TECHNOLOGICAL CHALLENGES FOR THE PRODUCTION … · Universidad de Córdoba (España) TECHNOLOGICAL CHALLENGES FOR THE PRODUCTION OF BIODIESEL IN ARID LANDS Diego Luna Departamento

Universidad de Córdoba (España)

TECHNOLOGICAL CHALLENGES FOR THE PRODUCTION OF BIODIESEL IN

ARID LANDS

Diego Luna

Departamento de Química Orgánica, Universidad de Córdoba, Campus de Rabanales, Edificio. Marie Curie, E-14014 Córdoba, Spain. ([email protected])

Seneca Green Catalyst, Campus de Rabanales, E-14014 Córdoba, Spain.

www.senecagreen.com

BIODIVERSITY FOR BIOFUELS AND BIODIESEL IN ARID LANDS

(BIO3)

Friday, November 26, 2010


Hexadecane (also called cetane) is an alkane hydrocabon with the chemical formula C16H34, a chain of 16 carbon atoms

Molecular formula C16

H34

Molar mass 226.44 g/mol

Melting point 18 °C, 291 K, 64 °F

Boiling point 287 °C, 560 K, 549 °F

Solubility in water Insoluble

Flash point 135 °C

Autoignition temperature 201 °C

Triglyceride molecule model


http://en.wikipedia.org/wiki/File:Hexadecane.png












































































































































Conventional

Transesterification

process of

triglyceride

molecules

Biodiesel typically

comprises of fatty

acid (chains C14–

C22) esters of

short-chain

alcohols, mainly

methanol Three molecules of fatty acid methyl esters (FAME) and

one molecule of glycerol are generated for every molecule



Strengths and weaknesses of the available different methods for the production of the mixtures of methyl esters of fatty acids that constitute FAME, the conventional biodiesel.

Technology

Catalyst

Working

Temperature/ °C

Economic

charges

Improvements

Basic reaction

N a O H , KOH

60 Low Available

technology

A c i d reaction

H2SO4 55 - 120 Low Do not form

soaps

supercritical alcohol

- 239-385 Medium Uses

no catalyst

e n z y m a t i c process

Lipases 45 -55 High Low level

of wastes



Pilot scale material

balance for

Jatropha oil

transesterification

using NaOH (1 %)

as catalyst



Lurgi Transesterification Process.


National Sustainable Agriculture Information Servicewww.attra.ncat.org

ATTRA is the national sustainable agriculture information service operated by the National Center for Appropriate Technology, through a grant from the Rural Business-Cooperative Service, U.S. Department of Agriculture. These organizations do not recommend or endorse products, companies, or individuals. NCAT has offices in Fayetteville, Arkansas (P.O. Box 3657, Fayetteville, AR 72702), Butte, Montana, and Davis, California

By David Ryan, P.E.NCAT Energy SpecialistDecember 2004

©NCAT 2004

Biodiesel - A Primer

Abstract: This publication is an introduction to biodiesel production

Washing BiodieselUnwashed biodiesel will not meet ASTM (American Society of Testing and Materials) standards. For more information about ASTM standards, and testing and specifications for biodiesel and other diesel fuels, see Resources. Remember, equipment and engine manufacturers only warranty their equipment and engines for their material and manufacturer defects. Fuel manufacturers (in this case, you) assume responsibility for any damage caused by the fuel. Washing biodiesel is easy to do, and requires only water and time.




Processes of Dehydration (1), Oxidation (2) and Polymerization (3), undertaken by the residual glycerol in the biodiesel, inside the engines working at higher temperatures.



Polymer deposition resulting from a use of biodiésel with an inadequate oxidation stability.

Damage resulting from soap deposition (bio-diesel

with an excessively high alkaline or alkaline earth

content).





Production of high-quality biofuel from vegetable oils through removal of oxygen in triglyceride molecules by overall hydrotreatment in conventional refineries.



Composition of

the high-quality

biofuels

obtained from

vegetable oils

through the

hydroprocessing

routes to

transportation

fuels in

conventional

refineries.

bioLPG

biogasoline

hydrobiodiesel

(or H-biodiesel)



DMC-BIOD® is a patented biofuel (Notari and Rivetti, 2004) that integrates the glycerine as glycerol carbonate, in a process that can be developed by enzymatic technology (Su et al, 2007) obtained by crossed transesterification reaction of a triglyceride with dimethyl carbonate, obtaining a mix of three moles of FAMEs and one mole of glyceryl carbonate (GC).



Gliperol® is a biofuel patented by the Industrial Chemistry Research Institute of Varsow (Poland), (Kije!ski et al, 2004), consisting of a mixture of three moles of FAME or FAEE and a mole of triacetin, that can be obtained by the cross transesterification of ethyl acetate and the corresponding triglycerides in an enzymatic catalyzed process (Modi et al., 2007).



Ecodiesel®, is a biofuel which incorporates the glycerol as monoglyceride, produced by enzymatic technology and patented by the University of Cordoba (Luna et al, 2007). It is composed of two moles of ethyl esters of fatty acids (FAEE) and a mole of monoglyceride ( MG).



