new$analytical$methods$for … · 10 global vegetable oil production food and agriculture...

NEW ANALYTICAL METHODS FOR DETERMINATION OF CHEMICAL SPECIES

OF INTEREST IN BIOENERGY AREA

Nelson Ramos Stradio0o

UNIVERSIDADE ESTADUAL PAULISTA “JÚLIO DE MESQUITA FILHO”

INSTITUTO DE PESQUISA EM BIOENERGIA

1

WORLDWIDE ENERGY SUPPLY

Brazilian Energy Balance 2014 Year 2013 / Empresa de Pesquisa Energética – Rio de Janeiro: EPE, 2014. 2

WORLDWIDE ENERGY COMSUMPTION BY SECTOR

3 Brazilian Energy Balance 2014 Year 2013 / Empresa de Pesquisa Energética – Rio de Janeiro: EPE, 2014.

Commercial

Residential Transportation Industrial

2.4%2.6%4.4%

11.3%

1.1%7.6%

70.6%

H ydro B iomas s W ind Natura l g a s O il products Nuc lea r C oa l and coa l products

O il G as C oa l Nuc lea r H ydro W ind S ola r G eotherma l & B iomas s B iofuels

30% 24%

33%

4%

7% 1%

0% 1% 0%

BRAZIL GLOBAL ENERGY

ENERGY CONSUMPTION IN 2013

BEN 2014: Ano base 2013. Empresa de Pesquisa Energética, 2014, 288 p. MEARNS, E. Global Energy Trends – BP Statistical Review 2014 (http://euanmearns.com/)

4

BRAZILIAN ENERGETIC RESOURCES

Seventh-largest reserve in the world uranium concentrate

70% of the energy is hydroelectric – -ANEEL

Today: oil reserves is 15,6 billion barrels -ANP

459,187 million cubic meters (m³) -MME

Installed capacity: 6,08 GW Brazilian Association of Wind Energy - Abeeólica

7,0% of the energy -MME

Brazilian Energy Balance 2014 Year 2013 / Empresa de Pesquisa Energética – Rio de Janeiro: EPE, 2014. 5

BRAZILIAN PRODUCTION 2000/2001 – 2012-2013

MAPA (Ministério da Agricultura, Pecuária e Abastecimento) 2012 Nova Cana 2015

anhydrous ethanol

hydrous ethanol

total ethanol

m³

SUGARCANE PRODUCTION ETHANOL PRODUCTION

6

Study

Implanta<on

in opera<on

ETHANOL PLANTS IN BRAZIL

Ethanol Plants Operational: 434 plants

Total: 27 billion liters/year

7 ANP 2013

NORTH NORTHEAST

SOUTHEAST

SOUTH

MIDWEST

dende co0on

peanut

mammon

Jatropha soybean

co0on

peanut

Sunflower mammon soybean

co0on

canola Sunflower soybean

peanut

Sunflower mammon

Jatropha soybean

BIODIESEL - MAIN CULTURES

ÚNICA 2010 8

q  Soy: large-scale farming, helped make Brazilian Biodiesel Program possible

q  Castor beans production: helping family farming

q  Jatropha, Macauba, Sunflower and Others: small scale or still in development

q  Animal Fat: the second largest feedstock for brazilian biodiesel

q  Palm oil in the north region: the new frontier Soy Animal Fat Cottonseed

BRAZILIAN VEGETABLE OIL PRODUCTION

9 EPE 2012

10

GLOBAL VEGETABLE OIL PRODUCTION

Food and Agriculture Organization of the United Nations, 2011

Palm oil is the most widely used vegetable

oil in the world.

As shown in the chart , palm and palm

kernel oils accounted for 35% percent of total

vegetable oil production in 2011. At 27% of total

production, soybeans were the next largest source of

vegetable oil, followed by rapeseed (the basis of

canola oil).

