Industrial Use of Vegetable Oil

IndustOils (FM)(i-vii)Final 3/23/05 6:00 PM Page 1
Industrial Uses of
Vegetable Oils
Editor
Sevim Z. Erhan
Food and Industrial Oil Unit
National Center for Agricultural Utilization Research
Agricultural Research Service
United States Department of Agriculture
Peoria, IL 61804
Champaign, Illinois
Copyright 2005 AOCS Press

AOCS Mission Statement

To be the global forum for professionals interested in lipids and related materials
through the exchange of ideas, information science, and technology.
AOCS Books and Special Publications Committee

M. Mossoba, Chairperson, U.S. Food and Drug Administration, College Park, Maryland
R. Adlof, USDA, ARS, NCAUR, Peoria, Illinois
P. Dutta, Swedish University of Agricultural Sciences, Uppsala, Sweden
T. Foglia, ARS, USDA, ERRC, Wyndmoor, Pennsylvania
V. Huang, Abbott Labs, Columbus, Ohio
L. Johnson, Iowa State University, Ames, Iowa
H. Knapp, Deanconess Billings Clinic, Billings, Montana
D. Kodali, Global Agritech, Inc., Plymouth, Minnesota
T. McKeon, USDA, ARS, WRRC, Albany, California
R. Moreau, USDA, ARS, ERRC, Wyndoor, Pennsylvania
A. Sinclair, RMIT University, Melbourne, Victoria, Australia
P. White, Iowa State University, Ames, Iowa
R. Wilson, USDA, REE, ARS, NPS, CPPVS, Beltsville, Maryland
Copyright (c) 2005 by AOCS Press. All rights reserved. No part of this book may be reproduced
or transmitted in any form or by any means without written permission of the publisher.
The paper used in this book is acid-free and falls within the guidelines established to ensure
permanence and durability.
Library of Congress Cataloging-in-Publication Data
Industrial uses of vegetable oils / editor, Sevim Z. Erhan.

p. cm.
Includes index.
ISBN 1-893997-84-7
1. Vegetable oils--Industrial applications. I. Erhan, Sevim Z.
TP680.I555 2005
665'.384--dc22 2005007927
Printed in the United States of America.

08 07 06 05 04 5 4 3 2 1

Preface
Vegetable oils are used in various industrial applications such as emulsifiers, lubri-
cants, plasticizers, surfactants, plastics, solvents and resins. Research and develop-
ment approaches take advantage of the natural properties of these oils. Vegetable
oils have superb environmental credentials, such as being inherently biodegradable,
having low ecotoxicity and low toxicity towards humans, being derived from
renewable resources, and contributing no volatile organic chemicals.
United States agriculture produces over 25 billion pounds of vegetable oils
annually. These domestic oils are extracted from the seeds of soybean, corn, cotton,
sunflower, flax, and rape. Although a major part of these oils are used for food prod-
ucts such as shortenings, salad and cooking oils and margarines, large quantities
serve feed and industrial applications. Other vegetable oils widely used industrially
include palm, palm kernel, coconut, castor, and tung. However, these are not of
domestic origin. The three domestic oils most widely used industrially are soybean,
linseed from flax, and rapeseed.
Nonfood uses of vegetable oils have grown little during the past 40 years.
Although some markets have expanded or new ones added, other markets have been
lost to competitive petroleum products. Development of new industrial products or
commercial processes is the objective of continued research in both public and pri-
vate interests. The following selected examples illustrate progress in identifying and
developing new technologies based on vegetable oils.
Great progress has been made in understanding of the biochemical basis for
biosynthesis of oils containing fatty acids. This biochemical information is in turn
used to identify and isolate genes that are needed to make these oils. By genetical-
ly engineering the introduction and expression of these genes, domesticated crops
that can produce these potentially useful fatty acids have been engineered and are
continuing to be developed to produce an ever wider range of novel oils.
Chapter 1 explains the biochemical changes that can be introduced to alter fatty
acid composition. It also discusses industrial oils that have been developed through
genetic engineering, as well as some that have been developed on the laboratory
scale, but have not yet been introduced commercially.
Recent environmental awareness and depletion of world fossil fuel reserves
have forced to look a substitute for mineral oils with the biodegradable fluids such
as vegetable base oils and certain synthetic fluids in grease formulations. The non-
toxic and readily biodegradable characteristics of vegetable oil based greases pose
less danger to soil, water, flora, and fauna in case of accidental spillage or during
disposal. Biodegradable greases are particularly useful in open lubrication systems
where the lubricant is in direct contact with environment, and total loss lubricants
like railroads, where immediate contact with the environment is anticipated. Chapter
2 discusses the various components (base oils, thickeners and additives), functional
properties, and characteristics of biodegradable greases. The base oils included syn-
thetic esters, castor, rapeseed, and soybean oil.
iii

iv Preface
Chapter 3 reviews some of the advantages and disadvantages of using vegetable

oil lubricants and their availability. Some of the history in the development of veg-
etable-based engine oils and their current status is described. The requirements for
further development and penetration of the petroleum based engine oil market are
discussed.
Besides transesterification to alkyl esters, three other approachesdilution with
conventional, petroleum-based diesel fuel, microemulsions (co-solvent blending),
and pyrolysishave been explored for utilizing vegetable oils as fuel. However, as
the mono-alkyl esters of vegetable oils and animal fatsbiodieselare the only
approach that has found widespread use (and, accordingly, the vast majority of
research papers deal with this approach), Chapter 4 focuses on such mono-alkyl
esters in terms of use, properties, economies, and regulatory issues.
Chapter 5 presents a background on home heating systems and highlights recent
research to develop renewable biofuels for home heating applications. Petroleum-
based liquid home heating oil is used to heat over 8 million homes in the U.S., pre-
dominantly in the northeastern U.S. This comprises approximately 6.6 billion gal-
lons of fuel oil annually. With recent rises in petroleum prices to over $50 per bar-
rel and anticipated future price increases as petroleum resources become less avail-
able, many applications that depend on petroleum are searching for alternatives.
Additional concerns over environmental issues involving sulfur and nitrogen oxide
emissions from oil-based home heating systems have sparked a search for alterna-
tive fuels to supply this market.
Polyurethanes are the most versatile group of polymers which can be used in the
form of foams, cast resins, coatings, adhesives and sealants. Polyols used in the
polyurethane industry currently exceed 2.4 million tons/year in the U.S. To use nat-
ural oils as raw materials for polyurethane production, multiple hydroxyl function-
ality is required. Castor oil has hydroxyl functionality naturally built in, thus it has
received extensive exploration as polyurethane building blocks, such as casting
resins, elastomers, urethane foams, and interpenetrating networks. Hydroxyl func-
tionality can be introduced synthetically in other natural oils. This process involves
a number of approaches and has been studied extensively by scientists around the
world, but commercial production of oil-based polyols has been scarce. Chapter 6
discusses the four main approaches for the hydroxylation of vegetable oils.
In Chapter 7, the authors summarize the type of natural composites reinforced
with different fibers along with different composite molding methods. The Solid
Freeform Fabrication Method and its advantages are included in the discussion.
Technologies that have improved the use of oils in coatings are highlighted in
Chapter 8.
The petroleum shortage in the 1970s stimulated research on vegetable oil-based
inks as a substitute for petroleum based products. Vegetable oils are mainly used in
paste inks; therefore the role of vegetable oils in the paste ink formulations and their
environmental properties are the main subject of Chapter 9.
Chapter 10 explains that vegetable oils provide a renewable source of fatty
acids that can serve as raw materials for the production of numerous surfactant com-
pounds. Structural modification of the fatty acids can impart unique physical prop-

Preface v
erties that alter the performance of the product in a predictable manner. Chemical
functionality can be introduced at the carbonyl carbon or along the carbon chain by
appropriate selection of reactants, catalysts, and reaction conditions. A tremendous
diversity of products is available with these oleochemical substrates. In addition,
vegetable oils provide a favorable alternative to petrochemical feedstocks.
The editor of this timely publication thanks the authors and their organizations
for their technical contributions in the chapters of this book. A special thanks goes
to Brittney Mernick for her assistance in the preparation of chapters for publication.
Sevim Z. Erhan
February 14, 2005

Contents vii
Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii
Chapter 1 Genetic Modification of Seed Oils for Industrial

Applications
Thomas A. McKeon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Chapter 2 Current Developments of Biodegradable Grease

Atanu Adhvaryu, Brajendra K. Sharma, and Sevim Z. Erhan . . 14
Chapter 3 Vegetable Oil-Based Engine Oils: Are They Practical?

Joseph M. Perez . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Chapter 4 Biodiesel: An Alternative Diesel Fuel from Vegetable

Oils or Animal Fats
Gerhard Knothe and Robert O. Dunn . . . . . . . . . . . . . . . . . . . 42
Chapter 5 Biofuels for Home Heating Oils

Bernard Y. Tao . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
Chapter 6 Vegetable Oils-Based Polyols

Andrew Guo and Zoran Petrovic . . . . . . . . . . . . . . . . . . . . . . . . 110
Chapter 7 Development of Soy Composites by Direct Deposition

Zengshe S. Liu and Sevim Z. Erhan . . . . . . . . . . . . . . . . . . . . . 131
Chapter 8 Vegetable Oils in Paint and Coatings

Michael R. Van De Mark and Kathryn Sandefur . . . . . . . . . . . 143
Chapter 9 Printing Inks

Sevim Z. Erhan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
Chapter 10 Synthesis of Surfactants from Vegetable Oil Feedstocks

Ronald A. Holser . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
vii

Ch1(IndOils)(1-13)Final 3/23/05 6:12 PM Page 1
Chapter 1
Genetic Modification of Seed Oils for

Industrial Applications
Thomas A. McKeon
USDA, ARS, WRRC, Albany, CA 94710
Introduction
While most vegetable oils are produced for food and feed uses, up to 15% of soy
(as well as other food oils) and up to 100% of certain commodity oils are used for
industrial purposes. Most food oils, such as soybean or canola, are composed pri-
marily of five fatty acids (FA): palmitic, stearic, oleic, linoleic, and linolenic; these
oils are used to produce surfactants, lubricants, inks, coatings, and polymers.
Commodity oils containing uncommon FA, such as castor (90% 12-hydroxy-
oleate) and tung (up to 80% conjugated FA), have no nutritive value, but due to the
unusual properties of the FA, they prove very useful for industrial applications. It
is the chemical functionality of a vegetable oil that can make it useful to industry;
chemical functionality can alter physical properties or allow chemical precursors
or useful derivatives to be made. For example, ricinoleate, the FA from castor oil,
has a mid-chain hydroxyl group that enhances its viscous properties for use as
grease and also enables production of an extensive range of chemical derivatives
(1). Coconut oil contains laurate (12:0) which has excellent foaming properties and
is used to make anionic surfactants. Hydroformylation of petroleum provides an
equivalent surfactant (2). The possibility of replacing such petroleum products
with plant-derived FA is a major goal of seed oil utilization research.
There are hundreds of FA with unusual functionalities, at least some of which
would have immediate application if readily available from a suitable crop. To the
extent that uncommon FA are produced in a given plant, these are a result of evolu-
tion, perhaps providing selective advantage as a result of toxic or other protective
effects of the FA on pathogens. Though it operates on a long time scale, evolution
has provided an unusual array of genetic material for production of useful FA.
However, many of these FA are produced in plants that are unsuitable as crops.
Traditional breeding techniques can alter levels of FA present in the oil and,
with suitable germ plasm, can reduce or eliminate one or more of the FA normally
present, as was the case in the development of canola (low-erucic acid rapeseed)
(3,4). Breeding has been used to develop plant selections with a high proportion of
a single component, e.g., such as high oleic safflower. High enrichment of a single
component such as oleate represents another industrially useful feature, as it

2 T.A. McKeon
reduces the expense of purifying the desired component. But breeding cannot be used
to introduce a FA not already present in one of the crossed plants. Random mutagene-
sis using chemical or radiation agents to alter the genome followed by screening and
breeding has also produced varieties with altered FA composition in oil (5). Genetic
identification and chemical characterization of FA biosynthetic mutants in mutated
Arabidopsis thaliana has provided an extensive genetic map of FA and lipid biosyn-
thetic steps during plant growth and development (6), in many cases providing null
mutants lacking a specific enzymatic activity. Since the mutagenic approach is
geared toward eliminating genes, this approach has been used as part of breeding
programs to reduce levels of undesirable FA components such as high polyunsatu-
rates from linseed oil (7) or to increase levels of a desired FA, e.g., oleate in sun-
flower by eliminating the enzyme that normally converts it to linoleate (8). A
recent innovation in this approach is TILLING (Targeting Induced Local Lesions
IN Genomes), which uses a mutagenic approach, but introduces high-throughput
screening of the M2 generation (the second generation of self-pollinated, mutated
lines) in order to identify specific genes that have been altered or inactivated by
mutagenic events (9). Plant selections carrying these mutated genes can then be
screened directly for desired characteristics. The TILLING process thus moves
most of the screening effort into the laboratory, considerably reducing the popula-
tion that would otherwise have to be grown in the field for phenotypic screening.
With the advent of genetic engineering, the technology needed to introduce novel
traits became available to breeders. A driving force behind development of genetically
engineered oils is the perennial surplus of oils produced. The unused inventory of soy-
bean oil may reach nearly two billion pounds in any year. Crops with altered oil com-
position hold the promise of reducing or preventing annual inventory carryover, thus
stabilizing or improving farm income. This chapter will explain the biochemistry
underlying the alteration of FA composition, briefly describe some oils that have been
developed through genetic engineering and mention some of the target FA of inter-
est for production in transgenic oilseed crops.
FA Biosynthesis
FA biosynthesis in plants proceeds from acetylCoA, which initiates a set of condensa-
tion reactions with malonyl-ACP through six or seven additional condensations with
malonyl-ACP. This yields the saturated FA palmitate or stearate, respectively, as
depicted in Figure 1.1, which depicts the pathway of FA biosynthesis to linoleic acid,
with the reactions leading to palmitate, stearate, and oleate occurring in the plastid,
separate from reactions leading to oil biosynthesis. Given the dependence of FA pro-
duction on malonyl-CoA production (to provide malonyl-ACP), the acetyl-CoA car-
boxylase (ACCase) is generally thought to play a regulatory role in FA production
and oil biosynthesis (10). This hypothesis is supported by research in which ACCase
from Arabidopsis was overexpressed in potato, leading to an increase in FA produc-
tion and a fivefold increase in triacylglycerol levels in the tuber (11).

Genetic Modification of Seed Oils 3
Fig. 1.1. The pathway of fatty acid biosynthesis to linoleic acid.

4 T.A. McKeon
Medium Chain-Length FA Biosynthesis

In seeds of certain plants such as coconut, palm kernel, bay laurel, and cuphea, the
flow of carbon to the long-chain saturated FA is disrupted, and this occurs as the
result of an acyl-ACP thioesterase (product of the FAT B gene), which removes
the ACP from the elongating FA chain prior to achieving full length. This produces
a medium chain-length FA which is transported from the plastid and enters the oil
biosynthetic pathway. This approach copied from nature led to the development of
the first transgenic oilseed modified to produce an industrial oil product, namely
Laurate Canola (12). By inserting into Canola the cDNA for a medium-chain spe-
cific acyl-ACP thioesterase (13) from California bay laurel, a plant which produces
seeds containing >60% laurate(dodecanoate) in its oil, plastidial FA synthesis was
diverted to the production of laurate, which was incorporated into the seed oil (14).
Although this achievement was a key early success in the contribution of genetic
engineering to agriculture, the underlying science also pointed to a number of tech-
nical problems that have since been widely recognized. The production of a FA not
normally produced by the seed may trigger a counter-reaction. In the case of lau-
rate, considerable amounts of the laurate were -oxidized, since the cytoplasmic
lauroyl-CoA used to acylate glycerolipid is also an intermediate in -oxidation
(15,16). While increased carbon flux through the FA biosynthetic pathway
enhanced laurate production, the overall outcome was a canola cultivar with
reduced oil yield, since some of the carbon incorporated into laurate production
was oxidized through the futile cycle.
The laurate canola oil produced also lacked laurate in the sn-2 position of the
triacylglycerol (TAG) (17). The canola seed lacked a lyso-phosphatidic acid acyl-
transferase (LPAAT) that could use lauroyl-CoA as an acyl donor for the sn-2
position of glycerolipid. Researchers at Calgene solved this problem by crossing a
canola plant containing an LPAAT gene from coconut (17), with a laurate canola
plant (18). The resulting plant produced an oilseed in which laurate is distributed
among all three positions of the TG. The resulting High-Laurate Canola had a
laurate content of up to 70%. The successful design of a novel, temperate-climate
industrial crop provided a great impetus to follow this approach for other industri-
ally useful products, especially oils. It also provided a foreshadowing of the diffi-
culties to be encountered in engineering production of uncommon FA in oilseeds.
Monounsaturated FA Biosynthesis
In general, once saturated FA are released from acyl-ACP, they are incorporated
into oil without any apparent modification except, to a minor extent, elongation. In
the plastid, though, the saturated fatty acyl-ACP can be desaturated by the 9-
desaturase, a class of soluble enzymes (as opposed to membrane-bound) formerly
identified as the stearoyl-ACP desaturase, which is the type present in most
oilseeds. These enzymes share a considerable degree of amino acid sequence
homology and the same type of active site in which the desaturation is carried out.

In most plants, the 9-desaturase produces oleate which, for purposes of oil
biosynthesis, is transported from the plastid to the endoplasmic reticulum and
incorporated into CoA, phospholipid, and acylipid. Oils high in oleic acid content
have been considered desirable both for food and nonfood uses. A high-oleate soy-
bean oil containing greater than 80% oleic acid was developed by suppressing
expression of the desaturase enzyme that converts oleate to linoleate in soybean.
This oilseed has been commercialized and for industrial purposes find applications
as a stable, biodegradeable hydraulic oil and is likely useful for developing other
bio-based lubricant applications (19).
Some plants produce monounsaturated FA of differing chain-length or with
the double-bond in a different position on the carbon chain, or both. Many such
desaturases have been cloned, the crystal structure of the soluble desaturase from
castor (Ricinus communis) has been determined, and considerable insight on fac-
tors involved in chain-length and positional specificity of the desaturase reaction
have been revealed (20,21). The ability to engineer this type of enzyme to intro-
duce a cis-double bond at a specific position on a selected chain-length represents
a bench chemists dream for saturated hydrocarbon chemistry. However, despite
the apparent similarity of some products to oleate, e.g., 18:1 6 (petroselenate),
their production can differ from that of oleate, resulting in limited amounts of the
product when introduced into a transgenic plant (10). It has been shown that, in
some cases, co-factors such as ferredoxin and ACP isoforms that interact specifi-
cally with the enzyme are required. Moreover, the FA may also require altered
lipid metabolism to be suitably incorporated into TAG (10). Thus, further under-
standing of lipid biochemistry leading to TAG production will underly successful
attempts to engineer oil composition.
Modification of Oleate
In most temperate climate oilseeds, the oleate may be further desaturated to
linoleate and -linolenate. In rapeseed, crambe and na-sturtium, the oleate may be
elongated to erucic acid by the action of an acylCoA based elongation reaction,
mediated in part and possibly regulated by expression of a keto-acyl synthase
(KAS) specific to elongation of long-chain FA. The products of elongation, usually
20:1 11 and 22:1 13 are incorporated into the TAG fraction (oil). In some
plants, the oleate is oxidized to uncommon FA. For example, in Vernonia, 18:1 9,
12-13 epoxy (vernolate) is formed and then incorporated into TAG (21,22). The
possibilities resulting from oleate production provided the basis for the original
concept of oleate as the central substrate in plant FA biosynthesis (23). The set of
modification reactions that can alter oleate is unusual, in that it comprises a family
of homologous enzymes that have evolved from the FAD2 genes, which encode
the oleoyl desaturase in oilseeds. Enzymes that have evolved from the FAD2 have
been found to carry out an unusual array of conversions, using an oleoyl-phospho-
choline (oleoylPC)-based substrate. These reactions include hydroxylation, epoxi-

6 T.A. McKeon
dation, desaturation-conjugation and desaturation to a triple bond (22,24,25). In the

case of hydroxylation and desaturation, changes in as few as 46 amino acid
residues result in an interchange of the two types of activity (24,26). In fact, the
oleate 12-hydroxylase from Lesquerella has mixed functionality, and can introduce
a hydroxyl group or double bond (27). Interestingly, as with some other uncom-
mon FA described in previous sections, introduction of genes with suitable production
of these uncommon FA in the oil of a transgenic plant has also proven difficult.
The next section will elaborate on this theme by describing the biochemistry of
castor oil, an important commodity oil with numerous applications (1).
Castor Oil Biosynthesis

Castor oil is a product of great interest to plant lipid scientists. It is an established
commercial product with a significant market and a cost of 4550 cents per pound
versus soybean oil at 1525 cents, yet is entirely imported by most industrialized
nations. Because castor seed contains noxious proteins, it is problematic as a crop.
Therefore, producing castor oil transgenically represents an enticing target and a
long-term challenge. Understanding the basis for the regulation of seed oil yield is
also a major research goal and castor, at 60% oil, has served as a benchmark for
high oil content.
Interest in castor oil biochemistry precedes the genetic engineering revolution.
In the 1960s, both the Stumpf research group at University of California, Davis,
and the Morris group at Unilever Research in Great Britain, carried out basic
research investigating the hydroxylation reaction that converts oleate to ricinoleate
(28,29). These early biochemical developments were followed by the research
groups of Stymne at Uppsala and Somerville and colleagues from MSU. These
groups contributed greatly to current understanding of ricinoleate production, and
the latter two groups elucidated the genetic basis for castor oil production by iden-
tifying and cloning two of the key genes (30,31)
The oleoyl-12-hydroxylase enzyme proved challenging to purify (3236).
Although the enzyme has not been purified to date, the cDNA for its gene was
cloned by a genomics approach (30). Based on the hypothesis that the hydroxyla-
tion reaction is analogous to, or the first step in, the desaturation reaction, this
research group proposed that the hydroxylase would share sequence elements in
common with FA desaturases. Using this approach, hundreds of cDNAs from
developing castor seed were sequenced, prospective hydroxylase cDNAs
expressed in tobacco seed, and the seed oil assayed for hydroxy FA. Although rici-
noleate production was low, 0.1%, it was sufficient to show that the hydroxylase
had been cloned and successfully expressed in a transgenic plant. However, to
date, oilseeds transformed to express the gene for oleoyl-12-hydroxylase produce
much less than the 90% present in castor oil, with most transgenes producing less
than 20% hydroxy FA content in oil (37). It has been hypothesized that the rici-
noleate incorporated in lipid inhibits membrane function in most plants, so it may

be eliminated from the membrane by endogenous phospholipases (38) and beta-

oxidized (39) by analogy to laurate. On the other hand, castor has evolved bio-
chemically to produce and incorporate ricinoleate into oil. This led to the approach
of identifying additional enzyme components in castor that enable it to produce an
oil with 90% ricinoleate. Based on a considerable body of research
(31,33,38,4043), a number of enzymes have been identified that appear to be
involved in high ricinoleate production, ricinoleate incorporation into oil, or maxi-
mizing oleate conversion to ricinoleate (44). The latter role is clearly fundamental,
since the final content of oleate in castor oil is less than 4%, and the castor oil
biosynthetic pathway is 96% efficient in converting oleate.
This research has been aided by development of methods for metabolic pro-
filing castor oil biosynthesis. In an effort to develop an alternative oilseed that
could produce castor oil, a microsomal system that carries out the biosynthesis of
castor oil in microsomes prepared from immature castor seed endosperm and
embryo has been developed (36,42). The microsomal system is effective in synthe-
sizing the TAG produced by the intact seed and provides a realistic model system
for investigating castor oil biosynthesis. Using this system and analysis of lipid
metabolites by high-performance liquid chromatography with selected columns
and solvent conditions, intermediates that accumulate during castor oil biosynthe-
sis can be separated and identified (44). This approach has enabled the identifica-
tion of additional enzymes that provide the unique basis for biosynthesis of castor
oil, since the gene for FA hydroxylation by itself is not sufficient to produce high
levels of ricinoleate in other oilseeds (37). Based on these research results and
other published research, the pathway in Figure 1.2 has been proposed.
The following narrative of the pathway summarizes these findings, with key
reactions and their role described briefly:
(i) The lyso-phosphatidylcholine acyltransferase (LPCAT) transfers the oleoyl-

moiety from oleoyl CoA into the sn-2 position of PC for hydroxylation.
(ii) The oleoyl-12-hydroxylase hydroxylates the sn-2 oleate to form sn-2 rici-
noleoyl-PC.
(iii) The phospholipase A2 preferentially removes ricinoleate from the sn-2 posi-
tion of PC and releases lyso-PC for reincorporation of oleate by LPCAT.
(iv) The free ricinoleate is preferentially incorporated into ricinoleoyl-containing
diacylglycerols by the diacylglycerol acyltransferase (DGAT) to form dirici-
noleins and triricinolein, which make up castor oil.
(v) The phospholipid-diacylglycerol acyltransferase (PDAT) incorporates the
sn-2 ricinoleate directly from the ricinoleoyl-PC product of the hydroxylase
reaction into the TAG end product.
The final step in oil biosynthesis (Fig. 1.2) shows a high degree of selectivity for
incorporating ricinoleate preferentially. Based on in vitro results, both the DGAT
and PDAT (45) appear to be active in carrying out the incorporation of ricinoleate

8 T.A. McKeon
Fig. 1.2. Castor oil pathway.
into castor oil. The DGAT cloned from castor shows a preference for using dirici-
nolein as a substrate in comparison to the DGAT from Arabidopsis, a plant that
does not produce hydroxy FA in its seed oil (46).
New and Improved Crops

The production of industrially useful FA in transgenic crops is complicated by the
need for greater understanding of how such FA are efficiently made in the plants
that make them, and how their incorporation into oil is directed. Table 1.1 lists a
number of FA and related products that are of interest to researchers seeking to
expand the role of seed oils in the hydrocarbon economy. The plants developed
would be renewable resources, enhance opportunities for rural development, and
contribute to the improvement of the environment. Current research efforts are on
the appropriate control of gene expression, elucidating the synthesis of the FA, and
controlling its destinyassuring its incorporation in oil and preventing it from
being further metabolized.
Another application of transgenic technology is the development of oilseeds with
improved agronomic characteristics. In fact, this has been the primary goal of agricul-
tural chemical producers that have initiated programs to produce GM crops.
Currently, the four genetically engineered crops that have been adopted are all oilseed
crops: soy, corn, cotton and canola. They account for 99% of transgenic crops planted

TABLE 1.1
Industrially Useful Fatty Acids for Transgenic Plant Production
Fatty acid Functionality Source Use

Eleostearic Conjugated Tung, bitter Drying oil
Octadeca-9c,11t,13t-trienoic double bonds melon
Erucic Very long-chain Rapeseed, Lubricants, anti-
Docosa-13c-enoic (VLC) crambe slip agent
-Linolenic Polyunsaturate Borage, Nutraceutical
Octadeca-6c,9c,12c-trienoic blackberry
Caproic to Myristate Medium chain-length Cuphea, coconut, Detergents
6 to 14 carbons bay laurel
Oleic Monounsaturate Many Hydraulic oil,
Octadeca-9c-enoic oleochemicals
Petroselenic Monounsaturate Coriander Nylon 6,6
Octadeca-6c-enoic isomer
Ricinoleic Hydroxylated Castor Lubricants,
Octadeca-9c,12-OH-enoic polymers
Vernolic Epoxy Vernonia, Coatings,
Octadeca-9c, 12,13-O-enoic Euphorbia plasticizer
lagascae
Docosahexaenoic VLC polyunsaturated Algae Nutraceutical
Nervonyl Erucate VLC wax ester Jojoba High-temperature
lubricant
worldwide. Over 70% of the soy grown in the U.S, 50% of the corn and 70% of the
cotton are genetically engineered. Most of the canola grown in Canada, a leading
producer, is transgenic. An increasing number of countries have adopted the tech-
nology. The U.S., Argentina, Canada, Brazil, China, and South Africa account for
99% of the transgenic crops produced, with an additional 12 countries adopting the
technology (47). The growth in planting of transgenic crops is remarkable in that it
has all occurred in the last eight years, from the time the first transgenic crops were
introduced in 1996. At this time, each of these crops has been modified for input
traits, reducing or eliminating the need for chemical applications by the introduc-
tion of genes encoding herbicide tolerance (soy, canola), insect resistance (corn,
cotton), or both (cotton). As plant genomics and proteomics programs identify
other agronomically useful genes, other transgenic traits will also be incorporated.
These can range from elimination of noxious components (48) to introduction of
dwarfing genes for greater plant efficiency. Small volume crops, such as papaya
and squash, have already been genetically modified for viral resistance. Crop
genetic engineering holds great promise as a means for developing oilseed crops
with unique characteristics that add both commercial and nutritive value, increase
utilization, and benefit the environment.

10 T.A. McKeon
Summary
Oilseeds are an important source of chemicals for industry. Most temperate climate
oilseeds produce oils containing the same five FA (palmitate, stearate, oleate,
linoleate, and -linolenate) in different proportions. In addition to nutritive uses,
these FA are used to produce soaps and detergents, coatings, lubricants, cosmetics,
plastics, plasticizers, and numerous chemical derivatives. For specific uses, certain
FA are more desirable. For example, the conjugated double bond system present in
FA of tung oil gives it excellent properties as a drying oil. Lauric acid from coconut
provides a chemical feedstock for producing detergents. Laurate canola was the first
commercial crop that was genetically designed to produce an industrial FA. The abil-
ity to manipulate FA composition in oilseeds resulted from a combination of three
approaches. First, biochemical characterisation has identified most of the steps in FA
biosynthesis. Secondly, genetic identification and chemical characterization of
Arabidopsis thaliana mutants has provided an extensive genetic map of FA and lipid
biosynthetic steps during plant growth and development. Finally, the additional
information needed to broaden the spectrum of FA available from oilseeds has been
provided by the identification, characterization, and cloning of unusual enzyme
activities from plants that produce uncommon, industrially useful FA.
Hundreds of uncommon FA, with unusual chemical functionalities, are pro-
duced by one or more oilseed plants. A considerable amount of research has gone
into elucidating the biosynthetic process by which such FA are made; much of the
enzymology underlying the introduction of unsaturation, conjugated unsaturation,
and hydroxyl, acetylenic, and epoxy functionality is now understood. As knowl-
edge of the mechanistic and structural knowledge of these enzymes expands, there
is potential for engineering production of FA that are not yet known. The specifici-
ty of the chemistry carried out on what is essentially a straight hydrocarbon chain
is unprecedented for the bench chemist, and presents the possibility of green
chemistry carried out in green plants to produce a wide array of chemicals
designed for industrial applications.
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Chapter 2
Current Developments of Biodegradable Grease

Atanu Adhvaryua,b, Brajendra K. Sharmaa,b, and Sevim Z. Erhanb
aDepartment of Chemical Engineering, Pennsylvania State University, University Park, PA
16802, USA; bUSDA, Food and Industrial Oil Research, 1815 N. University Street, Peoria,
IL 61604, USA
Introduction
The modern definition of lubricating grease, according to the American Society for
Testing and Materials (ASTM), is a solid or semi-solid product obtained by the
dispersion of a thickening agent in a liquid lubricant. This system may also include
other ingredients that impart special properties (see the American Society for
Testing and Materials, Standard Definition of Terms Relating to Petroleum
Products, 2000). This definition was further extended by the National Lubricating
Grease Institute (NLGI): The material we disperse in a liquid lubricant is usually
a solid. The dispersion . . . will not settle out when left standing. In order to devel-
op thickening, the solid and the lubricating liquid had best have some affinity for
each other. This affinity also helps keep the dispersion stable (1).
Lubricating greases are semi-solid colloidal dispersions of a thickening agent
in a liquid lubricant matrix. They owe their consistency to a gel-forming network
where the thickening agent is dispersed in the lubricating base fluid. The fluid
lubricant that performs the actual lubrication can be petroleum (mineral) oil, syn-
thetic oil, or vegetable oil. The thickener gives grease its characteristic consistency
(hardness) that is sometimes thought of as a three-dimensional fibrous network
or sponge that holds the oil in place. Therefore, the base fluid imparts lubricating
properties to the grease while the thickener, essentially the gelling agent, holds the
matrix together. This is a two-stage process. First, the absorption and adhesion of
base oil in the soap structure results, and secondly, there is a swelling of the soap
structure when the remaining oil is added to the reaction mixture.
A typical grease composition contains 6095% base fluid (mineral, synthetic,
or vegetable oil), 525% thickener (common thickeners are fatty acid soaps and
organic or inorganic non-soap thickeners), and 010% additives (antioxidants, cor-
rosion inhibitors, anti-wear/extreme pressure, antifoam, tackiness agents, etc.) (2)
(Fig. 2.1). Additives enhance performance and protect the grease and lubricated
surfaces (3).
Grease has been described as a temperature-regulated feeding device: when
the lubricant film between wearing surfaces thins, the resulting heat softens the
adjacent grease, which expands and releases oil to restore film thickness. The
14

Biodegradable Grease Developments 15
Fig. 2.1. Grease composition.
semi-solid nature of lubricating grease has several advantages over lubricating oils.
Oxidative stability and consistency of the grease matrix controls a wide variety of
performance properties in grease lubrication. Some of these properties are the abil-
ity to flow under force and subsequently lubricate hard-to-reach points; lower fric-
tion coefficient through adhesion on surface (4); wide temperature range effective-
ness; water stability; the ability to seal out contaminants as a physical barrier;
decreased dripping, spattering, and frequency of relubrication (act as sink for lubri-
cating oils). It is important to note at this point that grease structure and composi-
tion undergoes significant modification while working by shearing and oxidation.
The usefulness of grease in a particular application is controlled to a large extent
by the ability of the grease to sustain change in temperature, pressure, operating
environment, and shearing force.
Liquid lubricants possess certain shortcomings and are not able to cope with an
exponential rise in performance requirements in automotive and industrial sectors.
Technology is constantly being challenged to develop multifunctional lubricants to
operate at higher temperatures, higher pressures, and with a variety of contact sur-
faces to minimize friction and increase system efficiency. This has triggered a
steady rise in the development and application of greases in elastohydrodynamic
regimes. Thickness and stability of lubricant film is largely dependent on the
unique chemistry and composition delivered by greases. The function of grease is
to remain in contact with and lubricate moving surfaces without leaking out under
gravity or centrifugal action, or be squeezed out under applied pressure.
Development of vegetable oil-based greases has been an area of active
research for several decades (5,6). Technical progress taking place in industry and

16 A. Adhvaryu et al.
agriculture has caused an intensive exploitation of natural resources like mineral

oil. The search for environmentally friendly materials to replace mineral oil is cur-
rently being considered a top priority research in the fuel and energy sector. This
emphasis is largely due to the rapid depletion of world fossil fuel reserves and
increasing concern for environmental pollution from excessive mineral oil use and
disposal. Renewable resources like seed oils and their derivatives are being consid-
ered as potential replacements for mineral oil base stocks in certain lubricant appli-
cations, where immediate contact with the environment is anticipated. The nontox-
ic and readily biodegradable characteristics of vegetable oil based lubricants pose
less danger to soil, water, flora and fauna in case of accidental spillage or during
disposal (7).
Environmentally friendly lubricants and greases are already in market (8). These
products are highly desired in total loss lubricants like railroads, as their accidental
spillage doesnt invoke alarm and cause any harm to environment. Dwivedi et al.
described the preparation of total vegetable oil-based grease using castor oil (9).
Florea et al. have studied the effect of different base fluids on the properties of
biodegradable greases (10). A suitable composition of grease is desired with good
performance properties capable of use in multifunctional products. Despite the over-
whelming importance of biodegradable greases, very little is known about the rela-
tionship between their composition and performance properties.
Biodegradable Grease
Base Oils
Base fluids make up to 75 to 95% of the total composition of grease. Generally, the
base oils can be divided into two main categories: (i) water miscible, and (ii) non-
water miscible. Glycols are exclusively water soluble; the most frequently used are
monopropylene glycol or polyethylene glycol with an average molecular weight of
2001500. The advantages of these compounds lies in their resistance to aging and
hydrolysis, while the major disadvantages are solubility in water and incompatibility
with mineral base oils. Non-water soluble base oils can be subdivided into two groups:
(i) vegetable oils, and (ii) synthetic esters (11,12). This class of compounds basically
has the same structure, and therefore, similar physical and chemical properties.
The search for bio-based material as industrial and automotive lubricants has
accelerated in recent years. This trend is primarily due to the nontoxic and
biodegradable characteristics of seed oils and esters (13) that can substitute mineral
oil as base fluid in grease making. The performance properties of grease are pri-
marily dependent on their ability to provide lubrication to mechanically operating
moving parts by supplying base oil as a thin film separating the metallic surfaces,
and also removing heat and wear debris from the friction zone. Today, greases are
expected to work under extreme operating conditions, including shock load, wide
temperature range, varying pressure, surface material and environment. As

mechanical systems become more complex in operation, eco-friendly base oils are
used that can deliver performance properties similar to mineral base fluids and yet
are nontoxic to the environment.
Synthetic esters are generally obtained from branched alcohols and long-chain
fatty acids (e.g., oleic acids) for better properties. Long-chain esters with several
branching sites exhibit good low-temperature properties and resistance to hydrolyt-
ic degradation (14). Among the esters used for grease making are trimethylol-
propane, pentaerythritol, and neopentylpolyol. Compared to vegetable oils, these
fluids deliver good thermal stability, solvency, low temperature fluidity, sub-ambi-
ent storage stability, lubricity, compatibility with mineral oil, biodegradability, and
longer service life. Diesters of a number of fatty acids like oleic and stearic acid or
dibasic acids like adipic, azelaic, phthalic and sebacaic acids are widely used for
grease making.
A real need exists for research and development of new technologies for pro-
duction of lubricants according to the most advanced, ecological trends. The best
approach seems to focus on alternative, renewable, widely available, natural
resources, such as vegetable oils. They are naturally occurring triacylglycerols that
are formed by the reaction of one mole of glycerol with three moles of fatty acids
or a mixture of fatty acids (Fig. 2.2). Preferably the fatty acids are oleic acid,
linoleic acid and linolenic acid or mixtures thereof. Vegetable oils are a potential
source of environmentally friendly base oils that have the additional advantage of
not disturbing the global carbon dioxide equilibrium. They exhibit excellent lubri-
cation properties due to unbalanced electrical charges which make them attach to
metal surfaces. Vegetable oils that are extensively used for biodegradable grease
preparations are soybean, rapeseed, sunflower, and castor oil. Other vegetable oils
used are olive, peanut, palm, corn, cottonseed, safflower, lesquerella, coconut and
linseed. Genetically modified vegetable oils typically contain higher than normal
oleic acid content. For example, normal sunflower oil has an oleic acid content of
2030% which can be up to 6090% in genetically modified high oleic sunflower
Fig. 2.2. Typical vegetable oil structure.

