Luiz Ramos_IFBC_2017-1_pdf · Recent Developments and Current Situation of Cellulosic Ethanol R&D in Brazil Luiz Pereira Ramos ... vs. total sugar yield 31

Recent Developments and

Current Situation of Cellulosic

Ethanol R&D in Brazil

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]

Química - UFPR

CEPESQ Luiz Pereira Ramos

1st IFBC – Thunder Bay, ONT

May 9-11, 2017

By type By Country

Source: Brazilian Energy Report - REN 21 - 2016

Renewable fuels

Estimation of the world biofuel production

2

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May 9-11, 2017

Etanol Hidratado

Etanol Anidro

Coal and firewood

Biodiesel

Ethanol (hydrated)

Ethanol (anhydrous)

Cane bagasse

BR energy matrix

3

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May 9-11, 2017

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 contributing with 18% of the total renewable energy;

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

biogas, biomethane and biokerosene, among others

Biofuels in Brazil

4

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.

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May 9-11, 2017 Biofuels in Brazil

5

RenovaBio for 1G ethanol

New policies will be needed to raise our ethanol production

from the current 30 to more than 50 billion liters per year:

o Innovative financial mechanisms to reduce the risk of

commercialization

o Tax differentiation and incentives based on sustainability

• Social and environmental externalities

• Regulation of bioelectricity production and use

o Decarbonization of light fuels

• Reduction in annual CO2 emissions

• New policies for stimulating clean renewable energy

• Creation of an effective program for monitoring and control

• Commercialization of emission certificates (trading)

• Improvements of engine performance in flex fuels

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6


Proposed strategic planning to reach an annual production

of 50 billion liters of ethanol by 2030:

o Market development = premium of R$ 1.00 per liter until

2030 or until production reaches 2.5 billion liters year-1

o Creation of an high-level advisory committee for industrial

biotechnology involving government and stakeholders

o Establishment of new policies involving tax incentives,

subsidies, warranties and grace period for financing

o Establishment of a regulatory regime for carbon trading

o Economic valuation of environmental externalities that are

associated with the use of low carbon biofuels

o Attention to the food vs. fuel dilemma and to sustainability

issues such as availability of arable land, effect on soil

fertility and impact on biodiversity

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7


Proposed strategic planning to reach an annual production

of 50 billion liters of ethanol by 2030:

o 2G ethanol is one of the most important doors way towards

a solid and advanced bioeconomy in Brazil

o Roadmap challenges: the current technological gaps

must be overcome, a dedicated market share must be

consolidated and the annual production capacity must be

expanded

o Goal: one new medium-size plant (60 million liters year-1)

per year speeding up to progressively to ten new plants per

year to reach 120 plants in operation by 2030, with the

production capacity ascending to 110 million liters year-1

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May 9-11, 2017 Sugarcane

8

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May 9-11, 2017

Ethanol 1G

WTT BIOGÁS BOILER

Vinasse

CRUSHING CLARIFICATION CANE

HARVESTING

HOT WATER WASHING

DISTILLATION EVAPORATION FERMENTATION

(1G) YEAST

RECOVERY

YEAST ACID WASH

Residue

Steam

2.5 bar

CO2

BAGASSE HANDLING

STEAM TURBINE

Electricity

Nutrients

Autonomous distillery (75-80 L/ton sugarcane)

2016/17 harvesting:

691 million ton cane

30.3 million m3 ethanol

37.5 million ton sugar

~184 million ton trash

Simplified flowsheet

First generation (1G)

or saccharinic ethanol

Adapted from Macrelli, S.; Mogensen, J.; Zacchi, G. (2012) Biotechnology for Biofuels 5, 22. 9

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May 9-11, 2017

1G/2G process integration Adapted from Macrelli, S.; Mogensen, J.; Zacchi, G. (2012) Biotechnology for Biofuels 5, 22.

Ethanol 1G

WTT BIOGÁS

STEAM TURBINE BOILER

Vinasse

DRYING

PRETREATMENT

FILTRATION ENZYMATIC HYDROLYSIS

SOLID/LIQUID SEPARATION

FERMENTAÇÃO (2G)

YEAST RECOVERY

DISTIlLATION

C5 stream

Ethanol 2G

BAGASSE HANDLING

Enzymes

CRUSHING CLARIFICATION CANE

HARVESTING

HOT WATER WASHING

DISTILLATION EVAPORATION FERMENTATION

(1G) YEAST

RECOVERY

YEAST ACID WASH

Electricity Vinasse

Residue

Steam

2.5 bar

CO2

Bringing 1G and 2G

cellulosic ethanol together Simplified flowsheet

10

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May 9-11, 2017

Hydrolysis at 20 wt%, 200 rpm, 0.1 g Cellic CTec2 g-1 cellulose released of

76.8 g L-1 of GlcEq in 72 h (equivalent to 39.2 g L-1 ethanol from cane bagasse)

Based on this, the ethanol production from sugarcane could be increased by 40

%, from 80 to 115 L ton-1

The use of cane straw (leaves and tops, also referred to as cane trash) and C5

sugars may improve these numbers even further

Ramos et al. (2015) Bioresour. Technol. 175, 195-202. 11

Bringing 1G and 2G

cellulosic ethanol together

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May 9-11, 2017

Szczerbowski et al. (2014) Carbohydr. Polym. 114, 95-101.