PROJECTED CONSUMPTION OF BIODIESEL IN BRAZIL (billion liters)

ANP 2014 11

Biodiesel plants authorized ANP 2015.

BIODIESEL PLANTS IN BRAZIL

12

BIODIESEL IN THE WORLD

o  In 2013, the USA, Brazil and Germany were the top countries in terms of biodiesel production capacity; their combined share in the world’s total capacity was equivalent to 36.7%.

o  In 2013, Europe was the top biodiesel producer in the world with a share of around 38% in the global supply. The top five biodiesel producing countries (namely the USA, Brazil, Germany, Indonesia and France) held a share of 51.08% in the world’s total produc<on volume in 2013.

www. mcgroup.co.uk/ -‐ 2014 13

14

WORLDWIDE BIODIESEL AND BIOETHANOL PRODUCTION

F.O Licht In:Global Renewable Fuels Allianc (2013) Hart Energy 2012

GLOBAL DEMAND FOR BIOFUELS WILL GROW 133% UNTIL 2020 !!!

15

ANALYTICAL METHODS

EvaluaIon of raw material

Bioethanol: sugarcane, corn and sugar beet.

Biodiesel: soybeans, palm oil and cassava.

Monitoring of manufacturing processes

Bioethanol: extrac<on,

fermenta<on and

dis<lla<on.

Biodiesel: extrac<on,

transesterifica<on and separa<on.

MarkeIng of products obtained

Biofuels: Quality,

market and inspec<on.

16

BIOFUELS QUALITY

SPECIFICATION

ANALYTICAL METHODS

REFERENCE MATERIAL

17

OFFICIAL METHODS Hydrate Ethanol Fuel Specifications

ANALYSIS NORM METHODS ACID ETHANOL NBR 9866 Colorimetric titration

CONDUCTIVITY NBR 10547 Electrical conductivity, cell platinum

SPECIFIC MASS NBR 5992 or ASTM 4052 Glass the densimeter method

LEVEL ALCOHOL NBR 15639 Electronic densitometry method pH NBR 10891 Potentiometric method

LEVEL ETHANOL D5501 Gas chromatography

WATER DETERMINATION NBR 15531 NBR15888

Volumetric or potentiometric method Karl Fischer

EVAPORATION RESIDUE NBR 8644 The sample is evaporated in kiln

SODIUM NBR 10422 Flame photometry

HYDROCARBONS BR 13993 Reaction of alcohol with sodium chloride

CHLORIDE AND SULFATE NBR 10894 Ion Chromatography

COPPER AND IRON NBR 8644 Atomic absorption spectrophotometry

ANP, RESOLUTION Nº 7, DE 9.2.2011

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ANALYSIS NORM METHODS

PHOSPHORUS AND SULFUR

NBR 15553 e ASTM D4951, ASTM D6751

Atomic emission spectroscopy with inductively coupled plasma (ICP OES)

CORROSIVENESS TO COPPER

EN 14214, ASTM D6751

Copper plate is submerged in fuel at 50 ° C for 3 h.

CALCIUM AND MAGNESIUM EN 14538 ICP OES

ASPECT RANP 07/08 Visually

TOTAL CONTAMINATION EN 14214, RANP 07/08 Filtration

FREE AND TOTAL GLYCERIN

EN ISO 14105, EN ISO 14106, ASTM D6584 Chromatographic method

CARBON RESIDUE ASTM D4530 EN ISO 10370

Burned sample and the final residue is weighed

ESTER ABNT NBR 15342 Chromatographic method

FLASHPOINT ABNT NBR 14598 Observation of the release of vapors

METHANOL AND ETHANOL ABNT NBR 15343 Chromatographic method

SODIUM AND POTASSIUM

EN ISO 14108 EN ISO 14109 Flame photometry

LOBO, I. V. et. al. Quim. Nova, 32 (6) 1596, 2009.

