Processing of Biodiesel Fuel By-Products into Environmentally Friendly Materials ; Biodyzelino gamybos šalutinių produktų perdirbimas į aplinkai draugiškus produktus

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LITHUANIAN UNIVERSITY OF AGRICULTUREMilda GumbytėPROCESSING OF BIODIESEL FUEL BY-PRODUCTS INTOENVIRONMENTALLY FRIENDLY MATERIALSSummary of the Doctoral DissertationTechnological Sciences (T000)Environmental Engineering and Land Management (04T)Kaunas, 2011Dissertation was performed in 2006-2010 at Lithuanian University of Agriculture.This work was supported by the State Science and Studies Foundation of the Republic ofLithuania.Scientific supervisor:Prof. Dr. Violeta MAKAREVIČIENE (Lithuanian University of Agriculture,Technological Sciences, Environmental Engineering and Land Management –04T)Council of Environmental Engineering and Land Management:Chairman:Prof. Dr. Valdas PAULAUSKAS (Lithuanian University of Agriculture,Technological Sciences, Environmental Engineering and Land Management –04T)Members:Assoc. Prof. Dr. Laima ČESONIENĖ (Lithuanian University of Agriculture,Technological Sciences, Environmental Engineering and Land Management –04T)Prof. Dr. Gintaras DENAFAS (Kaunas University of Technology, TechnologicalSciences, Environmental Engineering and Land Management – 04T)Prof. Habil. Dr. Vladislovas KATINAS (Lithuanian Energy Institute,Technological Sciences, Environmental Engineering and Land Management –04T)Prof. Habil. Dr. Algirdas Jonas RAILA (Lithuanian University of Agriculture,Technological Sciences, Environmental Engineering and Land Management –04T)Opponents:Prof. Dr.
Publié le : samedi 1 janvier 2011
Lecture(s) : 55
Source : VDDB.LABA.LT/FEDORA/GET/LT-ELABA-0001:E.02~2011~D_20110421_152414-39664/DS.005.1.01.ETD
Nombre de pages : 30
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LITHUANIAN UNIVERSITY OF AGRICULTURE
Milda Gumbytė
PROCESSING OF BIODIESEL FUEL BY-PRODUCTS INTO
ENVIRONMENTALLY FRIENDLY MATERIALS
Summary of the Doctoral Dissertation
Technological Sciences (T000)
Environmental Engineering and Land Management (04T)
Kaunas, 2011Dissertation was performed in 2006-2010 at Lithuanian University of Agriculture.
This work was supported by the State Science and Studies Foundation of the Republic of
Lithuania.
Scientific supervisor:
Prof. Dr. Violeta MAKAREVIČIENE (Lithuanian University of Agriculture,
Technological Sciences, Environmental Engineering and Land Management –
04T)
Council of Environmental Engineering and Land Management:
Chairman:
Prof. Dr. Valdas PAULAUSKAS (Lithuanian University of Agriculture,
Technological Sciences, Environmental Engineering and Land Management –
04T)
Members:
Assoc. Prof. Dr. Laima ČESONIENĖ (Lithuanian University of Agriculture,
Technological Sciences, Environmental Engineering and Land Management –
04T)
Prof. Dr. Gintaras DENAFAS (Kaunas University of Technology, Technological
Sciences, Environmental Engineering and Land Management – 04T)
Prof. Habil. Dr. Vladislovas KATINAS (Lithuanian Energy Institute,
Technological Sciences, Environmental Engineering and Land Management –
04T)
Prof. Habil. Dr. Algirdas Jonas RAILA (Lithuanian University of Agriculture,
Technological Sciences, Environmental Engineering and Land Management –
04T)
Opponents:
Prof. Dr. Egidijus ŠARAUSKIS (Lithuanian University of Agriculture,
Technological Sciences, Environmental Engineering and Land Management –
04T)
Assoc. Prof. Dr. Eugenijus VALATKA (Kaunas University of Technology,
Technological Sciences, Chemical Engineering – 05T)
The official defence of the dissertation will be held at the open meeting of the doctoral
council at 1 p.m. on March 24, 2011 in the 261 room, central building of the Lithuanian
University of Agriculture.
Address: Lithuanian University of Agriculture,
Studentų 11, LT-53361 Akademija Kauno r., Lithuania.
The send out date of the Summary of the Dissertation is February 24, 2011.
