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Published by MALAYSIAN PALM OIL COUNCIL 2nd Floor, Wisma Sawit Lot 6, SS6, Jalan Perbandaran, 47301 Kelana Jaya, Selangor, Malaysia.

Copyright © 2010 Kurt G. Berger All rights reserved. No part of this book may be reproduced in any form or by any means without prior permission from the Publisher.

National Library of Malaysia

Cataloguing-In-Publication Data

Berger, Kurt G. Quality and functions of palm oil in food applications: a layman's guide/ Kurt G. Berger ISBN 978-983-9191-09-7 I. Palm oil -- Quality. 2. Palm oil--By product. 3. Palm Products--Malaysia I.Title 633.85109595

FOREWORD
While working at the Palm Oil Research Institute of Malaysia (now the Malaysian Palm Oil Board) in the 1980s I received a phone call from a social acquaintance involved in the palm oil trade, asking "I say old chap, what's a fatty acid then?" It was not difficult to help him. Reflecting on the question later it occurred to me that many of the people involved in palm oil, from growing through to end use, would surely find it interesting and of benefit to know something of the basic technology. That thought led to a series of articles in the Global Oils & Fats Business Magazine (GOFB). There were two main objectives.The first was to describe the parameters used to judge the quality of the product and the measures needed to ensure its good arrival at the user, and the second was to provide information on how it is used in food production around the world and, with it, to give some insight into the fascinating scientific aspects of food. My own involvement in palm oil dates back to my time in the London research laboratories of a large food manufacturer. In 1953 the British food industry was finally liberated from the shackles of the wartime Food Ministry control, and we started to experiment with palm oil, which was a new ingredient to us. We found that it was functional and economic in a number of our products. This work led 20 years later to an invitation to talk about our experience at a two-day conference in London dealing with palm oil from the planting to the eating. One of the other speakers was Tan Sri Borg Bek-Nielsen. When we met again in 1976 he remembered my presentation and said: "We are thinking of starting a Research Institute for palm oil and you must come and help us when we are ready."

feeding back to the Food Technology Unit any problems that needed practical investigation. Kurt Berger Food Technology Consultant. Chemical research started in 1979 and within two years yielded results that were suitable for presenting at an international palm oil conference organised by the Incorporated Society of Planters. and then came the planning of permanent buildings and selection of a site for the Institute. It was important to publicise useful results at international conferences and to take part in government-led trade missions. the refineries and the work of the research institute and given opportunities to talk to all those concerned. This programme continues today. next. key people in government offices and industry in developing countries were invited at the Institute's expense to visit Malaysia for two weeks.Two years later a formal invitation came.This book is based on the GOFB series of articles. At that time. It proved particularly useful in a number of countries where purchasing decisions were made in government offices with little technical knowhow. for which we found two shophouses in the suburbs of Kuala Lumpur. edited and brought up to date. a Familiarisation Programme was instituted. we found people who were suspicious of an ingredient unknown to them after using only their traditional ingredients for many years. To develop some confidence in the product. It is similarly urgent today to inform present and potential importers of palm oil's versatility in application in their accustomed food products. and there is no doubt that the friendly contacts made have oiled the wheels of commerce. which I was able to accept. only western Europe was knowledgeable about palm oil.They were shown the plantations. First we needed to draft a research programme and agree it with the technical committee of the industry. UK . There followed an exciting and busy eight years in Malaysia. Staff for the Technical Advisory Service were recruited in 1980 and soon started to investigate the potential uses of palm oil around the world. to establish temporary laboratories. Not surprisingly perhaps.

CONTENTS CHAPTER 1 Basic chemistry of fats 8 CHAPTER 2 Tests of quality 14 CHAPTER 3 Quality during transport 21 CHAPTER 4 Bakery products 29 CHAPTER 5 Aerated dairy products 39 CHAPTER 6 Butter alternatives 46 CHAPTER 7 The lauric oils 65 CHAPTER 8 Confectionery fats 70 CHAPTER 9 Frying oils 79 CHAPTER 10 Low trans fats formulae 87 CHAPTER 11 Palm-based oleochemicals 93 CHAPTER 12 Oils and fats properties 106 .

This chapter examines the chemical composition of oils and fats. Nine propositions cover the basic chemical information required to understand the main technical terms used in the oils and fats industry (see Box). .8 CHAPTER 1: BASIC CHEMISTRY OF FATS Technical aspects of oils and fats are of importance to those in the business.

a double bond is actually weaker.9 PHYSICAL PROPERTIES What makes fats solid and oils liquid? More details about fatty acids are useful in answering this. However. At first sight. one would think that a double bond would be stronger than a single one in linking the Carbon chain. the two bonds involved are bent out of their natural position and therefore are under strain. . So.

Trans fats are now known to be nutritionally undesirable. and you can't spread olive oil on bread. so they stay liquid. they are available in relatively small amounts. for bakery products. so increasing the average saturation of the oil. Hydrogen is added to some of the unsaturated component fatty acids. It is now a 'trans' unsaturated fatty acid (trans fat). In terms of world supply. The most important exception is palm oil. The kink in the unsaturated acids makes it more difficult for their triglycerides to align and form crystals. Historically. The liquid oils can be modified to have a solid consistency by hydrogenation. for ice cream. This sounds very simple but at the molecular level there is a complication. olive and maize oils. These consist of soybean. it has a solid consistency at room temperature and is therefore unusual among vegetable oils. this solid character was provided by animal fats. groundnut.10 So triglycerides containing only or mainly straight saturated acids align easily together to form crystals. unchanged unsaturated acids and trans fats. rapeseed. A solid character to a varying degree is necessary in fats for margarine. Most of the major vegetable oils contain mainly unsaturated fatty acids and are liquid at room temperature. Such triglycerides are solid at room temperature. sunflower.With 50% unsaturated and 50% saturated acids. Coconut and palm kernel oils are also solid due to their unusual content of short and medium chain saturated acids. The process takes place at around 100°C when the oil is mixed with hydrogen gas in the presence of a catalyst. A simple example . They have special applications in food and in the oleochemical industry. During hydrogenation the unsaturated acid has to go through an intermediate stage.you can't pour margarine or butter on salad. the chain becomes straight but the double bond is still there. since research has shown that they raise the level in the blood of undesirable 'LDL cholesterol' which is involved in the . FOOD USES Many of the food uses of oils and fats depend on the consistency or body. cottonseed. but these are little used in margarine and bakery fats nowadays. At this point the kink at the double bond is ironed out. Partly-hydrogenated oils always contain a mixture of saturated acids.