.

(TRIOLEIN) (TG !!>DG) [MW: TG " 3/2 DG]

CH3-(CH

2)7-CH=CH- (CH

2)7-COO-CH

2 CH

3-(CH

2)7-CH=CH-(CH

2)7-COO-CH

2

# k

1 #

CH3-(CH

2)7-CH=CH- (CH

2)7-COO-CH !!>CH

3-(CH

2)7-CH=CH-(CH

2)7-COO-CH

# #

CH3-(CH

2)7-CH=CH- (CH

2)7-COO-CH

2 +

CH

2OH

CH3-(CH

2)7-CH=CH-(CH

2)7-COOCH

2CH

3 (FAEE)

(DG !!>MG) [MW: DG " 1/2 MG]

CH3-(CH

2)7-CH=CH- (CH

2)7-COO-CH

2 CH

2OH

# k

2 #

CH3-(CH

2)7-CH=CH- (CH

2)7-COO-CH !!>CH

3-(CH

2)7-CH=CH-(CH

2)7-COO-CH

# #

CH2OH

+

CH

2OH

2 CH3-(CH

2)7-CH=CH-(CH

2)7-COOCH

2CH

3 (FAEE)



Fuel properties of mineral diesel, Jatropha biodiesel, Jatropha oil.

Property Mineral Diesel

Jatropha Biodiesel

Jatropha Oil

Density(kg/m3) 840±1.732 879 917±1

Kinematic Viscosity at 40 ºC (cst) 2.44±0.27 4.84 35.98±1.3

Pour Point (ºC) 6±1 3±1 4±1

Flash Point (ºC) 71±3 191 229±4

Conradson Carbon Residue (%,w/w)

0.1±0.0 0.01 0.8±0.1

Ash Content (%, w/w) 0.01±0.0 0. 013 0.03±0.0

Calorific Value (MJ/kg) 45.343 38.5 39.071

Sulphur (%, w/w) 0.25 <0.001 0.0

Cetane No. 48-56 51-52 23-41

Carbon (%, w/w) 86.83 77.1 76.11

Hydrogen (%, w/w) 12.72 11.81 10.52

Oxygen (%, w/w) 1.19 10.97 11.06



Propertiessoybean oil

FAMEa FAMEb FAEE

c Diesel

Specific gravity (g cm-3) 0.920 0.86 0.8802 0.876 0.8495

Viscosity (40oC, cSt or m2/s) 46.68 6.2 5.65 6.11 2.98

Cloud point (oC) 2 -2.2 0 -2 -12

Pour point (oC) 0 -9.4 -15 -10 -18

Flash point (oC) 274 110 179 170 74

Boiling point (oC) 357 366 347 273 191

Cetane number 48.0 54.8 61.8 59.7 49.2

Sulphur (%wt) 0.022 0.031 0.012 0.012 0.036

Heat of combustion (KJ/Kg) 40.4 40.6 40.54 40.51 45.42

a FAME stands for fatty acid methyl esters from soybean oilb FAME stands for fatty acid methyl esters from rapeseed oilC FAEE stands for fatty acid ethyl esters from rapeseed oil

Physico-chemical properties of soybean oil, biodiesel (B100) obtained from soybean oil and rapeseed oil and No. 2 diesel (D2) (Peterson and Reece, 1996).


.

Kinematic viscosity values, ! (cSt or mm2/s) at 40 ºC of various

representative biodiesel blends as well as commercial diesel and biodiesel.

Nº Oil/Alcohol FAE MG+DG

TG Yield Conv. !

1 Sunflower oil - - 100 - - 31.9

2 Commercial Diesel - - - - - 3.1

3 Commercial Biodiesel - - - - - 2.9

4 Used /MeOHa 95.7 4.3 - 95.7 100.0 3.9

5 Sunflower / EtOHb 94.8 5.2 - 94.8 100.0 6.6

6 Sunflower /EtOHc 55.7 44.2 - 55.7 100.0 6.9

7 Sunflower / EtOH 61.3 38.7 - 61.3 100.0 4.1

8 Sunflower /1-PrOH 62.0 35.8 - 62.0 100.0 9.2

9 Sunflower /2-prOH 33.9 55.6 10.8 33.9 89.5 12.9

10 Sunflower /EtOH 44.3 33.6 22.1 45.3 77.9 19.6

11 Used/EtOH 54.3 41.2 4.5 54.3 95.5 23.4

12 Used/EtOH 51.4 40.9 7.7 51.4 92.3 24.5

13 Used/EtOH 66.0 31.0 3.0 66.0 100.0 19.7

14 Sunflower /EtOH 58.4 41.6 - 58.4 100.0 15.0

15 Sunflower / EtOH 60.8 39.2 - 60.8 100.0 5.4

16 Sunflower /EtOH 26.5 53.4 20.1 26.5 76.6 20.7

17 Sunflower /EtOHd 13.4 84.6 2.0 13.4 98.0 24.5

18 Used/MetOH 71.9 28.1 - 71.9 100.0 13.1

19 Diesel/biodiesel (1:1)e B50 - - - - - 6.4

20 Diesel/biodiesel (8:2)e B20 - - - - - 4.2

aHomogeneous catalyst NaOHbHomogeneous catalyst KOHcFree PPLdSynthetic biodiesel blendeBlend of commercial diesel and

biodiesel with viscosity, $ = 13.1 cSt.(Caballero, V., et al., 2009; Process Biochem. 44, 334–342)


.