The Dissertation is available at the library of Lithuanian University of Agriculture.LIETUVOS ŽEMĖS ŪKIO UNIVERSITETAS
Milda Gumbytė
BIODYZELINO GAMYBOS ŠALUTINIŲ PRODUKTŲ
PERDIRBIMAS Į APLINKAI DRAUGIŠKUS PRODUKTUS
Daktaro disertacijos santrauka
Technologijos mokslai (T000)
Aplinkos inžinerija ir kraštotvarka (04T)
Kaunas, 2011Disertacija rengta 2006-2010 metais Lietuvos žemės ūkio universitete.
Darbą rėmė Lietuvos Valstybinis mokslo ir studijų fondas.
Mokslinis vadovas:
Prof. dr. Violeta MAKAREVIČIENĖ (Lietuvos žemės ūkio universitetas,
technologijos mokslai, aplinkos inžinerija ir kraštotvarka – 04T)
Disertacija ginama Lietuvos žemės ūkio universiteto Aplinkos inžinerijos ir
kraštotvarkos mokslo krypties taryboje.
Pirmininkas:
Prof. dr. Valdas PAULAUSKAS (Lietuvos žemės ūkio universitetas,
technologijos mokslai, aplinkos inžinerija ir kraštotvarka – 04T)
Nariai:
Doc. dr. Laima ČESONIENĖ (Lietuvos žemės ūkio universitetas, technologijos
mokslai, aplinkos inžinerija ir kraštotvarka – 04T)
Prof. dr. Gintaras DENAFAS (Kauno technologijos universitetas, technologijos
mokslai, aplinkos inžinerija ir kraštotvarka – 04T)
Prof. habil. dr. Vladislovas KATINAS (Lietuvos energetikos institutas,
technologijos mokslai, aplinkos inžinerija ir kraštotvarka – 04T)
Prof. habil. dr. Algirdas Jonas RAILA (Lietuvos žemės ūkio universitetas,
technologijos mokslai, aplinkos inžinerija ir kraštotvarka – 04T)
Oponentai:
Prof. dr. Egidijus ŠARAUSKIS (Lietuvos žemės ūkio universitetas, technologijos
mokslai, aplinkos inžinerija ir kraštotvarka – 04T)
Doc. dr. Eugenijus VALATKA (Kauno technologijos universitetas, technologijos
mokslai, chemijos inžinerija – 05T )
Disertacija bus ginama viešame Aplinkos inžinerijos ir kraštotvarkos mokslo krypties
tarybos posėdyje 2011 m. kovo 24 d. 13 val. Lietuvos žemės ūkio universiteto centrinių
rūmų 261 auditorijoje.
Adresas: Lietuvos žemės ūkio universitetas,
Studentų 11,
LT-53361 Akademija, Kauno r.
Lietuva.
Disertacijos santrauka išsiųsta 2011 m. vasario 24 d.
Disertaciją galima peržiūrėti Lietuvos žemės ūkio universiteto bibliotekoje.INTRODUCTION
Relevance of the topic. Environmental protection is one of the most
important goals of the policy of the European Union. Recently, especially high
importance has been placed on the reduction of emissions of greenhouse gases.
Taking into account the fact that motor transport pollutants account for a
considerable part of greenhouse gases, the European Commission, by its
Directives and Regulations, promotes maximum replacement of fossil fuels with
biofuels produced from agricultural products.
Back in 2003, the European Parliament and the Council issued Directive
2003/30/EC encouraging all Member States to replace 5.75 % of all fuel
consumption with biofuel until 2010. A new Directive of the European
Parliament and of the Council 2009/28/EC, was issued in 2009. It envisages the
replacement of 10 % of all fuels consumed in transport with biofuels by 2020.
Lithuania, as well as other Member States of the EU, has been constantly
developing the production of biofuels. There are two types of biofuels produced
in the country: biodiesel (from rapeseed) and bioethanol (from wheat and
triticale). In 2009, biodiesel fuel accounted for 82 % of all biofuels. By-products
such as technical-grade glycerol, free fatty acids and rapeseed cake are also
produced in the course of biodiesel fuel production beside the main product,
fatty acid methyl esters.
In order to compensate material costs, free fatty acids can be returned to
the production of biofuels applying their esterification process by using acid
catalyst. In addition to chemical catalysis, it would also be possible to apply
biochemical catalysis with the use of lipases. Such esterification process has
been studied inconsiderably; therefore, it is necessary to carry out comparative
studies of chemical and biochemical catalysis in order to select the optimal
option.