oil. It may be noted that genetically modified vegetable oils have a high oleic acid
content at the expense of the di- and tri-unsaturated acids.
The presence of a polar group with a long hydrocarbon chain makes vegetable
oil amphiphilic in nature, allowing it to be used as a boundary lubricant. The mole-
cules have strong affinity for and interact strongly with metal surfaces. The long
hydrocarbon chain is oriented away from the metal surface to form a monomolecu-
lar layer with excellent boundary lubrication properties. When the molecule is
adsorbed on the metal surface, two types of interactions occur. The adhesive inter-
action between the ester group and metal is very sensitive to the type and number
of functional groups. The lateral interaction caused by dipole-dipole and dispersive
interaction between the hydrocarbon chains is sensitive to structural properties
including chain length, unsaturation, and stereochemistry (15).
Castor Oil. Castor oil consists of triacylglycerols with the major fatty acid compo-
nent being ricinoleic acid (~89 wt%) (16). It is a nondrying oil with high viscosity
and is quite suitable for various lubricant applications. It can be mixed with other
vegetable oils to obtain various viscosity grades (17) and offer excellent viscosity-
temperature characteristics. Phoronic acid (having shorter chain length as com-
pared to 12-hydroxystearic acid) derived from castor oil is superior in making
greases since it has a higher metal content, delivering long grease life at higher
temperatures. The shorter chain of phoronic acid is less subject to shear degrada-
tion when used in a grease matrix (18). Castor oil has also been used to prepare
total vegetable oil based grease with sodium and lithium gallants. Vegetable oil,
alcohol, and alkali are taken in such a ratio as to give a predetermined ratio of soap
and ester in the product. The alkali is selected based on the type of grease to be
formed (Li, Na or Ca) and alcohol selection controls the viscosity of the lubricant.
Higher carbon number and molecular weight of the alcohol produces lubricants
with higher viscosity (19). The residual hydroxyl group in the ricinoleic acid chain
offers an active site for adherence to metal surfaces. It is therefore expected that
greases prepared from castor oil will have better extreme pressure characteristics.
Rapeseed Oil. Rapeseed oil has a high viscosity and is often used as a lubricant
base oil mixed with other seed and mineral oils. Lithium greases prepared with
soap made from rapeseed oil and lithium hydroxide had better mechanical stability
if some calcium hydroxide was used in the mixture (20).
Soybean Oil. Soybean is the second highest value cash crop in the United States.
The farm value of soybean production in the crop year 2000 was $13 billion. The
3.1 billion gallons of soybean oil produced in the United States is half of the 6.2
billion gallons produced worldwide. Soy oil (typically 18% of the weight of the
soybean) can be used in its raw or refined form in a variety of industrial products
(fuels, inks, paints, industrial fluids, etc.). This oil is a good source if a high unsat-
uration in the triacylglycerol is desired for grease formulation. Current develop-

ments on bioengineered (high oleic and/or low linoleic) soybean oil may provide
highly desirable improvements for fuels and other industrial products. Unlike
petroleum-based grease that takes 12 to 18 months to decompose, soy-based prod-
ucts are less toxic than traditional products and are less likely to catch fire. The use
of oils from genetically modified seeds has opened up several possibilities in the
field of nonfood uses of vegetable oils. DuPont has developed a genetically modi-
fied soybean that would produce soy oil with enhanced stability for a variety of
industrial uses including application in grease making (21).
Soap Thickeners
Vegetable oil-based greases are semi-solid colloidal dispersions of a thickening
agent (a metal soap), in a liquid lubricant matrix (vegetable oil). The thickener is a
reaction product of a metal (alkali or alkaline earth metal) based material (oxide,
hydroxide, carbonate or bicarbonate) and carboxylic acid or its ester. Acids can be
derived from animal fat such as beef tallow, lard, butter, fish oil, or from vegetable
fat such as olive, castor, soybean, or peanut oils. The most common alkalies used
are the hydroxides from earth metals such as aluminum, calcium, lithium, sodium,
and titanium. Soap is created when a long-carbon-chain fatty acid reacts with the
metal hydroxide. This reaction often produces some amount of water. For certain
types of grease, the water assists in forming the soap structure. The metal is incor-
porated into the carbon chain and the resultant compound develops a polarity. The
polar molecules form a fibrous network that holds a certain amount of base fluid
by interaction forces. The soap structure is very important to the performance of
the grease and will vary in thickness, length and oil solubility, depending on the
type of metal hydroxide used. These variations are ultimately displayed in the final
properties of the grease. Listed in Table 2.1 are some of the important physical
properties of grease affected by the structure of fatty acids.
Vegetable oil-based grease thickened with polyurea is environmentally friendly
and biodegradable in nature (22). Polyurea is the most important organic nonsoap
thickener and has excellent oxidation resistance due to the absence of metal soaps
(which tend to initiate oxidation). It effectively lubricates over a wide temperature
range (20 to 177C) and has a long service life that makes it suitable in sealed-for-
life bearing applications. Polyurea complex grease is produced when a complexing
agent, most commonly calcium acetate or calcium phosphate, is incorporated into the
polymer chain. Such greases showed good shear stability when subjected to the roll
stability test.
Organic clay, though readily biodegradable, is a naturally occurring nontoxic
material, so its carbon content is not counted in the determination of ready bio-
degradability (23). Thickeners based on organic clay pose the least manufacturing
challenges for biodegradable greases. When vegetable oil is used, the required con-
centration of organo-clay is typically 14%, which may be higher for NLGI No. 2
consistency. Organo-clay thickeners have amorphous gel-like structure rather than

TABLE 2.1
Fatty Acid Structures and Grease Properties
Fatty acid structure Grease property

Distribution of chain length Variations in grease hardness
Amount of unsaturation Variations in dropping point
Degree of branching Non-uniform crystalline structure
Polar groups in the fatty acid structure Positive effects on intermolecular interactions
the fibrous, crystalline structures of soap thickeners. This grease has excellent
heat-resistance since clay does not melt and can effectively lubricate up to 260C.
The high temperature application of modern machinery has lead to the devel-
opment of complex soap greases. A complex soap is formed by the reaction of a
fatty acid and alkali (soap), and the simultaneous reaction of the alkali with a
short-chain organic or inorganic acid to form a metallic salt (the complexing
agent). Basically, complex grease is made when a complex soap is formed in the
presence of base oil. Common organic acids are acetic or lactic, and common inor-
ganic acids are carbonates or chlorides. The dropping point of complex grease is at
least 38C (100F) higher than its normal soap-thickened counterpart, and its maxi-
mum usable temperature is around 177C (350F). Generally, complex greases
have good all-around properties and can be used in multipurpose applications.
Grives has discussed commercial methods of biodegradable grease preparation
using different thickener systems (24).
Although it is known that the general structure of the soap phase in grease
consists of crystallites, which take the form of fibers, this does not clearly explain
why a small amount of a solid (soap) could immobilize a large volume of the base
oil in grease. These fiber structures form a complex network that traps the base oil
molecules in two ways: (i) by direct sorption of the oil by polar ends of soap mole-
cule, and (ii) penetration of base oil in the interlacing structure of soap fiber. The
oil-retaining property of grease may be due to the attractive influence of soap
fibers extending through many layers of the base oil molecule and not to the
swelling of the fibers (25). Therefore, the physical and chemical behavior of grease
is largely controlled by the consistency or hardness, which is dependent upon the
microstructure of soap fibers. Thus, a somewhat rigid gel-like material grease is
developed. Base oil and composition of the thickening agent plays an important
role in grease consistency. For low and high temperature applications, regulating
the base oil quantity and fatty acid composition can be used to control grease hard-
ness. Therefore, preparation of lubricating grease is a complicated trial-and-error
process in which the optimization of the reactants and the reaction protocol are
critical to achieve the desired grease consistency.
The chemistry of the fatty acid soap structure is responsible for certain perfor-
mance characteristics of grease including rust/corrosion inhibition, friction, and
wear resistance (26). Polar components in grease are surface active and therefore

have a strong affinity for metal surfaces while the hydrocarbon tail is directed
away resulting in the prevention of oxygen and water (rust and corrosion agents),
and dust particles from coming in direct contact with metal surfaces. Also, the
tightly adsorbed grease layer on metal is highly effective in lowering metal-to-
metal friction (27). Therefore, the application of bio-based grease is particularly
useful in open lubrication systems where the lubricant is in direct contact with
environment.
Grease is the preferred form of lubrication in hard-to-reach places in a mechan-
ically rubbing or dynamic system. Much of the functional properties of grease are
dependent on their ability to flow under force, have shear stability, resist viscosity
changes with temperature and pressure, maintain water stability, seal out contami-
nants, and decrease dripping and spattering. The dependability of lubricating
grease relies on physical properties that are structurally related, which are obtained
by the proper selection of ingredients and processing. Thus, it is pertinent to under-
stand the grease microstructure as it contributes significantly to various functional
properties of grease. Grease consistency [or National Lubricating Grease Institute
(NLGI) hardness] (28) is largely dependent upon the thickener fiber structure and
its distribution in the grease medium.
Grease hardness depends primarily on a metal soap thickener microstructure and
experimental data show that the fatty acid chain length and C-C unsaturation influ-
ences soap fiber structure/networking mechanisms. An understanding of fiber growth
and their network structure in a grease matrix is required to relate base oil holding
capacity and oil release by shear degradation of soap thickener during operation to
additive compatibility, bleed resistance, viscosity, thermal stability, texture, and
appearance. Critical physiochemical properties are, therefore, dependent on the con-
sistency of grease and their behavior in the mechanical system. Controlling the growth
and distribution of soap fiber during grease manufacturing processes can result in
products with the desired physical, chemical, and performance properties.
The soap fibers derived from short-chain fatty acids are not well developed
and sufficiently elaborate to create a strong interaction with the base oil. Increasing
the fatty acid chain length (Cn; n = number of carbon atoms) in soap resulted in
stronger bonding interaction and a harder grease matrix. Beginning with a C13 fatty
acid chain length, there is a significant increase in grease hardness up to C15, with
an optimum at C17 resulting in NLGI grade 2 grease (using a 1:1 equivalent ratio
of metal to fatty acid and 75 wt% of soy oil in the grease mixture) (Fig. 2.3).
In a study using transmission electron microscopy (TEM), formation of dis-
persiod structure with compact network with an increase in the chain length of the
fatty acid in lithium soap was observed. With more interlocking resulting from the
long-chain fiber structure, increased interactions with base oil in the matrix can be
achieved. Grease developed under such conditions shows high consistency result-
ing in higher hardness. The TEM of palmitic [CH3(CH2)14COOH] and stearic
[CH3(CH2)16COOH] acids used in the lithium soap to develop soybean oil-based
grease are shown in Figures 2.4a and 2.4b, respectively.

Fig. 2.3. Lithium soap fatty

acid chain length effect on
soy-grease NLGI hardness.
It appears that such compact mesh structure can hold relatively larger amounts
of base oil in the soap matrix due to the excellent interaction. This increases the
ability of the grease to resist deformation with increasing fiber length, because a
long fiber can make more contacts with neighboring fibers than a short fiber with
the same diameter. It may be noted at this stage that during extreme shear stress,
when a fiber breaks into smaller fragments, the consistency will decrease, whereas
when they split into thinner fragments, the consistency will increase. Therefore, the
hardness of grease as a result of soap structure can affect oxidation stability, water
washout, oil bleeding at higher temperature, and lubricity (29,30).
Unsaturation in the fatty acid structure of soap molecules has significant
impact on the grease fiber structure. Linoleic acid (C18:2) (Fig. 2.5b) with two sites
of C-C unsaturation in the chain shows a much thinner and compact fiber network
Fig. 2.4. TEM of (a) palmitic and (b) stearic acid used to develop soybean oil-based
grease.

than oleic acid (C18:1) (Fig. 2.5a) in the soap composition. Excessive thinning of
the fiber strand may result in softer grease due to a weak mesh structure that is
unable to hold the base oil in the grease matrix. Furthermore, the presence or
absence of C-C unsaturation with the same chain length acids (Fig. 2.4b and 2.5b)
in the soap structure results in a distinct difference in the shape and distribution of
the fibers. With process parameters and composition remaining the same, and with
a decrease in the soap fiber length, there is a tendency to form softer grease (31).
Because the growth of soap fibers in the grease matrix is a result of fusion and
solidification of adjoining short fibers, this phenomenon is also controlled to a
large extent by the procedure used to manufacture grease (32). Soap molecules
with oleic acid show a comparatively larger fiber structure than linoleic acid.
It has been observed that decreasing the soap concentration or lowering the
cooling rate could produce long-fiber grease. Moreover, fiber length of grease
increases with an increase in the heat-retention time. Especially the addition of
soap powder to grease in the heat retention process resulted in gigantic fibers. In
contrast, short-fiber grease could be produced by increasing the soap concentration
or raising the cooling rate. A very high cooling rate results in lowering the ratio of
fiber length L to width D, L/D, resulting in a softer grease. The soap fibers in
grease are considered to grow when the grease is maintained near the melting point
of soap (33). The fluctuation in temperature leads to the fusion and solidification of
the soap fiber, leading to the disappearance of short fibers and the growth of long
fibers (34).
Additive Effects
Additives are usually introduced during the cooling phase of grease making and
remain dispersed in the matrix. These additives are found to enhance some of the
functional properties of the base oil in the grease such as oxidation, load-bearing,
anti-wear, anti-corrosion and anti-rust (7,3537). Due to the presence of additives,
the soap thickener structure can be influenced to a large extent by either changing
the solubility of the soap in the base oil or influencing its crystallization. Similarly,
Fig. 2.5. TEM of (a) oleic acid and (b) linoleic acid.

the optimum condition for fiber growth through crystallization may vary with dif-
ferent additives. It is believed that the additive molecules are first bound to the
soap fibers and the chains attached to additives hold the oil. The TEM (Figs. 2.6a
and 2.6b) show the effect of antimony dithiocarbamate additive on Li-stearate soap
structure. Under magnification (1.81 m), the additive-doped grease has a looser
network structure with larger fibers than the nonadditive-doped grease with a simi-
lar metal, fatty acid, and base oil composition. It may be noted, however, that due
to the presence of additive molecules, grease hardness is not altered significantly
as a result of changes in the soap fiber length and their distribution in the matrix.
There are various reports in the literature where researchers have investigated
additive effects on grease performance. Kato et al. (38) have reported the effective-
ness of antioxidants in obtaining long lubricant life of grease with a rapeseed oil
base. It was observed that the main causes of a reduced grease life are chemical
deterioration due to oxidation and polymerization of the base oil. The antioxidants
can delay such processes, but as soon as they are consumed, the degradation starts
rapidly.
The performance properties of grease are primarily dependent on their ability
to provide lubrication to mechanically moving parts by supplying base oil as a thin
film to separate the metallic surfaces, and also by removing heat and wear debris
from the friction zone. Similarly, the nature of the fatty acid in the soap structure
of grease has a significant influence on the physical and chemical properties. Soaps
can lubricate and are considered to be more important than the lubricating oil
because they can improve the lubricating ability of the oil. Elliott (39) found that
the chain length of the fatty acid was an important factor in determining grease
characteristics. The starting and running torques are less for the grease than for the
oil itself. Using the Four-Ball Tester, Jiang (40) showed that a lithium grease could
prevent seizure at a load of 35 Kgs., whereas the oil film broke and failed. Physical
and chemical degradation of grease during use (41,42) and failure of various
Fig. 2.6. TEM showing the effect of antimony dithiocarbamate additive on Li-stearate
soap structure.

mechanical parts due to inadequate lubrication (43) have been reported. Several
mechanisms have been proposed on timed lubricant release and replenishment of
starved lubricant sites during operation. Laboratory simulations range from simple
thermal stability tests to more complex lubrication measurements (4446).
Functional Properties
Grease is used when it is not practical or convenient to use oil in a dynamic system.
The use of grease is largely dictated by the design of the machinery and operating
conditions that are suitable for a desired lubricant characteristic. Grease functions as a
sealant (based on consistency) to minimize leakage, keep out contaminants and pre-
vent entrance of corrosive foreign materials into the system. Grease, unlike oils, by
virtue of its rigidity, is easily confined with simplified, less costly retention devices.
The major practical requirement of grease is to retain its functional properties under
shear at all temperatures it is subjected to during use. They have the ability to hold
finely ground solid lubricants and additives in a stable dispersed condition and are
able to deliver them at the point of metal contact for better lubrication. Grease main-
tains thicker films in clearances enlarged by wear and can extend the life of worn
parts that were previously oil lubricated. Thicker grease films also provide noise insu-
lation. Therefore, grease is mainly applied in equipment that is seldom used or is in
storage for an extended period of time. High quality greases are also used in areas that
are inaccessible to frequent relubrication and sealed-for-life type devices (e.g., motors
and gear boxes). They also find use in applications involving extreme temperature,
pressure, shear stress, shock loads, etc. Under these circumstances, grease provides
thicker film cushions to protect and deliver adequate lubrication, where oil films can
fail due to thinning.
Grease Characteristics
Consistency. This is an important parameter of grease that controls most of its
physicochemical characteristics. Hard grease will not lubricate properly while very
fluid grease may leak out of the system. Grease consistency depends on the type
and amount of thickener used and the viscosity of its base oil. Greases consistency
is its resistance to deformation by an applied force and is generally measured by
ASTM D 217 and D 1403 methods (47).
Corrosion and Rust Resistance. This denotes the ability of grease to protect
metal parts from chemical attack. The thickener type provides most of the natural
resistance of grease; however corrosion and rust inhibitors are often used in actual
formulations.
Oxidation Stability. Oxidation is the most important chemical property of grease

that results in insoluble gum, sludge, deposits and therefore leads to sluggish oper-
ation, reduced metal wetability, decreased wear protection and increased corrosion,

among others. Oxidation is also associated with evaporation which causes grease
to harden due to increased thickener concentration. Excessive temperatures result
in accelerated oxidation or even carbonization where grease hardens or forms a
crust. Therefore, higher evaporation rates require more frequent relubrication. A
number of studies have been reported on various aspects of thermo-oxidative sta-
bility (42,48,49) and oxidative degradation using chromatographic and spectro-
scopic techniques (41).
Bleeding. This is a condition where long storage periods and high temperatures
induce a liquid lubricant to separate from the grease thickener. When the oil sepa-
rates from the grease, thickener concentration increases resulting in grease plug-
ging. Under certain circumstances, when two greases are in contact, the oil may
migrate from one grease to the other, changing the structure of either grease.
Grease, when subjected to high temperature for an extended length of time, loses
its consistency and becomes fluid enough to drip. The dropping point indicates the
upper temperature limit at which the grease retains its structure. However, a few
greases have the ability to regain their original fiber structure after cooling down
from the dropping point.
Low Temperature Stability. Grease hardens at low temperatures, leading to poor

pumpability and rheological properties. Typically the base oils pour point is con-
sidered the low-temperature limit of grease.
Biodegradability
In 2002, around 57 million tons of lubricant was used worldwide, and it is estimat-
ed that as much as 35% finds its way back into the environment unchanged. Some
of this will degrade but there are potential dangers to the environment such as
bioaccumulation and biocidal effects.
During biodegradation, the material is gradually broken down through the meta-
bolic action of such living organisms as bacteria, fungi, yeast and algae. Naturally,
this process is not entirely predictable and can be influenced by the mix of living
organisms present, the ambient temperature, and the humidity. Sometimes a material
that may easily degrade under one set of circumstances may not readily degrade under
others. The minimum basic requirements are sufficient bacteria population, correct
oxygen levels and a suitable temperature range. The rate of biodegradation is also
affected by parameters such as fluid viscosity, pH levels, sunlight, mineral salt con-
tent, nitrogen availability, solubility and the ability of the bacteria to adapt to the
source of oil nutrient. Ideally, in due course of time, the lubricant should be reduced to
its simplest natural form while leaving no harmful by-products that could have a detri-
mental and long-term effect on the local environment.
Biodegradability and renewability are becoming increasingly important to for-
mulators as new federal environmental regulations go into effect. Environmentally

sensitive application areas typically involve exposure to the elements, where there
is a definite potential for the grease to contaminate the ecosystem through washout
or accidental leak. Further, it is almost impossible to prevent accidental breaking of
one of the small grease lines, the consequence of which is that grease can find its
way into the water or at the very least into landfills. Currently, many greases are
used in loss-lubrication systems, where a certain amount of grease ends up in the
environment. Such applications include but are not limited to: forestry (chainsaw/
grapples); agriculture (tractors, harvesters); lubricants (marine, boat trailer bearings);
railway (curve/axle greases); mining (conveyor greases); manufacturing (hot and cold
rolling mills); construction (waterways, bridges, locks, dams). Accordingly, bio-
degradability has become vital.
It is well known that mineral oils are not readily degradable under normal envi-
ronmental conditions. Therefore, they have a high potential to accumulate in the envi-
ronment. Mineral oils are also known to taint water and fish, making them unsuitable
for consumption. Vegetable oils are not toxic to aquatic organisms and biodegrade rel-
atively fast and completely. Soybean grease, for instance, decomposes within weeks;
petroleum-based grease, however, takes from a year to 18 months to decompose.
Metal soaps used in greases are commonly based on stearates, the main component of
a natural soap, and are biodegradable to a large extent with the only exception of the
type of metal present. Inorganic thickeners such as clay-like materials, that are found
abundant in nature, however, are not entirely biodegradable, but are also not toxic to
aquatic organisms. The additives constitute a very diverse range of chemicals and are
often present in small quantities, possessing a wide range of biodegradability and
aquatic toxicity. Some additives present in smaller quantity in the grease, and sparingly
soluble in water, may increase several-fold due to the presence of other solubility-
enhancing materials. Therefore, its effect is much higher than could be expected based
on the small amount present in the grease. Therefore, it is difficult to make any gener-
alized statement on additive biodegradation and aquatic toxicity (50).
One of the most important methods used to determine biodegradability is also the
only one available for testing products immiscible with water: CEC-L-33-A-93 (for-
merly CEC-L-33-T-82). All of the test methods were initially designed mainly for use
with single chemical species that have demonstrated water solubility. In a biodegrada-
tion test the microbe feeds on the substrate (compound to be tested) and degrades it. In
general, this process is monitored by measuring oxygen consumption, carbon dioxide
production, and the drop in dissolved organic carbon. According to CEC test methods,
the biodegradability of a lubricant (i.e., grease) is plotted over a period of 21 days in
comparison with white oil (2030% biodegradability) and di-iso-tridecyladipate
(100% biodegradability). The results are evaluated by measuring the fluctuations in the
CH3CH2 bands at the 2930 cm1 using an infrared spectrometer. According to CEC-
L-33-T-82, if the product is more than 80% biodegradable the German Blue Angle
criteria makes it readily biodegradable (51,52). Biodegradability of used lubricants can
be altered by contamination and can be as much as 15%. A lubricant that is 90%
degradable when fresh may only be 75% degradable when used.

Conclusions
Lubricants based on renewable materials have been around for a long time and have
only recently been extensively researched for nonfood industrial applications to be
more competitive with petroleum-based products. Pollution from petroleum products
has been a big concern for the environment. Of the 2.5 billion gallons of lubricant
sold in the U.S. market, 30 to 40% escape into the environment through accidental
spillage, leaks and evaporation. Since these lubricants are directly released on the
ground or into the water, it is important they are biodegradable and will not persist in
the environment for too long. Lubricants based on fossil fuels are persistent, and
therefore not suitable in these applications. Vegetable oil-based lubricants in the form
of greases are biodegradable and can be formulated to meet or exceed industry speci-
fications. This will increase the use of agricultural products such as vegetable oils in
industrial (nonfood) applications and therefore increase the agricultural land use and
work. Further, the environment is protected by the introduction of an environmentally
friendly lubricant in an industrial application, and finally, the dependence on import-
oriented mineral oil is largely averted.
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Chapter 3
Vegetable Oil-Based Engine Oils: Are They Practical?

Joseph M. Perez
Tribology Group, Chemical Engineering Department, The Pennsylvania State University,
University Park, PA 16802
Introduction
Vegetable oils were the primary lubricants for machinery and transportation vehi-
cles for thousands of years until the discovery of petroleum. Petroleum, primarily
on the bases of lower cost and improved performance, quickly replaced vegetable
oils as the lubricant (1). Now, with increased petroleum costs, decreased petroleum
reserves, and environmental concerns as major factors, vegetable-based oils for
lubricants are making a slow but steady comeback. In the past decade, the initial
applications have been niche markets such as chain saws, track lubricants, and
other total loss lubricants. In Europe, legislation has helped to expand the use of
vegetable-based lubricants to the hydraulic fluid market, a potentially large market
for biodegradable vegetable oils and synthetic fluids. Looking ahead, the engine
oil market is a larger market, one in which vegetable-based lubricants might
achieve penetration. However, are vegetable oil-based engine oils practical?
The 2004 Soy Products Guide (2), a listing of commercially available industri-
al products made from soybeans, lists only three companies selling hydraulic flu-
ids and six selling engine oils containing soybean oil. There are a number of com-
panies selling biodegradable or environmentally friendly hydraulic fluids but
these contain other oils such as rapeseed, canola, or synthetic oils. Of the six com-
panies selling engine oils, three sell the same product. There is at least one addi-
tional company selling engine oil based on sunflower oil. None of the products
have undergone the Society of Automotive Engineers (SAE)/American Society of
Testing Materials (ASTM) engine oil test series required to receive American
Petroleum Institute (API) certification. Of the vegetable oils on the market, limited
field test data are available. There are a number of factors that must be considered
to determine whether vegetable oils are practical, including whether they can
match the performance required to displace petroleum-based engine oils.
Available Vegetable Oil. In the United States, the major source of in-house veg-
etable oil for lubricant applications is soybean oil. The total estimated supply of
soybeans in 2004 was 2.9 billion bushels; of these, 1.6 billion bushels were
crushed to supply 18 billion pounds (2.3 billion gallons) of oil (3,4). Most of this
oil enters the food chain and only ~10% is available for use in plastics, solvents,
31

32 J.M. Perez
coatings, printing inks, adhesives, and some lubricants. Another competitor for this
oil is the growing biodiesel fuel market. Even by blending vegetable oil with syn-
thetics, to control low temperature characteristics of the basestocks, other oils such
as sunflower, canola, corn, or palm oil may be needed to have a significant effect
on the market. This could result in a continued dependence on foreign oil, but from
different sources such as Canada, Brazil, and Indonesia.
Engine Oil Market Size. In 2002, 46% of the 2.4 billion gallons of lubricants sold
in the U.S. market were crankcase oils; 13% were transmission, hydraulic fluids,
and other automotive oils (5). Various industrial oils make up the remaining 41%
of the lubricant market. With current farm production, only ~10% of this market
could be supplied by vegetable oil products.
Foreign Oil Replacement. One frequently stated advantage of using renewable

lubricants is the replacement of petroleum-based products. Any displacement of
petroleum oil affects the balance of payments. Use of renewable lubricants in
crankcase oils would result in a small but positive displacement. The total use of
petroleum in the U.S. in 2005 was projected to be ~23 million barrels/d. The U.S.
transportation demands were projected to use ~55% of the total or >13 million bar-
rels of oil/d (6,7). Basestocks for use in lubricants comprise a small but significant
quantity. From each 42-gallon barrel of oil processed, 1.2% is used for lubricants.
However, in 2002, the automotive lubricant market alone was >2.4 billion gallons
(57 million bbls).
Basestock Cost. Economics is a major factor in the market growth of new prod-
ucts. The cost of vegetable base oils exceeds the current petroleum base oil price of
$1.5/gallon by at least 50%. As the price per barrel of oil increases the difference
becomes smaller. However, it will take years to significantly reduce the cost differ-
ences. If the size of the market increases, the cost of the vegetable base oil will
decrease. However, the engine oil market will not increase significantly without
API certification, and running the required bench and engine tests will not occur
until the market increases. The drivers to produce vegetable-based engine oil lubri-
cants include environmental concerns, improved performance, increased value for
farm products, jobs, and the worlds disappearing petroleum reserves.
Environmental Concerns. Currently, the major driver in many countries of the

world is the concern over air, water, and soil contamination by petroleum products.
In many European countries, these concerns have resulted in regulations that
require the use of biodegradable lubricants in hydraulic systems of equipment used
in forestry and waterways projects. In the United States until recently, no such fed-
eral regulations existed outside of Presidential Directives. Some states are requir-
ing the use of low levels of biodiesel, but no hydraulic or engine oil regulations
currently exist. However, the 2002 Farm Bill (Farm Security and Rural Investment

Vegetable Oil-Based Engine Oils 33
Act, published January 11, Federal Register), Section 9002 includes language
directing all federal government agencies to give preference to biobased prod-
ucts, unless it is unreasonable to do so, based on price, availability, or perfor-
mance. Lubricants are one category specified in the guidelines to be published. The
USDAs Office of Energy Policy and New Uses was delegated the authority to
implement Section 9002 (8).
Lubricant loss to the environment is another concern. Reportedly, this is the
fate of >60% of all lubricants (9). Some obvious areas for increased use of
biodegradable hydraulic fluids and engine oils are construction, forestry, farming,
and waterways where losses directly affect the environment. Spill cleanup costs in
some states are significant. The use of biodegradable lubricants can reduce these
costs. Reduction in cleanup costs neutralizes the increased cost of using biodegrad-
able hydraulic fluids made from renewable resources.
For waterways, biodegradable 2-cycle or 4-cycle engine oil lubricants are cur-
rently available for use in motorboat engines used on our many lakes and rivers.
The 2-cycle oil market is ~2% of the total lubricant market.
Environmentally, biodiesel is a separate issue but it does affect the availability
of vegetable oils for lubricants. Diesel engines are more efficient than gasoline
engines. This results in a reduction in greenhouse gases. The need to reduce diesel
particulate emissions has led to the widespread use of biodiesel. Use of B20 and
vegetable-based lubricant results in reduced particulates and possibly a change in
the morphology of the particulates. This is discussed elsewhere in detail in the lit-
erature (1012).
Performance Requirements
The major concern of original equipment manufacturers (OEM) is whether the
lubricants made with vegetable-based oils are going to give equivalent perfor-
mance to petroleum products currently in use. This affects engine and equipment
durability and warranty costs. Some of the desired fluid properties for hydraulic
fluids and engine oils are found in Table 3.1. Of these, oxidation stability and low
temperature fluidity are known weak links for vegetable-based stocks. Engine oil
performance requirements are more severe than hydraulic fluid requirements due
to differences in the operating conditions. In hydraulic system applications, fluid
compressibility, hydrolytic stability, foam, and air entrainment requirements are
the more important properties. In an engine, oil oxidation stability, deposit forma-
tion, friction, and wear are the major concerns. Low temperature fluidity is critical
to both applications.
Engine Oil Specifications

The requirements for engine oils are well defined in ASTM and SAE specifications
(1316). SAE J300 defines the viscosity requirements for the various viscosity
grades (Table 3.2). ASTM Method D455 is used to define the kinematic viscosity.

34 J.M. Perez
TABLE 3.1
Desired Fluid Properties
Automotive lubricants Hydraulic fluids

High temperature oxidation and thermal stability Oxidation stability
Temperature-Viscosity (VI) Viscosity (ISO 32/42)
Low temperature fluidity Low temperature fluidity
Control friction and wear Control friction & wear
Suspend contaminants/cleanliness Control contaminants/cleanliness
Acidity/rust Hydrolytic stability
Foam control Foam/air entrainment control
Component compatibility Component compatibility
Fuel compatibility Fluid compatibility
Volatility Volatility
Environment, safety, and health Environment, safety, and health
Cost Cost
aVI, viscosity index; ISO, International Organization for Standardization.
To simulate viscosity of an operating engine, ASTM High Temperature High

Shear Method D4624 is used. ASTM D4684 Mini-Rotary Viscometer Method
defines low-temperature pumping properties. Some military requirements are
found in Table 3.3.
There are vegetable-based engine oils available on the current market. The
basestock of some oils is essentially all vegetable oils and others are blends of veg-
etable oils and petroleum or synthetic basestocks. In an earlier study by
Cheenkachorn at Penn State (17), a number of the oils obtained did not meet their
stated viscosity grade as specified in SAE J300. It is more significant that none
were API certified.
TABLE 3.2
Society of Automotive Engineers (SAE) Viscosity Requirements-J300/95
Kinematic viscosity
HTHSa (min)
cSt at 100C
Pumping cSt at 150C
SAE viscosity grade Max cP at (C) min max and 106 s1
5W 60,000 at (35) 3.8
10W 60,000 at (30) 4.1
15W 60,000 at (25) 5.6
20W 60,000 at (20) 5.6
25W 60,000 at (15) 9.3
20 5.6 <9.30 2.6
30 9.3 <12.5 2.9
40 12.5 <16.3 2.9
50 16.3 <21.9 3.7
aHTHS, high temperature high shear.

TABLE 3.3
Military Requirements
Requirement 10W 30 40 5W30 10W30

Pumping viscosity 30,000 30,000 30,000
cP max at (C) at (25) at (30) at (25)
cSt Viscosity at 100C 4.1/<7.4 9.3/<12.5 12.5/<16.3 9.3/<12.5 9.3/<12.5
min/max
VI, min 80 80
HTHS, cP, min 2.9 2.9 2.9
Pour point, Cmax 30 35 30
Flash point, C 205 220 225 200 205
COC, min
Evaporation, %max 18 20 17
aAbbreviations: VI, viscosity index; HTHS, high temperature high shear; COC, Cleveland Open Cup.
To be certified requires a number of fired engine tests and bench tests. The
requirements for gasoline engine oils are discussed elsewhere (18). For diesel
engines, the current API CI-4 engine oil requires eight fired engine tests and seven
new and used oil bench tests found in Tables 3.4 and 3.5. The number of engine
tests for certification has increased from two (CD Oil) to eight (CI-4 oil) as
requirements for improved quality have increased in the past 50 years.
Conducting development and certification tests on crankcase oils exceeds
1000K. The time for recovery of investment on these costs is now ~5 years before
the next generation of oil must be certified. The target for PC-10, the next genera-
tion of diesel engine oils is 2007. CI-4 certifications started in 2002.
Vegetable Oil Properties

The advantages and weaknesses of vegetable oils for lubricant applications are
well known (Table 3.6). Vegetable oils have improved lubricity and natural viscosity-
TABLE 3.4
Fired Engine Test for American Petroleum Institute (API) CI-4a
Performance requirement Engine test

Ring, liner, bearing wear and oil consumption Mack T-10 (EGR)
Ring, valve train wear, filter pressure Cummins M11-EGR
Differential and sludge content
Roller-follower wear GM 6.5 Liter
Piston deposits and oil consumption, two-piece piston Caterpillar 1R SCTE
Piston deposits and oil consumption, aluminum piston Caterpillar 1K or 1N SCTE
Engine oil viscosity control due to soot Mack T-8E
Oil aeration control International 7.3 L
Oil oxidation GM 3.8 Liter Sequence IIIF
aAbbreviations: EGR, exhaust gas recirculation; SCTE, single cylinder test engine.

36 J.M. Perez
TABLE 3.5
Bench Tests for American Petroleum Institute (API) CI-4
Performance characteristics Bench test

Shear stability Bosch injector ASTMa D3945
High temperature high shear (HTHS) ASTM D4683
Volatility NOACKASTM D5800
Low-temperature pumpability Used oil containing 5% soot from Mack T10MRV
TP-1, ASTM D4684
Elastomer compatibility ASTM D471
Corrosion control ASTM D5968
Foaming ASTM D892
aASTM, American Society of Testing Materials.
temperature properties compared with petroleum-based mineral oils. However,

serious negative characteristics of vegetable oils are poor oxidation stability and
low-temperature properties. Also of concern are corrosion and hydrolytic stability.
Research in the 1990s by a number of organizations including ADM, Cargill, Dow,
Dupont, Lubrizol, Penn State, Renewable Lubricants, the USDA (Food &
Industrial Oil Research Unit, Peoria, IL), and others was aimed at improving these
weak links. Research focused on using additive technology, chemical modifica-
tions, genetic engineering, and blending with other biodegradable synthetic fluids.
Oxidation Stability. Basically, the key to oxidation stability is chemical structure.

The more oleic double bonds in the fatty acid chains of the triglyceride, the better
the oxidation stability. The more conjugated double bonds in the fatty acid chain
the poorer the oxidation stability. Typical vegetable fatty acids are oleic, linoleic
and linolenic, Figure 3.1. The relative rates of reactivity are found in Figures 3.2
and 3.3. The composition varies depending on the source, Table 3.7. Studies have
shown that oxidation stability can be improved by the use of selected additives,
TABLE 3.6
Vegetable Oils
Advantages
Environmental Properties
Biodegradable Low volatility
Renewable Viscosity-Temperature (High viscosity index)
Nontoxic Friction and wear
Disadvantages or unresolved issues

Environmental Properties Other
Oxidation issues Low temperature Cost
Oxidation stability Volume
Hydrolysis Quality

Fig. 3.1. Vegetable oil structures.
genetic engineering and chemical modifications. However, some of these improve-

ments result in poor low-temperature properties. These properties can be improved
by blending the vegetable oils with low pour point basestocks that have acceptable
biodegradability. In some cases, chemical modification, such as alkylation and
esterification with selected polyol alcohols, can also improve low-temperature
properties.
Engine Oil Status

Currently, a few small companies are marketing 2- or 4-cycle vegetable-based
engine oils on a limited basis, and some major companies have active research in
progress in this area. Companies in the United States that are marketing 4-cycle
vegetable oil-based engine oils include Agro Management Group of Colorado
DOUBLE ALLYLIC >
Fig. 3.2. Relative reactivity of hydrogens in vegetable oils.