Bagasse

Straw (trash)

Sugarcane

12

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May 9-11, 2017 Pretreatment

Hemicelluloses Lignin

Cellulose

Pectins

Adapted from Silveira et al. (2015) ChemSusChem 8, 3366-3390 13

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May 9-11, 2017 Enzymatic hydrolysis

Synergism among cellulases and auxiliary proteins

such as swollenins and GH61 (AA9)

Cellobiose

Cellobiose

TrCel12A

TrCel5A

TrCel7A TrCel6A

CBM

Glucose GH61

Swollenins

bG

Silveira, M. H. L. et al. In: S. S. Silva and A. K. Chandel. Biofuels in Brazil. Switzerland:

Springer International, 2014. p. 151-172. 14

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May 9-11, 2017

Arantes, V. and Saddler, J. N. (2011) Biotechnology for Biofuels 4, 17.

(h)

12 72

Enzymatic hydrolysis

Typical hydrolysis profile of cellulosic materials

15

Substrate TS > 20 wt.%

pSSF

SHF

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May 9-11, 2017

Pre-hydrolysis at 20 wt% TS C5/C6 fermentation with 2 g/L of yeast cells (Nedalco)

Fermentation

Typical SSCF profile

16

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May 9-11, 2017 Fermentation

17

Inhibitory compounds arisen from pretreatment

Cellulose Hemicelluloses

Glucose

MannoseGalactose Xylose

Arabinose

Acetic acid

HMF Furfural

LevulinicacidFormic acid

Lignin

Phenolics

Adapted from Palmqvist, E.; Hahn-Hagerdal, B. (1999) Bioresour. Technol. 74, 25-33.

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May 9-11, 2017

Piracicaba – SP

40 mi L ethanol year-1

Costa Pinto mill

Ethanol 2G in Brazil

18

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May 9-11, 2017

São Miguel dos Campos – AL

82 mi L ethanol year-1

Bioflex 1

Ethanol 2G in Brazil

19

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May 9-11, 2017

First Cellulosic Ethanol Plant of

the South Hemisphere – Set/2014 20

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May 9-11, 2017

First Cellulosic Ethanol Plant of

the South Hemisphere – Set/2014 21

Bagasse Cane Electricity (grid) Extraction

1G

EtOH

Juice

Vinasse

Ethanol 2G

EtOH

Lignin Steam & energy

CoGen

Straw

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May 9-11, 2017

Sugarcane straw

22

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May 9-11, 2017

Large scale storage of cane straw

23

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May 9-11, 2017

Conventional sugarcane

Energy cane

Cane plantations after 7.5 months Average rainfall: 350 mm

24

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May 9-11, 2017

360

70

951

185

17

223

90 60

30

495

110

385

Production / Productivity Energy Bagasse

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

(106 ton)

Sugarcane

Energy cane

> 1

64%

> 1

200

%

> 4

50%

25

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May 9-11, 2017

13

135

26

93

6

20

26

4

47

53

Fibers / Sugars Ethanol Ethanol

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

per ha per year

Sugarcane

Energy cane

1G 2G

> 1

64%

< 3

1%

> 2

32%

26

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May 9-11, 2017

Biomass productivity

Gre

en b

iom

ass (

ton

ha

-1)

Harvesting (years)

Average

Energy cane

Average

Sugarcane

27

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May 9-11, 2017

Properties Sugarcanea Energy cane

Fiber (%) 17.4 35

Sugars (%) 12.6 7

Productivity (green biomass, ton ha-1)b 92 250

Productivity (fiber, ton ha-1) 16 88

Productivity (sugars, ton ha-1) 12 18

Annual energy gain (%) 1.5 3

Demand for fertilizers High Low

Plague/disease resistence Low High

Harvesting cycles 5 10

Propagation rate 1:10 1:400

Breeding cycle (years) 8 to 12 4 to 6

a 80 tons ha-1 containing 50% straw in harvesting

b State of São Paulo, low fertility soil

28

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May 9-11, 2017

Pretreatment o Sugar yields

o Accessibility

o Inhibitors

o Cost

Severity factor (log Ro)*

SF = log Ro = eT−100

14.75 . 𝑡

* Overend, R. P., Chornet, E., Gascoigne, J. A. (1987) Phil. Trans. R. Soc. Lond. A, 321, 523-536. 29