OFFICIAL METHODS Biodiesel Specifications

19 SANTOS, A. L. et al. Electroanalysis 24 (8) 1681 2012.

Electrochemical methods for determination of inorganic compounds in bioethanol and biodiesel.

20 SANTOS, A. L. et al. Electroanalysis 26 (2) 233 2014.

Electroanalytical methods for determination of organic compounds in bioethanol and biodiesel

21

Cyclic voltammograms obtained with GCE, Nafion/GCE and CNT/Nafion/GCE with ν=50 mV s-1.

SEM-FEG images of surface of the CNT (A) and CNT/Nafion/GCE in different magnifications: (B) 20 000 and (C) 100 000.

SILVA, J. J.; PAIM, L. L.; STRADIOTTO, N. R. Electroanalysis 26 (8) 1794 2014.

Simultaneous Determination of Iron and Copper in Ethanol Fuel Using Nafion/Carbon Nanotubes Electrode

22

Comparing the performance achieved by LSSV, DPSV and SWSV, n=4.

Voltammograms obtained in hydro-alcoholic medium with 30% (v/v) ethanol by LSSV (A), DPSV (B) and SWSV (C) with scan direction from -0.4 V to 0.8 V.

Comparing the performance achieved by the diferents methods.

Recovery study. A) Voltammograms obtained for ethanolfuel sample, spiked sample and standard additions by LSSV. B) and C) Curves of standard a d d i t i o n s f o r F e 3 + a n d C u 2 + , respectively.

23

24

Cyclic voltammograms for the electropolymerization of o-PD in the absence (A) and in presence (B) of glucose. Inset: pH 4.8 acetate buffer solutions and v=50 mVs-1.

Electropolymerization reaction of o-PD.

An Electrochemical Sensor for Reducing Sugars Based on a Glassy Carbon Electrode Modified with Electropolymerized Molecularly Imprinted Poly-ophenylenediamine Film

Wang, Q. et al. Electroanalysis 26 (7) 1612 2014.

SEM-FEG images of the surface of the bare glassy

carbon electrode (A), the electrode covered with

the PPD film(B).

25

(A) CV and (B) EIS of 5.0 mM K3Fe(CN)6 o n t h e b a r e G C E ( a ) ; a f t e r electropolymerization (b); Glu-PPD/GCE after removal of glucose (c); Glu-PPD/GCE after incubation in 2.5 mM glucose (d).

26

(A: glucose) and (B : fructose) DPV of increasing reducing sugars concentration in acetate buffer solution (pH 4.8). (C) Dependence of the current change (ΔIp) on the concentration of sugar on Fru-PPD/GCE, Glu-PPD/GCE and NIP (curve c) sensors. (D) linear calibration curve (a: fructose; b: glucose).

27

Comparison of analytical performance for the electrochemical determination of glucose.

The black columns are the current change of Glu-PPD/GCE in NaAc-HAc solution (pH 4.8) . The red column is the current change of Fru-PPD/GCE in NaAc-HAc solution (pH 4.8).

28

Recovery study of glucose and fructose in standard solutions.

Determination of glucose and fructose in sugarcane industries samples.

29

Formation of the NiHCFNP in a solution containing 1.0 mmol L-1 Ni(NO3)2, 0.5 mmolL-1 K3[Fe(CN)6] and 500 mmolL-1 KCl in 100 mmol L-1 HCl on the GC electrode (scan rate of 100 mVs-1).

Images from electron microscopy (2.0 kV) of NiHCFNP in GC (a) magnification 50 000 times (b) magnification 20 000 times.

Simple and direct potentiometric determination of potassium ions in biodiesel microemulsions at a glassy c a r b o n e l e c t r o d e m o d i f i e d w i t h n i c k e l ( I I ) hexacyanoferrate nanoparticles

SEDENHO, G. C.; PAIM, L. L.; STRADIOTTO, N. R. Anal. Methods 5 (16) 4145 2013.