38 J.M. Perez
Fig. 3.3. Order of reactivity of hydrogens: ALLYLIC >> TERTIARY > SECONDARY >
PRIMARY.
Springs, CO (AGM) and Renewable Lubricants (RLI) of Hartsville, OH. Others

such as Penn State and the USDA Food & Industrial Oil Research Unit are con-
ducting research aimed at understanding and improving the performance of these
oils. Lubrizol was one of the early leaders and focused on additive chemistry.
Other major lubricant and additive suppliers have active programs. Valvoline, a
Division of Ashland Chemical, is one of the leaders in this area and has shared
some of the progress and problems in the development of vegetable-based engine
oils (19).
The Agro Management Group developed a canola-based 4-cycle engine oil in
the early 1990s. The oil (AGM 2000) was evaluated in various vehicles by AGM
including tests on ~75 vehicles operated by the U.S. Postal Service in the state of
Michigan. Results of these tests were reported earlier (18). According to the
authors, Rhodes and Johnson, vegetable-based oils performed well in well-man-
aged fleets, resulting in a significant reduction in emissions and improved engine
performance.
RLI collaborated with the Tribology Group, Chemical Engineering Department
of Penn State in the early 1990s to develop vegetable-based engine oils. Various veg-
etable oils were evaluated including genetically modified high-oleic vegetable oils
(2023). An understanding was developed regarding the mechanism of oxidation and
TABLE 3.7
Composition of Soybean Oils
Normal Genetically TMPa

soybean modified Epoxidized (Oleic)
Composition (%) (%) (%) (%)
18:0 15 11 (100) 0
18:1 23 83 0 100
18:2 53 3 0 0
18:3 7 2 0 0
TOTAL-C=C- per 100 molecules 150 95 0 100
aTMP, trimethylolpropane.

the formation of deposits. A high-oleic basestock containing a unique additive pack-

age was tested in several RLI vehicles for several years. Vehicles included a 3.8 L
Oldsmobile engine, a flex-fuel Ford Taurus, a 3500 HP ethanol drag racing funny car
and a three-quarter ton Ford pickup diesel truck. The vehicles accumulated >200,000
miles, and some test results were reported previously (24). This resulted in one of the
first U.S. patented 4-cycle vegetable-based engine oils (25) and subsequently resulted
in several additional biobased lubricant patents by RLI (26,27). Research by RLI has
continued, and currently a fleet of 17 vehicles are being tested. RLI has an excellent
track record with their fluids and is one of the leaders in vegetable oil technology
(www.renewablelube.com).
The Food & Industrial Oil Research Unit, National Center for Agricultural
Research Unit, Agricultural Research Service, USDA in Peoria, IL and Penn State
University have collaborated in studying industrial uses of vegetable oils since the
late 1990s. This research resulted in various products and one patent but more
importantly in an understanding of the chemistry affecting oxidation stability and
low-temperature properties (2832).
Valvoline, a division of Ashland Chemicals, is aggressively pursuing the use
of vegetable oils in engine oils. They are currently testing mid-oleic soybean oil for
use in crank formulations. The project involves full bench test screening of formu-
las containing soybean oil and other basestocks. The formulations contain addi-
tives used in the latest engine oil categories. One of the benefits seen is cost reduc-
tion for new oils that would come from a reduction in the use of expensive Group
III and II+ petroleum basestocks required to meet NOACK volatility requirements.
Cold crank properties, high viscosity index (VI; temperature-viscosity properties),
and friction and wear benefits are drivers in this ongoing study (19).
Summary
Can vegetable oils make good engine oil basestocks? The research conducted to
date indicates that chemically and genetically modified vegetable oils have excel-
lent potential to perform adequately in engine oils. Some technical and logistic
concerns remain regarding the ability to maintain consistent quality oils that would
meet oil property and performance specifications. Limited data exist on the blend-
ing of vegetable oils; to produce adequate volumes, refineries using different
vegetable oils and producing various products will be required. Currently, the pub-
lication, Physical and Chemical Characteristics of Oils, Fats and Waxes (33), lists
350 oils that could be considered for use as engine oil basestocks.
The bottom line is that vegetable oils have shown acceptable property and per-
formance characteristics. However, to make a major penetration of the engine oil
market in the next 10 years as a major competitor for petroleum-based engine oils,
certification must be obtained by passing the current automotive engine perfor-
mance tests. These are very expensive and must be justified by a large market.
Therefore, at the present time, the chicken and egg syndrome persists.

40 J.M. Perez
References
1. Dowsan, D., History of Tribology, Longman Group, Ltd., New York, 1979.
2. United Soybean Board, Soy Products Guide, www.unitedsoybean.org, 2005.
3. Campen, J., USB Overview, Lubricants Technical Advisory Board Presentation,
Chicago, IL, Sept. 22, 2004, www.unitedsoybean.org.
4. Erhan, S.Z., The Use of Vegetable Oils as Lubricants, in Baileys Industrial Oil and Fat
Products, 6th ed., John Wiley & Sons, New York, 2004.
5. Lubricants Industry Sourcebook, LubesnGreases, 20042005.
6. Transportation Energy Book: Edition 21,DOE/ORNL-6966.
7. Energy Information Administration Annual Energy Outlook 2002, DOE/EIA-0383
(2002), December, 2001.
8. ron.buckhalt@nps.ars.usda.gov.
9. McFall, D., Almost 1.5 Billion Gallons, LubesnGreases 10: 6 (November 2004).
10. Boehman, A.L., W.H. Swain, D.E. Weller, and J.M.Perez, Use of Vegetable Oil
Lubricant in a Low Heat Rejection Engine to Reduce Particulate Emissions, SAE
Technical Paper 980887, Detroit, MI (February 1998).
11. Weller, D.E., W.H. Swain, H. Hess, A.L. Boehman, and J.M. Perez, Changes in
Particulate Composition and Morphology When Using Vegetable Oil Lubricant in a
Low Heat Rejection Engine, SAE Technical Paper No. 1999-01-0975.
12. Perez, J.M., and A.L. Boehman, Environmentally Friendly Fuels and Lubricants, in
Biobased Industrial Fluids and Lubricants, edited by S.Z. Erhan and J.M. Perez, Ch. 6,
AOCS Press, Champaign, IL, 2002.
13. SAE Recommended Practice J300, SAE Handbook, Society of Automotive Engineers,
Warrendale, MI.
14. ASTM D4684, Standard Test Method for the Determination of Yield Stress and
Apparent Viscosity in Engine Oils at Low Temperatures (1994), ASTM, West
Conshohocken, PA 19428-2959.
15. ASTM 5481, Standard Test Method for Measuring Apparent Viscosity at High Shear
Rate by Multicell Capillary Viscometer (1994), ASTM, West Conshohocken, PA
19428-2959.
16. ASTM D445, Standard Test Method for Kinematic Viscosity of Transparent and
Opaque Liquidsthe Calculation of Dynamic Viscosity (1988), ASTM, West
Conshohocken, PA 19428-2959.
17. Cheenkachorn, K., A Study of Environmentally Friendly Lubricants for Automotive
Engine Oils, M.S. Thesis, The Pennsylvania State University, May 1999.
18. Rhodes, B.N., and D. Johnson, Vegetable-Based Motor Oils, in Biobased Industrial
Fluids and Lubricants, edited by S.Z. Erhan and J.M. Perez, Ch. 8, AOCS Press,
Champaign, IL, 2002.
19. McCoy, S., Valvoline Engine Oil Development, Proceedings of the 9th United Soybean
Board Lubricants and Fluids Technical Advisory Panel Meeting, Ch. 8, Chicago, IL,
September 22, 2004.
20. Asadauskas, S., J.M. Perez, and J.L. Duda, Suitability of Basestocks for Biodegradable
Lubricants, Petroleum Division Preprints, Vol. 42, No. 1, Feb. 1997, presented at 213th
ACS Meeting, San Francisco, CA, April 15, 1997.
21. Asadauskas, S., J.M. Perez, and J.L. Duda, Oxidative Stability and Antiwear Properties
of High Oleic Vegetable Oils, Lubr. Eng. 52: 877882 (December 1996).

22. Asadauskas, S., J.M. Perez, and J.L. Duda, Lubrication Properties of Castor OilPotential
Basestock for Biodegradable Lubricants, Lubr. Eng. 53: 3540 (December 1997).
23. Perez, J.M., S. Asadauskas, and W.W. Garmier, Vegetable Based Engine Oils, present-
ed at 52nd Annual STLE Meeting, Kansas City, MO, May 29, 1997.
24. Garmier,W.W., Vegetable Oil Stabilization, Proceedings of the 4th United Soybean
Board Lubricants and Fluids Technical Advisory Panel Meeting, Chicago, IL,
September 1999.
25. Garmier,W.W., U.S. Patent No. 5,736,493 (1998).
28. Adhvaryu, A., S.Z. Erhan, and J.M. Perez, Oxidation Kinetic Studies of Unmodified
and Genetically Modified Vegetables Using PDSC and NMR Spectroscopy,
Thermochim. Acta 364: 8797 (2000).
29. Asadauskas, S., and S.Z. Erhan, Depression of Pour Points of Vegetable Oils by
Blending with Diluents Used for Biodegradable Lubriants, J. Am. Oil Chem. Soc. 76:
313316.
30. Weller, D.E., Jr., and J.M. Perez, The Effect of Chemical Structure on Friction and
Wear, Lubr. Eng. 56: 3944 (November 2000).(AQ3)
31. Weller, D.E., Jr., and J.M. Perez, A Study of the Effect of Chemical Structure on
Friction and Wear: Part 2 Vegetable Oils and Esters, Lubr. Eng. 57: 2026 (May 2001).
32. Cheenkachorn, K., Ph.D. Thesis, The Pennsylvania State University, May 2003
33. Firestone, D., ed., Physical and Chemical Characteristics of Oils, Fats and Waxes,
AOCS Press, Champaign, IL (1999).

Chapter 4
Biodiesel: An Alternative Diesel Fuel from Vegetable

Oils or Animal Fats
Gerhard Knothe and Robert O. Dunn
USDA, Agricultural Research Service, 1815 N. University Street, Peoria, IL 61604, USA
Introduction
Biodiesel is defined as a fuel comprised of the mono-alkyl ester of long chain
fatty acids derived from vegetable oils or animal fats (1). Accordingly, biodiesel
is derived from vegetable oils or animal fats by a transesterification reaction
(Scheme 4.1), in which the oil or fat is reacted with a monohydric alcohol in the
presence of a catalyst. Methanol is the alcohol used most commonly to produce
biodiesel as it is the least expensive alcohol in many countries.
Besides transesterification to alkyl esters, three other approachesdilution
with conventional, petroleum-based diesel fuel (DF), microemulsions (co-solvent
blending), and pyrolysishave been explored for utilizing vegetable oils as fuel
(2). However, as the mono-alkyl esters of vegetable oils and animal fats
biodieselare the only approach that has found widespread use (and, accordingly,
the vast majority of research papers deal with this approach), this article will focus
on such mono-alkyl esters.
History and Overview

The use of vegetable oils as a DF is a concept nearly as old as the diesel engine
itself. At the Paris World Exhibition in 1900, at the request of the French govern-
ment, a diesel engine was demonstrated using a vegetable oil (peanut oil) as fuel
Scheme 4.1. The transesterification reaction.
42

Biodiesel as an Alternative Diesel Fuel 43
(3) and was described in reports by Rudolf Diesel (4,5), the inventor of the engine
that bears his name. Numerous papers were published until the late 1940s regarding
the use of vegetable oils as fuel (3). The background in most cases was a rather mod-
ern onenamely, to provide an alternative source of energy. This was the case also
in European countries with African colonies. Among those numerous reports are sev-
eral articles (68) from Belgium and its former colony, the Belgian Congo, which are
presumably the first to describe the use of what is today termed biodiesel as fuel (3).
In that work, ethyl esters of palm oil were utilized, however, other oils and esters
were described as suitable. During the age of inexpensive and easily accessible petro-
leum from approximately 1950 until the 1970s, hardly any reports on vegetable oil-
based fuels were published. As a result of the energy crises of 1973 and later years,
the interest in alternative fuels, among them vegetable oils was renewed. In 1980, the
use of esters of sunflower oil as DF was reported (9). These authors explicitly pointed
out that viscosity of the esters is significantly decreased compared to the parent veg-
etable oil, now being close to that of conventional DF. The lower viscosity nearly
eliminated engine problems such as injector coking and deposits which are a problem
with neat vegetable oils. Besides the energy security aspect, environmental concerns
(with regulations and legislation arising therefrom) as well as utilization of excess
agricultural commodities have become significant driving forces for the use of alter-
native fuels such as those derived from vegetable oils. Commercialization has
occurred in numerous countries around the world with varying economic and legisla-
tive conditions. Standards have been or are being developed in Europe, the U.S. and
elsewhere. Countless research papers on biodiesel as well as numerous reviews, book
chapters, and general interest articles have been published.
Sources of Fuels
Biodiesel is obtained from various sources depending largely on the country and its
climate. Accordingly, soybean oil is the vegetable oil most commonly used for
biodiesel production in the U.S. Rapeseed oil (in low-erucic form canola oil) is the
major feedstock in Europe, although it is also used in the Pacific Northwest of the
U.S. Countries with tropical climate utilize tropical oils such as coconut and palm
oil. Other common oils such as cottonseed, peanut (groundnut) and sunflower oils
have been studied. Potential sources of biodiesel with some emphasis on develop-
ing countries were discussed in more detail (10). Less common or less studied veg-
etable oils that have been investigated as sources of biodiesel include Cynara car-
dunculus (Castillian thistle) (11), rubber seed oil (12), karanja (Pongamia glabra)
and nahor (Mesua ferrea L.) oils (13), Cuphea viscosissima (14), and Jatropha
curcas L. (15), tobacco seed oil (16) as well as other non-conventional oils (17).
Various feedstocks for biodiesel were also explored in earlier times (3). Animal
fats such as tallow have also been investigated. More recently, increasing emphasis
has been placed on low-cost feedstocks such as used frying oils and soapstock.
Microalgae were also suggested as a source of biodiesel (18).

44 G. Knothe and R.O. Dunn
Economics, Regulatory Issues, and Utilization
A major obstacle facing biodiesel commercialization is economics. The higher

price of the feedstock compared to petroleum translates into a higher price for the
resulting fuel. In the U.S. the price of a gallon (about 3.8 liters) of soybean oil is
approximately $1.40$1.50. Other feedstocks are even more expensive. After com-
pletion of fuel production, the price of a gallon of methyl soyate is even higher,
approximately three to four times that of conventional DF. On the other hand,
glycerol, which has numerous uses as a by-product of the transesterification
process, may help offset some of the costs. Biodiesel with accompanying glycerol
production has had a significant influence on glycerol prices in recent years (19).
Incentive-providing legislation and regulations regarding taxes, the environ-
ment and energy security offset the inherent economic disadvantage of biodiesel
toward conventional DF. In some European countries such as Germany, biodiesel
is not subject to the excise tax levied on petroleum-derived fuels. Since the total
taxes on conventional fuels are so high, biodiesel becomes economically competi-
tive with conventional DF if it is not subject to these taxes, causing biodiesel to be
fairly widely available at filling stations for general use. However, beginning in
2003, tax incentives proportional to the level of biodiesel were applied in Germany
to blends of biodiesel with conventional DF. In France, biodiesel is being promot-
ed by approval of a 5% blend of biodiesel in conventional DF available at the
pump and as 30% blend available to fleets of urban vehicles. In the U.S., envi-
ronment and energy security-related issues have been the major driving forces
apply, expressed in the Clean Air Act Amendments of 1990 and the Energy Policy
Act (EPAct) of 1992 as well as the Energy Conservation Reauthorization Act of
1998. Both neat biodiesel and B20 (a blend of 80 vol% conventional DF with 20
vol% biodiesel) are recognized as alternative fuels in the U.S. under EPAct crite-
ria. Regulated fleets (government and other public fleets) can earn credits for using
a certain amount of both neat biodiesel and B20. Therefore, in the U.S. biodiesel
has been mainly promoted for use in regulations-affected and niche markets (regu-
lated fleets, urban bus fleets, marine and mining markets). In developing countries,
especially those that produce significant amounts of tropical oils, the main incen-
tive for using biodiesel is to become independent of petroleum imports.
A major development which will likely serve to additionally promote the use of
biodiesel is upcoming mandates prescribing the use of low-sulfur conventional DF.
Removal of the sulfur-containing components from conventional DF causes the
lubricity of the conventional DF to be significantly reduced or even eliminated.
Inherent lubricity of the fuel is important for the functioning of engine components
such as fuel pumps and injectors. Adding biodiesel in low amounts (12%) to low-
sulfur conventional DF restores the lubricity. An advantage of biodiesel in that case is
its inherent fuel value, which is not necessarily the case with lubricity additives.
Agricultural policies play a role in the production of biodiesel. In the U.S., the
goal is to find a significant use of excess soybean oil and provide price support for

that commodity. Increased demand for soybean oil as a result of biodiesel produc-
tion could increase soybean oil prices by up to 14% (20). The 2002 Farm Bill con-
tains an energy title which provides for payments to biofuels producers who pur-
chase agricultural commodities for that purpose. In countries of the European
Community, set-aside land taken out of crop production for food use may be used
for growing crops for nonfood uses. Affected farmers would still receive the gener-
al set-aside premium, providing an additional incentive to grow crops for nonfood
uses.
Biodiesel production has increased significantly over the past few years and is
likely to increase further (21, 22). According to some estimates, the capacity for
biodiesel production in Europe in 2003 was approximately as high as 2.5 to 2.7
million metric tons (22). More than 90% of this capacity is in Europe with the U.S.
accounting for the rest. Numerous biodiesel plants are under construction or in
planning stages with accompanying significant increases in production.
According to a life-cycle analysis of biodiesel (23) in the U.S., biodiesel is
competitive with other alternative fuels such as compressed natural gas (CNG) and
methanol in the urban transit bus market. An advantage of biodiesel is its near full
compatibility with existing fuel distribution and use infrastructure. No engine mod-
ifications (with the exception of some seals and gaskets) are required to commer-
cial diesel engines and storage is similar to conventional DF. This advantage can
offset the higher price of the biodiesel fuel in comparison to other alternative fuels
which may require significant and expensive infrastructure changes. On the other
hand, life-cycle assessments should be carried out individually for each source as
the results can vary significantly and the methods used also have great influence
(24).
With the exception of nitrogen oxides (NOx), the use of biodiesel reduces
exhaust emissions compared to conventional petroleum-based DF. Due to its lack
of sulfur, biodiesel does not cause SO2 emissions. The lower emissions make
biodiesel attractive for use in urban bus fleets and other niche markets such as min-
ing and marine engines. Besides environmental and health reasons with accompa-
nying regulations, focusing on the use of biodiesel in niche markets is additionally
attractive because not enough feedstocks are available to supply the whole diesel
market with biodiesel.
Cetane Numbers and the Suitability of Fatty Compounds

as Diesel Fuel
A scale conceptually similar to the familiar octane scale used for gasoline (petrol),
the cetane number (CN), exists for describing the ignition quality of conventional
DF or its components. The CN is determined by standards such as ASTM D613.
The CN of a DF is determined by the ignition delay time, that is, the time that
passes between injection of the fuel into the cylinder and onset of ignition. The
shorter the ignition delay time, the higher the CN and vice versa. Generally, a com-

pound that has a high octane number tends to have a low CN and vice versa. Thus,
2,2,4-trimethylpentane (iso-octane), a short, branched alkane, is the high-quality
standard (a primary reference fuel; PRF) for the octane scale (and also gives it its
name) of gasoline with an octane number of 100 while n-heptane is the low-quality
PRF with an octane number of 0 (25). For the cetane scale, a long straight-chain
hydrocarbon, hexadecane (C16H34; trivial name cetane, giving the cetane scale its
name) is the high-quality standard and has been assigned a CN of 100. At the other
end of the scale, a highly branched compound, 2,2,4,4,6,8,8,-heptamethylnonane
(HMN, also C16H34), a compound with poor ignition quality in a diesel engine, has
been assigned a CN of 15. Thus branching and chain length influence CN with CN
decreasing with decreasing chain length and increasing branching. Aromatic com-
pounds occur in significant amounts in conventional DF and have low CN but their
CN increase with increasing size of n-alkyl side chains (26,27). The cetane scale is
arbitrary and compounds with CN >100 (although the cetane scale does not pro-
vide for compounds with CN >100) or CN <15 have been identified.
The cetane scale demonstrates the suitability fatty compounds as alternative
DF. The structure of the long, unbranched chains of fatty acids (FA) is similar to
those of n-alkanes which yield good conventional DF. CN of fatty compounds and
alkyl esters of vegetable oils and animal fats are presented in Tables 4.1 and 4.2.
However, besides ignition quality as expressed by the cetane scale, several
other properties determine the overall quality of any DF. Especially heat of com-
bustion, pour point (PP), cloud point (CP), viscosity, oxidative stability and lubric-
ity are of importance.
General Comparison of Fuels from Vegetable Oils and

Animal Fats
Some relevant properties of the most common FA occurring in vegetable oils and ani-
mal fats as well as some of their esters are listed in Table 4.1. Besides these FA,
numerous other FA occur in vegetable oils and animal fats, but their amounts usually
are considerably lower. Properties of esters of oils and fats are given in Table 4.2.
The most common derivatives of TG (or FA) for fuels are methyl esters. These
are formed by transesterification of the TG with methanol in the presence of usual-
ly a basic catalyst to give the methyl ester and glycerol (see Scheme 4.1). Other
alcohols have been used to generate esters such as the ethyl, propyl, and butyl
esters. As discussed above, the suitability of fats and oils as DF results from their
molecular structure and high energy content. Long, saturated, unbranched hydro-
carbon chains as they are found in fatty compounds are especially suitable for con-
ventional DF as shown by the CN scale. CN generally increase with increasing
chain length (28). Other observations (29) are (i) that double bonds decrease CN
(therefore, the number of double bonds should be small rather than large), (ii) that
a double bond, if present, should be positioned near either end of the molecule, and
(iii) no aromatic compounds should be present. However, branching in the ester

moiety (iso-propyl esters, etc.) does not negatively influence CN of fatty com-
pounds (30). The combustion of the glyceryl moiety of triacylglycerols could lead
to the formation of acrolein and this in turn to the formation of aromatics (29),
although no acrolein was found in precombustion of triacylglycerols (31). This
may be one reason why fatty esters of vegetable oils perform better in a diesel
engine than oils containing the TG (29).
The above statements on CN correlate with the values given in Tables 4.1 and
4.2. The CN of mixtures are influenced by the nature of their components. Fuel
components with higher CN impart these higher CN to the biodiesel fuel.
It is occasionally emphasized that biodiesel is an oxygenated fuel, implying
its oxygen content plays a role in making fatty compounds suitable as DF by
cleaner burning. The responsibility for this suitability rests, however, mainly
with the hydrocarbon portion which is similar to conventional DF. Furthermore,
the oxygen in fatty compounds may be removed from the combustion process by
decarboxylation, which yields incombustible carbon dioxide (CO2), as precom-
bustion (31), pyrolysis and thermal decomposition studies discussed below imply.
Also, pure unoxygenated hydrocarbons, like cetane, have CN higher than
biodiesel.
The CN of esters correlate well with boiling points (28). Quantitative correla-
tions and comparisons to numerous other physical properties of fatty esters con-
firmed that the boiling point gives the best approximation of CN (32).
ASTM D613 is used in determining CN. For vegetable oil-derived materials,
an alternative scale utilized a constant-volume combustion apparatus (CVCA) (33).
The amount of material needed for CN determination was reduced significantly
with this bomb and it also allows studying materials with high melting points (mp)
that cannot be measured by ASTM D613. Estimated cetane numbers (ECN) were
determined on a revised scale permitting values greater than 100. In this case, the
ECN of methyl stearate is 159 and that of methyl arachidate (20:0) is 196 (33). The
ECN of other esters were methyl laurate 54, methyl myristate 72, methyl palmitate
91, and methyl oleate 80. The ECN of the TG trilaurin and trimyristin exceeded
100, while in another series of experiments the ECN of tripalmitin was 89, tris-
tearin 95, triolein 45, trilinolein 32, and trilinolenin 23. The term Lipid Combus-
tion Quality Number with an accompanying scale was suggested instead of CN to
provide for values in excess of CN 100 (33).
Often the cetane index of a fuel is published and should not be confused
with CN. This is an ASTM-approved alternative method for a non-engine pre-
dictive equation of CN for petroleum distillates (34). Equations for predicting CN
are usually not applicable to nonconventional DF such as biodiesel or other lipid
materials (35). Cetane indices are not given here. Methods for estimating the
cetane indices of esters of FA and vegetable oils were presented (36,37).
Besides CN, gross heat of combustion (HG) is another property of fatty com-
pounds that is essential in proving the suitability of these materials as DF as the
heat content of vegetable oils is nearly 90% that of DF2 (3841). The heats of

Ch4(IndOils)(42-89)Final
48
TABLE 4.1
Properties of Fatty Acids and Esters of Relevance to Biodiesela
3/23/05
m.p. b.p. Kinematic viscosity HG
Trivial (Systematic) name; Acronymb (C) (C) Cetane no. (40C; mm2/s = cSt) (kg-cal/mole)
Lauric (Dodecanoic); 12:0 44 1311
G. Knothe and R.O. Dunn
6:20 PM
Methyl ester 5 266766 61.4 (99.1) 1.95c; 2.38 1940
Ethyl ester 1.8fr 16325 2.88c 2098
Myristic (Tetradecanoic); 14:0 58 250.5100
Page 48
Methyl ester 18.5 295751 66.2 (96.5) 2.69c, 3.23 2254
Ethyl ester 12.3 295 66.9 (99.3) 2406
Palmitic (Hexadecanoic); 16:0 63 350

Methyl ester 30.5 4154418747 74.5 (93.6) 3.60c; 4.32 2550
Ethyl ester 19.3/24 19110 85.9 2717
Propyl ester 20.4 19012 93.1
Iso-propyl ester 1314 1602 85.0
82.6
Stearic (Octadecanoic); 18:0 71 360d 61.7

Methyl ester 39 4423747 86.9 (92.1) 4.74c, 5.61 2859
Ethyl ester 3133.4 19910 101 3012
Propyl ester 76.8; 97.7
Iso-propyl ester 69.9; 90.9
96.5

Palmitoleic (9(Z)-Hexadecenoic); 16:1
Methyl ester 51.0 2521
Oleic (9(Z)-Octadecenoic); 18:1 16 286100 46.1

Methyl ester 20 218.520 55; 59.3 3.73i; 4.45
Ethyl ester 2162217151 53.9; 67.8 5.50 (25)c
Iso-propyl ester 86.6
3/23/05
Linoleic (9Z,12Z-Octadecadienoic); 18:2 5 22923016 31.4
21520 3.05c; 3.654
Biodiesel as an Alternative Diesel Fuel

Methyl ester 35 42.2; 38.2 2794
Ethyl ester 270275180 37.1; 39.6
6:20 PM
Linolenic (9Z,12Z,15Z-Octadecatrienoic); 18:3 11 23023217 20.4

Methyl ester 57/52 1090.018 20.6; 22.7 2.65c; 3.27 2750
Ethyl ester 1742.5 26.7
Page 49
Propyl ester 26.8
Erucic (13Z-Docosenoic); 22:1 3334 26515

Methyl ester 222225 5.91c; 7.21i 3454
Ethyl ester 2292305
aMelting points (m.p.) and boiling points (b.p.) obtained from References 42 and 309. Superscripts denote pressure (mm HG) at which the boiling point was determined.
Heats of combustion obtained from References 40 and 42. Cetane numbers obtained from References 28, 30, and 180. Number in parentheses indicates purity (%) of the
material used in CN determinations in Reference 28. Kinematic viscosity values from Reference 310. Dynamic viscosity values from Reference 313.
bThe numbers denote the number of carbons and double bonds. For example, in oleic acid, 18:1 stands for eighteen carbons and one double bond.
cDynamic viscosity values, see footnote a.
49
50
3/23/05
TABLE 4.2
Fuel-Related Physical Properties of Esters of Oils and Fats
Cetane HG high/low Kinematic viscosity Cloud point Pour point Flash pointa
G. Knothe and R.O. Dunn
6:20 PM
Oil or fat; ester number (kJ/kg) (mm2/s) (C) (C) (C) Reference
Coconut
Ethyl 67.4 38158 3.08 5 3 190 223
Page 50
Corn
Methyl 65 38480 (lower) 4.52 3.4 3 111 312
Cottonseed
Methyl 51.2 6.8 (21) 4 110 313
Palm
Ethyl 56.2 39070 (h) 4.50 (37.8C) 8 6 314
Rapeseed (low-erucic; canola)

Methyl 53.7 38850 (h/l) 4.96 CFPP: 6 315
Methyl 47.9 39870 (h) 4.76 3 9 166 314
Ethyl 67.4 40663 6.02 1 12 170 223
Safflower
Methyl 49.8 40060 6 180/149 316

Soybean
Methyl 49.6 39823/37372 4.18 (40C) 1.1 3.9 190.6 317
Methyl 55.9 39753 4.27 1 0 185 223
iso-Propyl 9 12 218
Sunflower
3/23/05
Methyl 58 38472 4.39 1.5 3 110 312
Biodiesel as an Alternative Diesel Fuel

Tallow
Methyl 61.8 39961/37531 4.99 (40C) 15.6 12.8 187.8 317
6:20 PM
iso-Propyl 7.10 8 0 220
Hydrogenated soybean
Ethyl 65.1 40093 5.54 7 6 174 223
Page 51
Yellow grease
Methyl 62.6 39817/37144 5.16 318
aSomeflash points are very low. These may be typographical errors in the references or the materials may have contained residual alcohols.
bDynamic viscosity.
51
combustion of fatty esters and triacylglycerols (40) as well as fatty alcohols (41)
were determined and shown to be within the same range. Heats of combustion
range from about 1,700 kg-cal/mole to about 3,500 kg-cal/mole for C12C22 FA
and esters, increasing with chain length (40,42). For purposes of comparison, the
literature value (42) for the heat of combustion of hexadecane (cetane), the high
CN standard for conventional DF, is 2559.1 kg-cal/mole (at 20C), which is in the
same range.
Other important fuel properties are viscosity and those related to low tempera-
tures. This is shown by the data in Tables 4.1 and 4.2, which list the mp (and boil-
ing points) of neat fatty compounds as well as the viscosities of neat fatty com-
pounds and methyl esters of some oils and fats. The viscosity of vegetable oils is
approximately one order of magnitude greater than that of conventional DF. The
high viscosity with resulting poor atomization in the combustion chamber was
identified early as a major cause of engine problems such as nozzle coking,
deposits, etc. (9,40,4346). Therefore, neat vegetable oils have been largely aban-
doned as alternative DF. However, as the data show, the viscosity of the alkyl
esters is close to that of conventional DF. Accordingly, the ranges for kinematic
viscosity in biodiesel standards are 1.96.0 mm2/s (ASTM D6751) and 3.55.0
mm2/s (EN 14214).
FA methyl esters have higher CP and PP than their parent oils and fats and
conventional DF. This is important for engine operation in cooler environments.
The CP is defined as the temperature at which the fuel becomes cloudy due to for-
mation of crystals which can clog fuel filters and supply lines. The PP is the lowest
temperature at which the fuel will flow. It is recommended by engine manufactur-
ers that the CP be below the temperature of use and not more than 6C above the
PP. A more detailed discussion of low temperature of esters from vegetable oils
and animal fats can be found below.
Numerous reports exist showing that fuel economies of certain biodiesel
blends and conventional DF are virtually identical. In numerous on-the-road tests,
primarily with urban bus fleets, vehicles running on blends of biodiesel with con-
ventional DF (usually 80 vol% conventional DF and 20% biodiesel) required only
about 25% more of the blended fuel than of the conventional fuel. No significant
engine problems were reported.
The methyl and ethyl esters of soybean oil generally compared well with DF2
with the exception of gum formation which leads to problems with fuel filter plug-
ging (45). Another study reports that methyl esters of rapeseed and high-linoleic
safflower oils formed equal and lesser amounts of deposits than a DF standard
while the methyl ester of high-oleic safflower oil formed more deposits (47).
Soybean methyl and ethyl esters were evaluated by 200-h EMA (Engine
Manufacturers Association) engine tests and compared to DF2. Engine perfor-
mance with soybean esters differed little from that with DF. In that work, also a
slight power loss was observed, together with an increase in fuel consumption due
to the lower heating values of the esters. The emissions for the two fuels were sim-

ilar, with the exception of NOx which are higher for the esters as discussed above.
Engine wear and fuel-injection system tests showed no abnormal characteristics for
any of the fuels. Although deposit amounts in the engine were comparable, the
methyl ester showed greater varnish and carbon deposits on the pistons. Operating
DI engines with neat soybean oil esters under certain conditions produced lubricat-
ing oil dilution which was not observed with an IDI engine (50).
Vegetable oil-based fuels possess inherent lubricity. This is significant because
environmental concerns and resulting future regulations dictate the use of conven-
tional DF with low sulfur levels. Conventional DF serves as its own lubricant with-
in the fuel system. At low sulfur levels, that ability is lost. Even at low blend levels
(additive levels, approximately 2 wt%), biodiesel could serve not only as a fuel
component but as a lubricity-improving additive. Methyl soyate was a more effec-
tive lubricant than soybean oil at equal treatment rates but a soybean oil-based
additive was even more effective (49). For the conventional DF with poorest inher-
ent lubricity, 1% or slightly higher treatments rates with soybean oil were neces-
sary to meet specifications.
Biodiesel is readily biodegradable, which contrasts with conventional DF.
This was shown by the CO 2 evolution method in an aquatic system (50).
Conventional DF degraded faster in the presence of biodiesel. Another advantage
of esters from vegetable oils and animal fats as fuels is their higher flashpoint
which makes them safer to handle and store than conventional DF.
Due to its solvent properties (see above), ester fuels are not compatible with
some polymers used in fuel system components such as seals and gaskets of con-
ventional DF. Accordingly, it has been reported that Teflon and other fluoroelas-
tomers are least affected by biodiesel and its blends with conventional DF while
nitrile rubber, nylon 6/6 and high-density polypropylene showed less resistance
(51). It was reported in the same study that copper-containing metals are severely
corroded by biodiesel and its blends and also showed gum formation. Steel and
aluminum did not show gum formation but caused high acid numbers which could
cause corrosion. Storage stability is discussed below.
Biodiesel Standards
As mentioned above, some biodiesel standards have been established, including in
the U.S. and Europe. While similar in many aspects, they also contain some
notable differences as briefly discussed here and elsewhere in this chapter.
The iodine value (IV) has been included in the European standard and is based
on rapeseed oil as biodiesel feedstock. The maximum IV in EN 14214 is 120,
which would largely exclude soybean oil and some other common vegetable oils
(neat vegetable oils and their methyl esters have nearly identical IV) as biodiesel
feedstock. However, the use of the IV is not without problems (52), including the
fact that it does not adequately reflect that a specific IV can arise from a nearly
infinite number of FA profiles. Biodiesel from vegetable oils with high amounts of

saturates (low IV) will have a higher CN while the low-temperature properties are
poor. Biodiesel from vegetable oils with high amounts of unsaturates (high IV)
will have low CN while the low-temperature properties are better. Thus, CN and
low-temperature properties run counter to each other and this must affect IV for
biodiesel standards. The IV also does not take into consideration structural factors
of fatty compounds as discussed above where the CN depend on double bond posi-
tion, etc. It was suggested that it appears better to limit the amount of higher unsat-
urated FA (e.g., linolenic acid) than to limit the degree of unsaturation by means of
the IV (53). In the standard EN 14214, the amount of linolenic acid is now limited
to 12%, which may be difficult to reconcile with an IV limit of 120. Soybean oil,
rapeseed oil, and canola oil (low-erucic rapeseed oil) have very similar 18:3 FA
content, which is the most problematic in the formation of engine deposits through
polymerization. However, linseed oil methyl ester (high 18:3 content and IV) satis-
factorily completed 1000 h of testing in a DI engine while neat linseed oil caused
the engine to fail (54). In a study on prepared ester fuels of medium to high iodine
values, no significant differences in engine performance and deposits were
observed and no limit for the IV could be given (55). EN 14214 calls for a maxi-
mum of 12% C18:3 in biodiesel, which would permit soybean oil as feedstock. A
major difference therefore affecting feedstocks and their IV is the C18:2 content.
Additionally, EN 14214 limits the amount of FA with 4 double bonds to 1%,
which would mainly appear to affect biodiesel from animal sources (fish oils).
Since most esters have higher CN than neat vegetable oils and conventional
DF, the esters could accommodate higher CN than the minimum of 40 given in the
ASTM standard for conventional DF. For example, the lowest reported CN for
methyl soyate is 46.2. The minimum CN in the European standard is higher.
The European biodiesel standard EN 14214 includes the cold-filter plugging
point (CFPP) that pertains to the low-temperature flow properties of biodiesel. This
low-temperature property test is used in Europe, South America, and the Pacific
rim. Each European country can determine the limit for CFPP individually depend-
ing on the time of year. In North America, a more stringent test, the Low-
Temperature Flow Test (LTFT), is used and specified by ASTM D4539. Although
the LTFT is more useful in evaluating low-temperature flow properties, ASTM
D6751 requires only specification of CP for certification without a limit being
given in the standard due to varying climate conditions in the U.S.
Combustion and Emissions