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May 9-11, 2017

Xylose

Glucose

Pretreatment optimization

o Severity factor (log Ro) vs. sugar recovery

30

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May 9-11, 2017

A B C D

E F

50

60

70

80

90

100

A B C D E F

Yie

ld (

%)

Hydrolysis efficiency Fermentable sugars

Pretreatment optimization

o Severity factor (log Ro) vs. total sugar yield

31

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May 9-11, 2017

Substrate accessibility

New (accessory) enzymes

Customization

Production system

Offsite

Onsite

Integrated

Activity enhancement

40

60

80

100

120

60 65 70 75

Enzym

e d

osag

e (

rela

tive

valu

es)

Efficiency (%)

U$100

U$90

U$70

1 Gen 2 Gen 3 Gen

Enzymatic hydrolysis

o Optimal enzyme dosage

32

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May 9-11, 2017

o Process:

• 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

Hemicellulose C5

C6 Ethanol

Sugars PT EH F EtOH

0.68 0.90 0.65 0.45 17.9

0.60 0.45 16.5

Ethanol production

33

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May 9-11, 2017

Current situation and future challenges

34

So far, the plant has operated without interruption for a total of 5

months, from October 2016 till February 2017, reaching 50% of

its total production capacity

The plant stopped its operation in March 2017 due to the end of

the cane harvesting season

The cane productivity in the last harvest was far below the initial

predictions due to a severe draught in the Northeastern region

of the country

There was a major shortage of biomass supply for the entire

process: bagasse for the industrial boilers and straw for

cellulosic ethanol production

Current challenges: reduce production costs, improve yields

and increase production close to the full production capacity

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May 9-11, 2017

35 Torres da Silva et al. (2016) Catalysis Today 269, 21-28.

Alkali delignification

Experiment AnGlc (%) AnXyl (%) AnAra (%) Lignin (%)

Insoluble Soluble Total

AWB 52.15 ±0.27 19.70 ±0.29 1.99 ±0.15 15.42 ±0.56 0.01 ±0.00 15.45 ±0.56

SEB 59.73 ±0.42 3.59 ±0.07 bdl 33.44 ±0.23 0.04 ±0.23 33.48 ±0.23

SEB-AW 77.25 ±2.00 5.50 ±0.38 bdl 10.42 ±0.20 0.01 ±0.20 10.43 ±0.20

0

20

40

60

80

100

0 24 48 72 96

Glu

co

se

(%

)

Time (h)

SEB-AW AWB

SEB

Hydrolysis at 4 wt% TS, 50 °C,

150 rpm for 96 h, with 33 mg of

Cellic® CTec3 (Novozymes)

g-1 TS or 7.1 FPU g-1 TS in a 50

mmol L-1 acetate buffer, pH 5.2.

Analysis by HPLC in an Aminex

HPX-87H.

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May 9-11, 2017

36 To

rre

s d

a S

ilva

et a

l. (

20

16

) C

ata

lysis

To

da

y 2

69

, 2

1-2

8.


Experiment AnGlc (%) AnXyl (%) AnAra (%) Lignin (%)

Insoluble Soluble Total

AWB 52.15 ±0.27 19.70 ±0.29 1.99 ±0.15 15.42 ±0.56 0.01 ±0.00 15.45 ±0.56

SEB 59.73 ±0.42 3.59 ±0.07 bdl 33.44 ±0.23 0.04 ±0.23 33.48 ±0.23

SEB-AW 77.25 ±2.00 5.50 ±0.38 bdl 10.42 ±0.20 0.01 ±0.20 10.43 ±0.20

0

20

40

60

80

100

0 24 48 72 96

Glu

cose (

%)

Time (h)

SEB-AW

AWB

SEB

Hydrolysis at 4 wt% TS, 50 °C, 150 rpm

for 96 h, with 33 mg of Cellic® CTec3

(Novozymes) g-1 TS or 7.1 FPU g-1 TS.

0

5

10

15

20

25

30

0

10

20

30

40

50

60

70

0 3 6 9 12 15 18 21 24

E

tha

nol (

g L

-1)

Glu

cose (g

L-1

)

Time (h)

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May 9-11, 2017

37

0

20

40

60

80

100

Total solids Glucan Ethanol

Yie

ld (

%)

AWB6 SEB SEB-AW


Torres da Silva et al. (2016) Catalysis Today 269, 21-28.

38

http://www.biodiesel.gov.br/index_arquivos/index_centro.htm

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May 9-11, 2017

Thank you!

[email protected]

Documents

Luiz Ramos_IFBC_2017-1_pdf · Recent Developments and Current Situation of Cellulosic Ethanol R&D in Brazil Luiz Pereira Ramos ... vs. total sugar yield 31