On an average, around 10 % of technical-grade glycerol is produced in the
course of biodiesel fuel production. The demand for pure glycerol is limited;
therefore, it is necessary to look for new methods and technologies for the
processing of this by-product of biodiesel production. The production of liquid
fuel by mixing technical-grade glycerol with various oil products could be one
of the methods for the utilisation of glycerol. In this way, biofuel producing
enterprises could compensate their energy costs by rationally utilising glycerol
produced in the course of the process. The production of mono- and diglycerides
could be another area for the utilisation of glycerol. Currently, mono- and
diglycerides are produced chemically; however, enzymatic production methods
could be applied for their synthesis as well.
Rapeseed cake is another by-product of biodiesel fuel production. This
product is usually used in the production of feeding stuffs as a protein additive;
however, its use is limited because of harmful compounds contained in
rapeseeds. Besides, with the production volumes of biodiesel growing,
3increasingly big quantities of rapeseed cake are generated; therefore, it is
necessary to look for new options for their use, where the production of
biocomposites should be mentioned.
Hypothesis. By-products of biodiesel fuel production, i.e. free fatty acids,
technical-grade glycerol, and rapeseed cake, can be effectively converted into
useful products by applying biotechnological and chemical methods thus
reducing costs of biodiesel fuel production.
Research goal and objective. To study biochemical and chemical
methods of transformation of by-products of biodiesel fuel production.
The following tasks were solved in order to achieve the goal of the
study:
1. To study the process of esterification of free fatty acids with methanol
and to select optimal conditions.
2. To study the process of esterification of free fatty acids with technical-
grade glycerol and to select optimal conditions.
3. To study the options for the use of the products produced during free
fatty acid esterification with glycerol for the production of
biolubricants and their impact on environment.
4. To study the options for the use of technical-grade glycerol for the
production of liquid fuel and to assess the operational and
environmental properties of this fuel.
5. To study the options for the use of rapeseed cake and technical-grade
glycerol for the production of biocomposites and to assess the
exploitational and environmental properties of the resulting products.
Scientific innovation. For the first time in Lithuania, the options for the
application of biochemical methods for the processing of by-products of
biodiesel fuel production into environmentally friendly materials were studied.
The esterification of free fatty acids with methanol and technical-grade glycerol
using biotechnological method was studied; the efficiency of the locally and
industrially produced biocatalysts was assessed. The options for the use of the
products of the process of free fatty acid esterification with glycerol were
assessed; the fact that introduction of such additive into rapeseed oil improves
its lubricating properties, while the environmental properties of the mixture
meet the requirements set for biolubricants, was established. The feasibility
studies for the use of technical-grade glycerol for the production of liquid fuel
demonstrated that usage of glycerol can allow receiving stable fuel emulsions,
which results in the reduction of concentration of harmful components in
exhaust gases compared to ordinary fuel, i.e. heavy fuel oil and heating fuel.
The options for the use of rapeseed cake and technical-grade glycerol for the
production of polymeric biocomposites as well as their mechanical and
environmental properties were also studied.
Practical value of research. Effective biocatalysts for the processes of the
esterification of free fatty acids with methanol and technical-grade glycerol were
4selected and optimal conditions of biocatalysis were established. Principle
technological design of free fatty acids esterification with methanol and
technical-grade glycerol was developed, which can be applied by biofuel
producers and other interested enterprises. The formulations of liquid fuel
emulsions containing technical-grade glycerol were developed and principle
technological design for the production of these emulsions was suggested.
Optimal composition of biofilms containing technical-grade glycerol and
deoiled rapeseed cake was determined, on the basis of which the industrial scale
production of biodegradable composites can be implemented.
Validation and publication of the study results. The topic of the thesis
work has been published in 18 journals: 1 – in journal, included into the list of
reviewed scientific papers in ISI data basis with a citation index, 3 – in other
journals, included into the list of reviewed scientific papers in ISI data basis, 7 –
in peer-reviewed scientific journals, included into the list of reviewed scientific
papers in Lithuania, 3 – in other peer-reviewed scientific journals, and 4 – in
other journals.
