biomass conversion processes: biorefining strategies for a...

Biomass conversion processes:

biorefining strategies for a

sustainable bioeconomy

Luiz Pereira Ramos

Research Center in Applied Chemistry

Department of Chemistry

Federal University of Paraná (UFPR), Brazil

www.quimica.ufpr.br/paginas/luiz-ramos; [email protected]

Montevideo, 21 de agosto de 2018

Estimado Doctor Pereira Ramos

Es un gusto para nosotros, invitarlo al Congreso Internacional de Academias de Ingeniería, a

realizarse en Montevideo , entre el 10 y el 14 de setiembre (CAETS 2018) .

Dicho congreso que se realiza anualmente, este año tratara el tema de Bioeconomia y su desarrollo,

abarcando desde la producción forestal, bioproductos, madera como material de construcción, etc.

Adjuntamos programa actualizado al día de hoy.

Contamos con su presencia para desarrollar el tema de “Conversion processes, biorefineries

strategies for a sustainable bioeconomy” el dia 12/09.

En los días 13 y 14, se desarrollara con su participación , un taller en el Laboratorio Tecnológico del

Uruguay (Latu), actividad con investigadores locales y académicos presentes en el CAETS 2018.

Esperamos contar, asimismo con Ud, para el análisis de proyectos conjuntos con el Instituto de

Ingeniería Química de la Facultad de Ingeniería de la Universidad de la Republica.

La organización del evento , se encarga , como se acordó oportunamente , de la financiación de los

gastos incurridos por su participación .

Saludos cordiales,

Norberto Cassella

Prof. Agregado de Proyecto Industrial

Instituto de Ingeniería Química

Coordinador CAETS 2018

Montevideo, 21 de agosto de 2018

Estimado Doctor Pereira Ramos

Es un gusto para nosotros, invitarlo al Congreso Internacional de Academias de Ingeniería, a

realizarse en Montevideo , entre el 10 y el 14 de setiembre (CAETS 2018) .

Dicho congreso que se realiza anualmente, este año tratara el tema de Bioeconomia y su desarrollo,

abarcando desde la producción forestal, bioproductos, madera como material de construcción, etc.

Adjuntamos programa actualizado al día de hoy.

Contamos con su presencia para desarrollar el tema de “Conversion processes, biorefineries

strategies for a sustainable bioeconomy” el dia 12/09.

En los días 13 y 14, se desarrollara con su participación , un taller en el Laboratorio Tecnológico del

Uruguay (Latu), actividad con investigadores locales y académicos presentes en el CAETS 2018.

Esperamos contar, asimismo con Ud, para el análisis de proyectos conjuntos con el Instituto de

Ingeniería Química de la Facultad de Ingeniería de la Universidad de la Republica.

La organización del evento , se encarga , como se acordó oportunamente , de la financiación de los

gastos incurridos por su participación .

Saludos cordiales,

Norberto Cassella

Prof. Agregado de Proyecto Industrial

Instituto de Ingeniería Química

Coordinador CAETS 2018

Química - UFPR

CEPESQLuiz Pereira Ramos

CAETS/UdelaR, 10-14/09/2018

Montevideo, Uruguai

Trying to leave behind the concept of linear economy…

Energy sources

http://www.keentobegreener.com/new-blog/2017/7/10/the-circular-economy-the-new-thing

TAKE MAKE DISPOSE

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❖ Natural resources could be

further exploited to chemicals,

fuels and materials

❖ Life cycles could be improved

(better carbon footprint)

❖ Wastes are not produced

❖ Wastes are used as resources

for new conversion processes

Energy sources

... and develop the circular

economy, where:

http://www.keentobegreener.com/new-blog/2017/7/10/the-circular-economy-the-new-thing

http://eng.beeco.hr/beeco/

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Montevideo, Uruguai

Energy sources

https://ec.europa.eu/research/bioeconomy/images/bioeconomy_graphic_full.jpg 4

❖ Natural resources could be

further exploited to chemicals,

fuels and materials

❖ Life cycles could be improved

(better carbon footprint)

❖ Wastes are not produced

❖ Wastes are used as resources

for new conversion processes

... and develop the circular

economy, where:

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Energy sources

Transition from a linear to a circular economy

https://www.government.nl/topics/circular-economy/from-a-linear-to-a-circular-economy 5

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6

Transition to a biobased economy

o Agricultural productivity (“food vs. fuel”): ultimate

constraint on production;

o “Sustainability”: dominant socio-environmental

constraint… soil fertility on first place;

o Industry will be influenced to an unprecedented degree

by local issues

o “All biomass is local”: its availability depends on

climate, soil, crops, and public policies, among others

Energy sourceshttp://eng.beeco.hr/beeco/

http://www.engineersjournal.ie/2016/08/09/ucd-engineers-lead-e8-million-agrocycle-circular-economy-project/

UCD School of Biosystems and Food

Engineering – Prof. Shane Ward

Horizon 2020 EU-China

collaborative project

26 partners from across the

EU, China and Hong Kong

6

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Montevideo, Uruguai

Definition from IEA (International Energy Agency):

Biorefinery is the sustainable processing of biomass into a spectrum

of marketable products (food, feed, materials, chemicals) and energy

(fuels, power, heat)”.

