INVESTIGATION OF BIODIESEL PRODUCTION FROM VARIOUS OILS BY USING DIFFERENT EXCHANGED HYDROTALCITE CATALYSTS

BYMr. Chaitanyakumar. D

(06031 G 1426)

Under the esteemed guidance ofDr.Sreedhar.B (Scientist-E1)

Inorganic & Physical Chemistry Division, IICT.

A dissertation submitted toJawaharlal Nehru Technological University

KUKATPALLY, HYDERABAD

OVERVIEWPollution is the introduction of contaminants into an environment that causes instability, disorder, harm or discomfort to the physical systems or living organisms.

Thermal Pollution

Radioactive Pollution

Noise Pollution

Land Pollution

Water Pollution

Air Pollution

POLLUTION

AIR POLLUTION

Direct method Indirect Method

Hydrogen gas Biodiesel

What is Biodiesel ? A mixture of fatty acids lower alkyl esters, Ex: FAME Alternative fuel for diesel engines Made from vegetable oil or animal fat Meets health effect testing Lower emissions, Safer Biodegradable, Essentially non-toxic. Chemically, biodiesel molecules are mono-alkyl esters

produced usually from triglyceride esters

ENVIRONMENTAL ISSUES

0 20 40 60 80 100 120 140

160

GasolineCNGLPG

DieselEthanol 85%

B20Diesel Hybrid

ElectricB10

0

Data from “A Fresh Look at CNG: A Comparison of Alternative Fuels”, Alternative

Fuel Vehicle Program, 8/13/2001

B100 = 100% BiodieselB20 = 20% BD + 80% PD

Relative Greenhouse Gas Emissions

** B100 (100% biodiesel) with NOx adsorbing catalyst on vehicle

0 20 40 60 80 100

Total Unburned HCsCO

Particulate Matter**NOx

SulfatesPAHs

n-PAHsMutagenicity

CO2

Percent

B100 **B20Diesel

Relative emissions: Diesel and Biodiesel

METHODOLOGYSource Oil BiodieselExtraction Trans-

esterification

CHEMISTRY INVOLVED IN THE REACTIONS:Its a multi-step process:

TYPES OF CATALYSTS

CATALYST

Homogeneous catalystsDefined on

molecular level, scope, variability

Heterogeneous catalystsSeparation, recovery, handling,

Stability,reuse

Clays

Cationic clays Anionic clays

------------------------

------------------------

++++++++++++++

+++++++++++++++

+++++++++++++++

--------------------------

e.g., SiO2 and Al(OH)3

e.g., Hydrotalcite-Mg6Al2(OH)16(CO32-).4H2O

DIFFERENT PROCESSES USED IN BIODIESEL PRODUCTION

This involves the following:

Acid-Catalyzed ProcessesBase-Catalyzed ProcessesLipase-Catalyzed ProcessesNon-Ionic Base-Catalyzed Processes

EXPERIMENTAL For our convenience experimental work divided into three steps

i) Catalyst screening

Catalyst Reaction time Stirring speed (rpm) Temperature Result

Mg-La 6h Medium 650C-700C No reaction

Mg-Cl 6h Medium 650C-700C No reaction

SiHClO4 6h Medium 650C-700C No reaction

3-Amino Propyl fictionalized silica gel

6h Medium 650C-700C No reaction

Boric acid 6h Medium 650C-700C No reaction

DABCO 6h Medium 650C-700C No reaction

KOtBu 1h Medium 650C-700C Reaction occurred

ii) Heterogenisati

on 1.Preparation of HT-NO3 (Mg-Al, 3/1 ):

(Mg(NO3)2.6H2O+ Al(NO3)3.9H2O)

solution KOH solution

precipitate

Drying

398K

HT

+

2.Preparation of HT-NO3(Ni-Al, 2/1):: (Ni(NO3)2.6H2O + Al(NO3)3.9H2O)

solution

+ NaOH+Na2CO3 solution

precipitate

HT

Drying

1250C

3. HT-O tBu:

HTcalcined at 723 K

Calcined HT

KOtBu in freshly dried THF stirred for 24 h in a nitrogen atmosphere

HT-OtBu

+

iii ) OptimizationThree parameters are considered for optimization and that

include the following i) Methanol ii) Amount of catalyst and iii) Temperature.

Methanol molar ratio table.

Methanol molar ratio

Methanol volume

Isolated yield

5% 0.14mL 69.1%

10% 0.28mL 75.0%

15% 0.43mL 78.6%

20% 0.56mL 94.5%

25% 0.70mL 98.6%

Catalyst percentage tableCatalyst amount

Isolated Yield

10% 34.5%

15% 62.5%

20% 90.0%

25% 90.5%

 

Temperature: We started the reaction at 65-700C, as a part of optimization we had

carried out the reaction at room temperature and this

yielded best results.

RESULTS & DISCUSSION:Catalyst characterization

FTIR Result

Mg-Al 3/1 pure

Mg-Al 3/1 calcined

Mg-Al 3/1 exchanged

Ni-Al 2/1 pure

Ni-Al 2/1 calcined

Ni-Al 2/1 exchanged

XRD Result:

Mg-Al 3/1 pure

Mg-Al 3/1 calcined

Mg-Al 3/1 exchanged

Ni-Al 2/1 pure

Ni-Al 2/1 calcined

Ni-Al 2/1 exchanged

XPS Results:

SEM quantity results

SEM Exchanged catalyst photograph

SEM Used catalyst photograph

Transesterification reaction result:

Type of Oil Isolated yield%

Coconut oil 96.0Soybean oil 88.0

Sun flower oil 78.5Sesame oil 73.5

Palm oil 68Castor oil 20

Reaction conditionsAmbient temperature, 25% methanol molar ratio 20% catalyst amount with respect to oil.

PROTON NMR

RESULTS

CONCLUSIONMg-Al LDH gave lower methyl ester yield, but calcined Ni-Al HT did not have the ability to do transesterification reaction .After exchanging HT with strong base like KOt Bu Mg-Al HT gives 86% isolated yield. Where as Ni-Al HT gave 94% yield for the 1st cycle and after 5th cycle it will gives 62% isolated methyl ester yield .Highest biodiesel yield was obtained at an ambient temperature, 25% methanol molar ratio and 20% catalyst amount with respect to oil. The highest yield observed in the coconut oil, i.e 96%, soybean oil 88.0%, sun flower oil 78.5%, sesame oil 73.5%, palm oil 68.0% and lowest yield observed in the castor oil 20.0%.Here we for the first time reported that the reaction can be carried at ambient temperature by using HT.