RENEWABLE BASED ECONOMY: ENERGY , FUELS AND CHEMICALS … · RENEWABLE BASED ECONOMY: ENERGY , FUELS AND CHEMICALS ... Sugar cane, Soya bean, Palm , Coconut Orange, ... (extractive

RENEWABLE BASED ECONOMY:

ENERGY , FUELS AND

CHEMICALS

Prof. Dr. Rubens Maciel Filho

School of Chemical Engineering

Laboratory of Optimization, Design and Advanced Process Control

State University of Campinas – UNICAMP – Brazil

Fapesp/Bioen- Process Engineering Coordination

Renewable Feedstock for Biofuels, Energy and Chemicals

Sugar cane, Soya bean, Palm , Coconut Orange, Agriculture residues ,Animal Fatty among others. Any lignocellulosic material. Many alternatives to use such raw materials – production scale and logistic has to be accounted for

Saccharose Bagasse Tip and Straw

Sugar Cane

•Applications Biofuels •Bioethanol for light cars •Biobutanol for light cars •Additives for bioethanol use in heavy engines •Biodiesel for heavy engines •Biokerosene for jet fuels •H2 Production from Ethanol •Biogasoline

•Biorefineries-High Added Value Chemicals and Special Polymers Biofabrication-Human and •Flexible organic photovoltaic cells Healt

•Electricity and Power Generation

As vantagens dos biocombustíveis

Environmental Benefits

- carbon sequestration

- lower emissions

Renewable

- short production cycle

- good sustainability indicators

Economic Aspects

- Alternative to petroleum

- Bilateral trade

Social Aspects

- new jobs

- benefits to human health due to air quality improvement

Advantages of Biofuels and Renewable Based Products

Political Reasons -Strategic independence -Energy independence

2-) Perception Draining Oil Reserves and/or high costs to oil exploration Nowadays alternative sources as shale oil (no renewable

source), wind, solar may play an important role 3-) Energy from biomass Strategic and energy security as well as

competive prices Source: BBasic

1-) Environmental aspects

Ethanol as a raw material for chemicals- already a suitable approach Production in large scale – as a commodity is beneficial (Source: BBasic)

7

Achoholchemistry Products

Ethanol

Propylene

Acetaldehyde

Ethylene

Acetic Acid

Ethylene-Dichloride

Styrene

Vinyl Acetate

Ethylenediamine

Acetic Anhydride

Monochloroacetic Acid

Ethyl + Other Acetates

2-Ethylhexanol

N-Butanol

Ethylene Oxide/Glycol

Polyethylene

Butadiene

Polyvinil Acetate

Polyvinyl Chloride

Polystyrene

Crotonaldehyde N-Butyral-Dehyde

Ketene

Vinyl Chloride

Use of ethanol as feedstock – that means obtain chemicals from ethanol

Ethene Production by Ethanol Dehydration

Multitubular Reactor

Reaction Mechanism

C2H5OH → C2H4 + H2O

2C2H5OH → C2H5OC2H5 + H2O

C2H5OC2H5 → C2H5OH + C2H4

C2H5OC2H5 → 2C2H4 + H2O

Green Ethene Process (Ethanol Dehydration)

Bioethanol chemistry Patent required- Unicamp

* Currently under development at Laboratory of Optimization, Design and Advanced Control (LOPCA)

Bioethanol

Green Ethene

Acetaldehyde

Green Propene Dehydration

Oxidation

1-Buthene / 2-Butene

Dimerization

Metathesis

Green Acetaldehyde – Green Ethene – Green Propene

Patent pending - Unicamp

10

higher alcohols

Ethanol

Acetaldehyde

Acetic acid

Propene

Propylene

___Acrylic Acid

Glycerol

Lactic acid

Butadiene

Butanodiol

Succinic acid

BIOMASS H

YD

RO

LY

SIS

Sugar

Glycose

Sacarose

Xylose

Arabynose

FE

RM

EN

TA

TIO

N

Other Products to be obtained from biomass

Learning curve costs have to be reduced

Biomass – C6 and C5

Power Consumption and GDP (World Regions)

Relationship between 2009 per capita primary energy consumption and GDP per capita for main regions of the world and income levels (as specified by the World Bank). GDP values are adjusted for Purchasing Power Parity and reported in current international $. GDP per capita is from the World Bank, and per capita primary power consumption is derived from other indicators provided by the World Bank: http://data.worldbank.org/indicator . Accessed on Jan. 4 2012. Information on which countries are included in the classifications is available at: http://data.worldbank.org/about/country-classifications/country-and-lending-groups The regression line is derived with the constraint that 0 kilowatts per person = $0 GDP per capita.

