Biodiesel Production:

Process Optimization
Stuart Farquharson

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www.rta.biz

Abstract
Biodiesel has become the foremost alternative fuel to those refined
from petroleum products. It can be produced from renewable sources, such as
vegetable and animal oils, as well as from wastes, such as used cooking
oil. Transesterification is the primary method of converting these oils to
biodiesel.
However, due to the variability in the starting materials, both type
and composition, it is highly desirable to monitor the reaction as it proceeds to
optimize yield. For this reason we have been examining the ability of Raman
spectroscopy to monitor the esterification reaction, the disappearance of the
triglyceride raw material and the appearance of the methyl ester and glycerin
products, with the goal of controlling yield.
Here we present our preliminary measurements performed on a batch
(lab scale) reactor and a continuous-feed (prototype) reactor.

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Transesterification Reaction

Transesterification of Vegetable Oil to Methyl Ester (Biodiesel)

using KOH as a catalyst.

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Biodiesel Reactors

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Project Goals:
Characterize Starting Materials
How do different source oils differ in composition?
Can Raman distinguish these differences?

Monitor & Control Reactor

Can Raman differentiate the Reactants (vegetable oil, methanol)
from the Products (biodiesel, glycerol)?
Can Reaction Paths and/or Rates be monitored as a function of
conditions (reactant concentrations, reactant temperature, catalyst)?
Can a Control model be developed?

Characterize Product
Can Raman differentiate the products (biodiesel, glycerol)?
Can percent yield be determined?
Can product properties be determined?

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RTAs Raman Analyzer

Advantages:

No sample preparation
Simple integration via fiber optics
Remote analysis, multi-component
No fluorescence interference
Complete spectral coverage
Wavelength stability
Confident spectral subtraction
and library search/match
Real-time, On-demand analysis
Long term stability
Temperature and vibration immune
Shock resistant

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Raman: Reactants

Vegetable Oil

5M KOH
in Methanol

Quality Raman spectra are obtained

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Raman: Characterize Raw Materials

fish oil
soybean oil
canola oil
sesame oil
olive oil

Each oil produces unique Raman spectra

in the fingerprint region
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Products:

Biodiesel

Glycerol

Quality Raman spectra are obtained

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Small-Scale Reactor: Photograph

Laser focal point

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Reactant Solution Product Solution

Biodiesel
Glycerol

Expanded spectra highlighting product ID

peaks
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Real-Time Monitoring by Raman

Real-Time data from lab-batch reactor;

Note growth of glycerol peak at 1030 cm-1
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Product Formation

Real-Time Monitoring by Raman

20

40

60

80

100

120

140

160

Time (min)
Plot of glycerol peak intensity
(preliminary data)
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Biodiesel Reactor: UConn Continuous-Flow

Fiber
Optic
Probe

Raman Advantages
1 Minute
In-Line (real-time)
Eliminates Bad Batches
No Reagents

RTAs RamanProTM
Process Controller

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Characterizing the Reactor

Raman spectra at bottom, middle and top of

the reactor
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Process Control Software

RTA has full functional software to monitor

batch and continuous-feed reactors
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Diesels: Major Diesel Types

Biodiesel (Canola)

Synthetic Diesel

alkane

phenyl

biphenyl

Diesel-2

stearate

Fingerprint region highlights differences

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Real-Time Biodiesel Analysis

Analysis that can be done:
Percent Biodiesel
Cetane Index
Cloud Point
Density
Distillation values
Flash point
Sulfur
Viscosity

B100
B50
B20
B5

Raman Calibration Curve

Precision 1.5%

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Real-Time Analyzers Portable Fuel Analyzer

The Analyzer Determines Fuel Properties (Blue

Indicators) and Determines if it Acceptable for use.
Green = Acceptable Range
Yellow = Marginal Range
Red = Unacceptable Range
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Summary of preliminary data

Characterize Starting Materials
How do different source oils differ in composition?
Can Raman distinguish these differences?

In literature
YES

Monitor & Control Reactor

Can Raman differentiate the Reactants (vegetable oil, methanol)
from the Products (biodiesel, glycerol)?
YES
Can Reaction Paths and/or Rates be monitored as a function of
conditions (reactant concentrations, reactant temperature, catalyst)? Likely
Can a Control model be developed?
Likely

Characterize Product
Can Raman differentiate the products (biodiesel, glycerol)?
Can percent yield be determined?
Can properties be determined?

YES
Likely
Likely

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