One of the main drivers for the establishment of biorefineries is the

call for sustainability. All biorefineries should be designed for

sustainability along the entire value chain. This assessment should

also take into account the possible unintended consequences such

as the competition for food and biomass resources, the impact on

water use and quality, changes in land-use, soil carbon stocks and

long term fertility, net balance of greenhouse gases, impact on

biodiversity.

7

Biorefinery

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Biorefinery typesType 1 Biorefinery

Almost no processing flexibility e.g. a dry-milling ethanol plant which

uses grain as a feedstock or esterification plant using plant oils, has

a fixed processing capability and produces a fixed amount of fuel,

and co-products.

Type 2 Biorefinery

Flexibility in end product production e.g. wet milling technology using

grain feedstocks which can produce various end products depending

on demand. Products include ethanol, starch, high fructose syrups,

oils and meals.

Type 3 Biorefinery

Flexibility of feedstocks and end products i.e. uses various types of

feedstocks and processing methods to produce products for the

industrial market.

Kamm, B. and M. Kamm, Principles of Biorefineries. Appli. Microbiol. Biotechnol., 64, 137-145, 2004. 8

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TypesBiorefiningprocesses

FeedstocksProducts

Energy Materials

C6 sugars Hydrolysis,fermentation

Starch crops Bioethanol Animal feed

Oil Pressing, transesterification

Oil crops Biodiesel Animal feed, glycerin

Syngas Pre-treatment, gasification and alcohol synthesis

Lignocellulosicmaterials

Syntheticbiofuels, FT-fuels

Chemicals(alcohols)

Sugar andsyngas

Biochemical conversion,thermochemical

Biomasses (75%carbs on average)

Conditioning gas, fuels

Chemicals, polymers

C6/C5 sugars,lignin, syngas

Pretreatment, hydrolysis, fermen-tation, gasification, FT-synthesis

Lignocellulosicmaterials, energycrops

FT-fuels,ethanol

Animal feed

9Wang et al. Renew. Sustain. Energy Rev., 13, 2263-2278, 2009.

Biorefinery

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Montevideo, UruguaiBiorefinery

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Principles Criteria/dimensions of the assessment

Systems Technical and process design of biorefinery: processing efficiency, mass flow,aims for the potential substitution/displacement of fossil-fuel based productsby biobased products

Consistency In coherence with the national/regional/global strategies on sustainabledevelopment, e.g. the EU–biofuel and bioeconomy strategy. Resourcemanagement and diversification of use in relation to sustainability goals

Independency Comparative economic and environmental performance of the biomassconversion in biorefinery with respect to alternatives (e.g., thermochemical,combustion, pyrolysis, gasification, liquefaction, etc.). Socio-economic andenvironmental differences with respect to biorefinery pathways but differingthe feedstock supply and the product scenarios (extent of processing)

Measurability Qualitative and quantitative analysis of the process and product system.Quantification of sustainability assessment criteria/indicators (e.g. GWP per kgof bioethanol, annualized cost of producing 1 kg of ethanol, animal feed etc.,potential employment generation per kg of ethanol, etc.)

Comparability In relation to the principle of Independency as stated above, ecological andsocio-economic aspects of utilizing various inputs to produce marketableproducts in a biorefinery process

Wang et al. Renew. Sustain. Energy Rev., 13, 2263-2278, 2009.

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Montevideo, Uruguai

Adapted from Lucia, L.A. and Rojas, O.J., In:

Proceedings of the CIADICYP Meeting,

Santiago, 2006

STRUCTURAL

MATERIALS

THERMOCHEMICAL

CONVERSION

RESIDUES AND

ENERGY CROPS

FORESTRY

PRODUCTS

BIOTECHNOLOGY,

GENETICS, ...PULP AND PAPER

INDUSTRY

Furniture

Supporting materials

Plastic fillings

Cement additives

Composites

Alcohols, esters

Chemicals

Polymers

Hydrocarbons

Hydrogen

Pharmaceutics

Bio-oil

Synfuels

Energy

Chemical building blocks

syng

as

blac

k

liquo

rco

-

prod

ucts

Pulp and paper

Ethanol, butanol

Organic acids

Biomolecules, enzymes

Biomaterials

BIOLOGICAL

CONVERSION

CHEMICAL

CONVERSION

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Biorefinery

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Montevideo, Uruguai

Biomass-based derivatives

Adapted from: Huber, G.W., Iborra, S. and Corma, A., Chemical Reviews, 106, 4044-4098, 2006 12