Denmark has imposed a legal limit on the amount. which induces all the fatty acids to disconnect from their glycerol and re-attach to some other available glycerol in a random manner. At the same time they also decrease the blood level of the desirable 'HDL cholesterol' which removes excess cholesterol from the blood stream. The second approach uses palm oil or its higher melting fraction. .The fully saturated fat is melted and mixed with liquid oil. A catalyst is added. Two approaches are used to make consistent fats without trans fats: 1. palm stearin. This trend can confidently be predicted to continue. or by using the interesterification procedure on a mixture designed to get the characteristics needed. 2. such a fat is as hard as bricks and. as in the USA. The choice between the two approaches will depend on circumstances. This doubly adverse result is now universally recognised and has led national and international expert bodies to advise minimising trans fats in foods.11 process of clogging up the arteries. either in a mixture with other oils. In many situations the palm oil method is the more economic. Consumer awareness of nutritional issues is high everywhere and food industry management is therefore strongly motivated to remove trans fats from products. clearly you no longer have any trans fats. on its own. If you completely hydrogenate liquid oil. of no use in food. you finish with a fat of just the desired consistency. If you get the right proportions of the ingredients. and the rest are following. the availability of locally produced oils may point to the first method. so that all double bonds are saturated. However. Some countries have labelling laws to declare the trans fats content in food products. 'interesterification' comes into play. for example. Some commercial firms in the USA already offer palm-based products for formulations that are free of trans fats. The steady increase in recent USA imports (Figure 1) shows that some manufacturers have been taking advantage of the 'solid fat' properties of palm oil and palm stearin since 2000. Another simple chemical process. In the UK a large supermarket is stating that most of its products are now free of trans fats.

when selecting the solid component for a margarine formula. Today this option is much less available due to marketing considerations. palm oil is therefore a unique ingredient for this purpose. rapeseed or other liquid oil and palm oil. . it was possible to choose between partly hydrogenated soybean. For example. But just how interchangeable are vegetable oils? This answer very much depends on the intended use.12 Interchangeable use A degree of interchangeability of oils is welcomed by the food industry as it gives the buyer a choice of the cheaper supply.

there are still aspects of consumer choice. At present. all these oils can be regarded as interchangeable. Extensive full-scale trials with a 'high oleic' sunflower oil (and low in linoleic acid) have proved its good performance in potato crisps. Use in frying The important use of oils and especially palm oil for frying will be discussed in Chapter 9. Both groundnut and cottonseed oil tend to crystallise in the refrigerator. It is clearly important for the long term that research into creating a palm oil low in saturates and high in unsaturates should be successful. rapeseed. They are succeeding in producing oils with reduced levels of the more unsaturated acids. the present type of palm oil. as does palm olein.There may be a preference for sunflower oil or maize oil because they have long been promoted as being healthy. . It is also met by maize oil. This is likely to change in the future due to the efforts of plant breeders. but secondly an unsatisfied demand for a palm oil that is truly competitive in its characteristics with the liquid vegetable oils. which is the more liquid fraction of palm oil. While the above salad oils are interchangeable as regards technical performance.This demonstrates the dynamic nature of the competition between the different oils and of their interchangeability. To take full advantage of the productivity of the oil palm. olive and sunflower oils. provided its traces of natural waxes have been removed. So.This criterion is met by soybean.firstly. The reason for the decision to change is the perception that the more unsaturated sunflower oil is healthier. Rapeseed and soybean oils of modified composition suitable for frying are now available in limited quantity.13 For use as a salad oil it is desirable that the oil should remain clear at the temperature of a domestic refrigerator (5°C or 40°F). due to their high content of the nutritionally essential linoleic acid.Thus olive oil is often prized for its special flavour characteristics and commands a high price. interchangeability of oils is limited in deep frying. so valuable in the production of consistent fats. the world market has a clear demand for two types of palm oil . Some snack food operations have already changed from palm olein to the high oleic sunflower oil despite its significantly higher price.

or the Codex Alimentarius Commission set up under the United Nations. Over 100 nations collaborate in the Codex system and its standards carry a great deal of weight in commerce. which the dictionary defines as: a. For credibility. degree or grade of excellence In practical terms. An inherent or distinguishing characteristic. It describes how analysis methods are standardised and applied in determining ‘quality’. in view of the need to protect against deliberate or accidental adulteration. we look at how the quality of vegetable oil is analysed – how quality of oil is defined at the time of purchase in global trade. a property. essential character or nature b. Superiority of kind. how this affects their use in foods. A ‘recipe’ is circulated together with appropriate samples and the results are analysed statistically. International Standards Organisation. STANDARD METHODS OF ANALYSIS The process of standardisation is elaborate and is organised by national bodies such as the British Standards Institute or American Oil Chemists Society. the details of the ‘recipe’ are discussed. these must be carried out by qualified analysts using standardised procedures. In this chapter. Eventually acceptable results are obtained and the agreed method is given official status. is the oil what it is supposed to be and is it in good condition? Both these aspects are defined by means of chemical analyses. A number of reputable laboratories volunteer to take part in the study of a method. Technical committees develop the standards which are adopted at government level. and why the special characteristics of palm oil are valued.14 CHAPTER 2: TESTS OF QUALITY Chapter 1 explained the chemistry of oils and fats. modified and further tests arranged. or international bodies like the International Union of Pure and Applied Chemistry. The Codex commission’s objectives are to agree on codes of practice and standards for food commodities in order to facilitate international trade. Codex stan- . If not within acceptable limits of agreement.

For example. For example.The total number of unsaturated bonds is readily measured by the Iodine Value – literally the number of grams of iodine needed to react with the double bonds in 100gm of oil. A conventional method of obtaining a clear-cut result is used. both saturated and unsaturated. CHEMICAL AND PHYSICAL DEFINITIONS OF IDENTITY Source of oil The first thing is to define the source of the oil. so they melt over a range of temperatures. mainly with refined oils. The ‘slip melting point’ is obtained by filling a capillary tube with the sample in liquid form. soybean oil is derived from seeds of the soybean (Glycine max). Codex gives these ranges for three oils: The Palm Oil Refiners Association of Malaysia (PORAM) has adopted the range for palm oil products in its standard specifications. Fats are mixtures of different glycerides. since it is mainly used for direct consumption as crude oil.15 dards deal with products in consumable condition and. Slip melting point The melting point is a useful measure of the physical properties of oil. Iodine number All oils contain a mixture of fatty acids. therefore. Olive oil and palm oil are the only major vegetable oils derived from fruit flesh. and palm oil from the fruit flesh of Elaeis guineensis. Olive oil is an exception. Being natural products. and . However.The proportion of unsaturated acids is a useful identity characteristic. All others are extracted from seeds. a range of Iodine Values normal for each oil can be established. olive oil from the fruit flesh of the tree Olea europea. crystallising it under precise cooling conditions. oils show some variation due to variety and growing conditions.