30

Potentiometric parameters of NiHCFNP/GC electrodeposited at different concentrations of K3[Fe(CN)6] and Ni(NO3)2 in solution of 500 mmolL-1 KCl and 100 mmolL-1 HCl.

Surface excess and potentiometric parameters obtained in aqueous medium of nanoparticles electrodeposited on GC in solution of 500 mmol L-1 KCl and 100 mmolL-1 HCl, containing 0.5 mmolL-1 K3Fe(CN)6 and 1.0 mmolL-1 Ni(NO3)2.

31

CV of GC in 0.1 molL-1 HCl containing 1.0 mmolL-1 K3Fe(CN)6 at a scan rate of 100 mVs-1 in (a) a q u e o u s m e d i u m a n d ( b ) microemulsion 5:70:25 (v/v/v) for biodiesel: propan-1-ol:aqueous solution.

CV of NiHCFNP/GC at a scan rate of 100 mVs-1 in (a) 1.0 molL-1 KCl (b) microemulsion biodiesel:propan-1-ol:aqueous phase (5:70:25 in volume).

32

Potentiometr ic response to potassium ion in a microemulsion of biodiesel:propan-1-ol:aqueous phase (5 : 70 : 25 in volume) using the NiHCFNPmodified electrode.

Comparison between different methods using potentiometry for potassium determination.

33

Potentiometric selectivity coefficients determined with the modified electrode with NiHCFNP using an interfering constant concentration of interfering ion of 1.0 mmolL-1 and a potassium concentration of 1.0x10-7 molL-1 to 5.0 mmolL-1 in the microemulsion.

Recovery results for the determination of

potassium ions in biodiesel

microemulsions by potentiometry using

GC modified electrode with NiHCFNP.

_____________________________________ _____________________ _

34

SEM images of nano-copper oxide electrodeposited on GCE surface.

Particle size histogram of the nano-copper oxide.

Determination of uronic acids in sugarcane bagasse by anion-exchange chromatography using an electrode modified with copper nanoparticles

BELUOMINI, M. A.; da SILVA, J. L.; STRADIOTTO, N. R. Stradiotto, Anal. Methods 7 2347 2015.

35

Cyclic voltammograms of 5.0 mmol L-1 D-galacturonic (-) and D-

glucuronic (--) acids in the presence of 0.1 mmol L-1 NaOH on modified

electrode (CuNP), υ = 50 mVs-1.

Chronoamperometric response to 1.0 mol L-1 of

D-glucuronic acid in alkaline medium during

the period of 1000 s, potential of 0.55 V.

36

Isocratic separation chromatogram of standard solution (1) glucose, xylose, mannose, arabinose, (2) D-galacturonic acid, and (3) acid D-glucuronic in CuNP detector

Analyte tm tr tr’ Rs N α k

galacturonic 1.60 8.72 7.12 4.04 3238 1.40 4.45

glucuronic 1.60 11.55 9.95 2.07 3441 6.22

Parameters for the chromatographic separation of D-galacturonic acid and D-glucuronic.

37

Chromatogram for sample hydrolyzed of sugarcane bagasse. In (a) the peak (1) shows ox ida t ion o f the sample componen ts , 2 .02 m in and (b ) magnification of the retention times for (2) D-galacturonic acid 8.82 min and (3) D-glucuronic acid, 11.67.

D-galacturonic/ mol L-1 Amount found/ mol L-1 Recovery % 2.5x10-5 2.1 x10-5 84.8 5.0 x10-5 4.8 x10-5 96.0 1.0 x10-5 1.0x10-4 101.5

D-glucuronic 2.5x10-5 2.5 x10-5 101.9 5.0 x10-5 4.7x10-5 95.5 1.0 x10-5 1.0x10-4 100.9

Percent recovered in HPLC technique for the D-galacturonic and D-glucucronic acid.