Biorefinery

GASIFICATION

PYROLYSIS

HYDROLYSIS

SYNGAS

BIO-OILS

SUGARS

LIGNIN

Fischer-Tropsch

Methanol

Water-gas shift

…………….. Alkanes

…………………….. Methanol

.…………… Hydrogen

Dehydrogenation

Zeolite upgrading

..……... Liquid fuels

..…..…. Liquid fuels

Fermentation

Dehydration

Hydrotreatment

………….….….. Ethanol

…..…………….. Methanol

..…………… Alkanes

or hydrogen

Upgrading…...……....…….….. Ethers,

hydrocarbons

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Hemicellulose

(Pentosans-Xylan)

Cellulose

(Hexosans-Glucan)

Lignin

Biomass

Pre-treatment

Sugars

C5/C6

sugars

(Xylose-

Glucose)

Xyiytol

Chemical pathway from pentoses

Direct Product use

Non-nutritive sweetener

Buiding block for Xylaric acid, glycols

Sorbitol

Chemical pathway from hexoses

Non-nutritive sweetener

Building block for Isosorbide, propylene

glycol

Product’s derivatives

use

Antifreeze, unsaturated polyester resins

PET like polymers, anrifreeze, water

soluble polymers for water treatment

Levulinic acid

Chemical pathway from hexoses/

pentoses

Building block for Methyl

tetrahydrofuran, butyrolactone,

Diphenolic acid

Fuel oxigenates, pesticedes,solvents,

polycarbonate resins

Succinic acid

Biotechnological pathway from hexoses

Building block for Butanediol

(BDO),Tetrahydrofuran (THF), gamma-

Butyrolactone (GBL). pyrrolidones

Fibers such as Lycra, green solvents,

water soluble polymers for water

treatment

3-Hydroxypropionic acid


Building block for 1,3 propane diol,

acrylates

Sorona Fiber, contact lenses, super

adsorbant polymers (Diapers)

Ethanol

Biotechnological pathway from hexoses/

pentoses

Fuel for transport, Building block for

Ethylterbutylether (ETBE), ethyl estersFuel, Fuel Oxigenate,

Ferulic acid

Biotechnological pathway from lignin by

enzymatic depolymerization

Building block for vanilin, polymers Flavouring agents, phenolic resins

OH

Furfural

Chemical pathway from pentoses

Solvent in petrochemical refining,

Building block for Tetrahydrofuran

(THF), Nylon 6 Nylon 6,6

Thermoplastic fibers, resins, solvents O

H

O

Lactic acid


Building block for polylactides such as

polylactide acid (PLA)

Biodegradable Polyethylene-like

polymers

OH

OH

O

Sulfur-free solid fuel

Pelletization of lignin rich solid residueFuel for heat and power generation

Product

http://bpe.epfl.ch/ 13

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The holistic biorefinery

Venkata Mohan et al. Biores. Technol., 215, 2-12, 2016

CO2 sequestration

14

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The holistic biorefinery

Venkata Mohan et al. Biores. Technol., 215, 2-12, 2016 15

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By type By Country

Source: Brazilian Energy Report - REN 21 - 2016

Renewable fuels

Estimation of the world biofuels production

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RenovaBio

National program launched in December 2016 by the Brazilian

Ministry of Mines and Energy to expand the production of

biofuels in Brazil, having as main foundations its predictability,

compatible scaling according to the market demand and its

social, environmental and economic sustainability.

✓ 43% reduction in GHG emissions by 2030;

✓ Zero tolerance for illegal deforestation in the Amazon basin;

✓ Up to 45% renewable energy in the Brazilian energy matrix;

✓ Bioenergy component raised up to 18% of the energy matrix;

✓ New biofuels: 2G ethanol, green diesel, HVO, biohydrogen,

biogas, biomethane and biokerosene, among others

Biofuels in Brazil

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o The food vs. fuel dilemma: the ultimate constraint

on production and/or productivity

o Sustainability: the dominant socio-environmental

constraint

• Soil fertility first of all

• Immediate environmental impact

• Respect for local productive arrangements

o Industry will be influenced to an unprecedented

degree by local issues

o All biomass is local18

Social issues

Biofuels in Brazil

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http://www.time.com/time/magazine/0,9263,7601080407,00.html

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Montevideo, UruguaiSugarcane

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Cane energy

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Montevideo, UruguaiCane energy

360

70

951

185

17

223

9060

30

495

110

385

Production / Productivity Energy Bagasse

(106 ton) / (ton ha-1) (MW year-1) Production Consumption Surplus

(106 ton)