Conventional DF and vegetable oil-derived fuels generate similar types of compounds
in exhaust emissions. This is another indication of the suitability of fatty compounds
as DF because there presumably exist similarities in their combustion behavior.
Emissions from any engine are the result of the preceding combustion within
in the engine. The combustion process, in relation to the properties of the fuel, and
its (in)completeness are responsible for any problems associated with the use of

any fuel, such as formation of deposits. Ideally, the products of complete combus-
tion of hydrocarbons are CO2 and water. Combustion in a diesel engine occurs
mainly through a diffusion flame and thus is incomplete (56). This causes the for-
mation of partially oxidized materials such as carbon monoxide (CO), other oxy-
genated species (aldehydes, etc.), and hydrocarbons.
In the case of biodiesel, liberation of CO2 (decarboxylation), as discussed
above, can occur besides combustion formation of CO2 from the hydrocarbon por-
tions of biodiesel. The formation of incombustible CO2 shows that oxygenated
compounds as combustion enhancers need to be chosen judiciously since the com-
bustion-enhancing properties depend on the nature of the oxygen (bonding, etc.) in
these compounds. Therefore, the higher oxygen content of biodiesel does not nec-
essarily imply improved combustion compared to conventional DF as oxygen may
be removed from the combustion process by decarboxylation. CO2, however, may
contribute to combustion in other ways.
Exhaust emissions observed in the combustion of conventional DF and
biodiesel are smoke, which is a mixture of fuel and lubricating oil particles in
unburned, partially burned or cracked states (57), particulates [particulate matter
(PM)], polyaromatic hydrocarbons (PAH), hydrocarbons, CO, and oxides of nitro-
gen (NOx, also referred to as nitrous oxides, or nitrogen oxides). Sulfur-containing
emissions are not formed from neat biodiesel due to its lack of sulfur. Rapeseed
contains low amounts of sulfur but in variations such as canola, erucic acid and
sulfur content are further reduced (58). The rapeseed oil mentioned in European
publications on alternative fuels usually refers to canola-type oil.
The composition of particulate matter has been studied for conventional DF.
Particulates are soot that has collected high molecular weight hydrocarbons (and
sulfates in the case of conventional DF) (57,59). Thus, particulates from conven-
tional DF have a high carbon to hydrogen ratio. Soot particles consist of spherules
(somewhat spherical species) arranged in irregular clusters or chains (57). The size
of particulates is of concern because smaller species (diameters less than 10 m)
can be inhaled deeply into the lungs. Therefore, the size distribution of particulate
matter may be of greater significance than its mass.
PAH are compounds composed of fused aromatic rings that may carry alkyl
substituents such as a methyl group. They are of concern because many of them
are known carcinogens.
Hydrocarbons represent a broad category of compounds including hydrocar-
bons and oxygenated species such as aldehydes, ketones, ethers, etc. Although
some of these emissions such as aldehydes are unregulated (not limited by legisla-
tion), many of these species such as formaldehyde are ozone precursors.
As precursors of ozone, which in turn is a major component of urban smog,
NOx exhaust emissions are of particular concern. Accordingly, both NOx exhaust
emissions and ozone in ambient air are subject to environmental regulations. NOx
species arise by the reaction of nitrogen and oxygen from air at an early stage in
the combustion process (56,60). NOx emissions are difficult to control because

such techniques may increase other emissions or fuel consumption. Soot can be
reduced by higher injection pressures and higher air swirl levels but this enhanced
combustion increases NOx (59). The trade-off between particulates and NOx as a
result of changes in engine design or operational parameters is a general problem
(59).
Neat vegetable oils give satisfactory engine performance and power output,
often equal to or even slightly better than conventional DF. However, vegetable
oils cause engine problems. This was recognized in the early stages of renewed
interest in vegetable oil-based alternative DF. Studies on sunflower oil as fuel
noted coking of injector nozzles, sticking piston rings, crankcase oil dilution, lubri-
cating oil contamination, and other problems (9,44). These problems were con-
firmed and studied by other authors (6168). A test for external detection of coking
tendencies of vegetable oils was reported (69). The causes of these problems were
attributed to the polymerization of TG via their double bonds which leads to for-
mation of engine deposits as well as low volatility and high viscosity with resulting
poor atomization patterns. For blends of vegetable oils and conventional DF, it was
postulated that carbon buildup was a result of a polymerization growth process on
preferred metallic surfaces (70). The engine problems have caused neat vegetable
oils to be largely abandoned as alternative DF and have led to the research on the
aforementioned four solutions (2).
The Transesterification Process

Several reviews on transesterification are available (7174). The most commonly
prepared esters are methyl esters, which is largely a result of methanol being the
least expensive alcohol.
Alkali catalysis (sodium or potassium hydroxide or alkoxides) is a much more
rapid process than acid catalysis in the transesterification reaction (7577). For the
transesterification to give maximum yield, the alcohol should be free of moisture
and the free FA content of the vegetable should be less than 0.5% (76). At 32C,
transesterification was 99% complete in 4 h when using an alkaline catalyst
(NaOH or NaOMe). At 60C and an alcohol:oil molar ratio of at least 6:1 and with
fully refined oils, the reaction was complete in 1 h to give methyl, ethyl, or butyl
esters. The reaction parameters investigated were molar ratio of alcohol to veg-
etable oil, type of catalyst (alkaline vs. acidic), temperature, reaction time, degree
of refinement of the vegetable oil, and effect of the presence of moisture and free
FA. Although the crude oils could be transesterified, ester yields were reduced
because of gums and extraneous material present in the crude oils.
Another paper reports on the use of both NaOH and KOH in the transesterifi-
cation of rapeseed oil (78). Recent work on producing biodiesel from waste frying
oils employed KOH. With the reaction conducted at ambient pressure and tempera-
ture, conversion rates of 80 to 90% were achieved within 5 min, even when stoi-
chiometric amounts of methanol were employed (79). In two steps, the ester yields

are 99%. It was concluded that even a free FA content of up to 3% in the feedstock
did not affect the process negatively and phosphatides up to 300 ppm phosphorus
were acceptable. The product met the quality requirements for Austrian and
European biodiesel without further treatment. In a study similar to previous work
on the transesterification of soybean oil (7576), it was concluded that KOH is
preferable to NaOH in the transesterification of safflower oil of Turkish origin
(80). The optimal conditions were given as 1 wt% KOH at 691C with a 7:1 alco-
hol:vegetable oil molar ratio to give 97.7% methyl ester yield in 18 min.
Transesterification is a reversible reaction. The transesterification of soybean
oil with methanol or 1-butanol was reported to proceed with pseudo-first-order or
second-order kinetics, depending on the molar ratio of alcohol to soybean oil (30:1
pseudo-first order, 6:1 second order; NaOBu catalyst) while the reverse reaction
was second order (81). The methanolysis of sunflower oil at a molar ratio of
methanol:sunflower oil = 3:1 was reported to begin with second-order kinetics but
then the rate decreased to formation of glycerol (82). The originally reported kinet-
ics (81) were reinvestigated (8285) and differences were found. A shunt reaction
originally proposed (81) as part of the forward reaction was shown to be unlikely,
that second-order kinetics are not followed and that miscibility phenomena play a
significant role (8285). The addition of co-solvents such as tetrahydrofuran (THF)
or methyl tert-butyl ether (MTBE) to the methanolysis reaction was reported to
accelerate the methanolysis of vegetable oils as a result of solubilizing methanol in
the oil and to a rate comparable to that of the faster butanolysis (83,85). Other pos-
sibilities for accelerating the transesterification appear to be microwave (86) and
ultrasonic (87) irradiation. Factorial experiment design and surface response
methodology have been applied to different production systems (88). A continuous
pilot plant-scale process for producing methyl esters with conversion rates greater
than 98% was reported (84) as well as a discontinuous two-stage process with a
total methanol:acyl ratio of 4:3 (89). The kinetics of noncatalyzed alcoholysis of
soybean oil were also investigated (90).
The transesterification of beef tallow was studied with regard to effects of
mixing (91), catalyst, free FA and water as well as solubilities of different alcohols
in the fat (92). Water had the greatest undesirable effect (93).
With increasing emphasis on utilizing low-cost sources of biodiesel, the ques-
tion of the quality of these sources is of utmost importance. The low-cost sources
such as restaurant greases and soapstock are of lower quality than refined veg-
etable oils. A major problem associated with them is the high content of free FA,
which, as indicated above, the feedstock should contain a minimum of. Thus the
processing of high-free FA feedstocks requires some changes to the overall pro-
duction process. A two-step alkali-catalyzed transesterification was reported for
high-free FA feedstocks (94). Pretreatment of the free FA by acid-catalyzed esteri-
fication prior to converting the triacylglycerols by alkali-catalyzed transesterifica-
tion is an effective method for producing biodiesel from high-free FA feedstocks
(95). A pilot plant based on this process was described (96). For the production of

biodiesel from soapstock, all ester bonds were hydrolyzed by alkali catalysis and
the resulting FA sodium salts converted to methyl esters by acid catalysis (97).
This procedure was also taken to the small pilot scale (98). Relatedly, acid oil was
converted to biodiesel (99). More aspects are given below.
Other Transesterification Processes

Besides the methods discussed here, other catalysts have been applied in transes-
terification reactions (100). Some recently studied variations of the above methods
as applied to biodiesel preparation are briefly discussed here.
Enzymatic transesterification methods are receiving attention for producing
esters suitable as biodiesel. Advantages of enzymatic reactions can be specificity,
mild reaction conditions, reduced product isolation problems and reduced waste
(101), although they are more expensive. Lipases from Pseudomonas fluorescens
as well as two immobilized enzymes from Mucor miehei and a Candida sp. with
petroleum ether as solvent yielded methyl and ethyl esters of sunflower oil (102).
The lipase from Mucor miehei was most efficient in yielding esters of primary
alcohols while the lipase from Candida antarctica was most efficient for yielding
branched esters from secondary alcohols (103). Some other reports on enzymatic
production of esters mainly for fuel purposes include ethanolysis of sunflower oil
with a solvent-free, immobilized 1,3-specific Mucor miehei lipase (104); a variety
of enzymes used for producing different materials (105) with dependence on the
presence of solvent (106) as well as stepwise addition of methanol (106,107); the
synthesis of esters of restaurant greases (108110); stepwise use of immobilized
Candida antarctica lipase (111) modified later for continuous use (112), methyl
acetate as an acyl acceptor (113); use of Rhizopus oryzae lipase in a water-contain-
ing system without an organic solvent (114); and in the methanolysis of vegetable
oils contained in waste activated bleaching earth (115).
Supercritical technology has also been employed for transesterification (116
119). Alkylguanidines attached to modified polystyrene or siliceous MCM-41,
encapsulated in the supercages of zeolite Y or entrapped in SiO2 sol-gel matrices
were used as transesterification catalysts (120).
Various alkaline-earth metal compounds such as calcium oxide, calcium methox-
ide and barium hydroxide were used as heterogeneous catalysts for producing rape-
seed oil methyl esters (121) as was calcium carbonate (122). Diorganotin (IV) com-
pounds were studied as catalysts for the methanolysis of tripalmitin (123).
Methyl and ethyl esters of palm and coconut oils were produced by alcoholy-
sis of raw or refined oils using boiler ashes, H2SO4 and KOH as catalysts (124).
Fuel yields >90% were obtained using alcohols with low moisture content and
EtOH-H2O azeotrope.
One-step in situ processes in which the alcohol acts as extraction solvent for the
oil-containing material and as esterifying reagent have been reported. Sunflower seed
oils were transesterified in situ using macerated seeds with methanol in the pres-

ence of H2SO4 (125). Higher yields were reported than from transesterification of
the extracted oils although seed moisture reduced the yield of methyl esters. The
CP of the in situ prepared esters appeared slightly lower than those prepared by
conventional methods. In a related study, best yields were achieved with a 300:1
molar ratio methanol: oil (126). Similarly, macerated soybeans were treated with
methanol, ethanol, n-propanol and n-butanol to give the corresponding esters
(127), although due to the insolubility of soybean oil in methanol, conversion was
low in that case.
The synthesis of methyl or ethyl esters with 90% yield by reacting palm and
coconut oil from the press cake and oil mill and refinery waste with methanol or
ethanol in the presence of easily available catalysts such as ashes of the waste of
these two oilseeds (fibers, shell, and husk), lime, zeolites, etc., was reported (128).
Similarly, the methanolysis of vegetable oils was catalyzed by ashes from the com-
bustion of plant wastes such as coconut shells or fibers of a palm tree that contain
K2CO3 or Na2CO3 as catalyst (129). Thus the methanolysis of palm oil by reflux-
ing 2 h with MeOH in the presence of coconut shell ash gave 9698% methyl
esters containing only 0.81.0% soap. The ethanolysis of vegetable oils over the
readily accessible ash catalysts gave lower yields and less pure esters than the
methanolysis.
Several catalysts (CaO, K2CO3, Na2CO3, Fe2O3, NaOMe, NaAlO2, Zn, Cu,
Sn, Pb, ZnO, and an anion exchange resin) were tested for catalytic activity in the
reaction of low-erucic rapeseed oil with MeOH (130). The best catalyst was CaO
on MgO. At 200C and 68 atm, the anion exchange resin produced substantial
amounts of fatty methyl esters and straight-chain hydrocarbons.
The transesterification reaction is also the subject of numerous patents. A
transesterification process permitting the recovery of all by-products such as glyc-
erol and FA has been described (131). Some patent procedures were briefly
reviewed (132). The procedures used in the proprietary literature generally resem-
ble those published in journals.
Analysis of Transesterification Products

Potential contaminants of biodiesel include unreacted triacylglycerides; residual
alcohol and catalyst may be present as well as intermediate mono- and diacylglyc-
erides and glycerol co-product. Various methods have been investigated for ana-
lyzing biodiesel accordingly (133).
Glycerol mixtures were analyzed by TLC-FID (thin-layer chromatography/
flame ionization detection) (134), which was also used in the studies on the vari-
ables affecting the yields of fatty esters from transesterified vegetable oils (76).
The TLC- FID method has been abandoned (134135). Gas chromatography (GC)
is the most commonly used method for detailed analysis of transesterification and
biodiesel. Analysis of reaction mixtures by capillary GC determining esters, mono-,
di- and triacylglycerols was carried out in one run (136). Free glycerol was deter-

mined in transesterified vegetable oils (137138). Besides analyzing esters for

sterols (139141), which are often minor components in vegetable oils, and differ-
ent glycerides (142143), the previous GC method (136) was extended to include
analysis of glycerol (144). In both papers (136,144), the hydroxy groups were
derivatized by silylation with N-methyl-N-trimethylsilyltrifluoroacetamide. The
GC method simultaneously analyzing for glycerol, methyl esters, and the various
acylglycerols (144) forms the basis of standards such as ASTM D6584 and EN
14105. Simultaneous analysis of methanol and glycerol was also described (145)
as was a sole determination of methanol (146). Flame-ionization detectors (FID)
were usually employed although use of a mass selective detector was reported
(138,145).
Other authors, using GC to determine the conversion of TG to methyl esters,
gave a correlation between the bound glycerol content determined by TLC/FID
and the acyl conversion determined by GC (135). Glycerol was also analyzed by
high-performance liquid chromatography (HPLC) using pulsed amperometric
detection, which offers the advantage of higher sensitivity compared to refractome-
try and being suitable for detection of small amounts for which GC may not be
suitable (147). An enzymatic method for glycerol analysis was reported (148). An
enyzme-based analysis method for glycerol is now commercially available (149).
Several other studies have been performed using HPLC analyses. The first
HPLC-related report (150) used density detection to analyze for the various glyc-
erides and methyl esters as classes of compounds in order to determine the conver-
sion of transesterification reactions. An evaporative light scattering detector
(ELSD) was employed for analyzing the product, glycerides, and free FA from an
enzymatic transesterification (151). Atmospheric pressure chemical ionization
mass spectrometry was more suitable as a detection method for reversed-phase
HPLC than ELSD and UV (152). Several LC-GC methods were also reported
including methods for analyzing for sterols (140,141,153). High-performance size
exclusion chromatography was applied in the ethanolysis of rapeseed oil (154) or
methanoloysis of palm oil (155). Other analyses include the determination of
biodiesel in conventional DF by silica cartridge chromatography (156).
Spectroscopic methods applied to the analysis of transesterification and
biodiesel are nuclear magnetic resonance (NMR) and near-infrared (NIR) spectro-
scopies. In 1H-NMR spectrometry, the protons of the methylene group adjacent to
the ester moiety in triacylglycerols and the protons in the alcohol moiety of the
methyl esters were used to monitor the methanolysis of rapeseed oil (157). For
determining conversion and kinetics by 13C-NMR, the unchanging signal of the
terminal CH3 groups as well as the signals of the glyceridic moieties in the triacyl-
glycerols (158) were used. NIR peaks at 4428 cm1 and especially 6005 cm1
which distinguish methyl esters and triacylglycerols can be used for monitoring
transesterification and assessing biodiesel fuel quality by an inductive method
(159). The use of a fiber-optic probe for acquiring the spectra renders the method
rapid and easy. NIR and 1H-NMR results can be correlated (160).

Viscosity was used for determining the methyl ester content based of a trans-
esterification mixture (161). The results agreed well with GC. The method is
reportedly more rapid than GC and therefore especially suitable for process con-
trol.
IR spectroscopy (carbonyl absorption at 1750 cm1) with (162) and without
(163) a fiber-optic probe was used to assess the amount of biodiesel in lubricating
oil. The problem is important because biodiesel can cause dilution of lubricating
oil, ultimately resulting in engine failure.
With the increased use of biodiesel blends, the determination of blend levels
of biodiesel has recently received more attention. Methods that have been
employed include NIR and NMR spectroscopy (164), ester number (165), IR spec-
troscopy (165) and silica cartridge chromatography (166). A European standard,
EN 14078, utilizing the carbonyl absorption in the IR range is being developed. An
interesting problem involves the in-vehicle detection of biodiesel blends in order to
adjust relevant engine functions to the blend level. For this purpose, sensors have
been developed (167,168).
Emissions from Ester Fuels (Biodiesel)

Generally, most exhaust emissions observed when using conventional DF are
reduced when using biodiesel. NOx emissions, however, are an exception. In an
early paper reporting emissions with methyl and ethyl soyate as fuel (45), it was
found that CO and hydrocarbons were reduced but NOx emissions were produced
consistently at a higher level than with the conventional DF. The differences in
exhaust gas temperatures corresponded with the differences in NOx levels. Similar
results were obtained from a study on the emissions of rapeseed oil methyl ester
(169). NOx emissions were slightly increased, while hydrocarbon, CO, particulate
and PAH emissions were in ranges similar to the DF reference. Alkyl esters emit-
ted less aldehydes than the corresponding neat rapeseed oil. Unrefined rapeseed oil
methyl ester emitted slightly more aldehydes than the refined ester, while the
opposite held for PAH emissions. A 31% increase in aldehyde and ketone emis-
sions was reported when using rapeseed oil methyl ester as fuel, mainly due to
increased acrolein and formaldehyde, while hydrocarbons and PAH were signifi-
cantly reduced, NOx increased slightly, and CO was nearly unchanged (170).
Another study on agricultural tractors found that aldehydes increased by 20% with
CO and NOx similar to those from conventional DF (171). The general trend on
reduced emissions except NOx was confirmed by later studies (172), although
some studies report little changes in NOx (173,174). Little differences compared to
conventional DF were also reported for formaldehyde emissions when using soy
methyl ester (174). It was suggested that the average slight rise in NOx exhaust
emissions when using biodiesel can be at least partially traced to isentropic bulk
modulus and speed of sound of fatty esters, which are higher than for conventional
DF (175). This means that the fuel is less compressible (due to the larger mole-

cules) which in turn causes early injection timing leading to higher combustion
temperatures and pressures responsible for the rise in NOx exhaust emissions. High
temperatures are known to increase the formation of NOx in fuel combustion (60).
However, the structure of the FA chains was found to have a significant impact on
emissions. Increasing the number of double bonds increased NOx exhaust emis-
sions (176). This could not be explained by the known trade-off between NOx and
particulate emissions, also indicating that NOx formation when using biodiesel is
not driven thermally. Particulate emissions were essentially constant if CN >45 and
density <0.89 (176). NOx exhaust emissons can be reduced by retarded injection
timing (177) and comparing at the same start of combustion led to lower NOx
exhaust emissions than from conventional DF.
Various compounds such as alkyl nitrates and peroxides are used as cetane-
enhancing additives in conventional DF (27). NOx exhaust emissions reportedly
are lowered by increasing the CN of conventional DF (178). Thus, an approach uti-
lizing cetane improvers with biodiesel to lower NOx exhaust emissions appears
feasible. It was reported (179) that in a turbulence combustion chamber and at an
intake air temperature of 105C, 8% hexyl nitrate in vegetable oils (cottonseed,
rape, palm) was necessary to exhibit the same ignition delay as conventional DF.
Recently, some oxygenated compounds were identified as cetane improvers for
fatty esters (180) which apparently had selective effects on fatty compounds
depending on the kind of alkyl ester and nature of the FA chain, This may offer the
possibility of tailoring the cetane improver to the predominant fatty compound in a
specific biodiesel fuel. In a comparative study (181) of exhaust emissions at vari-
ous injection timings of conventional DF, B20, B20 with a peroxide cetane
improver and other DF, it was observed that retarded timing reduced NOx and
increased particulate matter for all settings. The fuel blend with cetane improver
had the lowest PM emissions of all fuels. NOx emissions for the additized blend
were slightly lower than for the unadditized blend. Furthermore, cetane improvers
derived from fatty compounds have been reported (182185).
A study on PAH emissions (186), in which the influence of various engine
parameters was also explored, found that these emissions from sunflower ethyl
ester were situated between DF and the corresponding neat vegetable oil. Reduced
PAH emissions may correlate with the reduced carcinogenicity of particulates
when using rapeseed methyl ester as fuel (187). With the same ester fuel in DI
engines, particulate matter showed large amounts of volatile and extractable com-
pounds adsorbed on the soot, which caused the PM emissions to be higher than
with conventional DF, although the soot itself was reduced (171). While total par-
ticulate matter was lower for methyl soyate than for conventional DF, an oxidation
catalytic converter (OCC) reduced those emissions by 5080% (188). Greater
reductions in mutagenicity were observed for the biodiesel fuel when using the
OCC. Other authors (189) reported similar results when using a catalytic converter.
However, conflicting results were obtained when using a ceramic trap. These and
additional authors (190) also found that exhaust emissions from biodiesel fuel,

both rapeseed and soybean oil methyl esters, had reduced environmental impact
and mutagenicity compared to conventional DF. Emissions from low-sulfur con-
ventional DF was also reported to be in the range of those from biodiesel, thus high
sulfur content as well as high engine speeds and loads were associated with
increased mutagenicity of diesel exhaust particles (190). In another study (191),
the emitted mass of PM from rapeseed methyl ester fuel was higher compared to
that from conventional DF but mutagenicity again was reduced. In the U.S.,
biodiesel is the only alternative fuel that has completed Tier 2 Health Effects
Testing required by the Clean Air Act Amendments of 1990 (192).
In a DI engine, sunflower methyl ester produced equal hydrocarbon emissions
but less smoke than a 75:25 blend of sunflower oil with DF (193). A diesel oxida-
tion catalyst (DOC) in conjunction with soy methyl ester was reported to be a pos-
sible emissions reduction technology for underground mines (194). Soy methyl
esters reportedly were more sensitive toward changes in engine parameters than
conventional DF (195).
Precombustion phase studies of methyl, ethyl, n-propyl, and n-butyl fatty
esters in a reactor simulating conditions in a diesel engine showed that various
species such as branched and straight-chain alkanes, alkenes, cyclic hydrocarbons,
aldehydes, ketones, esters, substituted benzenes as well as other compounds can
arise at this stage (196). Aromatic compounds, which possess low CN, were
observed more frequently for unsaturated fatty compounds. This observation may
constitute a possible partial explanation for the differing CN of fatty compounds
and may correlate with emissions studies.
Cold Flow Properties

All DF are susceptible to start-up and operability problems when subjected to cold
temperatures. As ambient temperature decreases below saturation temperature(s) of
high-molecular weight paraffins (C18C30 n-alkanes) present in conventional DF,
these paraffins nucleate to form crystals suspended in a liquid phase composed of
shorter-chain n-alkanes and aromatics (197201). Leaving the fuel unattended in
cold temperatures overnight can cause start-up and operability problems the next
morning.
The tendency of DF to solidify at low temperatures may be quantified by the
following parameters: CP, PP, cold filter plugging point (CFPP) and low tempera-
ture flow test (LTFT). The CP is defined as the temperature where crystalline
growth becomes visible in the form of a hazy or cloudy suspension of small solid
crystals ~0.5 m in diameter (197,198,202204). As temperatures decrease below
the CP larger crystals interlock and form agglomerates that restrict or cut off flow
through fuel lines and filters (197,198,200,201,204209). The temperature where
sufficient agglomeration prevents free pouring of fluid is determined by measuring
PP (199,202204). In terms of predicting tendency of crystals to cause start-up or
operability problems after cooling overnight, the CP tends to be over-cautious and

the PP tends to be over-optimistic (197,199,205). Therefore, low temperature fil-

terability tests (CFPP and LTFT) were developed based on results from cold
weather operability field studies (197,199,201,205,207210). Both parameters are
measured by cooling a sample under controlled conditions then drawing a speci-
fied volume through a wire mesh filter screen within 60 sec. Conditions for mea-
suring CFPP are volume = 20 mL, vacuum force = 0.0194 atm and mesh size = 45
mm. Corresponding conditions for LTFT are 180 mL, 0.197 atm and 17 m (197,
199,202,203,211). The CFPP serves as the standard low temperature operability
parameter for most of the world while the more stringent and less user-friendly
LTFT is the standard for North America.
Thermal analytical methods such as sub-ambient differential scanning
calorimetry (DSC) have also been applied in analysis of conventional DF
(206,212216). DSC has advantages including relatively small sample sizes (<20
mg) and applicability to samples that are solid at room temperature. Most impor-
tantly, cold flow properties may be directly correlated to crystallization onset tem-
perature (TCO) and mp.
Biodiesel made from feedstocks containing larger amounts of high-mp long-
chain saturated FA tends to have relatively poor cold flow properties (see Tables
4.1 and 4.2). For example, tallow contains 23.727.6 wt% palmitic acid (C16) and
18.425.0 % stearic acid (C18) (217,218), compounds whose corresponding methyl
esters have mp = 30 and 39.1C, respectively (219). As a consequence, tallow
methyl esters have a relatively high CP (1517C) (220). In contrast, feedstocks
with relatively low concentrations of saturated long-chain FA generally yield
biodiesel with much lower CP and PP. Thus, linseed, olive, rapeseed, safflower
and soybean oils are examples whose biodiesel product has CP near or below 0C
(47,80,221223). Nevertheless, comparison with No. 2 conventional DF (CP =
16C; PP = 27C (224) suggests that biodiesel from most common feedstocks
will have less reliable operability during cold weather.
Previous studies (224226) reported a nearly linear correlation between low-
temperature filterability (CFPP and LTFT) and CP of soybean oil methyl esters
and its blends with conventional DF. Results showed that a 1C decrease in CP
reduced CFPP or LTFT by 1C (224). This work concluded that efforts to improve
cold flow properties of biodiesel should emphasize development of approaches that
significantly decrease CP. This conclusion was applicable to neat biodiesel and its
blends with conventional DF and was later reported to apply to blends treated with
commercial DF cold flow improver additives (226).
Analyses of methyl esters of soybean oil, tallow, admixtures thereof and win-
terized soybean oil methyl esters showed that CP, PP and other cold flow proper-
ties could be accurately correlated to parameters inferred from sub-ambient DSC
analyses (227). The temperature of maximal heat flow for freezing peaks yielded
the most accurate correlations with respect to CP, PP and CFPP; LTFT was most
accurately correlated to freezing point. Onset temperature (TCO) yielded good cor-
relations for predicting PP, CFPP and LTFT. Although parameters from analysis of

cooling curves were found to be more reliable than those from heating curves,
other studies (217,218,228) successfully correlated CP of the soybean oil, tallow
and waste grease alkyl esters to results from analysis of DSC heating curves.
Approaches investigated or under investigation to address improvement of
cold flow properties of biodiesel include the following: blending with conventional
DF, cold flow improver additives, branched-chain esters and fractionation/winteri-
zation. Blending of esters is the simplest method for improving cold flow operabil-
ity and will be discussed in the next section.
Studies of commercial DF cold flow improver additives as modifiers for
biodiesel revealed these additives were very effective in reducing PP and CFPP
(225,226,229232). These additives depressed PP by up to 18C for 20 vol%
blends of soybean oil methyl esters in No. 2 conventional DF (226). Increasing
additive loading (concentration) resulted in nearly linear reductions in PP, though
some additives were more effective than others (225,226). These results demon-
strated that additives may be used to ease biodiesel pumping operations during
cooler weather. Some additives depressed CFPP, demonstrating they had greater
selectivity for modifying wax crystallization of biodiesel than simple PP depres-
sants (197,199201,207,208,233,234). None of the additives demonstrated suffi-
cient selectivity to significantly affect nucleation in neat or blended biodiesel,
resulting in little effect on CP or LTFT (224226). Thus, additives designed pri-
marily to modify wax crystallization in conventional DF also demonstrated some
degree of selectivity for modifying crystal nucleation mechanisms prevalent in
biodiesel.
The use of fatty compound-derived materials with bulky moieties in the chain
at additive levels is another approach (235). The background is that the bulky moi-
eties would destroy the harmony of the solids which are usually oriented in one
direction. However, these materials had only slight influence on the CP and PP.
Efforts to employ glycerol yielded as co-product from biodiesel production in syn-
thesis of agents that effectively improve cold flow properties of biodiesel were also
studied (236). Glycerol ether derivatives from reaction with isobutylene or isoamy-
lene in the presence of strong acid catalyst were shown to improve cold flow prop-
erties of in blends with biodiesel.
Transesterification of oils or fats with medium chain-length (C3C8) or branched-
chain alkyl alcohols is known to improve the cold flow properties of biodiesel. Large
or bulky headgroups disrupt spacing between individual molecules in the crystal
lamellae causing rotational disorder in the hydrocarbon tailgroup chains, resulting in
formation of crystal nuclei with less stable chain packing. Transition to a more stable
form eventuates at lower temperatures (237).
Comparison of data in Table 4.1 illustrates many examples of the effects of
chain-length and branching in the alkyl moiety of the ester headgroup on the melt-
ing properties of esters. Consistent with the first part of this comparison, biodiesel
made from canola, linseed and soybean oil shows decreases in both CP and PP with
increasing alkyl chain-length from methyl to n-butyl (220,222,224,238). Similar

decreases in CFPP and LTFT for tallow alkyl esters were also reported (220).
Consistent with the second part of the comparison of data in Table 4.1, biodiesel made
from soybean oil showed decreases in TCO (measured by DSC) of 711C for iso-
propyl esters and 1214C for 2-butyl esters relative to methyl esters (218). Other
studies (224,239) showed significant decreases in CP and PP for branched-chain alkyl
esters of soybean oil. Although decreases in CP and PP were reported for isopropyl
and isobutyl esters of tallow, CFPP and LTFT only decreased slightly (220).
Crystallization fractionation is the separation of components of fatty deriva-
tives based on differences in MP (240247). The physical nature of biodiesel sug-
gests that this technique may be a useful for improving cold flow properties by
reducing total concentration of high-mp saturated esters. Traditional crystallization
fractionation features two process stagesnucleation and crystalline growth under
carefully controlled conditions followed by separation of fractions by filtration or
centrifugation. Cooling rate and agitation in the crystallizer must be controlled to
reduce the rate of entrainment of liquid inside crystal agglomerates (240245,
247,248). Efficient separation of solid from low-mp unsaturated esters (liquid)
yields fractions with significantly altered physical properties (242244).
Dry fractionation, sometimes referred to as winterization, is the simplest and
least costly technique for separating high- and low-mp fatty derivatives (240244).
Bench-scale dry fractionation studies on soybean oil methyl esters indicated that
CP and PP may be decreased to 16C, a temperature close to LTFT of No. 2 con-
ventional DF (226,228). Although fractionation reduced total concentration of sat-
urated methyl ester (C16 and C18) to <6 wt%, yields of liquid fractions were very
low at only 2530% relative to starting material. Cooling times were typically
overnight (~16 h) and multiple crystallization steps were necessary to significantly
impact CP. Similar fractionation of tallow methyl esters (IV = 41; CP = 11C)
resulted in yields of 6065% liquid fraction characterized by IV = 60 and CP =
1C (244). Fractionation of waste cooling oil methyl esters was reported to
decrease CFPP by 24C (249). Addition of commercial DF cold flow improver
additives improved separation efficiency of to 8087% liquid fraction but still
required multiple crystallization steps to reduce CP to 10C (250).
Solvent fractionation was also applied to separation of alkyl esters. Soybean
oil methyl esters have been successfully fractionated from acetone, isopropanol
and hexane solvents. In isopropanol, one 5-h crystallization step at 15C was nec-
essary to reduce CP to 8C (250). Liquid fraction yields were in the range
improved to 7786% (226,250). Other solvents that have been applied to partial
separation of alkyl esters include methanol, Skellysolve B and ether (246).
Trace contaminants of biodiesel as they could remain after refining and trans-
esterification affected the cold flow properties of methyl soyate and blends thereof
with No. 1 conventional DF (251). Mono- and diglycerides did not influence the
PP of the esters, but the CP increased with increasing amounts of saturated mono-
or diglycerides. Even low concentrations of 0.1 wt% saturated mono- or diglyc-
erides raised the CP. Monoolein did not affect CP and PP. Unsaponifiable material

at concentrations as low as 3% raised the TCO, CP and PP of soybean oil methyl

esters but had virtually no effect on a 20% blend in No. 1 conventional DF.
Storage Stability
In terms of handling and storage safety, biodiesel compares favorably with conven-
tional DF. The reason is the significantly higher flashpoint of vegetable oils and
their methyl esters. However, due to the content of unsaturated fatty compounds,
storage stability can be an issue when using biodiesel. The more conjugated or
methylene-interrupted double bonds in a fatty molecule, the more susceptible the
material is to oxidation and degradation.
Generally, storage stability is defined by the relative resistance of liquid fuels
to physical and chemical changes resulting from interaction with the environment
(202). Stability takes into account interactions of olefins, dienes and nitrogen-, sul-
fur- and oxygen-containing compounds that can lead to sediment formation and
changes in color that depend on type and quantity of unstable materials present.
Cleanliness of the fuel with respect to the presence of water, particulate solids, fuel
degradation products and microbial slimes can also influence stability (252).
Degradation in fuel properties during long-term storage occurs primarily by
the following mechanisms: (i) oxidation (autoxidation) from contact with air; (ii)
thermal or thermal-oxidative decomposition from excess heat; (iii) hydrolysis from
contact with water or moisture in tanks and fuel lines; and (iv) microbial contami-
nation from the migration of dust particles or water droplets containing bacteria or
fungi into the fuel (202,252). A book on oxidation of fatty compounds has been
published (253).
Numerous studies usually relating to the first two aforementioned mechanisms
have been carried out regarding stability of biodiesel (254272). Summarily, these
studies have shown that storage stability of biodiesel is affected by factors such as
presence of air, heat, traces of metal (including influence of metal storage contain-
ers), peroxides, light, structural features of the compounds themselves as well as
degree of refining. High temperature, presence of light, presence of air and pres-
ence or metals, copper being especially effective (257), usually accelerate oxida-
tion of fatty compounds and their ultimate degradation. Antioxidants such as toco-
pherols (which occur naturally in vegetable oils), TBHQ (tert-butyl hydroquinone),
BHA (butylated hydroxyanisole), BHT (butylated hydroxytoluene), pyrogallol and
propyl gallate were investigated and shown to often have beneficial effects of
increasing storage stability. Methods that were used for investigating storage sta-
bility include peroxide value, acid value, viscometry, oxidative stability index
(OSI) which is closely related to the Rancimat, and other procedures. Acid value
and viscosity were shown to be especially appropriate methods (258). Methods
such as ASTM D2274 for testing the oxidative stability of conventional DF were
found to be inappropriate for biodiesel (265). Sometimes contradictory results are
reported, also in regard to the effectiveness of specific additives affecting oxida-

tion. They may be due to different reaction conditions and other parameters,
including feedstock quality, employed by different researchers.
An oxidative stability parameter has not been included in the ASTM standard
D6751. Several properties in the European standards EN 14214 and EN 14213 are
a result of concerns regarding oxidative stability. In the years 19982002, the
BIOSTAB project in Europe involving research groups in several countries carried
out related experiments. Some results were summarized in several publications
(254256,261). In the standards EN 14213 and EN 14214, a parameter on oxida-
tive stability was added as a result. This parameter prescribes the use of the stan-
dard EN 14112 (Rancimat) for determining the oxidative stability. At 110C, the
minimum induction time for biodiesel as transportation fuel (EN 14214) is pre-
scribed as 6 h and for heating purposes the time is 4 h.
Other studies (257258,260) evaluated oxidation induction periods by running
OSI analyses in accordance with standard methods such as AOCS Cd 12b-92 mod-
ified for lower temperatures. Milder reaction conditions were necessary because
many biodiesel samples contained high concentrations of more readily oxidizable
polyunsaturated FA esters.
Thermal analytical techniques such as thermogravimetric analysis (TGA) and
differential scanning calorimetry (DSC) have been applied in the analysis of oxida-
tion of petroleum-based and synthetic lubricants (273279). These studies general-
ly showed that DSC analysis under pressure (P-DSC) increases the total number of
moles of oxygen present in the cell accelerating oxidation at lower temperatures.
Cross (280) and Hassel (281) were among the first to apply DSC and P-DSC in
analysis of edible fats and oils. Results from these studies together with later work
(282) showed good correlations between isothermal induction periods measured by
P-DSC (in minutes) and OSI (in hours or days).
Perhaps the first study to examine oxidation of FA methyl esters was per-
formed by Raemy et al. (283). Results from that study showed that increasing tem-
perature or degree of unsaturation decreased induction period as measured by con-
ventional DSC. Results showed a direct correlation with those from the Rancimat
test, with respect to 612% variation. P-DSC analysis was also identified as an
efficient means for screening the activity of antioxidants with respect to type and
concentration in biodiesel (284).
Although most of the DSC and P-DSC studies cited above featured isothermal
analysis of oxidation induction period, non-isothermal (heat-ramping) thermal
analyses may provide a more rapid means for evaluating resistance to oxidation.
Several studies have reported on the use of non-isothermal DSC and P-DSC in
analysis of fatty derivatives. With respect to biodiesel, Litwinienko and co-workers
(285287) studied oxidation kinetics of unsaturated C18 FA and their ethyl esters.
Non-isothermal DSC and P-DSC analyses were applied in screening phenolic
antioxidants in methyl soyate (259) and linolenic acid (288). Finally, induction
period results showed a good correlation between non-isothermal P-DSC scans and
those from analysis of OSI (259).

