIODIESEL: mono-alkyl esters from fatty acids

Shorter molecules, linear chain, less carbono content Lower viscosity and characteristics similar to fossil diesel

*PURE PLANT OILS (PPO):

Large and branches molecules, high carbon content High viscosity

PPO VERSUS BIODIESEL

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OIL/FAT

TRANSESTERIFICATION

MIXING

SEPARATION

PURIFICATION

BIODIESEL

RAW BIODIESEL

CATALYST

ALCOHOL

RAW GLYCERINE

FATTYACIDS

ALCOHOL (50%)

GLYCERINE

PURIFICATION

BIODIESEL PRODUCTION

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catalyst

TG + 3 ROH G + 3 FAAE

Catalyst: Alkaline, acid, enzymaticTG: triglyceride, ROH: alcohol, G: glycerineFAAE: fatty acid alkyl esters.

TRANSESTERIFICATION

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• It can transform free fatty acids and use ethanol

•High purity product

• Easier downstream process

• High enzyme cost

• Inactivation during the process (methanol y glycerol)

Mucor miehei

Rhizopus oryzae

Candida antarctica

Pseudomonas cepacia

Lipasa extracelular

Lipasa intracelular

Immobilization

BIODIESEL FROM ENZYMATIC CATALYSIS (Lipases)

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Transesterification proccess depends on:

• Temperature• Reaction time• Molar ratio alcohol:vegetable oil, • Alcohol type• Catalyst concentratio• Mixing intensity• Free fatty acids• Moisture

Lipases

• Solvent type (alcohol low solubility and effect of glycerol on enzyme) • pH• Microorganisms• Free or immobilized

OPERATIONAL VARIABLES

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R ecep c ió n d e l m ate ria l

C A Ñ A D E A Z Ú C A RR E M O L A C H A

H id ró lis is en z im á tica

Tritu rac ió n


C E R E A L

H id ró lis is en z im á tica H id ró lis is á c id a

Tritu rac ió n


L IG N O C E L U L O S A

Fermentación

Destilación

ETANOL

ETHANOL PRODUCTION PROCESSES

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STARCH CARBOHYDRATES COMPOSITION

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ETHANOL PRODUCTION PROCESS FROM GRAIN

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STARCH HYDROLYSIS

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Source: Medium Term Oil Market Report, OECD/IEA, Paris (2009)

BIOFUELS: An expanding industry

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Directive 2009/28:

20% TOTAL ENERGY MUST BE RENEWABLE 10% OF TRNSPORT ENERGY

THE EUROPEAN OBJECTIVETHE EUROPEAN OBJECTIVE

No areas with high biodiversity

No areas with high carbon stocks

Primary forests and wooded land

Protected natural areas

Highly biodiversity land (grassland and non-grassland)

Cont. forested areas (trees higher 5m)

Peatland / wetlands

Minimum GHG savings

35% by 2009/201350% by 201760% after 2017

Only direct land use change consideredOnly if it affects carbon

stocks

Reference date: January 2008

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First generation

Second generation

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Advantages Better energy balance Reductions in:

• Greenhouse gas emissions• Land use requirements

No competition with food, fiber and water

Barriers High cost of production Logistics and supply Industry & consumer

acceptance Perceived risky investments

THE EUROPEAN OBJECTIVETHE EUROPEAN OBJECTIVE

10% replacement by 2020

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CONVERSION PATHWAYSCONVERSION PATHWAYS

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STATUS OF BIOFUELS TECHNOLOGIESSTATUS OF BIOFUELS TECHNOLOGIES

Source: DG-TREN

21O-acetil - galactoglucomanano

THE REAL HEADACHE FOR DEVELOPING BIOFUELSTHE REAL HEADACHE FOR DEVELOPING BIOFUELS

The contrast between what we have (carbohydrates) and

what we want (oxygen-deficient fuels)

O-acethyl- 4- O- methylglucuronoxylan

arabin- 4- O- methylglucuronoxylan

glucomanan

Carbohydrates are large polymer chains containing C5 and C5 sugars and a similar number of oxygen atoms

Optimal fuel molecules for automobile engines must be small (5-15 carbons) and contain little oxygen

The challenge is finding a way of breaking down carbohydrates to form small molecules, while simultaneously removing the oxygen and minimizing the loss of energy value of original biomass