Influence of lipase (from Termomyces lanuginosus) amount in conversion and

kinematic viscosity, of reactions carried out at oil/ethanol volume ratio 12/3.5 and

pH near to 12, and 20 ºC of reaction temperature.Verdugo, C., et al. 2010; Cost Action CM0903 (UBIOCHEM), 1st Workshop, 13-15 May, Córdoba (Spain).


.

Figure 9. Influence of water content in conversion and kinematic viscosity of

reactions carried out with 0.03 g of lipase (from Termomyces lanuginosus), at oil/

ethanol volume ratio 12/3.5 and pH near to 12, and 20 ºC of reaction temperature.


.


.


.


.

! Regarding the introduction of renewable energies, in most cases we find today with an uncomfortable truth: currently available technologies require an excessive amount of water Therefore, in the absence of a major technological advancement in these technologies is predictable a scenario in which the availability of water would be a real limiting factor in the production of biofuels in arid lands, more important even that those due to the own production of crops where are obtained the corresponding raw materials.

" In this future scenery, nonirrigated vegetable oils could offer an increasingly integration within crude-petrol refineries for fuels blending after hydrotreating in flows of hydrogen with conventional catalysts. In this way introducing fuels based upon feedstocks other than petroleum will be smooth and gradual, providing a production of the same commodities currently demanded but considering their renewable character are now named Hidrobiodiesel, biogasoline and bioLPG, respectively.

Concluding remarks

" The logistical problems associated with the transport of the oils and fats, for its treatment in conventional refineries, can also to be decisive to indicate it’s processing in a specific plant for develop the transesterification process. In these cases, the biofuel plant can be considered as an additional treatment to that required by any energetical seed, after the oil extraction to be transformed in biofuel. However, in water-poor regions will be required use any of the processes that integrate the glycerine into the biofuel, because these technologies hardly need water to operate.


.

! Among the three alternative technologies currently available for the synthesis of new biofuels

that integrate the glycerine, those which is based on the selective production of monoglycerides is technologically the simplest and less demanding in water and energy because ethanol, the reagent used in this case, is clearly much less expensive and easier to obtain than diethyl carbonate or methyl acetate, which are the reagents used by the other alternative technologies.

! This technology that integrates glycerine as monoglyceride, can also be applied to a very

small production scale and with a minimal investment, compared with current oil refineries, so

that it could be installed in areas close to where crops are produced (the biofuel plant is become

actually in an additional treatment after the oil extraction of crops), so that it become clearly more

competitive than the hydrotreating technology for biofuel production in semi-desert areas of low

productivity and geographically dispersed, where logistical problems are particularly limiting.

The development and maturation of these new technologies, that produce biofuels applicable to

diesel engines that not generate unwieldy waste glycerine and which in turn requires its total

elimination in the biodiesel, with a high cost in water and energy, it is expected to boost up the

use of biofuels, and thus create a scenery to get opportunities for small and medium enterprises

for producing biofuels in very diverse geographical areas, including semi-desert areas, where

being possible the cultivation of plants suitable for its transformation "in situ" into biofuels, so

that agriculture can play an increasingly important role through the production of new crops

capable of supplying to industrial and energy sectors that now are completely dependent on

petroleum.


Acknowledgments

Prof. A. A. Romero

Prof. J. M. Campelo

Prof. J. M. Marinas

Prof. F. M. Bautista

Dra. V. Caballero

Dr. J. M. Hidalgo

Assistant Prof. R. Luque

Dr. C. Verdugo

Prof. J. Berbel

Prof. E.D. Sancho

Dr. A. Posadillo

mosque and City of Cordoba


Acknowledgments

Prof. A. A. Romero

Prof. J. M. Campelo

Prof. J. M. Marinas

Prof. F. M. Bautista

Dra. V. Caballero

Dr. J. M. Hidalgo

Assistant Prof. R. Luque

Dr. C. Verdugo

Prof. J. Berbel

Prof. E.D. Sancho

Dr. A. Posadillo

mosque and City of Cordoba

European Capital of Culture


MANY THANKS FOR YOUR KIND ATTENTION

[email protected]

(farmlands on the outskirts of Cordoba planted with sunflower)


Documents

TECHNOLOGICAL CHALLENGES FOR THE PRODUCTION … · Universidad de Córdoba (España) TECHNOLOGICAL CHALLENGES FOR THE PRODUCTION OF BIODIESEL IN ARID LANDS Diego Luna Departamento