By Bruce Dale–Michigan State University

Energy Consumption & Human Well Being are Linked

Relationship between 2008 per capita primary energy consumption and human development indices (HDI) for 170 countries. Qatar is not shown with a per capita primary energy consumption of greater than 30 kilowatts per person. Based on a figure by Martinez and Ebenhack, 2008; and the inset is based on a figure from the Human Development Report Office (HDRO) of the United Nations (UN): http://hdr.undp.org/en/statistics/hdi/ . Human development indices are also from the HDRO: http://hdr.undp.org/en/statistics/hdi/ . Per capita primary energy consumption data are from the U.S. Energy Information Administration (EIA): http://www.eia.gov/cfapps/ipdbproject/IEDIndex3.cfm . All data were accessed on Nov. 17, 2011.

By Bruce Dale–Michigan State University

Energy Consumption & Human Well Being are Linked: NO Countries have Both High HDI and Low Energy Use

Relationship between 2008 per capita primary energy consumption and human development indices (HDI) for 171 countries. Human development indices are also from the HDRO: http://hdr.undp.org/en/statistics/hdi/ . Per capita primary energy consumption data are from the U.S. Energy Information Administration (EIA): http://www.eia.gov/cfapps/ipdbproject/IEDIndex3.cfm . All data were accessed on Nov. 17, 2011.

By Bruce Dale–Michigan State University

Interesting to Note:

As we have presently configured our

economy it appears that national wealth

is almost a linear function of power

consumption…(By Bruce Dale–Michigan State University)

Biomass may be a reliable source of

energy supply including electricity and

transportation fuels

Commodity Prices

Prices are from the World Bank GEM Commodity Index Database: http://data.worldbank.org/data-catalog/commodity-price-data. Accessed: Jan 16, 2012. Prices were reported as 2005 US$/bbl for crude oil (spot price average of West Texas Intermediate, Brent, and Dubai), 2005 US$/mt for urea (E. Europe, bulk) and steel rebar, and 2005 US$ (2005 = 100) for food and metals & minerals.

By Bruce Dale–Michigan State University

Without a

rational

procedure

Decisions may

be difficult, time

consuming and

too late when

alternative, but not

necessarily better

solution, is

implemented

It is possible to

propose and

evaluate systematic

procedures to

attack the problem

Use of Process

System Engineering

(PSE) as tool

( Near Brussels )

Decision making – couple with different alternatives

A point to be considered is its possible integration with the first generation units and this may lead to a careful choice of the process that leads to economically and robust solution to use byproducts as feedstock for energy and chemicals

BIOEN: FAPESP’S BIOENERGY PROGRAM

INOVATIVE RESEARCH IN BIOENERGY

Mission: promote academic and industrial research in sugarcane and other renewable biofuel sources to guarantee Brazil’s position among the leading countries in bioenergy research and production.

http://bioenfapesp.org Glaucia Mendes Souza

Chemistry Institute - USP

Rubens Maciel Filho

School of Cemical Engineering- Unicamp

Heitor Cantarella

Agronomic Institute of Campinas

Marie-Anne Van Sluys

Biosciences Institute- USP

Andre Nassar

ICONE

Fundamental knowledge and new technologies for a bio-based society

• Academic Basic and Applied Research (US$ 30 million)

98 grants, over 300 brazilian researchers, 61 foreign researchers from 12 countries

– Regular, Theme and Young Investigator Awards

Open to foreign scientists who want to come to Brazil

• State of São Paulo Bioenergy Research Center (US$ 90 million)

• International partnerships

United States, United Kingdom and The Netherlands

(Oak Ridge National Laboratories, UKRC, BBSRC, BE-Basic)

• Innovation Technology, Joint industry-university research

• (5 years) (US$ 83 million)

Company Subject Value by industry

Oxiteno Lignocellulosic materials US$ 3,000,000

Braskem Alcohol-chemistry US$ 25,000,000

Dedini Processes US$ 50,000,000

ETH Agricultural practices US$ 5,000,000

Microsoft Computational development US$ 500,000

FAPESP Bioenergy Research Program BIOEN

Australia Austria

Belgium China

Denmark Finland France

Germany Guatemala

Italy Portugal

Spain The Netherlands United Kingdom

United States

BIOEN DIVISIONS

BIOMASS Contribute with knowledge and technologies for Sugarcane Improvement Enable a Systems Biology approach for Biofuel Crops

BIOFUEL TECHNOLOGIES Increasing productivity (amount of ethanol by sugarcane ton), energy saving, water saving and minimizing environmental impacts

ENGINES Flex-fuel engines with increased performance, durability and decreased consumption, pollutant emissions; hybrid flex fuels-electric engines

BIOREFINERY Complete substitution of fossil fuel derived compounds Sugar chemistry, alcohol chemistry and oil chemistry for intermediate chemical production and as a petrochemistry substitute

IMPACTS Studies to consolidate sugarcane ethanol as the leading technology path to ethanol and derivatives production Social, economic and environmental impact studies