Oral reports on the topic of the thesis work were presented at the following
thinternational scientific conferences: “BALTTRIB” (2007 and 2009), “RTU 48
International Scientific Conference” (2007), “Research and Experimental
Development of Biofuel and Biolubricant Production and Usage” (2008),
“Innovation in Materials and Lubrications for Advanced Eco-Oriented
Tribosystems” (2008), “Rural Development” (2009), and “Advanced Materials
and Technologies” (2010). The results of the studies were also presented at the
national scientific conferences “Chemistry and Technology of Inorganic
Compounds” (2007, 2009 a, b, and 2010).
Structure and content. Dissertation consists of the following parts:
Introduction, Literature Review, Research Methodology, Results and
Discussion, Conclusions, list of 254 cited Literature sources, and Appendixes.
Dissertation has 102 pages including 11 tables and 54 figures.
Statements of the thesis work to be defended
The results of the work allow defending the following important
statements:
1. By-products produced in the course of biodiesel fuel production, i.e.
free fatty acids and technical-grade glycerol, can be effectively utilised,
with the application of biotechnological methods, for the production of
other products with higher added value.
2. The product of the esterification of free fatty acids with glycerol can be
used as an additive for easily biodegradable lubricating materials.
3. The by-product of biodiesel production, i.e. technical-grade glycerol,
can be used for the production of stable liquid fuel emulsions.
4. Technical-grade glycerol and rapeseed cake can be used for the
production of biodegradable polymeric composites.
51. MATERIALS AND METHODS
In order to determine the dependence of the efficiency of the processes of
free fatty acids (FFA) esterification with methanol and glycerol on various
factors, optimization studies of esterification by the biotechnological method
were performed with the use of both reagent-grade chemicals (oleic acid;
methanol; glycerol) and by-products of the production of biofuel (technical-
grade glycerol; free fatty acids). Industrial lipases Lipozyme RM IM, Lipozyme
TL IM, Novozym 435, Lipase F-EC, and Lipase G Amano 50 and locally
produced experimental lipases: JSC Biocentras, Resinase HT, Lipozyme TL
100L, Lipase Ps. mend. were used as catalysts. Samples prepared for the study
were poured into a thermostatically controlled three-necked flask with a
connected condenser, thermometer, and leak-tight mixer. The mixture was
homogenised while maintaining a constant mixing speed and temperature with
the addition of the required quantity of biocatalyst. The quantity of reacted acids
was periodically evaluated according to the reduction of acidity in the reaction
medium. Acidity measurements were performed in accordance with the
requirements of the standard LST EN ISO 660. In order to optimise the
esterification process, the duration, temperature of the process and quantity of
biocatalyst were changed.
The efficiency of the process of esterification with methanol and glycerol
was studied by the thin-layer chromatography on boron-impregnated silicagel
plates G-25. A mixture of light fraction of petroleum ether, diethyl ether, and
acetic acid (80:20:1 volume parts) was taken as elution solution. In the case of
esterification with glycerol, solutions of a mixture of oleic acid, 1,3/1,2-diolein,
and 1-monooleine in diethyl ether were taken as control samples. In the case of
esterification with methanol, solutions of pure oleic acid and fatty acid methyl
esters (FAME) in diethyl ether were used as control samples.
After the end of the process of esterification with glycerol, non-reacted
glycerol was separated by centrifugation, and the composition of the mixture of
glycerides was studied by the gas chromatography in accordance with the
requirements of the standard LST EN14105. Control studies of the quantity of
produced fatty acid methyl esters were performed by the gas chromatography
method in accordance with the requirements of the standard LST EN 14103.
The tribological properties of lubricating materials were evaluated with the
application of the four-ball wear test in accordance with the standard
DIN51350/3. The studies were performed at the Mechanics Department of the
Faculty of Agricultural Engineering of the Lithuanian University of Agriculture.
The methodology provided in the standards ISO 14040-14049 was applied
for the Life cycle analysis of lubricating materials. The environmental impact of
the product was assessed according to the fossil energy consumption from the
“birth to death” of the product starting with raw materials, production,
consumption, and ending with waste disposal. Emissions of greenhouse gases
6(CO ) were also assessed by multiplying energy consumption by the relevant2
factor.
Comparative studies of biodegradation of lubricating materials were
performed in accordance with the requirements CEC L–33–A–93 (non-treated
bacterial culture used for the test was received from JSC Kauno Vandenys after
the first (mechanical) treatment stage).