16 then determining the point at which the sample rises in the tube when heated in a waterbath. In the Vitamin E group of substances (tocols). • For palm oil. Sterol composition of oils also reveals differences useful for identification (Table 3). Composition of oils Table 1 gives compositional data obtained by gas chromatography for typical samples of palm oil and its fractions. extensive surveys by the Palm Oil Research Institute of Malaysia (now the Malaysian Palm Oil Board) have established a range of 33-39°C. • PORAM and Codex have adopted a slip melting point of 24°C or less for palm olein. as well as for soybean and olive oils. Codex also gives a point of 19.5°C or less for palm super olein.The sample is not completely molten but a precise reproducible figure is obtained. . these consist of saturated tocopherols and unsaturated tocotrienols (Table 2). also used in PORAM trading specifications. For simplicity only the main fatty acid components are specified. Chromatographic methods are also useful for analysing the minor components of oils. and 44°C or more for palm stearin.

palm oil was mainly traded internationally as crude oil. maximum 5%) and moisture and impurities (maximum 0. The 5% ffa limit for standard CPO is higher than would be acceptable for other vegetable oils. .17 CRUDE PALM OIL (CPO) QUALITY Different tests are needed to determine the condition of oils. monoglycerides and diglycerides.25%) were adopted and are still used today for standard CPO. The enzyme is released from the fruit cells when the fruit is over-ripe or when it is bruised. Until the development of Malaysian refining capacity. Basic quality specifications of free fatty acids (ffa.This is because the palm fruit contains a very active lipase (fat splitting) enzyme. which rapidly breaks down the triglycerides to a mixture of ffa.

so it is likely that some will be over-ripe during harvesting. the 1. However. a special quality crude oil is offered by some producers. others will be bruised as the bunch falls.18 In practice. and the lipase then becomes active. cooked and pressed immediately it is possible to obtain oil with only 0. Malaysian refiners have adopted a more science-based procedure developed by PORIM. It is obtained by harvesting somewhat early to minimise over-ripe fruit. Bleachability test A pale near-white colour is regarded as an important characteristic of well-refined oil. which leads to the formation of persistent coloured products. but this is not practicable on a manufacturing scale.5% and minimal oxidation is produced and is easier to refine. European refiners use an empirically standardised bleaching test in the laboratory to estimate the bleachability of CPO.000 or more fruitlets in a bunch do not all ripen simultaneously. some loss of yield results. Bruising during transport is avoided by taking steriliser cages to the field for loading and sterilisation is carried out without delay.8% ffa. If fresh fruit is taken directly to the laboratory from the field. Moreover. • The other (B) measures the concentration of certain oxidation products of the fatty acids. Oil with a maximum ffa of 2. Fur ther bruising takes place in the various operations before the bunch is sterilised and the lipase is destroyed.and di-glycerides which can cause difficulty in fractionation. lower ffa means also a lower content of mono. known as the Deterioration of Bleachability Index (DOBI). The DOBI test involves the measurement of the absorption of ultraviolet light by a solution of the oil at two different wavelengths: • One (A) is a measure of the unchanged carotene present (carotene is easily destroyed by oxygen). . Since oil synthesis in the fruit is very active towards the end of ripening.The bleachability of CPO in the refining process is largely determined by the extent of oxidation.

resulting in shor t chain volatile compounds and residues of oxidised glycerides. . PORAM has adopted a minimum level of 2. The two are sometimes combined – 2 x Peroxide + 1 x Anisidine is defined as the Totox Value. These residues are measured by the Anisidine Value. The peroxide value is a direct measure of the amount of oxygen that has combined at the double bonds of the fatty acids. Test for oxidation Two measures of the oxidation level in crude oil are commonly used – Peroxide Value and Anisidine Value. The full specifications for special quality CPO are given in Box 1.30 as a standard. The PORAM trading specifications for refined palm oil are shown in Box 2. and there has been a loss of quality. A high figure is an indication that oxidation has taken place in the past.19 The ratio of A to B is a sensitive indicator of the extent of oxidation. In time these oxidised bonds are broken. it entails some loss of information. While convenient. REFINED PALM OIL QUALITY Fully refined palm olein and palm oil are the main exports today.

20 The Codex Alimentarius has extensive specifications (Box 3). . common to all vegetable oils traded as refined oils. Each figure represents the maximum specification.

In its early years. The best that can be expected is that it should arrive in unchanged condition. Any loss of quality has to be rectified by a second refinery treatment resulting in extra costs to the purchaser.The transport chain usually involves a number of steps. It needs to be kept warm to prevent excessive crystallisation.21 CHAPTER 3: QUALITY DURING TRANSPORT No commodity is improved by transport. Edible oils can suffer during transport in three ways: • Oxidation through contact with air. now the Malaysian Palm Oil Board or MPOB) collected information on the extent and causes of quality changes during transport. particularly at higher temperatures • Hydrolysis through the action of traces of water. Malaysian palm oil is mainly transported in fully refined form. catalysed by acidity or by enzymic action from microbiological contaminants such as moulds or yeasts • Foreign matter such as dirt or residues from previous cargoes Most of the major vegetable oils are transported as crude oils at ambient temperature. . Any chemical changes will occur faster at temperatures above ambient. the Palm Oil Research Institute of Malaysia (PORIM.

Measurements were made of the level of oxygen dissolved in the oil and of the peroxide value. .The South Korea shipment showed appreciable oxidation which had occurred partly during the journey and further during transfer by barge at the port of arrival. Each stage of the transport chain is under different management. Samples were taken from several ships’ tanks during a voyage and analysed on board (Table 2).The Pakistan shipment showed some increase in acidity. In order to provide an assurance of good practice. PORIM undertook to obtain first-hand information by sampling and analysing oil at various stages of transport.22 In some ports. independent surveyors are employed to approve the condition of the various facilities. At each stage the transfer involves pumps. The shipment to New Zealand (Table 1) arrived in unchanged condition. unloading also involves the use of barges. Some results are summarised in Tables 1 to 3. pipelines and tanks where contamination by previous cargoes or foreign matter can occur.