BIOMASS DIVISION

Improvement of Biomass

Agronomy, Breeding, Biotechnology

Identify new paths to genetically manipulate the energy metabolism of cultivated plants, creating new biofuel and bio-

based chemical alternatives

Sugar Cane Agro-industry Research to expand the industrial model

Sugarcane: the highest tonnage crop

Waclawovski et al., 2010; Costa et al., 2011

Theoretical maximum: 380 tons/ha

Current average: 75 tons/ha

By Brito Cruz- 2012

Integrating efforts: http://sucest-fun.org

Institute of Chemistry

Institute of Biosciences

Institute of Mathematics and

Statistics

Institute o Biomedical Sciences

Engineering School

State of São Paulo Bioenergy

Research Center

NAP Bioenergy and

Sustainability

University of São Paulo

BIOFUEL TECHNOLOGIES DIVISION

Engineering, processing and equipment design

Bottlenecks of biofuel production

Sucrose to Butanol (extractive fermentation)

Ethanol to Biokerosene (new chemical route, high purity)

Cellulosic ethanol (lower solids and reduced incubation time)

Biomass

Biomass Uses

Biofuels for Transportation

• Ethanol (as car fuel) • stand alone use;

• Flex fuel cars (Blends with petrol 0-100%)

• Closed carbon cycle

• In the case of sugar cane- very sustainable

• Biobutanol (drop in regarding gasoline) Alternative process is more attractive,

Almost a drop in fuel

• Biodiesel Use of vegetable oil or animal fat (good raw material logistic)

Large contribution for green house gas reduction

• Biokerosene Very competitive price with mineral kerosene

Flexible process for regional raw material use

Jet fuel- blends up to 50% with freezing point below 55 0 C

Oxygenated or hydrocarbons

•

Possible routes - bio-refinery concept - Technologies

Feedstock- renewable material, basically sugar (glucose) obtained straight from the crop crushing and the lignocellulosic material from crops or agriculture/forest residues, other residues (as glycerol from biodiesel) Technologies: •Fermentation •Thermochemical •Esterification/Transesterification •Reactions based technologies

Fermentation (main) •Starch/Sugar Feeds to Ethanol •Lignocellulosic Biomass to Ethanol •Biomethane •Biobutanol by Fermentation •Syngas to Ethanol •Hydrocarbons by Fermentation

Thermochemical (Lignocellulosic materials, vegetable oils, residues as glycerol) •Pyrolysis •Pyrolysis for Bio-Oil •Gasification •Hydrocracking •FCC based Cracking •Others

Esterification/Transesterification •Fatty acid esterification (Homogeneous /Heterogeneous) •Oil Transesterification (Homogeneous /Heterogeneous) •Supercritical •Others/Hybrids

Reactions based technologies (ethanol/higher alcohols/others) •Hydrogenation/Dehydrogenation •Oxidation •Hybrids

Technologies Commercial and in Development

It is possible to have bagasse surplus to produce electricity and ethanol

Co-generation in 2009/10 = 1.800 MW (3% of electricity matrix) In 2020 = 14.000 MW (14% equals 1 Itaipu) Investments of R$ 45 billion until 2015 on Co-generation (boilers from 21 bar to 92 bar)

Source: Thematic Project Fapesp 2008/57873-8– Coordinator Maciel Filho

Integrated Process Zero Generation ProcessChemicals

OBJECTIVE : a totally integrated bioethanol production

process with Zero CO2 Emission

•Improve the productivity of existing ethanol generation (sugar

cane molasse fermentation), the so-called First Generation

Bioethanol;

•Develop suitable processes (all steps) for improving the

Second Generation Bioethanol (from biomasses), integrated

with the first generation, and production of high added value

products;

•Develop and investigate the viability of the Third Generation

Bioethanol (micro algae and thermochemical route) in the

context of the Intrinsic Raw Material Potential (IRMP) (concept

developed in this Project)

•Process development evaluation for the production of

high added value chemicals from renewable feedstock

(chemicals, monomers, polymers…) – biorefinery concept

Zero Generation Products- straight use of sugar as feedstock

trough alternative processes

Zero Generation - straight use of sugar as feedstock

trough alternative processes

Use of supercritical conditions and water as a reactant/solvent

•retro-aldol condensation became predominant at higher temperatures, while that of

dehydration reaction (formation of furan derivatives) became significant at lower temperatures

•In supercritical condition, retro-aldol condensation became essential for reducing reaction

pressure, against the dehydration reaction

Flowsheet of high pressure unit- LOPCA-UNICAMP

Use of Global Optimization Techniques together thermodynamic models

to map possible operating conditions – Minimization of Free Gibbs energy

High pressure extraction-reaction unit.- LOPCA-UNICAMP Start point - homogeneous catalysts (H2SO4 and NaOH) and heterogeneous catalysts