Liquid fuel emulsions were produced from reagent-grade or technical-
grade glycerol, fatty acid methyl esters, heating fuel or heavy fuel oil, water or
methanol and emulsifying agents (monoglycerides of fatty acids and potassium
oleate), with the homogenisation of the mixture at the homogeniser IKA T25
Digital Ultra-Turrax at a high rotation speed. The stability of the resulting
emulsions was assessed by centrifuging them out and evaluating visually
whether the phases separate or not. Stable emulsions were kept for up to 2
months while constantly inspecting their stability visually.
Emulsion combustion tests and studies of exhaust gas emissions were
performed using organic fuel combustion bench at the Lithuanian Energy
Institute.
Polyvinyl alcohol of three types (JF-05, JF-17, and PVA-217), technical-
grade or reagent-grade glycerol, and defatted rapeseed cake were used for the
production of biopolymer composite films. The aforementioned components
were dissolved in water and poured into a thermostatically controlled flask
placed on a magnetic stirrer. The mixture was homogenised while maintaining a
constant rotation speed. While constantly mixing, temperature was raised to
80°C, and the solution was kept in this temperature for 60 minutes. Thereafter,
glycerol was poured into the solution and it was mixed for another 10 minutes.
Films were formed from hot mix. Films desiccated at room temperature were
dried further at temperature 60 °C for 60 minutes.
The following properties of the formed films were studied: mechanical
properties (studies were performed at the Faculty of Chemical Technology of
Kaunas University of Technology with the use of an original computerised
microtension system), hygroscopic properties (dry samples of films were
weighted with an accuracy of 0.001 g and placed into a desiccator where
temperature of 20±5 °C and relative air humidity were maintained; after a certain
period of time, the samples were taken out and immediately weighted again),
exploitational properties (small containers were formed using the produced
biocomposite, and plants were sprouted and cultivated in them for a one-month
period), and biodegradability in soil (samples with a size of 5 x 5 cm cut of the
films were put between layers of agro-film and kept in soil; the degradability of
the samples was assessed visually).
The obtained results of the experimental studies are presented in the form
of charts and tables. All experiments were performed using 3-4 repetitions. The
efficiency of the processes of esterification with methanol and glycerol was
assessed by the method of data envelopment analysis.
72. RESULTS AND DISCUSSION
2.1. Studies of the return of free fatty acids into the biodiesel fuel
production process
At the initial stage of the study, the process of esterification with methanol
using analytical-grade chemicals and industrial enzymatic preparations, lipases,
was studied.
The goal was to select the most effective enzymatic preparation. The
catalytic efficiency of industrial lipases (Novozym 435, Lipozyme RM IM,
Lipozyme TL IM, Lipase G, and Lipase F-EC) at the same reaction (40 °C)
temperature, initial molar ratio of oleic acid and methanol of 1:0.5, and the same
concentration of lipases (3 % of the quantity of oleic acid) was assessed. It was
determined that industrial enzymes according to their catalytic efficiency in the
process of esterification with methanol can be ranked as follows: Novozym 435
» Lipozyme RM IM > Lipozyme TL IM > Lipase G > Lipase F-EC (Fig. 2.1).
100
90
80
70
60
Novozym 435 Lipozyme TL IM
50 Lipozyme RM IM Lipase F-EC
Lipase G
40
0 1 2 3 4 5 6
Time, h
Fig. 2.1. The efficiency of lipases during oleic acid esterification with methanol at a
temperature of 40 °C, concentration of lipases – 3 %, and molar ratio of oleic
acid/methanol of 1:0.5 mole/mole
In order to improve the efficiency of the process, a number of tests were
performed, i.e. it was attempted to add some water into the initial reaction
mixture, the reaction temperature was increased, the multi-stage esterification
process was studied while gradually increasing the quantity of methanol in the
reaction medium until the final molar ratio of oleic acid and methanol would
reach 1:1.5; also the concentration of biocatalyst was increased. The tests
showed that it is not necessary to add water into the initial reaction mixture. It
was established that it is not reasonable to raise the temperature of the process
of esterification with methanol over 40 °C because it does not provide any
positive effect for biocatalysis when using enzymatic preparations but requires
additional energy consumption. When using Novozym 435 as biocatalyst, it is
not necessary to carry out the process in several stages with periodical addition
of methanol. On the other hand, Lipozyme RM IM is more sensitive to the
impact of methanol; therefore, it is reasonable to carry out the process of
esterification with methanol in a stage-by-stage manner.
8
Oleic acid content, %

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