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COMPOSITION OF LIGNOCELLULOSIC BIOMASSCOMPOSITION OF LIGNOCELLULOSIC BIOMASS

Source: DOE Genomics: GTL, 2008

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COMPOSITION OF LIGNOCELLULOSIC BIOMASSCOMPOSITION OF LIGNOCELLULOSIC BIOMASS

Feedstock

Cellulose (%)

Hemicellulose

(%)

Lignin (%)

Extractives

(%)

Ash (%)

Corn stover

36.4 22.6Xylose 18Arabinose 3Galactose 1Mannose 0.6

16.6 7.3 9.7

Wheat straw

38.2 24.7Xylose 21.1Arabinose 2.5Galactose 0.7Mannose 0.3

23.4 13 10.3

Hardwood

43.3 31.8Xylose 27.8Mannose 1.4

24.4 ---- 0.5

Softwood 40.4 31.4Xylose 8.9Mannose 22.2

28.0 --- 0.5

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ETHANOL PRODUCTION BY ENZYMATIC HYDROLYSIS

Lignocellulosicbiomass

Pretreatment Product recovery

ETHANOL

Enzymatichydrolysis

Cellulase complex

Fermentation

Fermenting microorganism

Xylose Fermentation

Heat and electricity production

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BIOMASS PRETREATMENTBIOMASS PRETREATMENT

Pretreatment

Cellulose

HemicelluloseLignin

CHARACTERISTICS: • Versatile

• Avoid expensive biomass . comminuting

• Use low cost chemicals

• Have low energy and capital cost . . requirements

• High hexose and pentose sugars . . yield

• Low inhibitors production

• Facilitate the recovery of lignin

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Biological, Physical, Chemical, Combination

Pretreatment Advantages Disadvantages

Dilute acid Hemicelluloses solubilization Enhances cellulose accessibility

High capital costsSugar degradationNeutralization

Concentrated acid

Lower temperatureReduction of degradation compounds

ExpensiveRequires acid recovery

Steam explosion Well knownPartial hemicellulose solubilization

Low pentose recoveryRequires washing to remove inhibitors

AFEX Rupture of lignin-hemicellulose bondsLow degraded products

High capital costs due to need to recycle the ammonia

BIOMASS PRETREATMENT CLASIFICATIONBIOMASS PRETREATMENT CLASIFICATION

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Treatment of biomass with steam at high temperature (180-220ºC), followed by explosive decompression.

STEAM EXPLOSION PRETREATMENT STEAM EXPLOSION PRETREATMENT

Extractives(%)

Cellulose(%)

Hemicellulose(%)

Lignin

(%)

Ash(%)

Straw 12 37 26 17 8

Pretreated

WIS --- 60 6 31 3

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ENZYMATIC HYDROLYSISENZYMATIC HYDROLYSIS

EnzymaticHydrolysis

RATE LIMITING FACTORS

SUBSTRATE STRUCTURE

Crystallinity of cellulose Low substrate surface area Lignin blocking reactive sites

ENZYMES

End-product inhibition Enzyme inactivation Non-specific binding

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• Endoglucanases• Cellobiohydrola

ses• β- glucosidases

Bacterial cellulosome

Cellulases secreted by fungi

CELLULASE COMPLEXCELLULASE COMPLEX

30Fuente: Novozymes, 2005

Enzimas accesorias:- xylanasas- pectinasas- beta-glucosidasa- extensinas

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AMORPHOGENESISAMORPHOGENESIS

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TECHNOLOGY CHALLENGES FOR BIOCHEMICAL ROUTETECHNOLOGY CHALLENGES FOR BIOCHEMICAL ROUTE

NEW AND/OR IMPROVED ENZYMESNEW AND/OR IMPROVED ENZYMES

• To reduce the costs of enzyme production by improving cellulase production and enzymatic cocktail efficiency

• To find the way for reducing enzyme loading without loss of performance

• To develop enzymes with improved thermo-stability and less susceptibility to sugars inhibition

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TECHNOLOGY CHALLENGES FOR BIOCHEMICAL ROUTETECHNOLOGY CHALLENGES FOR BIOCHEMICAL ROUTE