(TiO2 and ZrO2) operational conditions provided by the mapping studies

Improve the productivity of existing ethanol

generation (sugar cane molasse fermentation),

the so-called First Generation Bioethanol;

First ½ Generation – ethanol, sugar, electricity,

byproducts (higher alcohols)

FIRST GENERATION

SUGAR, ETHANOL AND ENERGY PROCESS

SUGARCANE

EXTRACTION Power

Generation

Juice Treatment Filtration

Juice Concentration

Crystallization

SUGAR

Fermentation

Distillation

ETHANOL

Filter Juice

Filter Cake

ELECTRICITY

Steam

Production

Molasses

Sugarcane in Brazil: 2011-2012

• Brazil: 8.5 Mha – SP: 5.1 Mha

• < 3% of arable land

Cantarella , 2013

Sugarcane numbers in Brazil

• 2011/12: 8.5 million ha

• Cane production 2011/12: 595 Mt – 52% for ethanol and 48% for sucrose

• Ethanol: 23 billion L

• Sucrose: 36 Mt

• 434 mills – 250: sucrose + ethanol – 168 exclusive for ethanol

40

Cantarella, 2013

70,000 growers 1.2 million jobs Annual revenue: US$ 48 billion Exports: US 15 billion

SUGAR CANE

First Generation Bioethanol

Advanced fuel – EPA (USA)

1 ton of sugarcane (80 ton/hectare) produce:

250 kg of bagasse

120 kg of sugar

85 liters of ethanol

Average values

Gasoline & ethanol anywhere

Flex-fuel cars: any combination of fuels. Price determines the choice

SUGARCANE PROCESSING

1. Harvest

2. Transport

3. Cleaning

Low density when Tops and leaves are considered

Production of 2nd generation ethanol

Block flow diagram - Integrated 1st and 2nd generation bioethanol, butanol and biogas production from sugarcane

Butanol

Integrated 1rst and 2nd Generation

KINETIC MODELING OF ALCOHOLIC FERMENTATION

INTEGRATING 1ST AND 2ND GENERATION PROCESS

• Parameter fitting for recycles at 34°C

(#) recicle number

Presence of inhibitors at low concentration (due to H2O2 pretreatment);

Term of acetic acid inhibition increased model’s accuracy;

R. R. Andrade; F.Maugeri Filho; R. Maciel Filho; A. C. Costa Bioresource Technology, 2012.

Productivity and ethanol yield for recycles

Yeast stability (containing acetic acid), even with cell

recycle (yp/s remained next to 86 % of the theoretical

maximum for all runs);

EVALUATION OF THE ALCOHOLIC FERMENTATION KINETICS OF ENZYMATIC

HYDROLYSATES FROM SUGARCANE BAGASSE

(Saccharum officinarum L.) Main findings for hydrolysates kinetics:

- µmax decreased due to acetic acid presence; -Pmax increased from 82.92 to 129.88 Kg/m3 (ethanol toxicity is increased) due to interactions between ethanol and acetic acid; - Ypx increased in acetic acid presence (cells require additional ATP to pump out the excess protons when intracellular pH is low. The extra ATP formation is related to produced ethanol).

R. R. Andrade; S.C. Rabelo; F. Maugeri Filho; R. Maciel Filho; A. C. Costa, Journal of

Chemical Technology and Biotechnology, 2012

Ethanol and electricity production for each configuration

SE: Steam explosion; H2O2: hydrogen peroxide; OS: Organosolv; NaOH: alkaline delignification

Comparison between different biomass pretreatment

methods

M.O.S. Dias et al., 2011. J. Ind. Microbiol. Biotechnol., 38:955-966

Parameters and yields of the pretreatment and hydrolysis processes obtained in the literature (hydrolysis with 5% and 15% of solids)

2G equipment sizes

Comparison between different biomass pretreatment methods (SuperPro)

M.O.S. Dias et al., 2011. J. Ind. Microbiol. Biotechnol., 38:955-966

SE: Steam explosion; H2O2: hydrogen peroxide; OS: Organosolv; NaOH: alkaline delignification

24 – 48 h of hydrolysis seems to be the best options for an integrated 1G and 2G process. For 72 h of hydrolysis, reactors are too large for small increments on production

Composition of

Biomass

Bagasse

pretreated with

NMMO *

Bagasse

pretreated

with H2SO4

**

Bagasse

pretreated

with om H2O2

***

Straw

pretreated

with H2O2

****

Straw

pretreated

with

lime****

Cellulose 37.89a±0.32 38.73±1.14 38.10±0.08 33.28±0.15 33.43

hemicellulose 19.11a±0.48 11.29±0.04 11.47±0.02 3.99±0,10 21.64

Lignin 17.64a±0.15 17.45±0.73 6.64±0.03 6.78 ± 0.16 14.63

*Martins (2010)

**Martins (2011)

***Martins (2012)

****Ayala (2012)

PRETREATMENTS AND ENZYMATIC HYDROLYSIS OF SUGARCANE BAGASSE Chemical composition of the pretreated material after pretreatment at the optimal conditions

Biomass components solubilization in each pretreatment

R. R. Andrade;Matins L; R. Maciel Filho; A. C. Costa- J. of Chem.Techn. Biot., 2012

Fuel Processing Technology

2012- http/doi.dx.org/10.1016/

j.fuproc/2012.09.041

Dias M.O.S. et.al.