Other parameters that can be seen as relating to oxidative stability include con-
tent of FA 3 double bonds limited to 1% in both EN 14213 or EN 14214.
Contained only in EN 14214 and not in EN 14213 is a provision that linolenic acid
be limited to a maximum of 12%. The IV is limited in EN 14213 to a maximum of
130 and in EN 14214 to a maximum of 120. However, structure indices termed
bis-allylic position equivalents and allylic position equivalents probably better
reflect the tendency of a fatty compound to oxidize than the iodine value (257,
289).
Blending of Esters
The most common application of esters (usually methyl esters; biodiesel) of veg-
etable oil in the U.S. is blends of conventional DF with these esters. The most
common ratio is 80% vol% conventional DF and 20% vegetable oil ester (also
termed B20, indicating the 20% level of biodiesel). There have been numerous
reports that significant emission reductions are achieved with these blends. Methyl
soyate can also be blended with jet fuels JP-5 and JP-8 (290). Winterization or use
of additives improves the low-temperature properties of those blends.
No engine problems were reported in larger-scale tests with, for example,
urban bus fleets running on B20. Fuel economy was comparable to DF2, with the
consumption of biodiesel blend being only 25% higher than that of conventional
DF. Another advantage of biodiesel blends is the simplicity of fuel preparation
which only requires mixing of the components. Ester blends were reported to be
stable. For example, a blend of 20 vol% peanut oil with 80% DF did not separate at
room temperature over a period of 3 mon (291).
A few examples from the literature demonstrate the suitability of blends of
esters with conventional DF in terms of fuel properties. In transient emission tests
on an IDI engine for mining applications (194), the soybean methyl ester used had
a CN of 54.7, viscosity 3.05 mm2/s at 40C, and a CP of 2C. The DF2 used had
CN 43.2, viscosity 2.37 mm2/s at 40C and a CP of 21C. A 70: 30 DF2: soybean
methyl ester blend had CN 49.1, viscosity 2.84 mm2/s at 40C, and a CP of 17C.
The blend had 4% less power and 4% higher fuel consumption than the DF2, while
the neat esters had 9% less power and 13% higher fuel consumption than DF2.
Emissions of CO and hydrocarbons as well as other materials were reduced. NOx
emissions were not increased here, although higher NOx emissions have been
reported for blends (DI engines) (169, 173).
Irregularities compared to other ester blends were observed when using blends
of the isopropyl ester of soybean oil with conventional DF (239). Deposits were
formed on the injector tips. This was attributed to the isopropyl ester containing
5.2 mol% monoglyceride which was difficult to separate from the isopropyl ester.
However, in another report (292), the isopropyl and methyl esters of soybean oil
performed well in blends with conventional DF. CO and unburned hydrocarbon
emissions were reduced as were particulates by 28% when using the isopropyl

ester (25% reduction with the methyl ester); however, NOx emissions increased a
maximum of 12% for a 1:1 isopropyl soyate/DF blend.
Ester Fuels from Animal Fats and Waste Oils

Animal Fats. The animal fat most commonly studied for potential biodiesel use is
tallow. Tallow contains a high amount of saturated FA (Table 4.2) and its mp is
above ambient temperature. Blends of tallow esters (methyl, ethyl, and butyl) with
conventional DF were studied (293). Smoke emissions were reduced with the esters,
particularly the butyl ester. Other features such as torque, power, and thermal effi-
ciency did not deviate from conventional DF by more than 3% in any case. Specific
fuel consumption was higher for the neat esters but only 1.8% higher for a 50:50
blend of butyl tallowate with conventional DF. A study on beef tallow and an inedi-
ble yellow grease both neat and a 1:1 (weight ratio) blend of tallow with DF in short-
term engine tests with DI and IDI engines was carried out (294). The deposits were
softer than those formed with reference to cottonseed oil but still excessive. In a 200-
h EMA test the deposits caused ring sticking and cylinder wear. Thus, animal fats,
like vegetable oils, are not suitable for long-term use unless modified.
Other researchers blended methyl tallowate with 35 vol% ethanol to achieve the
viscosity of conventional DF and the fuel properties were closely related to that of No.
2 DF (295). In an investigation of blends of DF2 with methyl tallowate and ethanol
(296), an 80:13:7 blend of DF2:methyl tallowate:ethanol reduced emissions the most
without a significant drop in engine power output. The same authors determined
numerous physical properties of blends of DF with methyl tallowate, methyl soyate
and ethanol and found them to be similar to the pertinent properties of DF2.
Waste Vegetable Oils. The use of vegetable oils as frying oils produces signifi-
cant amounts of used oils which may also present a disposal problem. A major
incentive for the use of waste oils is their lower price. Acid catalyzed-processes for
biodiesel production from waste oils is economically competitive with the alkali-
catalyzed processes applied to virgin vegetable oils (297). Used vegetable oils usu-
ally contain some degradation products of vegetable oils and foreign material. A
potential operational problem of biodiesel from waste oils is their less favorable
cold flow properties due to higher amounts of saturated fatty compounds. The pro-
duction of biodiesel from such sources is briefly discussed above. However, in
analyses of used vegetable oils it was reported (298) that the differences between
used and unused fats are not very great and in most cases simple heating and
removal by filtration of solid particles suffices for subsequent transesterification.
The CN of a used frying oil methyl ester was given as 49 (299), thus comparing
well with other materials, but little demand could be covered by this source.
Biodiesel in form of esters from waste cooking oils was tested and it was reported
that emissions were favorable (300). Used canola oil (only purified by filtration)
was blended with DF2 (301). Fuel property tests, engine performance tests and

exhaust emission values gave promising results. Filtered frying oil was transesteri-
fied under both acidic and basic conditions with different alcohols (methanol,
ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-ethoxyethanol) (301). The for-
mation of methyl esters with base catalysis (KOH) gave the best yields. The
methyl, ethyl, and 1-butyl esters obtained here performed well in short-term engine
tests on a laboratory high-speed diesel engine. However, during heating of frying
oil, chemical changes such as formation of polymers can occur. In a study on heat-
ed rapeseed (canola) oil as a source of biodiesel, heating caused the amount of
polymers to increase up to 15% in rapeseed oil but only 5% in the methyl esters
(302). Dimeric and trimeric triacylglycerols in the starting oil were mainly convert-
ed into monomeric and dimeric FA methyl esters. The monomeric and dimeric
species negatively influenced fuel properties. Thus, after 6 h heating Conradson
carbon residue and after 16 h viscosity exceeded biodiesel specifications. The
amount of polymers in waste oil was taken as an indicator for its suitability in
biodiesel production. Viscosity and Conradson carbon residue were taken as good
indicators for the existence of higher dimer levels.
Waste olive oil without any further derivatization was also studied in blends
with conventional DF and these blends were found to be suitable as fuel (303).
Used, underivatized sunflower oil was also studied (304). Methyl esters of waste
olive oil were reported to be a suitable fuel (305). Waste palm oil was transesteri-
fied with ethanol to biodiesel (306) and tested in a water-cooled furnace (307).
Waste oil was thermally cracked to obtain a fuel suitable for use in a diesel engine
(308). As discussed above, the FA in soapstock, a by-product of vegetable oil
refining consisting mainly of water, acylglycerols, phosphoglycerols and free FA
with a total FA content of 2530%, were also converted into biodiesel and the fuel
found to be competitive with biodiesel from other sources (97,98).
Summary and Outlook

The use of vegetable oil-based DF, particularly in the form of esters (biodiesel),
will probably continue to increase. Numerous reports in the popular and lay sci-
entific press discuss this topic and new biodiesel plants are constantly being con-
structed. Further refinement of existing standards is likely as well as development of
standards in more countries around the world. Although vegetable oil-based fuels
cannot replace all petroleum-based DF, they play an important role among the
alternative fuels and contribute to the goal of energy independence and security.
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Chapter 5
Biofuels for Home Heating Oils

Bernard Y. Tao
Purdue University, Department of Agricultural and Biological Engineering, West Lafayette,
IN 47907
Introduction
Petroleum-based liquid home heating oil is used to heat over eight million homes
in the U.S., predominantly in the northeastern U.S. (1). This comprises ~6.6 billion
gallons of fuel oil annually. With recent rises in petroleum prices to over $50 per
barrel, and anticipated future price increases as petroleum resources become less
available, many applications that depend on petroleum are searching for alterna-
tives. Additional concerns over environmental issues involving sulfur and nitrogen
oxide emissions from oil-based home heating systems have sparked a search for
alternative fuels to supply this market. This chapter presents a background on
home heating systems and highlights recent research to develop renewable biofu-
els for home heating applications.
Home Heating Technologies

History of Home Heating
Historically, interior home heating has progressed from open wood fireplaces to mod-
ern enclosed high-efficiency furnaces. Centralized heating systems were initially
developed during the early 19th century along with the demand for larger buildings
and residences. While wood was the initial fuel used in fireplaces, coal was often pre-
ferred due to its higher energy density. As population density in urban settings
increased, the environmental impacts of these heating systems became increasingly
evident in the form of smoke, soot, and smog, with accompanying health issues. With
the growth of the petroleum industry in the early 1900s, liquid fuels replaced solid
fuels due to their ease of transportation and simplicity of use. In the mid-1900s,
gaseous fuels, such as natural gas, became the fuel of choice, due to its ease of use and
clean-burning properties. With the growth of electrical transmission systems, electrical
heating/heat pumps have also become popular in the last four decades. Accompanying
these changes in fuel technology were improvements in environmental emissions,
such as reduced smoke/soot and sulfur oxides.
Looking at the U.S., the geographical distribution of home heating systems
follows this historical development of fuels technology. The northeast coast has
90

Home Heating Oils 91
Fig. 5.1. Residential heat-

ing fuel types (1).
the largest concentration of liquid fuel home heating systems, with natural gas and
electrical systems becoming the majority in the central and western U.S. Figure 5.1
shows natural gas and electrical heat residences made up 55 and 30%, respectively,
of the total heated households in the U.S., while fuel oil residences made up ~8%.
The geographical distribution of annual sales of heating fuel are shown below in
Figure 5.2.
Since the 1970s, the heating oil industry has dropped from 20% of American
households to less than 10%. Currently, most new housing is heated by natural gas or
electrical energy. However, with recent record high prices in natural gas, the oil heat
industry is eager to regain heating fuel markets. The National Oilheat Research
Alliance (NORA) was created to address this concern by supporting new oil heat tech-
nologies and fuels as well as improving the public perception of oil heat (2).
Fig. 5.2. Sales of resi-

dential heating oil by
location.

92 B.M. Tao
With the long-term prospect of diminishing petroleum resources, sharply

increasing prices, and environmental regulation, the oil heat industry is focusing on
developing alternative fuels. Biofuels are particularly attractive due to their renew-
able nature, environmental benefits, and chemical similarity to petrochemical
hydrocarbons. Additionally, there are potential political benefits based on domestic
production and partnering with agriculture, which include reduction of national
trade deficits, energy security, and domestic job creation.
Fuel Oil Furnace Technology

A typical home heating furnace is presented in Figure 5.3. Fuel is pumped into the
combustion chamber where it is combined with external air and burned. A heat
exchanger is used to transfer heat to a separate external air-flow to produce warm
air for home heating.
Due to low evaporative volatility, home heating oil furnaces require fuel to be
atomized by pumping through nozzles prior to combustion. Atomization is the
process of generating droplets from a liquid. The process is controlled by several
factors including physical properties of the liquid, operating conditions and atom-
izer geometry. Nozzle configuration can have a significant effect on both combus-
Fig. 5.3. Typical residential heating furnace.

tion and formation of nitrogen oxides. Liquid viscosity is the primary fuel factor in
spray formation and hence combustion. Standard pump pressures are normally
around 100 psi and produce nearly 55 billion drops/gal of fuel oil droplets which
range in size from 0.002 in (5.1 m) to 0.010 in (254 m) (3).
The efficiency of heat recovery is a critical performance factor. Therefore,
controlling combustion air-flow is a key performance parameter. High life-cycle
improves fuel combustion and may improve emissions, but results in loss of ener-
gy into the exhaust gases. Low air-flow may result in incomplete combustion and
increased emissions. Ideally, hydrocarbon fuels composed of carbon, hydrogen,
and oxygen would completely combust with oxygen to produce only water and
carbon dioxide. In reality, some carbon monoxide forms, even under high-excess
oxygen conditions due to incomplete combustion. Along with incomplete combus-
tion, the other main emissions of concern are sulfur/nitrogen oxides. Sulfur oxides
(SOx) are considered environmentally undesirable due to the formation of atmos-
pheric sulfuric acid when combined with rainwater. Nitrogen oxides (NOx) func-
tion as a catalyst in the chain reaction formation of ozone and carbonyl groups in
the upper atmosphere (4), creating smog. Natural sources of petroleum contain
varying amounts of sulfur. This can be adjusted by refining; current laws/regula-
tions exist to regulate SOx emissions. In general, SOx emissions are essentially
quantitatively related to fuel sulfur content (5).
Due to the presence of high amounts of nitrogen in the air used in combustion,
NOx are also formed. Many major cities, such as Los Angeles and Texas, have
restrictions on NOx emissions from sources including residential size boilers and
furnaces (6). Eastern states have not yet restricted these emissions from residential
boilers and furnaces, but that may change in the future. Since high temperatures
are believed to be the primary catalyst in NOx formation (4), increased NOx for-
mation occurs at higher combustion temperatures and in the presence of larger
excesses of oxygen.
To obtain complete combustion, excess air-flow is used (see Fig. 5.4). Ideally,
the amount of air used minimizes carbon monoxide formation/maximizes carbon
oxidation while trying to minimize the loss of energy in the outlet gases. However,
maximizing the furnace temperature to provide high heat transfer in the presence
of excess air produces increased levels of NOx. Therefore, furnaces must be care-
fully optimized to balance heating performance, while minimizing emissions by
controlling air-flow, fuel combustion, and heating temperature.
Fuel Oil Chemical Composition

Petroleum hydrocarbons are composed of ~86% carbon and 14% hydrogen. Small
amounts of sulfur, nitrogen, and oxygen may also be present depending on the
source of extraction. Transportation fuel (gasoline, diesel, aviation, etc.) is the
major use of petroleum in the U.S. This fuel requires significant refining to pro-
duce the highly refined hydrocarbon compositions needed by modern engine tech-

94 B.M. Tao
Lack of air Excess air

i
d Flue gas loss
e
Flue gas components
a
Fuel/air l
mixture
Carbon dioxide
(CO2)
R
a
n Oxygen (O2)
g
e
Carbon
monoxide
(CO)
=1 Excess air
Fig. 5.4. Combustion exhaust gas properties (7).
nologies. Since the fuel oil combustion in furnaces is less stringent, fuel oil is less
refined and contains higher molecular weight components (8). Typical carbon
number range for #2 fuel oil is from C11 to C20 and may contain higher percent-
ages aromatic hydrocarbons relative to kerosene or diesel fuel (9). Based on cold
weather temperatures, different blends with lower freezing points may be created,
for example heating fuels #1, #2, and #4 (10).
Similar to automotive and industrial petroleum fuel use, environmental emis-
sions are important for home heating fuels. The sulfur content is an important envi-
ronmental and economic factor in petroleum heating oil. In 1991, the environmen-
tal protection agency (EPA) regulated the sulfur content of on-highway diesel
vehicles to 0.05% or 500 ppm. Prior to that time, heating oil and on-highway diesel
both shared the maximum sulfur content value of 0.5% or 5,000 ppm. In an
attempt to simplify fuel distribution and improve emissions, the NORA board man-
dated that 80% of the heating oil consumed not contain more then 500 ppm by
2007 (5). This was supported by the recent ASTM adoption of specification for
low sulfur (LS) #2 heating oil. Research into ultra-low sulfur (ULS) with less then
15 ppm sulfur heating oil has recently been conducted and approaches nitrogen
free status (6). Additional environmental issues involved in fuel combustion tech-
nologies are the formation of nitrogen oxides, related to atmospheric smog forma-
tion, and particulate emissions (soot/smoke).

Biofuels
Biologically derived fuels from plant oils have four major benefits versus petroleum
or natural gas. First, they are environmentally renewable. The main product of hydro-
carbon combustion is carbon dioxide, which is believed to be related to global warm-
ing. Since growing plants actively recycle carbon dioxide to build oils and lipids,
combusted biofuels are ecologically recycled, resulting in zero net carbon dioxide pro-
duction. Second, plant oils from crops such as soybeans, corn, canola, etc., are domes-
tically produced versus petroleum from foreign sources. This is a significant issue in
todays U.S. environment where the concern for homeland security is paramount.
Third, the chemical structure of plant oils is chemically and physically similar to
petroleum hydrocarbons. They are composed of triacylglycerols, whose long-chain
fatty acid moieties are essentially hydrocarbons, hence the similarity in the common
name oil. Finally, the current economics of plant oils are similar or slightly favor-
able versus petroleum and this is anticipated to become increasingly beneficial in the
long-term future due to diminishing petroleum availability.
With respect to liquid biofuels, there are currently two plant oil-based fuels being
studied, degummed oil (triacylglycerides) and biodiesel fuel (monoalkyl esters).
Degummed Vegetable Oil. Vegetable oil from common domestic sources, such
as soybean oil, is a triacylglyceride composed of a glycerol molecule onto which
three long-chain fatty acids are attached (see Fig. 5.5).
The fatty acid chains are essentially linear hydrocarbons, some containing one
or more double bonds, and may be different chain lengths at each glycerol posi-
tion. Soybean oil is extracted from soybean seeds and purified through a series of
processing steps, which includes degumming. Degumming is the process of
removing phospholipids, such as lecithin, and is the initial processing step in the
production of food-grade vegetable oils (Fig. 5.6).
Degummed oil is an intermediate product in the production of food-grade veg-
etable oil and is approx. $0.05 to $0.10/gal cheaper than fully refined oil due to less
processing. Approximately 2.8 billion gallons of soybean oil are produced domestical-
ly in the U.S. annually, with world production at ~10 billion gallons annually. Recent
prices for food-grade soybean oil are in the range of $0.20$0.25/lb or ~$1.50/gal.
Mono-Alkyl Esters/Biodiesel. Alcohol transesterification of triacylglycerides

chemically rearranges fats into glycerin and alkyl esters. The most common ester
HO-CH2 CH3(CH2)7CH=CH(CH2)7C(O)O-CH2
| |
HO-CH CH3(CH2)7CH=CH(CH2)7C(O)O-CH
| |
HO-CH2 CH3(CH2)14C(O)O-CH2
Fig. 5.5. Glycerol and triacylglyceride structures.

96 B.M. Tao
Fig. 5.6. Soybean oil degumming process diagram (11).
currently formed uses methanol as the acceptor alcohol (ROH in Fig. 5.7) to make
methyl esters (ROCOR in Fig. 5.7), which is commonly called biodiesel fuel.
More information on this process can be found at www.biodiesel.org.
Since biodiesel can be made from any triacylglyceride source, significant dif-
ferences in physical properties have been observed. The use of animal fats or
hydrogenated fats which contain higher saturated fat content have much higher
freezing temperatures than standard soybean oil, which contains high levels of
polyunsaturated fatty acids. In comparison to triacylglycerides, fatty acid methyl
esters generally have lower viscosities and are much better solvents toward poly-
Fig. 5.7. Transesterification of fatty acid methyl esters.

mers and elastomers. Their cold temperature properties are somewhat similar, but
strongly depend on fatty acid structure and composition. In the U.S., current pro-
duction capacity is ~80 million gallons annually with significant investments being
made to increase production. Estimates of the current cost of biodiesel soy methyl
esters are in the range of $2.50$3.00/gal. Due to recent legislation for transporta-
tion applications of biodiesel fuel, subsidized support has been provided for this
biofuel to reduce the cost by ~$1/gal, but it is not clear if this subsidy will apply to
home heating fuels.
Recent Research on Biofuels Usage in Home Heating Applications

Low Temperature Behavior of Biofuel Blends. Solidification or gelling of home
heating fuel is a concern due to cold weather climates. This phenomenon is quanti-
fied by the cloud point and the pour point temperatures, which are the temperatures
at which the first crystals appear (cloud point) and at which the mixture no longer
freely flows (pour point). These thermal properties increase with degummed soy-
bean oil content in soybean oil heating fuels (SHO) (see Fig. 5.8). The cloud point
is ~7F (3.9C) higher than the pour point for each blend. This behavior is similar
to the results obtained for biodiesel blends published by Brookhaven National
Laboratory (BNL) (12). Therefore, higher blends of biofuels can be an issue with
respect to cold temperature fuel crystallization.
Flash Point. The flash point of a fuel is a measurement of flammability. Higher

flash points indicate fuels which are less flammable and hence safer to handle with
respect to volatility. The reported flash points for the degummed soybean heating
Soybean Oil Content (vol%)

Fig. 5.8. Cloud point of soybean oil/#2 home heating oil blends (13).

98 B.M. Tao

Fig. 5.9. Flash point of soybean oil/#2 home heating oil blends (13).
oil blends (13) are similar to biodiesel results published by Krishna and Butcher
(12). Analysis of both soybean oil and biodiesel heating oil blends showed a nearly
constant flash point up to a 30% blend, then an increase with biofuel component
composition (see Fig. 5.9). Therefore, higher blends of biofuels are safer from a
volatility perspective.
Energy Content. The energy content of the blended fuels is essentially linear with
composition. Fuel oil contains ~10% more energy than soybean oil. Soybean oil
has slightly higher energy content than methyl esters (see Table 5.1). Obviously,
the energy content would be linearly proportional to the amount of biofuel compo-
nent used. However, in practice, this difference in energy content is probably not
significant, given that the operational parameters of furnaces have much greater
impact on variations in energy output.
TABLE 5.1
Net Energy Content of Biofuels and Blends
Volume basis Mass basis

BTU/gal (MJ/L) BTU/lb (MJ/kg)
#2 Fuel oil 139,167 (38.8) 19,601 (45.6)
SHO20 (degummed) 135,490 (37.8) 18,871 (43.9)
SHO50 (degummed) 132,441 (36.9) 18,143 (42.2)
Degummed soybean oil 127,631 (35.6) 17,017 (39.5)
Soy methyl esters 125,314 (34.9) 17,405 (40.4)


Fig. 5.10. Soybean oil heating fuels kinematic viscosity at 100F (13).
Viscosity. Figure 5.10 shows the kinematic viscosity at 100F (37.8C) for SHO
heating oil blends. The kinematic viscosity of the SHO20 blend was 3.46 cSt
which is within the ASTM recommendation for petroleum fuel oil. The main
impact of the viscosity is in atomization of the fuel in the combustion chamber.
Higher viscosities tend to increase particle size and reduce combustion efficiency.
Research by VanLanningham (13) demonstrated that different atomization nozzle
configurations could be used to effectively atomize viscosity biofuel blends higher
than 20% if needed. Viscosity measurements by Krishna and McDonald (14) show
that biodiesel fuel composition below ~40% falls within the current ASTM stan-
dard range for heating fuel.
Environmental Impact of Heating Oil Replacement

Both VanLanningham (13) and Krishna (14) observed linear decreases in SOx
emissions with the addition of either biodiesel or vegetable oil fuels to #2 heating
fuels. Therefore, SOx emissions reduction is basically due to decreased sulfur con-
tent of the biofuels.
The nitrogen oxides (NOx) results from biofuel blends are less conclusive.
Two studies show soy methyl ester blends reduce NOx emissions while a third
study reports no statistical difference in emissions. The BNL biofuel study sug-
gests higher concentrations of biofuels produce lower NOx emissions over most
operating ranges (15). Lower flame temperatures and/or the presence of oxygenat-
ed compounds within the fuel were considered possible clues to the decrease in
NOx emissions for biodiesel (12). This is supported by Bowman (16) who demon-
strated that reducing either the burned gas temperature or the available oxygen will

100 B.M. Tao
reduce the NO formation rate. The Brookhaven study also stated an observed peak in
NOx emissions, and a general decrease in emissions as the excess combustion air
increased. However, it was noted that combustion chamber design and the furnace
design in general affected NOx emissions (17). This agrees with Vanlanninghams
observations that at 20% vegetable oil, different atomizing nozzle designs gave NOx
levels from 60120 ppm. Cold temperature combustion tests found NOx emissions
not to be statistically different for the 20% SME blend and the petroleum heating oil
(18).
Krishna and Butcher (12) observed decreased emissions with the addition of
biodiesel, but VanLanningham (13) observed no changes in NOx emissions with
vegetable oil. In both cases, the excess oxygen content in the exhaust gases was
~3% range with NOx levels in the 110120 ppm range. The reason for this disparity is
unclear, but the difference may be more dependent on the air-flow operating condi-
tions and fuel atomization than the type of biofuel. If higher excess air-flow is
used, the NOx concentrations will be lower due to dilution in the outlet gases.
Krishna and Butchers work shows slightly lower NOx emissions (115117 ppm)
at 3% oxygen in the exhaust, with decreasing NOx with increased air-flow down to
~90 ppm at 8% oxygen. VanLanningham only reports NOx levels at 3% oxygen in
the exhaust gases which range from 60120 ppm, depending on atomizing nozzle
configuration.
Alternatively, if higher combustion temperatures are obtained, NOx formation
rates may be greater. In the VanLanningham study of vegetable oil (13), it was
noted that increasing vegetable oil content above 50% did result in higher combus-
tion temperatures. However, no significant temperature differeneces were noted at
the 20% biofuel composition, so it is unclear why the observed NOx levels were
higher. Analysis of emissions from combustion of a mixture of 20% soybean oil
with #2 fuel oil showed a slight increase in NOx and slight decrease in SO2 (Table
5.2).
Since environmental impact is a primary benefit of biofuels, a life-cycle analy-
sis of the impacts of using soybean oil heating fuel blends was quantified (19)
using the factors indicated in Fig. 5.11.
Using a recently completed life-cycle inventory by the National Institute for
Standards and Technology (NIST) for soybean production (20), the energy use and
other environmental impacts from an acre of soybean production were calculated.
Table 5.3 from the NIST LCI shows the total for inputs and outputs from soy agricul-
tural production. Based on one kg of soybeans produced, the total primary energy
requirement is 2 MJ for production. The crushing process requires 92,880 kcal/ton of
soybeans or an additional 0.39 MJ/kg, bringing a total of 2.39 MJ/kg of oil or meal, if
energy is allocated equally. Combustion data shows 17113.5 BTU/pound which
equates to 39.7 MJ/kg of fuel burned for a net gain of 37.31 MJ/kg of oil. One kg of
heating oil would produce 45.8 MJ/kg of energy. The NREL biodiesel life-cycle esti-
mated a process energy requirement for diesel fuel of 9.16 MJ for extraction trans-
portation and refining, leaving a net gain of 36.6 MJ/kg.

TABLE 5.2
Emissions from #2 Fuel Oil/Soybean Oil Blends
T gas CO2 O2 CO SO2 NOx

Fuel C % % ppm ppm ppm
Fuel Oil 252 10.7 6.5 11.2 99 72
Fuel Oil 252 11.4 5.6 11 78 84
Fuel Oil 247 11.3 5.8 10.9 74 81
Fuel Oil 240 10.4 6.9 10.3 104 75
Fuel Oil 238 10.1 7.3 9.7 83 76
Fuel Oil 238 9.9 7.5 9.8 79 77
Fuel Oil 239 9.7 7.9 9.6 78 78
SHO20 246 11.9 4.8 11.3 92 91
SHO20 245 11.9 4.9 11.5 90 91
SHO20 239 10.3 7.1 10.9 94 92
SHO20 253 10.3 7 10.6 93 93
SHO20 258 11.3 5.7 11 82 98
SHO20 262 11.3 5.7 10.5 81 99
SHO20 239 11.9 4.8 9 77 93
SHO20 235 11.3 5.6 8.6 69 85
SHO20 236 11.3 5.7 8.5 69 84
Source: Reference 13.
Another significant and favorable difference is the sequestration of CO2 from

the atmosphere during the growth of the soybean crop. Combustion data shows
that both soybean oil and #2 oil fuels release CO2 in equal amounts, but the NIST
life-cycle shows that soybeans take up 1561 g of CO2/kg soybeans. Soybean oil is
actually more dense in carbon than whole soybeans, containing ~75% elemental
carbon by weight. Converting elemental carbon to CO2 shows that each kg of oil
contains the equivalent of 2.77 kg of CO2. Allocating the CO2 release from agri-
culture based on the oil yield of 12.5% yields a net sequestration of 2.76 kg of CO2
with a release from combustion of ~1,200 g of CO2/kg of fuel burned for either
soybean oil or #2 distillate. Therefore, the use of soybean oil for combustion shows
a net sequestration of CO2 of between 1.51.6 kg/kg of fuel burned versus #2 fuel
oil. Assuming a blend of 20% soybean oil with #2 distillate, the total CO2 contri-
bution to the atmosphere is reduced from 1.2kg/kg of fuel to 0.66 kg/kg of fuel, a
reduction in global warming potential of 45%.
Testing of Biofuels in Home Heating Systems

Current field testing of biofuels for home heating has focused on using blended
fuels which do not require any modification of existing furnaces or fuel delivery
infrastructures to minimize costs. Recent results reported by Batey (17) and Batey
et al. (21) indicate that lower emissions of SOx, NOx, and CO2 based on single
burner/boilers using 20% soy-based biodiesel blended with low sulfur (~0.05%)
diesel fuel. In 2003, a blend of 20% biodiesel was used by the Warwick School

102 B.M. Tao
Fig. 5.11. Life-cycle analysis parameters for soybean oil heating fuel blends.
Department in Rhode Island following a successful one year field testing where
10%, 15% and 20% blends of biodiesel were used experimentally (22).
Field testing of 20% SHO heating fuel blends was conducted at two private
residences over the past two years and demonstrated normal operations (14).
Industrial furnace field tests have not been performed for soybean oil fuel blends to
date. In all cases, no adverse performance or efficiency issues were noted.

TABLE 5.3
NIST Life-Cycle Analysis Parameter Values
Inventory: Soybeans Soybean Cultivation

Flow Units Total
Input (r) Coal (in ground) kg 0.0049
(r) Limestone (CaCO3, in ground) kg 0.15
(r) Natural Gas (in ground) kg 0.014
(r) Oil (in ground) kg 0.025
(r) Phosphate Rock (in ground) kg 0.014
(r) Potash (K2O, in ground) kg 0.0078
(r) Uranium (U, ore) kg 1.3E-07
Land Use: Cropland (Conservation Tillage) m2/yr 2.3
Land Use: Cropland (Conventional Tillage) m2/yr 1.0
Land Use: Cropland (Reduced Tillage) m2/yr 0.81
Water Used (total) liter 42
Water: River liter 26
Water: Well liter 15
Output Carbon Dioxide (CO2, biomass)a g (1,561)
Carbon Dioxide (CO2, fossil)a g 188
Carbon Monoxide (CO)a g 0.60
Methane (CH2)a g 0.16
Nitrogen Oxides (NOx as NO2)a g 1.1
Nitrous Oxide (N2O)a g 2.5
Particulates (unspecified)a g 11
Sulfur Oxides (SOx as SO2)a g 0.40
Nitrogenous Matter (unspecified, as N)b g 0.14
Phosphorous Matter (unspecified, as P)b g 0.021
Suspended Matter (unspecified)b g 2,816
Soybeans kg 1.0
Soybean Residues kg 2.1
Soybean Residues (collected) kg
Waste (total) kg 0.036
Reminders E Feedstock Energy MJ 0.10
E Fuel Energy MJ 1.9
E Nonrenewable Energy MJ 2.0
E Renewable Energy MJ 0.018
E Total Primary Energy MJ 2.0
aAir
emission.
bWater emission.
Abbreviation: NA, not available.
Economics
The partial replacement of #2 fuel oil through blending with crude degummed soy-
bean oil demonstrated that up to 40% soybean oil mixtures produced a clean flame
at manufacturer-recommended settings for air intake. On a heating energy basis,
the energy content of soybean oil or methyl esters is roughly 10% less than #2 fuel
oil on a weight basis (Table 5.4) and 8% less on a volume basis (Table 5.5).

104 B.M. Tao
TABLE 5.4
Energy Content of Heating Fuels (Mass Basis)
% Difference vs.
Material BTU/lb #2 Fuel oil
#2 Fuel oil 19,601 0
Methyl soyate 17,405 11
Crude degummed soybean oil 17,114 13
Assuming 20% blends, the blended fuel would contain ~99% of the heating
energy of #2 fuel oil, which would most likely not be significant for the average
fuel user. Additionally, due to lower volatility, soybean oil and methyl esters
would minimize the volatilization losses of the fuel during storage.
Relative Prices of Soybean Oil, Methyl Esters, and #2 Heating Oil

The prices of commodities such as heating oil and soybean oil fluctuate signifi-
cantly. Since methyl esters are made from soybean oil, their prices are directly
linked. Currently, methyl esters are ~$1/gal higher than the price of soybean oil.
Historically, the price of soybean oil per pound is twice the price of raw soybeans
per pound. Therefore, if soybeans are selling at $6.00/bu ($0.10/lb) the recovered
crude oil should be selling at $0.18$0.22/lb or $1.31$1.60/gal. For comparison,
recent soybean oil prices at the Chicago Board of Trade were at $0.2014/lb or
$1.47/gal, whereas #2 heating oil was selling at $1.401.50/gal range (wholesale)
and ~$2.00/gal (retail) in December of 2004. (Note: Degummed soybean oil is not
traded but would carry a price of ~$0.03$0.05/lb less than the CBT price.)
Historical trends indicate that soybean oil prices have declined overall and
appear to be trending downward despite the rise in 20032004 due to short crops.
Crude oil prices and therefore on-season prices for #2 heating oil prices have
increased more or less steadily with some fluctuation. The ten-year historical
prices of soybean oil and #2 diesel fuel are shown below. During 20002002 soy-
bean oil prices were actually lower than #2 heating fuel, despite being significantly
higher previously. The recent spike in soybean oil prices in 20032004 to histori-
cal highs was due to decreased production due to weather and availability, but have
TABLE 5.5
Energy Content of Heating Fuels (Volume Basis)
% Difference
Material Weight lbs/gal BTU/gal vs. #2 Fuel oil
#2 Fuel oil 7.1 140067 0
Methyl soyate 7.6 127984 8.63
Crude degummed soybean oil 7.3 130217 7.03

Per gallon Prices

Cents / gallon
June 1994June 2002

Fig. 5.12. Historical prices for heating oil and soybean oil.
now returned to the $1.40/gal range in late 2004. Figure 5.12 shows the ten-year
price history of soybean oil to #2 heating oil.
The #2 heating oil prices are all national averages and do not account for local
differences. An investigation of Energy Information Agency price history shows that
retail heating oil spot prices on season have been by as much as $0.32/gal above the
national average. Prices are generally highest in the east coast states with the highest
prices occurring in the mid-Atlantic.
In their March, 2004, U.S. Baseline Briefing Book, the Food and Agricultural
Policy Research Institute (FAPRI) noted that U.S. soybean yields in 2003 fell to the
lowest level in ten years. This, in turn, resulted in sharply higher soybean prices in
20032004 (23). Looking forward, FAPRI projects a rebound of soybean production
in 2004 to 2.87 billion bushels or an increase of 450 million bushels nationally. At this
level, farm prices should fall from an average of $7.24/bu to $5.63/bu.
FAPRI also projects soybean oil prices to fall steadily over the next decade
from an average of $27.97/cwt in 200304 to only $19.45/cwt in 20132014. This

106 B.M. Tao
Price Comparison with 20% Subsidy on Soy

Cents / gallon
June 1994June 2002
Fig. 5.13. Comparative historical prices for heating oil and subsidized soybean oil.
happens due to a gradual increase in carryover stocks from 1 billion to 1.6 billion
lbs. During this same period production increases by 500 million lbs while total
utilization increases by 400 million lbs. If this is correct, the price of soybean oil as
a biofuel for heating purposes would be ~$1.42/gal. One can only speculate what
the price of petroleum may be in 2014 for comparison.
Potential Economic Impact of Biodiesel Subsidies

For biodiesel alkyl esters, the Commodity Credit Corporation (CCC) of the USDA has
subsidized sales of biodiesel fuel replacements for petro-diesel fuel. While subject to a
variety of constraints, the subsidies generally pay ~20% of the cost of the raw com-
modity soybeans. If this same subsidy were applied to soybean oil for use as a heating
fuel, Figure 5.13 shows the relative prices versus #2 heating fuel. As this chart indi-
cates, at subsidized levels similar to biodiesel fuel, historical soybean oil prices would
have been consistently below wholesale prices for #2 heating oil for the last decade.

Recently, the passage of the American JOBS Creation Act of 2004 created an
economic incentive for the use of biodiesel fuels, including use as heating fuels. This
incentive essentially reduces the heating fuel cost approximately one cent per percent-
age of biodiesel used in fuel blends. While this type of incentive does not yet exist for
soybean oil used as heating fuel, a low level of subsidy would certainly be beneficial in
opening new markets for soybean oil utilization and could help stabilize consumer cost
for heating oil, as well as providing long-term domestic economic stimulus.
Conclusions
Technical Advantages/Limitations of Biofuels
The main technical advantages of vegetable-based biofuel blends are lower SOx
emissions, potentially lower NOx emissions, zero net carbon dioxide emissions,
and ease of use in existing fuel delivery and home furnaces without modification.
Both biofuels have limitations with respect to cold temperature behavior and vis-
cosity which restrict blends to ~2030% to meet existing ASTM standards. These
fuels also have significant benefits as domestically produced fuels to replace petro-
chemical fuels, with the commensurate benefits in energy security and support for
domestic agricultural industries. As noted by VanLanningham (13) it may be pos-
sible to use higher levels of biofuels in home heating applications provided furnace
designs can be modified to handle higher fuel viscosities. However, there are some
significant differences between these fuels as summarized in the Table 5.6.
It is unclear that the NOx emissions are significantly different for these fuels,
given the differences in air-flow and operating conditions. The higher viscosity of
vegetable oil is significant in that it affects the atomization process and hence the
combustion process. This can be managed by changing fuel nozzles. The issue of
methyl esters as excellent solvents may be an issue for existing furnaces. Methyl
ester blends have been anecdotally observed to actually clean old residues and pre-
cipitated materials from fuel oil tanks and systems. It has been noted that methyl
esters can swell and dissolve a variety of elastomers used in fuel applications, so
care must be taken to replace seals in older pumps/furnaces if this biofuel is to be
used. These issues do not occur with soybean oil biofuel blends.
TABLE 5.6
Advantages and Limitations of Biofuels
Type of biofuel Advantages Limitations

Vegetable oil Low cost Higher viscosity
Ready availability Possibly higher
NOx emissions
Biodiesel/methyl esters Lower viscosity Higher cost

Higher blend compositions Pump elastomer compatibility

108 B.M. Tao
The partial (20%) substitution of crude degummed heating oil or biodiesel for #2
heating oil is technically feasible with little or no change in existing equipment or
infrastructure. The economic feasibility of using biofuels in heating fuel depends on
the relative commodity prices of the fuels, which fluctuates significantly. Historically,
the price of soybean oil has been above that of #2 fuel oil, other than for the
20002002 period, but with recent trends of increasing petroleum prices and future
trends of soybean oil prices declining, soybean oil is predicted to be lower in cost than
#2 heating oil. Therefore, use of soybean oil in home heating fuel applications appears
to have a significant economic advantage. Biodiesel is currently significantly more
expensive than #2 heating oil, almost twice as much. The use of biodiesel as a substi-
tute for home heating oil is economically feasible only on a spot basis and only when
subsidies are applied. If current subsidies available for biodiesel as a transportation
fuel (roughly $1/gal) are available for home heating applications, this would bring the
price of biodiesel to approximately the same level as current #2 heating oil. If such a
subsidy were available for degummed soybean oil as a heating fuel, it would be a
tremendous economic advantage, bringing the price down to ~$0.40/gal. Of course all
this must be compared to the cost of petroleum as a heating fuel. Given the assump-
tion that the price of petroleum will significantly rise over the next decade, the use of
either biofuel in home heating applications promises to be both economically and
environmentally beneficial.
References
1. www.eia.doe.gov. Department of Energy, Residential Energy Consumption Survey
2001, Consumption and Expenditure Data Tables, http://www.eia.doe.gov/emeu/recs/
recs2001/detailcetbls.html#total, Total Energy Consumption in U.S. Households, 2001,
http://www.eia.doe.gov/emeu/recs/recs2001/ce_pdf/enduse/cel-9c_ne_region2001.pdf,
accessed 3/17/05.
2. DeRosa, L., BIOHEAT: Emerging Markets Emerging Markets, National Biodiesel
Conference, Palm Springs, CA (2004).
3. Bamberg, S. C., A Total Look at Oil Burner Nozzles, Delavan, Inc., Bamberg, SC, p. 36
(2000).
4. Poulet, G., General Description of Atmospheric Chemistry, in Pollutants from
Combustion: Formation and Impact on Atmospheric Chemistry, C. Vovelle, ed., Kluwer
Academic Publishers, Boston, MA, p. 339 (2000).
5. McDonald, R. J., and J. Batey, Benefits and Advantages of Marketing Low Sulfur Heating
Oil Including Results from a New York State Low Sulfur Market Demonstration, The 2003
National Oilheat Research Alliance Technology Symposium, Brookhaven National
Laboratory, Boston, MA (2003).
6. Butcher, T., and C. R. Krishna, NOxHow Low is Achievable with Oilheating
Combustion Systems, The 2003 National Oilheat Research Alliance Technology
Symposium, Brookhaven National Laboratory, Boston, MA (2003).
7. Hedden, B., ed., NORA Oilheat Technicians Manual, National Oilheat Research
Alliance, Alexandra, VA (2003).
8. Schmidt, P. F., Fuel Oil Manual, Industrial Press Inc., New York (1969).

