1

Proposal Proposal Simultaneous Simultaneous

transesterification and transesterification and esterification using esterification using

lanthanum-containing lanthanum-containing nanoparticles as catalyst for nanoparticles as catalyst for

biodiesl productionbiodiesl production Shuli YAN

20080310

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OutlineOutline

IntroductionIntroduction

Proposed ResearchProposed Research

Closing RemarksClosing Remarks

Effect of La 3+ on the structural and catalytic properties of nanaoparticles

Process for biodiesel production based on inexpensive oils and La-containing nanoparticles

Fuel properties of biodiesel

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IntroductionIntroduction

Biodiesel Biodiesel

•a mixture of fatty acid esters of low alkyl-chain alcohols

•one of the most promising substitutes for diesel engine fuels

•a major barrior in the commercialization

high manufacturing cost

the cost of the refined oil occupy 80% of the gross cost of biodiesel

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IntroductionIntroduction

Inexpensive oilsInexpensive oils

less-expensive raw materials are preferred for biodiesel production

yellow grease

crude vegetable oils

waste cooking oil

Large amount of free fatty acids (FFA)

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IntroductionIntroduction

A two-step method to convert A two-step method to convert inexpensive oils to biodiesel inexpensive oils to biodiesel

Initially, an acidic catalyst (H2SO4, HCl) is used to esterify FFA with methyl alcohol to form esters

Then in the second stage an alkaline catalyst (NaOH, KOH) is used to transesterify oil.

Highly corrosive

Difficult to remove catalyst from the biodiesel product

Deposit problems of waste water

Loss of catalyst

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IntroductionIntroduction

A two-step method to convert A two-step method to convert inexpensive oils to biodieselinexpensive oils to biodiesel

COOHR1 + CH3OH R1COOCH3 + OH2

Catalyst

Figure 2. Esterification of FFA with methanol in presence of catalyst

Figure 1. Transesterification of triglyceride with alcohol

O

COCH3 R1

O

COCH3 R3

O

COCH3 R2

H2C

HC

H2C

OH

OH

OH

+

O

H2C

HC

H2C

O

O

O

CO

R1

CO

R2

C R3

+ CH3OH3

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IntroductionIntroduction

Heterogeneous catalystsHeterogeneous catalysts

Non- corrosive

easy to remove catalyst from the biodiesel product

No waste water

Regeneration of catalyst

Development of a heterogeneous catalyst that is active in both transesterification and esterification reaction is crucial for decreasing the biodiesel manufacturing cos

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IntroductionIntroduction

Heterogeneous catalystsHeterogeneous catalysts

using Mg, Ca and Zn inorganic compounds in transesterification

Li, E (2008). "Transesterification of Vegetable Oil to Biodiesel over MgO-Functionalized Mesoporous Catalysts". Energy & fuels (0887-0624), 22 (1), p. 145

Ngamcharussrivichai, C (2007). "Modified dolomites as catalysts for palm kernel oil transesterification". Journal of molecular catalysis. A, Chemical (1381-1169), 276 (1-2), p. 24

Li, H (2006). "Transesterification of Soybean Oil to Biodiesel with Zn/I2 Catalyst". Catalysis letters (1011-372X), 107 (1-2), p. 25

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IntroductionIntroduction

Heterogeneous catalystsHeterogeneous catalysts

The catalytic activity is rather low

Due to the large crystal size of active compounds

In this research, nanopowder of Mg, Ca and Zn inorganic compounds is proposed to improve the transesterification results

Nanostructural compounds offer higher surface area, smaller crystal size and higher number of basic sites for transesterification.

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IntroductionIntroduction

Heterogeneous catalystsHeterogeneous catalysts

Our previous works

Fig. 3 Catalytic activities of homogeneous catalyst NaOH, CaO, MgO, and a binary alkaline earth metal oxides.

Reaction conditions: 64.5 oC, 12:1molar ratio of rapeseed oil to methanol, 2 % g catalyst/g oil, 8hr .