Energy, 2012 (43), 246-252

Dias MOS, e. all.,

Environmental Impact scores for ethanol production

Book Chapter-

European Symposium on Computer Aided Process Engineering-Elsevier-London, 2012

Maciel Filho R. et. al.

ADP- Consumption of non-renewable resources, such as zinc ore and crude oil, thereby lowering their availability for future generations.

Second generation – 2G

Block flow diagram - Integrated 1st and 2nd generation bioethanol, butanol and biogas production from sugarcane

Butanol

Sugarcane bagasse

Pretreatment

Solid fraction Liquid fraction

Lignin

Boilers/energy

Anaerobic digestion

Enzimatic Hydrolysis

Solid fraction Liquid fraction

Fermentation

Second generation bioehtanol

Distillation

Methane

Vinasse

Fertilizer

Integrated Process: Anaerobic Digestion of Hydrolysis Residues and Vinasse

Rabelo S. A.C Costa, Maciel Filho r. Production of bioethanol, methane and heat from sugarcane bagasse in a biorefinery concept.

Bioresource Technology, 102, 7887–7895, 2011.

Demonstration Flexible Plant- conventional and Extractive Fermentation Plug in concept

Multi-Purpose Pilot Plant

PRODUCTION OF ETHANOL AND CHEMICALS FROM

THIRD GENERATION

1-) Microalgae for Bioethanol Production

2-) Thermochemical Route

Gasification of Sugar Cane Bagasse for Syngas Production- fixed bed and fluidized bed reactors – FEQ-UNICAMP/ Thermoquip- Design Pyrolysis of Glycerol for Syngas Production

Ethanol and Chemicals from Syngas

Chemical Route – specific catalyst (Rh, Ru, Co based catalyst)

3-) Fermentation of Syngas – clostridium autoethanogenum bioethanol

and bioacetate

Cultivation

• Selected species: Chlorella vulgaris

• Selected culture medium: BG-11 (nitrate as nitrogen source)

• Photoautotrophic growth (CO2 and light)

Experimental design: 3 variables

Light intensity

Nitrate concentration in the culture medium

CO2 concentration in the feeding gas stream

Overall steps for third generation bioethanol production:

Chlorella vulgaris

Inoculum

preparation

Experimental

design

Post-

processing

Acid

hydrolysisFermentation

Undergoing researches :

Determination of fitting kinetic model for Chlorella vulgaris growth

Determination of microalgae carbohydrate content

Determination of the bioethanol production feasibility from microalgal biomass

(Carbohydrate accumulation in microalgae nitrogen suppression)

Bioetanol/ Biodiesel and High Added Values Products from Algae

Light utilization

1 2 3 4 5 6 7 8 9 10 11 12 130

5

10

15

20

25

30

35

40

45

Uti

liza

ção d

o f

luxo l

um

inoso

(µ

E s

-1 m

-2)

Cultivo

Luz azul

Luz vermelha

Total

1 2 3 4 5 6 7 8 9 10 11 12 1325

30

35

40

45

50

55

Efi

ciên

cia

foto

ssin

téti

ca (

%)

Cultivo

Luz azul

Luz vermelha

x

red component

blue component

)(*)()(*)()( redLredEFblueLblueEFtotalUL

Cultivation

Lig

ht

uti

liza

tion (μ

E s

-1 m

-2)

Blue light

Red light

Total

m

t

F

FEF 1 Photosynthetic efficiency

Exp T t Flow rate Oil TG DG MG G FAMEs (ºC) (min) (g/min) (ml/min) (wt%) (wt%) (wt%) total (wt%) (wt%)

Time reaction (min)

Trig

lyce

rid

es (

%)

150 ºC

180 ºC

200 ºC

Supercritical Transesterification Operating Conditions Temperature 150 – 200 ºC Oil to ethanol ratio molar 1:25 – 1:40

•Reaction time 3 – 9 min Pressure 200 bar Supercritical carbon dioxide/ethanol 75:25

Publications and Conference:

• Santana A., Jesus S. S., Larrayoz M. A., Filho, R.M. Optimization of Biodiesel Production by Supercritical Transesterification of Edible, Non-edible and Algae Oils. In: 10th International Symposium on Supercritical Fluids

(ISSF). San Francisco (USA) p. 28 (2012).