9. Irwin, R. J., Environmental Contaminants Encyclopedia: Fuel Oil Number 2Heating

Oil Entry, Fort Collins, CO, National Park Service: 29 (1997).
10. Williams, A., Combustion of Liquid Fuel Sprays, Butterworths, London, England,
(1989).
11. Snyder, H. E., and T. W. Kwon, Soybean Utilization, Van Nostrand Reinhold, New
York (1987).
12. Krishna, C. R., and T. A. Butcher, Update on Use of Biodiesel Blends in Boilers, The
2002 National Oilheat Research Alliance Technology Symposium, Providence, RI,
Brookhaven National Laboratory (2002).
13. VanLanningham, N.W., Soybean Oil Containing Triglycerides as a Renewable
Component in Residential Heating Applications, M.S. Thesis, Purdue University
(2003).
14. Krishna, C. R., Biodiesel Blends in Space Heating Equipment, National Renewable
Energy Laboratory, Upton, NY, NREL/SR-510-33579 (2001).
15. Krishna, C. R. and R.J. McDonald, The Green Fuel Option for the Oilheat Industry
Biofuel Research, The 2003 National Oilheat Research Alliance Technology Symposium,
Brookhaven National Laboratory, Boston, MA (2003).
16. Bowman, C. T., Gas-Phase Reaction Mechanisms for Nitrogen Oxide Formation and
Removal in Combustion, in Pollutants from Combustion: Formation and Impact on
Atmospheric Chemistry, C. Vovelle, ed., Kluwer Academic Publishers, Boston, MA, p.
339 (2000).
17. Batey, J., Combustion Testing of Biodiesel Fuel Oil Blends in Residential Oil Burning
Equipment, The 2003 National Oilheat Research Alliance Technology Symposium,
Brookhaven National Laboratory, Boston, MA (2003).
18. Lee, S. W., I. He, T. Herage, and B. Young, Laboratory Investigation on the Cold
Temperature Combustion and Emission Performance of Biofuel Blends, The 2003
National Oilheat Research Alliance Technology Symposium, Brookhaven National
Laboratory, Boston, MA (2003).
19. Martin, J., Value-Added Products from Soybeans: An Economic and Environmental
Assessment of Potential Products Using Expelled Soybean Oil and Meal, OmniTech
International (2004).
20. National Institute for Standards and Technology, NIST Life Cycle Analysis, 2004.
21. Batey, J., C.R. Krishna, T. Butcher, and R.J. McDonald, Combustion Testing of a
Biodiesel Fuel Blend, National Biodiesel Conference, Palm Springs, CA January
(2004).
22. Biodiesel, Next Step Home Heating Oil, www.biodiesel.org/markets, accessed 3/17/2005.
23. FAPRI, 2004 U.S. Baseline Briefing Book, FAPRI-UMC Technical Data Report 01-04
Published by the Food and Agricultural Policy Research Institute (FAPRI), University
of Missouri-Columbia, 2004.

Chapter 6
Vegetable Oils-Based Polyols

Andrew Guo and Zoran Petrovic
Kansas Polymer Research Center, Pittsburg, KS 66762
Introduction
Natural fats and oils normally consist of triglycerides of a mixture of fatty acids
(FA). The FA part represents around 90% by weight and the glycerine part around
10% of the fat/oil molecule. The individual FA are characterized by the number of
carbon atoms in the hydrocarbon chain, ranging generally from C8 (caprylic acid)
to C22 (erucic acid) and additionally by the number of the double bonds in the
chain. Typical FA compositions of selected natural oils are shown in Table 6.1.
One of the naturally occurring oils with an unusual chemical structure is castor oil,
which typically comprises about 87% ricinoleic acid and has an average hydroxyl
functionality of 2.7.
Polyurethanes are probably the most versatile group of polymers which can be
used in the form of foams, cast resins, coatings, adhesives, and sealants. Polyols
used in the polyurethane industry currently exceed 2.4 million tons/year in the U.S.
(1). To use natural oils as raw materials for polyurethane production, multiple
hydroxyl functionality is required. Castor oil has hydroxyl functionality naturally
built in, thus it has received extensive exploration as polyurethane building blocks,
such as casting resins, elastomers, urethane foams, and interpenetrating networks
(28). Hydroxyl functionality can be introduced synthetically in other natural oils.
This process involves a number of approaches and has been studied extensively by
scientists around the world (2,947), but commercial production of oil-based poly-
ols has been scarce. While the economics of the associated processes is certainly a
large factor, properties of the product conforming to end-use play an important
role.
Many problems remain to be solved. For example, commercial polyols for
rigid urethane foams require an OH number of 450500 mg KOH/g. Rigid foam
production also requires the viscosity of the polyol component to <2,000 centipois-
es under ambient conditions for the purposes of easy processing and optimal prod-
uct performance. Most oil-based polyols do not satisfy both requirements at the
same time. Some of them have the right viscosity but have a low OH content; oth-
ers have a high OH content but have turned to greases. Still others have lost their
triglyceride linkagesan additional crosslinking naturally built into each oil mole-
cule that enhances crosslinking and thus rigidity. Secondly, studies on the effect of
110

TABLE 6.1
Typical Fatty Acid Compositions of Selected Plant Oilsa
Carbon atoms: 8:0 10:0 12:0 14:0 16:0 16:1 18:0 18:1 18:2 18:3 20:0 20:1 22:0 22:1 24:0 Iodine
Double value
3/23/05
bonds range
Canola oil 0.1 4.0 0.3 1.8 60.9 21.0 8.8 0.7 1.0 0.3 0.7 0.2 100115
Castor oilb 2.0 1.0 7.0 3.0 8191
Coconut oil 7.1 6.0 47.1 18.5 9.1 2.8 6.8 1.9 0.1 0.1 712
6:29 PM
Corn 0.1 10.9 0.2 2.0 25.4 59.6 1.2 0.4 0.1 118128
Cottonseed oil 0.1 0.7 21.6 0.6 2.6 18.6 54.4 0.7 0.3 0.2 98118
Linseed oil 6.0 4.0 22.0 16.0 52.0 0.5 >177
Olive oil 9.0 0.6 2.7 80.3 6.3 0.7 0.4 7688
Palm oil 0.1 1.0 44.4 0.2 4.1 39.3 10.0 0.4 0.3 0.1 5055
Page 111
Palm kernel oil 3.3 3.4 48.2 16.2 8.4 2.5 15.3 2.3 0.1 0.1 1419
Peanut oil 0.1 11.1 0.2 2.4 46.7 32.0 1.3 1.6 2.9 1.5 84100
Rapeseed oil 0.1 3.8 0.3 1.2 18.5 14.5 11.0 0.7 6.6 0.5 41.1 1.0 100115
Safflower oil 0.1 6.8 0.1 2.3 12.0 77.7 0.4 0.3 0.1 0.2 140150
Safflower oil 0.1 3.6 0.1 5.2 81.5 7.3 0.1 0.4 0.2 1.2 0.3 8292
(high oleic)
Soybean oil 0.1 10.6 0.1 4.0 23.3 53.7 7.6 0.3 0.3 123139
Sunflower oil 0.1 7.0 0.1 4.5 18.7 67.5 0.8 0.4 0.1 0.7 125140
Sunflower oil 3.7 0.1 5.4 81.3 9.0 0.4 0.1 8191
(high oleic)
aSome oil compositions may not add to 100% due to the presence of minor fatty acids. Source: Reference 48.
bContains 87% OH-bearing ricinoleic acid (C18:1).

112 A. Guo and Z. Petrovic
polyol structures derived from different vegetable oils on polyurethane properties

have been largely lacking. However, such information is critical to the develop-
ment of oil-based polyols, particularly regarding whether the methodologies
employed for one oil can be adopted by another, or whether certain less available
oils can be replaced by abundant oils in general polyurethane applications. On the
other hand, oleochemical research peaked in the 1970s when a number of commer-
cially feasible processes were identified (49).
Since then the associated technologies have advanced a great deal, thus prompt-
ing new opportunities for research and development of better processes. For example,
most current commercial processes for the epoxidation of vegetable oils still rely on
methodologies developed in the late 1940s, which do not lead to complete epoxida-
tion, while a recent procedure using phase-transfer reagents was reported to result in
quantitative epoxidation (50,51). As a second example, hydroformylation of olefins
traditionally uses the vaporization technique for product-catalyst separation, which is
not feasible for low-volatile substrates such as vegetable oils. Such a situation
changed after Union Carbide developed the decantation process in the 1980s (5259).
Meanwhile, bulky phosphite-modified rhodium catalysts have been developed that
show high reaction rates toward less reactive internal or branched olefins including
fatty esters (5,6072). Therefore, the development of a commercial process for the
hydroformylation of fatty substances may have become imminent.
Preparation of Polyols from Vegetable Oils

The hydroxylation of vegetable oils can be achieved via four main approaches
(Scheme 6.1). The first approach is the epoxidation or oxidation of the unsaturation
followed by the ring-opening of the epoxides with proton donors (Scheme 6.1,
Route I) (9,1114,1618,21,38,43,44,7387). Secondary OH groups normally
result from these procedures. A second approach of introducing hydroxyl function-
ality is the catalytic hydroformylation of the oils followed by reduction of the alde-
hyde oils (Scheme 6.1, Route II) (10,37,39,68,74,88107), with primary OH
groups being formed. Hydroxyl functionality can also be obtained by transesterifi-
cation of oils with various types of polyols (Scheme 6.1, Route III) (84,108116).
Microbial conversion of oils to obtain polyhydroxy substances is also an emerging
field (Scheme 6.1, Route IV) (117121). A large number of publications and
patents have appeared in the literature over the years.
The selection of vegetable oils depends mainly on the unsaturation level.
While higher unsaturation of the oils leads to a higher OH content of the corre-
sponding polyol, above a certain hydroxyl level the polyol suffers from a high vis-
cosity. The theoretical OH numbers of vegetable polyols derived via the epoxida-
tion route and the hydroformylation route are presented in Table 6.2. While
coconut and palm kernel oils are of little value as polyol raw materials (i.e., OH
number is too low), linseed oil has been reported to give a polyol behaving as a
grease (10,96,97,122,123). Partial conversion of the double bonds in linseed oil

Vegetable Oils-Based Polyols 113
Scheme 6.1. Hydroxylation of vegetable oils.
may be optionally pursued to avoid high viscosity. The epoxidation of castor oil
will be complicated because of the coexistence of oxirane and hydroxy groups
(124). The hydroformylation of castor oil will produce a mixture of primary and
secondary OH groups (2). Some oils appear to have similar composition such as
soybean, corn, and sunflower oils. Triolein, trilinolein, and trilinolenin are includ-
ed for comparison purposes.
Epoxidation and Alcoholysis

Each double bond in the oil molecule can be monohydroxylated or dihydroxylated
depending on the use of oxidizing agents. The most studied monohydroxylation
reaction involves a first epoxidation step using hydrogen peroxide, followed by a
ring-opening step (Scheme 6.1, Route I) (9,1114,1618,21,32,38,43,44,7387).
Swern and Greenspan were among the first to epoxidize vegetable oils using per-
acetic acid (78,80,125138). Most commercial processes available today producing

TABLE 6.2
Theoretical OH Number of Polyols from Plant Oils and Model Triglycerides
Oil molecular Total OH number OH number

Oil type weight unsaturationa Ab Bc
Coconut oil 679 0.3 26 27
Palm kernel oil 707 0.6 46 46
Palm oil 848 1.8 109 113
Olive oil 878 2.9 158 166
Safflower oil (high oleic) 886 2.9 159 166
Sunflower oil (high oleic) 883 3.0 163 171
Triolein 885 3.0 163 171
Peanut oil 884 3.4 181 191
Rapeseed oil 953 3.9 190 201
Canola oil 882 3.9 206 219
Cottonseed oil 862 3.9 209 222
Corn 873 4.5 230 246
Soybean oil 874 4.6 236 253
Sunflower oil 877 4.7 239 256
Safflower oil 876 5.1 254 274
Trilinolein 879 6.0 288 314
Linseed oil 878 6.3 299 327
Castor oild 928 3.1 307 322
Trilinolenin 873 9.0 387 435
aNumber of double bonds per triglyceride based on Table 6.1.
bEpoxidation followed by methanolysis (addition of HO and CH3O on each side of the double bond).
cHydroformylation followed by hydrogenation (addition of HOCH and H on each side of the double bond).
2
dNatural OH groups have been counted into the total OH number.
epoxidized oils are still based on the same principle. The process involves the in situ
formation of peracid from glacial acetic or formic acid and H2O2 (Eq. 1), and oxida-
tion of double bond by peracid to form epoxide regenerating acetic/formic acid at the
same time (Eq. 2). H2O2 is consumed as a result:
[1]
[2]
Quantitative conversions of double bond to epoxide are expected if the reaction

time is long enough. However, side reactions become competitive after a certain
period of time. Such side reactions involve the ring-opening of oxiranes by acetic
acid or water (by-product), and further reaction of formed hydroxyl groups with
oxiranes leading to polyether formation, which results in loss of epoxide content
and/or rise in product viscosity (78,80,126). Therefore most epoxidation processes
are stopped prematurely, resulting in typically 7590% yield of epoxide.

While this level of epoxide content is sufficient for commercial productswhose

uses are as plasticizers for polyvinyl chloridethe preparation of polyols desires a
maximized epoxidation. A number of new procedures have developed in recent years
toward expediting the epoxidation process by using catalysts, applying pressure, using
phase-transfer reagents (PTR), or using other oxidizing agents (50,51,79,124,
139158). Among others, catalysts used include ion-exchange resins, sulfuric acid,
molybdenum or tungsten oxide, and methyltrioxorhenium/pyridine. Quaternary
ammonium salts of tetrakis(diperoxotungsto)phosphates(3-) are PTR reportedly effi-
cient for the epoxidation of vegetable oils (51). The use of these reagents in conjunc-
tion with medium-strength hydrogen peroxide (30%) as the primary oxidant in an
aqueous/organic biphase system provides an efficient, versatile, and synthetically valu-
able catalytic method for olefin epoxidation. By this method, a variety of water-insolu-
ble inactivated alkenes, internal or terminal, acyclic or cyclic, isolated or carrying
diversified functionalities, were epoxidized in high yields under mild conditions and
after relatively short reaction times. The process normally requires no solvents, and the
use of medium-strength hydrogen peroxide also lessens safety concerns associated
with the explosion hazard of various peroxides. Crivello has recently demonstrated
that a series of vegetable oils were epoxidized in high yield by using either a PTR or a
sulfonated ion-exchange resin (50,158162). Methyltrioxorhenium/pyridine has also
recently been reported to be a very efficient catalyst for the epoxidation of soybean oil
(139), although the process suffers from the toxicity of pyridine.
The dihydroxylation of fatty substances has been studied by a number of
workers (124,126,130,153,163167). Osmium, selenium, titanium, and other cata-
lysts have been reported. Although they are efficient for discrete FA derivatives,
some of the procedures involve strongly basic conditions that would hydrolyze the
triglyceride and thus are generally not applicable to vegetable oils. For example,
according to the authors observation, H2O2/OsO4 gives a grease for the oxidation
of soybean oil with a low OH content, while SeO2 is believed to form a complicat-
ed mixture of products if applied to neat linoleic acid. The toxicity of osmium
excludes its use in a commercial process, even in catalytic amounts. Therefore
dihydroxylation procedures have been pursued scarcely.
Although the very reactive oxirane groups in the epoxidized oil molecule enable
a number of ring-opening reactions to convert the epoxidized oils to hydroxylated oils,
such as carboxylation, alcoholysis, hydrolysis, or hydrogenation (Scheme 6.2)
(9,1114,1618,21,33,34,37,44,47,7387), not all are applicable to the preparation of
polyols. According to the authors experience with the soybean oil system, carboxyla-
tion (Route A) leads to a number of complications (oligomerization, cyclization and
esterification) resulting in a high viscosity and a low OH content of the polyol.
Hydrohalogenation or hydrohyperhalogenation (Routes B and C) gives rise to very
good conversion of the material, but the products are highly viscous greases under
ambient conditions. Hydrogenation of ESBO (Route F) gives a semi-solid with a
melting range of 4060C. Hydrolysis (Route E) produces a viscous product having
half of the expected OH content owing to the presence of a number of side reactions.

Scheme 6.2. Hydroxylation reactions of epoxidized oil, where Y = OC(O)R for (A); X
for (B); OX for (C); OR for (D); OH for (E) and H for (F), and X = Cl or Br.
Alcoholysis (Route D) is the only workable approach to prepare oil-based polyols.

Epoxidized soybean oil can be alcoholyzed almost quantitatively in the presence of an
acid catalyst, and the polyols produced as such possess low viscosities and nearly the-
oretical OH contents (18,33,34, 37,44,47).
A series of vegetable oil-based polyols have been prepared via a two-step
process starting from the vegetable oils, i.e., epoxidation by m-chloroperoxybenzoic
acid, or by hydrogen peroxide catalyzed by a PTR or a sulfonated resin (50,158), fol-
lowed by methanolysis (18,38). Some of the polyols prepared from m-chloroperoxy-
benzoic acid suffered from incomplete epoxidation as evidenced by Fourier trans-
form infrared (FT-IR) and nuclear magnetic resonance (NMR) results of epoxidized
samples, indicating that m-chloroperoxybenzoic acid is not an efficient peroxidant,
while the PTR or resin-catalyzed epoxidation proceeded smoothly. The epoxidation
products generally require purification before the hydroxylation step.
FT-IR has proved to be an effective tool for the analysis of epoxidized oils.
The double bond in the oil molecule shows a strong absorbance at 3011 cm1 (C-H
stretch), while the oxirane groups give a weak but distinctive twin band at 823
cm1 (deformation) and 845 cm1 (asymmetric stretch), and a shoulder band at
1263 cm1 (symmetric stretch). The intensity change in these bands during epoxi-
dation is sharp enough to monitor the progress, although 1H-NMR can be equally
effective (5.4 ppm for vinylene protons, and 2.9/3.1 ppm for epoxy methine pro-
tons). However, FT-IR is only qualitative for the measurement of polyol OH con-
tent since the OH band at 3440 cm1 is very broad and is highly sensitive to impu-
rities containing OH groups.
Catalytic Hydroformylation and Reductive Hydrogenation

Hydroformylation of olefins has become a very mature and important industrial
process since its discovery in 1938 (168). Olefins can be hydroformylated by treat-

ment with syngas and a catalyst, yielding aldehydes that contain an additional car-
bon atom. This reaction is a mild and clean procedure for functionalizing unsatu-
rated compounds and is compatible with many other functional groups, such as
esters, carboxyls, amides, ketones and even hydroxyls. The atom economy of the
reaction is 100%, i.e., all atoms of the reactants end up in the product (169), which
results in a minimum of chemical waste discharge (Scheme 6.3). The aldehydes
produced form the base for many subsequent transformations leading to alcohols
(reduction), amines (reductive amination), carboxylic acids (oxidation), acetals,
etc. Significant advancements in hydroformylation have been made over the last
few decades. Aspects involve: (i) catalyst/ligand modification; (ii) product/catalyst
separation; (iii) process modification including heterogeneous and biphasic cataly-
sis, low pressure hydroformylation, and the addition of decanting process and cata-
lyst recycling. Over the years, people all round the world have showed tremendous
interest in the oxo processes. Hundreds of scientific publications and patents
appear each year.
The three main types of catalyst used commercially are (i) simple cobalt car-
bonyl complexes, (ii) cobalt carbonyl complexes modified by tertiary phosphine/
phosphite ligands, and (iii) tertiary phosphine/phosphite rhodium carbonyl species.
Although most industrial processes still use cobalt, more than 90% of the oxo
plants built since 1977 use rhodium-based catalysts and low-pressure oxo (LP
OXO) technology developed by Union Carbide.
Other metals such as iridium, platinum, ruthenium, manganese, iron, copper,
silver, bimetallic species and metal clusters are also known catalysts. Polymer-sup-
ported and other heterogeneous catalysts have also been developed. These catalyst
systems are all in the research stage, and still far from commercialization.
Cobalt has been the conventional catalyst for hydroformylation. However,
cobalt is not a very active catalyst. It requires high temperatures and high pressures
[typically 140180C at 250350 bars, see Table 6.3 (170)]. High temperatures
Scheme 6.3. Hydroformylation of olefins.

TABLE 6.3
Comparison of Olefin Hydroformylation Catalystsa
Unmodified Phosphine-modified Phosphine-modified

cobalt cobalt rhodium
Temperature (C) 140180 160200 80120
Pressure (bar) 250350 50100 1525
Catalyst concentration 0.11.0 0.51.0 102103
(% metal/alkene)
Linear/branched ratio 34:1 68:1 1014:1
Aldehydes (%) 80 none 96
Alcohols (%) 10 80 none
Alkanes (%) 1 15 2
Other products (%) 9 5 2
aUsing -olefin as feedstock (170).
degrade selectivities since side reactions have become a problem. Such side reac-
tions include hydrogenation of aldehydes to alcohols and of olefin to alkanes, aldol
additions of aldehydes to give dimer aldehydes and ester triols, hydroformylation
of aldehydes to formate esters, and reaction of aldehydes with byproduct alcohols
to give acetals. Meanwhile, high-pressure operations require expensive construc-
tion of process plants. Phosphine or phosphite modification of the cobalt catalyst
leads to reduction of the process pressure (down to 50100 bars). However, there
is a significant amount of hydrogenation by-products being produced (15%) along
with the rapid reduction of the aldehyde to alcohol (80%) during hydroformylation
(although this anomaly may be advantageous to this project since the reduction
step is eliminated). On the other hand, the rhodium catalyst requires only very low
process pressures (1525 bars) and also lower temperatures (80120C) resulting
in nearly quantitative conversion (96%) of olefin to aldehyde.
The discovery in the early 1980s by Bryant (Union Carbide, Charleston, WV)
and van Leeuwen (Shell Lab, Amsterdam, The Netherlands) of bulky phosphite
ligand modified catalysts showing high reaction rate for otherwise unreactive
(internal and branched) olefins is a major breakthrough in hydroformylation cataly-
sis (5,6072). Owing to their high reactivity, these bulky phosphite-modified cata-
lysts have offered new possibilities for the development of a commercial process
for the hydroformylation of FA and derivatives including vegetable oils. Significant
progress has also been made in the area of product/catalyst separation for the hydro-
formylation of higher olefins. Hydroformylation as a homogenous process has tra-
ditionally used the vaporization technique in commercial processes, but they are
limited to those with volatile products, i.e., to the hydroformylation of lower
olefins. The recent introduction by Union Carbide of a single-phase oxo process by
using organic media-soluble ionic triarylphosphines or phosphites ligands and of
product/catalyst separation by decantation has revolutionized the hydroformylation
technology. This process permits the hydroformylation of higher molecular weight

and non-volatile olefins such as fatty substances. The single-phase rhodium-ionic

phosphine catalysts have the reactivity typical of conventional homogenous hydro-
formylation catalysts. However, they can be easily induced to separate into non-
polar (product) and polar (catalyst) phases, thereby providing an effective means
for product separation and catalyst recovery (52,5457,59,171182).
A variation of the Union Carbide single-phase oxo process has been under the
extensive investigation of Fell et al. (98,183,184). This process allows the hydro-
formylation of polyunsaturated substances such as FA esters in a polar solvent
(methanol) in the presence of a rhodium-ionic phosphine catalyst. After the reac-
tion, the methanol is distilled off; the catalyst system becomes insoluble and can be
separated from the reaction product by filtration or by extraction with water. The
aqueous catalyst solution is evaporated to dryness and the catalyst system dis-
solved in methanol for a new reaction. However, the process is limited to polar
media-soluble fatty substances applying a fairly high pressure (e.g., 70200 bars).
Heterogeneous systems using supported rhodium catalysts for the hydroformyla-
tion of fatty substances were also studied and it was concluded that these systems
are limited to the hydroformylation of mono- and diunsaturated FA (e.g., oleates
and linoleates) and are ineffective with triunsaturates (e.g., linolenates).
USDAs research activities on the hydroformylation of fatty substances were
during the 1970s (2,10,8890,9296,100103,106,107,122,185190). A number of
vegetable oils were investigated including soybean, linseed, castor, safflower oils,
and their derivatives. While the hydroformylated fatty products were suggested for
uses as plasticizers for polyvinyl chloride and as coatings, rigid urethane foams
prepared from hydroformylated polyols were also reported. The best catalyst sys-
tems used at the time were triphenylphosphine- or triphenylphosphite-modified
rhodium catalysts normally requiring at least 2,000 psig of syngas pressure,
although a much lower pressure (200 psig) is needed for methyl oleate. Although
monounsaturated fatty substances can be readily hydroformylated under mild con-
ditions, di- and triunsaturated FA derivatives were found to require higher pres-
sures owing to the presence of -allylic intermediates, which slowly undergo
hydroformylation. The isomerization of double bonds from cis to trans and that
from nonconjugated to conjugated have been noted by several workers, and it has
been understood that these phenomena are responsible for the slowdown in hydro-
formylation rate (61,62,64,69,71,72,95,103,191).
Although much attention has been paid to the regioselectivity issue on the hydro-
formylation of various olefins, this information may have limited value as far as the
preparation of oil-based polyol is concerned. The hydroxymethyl groups will be locat-
ed internally in the FA chains, the positions of which differ by only one carbon atom.
Since each triglyceride molecule contains many isomers randomly distributed in the
three fatty chains, it would be impossible to identify the effect of isomerization on the
properties of the crosslinked polyurethane materials, even if a model triglyceride is
used. The same is true of the polyols prepared from the epoxidation approach, where
the secondary OH groups may be placed in either side of the double bond.

A recent study has proved that the bulky phosphite-modified rhodium catalyst
is several times more active than triphenylphosphine-modified catalyst (64).
Vegetable oil-based polyols have been prepared using Rh/C (5% rhodium on car-
bon) or Rh(CO)2(acac) as catalyst precursors. Polyols of this type are expected to
have an OH number and a viscosity in the same range of polyols prepared via the
epoxidation route (see Table 6.2). When tris(2,4-di-t-butylphenyl) phosphite is
used as ligand using an olefin/Rh molar ratio of 8001,000, P/Rh ratio of 25, and a
total pressure of 5001,000 psig, the reaction is completed within a few hours at
100C, as is evidenced from the soybean oil system.
Bidentate phosphite ligands (192196) and ionic phosphite ligands (54,57,
59,178) have also been examined. Whatever the case, the spent rhodium must be fully
recovered in order to be commercially practical. The reductive hydrogenation of alde-
hyde oils has been conducted at 1,000 psig of hydrogen pressure using Raney nickel
as the catalyst as demonstrated by many workers (2,186,197). Sodium borohydride
can alternatively be used, but reaction conditions have to be controlled carefully in
order not to hydrolyze the triglyceride linkages. Kinetic study has been carried out to
characterize the catalyst reactivity. These aspects include varying the temperature, H2
and CO pressures, catalyst concentration, and ligand-to-metal ratio. Since the kinetics
for the hydroformylation of vegetable oils is very complicated owing to the presence
of a mixture of olefins (mono-, di-, and trienes), triolein, trilinolein, and trilinolenin
have been used for the kinetic study (104,105).
For the analysis of hydroformylated products, FT-IR is used. The aldehyde groups
give a strong band at 1728 cm1 (C=O stretch, shoulder to triglyceride carbonyl at
1744 cm1) and a medium broad band at 2701 cm1 (C-H stretch/bend). The intensity
change in these bands can be used to monitor the progress of hydroformylation. NMR
can also be optionally employed. Vinylene protons are at ca. 5.4 ppm and the aldehyde
proton appears further downfield (ca. 10 ppm). The carbonyl content of the aldehyde
oil can also be analyzed according to a titrimetric procedure (198).
Transesterification
The transesterification of vegetable oils with glycerine leads to the formation of mono-
and diglycerides. A polyol is formed in a single-step transformation and thus the
process is of interest from the commercial point of view (84,108116,199). Other
polyhydroxy compounds can be used in the place of glycerine such as trimethylol-
propane, pentaerythritol, among others. However, this process leads to no hydroxyla-
tion of the double bonds in the FA chain. The FA chains are simply dangling, and thus
may not contribute to mechanical strength of the end products. These chains may actu-
ally lower the mechanical properties of the products due to their plasticizing effect.
Microbial Conversion
The microbial hydroxylation of oils is an emerging field (117121,200). Polyols
are produced in a single step under mild conditions using an enzyme as the catalyst

and oxygen from the air and/or water as the reagents. In contrast to the chemical
processes mentioned above (i.e., epoxidation, and hydroformylation) where the
hydroxy groups are attached to the double bond positions in the FA chain, the
hydroxyls generated enzymatically are normally alpha to the double bonds in the
chain. Although these processes appear attractive environmentally, they are still far
from the commercial stage mainly due to the overwhelming cost of the catalysts.
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Chapter 7
Development of Soy Composites by Direct Deposition

Zengshe S. Liu and Sevim Z. Erhan
Food and Industrial Oil Unit, National Center for Agricultural Utilization Research,
Agricultural Research Service, United States Department of Agriculture, Peoria, IL 61604
Introduction
Composites are materials comprised of two or more components that differ in their
chemical and physical properties, which have been combined to promote specific
characteristics for particular uses. In general, composites correspond to a class of
heterogeneous multiphase materials. One of the components (discontinuous) sup-
plies the strength (structural component or reinforcement), and the other (continu-
ous) is the medium of stress transfer (matrix). These components are not mutually
dissolved, but they act in a synchronized way, and the material as a whole offers a
satisfactory performance (1).
The polymeric matrices are more common in composites, although there are
composites having other types of matrices, such as a metallic matrix. The most
used thermosetting resins in high-performance advanced composites are the pheno-
lics, epoxies, polyimides, bismaleimides, and cyanate ester resin systems. These
resins exhibit both excellent solvent and high-temperature resistance. It has been
estimated that >75% of all polymeric matrices in composites are thermoset poly-
mers. Thermosetting polymers are resins that crosslink during the curing. Curing
involves the application of heat and pressure or the addition of a catalyst.
Polymeric materials prepared from renewable natural resources have been
enjoying a continuous growing interest in the past decade from the academic and
applied point of view. The advantages of these polymers are their low cost, easy
availability, and possible biodegradability (2). Among products from agricultural
resources, natural oils may constitute raw materials useful in polymer synthesis.
Annually, the United States produces ~450 thousand tons of soybean oil in excess
of current commercial need. Thus, developing new materials from soybean oil for
industrial application has become highly desirable. These new materials can open
needed new markets for this important crop.
Epoxies have good adhesion, mechanical properties, low moisture absorption,
chemical resistance, little shrinkage, and ease of processing. These excellent proper-
ties make this family of compounds one of the best matrix materials for many com-
posites (3,4). However, epoxy resins are similar to other engineering resins in that
they are either brittle, notch-sensitive, or both. For load-bearing purposes, this means
that the product may be subject to catastrophic failure. A major effort over the years
has focused on improving the toughness of epoxy structural systems. Qureshi et al. (5)
131

132 Z.S. Liu and S.Z. Erhan
reported that the use of 25% epoxidized crambe oil as a reactive diluent in bisphenol
A and cycloaliphatic epoxy compounds improved resistance to fatigue crack propaga-
tion without significant sacrifice in tensile or impact strength and Youngs modulus.
Massingill et al. (6) formulated neat epoxidized crambe oil with epoxy-amine systems
to give two-phase thermosets. Fracture toughness values of the epoxy thermosets were
increased ~100% by 5 and 10% epoxidized crambe oil. The glass transition tempera-
ture and mechanical properties were affected modestly. Soybean oil is a triglyceride
that contains double bonds. These double bonds may also be converted into the more
reactive oxirane moiety by reaction with peracids or peroxides. In the past, epoxidized
soybean oil (ESO) has been used mainly as a plasticizer for polyvinyl chloride (PVC)
compounds, chlorinated rubber, and polyvinyl acetate (PVA) emulsions. Epoxy-con-
taining soybean oil used as raw material for the synthesis of new polymers suitable for
liquid molding processes was reported by Wool and co-workers (7,8). The preparation
of structurally strong soy-based composites is attractive from both the commercial and
environmental perspectives. Reinforcement materials in soy-based composites can be
glass or natural fiber.
Composites Reinforced with Glass, Carbon, or Mineral Fibers

Composites reinforced with carbon, aramid, and glass fiber dominate the aero-
space, leisure, automotive, construction, and sporting industries. Glass fibers are
most widely used to reinforce plastics due to their low cost (compared with aramid
and carbon) and fairly good mechanical properties. These fibers have serious draw-
backs as indicated in Table 7.1. The shortcomings have been highly exploited by
proponents of natural fiber composites. Table 7.1 compares natural and glass fibers
and clearly shows areas in which the former have distinct advantages over the lat-
ter. The carbon dioxide neutrality of natural fibers is particularly attractive.
Attempts have been made to use natural fiber composites in place of glass mainly in
nonstructural applications. A good number of automotive components previously
TABLE 7.1
Comparison Between Natural and Glass Fibers
Natural fibers Glass fibers

Density Low Twice that of natural fibers
Cost Low Low, but higher than NF
Renewability Yes No
Recyclability Yes No
Energy consumption Low High
Distribution Wide Wide
CO2 neutral Yes No
Abrasion to machines No Yes
Health risk when inhaled No Yes
Disposal Biodegradable Not biodegradable

Development of Soy Composites 133
made with glass fiber composites are now being manufactured using environmen-
tally friendly composites (10,11) .
Composites Reinforced with Natural Fibers

Currently, a great deal of research material is being generated on the potential of
natural fiber as a reinforcement for plastics. Natural fiber may include hairs (cot-
ton, kapok), fiber-sheaves of dicotylic plants, or vessel-sheaves of monocotylic
plants, i.e., bast (flax, hemp, jute, ramie) and hard-fiber (sisal, henequen, coir). The
availability of large qualities of such fiber with well-defined mechanical properties
is a general prerequisite for the successful use of these materials and the lack of
these large quantities is one of the drawbacks at present. Additionally, for several
more technically oriented applications, the fibers have to be specially prepared or
modified regarding the following:
homogenization of the fibers properties;
degrees of elementarization and degumming;
degrees of polymerization and crystallization;
good adhesion between fiber and matrix;
moisture repellence; and
flame retardant properties.
At present, the availability of plant fiber can be only partially ensured (as shown in
Table 7.2).
Their hydrophilic nature is a major problem for all natural fibers if they are
used as reinforcements in plastics. The moisture content of the fibers, dependent on
the content of noncrystalline parts and void content of the fiber, can be as much as
10 wt% under standard conditions (12). The hydrophilic nature of natural fiber
influences the overall mechanical properties as well as other physical properties of
the fiber itself (13). Physical (i.e., corona discharge) and chemical modification
methods (coupling agents such as silanes) are used to change the surface structure
of the fibers as well as to change their surface energy.
TABLE 7.2
Production of Plant Fibers Compared with Production of Glass Fibers (1993)a
Price in comparison to glass fibers Production

Fiber (%) (1000 t)
Jute 18 3600
E-glass 100 1200
Flax 130 800
Sisal 21 500
Banana 40 100
aSource: Reference 9.

Composite Molding Methods

A wide range of different processes have been developed for the molding of composite
parts ranging from very simple manual processes such as hand lay to very sophisticat-
ed highly industrialized processes such as sheet molding compounds. Each process has
its own particular benefits and limitations making it suitable for particular applications.
The choice of process is important to achieve the required technical performance eco-
nomically. The most common molding techniques for the manufacturing of fiber rein-
forcement composites are resin transfer molding (RTM), vacuum-assisted resin injec-
tion (VARI), reinforced reaction injection molding (RRIM), structural reaction injec-
tion molding (S-RTM), vacuum infusion (VI), and solid free-form fabrication (SFF).
These composite molding methods have been used successfully to manufacture prod-
ucts ranging from cosmetic parts with moderate demands for structural properties to
highly load bearing parts of military and aerospace quality.
Resin Transfer Molding (RTM) and Vacuum Assisted Resin Injection

(VARI)
Figure 7.1 shows a schematic of RTM. Fabrics are laid up as a dry stack of materials.
These fabrics are sometimes prepressed to the mold shape, and held together by a
binder. These preforms are then more easily laid into the mold tool. A second
Fig. 7.1. Schematic of resin transfer molding (RTM).

mold tool is then clamped over the first, and resin is injected into the cavity. A vac-
uum can also be applied to the mold cavity to assist resin in being drawn into the
fabrics. This is known as Vacuum Assisted Resin Injection (VARI). Once all of the
fabric is wet, the resin inlets are closed, and the laminate is allowed to cure. Both
injection and cure can take place at either ambient or elevated temperature.
Generally epoxy, polyester, vinyl ester and phenolic resins are used at ambient
temperature, although high-temperature resins such as bismaleimides can be used
at elevated process temperatures. Any kind of fiber can be used as reinforcement.
Stitched materials work well in this process because the gaps allow rapid resin
transport. Some specially developed fabrics can assist with resin flow. The main
advantages are that high fiber volume laminates can be obtained with very low
void contents and with better safety and environmental control due to the enclosure
of the resin. Both sides of the component have a molded surface. Medium large,
complex, and highly integrated components can be produced with low capital costs
and with a good working environment. The main disadvantages are that matched
tooling is expensive and has to be heavy to be able to withstand pressures.
Generally RTM is limited to smaller components.
Reinforced Reaction Injection Molding (RRIM) and Structural Reaction

Injection Molding (SRIM)
This is a fabrication technique involving the extremely rapid impingement mixing
of two chemically reactive liquid streams, injected into a mold that results in the
simultaneous polymerization, cross-linking and formation of the part. This tech-
nique is a form of reactive injection molding (RIM). Figure 7.2 shows a schematic
of RIM. When short fibers (1.6 mm), carbon, or glass or mineral fillers are incor-
porated into one of the two reactive constituents to increase the modulus and
reduce the coefficient of expansion, the process is referred to as reinforced reaction
injection molding (RRIM). The introduction of long-strand reinforcements, such as
continuous filament mats, fabrics, complexes, or chopped strand preforms, into the
mold before the injection takes place, allows parts with higher mechanical perfor-
mance to be obtained. In this case, the process is known as structural reaction
injection molding (SRIM). In each of these technologies, polymeric parts are pro-
duced directly from a mixture of the low-viscous reactants by its injection into a
mold accompanied by fast polymerization and cross-linking reactions. The inher-
ent advantages of RRIM and SRIM are that large parts can be produced with
dimensional stability, chemical resistance, weatherability, and surface reproducibility.
The main disadvantage is that it is difficult to control the volatile organic chemical
(VOC) emissions from the open mold process.
Vacuum Infusion (VI)

The vacuum infusion (VI) process has become prominent in recent years due to
increasing pressure on the control of VOC emissions from the open mold process.