However clean the latter are. only 20% landed with ffa below 0. fully refined oil is expected to have a free fatty acid (ffa) content below 0. and oxidation was quite moderate. A substantial proportion of oxygen remained in solution. from clean tanks with a perfect protective coating to those showing somewhat rusty surfaces. then 75% landed with ffa below 0. Samples were drawn from a pipeline delivering oil into a shore tank at a foreign destination (Table 3). If the initial ffa was 0. they catalyse oxidation reactions. Evidence from a number of shipments has shown that it is a case of the ‘the lower the better’.10%. Clearly the pipeline was not clean. A follow-up study of 20 shipments showed that when the acidity was 0. so that the dissolved oxygen was nearly all used up and oxidation was appreciable.05-0. The refined stearin had much lower iron content.10%.05 or less at loading. As explained in Chapter 2. Inspection of some ships showed wide variation in conditions. From the rate of pumping it was calculated that the first 30-40 tonnes of product were sub-standard. but contained some water and a quantity of some strongly coloured oil. .23 The high iron content in the crude palm oil stearin catalysed oxidation of the oil. The overall conclusion was that the effect of transport varied. with significant effects on oil quality in some instances.10%.10% (still within acceptable limits).

24 PREVENTING LOSS OF QUALITY Quality loss during transport is avoidable provided that exceptional care is taken in the cleanliness and condition of the equipment.This involves fitting an inlet tube so that nitrogen is forced into the oil under pressure.This is because the ‘sparging’ removes some of the low level of water dissolved in the oil (no more than about 0. which otherwise promotes some hydrolysis. Gas is ‘sparged’ into the oil as it is pumped through pipelines. Clearly nitrogen-blanketing largely prevented oxidation. especially if the cargo is protected by nitrogen throughout. and a nitrogen atmosphere is maintained in the headspace above the oil. nitrogen use involves extra costs and this has prevented its use for the majority of cargoes. Still. Storage tanks and ships’ tanks are flushed with nitrogen before being filled. as seen in the examples in Tables 4 and 5. but it also prevented any increase in acidity. and that access to the air is prevented. Arrival of oils in perfect condition can be achieved.1%).The latter requires the provision of nitrogen gas throughout the transport chain from the refinery to destination. However. the costs can be at least partly offset by avoiding any . Excellent results can be achieved.

The surveyor in turn completes a certificate of the cleanliness and suitability of the ship’s tank. Issues of quality are at the forefront of shipping contracts and are dealt with in government and international regulations. Seeds and Fats Associations (FOSFA). and the adoption of this handling procedure could form the basis of a brand image that could not at present be matched elsewhere. Clauses relate to the quality and specification of the oil and the responsibility for cleanliness of the ship’s tank. palm oil would set solid and become vir tually impossible to unload. to keep it totally liquid. have external heating coils. based in London. Loading and discharge procedures and the method of sampling for analysis are also laid down. but the likelihood of deterioration of the cargo is reduced. The ship’s master is required to complete a certificate regarding the suitability of the tank. SHIPPING CONTRACTS The quality of Malaysian palm oil intended for export is controlled by government regulations and monitored by the MPOB. The reputation of Malaysian palm oil is enhanced when such quality maintenance is achieved. The Federation of Oils.They hold about 21 tonnes of oil. top and bottom discharge points and are easily cleaned. The FOSFA operating procedures emphasise the control of temperatures of the cargo. For speciality products shipped in smaller quantities. At present only small quantities of oil are shipped with nitrogen protection. This is of par ticular impor tance for palm oil products. Their use is more expensive. These are stainless steel tanks conforming to specifications laid down by the International Standards Organisation (ISO). prepares formal shipping contracts. FOSFA provides training courses for the junior and middle management of surveying companies. ISO tank containers may be used. At ambient temperature. However. heating system and pipelines and the cleaning procedures used.25 reprocessing to clean up the oil. . The three previous cargoes carried in the tank must be specified. a temperature would be required which would risk a serious level of oxidation. The ship’s surveyor and the analytical chemists are expected to be members of FOSFA.

It prepares contracts. the National Institute of Oilseed Products (NIOP) carries out functions similar to those of FOSFA.The latest revision in 2002 uses the oil specification shown in Chapter 2. and there were variations in composition of the oil throughout the tank. disputes have arisen due to inadequate reheating. and its trading rules contain detailed requirements regarding the quality of the shipping operations. FOSFA also has recommendations for the handling temperatures for palm oil and palm kernel oil products. so that the oil arrives in a homogenous liquid condition. It is the surveyor’s responsibility to check that this condition has been reached at the time of arrival and sampling. In the past. Some crystallisation occurs during the voyage. In the USA. . Other items relating to quality are essentially the same as those given in the FOSFA contract. which is frequently used. the palm oil had partially fractionated into olein and stearin. In consequence. Substantially. the same temperatures are advised by Codex Alimentarius (Table 6).26 FOSFA requires the temperature to be controlled according to minimum and maximum limits laid down by the International Association of Seed Crushers. The Palm Oil Refiners Association of Malaysia has a shipping contract for processed palm oil. and controlled reheating is therefore applied some time before discharge to raise the temperature by no more than 5°C/day.

c. The question of possible contamination by previous cargoes required detailed study. FOSFA was asked to co-ordinate the extensive work programme required to provide answers. FOSFA adopts a similar ruling. An important recommendation is that the condition of the equipment involved in every transfer of the oil should be inspected by a qualified superintendent. Contamination of edible oils with traces of previous cargoes is undesirable and may be dangerous. . what analytical methods are to be used. tanks and heating systems. Previous immediate cargoes are divided into those that are banned and those that are acceptable. which products can be removed during a clean-up process of the oil. the Codex Alimentarius Committee on oils and fats was requested to put a Code of Practice for storage and transport into its programme of work. Most vegetable oil transport is from east to west. which cargoes are toxic. As a result a number of large industrial firms and some surveyors’ organisations collaborated with PORIM in preparing an advisory booklet on transport. and ships carry a variety of chemical cargoes on the return trip. It covered design of pipework. Document CAC/RCP 36 entitled ‘Recommended International Code of Practice for the Storage and Transport of Edible Oils and Fats in Bulk’ was issued by Codex in 1987 and most recently revised in 2005. b. Discussion in the Codex Committee identified a number of questions to be answered. Previous cargoes On the question of previous cargoes. It covers the design and operation of the facilities involved in the transport chain.The advisory booklet was used as a starting point. As a further step. including: a.27 CODE OF PRACTICE The quality aspects of transport were discussed at an international oils and fats technical conference in 1982. and d. which products are absorbed by the tank coatings and how can they be removed. and operating procedures. it advised that the three previous cargoes carried in a ship’s tank should be declared.