• Santana A., Jesus S. S., Larrayoz M. A., Filho, R.M. Production of biodiesel from algae oil by supercritical transesterication using continuous reactor. In: 10th Annual World Congress on Industrial Biotechnology and

Bioprocessing. Orlando (USA) (2012).

Continuous transesterification of algae oil under supercritical ethanol using CO2 as

cosolvent was attempted. In this study the effects of the process variables were

evaluated. Results showed that the best conditions are 200 °C, 200 bar, molar ratio of

ethanol-to-oil of 25, at a reaction time of 9 min. The reaction conversions were obtained

at mild temperature and pressure conditions in compare with other supercritical

process. Compared to conventional catalytic methods, which required at least 1 hour

reaction time to obtain similar yield, supercritical methanol technology has been shown

to be superior in terms of time and energy consumption. The merit of this method is

that much lower reaction temperatures and pressures are required due to add of a

cosolvent, which makes the process safer and the purification of products after

supercritical transesterification is much simpler and more environmentally friendly.

Future Work

• Biodiesel Plant Design and Construction for biodiesel production under supercritical conditions at State University of Campinas (UNICAMP) - Brazil.

• Optimization of operations conditions for maximizing biodiesel yield

• Develop a process model (measure kinetics)

Table 2. Operating conditions and FAME’s content on strongly acidic catalyst resin (Nafion SAC-13)

Figure 1. Triglyceride conversion

2-) Thermochemical Route

Syngas from Glycerin and Sugar Cane Bagasse

Syngas – raw material for ethanol and chemicals from chemical

routes and substract for fermentation to produce ethanol

Gasification Syngas

Bioethanol

Sugar Cane

Sugar cane bagasse

Fermentation

EXPERIMENTAL

CO H2

ASPEN PLUS

CFD

Production of Syngas from Sugar Cane Bagasse

http:/www.ruralpecuaria.com.br/

Typical sugar cane bagasse handling

http://www.saomartinho.ind.br/ www.esalq.usp.br

Run Set Independently

T (ºC) t (min) Ar (ml/min) % H2 % CO % H2+CO

23 factorial design

1 750 20 10 19.66 31.6 51.26

2 850 20 10 36.05 29.29 65.34

3 750 40 10 18.63 29.61 48.24

4 850 40 10 35.76 29.68 65.44

5 750 20 50 24.09 27.57 51.66

6 850 20 50 41.07 32.92 73.99

7 750 40 50 19.5 27.63 47.13

8 850 40 50 42.82 34.79 77.61

Central Points

9 800 30 30 33.74 32.32 66.06

10 800 30 30 33.24 32.76 66

11 800 30 30 33.5 32.54 66.04

The main gas products were H2 and CO. Besides these gases, CO2, CH4, C2H4 and C3H8 were

also obtained in smaller proportions.

The liquid product compositions were methanol, ethanol, acetone and acetaldehyde

Net energy recovered = 294kJ/mol of glycerol fed.

Models for Kinetic Parameter Arrhenius, Flyn-Ozawa-Wall (FWA), Kissinger

International Patent requested

Pyrolysis of Glycerin and Sugar Cane Bagasse Syngas Production

and H2 - Fixed bed catalytic reactor – catalyst and process development

Lab. Fluidized bed gasifier

Gasification system

Gasification: T= 700°C – 900°C

Using air or diluted oxygen

as gasification agent.

Biomass

Syngas

Gasification agent

Syngas Composition (dry basis)

Results

Figueroa J., Arila, Y.C., Lunelli, B. Wolf Maciel M.R. maciel filho R. “Evaluation of Pyrolysis and Steam Gasification Processes

of Sugarcane Bagasse in a Fixed Bed Reactor”. CHEMICAL ENGINEERING TRANSACTIONS - VOL.32, pp. 925-930, 2013.

Figure 3. Effect of SB on Syngas composition. Figure 2. Effect of ER on Syngas composition. Figure 4. Effect of temperature on Syngas composition.

BIOMASS

ELEMENTS

AGASIF

VOLAT

VOLATI1

RECIHAR

STEAM

AIR

GASIFI GASITGASIFI2

SOLIDS

ASH

SYNGAS

DESC

PYRO1

MIXGASI GASIFICA

SSOLID

CYCLONE

PYRO2

HEAT

Figure 1. Flowsheet of the syngas production in the circulating fluidized bed gasifier.

Ardila, Y. C., Figueroa, J. J., Lunelli, H., Maciel, R., Wolf Maciel, M. R. Syngas production from sugar cane bagasse in a circulating fluidized bed gasifier using Aspen Plus™: Modelling and Simulation. Computer Aided Chemical Engineering, Volume 30, 2012, Pages 1093–1097. 22nd European Symposium on Computer Aided Process Engineering, Londres.