> 1

64%

> 1

200%

> 4

50%

21

Sugarcane

Cane energy

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135

26

93

6

20

26

4

47

53

Fibers / Sugars Ethanol Ethanol

(%) / (%) (106 L) (109 L year-1)

per ha per year

Sugarcane

Cane energy

1G 2G

> 1

64%

< 3

1%

> 2

32%

22

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Biomass productivity

Gre

en b

iom

ass

(to

nha

-1)

Harvesting (years)

Average

Energy cane

Average

Sugarcane

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São Miguel dos Campos – AL (2014)

82 mi L ethanol/year

Bioflex 1

Ethanol 2G in Brazil

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BagasseCane Electricity (grid)Extraction

1G

EtOH

Juice

Vinasse

Ethanol2G

EtOH

Lignin Steam & energy

CoGen

Straw

Ethanol

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o Production:

• Integration at low cost

• Flexible (feedstock agnostic)

o Enzymatic hydrolysis:

• Total solids > 20%; time < 70h

• Efficiency > 70%

o Fermentation:

• C5/C6

• Efficiency > 90%

o Yield from 100 g:

G-3P

C6

Xylose

Xylulose

Cellulose

HemicelluloseC5

C6Ethanol

Sugars PT EH F EtOH

0.68 0.900.65 0.45 17.9

0.60 0.45 16.5

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Piracicaba – SP (1936-2015)

40 mi L etanol/ano

Usina Costa Pinto


27

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Sugarcane Crushing

Bagasse

Sugarcane+ straw

Separation Straw

Boiler

Dilute acid

pre-teatment

pH 1.2, 205°C, low

solids (5-10%), quarterinch particles, double

flash, 2min residence

Juice

Evaporation

Concentratedjuice

CrystallizationSugar

(sucrose)Molasses

Water

Pre-treated

biomassWashing

C5Concentration

Concentrated

C5120 g/L Sugar

15-20 g/L Acetate

C6

Hydrolysis

Novozymes custom

cocktail, ~100 h, pH 4.8-5.2, 53-57°C,

80-90% GLC yield

Citrotec multiple

effect evaporator

Washed, pre-

treated biomass

Fermentation

Fermentation

C5 beer

~20h

7-8% EtOH

C6-C12 beer~10% EtOH

Distillation

Lignin


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BIOMASS

PRETREATMENT

C5 STREAM C6 STREAM LIGNIN

LIPIDS EXTRACTION OTHERS

PYROLYSIS

BIOCHAR

BIO-OIL

SYNGAS

HYDROLYSIS

FERMENTATION

CO2

ETHANOL

FERMENTATION

HYDROGEN

BIOGAS

SYNTHETIC FUELS

ADDITIVES

GLYCEROL

BIODIESEL

CONVERSION

Process

Integration

DRY YEASTSFERTILIZERS

POLYMERS

Biorefinery

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Montevideo, Uruguai

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Conclusion

➢ Renovabio has enormous potential to further increase the

percentage of renewable fuels in the Brazilian energy matrix

➢ Biomass is local: primary production will play an important

role in the viability/competitivity of biobased products

➢ Cellulosic ethanol is paving the way for the development of

viable biomass biorefining processes (the same applies to

the pulp and paper sector)

➢ The proper destination of coproducts such as pentoses,

glycerin, lignin and extractable materials is critical for the

future of biomass conversion processes (biorefining)

➢ Although the recent economic downturn and inertia in the

commencement of new operations, the future prospects of

bioenergy/biofuels in Brazil are positive

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MICROALGAEAGRICULTURAL

RESIDUES

Choricystis minorAcutodesmus obliquus

Muriella decolor

Cane bagasseCane straw

Cotton residues

EucalyptSugarcane

Industrial residues

SELECTIVE EXTRACTION

PRETREATMENTCATALYTIC

CONVERSION

C6 FRACTION

ENZYMATIC HYDROLYSIS

FERMENTATION

ESTERIFICATION / TRANSESTERIFICATION

/ HYDROLYSIS

C5 FRACTION

FOREST RESIDUES

EthanolOrganic acids

Furans, EstersLactic acid

Levulinic acid

PigmentsFunctional lipids

HYDROLYSATE(C6 mostly)

Oligos (XOS)

Monosaccharides

FAST PYROLYSIS

Fatty estersAnimal feedFatty acids

Esters, FenolsLevoglucosanHydrocarbons

Soap stocksUsed frying oil

Spent fats

CELLULIGNINDISPOSABLE

OILS AND FATS

LignoforceTM

LignoboostTM

Hydrolysis lignin

LIGNINAS INDUSTRIAIS

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Invitation…

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Thank you!

[email protected]

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