resulting in elevated ffa.28 The NIOP rule is different. The International Maritime Organisation (IMO) has a number of regulations which impact indirectly on the quality of transport. The European Community (EC) has also adopted a positive list of acceptable previous cargoes. while a somewhat longer list is allowed for oils that are intended for reprocessing. of stainless steel. resulting in some oxidation. only the immediate previous cargo must be foodstuff or from the permitted list. and also from overheating. or lined with epoxy resin or similar coating. Where the oils are to be further processed. It only lists acceptable prior cargoes. An exception is made for cargoes from destinations only served by smaller. and b. using tanks as in (a). and when tank washings are discharged. Recent experience indicates that contamination by previous chemical cargoes is rare. These lists continue to be reviewed as necessary. Cargoes cause pollution if there is leakage due to an accident. A limited list is permitted prior to the shipment of edible oil that may or may not be reprocessed before use. because they harm sea birds and marine life. but believes that a negative list of banned immediate previous cargoes can cause confusion in administering the system. . Overheating may be due to a rapid heating-up process before discharge or from heat passing from adjacent tanks. Occasional quality problems occur due to the ingress of sea water. Vegetable oils are classified by IMO as hazardous. In due course an evaluation of the acceptable list will be required by the EC’s technical committee.They must therefore be carried in vessels with double bottoms and in tanks of stainless steel or suitable coatings. Oils that are not to be further processed must be carried in tanks that are: a. older vessels. It is chiefly concerned with preventing pollution of the environment. have been used for foodstuffs on the three previous voyages.

how its quality is measured. These are Vitamins A and E. A given amount of fat yields nearly twice the calories produced by the same quantity of the other major components of foods.This will be discussed. Nutritionally fat is an efficient source of energy. that is. Finally of particular interest to the food technologist is the part that fat plays in developing the structure of various food products. the proteins and carbohydrate (starch and sugar). the unleavened bread of the Bible. AIR CONTENT AND THE ROLE OF FAT We do not generally appreciate that air is an important component of many foods. Fats provide some essential dietary components. . usually measured in calories. We will now consider the function of the fat in the food products. both directly – for example in the use of butter or olive oil – and indirectly. those that cannot be synthesised in the body. For example a loaf of white bread contains about 60% of air by volume. A further function is to contribute to the flavour of the foods.29 CHAPTER 4: BAKERY PRODUCTS In the first three chapters. and how we can ensure that exports reach their destination in good condition. Without the air you would have a hard flat biscuit. pro-Vitamin D – which is converted into Vitamin D in the body – and the fatty acids linoleic (2 double bonds) and linolenic (3 double bonds). we discussed the chemical composition of fat. as a result of chemical changes and interaction with other ingredients during cooking. first in relation to bakery products.

and secondly it contributes to the tender ‘short’ eating quality of the baked cake. we do not want a tough chewy texture. When a product is baked the gluten dries. High protein ‘strong’ flours are needed for bread and puff pastry products. depending on variety and growing conditions. denatures and becomes tough. The protein content of wheat varies from 8-14% or more. the fat is first mixed thoroughly with about half of the flour and beaten to incorporate air. and the weak flour may be treated to reduce the activity of the gluten further. . During mixing of dough it hydrates and. In cakes. Low protein ‘weak’ flours are used for cakes. A Hobart-type of mixer fitted with a whisk type mixing arm is usually used both in the home and in the industry. Good aerating properties require a sufficient liquid oil content to enable air bubbles to be formed.The fat used in cake manufacture performs two important functions. and for most pastry and biscuit types. Cakes Our first example is a Madeira cake. as mixing continues. Firstly it enables air to be incorporated in the batter.The mix is aerated to 40-45% air. Examination under the microscope shows that the air bubbles are surrounded by fat. and also the presence of solids in the form of small crystals (Figure 1). The most interesting component of the wheat flour protein is gluten. it becomes elastic and stretches into thin filaments.30 Before discussing the different types of bakery products we need to understand the nature of wheat flour. the major ingredient (Table 2). In a typical two-stage mixing process for a Madeira cake.

The surface consists of liquid oil and looks smooth: however it shows a number of sharp lines. magnified about 5.These are edges of small fat crystals lying on the exterior surface of the bubble.The air content of the batter has now been diluted to about 15%. which has been cut in half. the remainder of the flour and the aqueous ingredients are added and mixed. We are looking at the internal surface of the bubble.The diagram in Figure 2 shows the need for small crystals that line the air cells efficiently. Large crystals would not be effective in containing and stabilising the air cells (Figure 2).000 times.31 Next. . Figure 1 is an electron micrograph of an air bubble in cake batter.

using polarised light to show up the crystals (Figures 3 and 4). .32 Small crystals are ensured both by correct formulation of the fat blend and by its processing. in contrast to the large crystals of the ‘beta’ form. A good shor tening requires the fat to be in the ‘beta prime’ polymorphic form. The difference is made clear under the optical microscope.

so the air bubbles are retained. The final air content is 65%. of 110 microns. it is now ready for the oven. Measurements under the microscope give air bubbles of an average diameter of 20 microns (1 micron = 1 millionth of a metre) in the batter. So. Figure 5 shows a slice of Madeira cake with its very fine air bubble structure. At this stage they are still surrounded by fat. and in the baked cake. . water vapour is generated and goes into the existing air cells. they are still very small. When baking star ts and the temperature rises. Eventually the egg protein sets and the cake structure is fixed.The word derives from the Greek for ‘many shapes’. The air cells become larger. As the temperature reaches about 40ºC the fat melts and the air bubbles move into the aqueous phase. Coming back to our well aerated cake batter.33 The aspects of polymorphism of fats will be discussed in a later chapter. Here the viscosity is increasing due to swelling and gelling of the starch. as does the carbon dioxide from the baking powder.

.34 Three tested formulae for bakery shortenings are given in Table 3.These fats have proved successful both in cakes and in pastry products.

It is essentially impor tant that the fat does not mix into the dough during the rolling process. Dough is made using a ‘strong’ flour of high protein content and a small proportion of fat. for a trans-free product. Figure 7 shows puff pastry samples prepared in a comparison of two fats. folding and turning results finally in many thin layers of dough inter-leaved with layers of fat. Figure 6 shows the effects of correct and incorrect processing of the dough. A high degree of plasticity and a somewhat high melting point is required.The third column shows the unusually high melting point of fat that is required to get good performance in a hot climate. turned through a right angle and rolled again.The other half of the dough is folded over and the parcel is progressively rolled down in thickness through a pair of pastry rollers. The proper ties of the fat must be rather special. It must therefore be very resistant to work-softening. Table 4 shows tested formulae. If there are too many. This pastry is baked in a very hot oven. Palm oil and palm stearin are suitable components for pastry margarine. and is formed into a flat rectangle. not enough layers are formed. A layer of special pastry margarine is then placed on half of the dough area. the fat has worked into the dough. If there are too few ‘turns’.35 Puff pastry Its distinctive character is derived from thin layers of a crisp pastry separated by large air spaces. Column 4 gives a softer blend. . It should be possible to use palm stearin instead.The dough is folded over once. which is suitable for the preparation of flaky pastry products. A complete sequence of rolling. The steam generated within the dough is retained by the layers of fat and can only escape after it has lifted the thin layers apar t. Formulae for a puff pastry fat Successful formulae based on hydrogenated palm oil are in use but have a content of the undesirable trans fats. They then cook to give an attractive crispy nature.