A simulation of a circulating fluidized bed biomass gasifier was developed using ASPEN PlusTM.

The effects of varying ER (equivalence ratio),

temperature and SB ( steam-biomass ratio) were investigated.

The CO2 percentage in the syngas composition

increases with ER, however the CO and H2 percentage decreases. Higher temperatures increase the percentage of CO, but decrease CO2 and H2. The H2 percentage increases with the increasing of SB, but CO decreases. It also must be highlighted that the composition of CO2 does not change significantly by altering this variable.

a) Steady state and isothermal. b) The pyrolysis or devolatilization is instantaneous . C) In the pyrolysis or devolatilization char and volatiles are formed, the volatiles include non-condensable, such as H2, CO, CO2, CH4, C2H2, condensable volatiles (tar), and water. D) The tar is represented only by naphthalene. E) Char only contains carbon and ash. F) Char gasification starts in the bed and completes in the freeboard.

69

Direct Conversion of Syngas to Ethanol

Thermodynamics Parameters

Reação ∆H° ∆G°

2CO(g) + 4H2(g) ↔ C2H5OH(g) +

H2O(g)

-253,6

kJ/mol

-121,1

kJ/mol

2CO2(g) + 6H2(g) ↔ C2H5OH(g) +

3H2O(g)

-173,8

kJ/mol

-65,7 kJ/mol

CO(g) + H2O(g) ↔ CO2(g) + H2(g)

-41,1 kJ/mol

-28,6 kJ/mol

CO(g) + 3H2(g) ↔ CH4(g) + H2O(g)

-205,9

kJ/mol

-141,9

kJ/mol

CO2(g) + 4H2(g) ↔ CH4(g) + 2H2O(g)

-146,0

kJ/mol

-113,6

kJ/mol

Hydrogenation of CO, CO2 and (CO+CO2)

Temperature

Pressure

H2/CO Ratio

Catalyst + Support + Promoter

Conversion and selectivity

Catalyst

Rh, Ru, Co

Support SiO2, TiO2, Al2O3, ZrO2

Promoter Li, K

La, Ce, Sm

Fe, Mn, Co, V Computers and Chemical Engineering –

to appear, 2014

Figure 1. Mesh of Bubbling fluidized bed gasifier of bagasse. CFD simulation

Study cases

Figure 2. Dry composition of Syngas obtained in bubbling fluidized bed

gasifier of bagasse.

Table 1. Comparison between experimental results and those obtained with the

CFD simulation.

* * Stoichiometric air ratio (AR) and the steam to bagasse ratio (SR)

Simulations validity

In the simulation presented in this work, the

gasifier was operated at temperature of 900°C

with AR= 0.29 and SR = 0.34, obtaining dry

compositions of 22.25, 13.21 and 63.54 vol%

for H2, CO and impurities, respectively.

Figure 3. Velocity profile.: a) Solid phase and b) Gas phase. T = 900 °C, AR =

0.29 and SR = 0.34.

SUGARCANE BAGASSE AS RAW MATERIAL TO SYNGAS PRODUCTION: 3D

SIMULATION AND DATA OF GASIFICATION PROCESS

BIOREFINERIES DIVISION

Integrated bioethanol, biogas and electricity production (double energy output) Zero carbon emission biorefinery system (consorted bioethanol-biodiesel-biokerosene production) Bio-based chemicals using a synthetic biology approach (production of lactic acid isomers from sucrose, $$$, 190,000 added value)

Products from ethanol via acetaldehyde and ethylene route (Green Ethane Process to 98.9% purity)

Source: Thematic Project Fapesp 2008/57873-8– Coordinator Maciel Filho

Integrated Process Zero Generation ProcessChemicals

Zero CO2 emissions

Production of Butanol in a First Generation Brazilian Sugar-Ethanol Plant using the Extractive Flash Fermentation Technology – C6 (C5)

• Process was built up and validated for bioethanol production in bench scale

by Atala (2004) and nowadays in a demonstration plant (increases from 10 to

15-18 % (w/w) of ethanol concentration).