ACKNOWLEDGEMENTS

38

o  Collaborators:

o  Acelino C. de Sá (D. Phil.);

o  Flávia C. U. Santos (Graduet Student);

o  Graziela C. Sedenho (Masters Student);

o  José L. da Silva (D. Phil.);

o  José R. Delfino (D. Phil.);

o  Maísa A. Beluomini (D. Phil.);

o  Milena E. Teixeira (Senior Researcher);

o  Tarso Ferrari (Graduet Student);

o  Thiago M. Mariano (Masters Student);

o  Thulio C. Pereira (D. Phil.).

ACKNOWLEDGMENT

39 OBRIGADO!

BIOENERGY IN SAO PAULO STATE

Divisions Researchers UNESP Unicamp USP Total

Use of biofuels in engines 5 10 8 23 Biofuel producIon 32 39 57 128 Biorefinery, chemical alcohol and chemical oil 5 10 8 23

Biomass for bioenergy 22 14 55 91 Sustainability: socioeconomic and environmental 20 39 42 101

Total 84 112 170 366

40

Ph.D. Program in Bioenergy

Name: Integrated Ph.D. Program in Bioenergy InsItuIons: University of São Paulo (USP) State University of Campinas (UNICAMP) State University of São Paulo (UNESP) Modality: Interdisciplinary Level: PhD CreaIon: 2013

41

•  InsItuIons: USP: 16 Researchers

UNICAMP: 16 Researchers UNESP: 15 Researchers

•  CNPq Researchers: 38

•  Total Supervisors: 47


42

•  Compulsory Courses: Fundamentals of Biomass Produc<on Transforma<on Processes of Biomass into Biofuel Social, Economic and Environmental Sustainability


43

•  ElecIve Courses: Advanced Topics in Biomass Produc<on for Bioenergy Advanced Topics in Biorefinery

Advanced Topics in Engines and Biofuel

Advanced Topics in Socio-‐Economic and Environmental Sustainability

Advanced Topics in Bioenergy

Advanced Topics in Biofuel Manufacturing Processes


44

•  Students NaIonaliIes : Brazil: 32 Argen<na: 2 Colombia: 2 Spain: 2 Honduras: 1 Portugal: 1 Russia: 1

TOTAL: 41


45

•  OrganizaIon: Coordinators:

Carlos Alberto Labate (USP)

Andreas Karoly Gombert (UNICAMP)

Jonas Con<ero (UNESP)


46

•  OrganizaIon: ExecuIve Commicee: Carlos Alberto Labate (USP) Igor Polikarpov (USP) Andreas Karoly Gombert (UNICAMP) Antonio José de Almeida Meirelles (UNICAMP) Eliana Gertrudes de Macedo Lemos (UNESP) Nelson Ramos Stradio0o (UNESP)


47

•  OrganizaIon: Advisory Commicee: José Eduardo Krieger (USP) -‐ Research Provost Bernade0e Dora Gombossy de Melo Franco (USP) -‐ Graduate Provost Gláucia Maria Pastore (UNICAMP) -‐ Research Provost Rachel Meneguello (UNICAMP) -‐ Graduate Provost Maria José Soares Mendes Giannini (UNESP) -‐ Research Provost Eduardo Kokubun (UNESP) -‐ Graduate Provost


48

•  Technical features: Courses: English

Advisors/Co-‐advisors: na<onal/ interna<onal/ state / federal

Internship: 6 months


49

•  University Units: USP: ESALQ, IFSC, IQ, FEL

UNICAMP: FEA, IQ, FEAGRI

UNESP: IPBEN, FCA, FCAV, FCF, FCL, FEG, FEIS, IB, IBILCE, IQ.