fat and sugar in varying proportions. together with a small proportion of water. . Minor components such as dried fruit or chocolate chips are added to biscuits to give a particular character.36 Short pastry and biscuits The major components of these products are flour. The eating properties – the texture – of biscuits and pastry vary over a wide range (Figure 8).

a shortbread biscuit which has a crumbly ‘dissolve in the mouth’ character. at the other extreme. In most products the air spaces play a minor role in the structure.37 Think for instance of a ginger biscuit with a crisp tough character and. .

as in Scotch shortbread. If liquid oil is used.38 The different textures are obtained by controlling the extent to which the gluten is enabled to develop. melt-in-themouth texture is obtained. The characteristics of fat are also important. . With a lower proportion of fat and more intense mixing. A fat blend must have small crystals and a smooth easily spreadable texture. it will fail to coat the flour particles efficiently because it has a tendency to form droplets. Palm oil is very effective as a major component of such a blend. A very short. By using a high proportion of fat and ensuring that the flour particles are well coated with fat. the gluten is developed to some extent and a somewhat tougher or crispier texture achieved. the access of water to gluten can be minimised.

then it is possible to form a rigid structure containing about 50% by volume of air. . aerated structures of greater stability than real creams can be produced. During the aerating process the small globules cluster together and impart sufficient strength to the air-cell walls to produce a stiff aerated cream. Whipped cream Whole milk contains about 4% of fat which is present as small globules averaging 7-8 microns in diameter. If the cream is agitated sufficiently the fat globules impact on each other and stick together. Cream is traditionally made by skimming the upper layer from milk that has been allowed to stand. In modern practice this concentration is achieved efficiently in a centrifuge and can be taken to the stage of single cream (18% fat) or double cream (about 42% fat). As a result the products have a more attractive texture and mouth-feel. By an appropriate selection of the fat used. The continuous phase which gives the product stability is the fat that has coalesced during the agitation. Their behaviour on aeration is then very similar to that described for homogenised dairy cream. Imitation cream Imitation creams are made by homogenising an emulsion of vegetable fat in skimmed milk with added sugar. In due course the fatty phase becomes more or less continuous and butter is obtained. If the cream is agitated in such a way that air is incorporated. The relatively low melting point of butterfat means that the aerated cream has limited stability up to about 25ºC in the European summer and in warmer climates. Each globule is enclosed by a coating or membrane of milk protein.39 CHAPTER 5: AERATED DAIRY PRODUCTS Dairy and vegetable oil based creams can be whisked or whipped in such a way that at least an equal volume of air is incorporated. a whipped cream of similar air content is obtained. In effect the fatty emulsion phase has been concentrated. During homogenisation the individual fat globules are broken down to a size of about 1 micron. If homogenised cream is agitated in the same way.

66 parts of the HPKO and 34 parts of the palm stearin are interesterified.40 A very suitable fat for ambient temperatures up to 25ºC is hardened palm kernel oil (HPKO) with melting point 35ºC and Iodine Value 1. The whipped cream made using this fat was stable at a temperature of 35ºC. For even higher temperatures an increase of a few percent of the stearin proportion can be used. . but without affecting the mouth-feel. This process causes all the fatty acids to change places in a random manner and alters the melting properties of the mixture. In this. For higher ambient temperatures.The shaded area of increased solids in the blend is responsible for its better stability at the higher ambient temperature.0. Curves for the solid fat content of HPKO and of the blend are shown in Figure 1. a formula of particular interest consists of fully hydrogenated palm kernel oil together with palm stearin (Iodine Value 19).

. The ‘stand up’ strength of the whipped cream is mainly dependent on the fat globules. Table 1 compares a typical composition of ice cream with that of milk.The air cell has a continuous surface layer of fat which is then lined by numerous intact fat globules.41 The structure of the cream is shown in an electron micrograph for a cross-section of an air bubble (Figure 2). ICE CREAM Ice cream is made with dairy cream or an emulsion of vegetable fat with skimmed milk.

In the latter type of product. Pasteurise it to destroy harmful bacteria.The development of ice crystals and the mechanical action in the freezer cause some breakdown of the emulsion. Freeze and aerate the mix The freezing takes place in a scraped surface heat exchanger. or minerals such as calcium and magnesium which strengthen bones. • Air is introduced into the mix and dispersed into fine bubbles by the intense agitation. and probably cause shape distortion. 4. Ice cream is also a good vehicle for introducing nutritional supplements such as vegetable sterols which lower blood cholesterol levels.04-3 microns) and make the emulsion. .Thus luxury grades containing 15% or more of fat and also reduced fat content products have been marketed. Cool the emulsion to 4ºC and store for 2-3 hours or more to allow it to settle down. 3. • Ice crystals force the fat globules into the decreasing spaces occupied by unfrozen material. Time is needed for the fat to partly crystallise and the milk proteins to coat the surface of the fat globules. the desired creaminess effect on the palate can be obtained by changes in the thickeners used. 2. The partial destabilisation of the emulsion in the freezer is now generally accepted as important in the formation of a stable ice cream structure. Prepare the mix. 5.The following events occur in the freezer: • An increase occurs in the collision frequency of the fat globules due to mechanical agitation. Homogenise the hot mix to break up the fat into small globules (0.42 There is considerable flexibility in the formulation of ice cream. It is the most dynamic stage in the processing and results in the development of the final structure. Processing steps in developing ice cream structure 1.

consisting of a layer of liquid oil.The scale is indicated by the one micron bar. It is lit from above. The air bubble is about 5 microns in diameter.43 On leaving the freezer about 50% of the water in the mix has turned to ice and the structure is fully formed. The ‘bumps’ in the surface are small fat globules (A) sitting on the outside of the oil layer. stability is provided partly by fat globules lining the air cells but also by the ice in the continuous phase. Structure of ice cream The final structure is similar to that obtained for whipped cream. Figure 3 shows an electron micrograph of ice cream. while fat globules are 0. An ice crystal (B) can be seen protruding into the air bubble.5 microns or smaller. . the lower part being brightly lit.The frozen sample has been cut across and what we see is half of an air bubble.The surface is smooth. hardened in a cold store at -30ºC and is then ready for distribution.The ice cream is filled into packages. It is generally held at -17ºC or -18ºC until retailed. so that the top part is in shadow.

this is not the case. as measured under the optical and the electron microscope. about 85% of the water is present as ice and it might be thought that the ice alone would be sufficient to maintain the structure. However. Figure 4 shows such broken fat globules. are shown in Table 2. By the time the product has reached the refrigerator at -18ºC. The dimension of some components of ice cream.44 The layer of liquid oil forming the surface of the air bubble is derived from fat globules which were broken open during the intense agitation in the freezer. .