Fig. 7.2. Schematic of reaction

injection molding (RIM).
Figure 7.3 shows a schematic of VI. The basic principal of VI is that reinforcing
fibers are placed in a mold, which is sealed using a plastic film or vacuum bag, and
resin is drawn into the mold under vacuum. It means lower injection pressure than
in the RTM, with the pressure limited to 0.1 MPa. Molds for VI are fitted with a
peripheral channel to enable a vacuum to be applied, and catalyzed resin is fed in
at the center of the part and allowed to diffuse through the reinforcement to the
edge of the mold. The design of the reinforcement and the setting up of the plastic
film or vacuum bag, which normally incorporates tubes or channels to help even
distribution of the resin, are absolutely critical. A major advantage of the VI
process is that it can be reproduced exactly each time without the need to use
skilled laminators. The mold is also fully enclosed during the molding process vir-
tually eliminating VOC emissions. A further advantage of the use of the vacuum is
Fig. 7.3. Schematic of vacuum infusion (VI).

that parts are extremely well consolidated, even with a high fiber content, with
very low air content giving very good structural performance. The investment costs
of VI molding are low, and it is possible to produce larger parts. One disadvantage
of VI is that the excellent consolidation favors thin high-fiber content parts, which
may not have sufficient stiffness. Other disadvantages are that the fiber content is
usually lower than RTM and only one surface of the manufactured composites is
well controlled. The thickness and consequently the fiber content are not as well
defined and uniform as in laminates manufactured by RTM.
Solid Free-Form Fabrication (SFF)

Solid free-form fabrication (SFF) is a method of making shapes without molds. It is
best known in its stereolithography forms as a method of rapid prototyping. In stere-
olithography a laser photopolymerizes successive thin layers of monomer to build up
a solid object. Extrusion solid free-form fabrication was developed by the University
of Arizona in collaboration with Advanced Ceramic Research (Tucson, AZ) (14). It
functions essentially as a three-dimensional (3D) pen plotter. In this case, a slurry is
extruded by a stepper motor pushing on a syringe and forcing the material through a
needle. By moving the syringe over a computer-controlled path, nearly any geometry
can be created (Fig. 7.4). Advantages are that this method has the potential to produce
new materials and complex composites that could not be made in any other way, for
example, objectives with loose enclosed parts (a ball in a box). A typical procedure
for formation of soy composites using SFF is given below.
Fig. 7.4. Sketch of the extrusion free-form fabrication apparatus.

Solid Free-Form Fabrication of Soy Composites

ESO and Epon 828 resin are mixed thoroughly in the weight ratio of 1:0.3. The
mixture is mixed with Aerosil R805 and fibrous fillers. A vacuum is applied to
remove air bubbles. The fiber-filled slurries show a yield point, such that formed
parts hold their shape until cured. A curing agent, diethylenetriamine (DETA), tri-
ethylenetetramine, 60% tech (TETA), or Jefamine EDR 148 is added and the paste
is placed into a 20-mL plastic syringe. Bars 75 mm 8 mm 4 mm were formed
by deposition of five layers, subsequently cured at higher temperature for some
time depending on the curing agent used. Solid free-form fabrication is conducted
using an Asymtek model 402 fluid dispensing system, equipped with small stepper
motors (Oriel stepper mike) to drive the delivery syringe. The Asymtek and
syringe are controlled by a program written in Microsoft Quick Basic. Solid bar
samples are written as a series of lines.
Characterization of Soy Composites Developed by SFF

Mechanical Testing
The mechanical property testing is done using a 3-point bend test method with an
Instron model 1100. The standard formula for the modulus, E and strength, in 3-
pt bending of a beam was used:
E = PL3 / 4bd3 , = 3PL / 2bd2
where P is equal to the break load, L is the support span, is the deformation at the
center under load P, d is the sample height, and b is the sample width.
Composite Morphology
Scanning electron microscopy (SEM) is performed to characterize the morphology
of soy composites. Figure 7.5 shows the SEM of a freshly fractured surface for soy
composites filled with (a) Franklin Fiber H-45 fiber, and (b) carbon fiber. They
clearly indicate that the interfacial adhesion between the fiber and matrix is fairly
good. This can be readily seen from the physical contact between the two compo-
nents. The fibers are broken up from the matrix. However, holes and spacing occur
along the fiber, resulting in poor contact and inferior stress transfer between the
phases. The use of a combination of glass or carbon fiber with mineral fiber in
thermoset matrix was investigated recently by Peng (15). The experimental results
show that the use of different fiber types combined in testing bars tends to yield a
higher flexural modulus compared with the single type fiber-epoxy composites at
same conditions. Liu et al. (16,17) reported the studies of single-fiber and fiber
combination reinforced soy composites. An example of using a fiber combination
is the use of short milled glass fibers (1/32 in) with Franklin Fiber H-45, as well
as short carbon fibers with Franklin Fiber H-45. Table 7.3 shows that the moduli

Fig. 7.5. Scanning electron

microscope (SEM) pho-
tomicrograph of the freshly
fractured surface of soy-
based composites filled
with (a) Franklin fiber and
(b) carbon fiber.
of the composites increase compared with single type fiber-epoxy composites

under the same conditions. SEM of the fractured surfaces of the composites after
the flexural test are shown in Figure 7.6 (a) and (b).The near absence of holes
around the fibers resulted in good contact between the phases. A combination of
two fibers can be used to achieve composites with higher strength and stiffness
properties than can be obtained with a single fiber type.
Influence of Fiber Orientation on Flexural Modulus

The high degree of alignment has a great influence on the properties of a compos-
ite. Peng et al. (18) reported in glass fiber/epoxy composites, 90% of fibers are
within 10 of the machine write direction, measured by microscopy of a polished
section. By writing a series of test bars with write axes at different angles to the

TABLE 7.3
Mechanical Properties of Free-Formed ESO/Epon/TETA or ESO/Epon/DETA with 32
vol% of E-Glass Fiber, 4.8 vol% Franklin Fiber H-45a
Flexural Flexural Strain at

strength modulus break
Curing agent Fiber 1 Fiber 2 (MPa) (GPa) (%)
TETA Glass Franklin 110.0 6.3 1.9
TETA Carbon Franklin 96.3 5.48 2.1
TETA Glass 69.0 4.1 1.8
TETA Carbon 63.0 3.6 2.4
DETA Glass Franklin 104.3 5.5 2.3
DETA Carbon Franklin 86.0 4.7 2.6
aAbbreviations: ESO, epoxidized soybean oil; TETA, triethylenetetramine; DETA, diethylenetriamine.
Fig. 7.6. Scanning elec-

tron microscope (SEM)
photomicrograph of the
freshly fractured surface
of soy composites filled
with the fiber combina-
tions (a) E-glass fiber and
Franklin fiber and (b) car-
bon fiber and Franklin
fiber.

TABLE 7.4
Effect of Orientation on Epoxidized Soybean Oil (ESO)/Epon/Jeffamine EDR-148
Reinforced with 23.4 wt% Franklin Fiber H-45
Flexural modulus Flexural strength Strain at break

Fiber orientation (GPa) (MPa) (%)
0 0.97 21.0 2.2
30 0.42 14.0 5.0
45 0.34 16.0 5.0
60 0.32 22.0 4.3
90 0.29 8.1 2.2
long axis, they can vary the modulus by approximately a factor of 3. Therefore test
bars from ESO/Epon/Jeffamine EDR 148 reinforced with 23.4 wt% of Franklin
Fiber H-45 are made by writing at varying angles relative to the axis of the test
bars. The modulus can be varied by a factor of ~3.5 at writing angles parallel to the
long axis than cross to the long axis (Table 7.4). This is significant because the
composite modulus is at least as sensitive to orientation as it is to the fiber aspect
ratio and volume fraction.
Summary
Among the various composite molding methods, the solid free-forming method has
the potential to produce new material and complex composites that could not be
formed by other methods. Fiber-reinforced soy composite materials of high
strength and stiffness can be formed by the free-form fabrication method. The
higher strength and stiffness of soy composites can be achieved by a combination
of two fibers. The fiber orientation follows the direction of motion of the write
head that deposits the resins and has a large influence on the properties of the com-
posite. These composite materials may be of great environmental interest because
they comprise a high amount of agricultural resources. These can be used in agri-
cultural equipment, the automotive industry, civil engineering, marine infrastruc-
ture, and the construction industry.
References
1. Mano, E.B., Polmeros como Materiais de Engenharia, Edgard Blucher Ltda, So
Paulo, 1991, pp. 115129.
2. Kaplan, D.L., Biopolymers from Renewable Resources, Springer, New York, 1998.
3. Richardson, T., Composites Design Guide, Industrial Press Inc., New York, 1987.
4. Seymour, R.B., Polymeric Composites, New Concepts in Polymer Science, Jonge,
CRHI, Utrecht, The Netherlands, USP, 1990.
5. Qureshi, S., J.A. Manson, R.W. Hertzberg, and L.H. Sperling, Mechanical Behavior of
Some Epoxies with Epoxidized Natural Oils as Reactive Diluents, in ACS Division of
ORPL Papers 48: 576 (1983).

6. Raghavachar, R., R.J. Letasi, P.V. Kola, Z. Chen, and J.L. Massingill, J. Am. Oil Chem.
Soc. 76: 511516 (1999).
7. Wool, R.P., S.H. Kusefoglu, S.N. Khot, R. Zhao, G. Palmese, A. Boyd, C. Fisher, S.
Bandypadhyay, A. Paesano, P. Dhurjati, J. LaScala, G. Williams, K. Gibbons, M.
Bryner, J. Rhinehart, A. Robinson, C. Wang, and C. Soultoukis, Affordable Composites
from Renewable Sources (ACRES), Polym. Preprints 39: 90 (1998).
8. Wool, R.P., S.H. Kusefoglu, R. Zhao, G. Palmese, A. Boyd, C. Fisher, S.
Bandypadhyay, A. Paesano, S. Ranade, P. Dhurjati, S.N. Khot, J. LaScala, G. Williams,
M. Ligon, K. Gibbons, C. Wang, C. Soultoukis, M. Bryner, J. Rhinehart, and A.
Robinson, Affordable Composites from Renewable Sources (ACRES), 216th ACS
National Meeting, Boston, August 2327, 1998.
9. Baumgartl, H., and A. Schlarb, 2. Symposium Nachwachsend Rohstoffe-perspektiven fr
die Chemie, Frankfurt, 56 May, 1993.
10. Larbig, H., H. Scherzer, B. Dahlke, and R. Poltrock, J. Cell. Plastics 34: 361379
(1998).
11. Leao, A., R. Rowell, and N. Tavares, 4th International Conference on Frontiers of
Polymers and Advanced Materials Conference Proceedings, Cairo, Egypt, Plenum
Press, New York, 1997, p. 755.
12. Gassan, J., and A.K. Bledzki, 6. Internationales Techtexil Symposium, Frankfurt, 1517
July, 1994.
13. Wuppertal, E.W., Die textilen Rohstoffe, Dr. Spohr-Verlag, Frankfurt, 1981.
14. Stuffle, K., A. Mulligan, P. Calvert, and J. Lombardi, Solid Freeform Fabrication
Symposium Proceedings, University of Texas, Austin, 1993, p. 60.
15. Peng, J., M.S. Thesis, The University of Arizona, Tucson, 1999.
16. Liu, Z.S., S.Z. Erhan, J. Xu, and P.D. Calvert, J. Appl. Polym. Sci. 85: 21002107
(2002).
17. Liu, Z.S., S.Z. Erhan, and P.D. Calvert, J. Appl. Polym. Sci. 93: 356363 (2004).
18. Peng, J., T.L. Lin, and P. Calvert, Composites A 30: 133138 (1999).

Ch8(IndOils)(143-162)In 3/23/05 6:40 PM Page 143
Chapter 8
Vegetable Oils in Paint and Coatings

Michael R. Van De Mark and Kathryn Sandefur
University of Missouri-Rolla Coatings Institute, Rolla, MO 654091020
Introduction
Triglycerides and their derivatives have been used as a binder or additive in coatings
for possibly as long ago as 30,000 years going back to the days of cave paintings. The
early oil-based products would simply be derived from the use of a drying oil selected
from any naturally occurring plant or several fish oils and a naturally occurring pig-
ment such as red iron oxide or carbon black. Because no catalyst was added, the
curing or oxidation process was slow and yielded a soft coating. Technology over
the centuries has improved the use of oils in coatings. In addition to the classic
triglycerides, sulfonated oils and many other derivatives are used today, including
lecithin, as additives to coatings.
The primary use of oils in coatings is as a drying oil. Drying oils are highly
unsaturated oils that will oligomerize or polymerize when exposed to the oxygen in
air, usually in the presence of a catalyst. The result is an increase in the molecular
weight including cross-linking. Oils have the distinct advantage of being able to
penetrate into wood before polymerization (1) and thus are ideal wood primers.
Some of the common fatty acids (2) found in drying oils are listed in Table 8.1.
Only linoleic, linolenic, pinolenic, dehydrated ricinoleic, and -eleostearic acids
are truly drying oils. These all have two or more units of unsaturation separated by
TABLE 8.1
Common Fatty Acids Found in Drying Oils
Common name Formula
Myristic acid CH3(CH2)12CO2H

Palmitic acid CH3(CH2)14CO2H
Stearic acid CH3(CH2)16CO2H
Oleic acid CH3(CH2)7CH=CH(CH2)7CO2H
Linoleic acid CH3(CH2)4CH=CHCH2CH=CH(CH2)7CO2H
Linolenic acid CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7CO2H
Pinolenic acid CH3(CH2)4CH=CHCH2C=CHCH2CH=CH(CH2)3CO2H
Ricinoleic acid CH3(CH2)5CH(OH)CH2CH=CH(CH2)7CO2H
-Eleostearic acid CH3(CH2)3CH=CHCH=CHCH=CH(CH2)7CO2H

no more than one methylene. It should be noted that moving the unsaturation into
conjugation, as is the case for -eleostearic acid, increases the reactivity.
Typical sources for drying oils include linseed, soybean, tung, sunflower, and
dehydrated castor, as well as many fish oils. Their cost, coupled with the distribu-
tion of the various drying acids in the triglyceride, often governs their use. Trace
contaminants in the oils can also influence their acceptability in a given market.
For example, the presence of various phenolic contaminants can increase the color
of the resin as it oxidizes in air. Formulations requiring a white or clear appearance
may not allow their use.
True Oil Coatings

True drying oil coatings are those based upon an unsaturated oil as the only binder.
Typically linseed or tung oil is used in these applications. Only oils with a high drying
index are used (3). The drying index is equal to the sum of the percentage of linoleic
acid plus two times the linolenic acid content of the oil. If this value is >70, it is con-
sidered to be a drying oil. Many use the iodine number which is the number of grams
of iodine required per 100 g of oil as an indication of oxidative drying ability (4).
Table 8.2 gives the iodine number, drying index, and a partial composition for some
typical oils. It should be noted that genetic engineering has resulted in plants that are
capable of producing oils with compositions substantially different from those shown.
In the coming years, the available oils may be significantly different with very high
unsaturation. Soybean oil currently can have the acid distribution shown in Table 8.3
or as much as 85% oleic acid with genetic engineering.
Oil coatings are used to finish wood carvings, as wood deck stains and finishes,
cedar shingle coatings, and other applications for which penetration is desired and a
slow cure rate is not a significant problem. The deck finish market has grown from
~$30 million in 1980 to >$400 million in 2000. The formulation and mechanism of
cure are discussed in the following section. Oils are classified as drying if the iodine
number is >130, semi-drying if between 115 and 130, and nondrying if <115.
TABLE 8.2
Iodine Number, Drying Index, and Partial Composition for Some Typical Oilsa
Oils Iodine number Drying Index % Saturated

Drying oils
Soybean 130 66 14
Linseed 185 123 10
Sunflower 139 66 8
Tung 165 >172 5
Semidrying oils
Corn 124 54 17
Nondrying oils
Coconut 8 2 92
aNote: Although oleic acid is unsaturated, it is not a drying acid.

Curing Mechanism and Catalysts

The curing mechanism for oil-based products, including alkyds, follows an air oxi-
dation mechanism (5). Oxygen diffuses into the film and reacts with the diallylic
hydrogens to produce a hydroperoxide (Fig. 8.1). The hydroperoxide is formed at a
relative rate of 1:120:330 for the trioleate:trilinoleate:trilinolenate (3). The curing
mechanism then involves the decomposition of the hydroperoxide by a redox cata-
lyst. The most popular catalysts for the decomposition of the hydroperoxides are
cobalt and manganese naphthenate salts. These add color to the coating and thus
are kept at a low concentration. Other additives are used to improve the drying
characteristics. These include calcium and zirconia salts as driers and 9,10-phenan-
throlene, a complexing agent that accelerates cure. To retard the curing process, a
cobalt complexing agent, called an antiskinning agent, ties up the cobalt in the can
but evaporates and thus activates the cobalt after application. The skinning of oil-
based products in the can has been a problem since they were first used.
Alkyds
Alkyds comprise a large class of coatings. It includes the three normal alkyd classes,
which are based upon the amount of unsaturated oils used in the manufacture of
the alkyd resin: (i) Long Oil Alkyds are used typically for architectural paints.
They contain >60% oil, are soluble in mineral spirits, and are slow drying and soft.
(ii) Medium Oil Alkyds are used typically for architectural paints and as a co-resin
in some original equipment manufacturers (OEM) coatings. Their oil content is
between 40 and 60%; they are soluble in mineral spirits and aromatic solvents and
are slow to dry but faster than long oil alkyds and slightly harder. (iii) Short Oil
Alkyds are used typically for OEM and other rapid dry applications. They contain
<40% oil, are soluble in aromatics but not mineral spirits, and are fast drying to
touch and significantly harder than medium and long oil alkyds.
Oils. The oils used to make alkyds vary based upon the cure speed desired, cost,
odor, and many other factors. Table 8.3 shows several of the oils used in the manu-
facture of alkyds. The unsaturation number is used again to aid the resin formulator
in choosing better drying oils. In general, the higher the unsaturation number, the
better the oil is for drying. The desire is to have many di- or trienes in the oil, con-
taining two and three double bonds, respectively. Excellent drying oils for alkyds
include soybean oil, linseed oil, tung oil, and dehydrated castor oil. These oils are
cooked with various polyols to produce a polyester resin called an alkyd. Figure
8.2 illustrates the formation of a typical alkyd.
All alkyds, including modified alkyds, cure through air oxidation and require
chemical driers, accelerators, and antiskinning agents as did the oils. Because the
molecular weight of alkyds is larger and cross-linking is more probable, skinning
or livering becomes a significantly larger problem than in simple oil coatings.

TABLE 8.3 (left)

Typical Composition of Vegetable Oils
Average fatty acid concentration (% of total fatty acid)

Iodine
Vegetable oil numbera Caprylic Capric Lauric Myristic Palmitic Stearic
Carbon atoms (n) 8 10 12 14 16 18
Double bonds (n) 0 0 0 0 0 0
Castor 85 1.0 2.0
Coconut 8 8.0 7.0 48.0 18.0 9.0 2.0
Corn 124 13.0 4.0
Cottonseed 107 1.0 22.0 2.0
Crambe 94 3.0 2.0
Linseed 185 6.0 4.0
Menhadenb 170 7.0 16.0 1.0
Mustard 120 2.0
Oiticicac 150 7.0 6.0
Olive 80 8.0 2.0
Palm kernel 20 3.0 6.0 50.0 15.0 8.0 1.0
Peanut 90 7.0 6.0
Rapeseed 101 2.0 2.0
Rice Bran 102 17.0 1.0
Safflower oil 141 6.0 2.0
Sardine, Pilchard 190 5.0 14.0 3.0
Sesame 110 9.0 4.0
Soybean 130 8.0 6.0
Sunflower 139 6.0 2.0
Tallow 40 3.0 31.0 22.0
Tung (Regular)d 165 4.0 1.0
Tung (African)e 160 4.0 1.0
Walnut (English) 150 1.0 9.0 1.0
aIndicatesthe degree of unsaturation.
bAlsocontains 17.0% palmitoleic fatty acids 16 C-1 double bonds.
cContains 82% licanic acid.
dContains 82% oleostearic acid.
eContains 71% oleostearic acid.
Alkyds, in general, do not function well over galvanized steel or on concrete.

The alkalinity of the substrate coupled with traces of water causes the oils to
hydrolyze to produce long-chained carboxylic acids. The calcium or zinc salts of
these fatty acids are basically a mold-release agent. Because this mold release
agent is formed under the paint film, it can cause the paint to easily peal off in
large sections. This phenomenon can be observed when alkyds are used to paint
galvanized duct work on the roof of many buildings. If moisture can be avoided,
alkyds may work on these substrates.
Soybean oil is often used as the base oil but will often yellow. Various types
of linseed oil are also very popular because are very readily cured. Several other

TABLE 8.3 (right)

(Continued)
Average fatty acid concentration (% of total fatty acid)

Palmitic- Unsaturated Saturated
Oleic Linoleic Linolenic Oleic Ricinoleic Erucic fatty acids fatty acids
18 18 18 16 18 22 2022 2024
1 2 3 1 1 1 3+
2.0 5.0 90.0
6.0 2.0
29.0 54.0
21.0 54.0
18.0 10.0 5.0 56.0 3.0 2.0
20.0 17.0 53.0
27.0 17.0 32.0
24.0 20.0 6.0 43.0 5.0
5.0
82.0 8.0
16.0 1.0
60.0 22.0 5.0
16.0 16.0 8.0 45.0 6.0 4.0
47.0 35.0
13.0 79.0
10.0 15.0 12.0 41.0
46.0 41.0
28.0 50.0 8.0
26.0 66.0
42.0 2.0
5.0 8.0
9.0 15.0
16.0 60.0 13.0
highly unsaturated oils such as sunflower oil are gaining popularity as the supply
grows. Sunflower oil is a very good drying oil and produces less color.
General Issues of Alkyds. Air dry curing may require several weeks to reach full
performance. In the laboratory, curing can be accelerated by aging at 50C for 7 d.
This is a well-accepted test criterion to evaluate corrosion, flexibility, hardness,
and many other variables.
To cure, the oxygen in the air must penetrate through the coating all the way to
the substrate. The coating thickness should be limited to <3 mil/coat. Recoating
should be done only when sufficient time has been allotted to allow the antiskin-
ning agent to escape and the oxygen to react with the alkyd. The common belief is
that solvent evaporation and oxygen permeation are the only issues; however, the
loss of the antiskinning agent may be more important to the overall performance.
Unless sufficient time has been allowed, the cohesive strength, adhesion and pro-

Fig. 8.1. Radical-induced polymerization.
tection may all be poor. Our tests indicated a direct proportional drop in adhesive
and cohesive performance of an alkyd with film thickness.
All alkyd waste, overspray, spray booth filters, rags, and applicators contain-
ing alkyd or its washes are prone to spontaneous combustion under certain circum-
stances. All of these materials should be stored properly to prevent storage fires.
Filters should be changed regularly and disposed of properly and safely. All of
these waste materials are capable of starting a fire. Most alkyds are solvent-borne
and require significant volatile organic chemicals (VOC). Aromatic solvents are to
be avoided in air quality control areas that are not in compliance. Utilization of
oxygenated solvents in conjunction with mineral spirits can substitute for the aro-
matics but do raise the cost slightly.
Modified Alkyds
Modified alkyds utilize the general alkyd backbone or chemistry and typically
modify it with a more costly component that improves the performance of the
resin. Many of the aspects of alkyds are very desirable. These properties include
penetration into wood and air oxidative cross-linking. However, alkyds are not

Fig. 8.2. The formation of

a typical alkyd.
very abrasion resistant, solvent resistant, or hard. Chemistries that enhance these
properties have been well received including urethane, epoxy, silicone, and many
other technologies (6).
Epoxy. Typically 545% of the resin is based upon epoxy chemistry. This imparts
better solvent resistance and the alkyd is often used as a primer. Ultraviolet (UV)

stability is poor. Both bisphenol A and other phenolic-based epoxy chemistries

have been used. These coatings are not as solvent resistant as the typical two-com-
ponent epoxy primers but offer better performance than a simple alkyd. The most
common modification of this type is based upon the fatty acid reacting with the
epoxy group to form an ester (Fig. 8.3). As for most alkyds, the final curing is
oxidative.
Acrylic. From 15 to 50% modification is typical and can produce a quicker hard
film. These are useful for OEM applications but require significant VOC. In this
chemistry, the normal low-molecular-weight alkyd is prepared and cooled to
~120140C and the monomers added with a radical initiator, usually benzoyl per-
Fig. 8.3. The formation of an ester from the reaction of the fatty acid with the epoxy
group.

oxide. The monomer polymerizes and is grafted onto the alkyd. This chemistry
works equally well for styrene and vinyl toluene (VT). Although this modification
improves the properties of the alkyd, it increases the molecular weight and thus the
viscosity also increases. Therefore, the VOC for these coatings is generally high.
Styrene. Typically a graft of styrene of 10 to 50% onto the alkyd is used. The proper-
ties it improves are gloss, cost, and hardness with rapid drying. The disadvantages
include poor UV stability with rapid yellowing, significantly higher VOC required for
application, and decreased adhesion to many substrates. Both styrene- and VT-modi-
fied alkyds will photooxidize. If three or more styrene units are in a row in a polymer
chain, it will appear as a yellowing with exterior exposure.
Vinyl Toluene. Commonly called VT-modified alkyds, these have properties and
problems very similar to those of the styrene-modified alkyds.
Melamine. The use of melamine derivatives allows alkyds and modified alkyds to
be cured thermally. These are baking systems. The melamine derivative acts as a
cross-linking agent to produce a cross-linked film when baked. These are typically
baked at 120C for 30 min, with shorter times for elevated temperatures. The struc-
ture of a typical melamine used in mineral spirits-based alkyds is shown in Figure
8.4. Toluene sulfonic acid or the amine salt of a sulfonic acid is usually used as a
catalyst at a concentration of 0.5% based upon resin solids. These resins are solu-
ble in aromatics, ketones, esters and, when hot, alcohols such an n-butyl alcohol.
Use of n-butyl alcohol as 10% of the solvent helps to keep the surface open longer
to allow solvent to escape during baking, thus preventing solvent popping.
Fig. 8.4. Melamine

derivatives for alkyd for-
mulations.

Urethane Modified Alkyds. This system is a one-can coating based upon the use of
an alkyd polymer that was modified with 1530% urethane chemistry (Fig. 8.5). These
systems have better solvent resistance, abrasion resistance, and overall properties than
typical alkyds. They are usually 3.54.5 lb/gal VOC and dry relatively quickly to han-
dle rates of 30 min to 24 h, depending upon the oil content. The higher the oil content,
the longer the drying time. These alkyds have been applied to OEM, maintenance, and
architectural coatings. Their performance is very good and their cost is relatively low
(3).
As with all urethane systems, these come in aliphatic or aromatic urethanes.
Usually toluene diisocyanate, an aromatic isocyanate, or hexamethylene diisocyanate,
an aliphatic isocyanate, are reacted with a monoglyceride made by reacting a di-, tri- or
tetraol with the oil. The resultant urethane oils are then used as clear or pigmented
coats for wood. The aliphatic systems are excellent for exterior use or where UV expo-
sure is possible. The aromatic-based urethane systems usually have better abrasion
resistance but will yellow and degrade if exposed to UV, even through a normal win-
dow. The higher the urethane content, the better the coating will generally perform, but
the more VOC will generally be required and the higher the cost. A novel approach to
the synthesis of urethane oils utilized a chemoenzymatic synthesis. The use of
enzymes produces better control of stereochemistry and thus can impart unique prop-
erties. This methodology may have future potential (7).
Silicone. Silicone coatings are based mainly on dimethyl or diphenyl siloxane with
significant cross-linking (Fig. 8.6). These coatings are very expensive because the
resin can cost >$14/lb. The advantage of silicone coatings is a high degree of thermal
stability, typically stable to 250C for >100,000 h. The coating is also relatively stain
resistant and nonstick. The dimethyl siloxanes are very flexible even at very low tem-
peratures, whereas the diphenyl siloxanes are hard. Due to their high cost, siloxanes
are often used to modify the properties of other resins such as acrylics or alkyds where
they can be used cost effectively.
New Oils and Their Use

Several new oils have been studied for their potential use in coatings. Today the oil
market is not local but global. Soybean oil is produced around the world and its pro-
duction in Brazil or elsewhere will affect its price and use in all parts of the world. Oils
formerly produced only in a remote area but found to be of value can be converted into
a new agricultural product.
Lesquerella oil (LO) and the dehydrated lesquerella oil (DLO) were studied for
use in alkyd-type coatings. Their performance was found to be comparable to that of
castor oil and dehydrated castor oil, respectively. The lesquerella oil resins were gener-
ally found to perform better in drying time, flexibility, and corrosion resistance (8).
Another interesting oil derived from Euphorbia lagascae and Vernonia galamen-
sis is 9c,12,13 epoxy-octadecenoic acid (vernolic acid) (9). This epoxy acid and its

Fig. 8.5. Urethane modified alkyd.

Alkyd-SiMe2-O-(SiMe2)n-OMe
Typically, n = 5-10 Fig. 8.6. Siloxane.
esters can function as a reactive diluent in many solvent and water-borne coatings. Its
use in UV cure systems will be discussed later (10,11). This epoxy system can be
polymerized through the action of any carboxylic or mineral acid. Thus, in a conven-
tional baking system, these epoxy groups could be used to cross-link an acid-rich
resin.
A rapid cure oil derived from Calendula officinalis, Marigold, was found to
comprise >63% of the C18 triene 8t,10t,12c-octadecatrienoic acid, calendic acid. This
acid is analogous to the well-known drying oil, tung oil (11). Conventional drying oils
can be modified through a conjugation of the double bonds. Various catalysts have
been employed to put the double bonds into conjugation, including bases and metal
catalysts. Here the new diene or triene is much more reactive and curing is more rapid.
The future of oils will continue through the use of genetic engineering. The
development of new soybean varieties as well as other oil-producing plants that can
produce highly specific fats will continue to increase. Today soybeans, which are high
in oleic acid, are available, and work is underway to produce high triene content soy-
bean oil. Having plants custom-make our chemicals will increase the performance of
these natural products. The high cost and lack of availability of tung oil makes the
high triene soybean oil an attractive technological breakthrough. The scientific and
social acceptance of this technology as well as the full evaluation as to the safety of
the use and production of such products through genetic engineering must first be
accomplished. Once proven safe, these new plant-based chemical producers will
reduce our need for petroleum-based products in coatings.
Water-Borne Coatings
Water-borne coatings can fit into any of the following types: water-soluble, emul-
sions, dispersions, latex, and water-reducible resins. Water-soluble resins are the least
important and are rare because most resins derived from oils are insoluble in water.
The true emulsions are based upon the emulsification of the oil or alkyd through either
the action of a surfactant or a resin that has a surfactant-like character; these are oil-in-
water emulsions. In this system, the resin must be a liquid emulsified in water. A few
systems utilize water dispersed in an oil or alkyd. This latter system is termed a water-
in-oil emulsion. If the resin is a solid and is dispersed in water, it is termed a disper-
sion. The last class is the latex. Here the resin is usually vinyl acetate, styrene, acry-
lates, or methacrylates radically copolymerized in a micelle to form particles 0.1 m
in diameter. Water-reducible resins are similar to the dispersions in that they are parti-
cles; however the particle size is generally <8 m in diameter.
In recent years, researchers have been developing an oil-modified latex tech-
nology (1214). The goal is to reduce the need for a coalescent aid by incorpora-
tion of the oil into the latex resin. After application, the oil portion of the resin,

which lowered the glass transition temperature of the resin to allow coalescence
into a film, cross-links the resin to produce a hard, durable finish. Acrylated oils
are an excellent co-monomer to use in the synthesis of the latex.
Alkyd emulsions are readily prepared and can be employed for OEM coatings
as well as for architectural applications. These resins have been utilized as an addi-
tive resin for years to improve the performance of latex paint on chalking surfaces.
Because the resin is a liquid, it can penetrate the chalk and improve adhesion.
Typical use levels are between 0.1 and 1 lb/gal. To emulsify the resin, typically an
acid-rich resin neutralized with an amine is sheared into the paint. The submicron
size droplets are stabilized by the thickeners (1517). The use of ultrasonic tech-
nology has also been utilized in the preparation of mini-emulsions (18).
Water-reducible technology relies upon the presence of water-loving groups,
usually the salt of carboxylic acids, on the polymer chain to act as an internal
emulsifying agent. The polymer is dissolved in a high-boiling, water-loving sol-
vent such as ethylene glycol monobutyl ether. An amine such as ammonia or tri-
ethyl amine is added to form the salt of the acid groups. Then water is added very
slowly. The result is the formation of very small particles of polymer, typically
from 5 to 100 nm. If formulated correctly, the polymer solution is clear and the
solution is thermodynamically stable due to Brownian motion keeping the particles
suspended. The polymer is not water soluble but is actually dispersed, and many of
the particles are single polymer chains. To obtain the requisite acid functionality
on the chain, maleated alkyds are often used. In Figure 8.7, maleic anhydride is
reacted thermally with a conjugated oil component in the alkyd through a Diels
Alder reaction.
Water-reducible resin systems have been available for over 50 years but did
not gain popularity until the mid-1980s when environmental regulations caused the
industry to move more to water-borne coatings. The formulation and manufacture
of these coatings are much more difficult and less forgiving than those of either
latex or alkyd coatings. The amount of added base, the molecular weight of the
resin, the acid value of the resin, and the rate and amount of water added all play
an important role in their properties. As water is added to the resin, the viscosity
drops with the first small amount of water, then it rises to a very high level. When
the solvent composition becomes more like water, the resin's polymer/polymer
interactions overcome the polymer/solvent interaction and the resin collapses into a
sphere with the carboxylate ions on the exterior. A spherical geometry is typically
observed because this places the ions at the furthest points from each other. After
application, the water evaporates and the solvent redissolves the particles and coa-
lesces into a film. The use of water-borne driers promotes air oxidation and the
subsequent decomposition of the hydroperoxide to cross-link the resin (19,20).
Water-reducible coatings can be used for many OEM and maintenance appli-
cations. For direct application of the coatings to metal, flash rusting is a frequently
encountered problem. Flash rust inhibitors must be used when water-borne coat-
ings are applied directly to metal, and nitrites are commonly employed.

Fig. 8.7. Diels Alder Reaction.
Inorganic/Oil Hybrid Coating

A new approach to producing coatings with better adhesion, corrosion resistance, and
hardness is to combine inorganic and oil technologies into a hybrid system. Several
different approaches have been used to produce high-quality durable films. Tuman and
Soucek (21) investigated the use of a sol-gel precursor based upon titanium(di-i-
propoxide) bis (acetyl-acetonate) and titanium (IV) isopropoxide in conjunction with
either linseed or sunflower oil with a zirconium drier. In this system, the titanium sol-
gel formed a cluster when moisture entered the film. To improve performance, the
coating was baked at 210C after ambient drying. The sol-gel inclusion at the 550%
level produced coatings that were stable at 284C to as high as 306C with only 5%
weight loss by thermogravimetric analysis. In the scheme depicted in Figure 8.8, the
OR, which originally was the isopropoxide, is presumably now the polymerized oil.
Thus the resin and inorganic segments are linked together after the baking process,
adding strength and cross-linking density. A similar approach was used with zirconi-
um n-propoxide, which performed analogously (22). Both the zirconate alone and tita-
nium (IV) isopropoxide sol-gel alone improved performance. However, the results
indicated a synergistic effect of a 5% titanium (IV) isopropoxide:5% zirconium n-

Fig. 8.8. Sol-gel.
propoxide sol-gel in linseed oil, which showed better hardness, up to 6H, and better
adhesion to metal substrates. The fracture toughness was also found to improve
through the use of titanium and zirconium sol-gels (2326).
High-solid alkyds have also been improved by the addition of aluminum com-
plexes. The addition of typically l% of an aluminum complex enhances the hardness
and general performance of alkyds. However, accelerated weathering or exterior expo-
sure results in crack formation due to embrittlement from oxidative degradation
(27,28).
UV and Radiation Cure Technology

One of the fastest growing areas of coatings is that of radiation cure. This area is
divided into three areas; radical UV cure systems, ionic cure systems, and e-beam.
Of the three, the radical cure systems are the most popular in part due to their cost

and their cure speed. Radical cure processes require only seconds to reach full
cure, whereas ionic cure systems can require 20 min. The e-beam and a few other
high-energy cure systems have small markets, but the ionic and radical systems are
the largest markets. The use of oils in this market is growing as new, more compat-
ible and reactive monomers are created from low-cost oil feedstocks.
Castor acrylated monomers as well as various acrylate adducts of epoxidized
oils such as lesquerella oil are a few of the monomers used in the radical curing
systems. In general, acrylates cure readily through UV radical polymerization,
whereas styrenic, methacrylates, and vinyl ethers react too readily with oxygen in
the air to be as useful. These latter monomers require a blanket of inert gas over
the coating during curing to reduce the oxygen radical scavenging. The scheme in
Figure 8.9 illustrates the typical reaction of an acrylate. Castor oil is simply esteri-
Castor Oil Triacrylate

The Acrylate group is free radically polymerizable
Fig. 8.9. Typical reaction of an acrylate.

fied as the triacrylate. When cured, all of the acrylates are incorporated into the
backbones of various chains creating a highly cross-linked film. The oil side chains
act as internal plasticizers to keep the coating flexible. It is important to note that
over time, these coatings will gain hardness due to the oxidative cure of the resid-
ual unsaturation (29). Many oil-based products are not compatible with the very
polar acrylate monomers, and urethane derivatives are also frequently used in the
radical cure systems to improve adhesion and impart toughness. In these cases, the
amount of oil-based monomer must be kept low to avoid phase separation during
polymerization.
Cationic cure systems have seen significant interest in recent years even
though they are only ~8% of the UV cure market. The cost of highly epoxidized
soybean, linseed, and other oils is relatively low compared with the typical aliphat-
ic epoxy monomers used in cationic cure systems. The epoxidized oils are signifi-
cantly more polar and thus more compatible with the other components of the
cation cure system. Unlike the radical cure systems, these have generally less
shrinkage, can cure more deeply on pigmented systems, and are much slower to
cure.
Vernonia oil and epoxidized soybean oil were studied by Thames and Yu (30).
They found excellent adhesion, impact, UV stability, gloss retention, and corrosion
resistance with the oils. However, the pencil hardness and tensile strength of the
coating decreased with increasing oil content. Gu et al. (31) found that as the per-
centage of epoxidized soybean oil increases in a cationic UV cure system with a
cycloaliphatic epoxy, the adhesion and solvent resistance increase. The hardness,
however, generally decreases unless a postbake is performed after UV exposure.
The postbake is often employed to cause a subsequent increase in the rate of
cationic reaction, including acid-catalyzed reactions. Usually the cross-link density
and subsequent hardness increase due to baking. Epoxidized palm oil was also
used and may prove useful for coatings in the immobilization of herbicides (32).
One study utilized oil-modified polyols derived from Chinese melon oil
(Momordica charantia) and tung oil. These oils are highly unsaturated and excel-
lent drying oils. The system was formulated with the oil-modified polyol,
cycloaliphatic epoxides, and a cationic initiator. These systems had excellent gloss
and adhesion with improved impact resistance and flexibility (33). Zou and Soucek
(34) successfully modified linseed oil by reaction with 1,3-butadiene and subse-
quent epoxidation. This new monomer can also be used for cationic UV cure sys-
tems and should be cost effective. In another study, Soucek et al. (35) utilized
tetraethoxysilane oligomers in conjunction with epoxidized norobornene-derivi-
tized linseed oil to form an organic/inorganic hybrid cationic UV cure coating. The
performance enhancement was attributed to the nanoscale phase separation of the
inorganic and larger organic phases. The inorganic phase was discontinuous,
whereas the organic formed a continuous phase around the islands of inorganic
polymer. The use of inorganic ceramic-type building blocks can enhance both the
abrasion resistance and the adhesion of the coating to metals.