NEW AND/OR IMPROVED ENZYMESNEW AND/OR IMPROVED ENZYMES

• To reduce the costs of enzyme production by improving cellulase production and enzymatic cocktail efficiency

• To find the way for reducing enzyme loading without loss of performance

• To develop enzymes with improved thermo-stability and less susceptibility to sugars inhibition

TO MAXIMIZE THE CONVERSION OF CELLULOSE TO SUGAR

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Saccharomyces cerevisiae EthanolGlucose

Mannose

Galactose

Xylose

Arabinose

ETHANOL PRODUCTIONETHANOL PRODUCTION

THEORETICAL YIELD• 0. 51 g ethanol / g sugar

1 ton wheat straw• 400 kg hexoses → 200 kg

etanol• 200 kg pentoses → 100 kg

etanol

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Acid hydrolysis

Enzyme production

1950

1970

Enzyme production

Enzymeproduction

Enzyme productionEnzymatic hydrolysisGlucose to ethanolHemicellulosic sugars to ethanoll

Glucose to ethanol No hemicelulose utilization

Enzymatic hydrolysis

Glucose to ethanol

Enzymatic hydrolysisGlucose to ethanolHemicellulosic sugars to ethanol

No hemicellulose utilization

Enzymatic hydrolysisGlucose to ethanol

Today

No hemicellulose utilization 1980

Tomorrow

ADVANCES IN RESEARCH

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• More efficient pretreatment technologies• Increase the efficiency of enzymatic

hydrolysis• Low enzyme and inoculum concentration • Fermentation of pentoses on real

substrates• Reduce energy demand in the

production process• Low concentration of product (ethanol)

IMPROVEMENTS IN THE PRESENT TECHNOLOLOGY

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OPERATOR LOCATION ETHANOL CAPACITY

SCALE STATUS

Abengoa Bioenergy

Salamanca, Spain 4000 t/yr DemoOperational, start-up 2009

BioGasol Bornholm, Denmark 4000 t/yr Demo Planned

DTU, BioGasol Copenhagen, Denmark 10 t/yr Pilot Operational, start-up 2006

SEKAB Örnsköldsvik, Sweden

100 t/yr4500 t/yr50,000 t/yr120,000 t/yr

PilotDemoDemoComm.

Operational, start-up 2004Planned, start-up 2011Planned, start-up 2014Planned, start-up 2016

Inbicon, DONG

Energy

Fredericia, DenmarkFredericia, DenmarkKalundborg, Denmark

110 t/yr1100 t/yr4,500 t/yr

PilotPilotDemo

Operational, start-up 2003Operational, start-up 2004Inauguration 2009

Procethol 2G,

FuturolPomacle, France

140 t/yr

2840 t/yr

Pilot

Demo

Under construction, start up 2010Planned

Süd-Chemie Münich, Germany 2 t/yr Pilot Operational, start-up 2009

Second generation bioethanol, pilot, demonstration and projectedcommercial plants in Europe.

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SCALE STATUS

Abengoa Bioenergy





100 t/yr4500 t/yr50,000 t/yr120,000 t/yr

PilotDemoDemoComm.


Inbicon, DONG

Energy


110 t/yr1100 t/yr4,500 t/yr

PilotPilotDemo


Procethol 2G,


140 t/yr

2840 t/yr

Pilot

Demo




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SCALE STATUS

Abengoa Bioenergy





100 t/yr4500 t/yr50,000 t/yr120,000 t/yr

PilotDemoDemoComm.


Inbicon, DONG

Energy


110 t/yr1100 t/yr4,500 t/yr

PilotPilotDemo


Procethol 2G,


140 t/yr

2840 t/yr

Pilot

Demo




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REDUCCIÓN DEL COSTE DEL ETANOL CELULÓSICO

Source: NREL

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• Ethanol from lignocellulose is close to commercialization

• Technological advances to reduce the costs of ethanol production of the bioetanol are still needed.

• Basic and applied research, technological development and demonstration projects must carried in a coordinated way

CONCLUDING REMARKS

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¡¡¡Thank you for your attention¡¡¡

[email protected]

biomasa a partir de catálisis enzimáticas_mercedes ballesteros

Technology

cellulose biodiesel

ce biodiesel

developing biofuels

high biodiversity

enzymatic catalyst catalysis

animal oil

biomass bioetbe

expensive biomass