Total number of students enrolled in the selec<on process: 79


50

•  LINKS:

hcp://genfis40.esalq.usp.br/pg_bio/

hcp://www.ipben.unesp.br


51

INSTITUTO DE PESQUISA EM BIOENERGIA IPBEN -UNESP

•  The IPBEN UNESP was created in 2011 to bring together researchers working in the relevant area of Bioenergy

52

Main Laboratory in Campuses of Rio Claro

(center of São Paulo State) Campuses Araraquara

Campuses Assis

Campuses Botucatu

Campuses Guara<nguetá

Campuses Jabu<cabal

Campuses São José Rio Preto

Integra<on of 7 associated laboratories spread throughout

the state of São Paulo

Campuses Ilha Solteira

Division Researchers

Produc<on of Biomass for Bioenergy (ethanol from sugarcane and biodiesel from soil bean)

22

Bioenergy Produc<on (Fuel, Heat, Electricity)

32

Applica<on of Bioenergy (Biofuels for Automo<ve Motors and fuel cell)

5

Biorefineries, Alcohol Chemistry and Oil Chemistry (produc<on of green products)

5

Sustainability Aspects (Biofuell Economical, Social and Environment Impact)

20

RESEARCHERS and DIVISIONS 84 researchers working in Bioenergy

53

54

AREA RESEARCH PROJECTS LABORATORIES

GENETIC IMPROVEMENT

Plant genomics Jabo<cabal

Func<onal genomics Lignin synthesis

Botucatu Plant systems biology

AGRICULTURE

Use of residues in sugarcane cul<va<on Araraquara

Biological control

Plant physiology Jabo<cabal Botucatu

Fer<lizers Botucatu BASIC SCIENCES Enzymes Jabo<cabal AGRICULTURAL ENGINEERING Refined agriculture Botucatu

BIOMASS FOR BIOENERGY

55


FIRST GENERATION

Energy op<miza<on Guara<nguetá/Ilha Solteira

New industrial arrangements Jabo<cabal

Fermenta<on control processes

Araraquara Reactant in ethylic biodiesel produc<on

BASIC SCIENCES

Biofuels quality

Biotechnology Araraquara/Jabo<cabal/Ilha Solteira

Enzymes São José do Rio Preto

CO-‐PRODUCTS Electricity from cane biomass Guara<nguetá/Botucatu/Ilha Solteira

SECOND GENERATION

Microorganisms gene<cs for enhanced cellulose degrada<on Jabo<cabal/Araraquara/Assis

Enzima<c hydrolysis São José do Rio Preto/Jabo<cabal

BIOFUELS PRODUCTION

56


ALCOHOL

ENGINES Use of ethanol in motorcycle engines

Ilha Solteira

Botucatu

Jabo<cabal

NEW ENGINES Use of ethanol in diesel engines

Guara<nguetá

Jabo<cabal

Ilha Solteira

FUEL CELLS Ethanol reformer Guara<nguetá

APPLICATION ON AUTOMOTIVE MOTORS

57


GREEN

PRODUCTS

Biopolymers Rio Claro

São José do Rio Preto

Biosurfactants Rio Claro

Jabo<cabal

BIOREFINERIES, ALCOHOL CHEMISTRY AND OIL CHEMISTRY

58


SOCIAL ASPECTS

Impacts of sugarcane ethanol expansion Jabo<cabal

Impacts of sugarcane Botucatu

Rural planning

ENVIRONMENTAL ASPECTS

Impacts on water resources São José do Rio Preto Araraquara

Impacts on biodiversity Araraquara Assis

ECONOMICAL ASPECTS

Modern biomass economy Guara<nguetá Ilha Solteira Botucatu

Cer<fica<on studies Araraquara Ilha Solteira

SUSTAINABILITY ASPECTS

59

Total: 350

•  SUPPORT RESEARCH -‐ 66 IN PROGRESS -‐ 27 COMPLETED

•  SCHOLARSHIP IN THE COUNTRY: -‐ 116 IN PROGRESS -‐ 136 COMPLETED

•  SCHOLARSHIP OUTSIDE THE COUNTRY

-‐ 04 IN PROGRESS -‐ 01 COMPLETED

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OBRIGADO

new$analytical$methods$for … · 10 global vegetable oil production food and agriculture...

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