-2 0 2 4 6 8 10 12 14 16

0

20

40

60

80

100

-2 0 2 4 6 8 10 12 14 16

0

20

40

60

80

100

-2 0 2 4 6 8 10 12 14 16

0

20

40

60

80

100

-2 0 2 4 6 8 10 12 14 16

0

20

40

60

80

100

MgO Sample 6

Time hr

NaOH

C

onve

rsio

n %

CaO

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IntroductionIntroduction

Heterogeneous catalystsHeterogeneous catalysts

Our previous works

0 2 4 6 8 10

0

20

40

60

80

100

-1 0 1 2 3 4 5 6 7 8

40

60

80

100

FFA

Acid value (FFA content) mgKOH/g

Co

nve

rsio

n (

FF

A)

%

Co

nve

rsio

n (

wa

ter)

%

Water content % water

Fig. 4 Effects of water and FFA on the equilibrium conversion ratioReaction conditions: 64.5 oC, 12:1molar ratio of rapeseed oil to methanol, 2 % g CaO catalyst/g

oil, 8hr .

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IntroductionIntroduction

Heterogeneous catalystsHeterogeneous catalysts

Lanthanum shows some activity in other esterification reactions

Small addition of La can improve both basic and acid sites on the surface of nano metal oxides

Lanthanum acts as:

1. Structural promoter

2. Electronic promoter

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IntroductionIntroduction

Heterogeneous catalystsHeterogeneous catalysts

The goal of this research is to prepare La-modified nanopowder of Mg, Ca and Zn inorganic compounds, and use them

as catalyst in converting inexpensive oils into biodiesel.

In this research, immobilization of La on nanopowder of Mg, Ca and Zn metal oxides is

suggested to be beneficial to simultaneous transesterification of oil and esterification of FFA

for the purpose of biodiesel production.

Therefore

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Proposed ResearchProposed Research

Effect of La 3+ on the structural and catalytic properties of nanaoparticles

Process for biodiesel production based on inexpensive oils and La-containing nanoparticles

Fuel properties of biodiesel

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Effect of La 3+ on the structural and catalytic

properties of nanaoparticles Using sol-gel method to prepare lanthanum-Using sol-gel method to prepare lanthanum-

containing nanoparticlescontaining nanoparticles La(NO3)3 transparent solutionpH = 6 ~ 7

Stirring for 3h at 60 oC

Placing for 48h at RM

Water-bath evaporating at 90 oC

Drying for 24h at 100 oC

Calcining for 2h at 600 oC

Grinding

CH3CH2OH Me(CH3COO)nmH2O

Figure 3 Process chart of the nanaoparticles

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Effect of La 3+ on the structural and catalytic

properties of nanaoparticles Material characterizationMaterial characterization

XRD patterns are taken with a Rigaku RU2000 rotating anode powder diffractometer equiped with CuKα radiation (40kV, 200mA).

SEM images are taken with a Scanning Electron Microscope (Hitachi S-2400) from the calcined samples.

The composition of the catalyst is measured by the SEM equipped with EDS. Maximum operating high voltage is 25kV.

FTIR are recorded on Spectrum Spotlight 200™. Accumulate 128 scans at a resolution of 2 cm-1 in the range of 400-4000 cm-1

Titration method, XPS, BET

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Effect of La 3+ on the structural and catalytic

properties of nanaoparticles Preliminary resultsPreliminary results

Figure 4 SEM of ZnO nanoparticles containing La

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Effect of La 3+ on the structural and catalytic

properties of nanaoparticles Preliminary resultsPreliminary results

Figure 5 Catalytic activities of ZnO nanoparticles containing La

0 100 200 300 4000

20

40

60

80

100

Pure La2O

3

Time min

Pure ZnO

Yie

ld o

f FA

ME

%

Zn1La1

Zn3La1

Zn9La1

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Effect of La 3+ on the structural and catalytic

properties of nanaoparticles Future worksFuture works

Manipulation of hydrolysis of acetate salts and calcination stages in catalyst preparation process, for the purpose of controling epitaxial growth of lanthanum-doped metal oxides to prepare nanaocatalysts.