Oil-Based Additives in Coatings

The environmental movement of the past 25 years has driven a deep interest in nat-
ural products and their potential use in coatings. The general goal of VOC elimina-
tion has been the primary driver. Oils have a high potential of reducing VOC
because they are a liquid at room temperature and polymerize, or at least oligomer-
ize, with air oxidation. Therefore, with time, they become a solid. Today, several
of the additives, especially in water-borne coatings, are being replaced with unsat-
urated oils and their derivatives. The goal is to replace additives that may degrade
the performance of the coating or are VOC with an additive that adds to the perfor-
mance but not the VOC.
The major VOC in a latex paint is the coalescent aid; typically an ester or
ether such as 2-butoxyethanol is used. Van De Mark and Jirautumnukul (36,37)
utilized simple monoesters of unsaturated oils with ethylene, diethylene, triethyl-
ene, propylene, and dipropylene glycols and other simple alcohols such as the
methyl and ethyl ester of unsaturated fatty acids as potential coalescent aids.
Vegetable oils as potential coalescent aids are not compatible with latex paint; they
are too nonpolar and phase separate from the resin. Oils such as soybean oil were
transesterified with a glycol. The simple monoesters were highly compatible for
most commercial latex resins, particularly ethylene glycol and propylene glycol
monoesters. Virtually a 1:1 replacement amount of the new coalescent aid was
effective for many conventional coalescent aids. The new oil-based esters were
nonvolatile. As they age, the properties of the latex paint improved very much like
the conventional aids as they evaporated over several days or weeks. The amount
of resin needed decreased slightly and the efficacy of the associative thickener
improved; thus less is required. This additive is now a commercial product.
Unsaturated oils are being used as surfactants as the fatty acid or are deriva-
tized. These additives are targeting the air oxidative cure mechanism of alkyds to
make the additive lose its mobility and become a binder in the coating. Thus the
additive does its job, and then becomes part of the binder (3840).
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Patent 20030187103 (2003).

Chapter 9
Printing Inks
Sevim Z. Erhan
USDA, ARS, NCAUR, Peoria, Illinois 61604
Introduction
Printing inks are applied to substrates by printing presses of various designs and are
divided into five categories according to the type of printing press. Major printing
processes used by the industry are lithography (offset), letterpress, flexography,
gravure, and screen printing (1). Letterpress and lithographic inks are viscous and
paste-like. Flexographic and gravure inks are extremely fluid and they are generally
called liquid inks. On the other hand, screen inks are intermediate in viscosity
between the liquid flexographic and gravure inks, and the paste-like lithographic
inks.
Vegetable oils are mainly used in paste inks; therefore, the role of vegetable
oils in paste ink formulations will be described.
Lithographic Inks
Lithographic inks, the leading type of ink both in volume and dollar shipments,
accounted for an estimated 1,230 lbs, valued at $1,770 million in 2001 (2). They
represent about 41% of all ink shipments as measured in dollars. Publication and
commercial printing represents an estimated 80% of consumption. Of this, news-
papers account for 40% of the total. In approximate order, the balance is: advertis-
ing printing; magazines and periodicals; catalogs and directories; financial and
legal printing; labels and wrappers; and other commercial printing, including pack-
aging. The petroleum shortage in the 1970s stimulated research into vegetable-oil
based inks as a substitute for petroleum-based products.
Inks containing vegetable oils have been formulated for various specialized
applications (36). In the early 1980s, the American Newspaper Publishers
Association (ANPA) (later changed to the Newspaper Association of America/
NAA) developed a series of ink formulations comprising a blend of gilsonite
and tall-oil fatty acids with carbon black pigment (79). The cost and availability
of tall oil and the difficulty of equipment cleanup created by the gilsonite limited
the acceptance of these inks by the industry. A later approach by ANPA to produce
an ink vehicle from renewable materials resulted in a lithographic news ink formu-
lated with a commercial ANPA vehicle consisting of alkali-refined soybean oil, a

hydrocarbon resin, and carbon black pigment (10). This black ink prints as well as
the mineral oil-based commercial ink, but costs 30 to 50% more. The color inks are
formulated similarly, with a good print quality, but cost about 5 to 10% more than
the petroleum-based commercial inks. Both the black and color inks contain 20 to
25% hydrocarbon resin. Thus, industry has continued to search for a 100% veg-
etable oil-based ink to replace the petroleum-based inks.
Ink Vehicles
Printing ink consists of two components: the colorant (pigment) and the vehicle.
The ink vehicle is the liquid or fluid portion of the ink which (i) functions as the
carrier and transport system for the pigment, and (ii) upon reaching the substrate,
must be converted to a solid and anchor the pigment to the substrate.
Important properties of the vehicle as a pigment carrier and transport system
include (i) pigment wetting and dispersion; (ii) ink rheology (ink transfer, ink mist-
ing, and press stability); and (iii) ink/water balance for lithography. Ink rheology
relates to both viscosity and body or structure of the vehicle (or ink). For example,
misting indicates that the vehicle has to have more rheology, or more body.
The lithographic (offset) printer plate consists of two distinct areas. One area has
been rendered hydrophobic (image area) while the non-image area is hydrophilic.
Thus, the offset printing process involves a two-phase system consisting of an oil
phase (the ink) and aqueous phase (the fountain solution). During the printing process,
these phases must not form stable emulsions, or they will not separate properly on the
printer plates. Poorly separated phases lead to smudged or ill-defined print (11).
Important properties of the vehicle as the pigment binder or anchor to the sub-
strate area (12) include (i) ink setting; (ii) ink drying; and (iii) gloss and rub-resis-
tance of dried ink.
Setting and Drying. Setting has to occur very quickly. Slow setting results in
undesirable smearing. Drying occurs after the ink was set and ink is considered dry
when its viscosity reaches one million centipoises (10,000 ps). Substrate plays an
important role during the setting and drying process. Setting and drying mecha-
nisms include one or more of the following (13): (i) solvent/oil penetration; (ii)
solvent evaporation; (iii) oxidation polymerization; (iv) catalytic polymerization;
(v) resin precipitation.
Drying Oils
Drying oils are mixtures of fatty acid triglycerides. Fatty acids can exist alone as free
fatty acids or in a combined form of esters. A majority of the combined forms are
esters with glycerol (propane 1,2,3-triol) (14). They are called triacylglycerols or
triglycerides. Upon hydrolysis, each triglyceride molecule can release three fatty acids
and one glycerol (Fig. 9.1). Types of fatty acids in common drying oils are tabulated
in Table 9.1.

Fig. 9.1. Triglyceride and hydrolyzed components.
In order to dry by oxidation polymerization, the predominant fatty acid com-

ponent of the vegetable oil must have at least two unsaturated groups. Oxidation
occurs across the double bonds and it involves absorption of oxygen from air. It
causes those double bonds to open up and form peroxides, which are unstable,
break down, and are crosslinked. One fatty acid chain gets attached to the next one
and they form a more rigid structure which essentially gives dry ink.
For example, in oleic acid, there is one double bond, which is not enough to
oxidize properly. On the other hand, linoleic acid has two double bonds but they
are not conjugated. A conjugated structure is very important to the oxidation
process. Therefore the linoleic acid is a slower oxidizer than linolenic or
eleostearic acid. The double bonds in eleostearic acid are conjugated. In the case of
linolenic acid, there are three double bonds and more opportunity for oxidation to
occur, but anything that changes the non-conjugated double bonds to conjugated
double bonds will enhance the drying process.
The drying index indicates how well or how poorly certain drying oils will
oxidize. The drying index of drying oil, semi-drying oil, and non-drying oil is >70,
5070, and <50, respectively. If a particular drying oil has a blend of two and three
double bond fatty acids, the percentages of the fatty acids should be included in the
determination of the drying index. For example, linseed oil has 52% linolenic and
TABLE 9.1
Fatty Acid Composition of Common Drying Oils
Soybean Safflower Linseed Tung

Common name Chemical name (%) (%) (%) (%)
Myristic Tetradecanoic Tr0.5 Tr
Palmitic Hexadecanoic 711 36 47 35
Stearic Octadecanoic 26 14 25 Tr1
Arachidic Eicosanoic 0.33 Tr0.2 0.31
Oleic 9-Octadecaenoic 1533 1321 1234 49
Linoleic 9,12-Octadecadienoic 4356 7379 1724 810
Linolenic 9,12,15-Octadecatrienoic 511 Tr 3560 23
Eleostearic 9,11,13-Octadecatrienoic 7786

15% linoleic acid, therefore the drying index of linseed oil is: (52 2) + 16 = 120.
Similarly, the drying index of tung oil (Chinawood oil), soybean oil, and safflower
oil is calculated as 170, 69, and 77, respectively.
Alkali refined vegetable oils are used in ink formulation. Alkali refining
removes the gums, waxes, free fatty acids and gives the oil greater clarity and
lighter color. The presence of any one of these materials will interfere with the
desirable hydrophobic characteristics of the vehicle and the ultimate ink formula-
tion (15).
The most frequent use of drying oils in ink vehicles is as the oil component in
liquid resins (alkyds). Alkyds are oil modified polyesters with well defined chem-
istry (16). Modified oil can be used as an ink vehicle without the need of resin in
the formulation.
The vehicles can be prepared from vegetable oils by two methods (1718). In
one method, vegetable oils are heat-polymerized at a constant temperature in a
nitrogen atmosphere to the desired viscosity. In another method, the heat polymer-
ization reaction is permitted to proceed to a gel point, and then the gel is mixed
with vegetable oils to obtain the desired viscosity.
To further characterize the gels and ink vehicles prepared from vegetable oils,
the viscosities and apparent molecular weights of these vehicles are determined by
gel permeation chromatography.
The prepared vehicles typically had viscosities in the range of GY on the
Gardner-Holdt viscometer scale, or about 1.618 P (1920). These viscosities cor-
responded to apparent average molecular weights of 26008900.
For all oils studied, the viscosity (from crosslinking and polymerization)
increased with time at the heat-bodying temperature of 330 3C. The reaction
time necessary to reach a desired viscosity depends on the mass and the structure
of the reactants and the rate of heat transfer and agitation. As expected, oils with
higher unsaturation polymerized more rapidly than those with lower unsaturation.
Gelling times for safflower (I.V. = 143.1), soybean (I.V. = 127.7), sunflower (I.V.
= 133.4), cottonseed (I.V. = 112.9), and canola (I.V. = 110.2) oil were 110, 255,
390, and 540 min, respectively. Although the iodine values of cottonseed and
canola oil are similar, canola oil with its greater oleic and low linoleic acid content
required a longer reaction time.
During heat-bodying, conjugated dienes are formed by bond migration in
polyunsaturated fatty acids. These can form six-membered rings by intra- or inter-
molecular reaction with the double bonds of other fatty acids. If these reactants
come from different triglycerides, the molecular weight increases for the system.
As heating continues, another conjugated group can add to the previously formed
unsaturated ring structure. Triglycerides consisting of three polyunsaturated fatty
acids where addition may occur increase the probability of forming very complex
highly branched structures. Viscosity increases are directly proportional to increas-
es in apparent molecular weight and the degree of polymerization. Apparent mole-
cular weight at the same viscosity of different oils may be due to differences in lin-

Fig. 9.2. (A) Gel permeation chromatograms of alkali refined, 60 and 105 minute
heat-bodied soybean oil. (B) Gel permeation chromatograms of 125, 150, and 270
minute heat-bodied soybean oil.
earity of the bodied oils. As heat-bodying time was increased, the ratio of polymer-
ized oil to unpolymerized oil increased. These behaviors are readily seen by the
plots in Figure 9.2. At the heat-bodying time of zero, the peak shows the unmodi-
fied soybean oil. When heat-bodying time of the oil increases to 60 minutes, a
shoulder appears, resulting from formation of the polymer, and this shoulder
becomes dominant as the heating time increases from 60 to 270 minutes.
Such heat-bodied oils of different viscosities can be blended to produce vis-
cosities of any desirable value. Also, blending different proportions of the gel and
unmodified oil gave different vehicle viscosities.
Additives which may be formulated into the inks include driers, lubricants and
antioxidants. The thickening effect of the pigment on the base vehicle should be
considered in preselecting a vehicle viscosity (2123).
Biodegradation
Biodegradation plays an important role in the transformation of many organic
compounds in the environment. Several articles speculate that vegetable oil (soy-
bean oil) should biodegrade more readily than mineral oil (2425). Cavagnaro and
Kaszubowski (26) have reviewed the biodegradation of food oils and greases.
Erhan et al. studied and reported the biodegradation of soybean oil and the ink
vehicles by using the microorganisms that are commonly found in soil (2728).
Also, biodegradation of printing inks was tested by using the Modified Sturm
Test by Erhan et al. (29). Rosinski (30) reported the results of a de-inking study
conducted at Western Michigan University, Kalamazoo, Michigan.

Conclusion
Technology is available for manufacturing vegetable oil-based printing ink vehi-
cles with the desired commercial characteristics. This technology allows manufac-
turers to increase the vegetable oil content of the ink formulations and in turn
improve environmental properties by increasing the biodegradability, lowering the
volatile organic compound content, and improving the de-inking properties.
References
1. Leah, R.H., The Printing Ink Manual, 4th ed., Society of British Printing Ink Manufacturers
Ltd., Van Nostrand Reinhold International, 1988, pp. 35.
2. The Rauch Guide to the U.S. Ink Industry, 20022004, Impact Marketing Consultants, pp.
9596.
3. Kobayashi, S. and Nozaki, K., Japanese Patent 17716 (1978).
4. Gupta, P. K., Rai, J., Singh, H., Indian Patent 154760 (1984).
5. Ono, T., Otake, K., Japanese Patent 61,123681 (86, 123681) (1986).
6. Kuzuwata, M., Japanese Patent 63,227287 (88, 227287) (1988).
7. Moynihan, J.T., U.S. Patent 4419132 (1983)
8. Moynihan, J.T., U.S. Patent 4519841 (1985).
9. Manufacturing Directions for Soybean Oil-Based ANPA-Ink, American Soybean
Association, St. Louis, Missouri, 1988, White paper. ANPA-INK, Reston, VA.
10. Moynihan, J.T., U.S. Patent 4554019 (1985).
11. Erhan, S.Z., and M.O. Bagby, Vegetable Oil-Based Printing Ink Formulation and
Degradation, Ind. Crops and Prod. 238 (1994).
12. Advanced Physical Chemistry of Printing Inks, Summer Course, Lehigh University,
National Printing Ink Research Institute, Bethlehem, PA, 1989.
13. Printing Ink Handbook, 5th ed., National Association of Printing Ink Manufacturers,
Woodbridge, NJ, 1999, p. 15.
14. Wan, P.J., Properties of Fats and Oils, in Introduction to Fats and Oils Technology, 2nd
edn., (OBrien, R.D., Farr, W.E., Wan, P.J., eds.), AOCS Press, Champaign, IL, 2000,
p. 23.
15. Erhan, S.Z., Vegetable Oil-Based Printing Inks and Environmental Advantages, in
Recent Research Developments in Oil Chemistry 1, Transworld Research Network,
Trivandrum, India. 159164 (1997).
16. Hui, Y.H., Baileys Handbook on Fats and Oils, 5th ed., Wiley Interscience, New York,
1996, p. 240.
17. Erhan, S.Z., and M.O. Bagby, Lithographic and Letterpress Ink Vehicles from
Vegetable Oils, J. Am. Oil Chem. Soc. 68: 635638 (1991).
18. Erhan, S.Z., and M.O. Bagby, U.S. Patent 5,122,188 (1992).
19. Erhan, S.Z., and M.O. Bagby, Gel Permeation Chromatography of Vegetable Oil-Based
Printing Ink Vehicles, J. Appl. Polym. Sci. 46: 18591862 (1992).
20. Erhan, S.Z., and M.O. Bagby, Polymerization of Vegetable Oils and Their Uses in
Printing Inks, J. Am. Oil Chem. Soc. 71: 12231226 (1994).
21. Erhan, S.Z., M.O. Bagby, and H.W. Cunningham, Vegetable Oil-Based Printing Inks, J.
Am. Oil Chem. Soc. 69: 251256 (1992).

22. Erhan, S.Z., and M.O. Bagby, Vegetable Oil-Based Sheetfed and Heatset Ink Formulations
and Comparison of VOC Test Results with Commercial Inks, TAGA Proceedings,
Technical Association of the Graphic Arts, TAGA Office, Book Crafters, Inc., Chelsea, MI,
1997, pp. 807814.
23. Erhan, S.Z., and M.O. Bagby, U.S. Patent 5,713,990 (1998).
24. Ticer, J.M., Environmental Factors in Disposal, Recycling, and Work Place, Soy Oil
Symposium Proceedings, Section VII, 1988.
25. Ellis, S., Soy Based Inks, American Ink Maker 69: 3638 (1991).
26. Cavagnaro, P.V., K.E. Kaszubowski, and H. Needles, Pretreatment Limits for Fats, Oil and
Grease in Domestic Wastewater, Proceedings of the 43rd Industrial Waste Conference,
Purdue University, West Lafayette, IN, 1988, pp. 777789.
27. Erhan, S.Z., and M.O. Bagby, Biodegradation of News Ink Vehicles, TAGA Proceedings,
Technical Association of the Graphic Arts, TAGA Office, Book Crafters, Inc., Chelsea, MI,
1993, pp. 314326.
28. Erhan, S.Z., M.O. Bagby, and T.C. Nelsen, Statistical Evaluation of Biodegradation of
News Ink Vehicles and Ink Formulations, J. Am. Oil Chem. Soc. 74: 707712 (1997).
29. Erhan, S.Z., M.O. Bagby, and T.C. Nelsen, Biodegradation of News Inks with Modified
Sturm Test, TAGA Proceedings, Technical Association of the Graphic Arts, TAGA Office,
Book Crafters, Inc., Chelsea, MI, 1995, pp. 184203.
30. Erhan, S.Z., and M.O. Bagby, Environmental Aspects of Vegetable Oil-based Lithographic
News Inks, TAGA Proceedings, Technical Association of the Graphic Arts, TAGA Office,
Vol. 1, Book Crafters, Inc., Chelsea, MI, 1995, pp. 952962.

Chapter 10
Synthesis of Surfactants from Vegetable Oil

Feedstocks
Ronald A. Holser
USDA, ARS, NCAUR, Food and Industrial Oils Research Group, Peoria, Illinois 61604
Introduction
Triglycerides obtained from domestic oilseed crops such as soybean represent a
renewable source of medium chain length fatty acids (FA) that are suitable for the
preparation of surfactants and related products (1). These compounds find numer-
ous industrial applications as detergents, dispersants, emulsifiers, softeners, and
wetting agents (2). The hydrolysis of vegetable oil yields FA and glycerol. The FA
provide the chemical structures that are the building blocks of surfactants. A FA
combines an alkyl structure that imparts hydrophobic properties with a carbonyl or
other solubilizing structure that imparts hydrophilic properties. Both attributes are
essential to surfactant performance (3). The length of the alkyl chain determines
the hydrophobic character while the solubilizing group determines the hydrophilic
character, e.g., anionic, cationic, or non-ionic (4). The presence and location of
substituent groups further influence surfactant properties and performance in a par-
ticular application (5). For example, the tropical oilseedscoconut and palm ker-
nelare rich sources of lauric and myristic acids which are used in the production
of detergents, whereas the derivatives of longer chain FA perform better as disper-
sants or emulsifiers (6).
FA may be neutralized with base to produce the corresponding salts. Such
salts or soaps combine the hydrophilic and hydrophobic functionalities that are
characteristic of surfactant compounds. However, the performance and production
of soaps is surpassed by the ether, ester, and amide derivatives that can be pre-
pared from FA (7).
Oilseed crops are an attractive source of FA since they represent a renewable and
sustainable raw material that can replace petrochemicals for industrial synthesis. A
surfactant will exhibit the same physical and chemical properties whether prepared
from oleochemical or petrochemical raw materials. In fact, certain structures may be
more advantageously prepared from an oleochemical raw material. For example, the
fatty alcohols that are commonly used in the preparation of surfactants may be pro-
duced by the reduction of FA obtained from oilseed triglycerides. Other factors that
affect the choice of oleochemical or petrochemical feedstocks include availability,
consumer preference, cost, process economics, and purity.

Additionally, initiatives to promote the development of biobased products that

can replace products currently derived from petroleum sources have been imple-
mented by the U.S. government and the European Union over the past several
years. In the U.S., the Biomass Research and Development Act of 2000 and execu-
tive order 13134, Developing and promoting bio-based products and bio-energy,
have established the goal to significantly increase the use of agricultural materials
as a source for the production of consumer goods, industrial chemicals, lubricants,
and alternative fuels. Historically, agricultural materials were used in this capacity
prior to the development of petroleum as a raw material for the chemical industry.
The shift from agriculture to petroleum as the source of industrial raw materials
occurred due to the availability of inexpensive petrochemicals. A return to agricul-
tural sources may be expected as petroleum prices increase.
Agricultural Raw Materials in Industrial Applications

The current interest in agricultural raw materials for industrial applications is a
response to both economic and environmental concerns associated with petroleum.
The reserves of petroleum and other fossil fuels are finite, in contrast to renewable
sources of oleochemicals, such as those obtained from oilseed crops. The cost of
petroleum is expected to increase as the supply is depleted, while the correspond-
ing cost of a sustainable agricultural raw material should remain relatively stable.
In addition, the use of domestically produced oleochemical materials instead of
petrochemical feedstocks helps to conserve the global supply of fossil resources
while reducing the dependence of the U.S. on foreign petroleum supplies. The U.S.
currently imports the majority of petroleum it uses. Much of this supply is located
in politically sensitive regions such as the Middle East, where a change in the
social order can interrupt the production of petroleum and lead to price fluctuations
or shortages. Reducing the levels of imported petroleum offers a strategic benefit
and promotes domestic economic security. The U.S. Department of Energy has
recognized this and established goals to increase the use of biomass as a source of
raw materials for the chemical industry (8).
The domestic petroleum resources in the U.S. are located in environmentally
fragile areas where development remains extremely controversial, such as the
Coastal Plain of the Arctic National Wildlife Refuge, and offshore regions of the
Gulf and the Pacific coasts. Leasing and drilling activities in these areas would
provide only a temporary solution to a long-term problem.
In contrast, agricultural raw materials offer a renewable alternative with dis-
tinct economic advantages to replace petrochemical feedstocks for industrial appli-
cations. The domestic production of industrial agricultural crops promotes a stable
and secure supply of the raw materials obtained from these sources. This presents
both economic and strategic benefits to the U.S. There is an economic benefit to
the farmers and local processors involved in the production and post-harvest hand-
ling of the crop. Additional economic stability exists for the farmer who is supply-

ing a crop with both edible and industrial applications. For example, a decline in
the price of a crop or derivative agricultural material in the edible market may be
offset by the price in the industrial market. This stability improves the rural econo-
my and stimulates diversity in the agricultural marketplace. The national economy
also benefits from this stability. The increased agricultural production of oilseed
crops for industrial oleochemicals will provide a secure source of raw materials for
the chemical process industry and reduce dependence on imported petroleum.
The economic benefit associated with substituting an agricultural raw material
for a petrochemical raw material may not be measured simply by the raw material
cost or through evaluation of conventional direct production costs. A more accu-
rate life-cycle analysis must be evaluated for each particular case. Comprehensive
life-cycle assessments are not trivial to perform and the results obtained for one
crop do not necessarily transfer to a similar crop (9). Such analyses must consider
the agronomic expenses of fertilizer, pesticides, cultivation, harvest, transport, and
storage of the crop plus the additional post-harvest processing that may be required
to recover or prepare the agricultural material for use as an industrial raw material.
For example, crushing, expelling, or refining operations are necessary to recover
the natural oils from an oilseed crop followed by hydrolysis or transesterification
of the component FA.
The strategic plan prepared by the Biomass Research and Development Board
in response to the Biomass Research and Development Act of 2000 and executive
order 13134 (which set the national goal of tripling the use of biobased products
and bioenergy by 2010) proposed the coordination of federal, state, and industrial
activities to accelerate the commercialization of biobased products and technolo-
gies without adversely affecting environmental and public health (10). The envi-
ronmental aspects of developing biobased products and implementing the corre-
sponding production technologies need to be evaluated critically.
Life-cycle analyses have also been performed to evaluate the environmental
impact of manufacturing a particular product from agricultural raw materials ver-
sus one manufactured from petrochemicals. A review performed in Germany
found that the use of vegetable oils, specifically rapeseed oil, to produce surfac-
tants presented definite advantages both in the reduction of greenhouse gases such
as carbon dioxide, and energy requirements (11).
Surfactants
Surfactants are applicable to both edible and industrial products. Edible applica-
tions include use as emulsifiers or thickening agents. The monostearate and oleate
glycerides are used in the highest volume in the food industry where these com-
pounds act as viscosity modifiers and stabilizers that provide texture to processed
foods (12). Industrial applications of surfactants are numerous. Surfactants are
important components in formulations of agrochemicals, corrosion inhibitors, cos-
metics, detergents, lubricants, metal working and oil drilling fluids, polymers, and

textile finishes (3). They can act as emulsifiers, dispersants, stabilizers for oil-in-
water (o/w) or water-in-oil (w/o) emulsions, viscosity modifiers or flocculents.
Surfactants can impart foaming, leveling, release, or wetting properties to formula-
tions. The attributes of the surfactant that make it suitable for a specific application
are determined by the chemical structure which can be designed for optimal perfor-
mance in a particular formulation.
Surfactants are classified as anionic, cationic, amphoteric, or non-ionic based
on the ionization of the structure in an aqueous system. Surfactants from all of
these classes may be produced from vegetable oils. The typical surfactant structure
consists of a hydrophilic group attached to a hydrophobic moiety. Common
hydrophiles include the carboxylate, sulfate, sulfonate, or phosphate groups for
anionic surfactants and amine or ammonium groups for cationic surfactants.
Common hydrophobes or lipophiles include the linear hydrocarbons of medium
chain length (C12C18). FA obtained from natural fats and oils provide this struc-
ture, and their salts were some of the earliest surface active compounds prepared.
However, FA may be easily converted into a variety of derivative compounds with
a wider range of surfactant properties through reaction of the carboxylic acid group
(13). The FA may undergo amidation, esterification, or ethoxylation to produce
derivative structures with specific surfactant properties. Alternatively, the FA may
be reduced to the fatty alcohol which is another important material for the produc-
tion of surfactants. Fatty alcohols produced from vegetable oils in this way com-
pete directly with those obtained from petrochemical sources.
In some instances the alkyl portion of the FA may contain hydroxyl or epoxide
functionalities. The presence of such functional groups permits chemical modifications
to be made along the hydrocarbon chain that can further alter the surfactant character-
istics. If these functionalities do not occur naturally in the FA they may be introduced
by addition reactions at unsaturated sites. Several important surfactant compounds that
may be synthesized from vegetable oils are described in the following sections.
Esters
FA esters are formed by the condensation of an alcohol with the free FA or by
transesterification of the triglyceride in the presence of an acid or base catalyst.
Esters of primary and secondary alcohols such as methyl, ethyl, isopropyl, butyl,
octyl, decyl, myristyl, and cetyl are commonly used in cosmetic and personal care
products (14). These compounds act as excipients, lubricants, plasticizers, soften-
ers, solubilizers, and wetting agents in cleansing creams, lipsticks, insect repel-
lants, nail varnishes, perfumes, bath oils, creams, lotions, antiperspirants, and
deodorant formulations. The methyl esters are also intermediates for the synthesis
of other surfactants such as the -sulfonates.
Esters produced by reaction of the FA with polyhydroxy alcohols such as gly-
col, glycerol, pentaerythritol, or sorbitol produce compounds with greater
hydrophilic characteristics (15). These materials act as emulsifying, opacifying, thick-

ening, dispersing, pearling, and anti-foaming agents that find applications in the
preparation of o/w and w/o emulsions, absorption bases, pomades, emollient creams,
and shampoos.
Sucrose esters display high biodegradability and physiological inertness (16).
The best detersive performance is reportedly obtained with saturated C18 FA. These
compounds find applications in cosmetic and detergent formulations.
Esters prepared with polyethylene glycol (PEG) provide a non-ionic o/w emulsi-
fier for cosmetic and pharmaceutical formulations. The emulsifier is used as a thicken-
ing agent in creams, a suspension agent for solid substances, and a stabilizer in formu-
lations with a high proportion of electrolytes. It has also been used as an anti-static
agent for plastics.
Ester Sulfonates. A sulfonated FA methyl ester is prepared by the transesterification

of a vegetable oil to obtain the corresponding methyl esters followed by sulfonation
with sulfur trioxide. The hydrophilic sulfonate group increases the water solubility
while the linear hydrocarbon moiety provides the necessary lipophilic character. Ester
sulfonates exhibit favorable wetting, emulsifying, and dispersant properties (17,18).
This is an efficient method for the production of these anionic surfactants (19). These
compounds have been prepared from coconut oil and compare favorably to C12C14
fatty alcohol ether sulfates and C14C16 olefin sulfonates (20,21).
Yields greater than 95% are obtained when the vegetable oil is hydrogenated
prior to sulfonation. If the oil is unsaturated then numerous reaction products are gen-
erated. Further reaction of the sulfonate with diethanolamine (DEA) or tri-
ethanolamine (TEA) produces improved foaming characteristics (22). The sodium
DEA and TEA salts of -sulfomyristate exhibit better detergency than sodium lauryl
sulfate with less irritation in physiological tests (23).
Ester Ethoxylates. Fatty ester ethoxylates are prepared by catalytic ethoxylation of

the FA methyl esters. These ethoxylates are comparable to the alcohol ethoxylates but
with increased water solubility (24). Glycerol esters prepared with 7 moles of ethoxy-
late are used as dispersing and solubilizing agents. These non-ionic ethoxylates pro-
mote the solution of other lipid ingredients in alcoholic formulations. Applications
include emulsifying, opacifying, thickening and dispersing agents for in oil-in-water
emulsions.
Sorbitan esters prepared with 420 moles of ethoxylate also act as emulsifying,
dispersing, and solubilizing agents for vitamins, essential oils, fragrances, tannins, and
other lipid components in cosmetic formulations and topical medicinal preparations.
Amides
FA or their methyl esters can react with primary and secondary amines such as
monoethanolamine (MEA) and diethanolamine (DEA) to produce the correspond-
ing amides (25). However, the reaction of FA with MEA or DEA can produce

unwanted ester by-products, whereas reaction of the corresponding methyl ester

with MEA or DEA produces the desired alkanolamide with over 90% yield.
Amido alkoxylated ammonium compounds are also prepared from either the
FA or the triglyceride by reaction with diethylamine triamine followed by ethoxy-
lation and conversion to the methyl sulfate derivative with dimethyl sulfate (26).
The amido imidizolines are produced by a similar reaction scheme but at elevated
temperatures cyclization occurs (27). These compounds are used industrially as
fabric softeners, flotation agents, corrosion inhibitors (13,28).
The amides also serve as intermediates for structures such as the betaines
which exhibit good foaming power and favorable skin tolerance. The reaction of a
FA with an amino acid such as N-methyl glycine produces the important class of
N-acyl-sarcosine surfactants. Additional condensation products may be obtained
by reaction of FA with protein hydrolysates. These compounds have diverse prop-
erties, and applications including use as rust inhibitors, fuel oil additives, and
emulsifiers.
Alcohols
Fatty alcohols are not produced in significant quantities by commodity oilseed
crops although some specialty crops such as jojoba produce wax esters rather than
triglycerides. However, it would not be practical to obtain fatty alcohols from jojo-
ba oil because of the value of the oil. Alternatively, fatty alcohols may be produced
by the hydrogenation of the triglycerides, FA, or FA esters obtained from veg-
etable oil (29,30). The resulting fatty alcohols provide an alternative to the petro-
chemical source. The fatty alcohol is reacted to form ethoxylated, sulfated, or ami-
nated surfactant compounds. The alcohol ethoxylates are prepared by reacting the
fatty alcohol with ethylene oxide. The ethylene oxide chain provides the hydro-
philic character for these non-ionic surfactants. These compounds are biodegrad-
able and are used in formulating low foaming degreasers and liquid cleansers
(3133).
Subsequent sulfation of these alcohol ethoxylates produces biodegradable sur-
factants that exhibit exceptional foaming and detergency, and are used in sham-
poos. The fatty alcohol may also be sulfated directly with sulfur trioxide to provide
the alcohol sulfates which are used extensively as foaming agents in personal care
products (34,35).
Amines
Amines can be produced by the reaction of fatty alcohols with alkylamines or by
reduction of the fatty nitrile (36). Primary, secondary, tertiary, and quaternary
amines are prepared via the fatty nitrile which is formed by the reaction of the FA
with ammonia, followed by hydrogenation to produce the corresponding fatty
amine. Amine oxides can be prepared from the fatty amine by heating with hydro-

gen peroxide. These compounds are mild with good foaming properties, and are
used in shampoos and cosmetic products.
Summary
Clearly, a variety of vegetable oil-based surfactants can be prepared from the reac-
tion of FA or the corresponding methyl esters with various alcohols or amines. A
surfactant of every type is represented, such as anionic, cationic, non-ionic, and
amphoteric, with applications in personal care products, household detergents, and
industrial cleansers. Surfactants are essential components in formulations in such
diverse areas as emulsion polymerization, textile treatments, agrochemicals, paper
and textile finishes, coatings, metal working fluids, and corrosion inhibitors.
Currently, the consumer has expressed interest in bio-based products. In
response, initiatives for using renewable raw materials have been established by
the federal government. Similarly, applicable industries will evaluate the economic
benefits of using natural raw materials to replace petrochemicals.
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Industrial Use of Vegetable Oil

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IndustOils (FM)(i-vii)Final 3/23/05 6:00 PM Page 1

Copyright 2005 AOCS Press

AOCS Mission Statement

AOCS Books and Special Publications Committee

Library of Congress Cataloging-in-Publication Data

Industrial uses of vegetable oils / editor, Sevim Z. Erhan.

Printed in the United States of America.

Copyright 2005 AOCS Press

Copyright 2005 AOCS Press

Chapter 3 reviews some of the advantages and disadvantages of using vegetable

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Copyright 2005 AOCS Press

Chapter 1 Genetic Modification of Seed Oils for Industrial

Chapter 2 Current Developments of Biodegradable Grease

Chapter 3 Vegetable Oil-Based Engine Oils: Are They Practical?

Chapter 4 Biodiesel: An Alternative Diesel Fuel from Vegetable

Chapter 5 Biofuels for Home Heating Oils

Chapter 6 Vegetable Oils-Based Polyols

Chapter 7 Development of Soy Composites by Direct Deposition

Chapter 8 Vegetable Oils in Paint and Coatings

Chapter 9 Printing Inks

Chapter 10 Synthesis of Surfactants from Vegetable Oil Feedstocks

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Genetic Modification of Seed Oils for

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Genetic Modification of Seed Oils 3

Fig. 1.1. The pathway of fatty acid biosynthesis to linoleic acid.

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Medium Chain-Length FA Biosynthesis

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Genetic Modification of Seed Oils 5

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dation, desaturation-conjugation and desaturation to a triple bond (22,24,25). In the

Castor Oil Biosynthesis

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Genetic Modification of Seed Oils 7

be eliminated from the membrane by endogenous phospholipases (38) and beta-

(i) The lyso-phosphatidylcholine acyltransferase (LPCAT) transfers the oleoyl-

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Fig. 1.2. Castor oil pathway.

New and Improved Crops

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Genetic Modification of Seed Oils 9

Fatty acid Functionality Source Use

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Genetic Modification of Seed Oils 11

6. Browse, J., and C. Somerville, Glycerolipid Synthesis: Biochemistry and Regulation,

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Genetic Modification of Seed Oils 13

40. Smith, M.A., L. Jonsson, S. Stymne, and K. Stobart, Evidence of Cytochrome b5 as an

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Current Developments of Biodegradable Grease

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Biodegradable Grease Developments 15

Fig. 2.1. Grease composition.

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agriculture has caused an intensive exploitation of natural resources like mineral

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Biodegradable Grease Developments 17

Fig. 2.2. Typical vegetable oil structure.

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