The air bubble is not lined by intact fat globules. a different picture is seen in the electron microscope (Figure 5). The frozen ice cream soon starts to lose air during storage. Evidently a good ice cream fat needs to have a solid fat content during processing.45 If an ice cream is made with liquid vegetable oil.Table 3 gives the proportion of liquid oil remaining of some satisfactory fats at +5ºC and -5ºC. and none can be seen in between the air cells. the temperature before and after freezing. . shrinks in the container and becomes unattractive.

. Contemporary English cookery books referred only to butter. but was only suitable for inedible applications such as lamp oil.The name was taken from oleic acid from the Greek word for ‘pearl’. Coalmine owners supplied candles to underground workers and had to colour them green to prevent theft.This was called ‘oleo-margarine’. without these. imported in small amounts from West Africa since 1780. beef fat and lard. 1 In Mediterranean Europe. resulting in shor tages of food from time to time. olive oil had been the main edible oil in use for some 5. He took carefully rendered beef fat. activity in the long winter evenings was very limited. He argued that the cow was able. In 1865 there was a shor tage of butter in Paris and in supplies to the army.The industry consisted of the rendering of carcase fats and a limited fractionation of beef fat to produce stearin for candles. to transform its high-melting body fats into the softer butterfat. the milk still contained fat. Rapeseed was crushed for oil in North Europe. by means of enzymes in the udder.000 years. Up to the 19th century the fats available for food use in North Europe were solely those produced in the farm yard. allowed it to crystallise at about 30ºC and separated the still liquid portion. was likewise of inedible quality. referring to the lustrous appearance of the fat when solid. 1 Candles were a valuable commodity in the home. French pharmacist and inventor Hyppolyte Mege Mouries took up the challenge. Palm oil. already in hand in 1867. In his experiments. This led the emperor Napoleon III to offer a substantial prize for the invention of a suitable butter substitute. he noticed that cows starved of food continued to produce milk. Although reduced in volume. The Industrial Revolution in Europe resulted in the movement of the population from the countryside into the cities.46 CHAPTER 6: BUTTER ALTERNATIVES It is no exaggeration to say that the invention and subsequent widespread manufacture of margarine initiated the development of the oils and fats processing industry as we know it.

to which 0. but soon local supplies of beef fat ran out.1% of minced cow’s udder was added.47 The oleo-margarine was melted and mixed with 30-35% skimmed milk. The resulting emulsion was churned as if it was real cream. in other words hardened. The dairy industry in many countries reacted strongly to the competition from margarine and lobbied for restrictive regulation. However the process was licensed to Jurgens in Holland in 1871 and production also soon started in Germany. For example. During the kneading some salt was added. The addition of cow’s udder was thought to help the emulsification. Mege Mouries won the prize: he patented his process in France. then in the UK in 1869 and in the USA in 1873. Austria. Some palm oil of superior quality then became available from Africa that was suitable for the edible fats industry. A reliable quality of palm oil has been available from Malaysia and Indonesia since the 1950s. other vegetable oils became suitable. in Germany. but the enterprise did not succeed. Scandinavia and the USA. the industry was no longer dependent on beef fat to provide the structure of margarine. in particular whale oil and fish oils. Any liquid oil could be hydrogenated. carefully prepared unrefined groundnut oil and coconut oil were used but. to a chosen extent. Initially. Although palm oil had been imported for over 100 years from West Africa it was of very high acidity and suitable only for industrial uses. Already in the 1870s some patents described the use of 10-20% of vegetable oils. Imports from the USA and Argentina were used. Free water was removed and the fat kneaded until no more water separated. New ingredients became available. Hydrogenation The invention of hydrogenation of unsaturated bonds and its development for edible oils early in the 20th century widened the ingredients available. butter and margarine could . He started manufacture in Poissy near Paris.The whole was stirred for 2-3 hours at the body temperature of the cow. but it was soon abandoned. The end product looked like butter. Then chilled water was added to crystallise the fat. So. as the refining process was developed. both of which needed partial hydrogenation. The product proved popular.

. introducing a tax on margarine and the purchase of licences by manufacturers and dealers. packed and distributed in small wooden barrels to be por tioned out and wrapped by the retailer. making it more expensive than butter at times. Attempts to colour it with natural palm oil were disallowed. Examples of state and federal tax stamps are shown in Figure 1. For a long time margarine could be bought white. A number of countries required the addition of sesame oil as a ‘marker’. federal taxes and licence fees were removed in 1950. As a result.48 not be sold on the same premises. Developments in the USA The industry in the USA had a par ticularly hard struggle under both federal and state restrictions. In Italy a campaign by agricultural organisations led to a ban on the manufacture of margarine for household use in 1934. followed by a complete ban in 1937. During World War II shortages lead to greater use of margarine and a generally favourable consumer attitude. Elsewhere a small amount of starch was added for the same purpose. In 1902 a tax of 10 cents/lb was imposed on margarine coloured yellow. with a sachet of colour which the consumer had to knead into the block. Later regulations required margarine to be packed and labelled in 1-1b blocks in the factory. but restrictive controls remained until food laws were unified in the European Union. This was relaxed after the war. Control was achieved under federal law in 1886 requiring proper labelling. Margarine was handled in the same way. and it was easy to mix both in the shop. A small percentage was added and could be easily detected in the laboratory. at this time butter was mainly made on the farm. thus preventing margarine from being mixed with butter. Additional 10-cent taxes were imposed at state level. Initial attempts to regulate the trade at state level were ineffective. Today the dairy and margarine industries coexist peacefully in the USA and elsewhere. Retailers had to erect partition walls and doors to satisfy the letter of the law. Margarine manufacture star ted in 1874.

present in animal products. Early regulations controlled the minimum fat and maximum water content and allowed fortification with Vitamins A and D. An emphasis developed on the use of ingredients containing the essential linoleic and linolenic acid which cannot be synthesised in the body. These are used in the body to make essential hormones and brain components. .49 NUTRITIONAL CONSIDERATIONS Margarine was accepted as a nutritionally satisfactory basic food. and therefore there was a move towards vegetable oil formulations.They are the precursors for longer chain acids of 20 carbons with 5 double bonds and 22 carbons with 6 double bonds. In the 1950s concerns over heart disease led to advice to reduce the intake of cholesterol.