Crystal structure, morphology of nanoparticles, thermal decomposition behavior of La-containing xerogel, and the surface basic and acid properties of nanocatalysts will be studied and correlated with their catalytic abilities in transesterification and esterification.

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Process for biodiesel production based on inexpensive oils and La-

containing nanoparticles GoalGoal

Design an environmentally friendly and low-cost technology for biodiesel

production using La-containing nanoparticles as catalyst and

inexpensive oils as oil feedstock.

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Process for biodiesel production based on inexpensive oils and La-

containing nanoparticles Research contentResearch content

As nanostructured catalysts have an enhanced activity in comparison with general catalyst powders, it becomes important to investigate the effects of reaction parameters on transesterification and esterification reactions using La-containing nanocatlaysts.

Reaction temperature

Reaction time

Catalyst dosage

Molar ratio of methanol to oil

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Process for biodiesel production based on inexpensive oils and La-

containing nanoparticles Preliminary resultsPreliminary results

180 185 190 195 200 205 210

0.010

0.015

0.020

0.025

0.030

0.035

0.040

0.045

Initi

al r

eact

ion

rate

m

ol m

l-1

min

-1

Temperature oC

0 100 200 300 4000

20

40

60

80

100

200 oC

Time min

Yie

ld o

f FA

ME

%

210 oC

180 oC

190 oC

a bFigure 6 Transesterification results of Zn3La1 at different temperatures

a: transesterification curves b: initial reaction rate

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Process for biodiesel production based on inexpensive oils and La-

containing nanoparticles OutcomesOutcomes

A technology for biodiesel production using La-containing nanoparticles as catalyst and inexpensive oils as oil feedstock will be built up.

Kinetic models for transesterification and esterification reactions will be determined.

Reaction mechanisms of transesterification and esterification on the surface of La-containing nanoparticles will be proposed.

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Fuel properties of biodiesel

GoalGoal

Research contentResearch content

Investigate the fuel properties of different biodiesels made using this new technology

fuel composition, lower heating value, kinetic viscosity, specific gravity, density, water, carbon, hydrogen, oxygen, sulfur,

boiling point, flash point, cloud point, pour point, cetane number etc

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Fuel properties of biodiesel

Effect of production technology Effect of production technology

As fuel properties definitely define the quality of biodiesel, it is essential to study

the effects of biodiesel production technology and oil species on biodiesel

properties.

1. At high temperature and high pressure (200 oC and 3.8 MPa) using La-containing nanoparticles as catalyst.

2. At low temperature and atmospheric pressure (65 oC and 0.1 MPa) using La-containing nanoparticles as catalyst.

3. At low temperature and atmospheric pressure (65 oC and 0.1 MPa) using traditional homogeneous KOH as catalyst.

three different technologies

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Fuel properties of biodiesel

Effect of oil speciesEffect of oil species

the variety of fatty acid profiles has an impact on biodiesel fuel properties

food-grade soybean oil

crude soybean oil

crude palm oil

chicken fat

Lard

Tallow

yellow grease

using La-containing

nanoparticles as catalyst

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Closing Remarks This project focuses on the development of a new This project focuses on the development of a new

technology for biodiesel production.technology for biodiesel production. The scope of this project encompasses synthesis and The scope of this project encompasses synthesis and

characterization of nanocatalyst, catalytic process characterization of nanocatalyst, catalytic process design and fuel property test. design and fuel property test.

We have shown in our preliminary results that La-We have shown in our preliminary results that La-containing nanoparticles can indeed offer a much containing nanoparticles can indeed offer a much higher surface area, basicity and acidity.higher surface area, basicity and acidity.

The proposed nano-structured material is a very The proposed nano-structured material is a very promising approach to cost-effectively produce high promising approach to cost-effectively produce high quality biodiesel. quality biodiesel.

This new class of nanostructured materials should have This new class of nanostructured materials should have significant impacts on biomass catalyst technology to significant impacts on biomass catalyst technology to overcome the conversion efficiency barrier of biomass overcome the conversion efficiency barrier of biomass to biofuel. to biofuel.

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Thank you!