New Process for Butanol Production: Extractive Fermentation- Pinto Mariano et.al. Biotechnology and Bioengineering , 2011) –

Vacuum fermentation

VACUUM

- continuous fermentation

- cell retention

- butanol recovery

stream enriched in butanol

Spotlight paper 2011

Batch – conventional strain MJ / kg ButOH 49.4

Flash – conventional strain MJ / kg ButOH 31.6

An Integrated Process for Total Bioethanol Production and Zero CO2

Emission

Thematic Project- Fapesp: Coordinator Rubens Maciel Filho

Integration of Butanol Production in a

Brazilian Sugar-Ethanol Plant

using the Flash Fermentation

Technology

Butanol plant

Per year (167 days): 2 MM ton sugar cane 102 mil ton sugar 104 MML ethanol

Biobutanol Plant Hierarchy

Biobutanol Production in a First Generation Brazilian Sugar Cane Biorefinery: Technical

Aspects and Econonomics of Greenfields Projects

(Mariano P. A., Dias M.O.S., Junqueira. T.L., Cunha M.P., Bonomi A.,

Maciel Filho R., 2013, Bioresource Technology, 135:316–323)

CAPEX/OPEX

11,3%

13,9% 15,2%

13,1% 13,9%

0%

5%

10%

15%

20%

BIO-G RS-C MS-C RS-F MS-F

Aft

er-

tax

IR

R

Biorefinery scenario

77

SECOND GENERATION BIOBUTANOL

Return on investment

Butanol

Chemical

Butanol

Biofuel Biogas

-

Net Revenue breakdown

(Mariano P. A., Dias M.O.S., Junqueira. T.L.,Cunha M.P., Bonomi A., Maciel Filho R., 2013,

Bioresource Technology, 142:390–399)

(Utilization of pentoses from sugarcane biomass: Techno-economics of biogas vs.

butanol production)

SECOND GENERATION BIOBUTANOL

Butanol

Plant

~ 20 MW

10%

ABE fermentation development of new process technologies

PILOT PLANT (500 L fermentor)

ETHANOL production

BIOBUTANOL – test phase

CTC / Unicamp

30 % energy saving

High Added value chemicals : Example

LACTIC ACID – Isomers D and L in a

controlled way

0 8 16 24 32 40 48 56 64 72

0

5

10

15

20

25

30

Lactic Acid

Time (h)

Co

nce

ntr

atio

n (

g/L

)

Sucrose

0

100

200

300

400

500

600

700

800

900

2º pulse

1º pulse

NaO

H so

lutio

n (m

L)

NaOH

Bio- materials from Renewable sources – An example of added value

1 ton of Sugar Cane – R$ 45,00 R$ 0,000045/gram

1 Kg of Sugar – R$ 1,30 R$ 0,0013/gram

1 liter of biethanol R$ 1.80 /liter

1 Kg of LA (purified) R$ 5.000,00 R$ 5,00/gram

1 Kg of in shape biomaterial R$ 180.000,00 R$ 180,00/ gram

In relation to the Sugar and added value of 190.000 times

BONE TISSUE ENGINEERING – Sugar cane sucrose PLA with Properties control – TEST IN VIVO

POLY LACTIC ACID

The polylactide (PLA) is one of the most promising biodegradable

polymers due to its mechanical property profile, thermoplastics,

biological and processing. It is very useful in medical area.

Applications: Reconstructive Surgical- head plastic surgery

ENGINES DIVISION

Research to consolidate ethanol as the renewable substitute for gasoline on a short to medium term (10 to 20 years), with the evolution of internal combustion engines, and on a long term with fuel cells.

Flex-fuel engines with increased performance, durability, less fuel consumption and less pollutant emissions

• Efficiency of a Flex-fuel Vehicle is 30% (hybrid flex fuels-electric engines)

• Design new more adequate fuels • Cold-starting problem • Decrease fuel consumption and CO2 emissions

Projects with PSA - CEPID

SÃO PAULO CITY

SÃO PAULO STATE

BRAZIL

Brazilian bioethanol demand: 50 billion L to substitute 45% of otto cycle cars by 2020

(Goldemberg, 2012)

More than 13 million Flex-fuel

Vehicles in Brazil

Mandates around the world: demand of 60 billion gallons by 2022

IMPACTS DIVISION

Ethanol as a global strategic fuel

Studies to consolidate sugarcane ethanol as the leading technology path to ethanol and derivatives production

Land use changes GHG emissions

Biomass and soil carbon stocks Water use

Biodiversity Regional income generation Job creation and migration

Integrating tools

Good for People, Planet and Profit

Economic Model for Food vs. Fuel vs. Land vs. Biodiversity

SUGAR CANE IS THE HIGHEST TONNAGE CROP – ONLY FIRST GENERATION IS CONSIDERED

Sugarcane is the highest tonnage crop Fast growth In 12 months the plant will reach 4-5 meters with the extractable stems measuring 2-3 meter Large amount of carbon partitioned into sucrose (up to 42% of the stalk dry weight)

Expanding sustainably

Southwest: dry winter

Marginal land, pastureland, and poor soils

• Drought resistance

• Crop breeding to new environments

• Revise nutritional needs and managing of

fertilizers

• Recycle nutrients of crop and industry

residues

• Land Use Change Models

South America Central America Africa: 0.43 GHa @ 10kL/Ha.yr

4,300GL 2050: Available land for biofuels

(Doornbosch and Steenblik, 2007)

http://bioenfapesp.org