They are very sensitive to oxidation and need special handling if they are to be used. Further studies have indicated that they raise the levels of triglycerides and the tendency towards inflammation. On the regulatory front. A government task force recommended that regulations should be made . In Denmark.The 20 and 22 carbon acids are present in fish oils. Other local authorities in the USA may follow suit.” LDL-cholesterol is the ‘bad’ compound associated with an increase in the risk of heart disease.50 Linolenic acid is present in rapeseed and soybean oils. an experienced researcher who reviewed the results of many studies: “A high intake [of trans fats] affects the ratio between LDL. and in practice would then use the new formulae for all their manufacture. having a significant content of trans fatty acids (trans fats). both are risk factors in heart disease. since the wholesale suppliers to the restaurants have had to reformulate their products. Trans fatty acids Partly hydrogenated oils were generally used. Their adverse health effects are now universally accepted. the USA has implemented since January 2006 new labelling regulations requiring the trans fats content in food products to be declared. The body of evidence against trans fats has grown. no adverse effect has been noted on the quality of food products. whereas HDL-cholesterol is the ‘good’ one that removes excess cholesterol. The position is well stated by Dr A Aro. legislation has restricted the trans fats content of all food oils and fats to below 2% since 2003. The New York City government has gone further to tell restaurants and food suppliers to reduce trans fats to the low level of 0.and HDL.This has had a knock-on effect. thereby inducing strong moves by manufacturers to reduce the use of hydrogenated oils. In Canada it became mandatory to give the trans fats content on product labels in December 2005.cholesterol in a way that is unfavourable compared with all other fatty acids.5g/serving. The consumer now understands that trans fats are undesirable. which can easily be used in margarines and spreads.

Reduced-fat spreads Another nutritional problem led to the development of reduced-fat spreads to meet the need to reduce calorie intake to combat the rise in obesity. A part of the fat content is replaced by water. small amounts of thickening agent dissolved in water are used.The consumer can then apply a generously thick layer to a slice of bread. and in order to maintain the desired consistency. .3gm sterol. CLA has one of its double bonds in the ‘cis’ and the second in the ‘trans’ position. in June 2007. and tends to reduce body fat. An additional daily intake of about 2gm reduces blood cholesterol by around 10%. A consequence of these moves against hydrogenated fats is that the use of palm oil products continues to increase. Vegetable sterols The most recent development with a nutritional objective is the enrichment of spreads with vegetable sterols. but this is not sufficient to be useful. It contains over 10% CLA. and therefore reduces blood cholesterol level (which is a risk factor for hear t disease if it is elevated). ‘Conjugated’ linoleic acid (CLA) An interesting recent finding is that one particular type of trans fats actually has beneficial health effect. Canola oil has been interesterified with CLA and used at the Malaysian Palm Oil Board (MPOB) to prepare margarine on a pilot-plant scale. which are nowadays consumed in lesser amounts. Products containing vegetable sterols are now readily available. but with fewer calories. to provide the required solid fat content. the government decided instead to request industry to reduce the trans fats content voluntarily to the lowest possible levels within two years.51 by 2008 but. It has been known for many years that the consumption of vegetable sterols reduces the absorption of dietar y cholesterol. to avoid legislation being imposed. CLA inhibits tumour growth and the risk of blocked arteries. The vegetable oils consumed normally contain about 0. These products cannot be called ‘margarine’ but need to behave and look like it. It is naturally present in small proportions in animal fats.

but it makes this olein more expensive. but palm oil has 4-5% solids. . Curves for the solid fat content (SFC) of palm oil and its products are shown in Figure 2 and compared with butterfat. enabling the technologist to choose the most suitable. As we know. then separating the olein. At body temperature (36-37ºC). By measuring at a range of temperatures we can construct a curve of solid fat percentage against temperature.52 FORMULATION OF FAT BLENDS How does the food technologist set about formulating products such as margarine or bakery fat? Two basic properties of the finished product are important – the proportion of solid fat present at temperatures relevant to its use: and the shape and size of the crystalline solids. The curves for butterfat and palm oil are remarkably close. unlike unsaturated vegetable oils such as soybean and rapeseed oils. Any natural fat is a mixture of a number of triglycerides and will contain a percentage of solid glycerides at intermediate temperatures. Curve 4 shows a standard palm olein with appreciable solid content at 15ºC and 20ºC. Individual triglycerides may have melting points as high as 60ºC or as low as -10ºC. usually in a filter press. butterfat becomes rather hard. What is clear from the curves is that palm oil is suitable as a major component of margarine formulae. The two curves for palm stearin (2 and 3) show that a variety of properties can be obtained.To obtain improved properties. but there is one important point of difference.The process involves holding the oil at a chosen temperature to allow partial crystallisation to occur.This means that it may leave a greasy feel on the palate. This percentage can be readily measured because the solid glycerides respond to a magnetic field differently from the liquid. butter taken straight from the refrigerator is not easy to spread. the properties of the fractions can be varied. Depending on process conditions. butterfat is completely molten. a double fractionation process is required (Curve 5). Palm oil is readily fractioned into a hard portion (stearin) and a more liquid portion (olein). Palm oil We need to look at palm oil and palm kernel oil in more detail. Below 15ºC.

and leads to some special applications at high value. PKO has high solid content at 15ºC and 20ºC and is a firm solid. This behaviour is even more pronounced in palm kernel stearin. in particular when palm oil is also used. bringing it closer to the behaviour of butter. Figure 3 shows this effect in terms of the liquid oil content. but above 20ºC it melts rapidly. PKO is a valuable ingredient in margarine blends. A mixture of 60% palm oil and 40% PKO is still liquid at temperatures where each of the components on its own would be solid. When used in a margarine formula. derived from the Greek. such mixtures improve the melting characteristics in the mouth. meaning ‘good melting’. which are described in Chapter 7. while the PKOL ensures good melt- . The stearin component provides the necessary firmness in the end product. An economically major ingredient for margarine and spreads is obtained by interesterifying palm stearin (60%) with palm kernel olein (PKOL.53 The SFC curves for palm kernel oil (PKO) products are shown in Figure 3.The mixture is technically described as ‘eutectic’. Mixtures of palm oil with PKO have some difficulty in crystallising because the diverse chain length fatty acids do not fit in together easily. 40%).

.54 in-the-mouth properties. The margarine will have a content of short and medium chain fatty acids similar to those in butter.

Experience shows that a SFC between about 15% and 35% is suitable. which move as a whole when pushed. As we have seen in relation to shortenings. but outside this range is either too hard or too soft in a warm climate. Physicists define the force needed to make the margarine flow as ‘yield value’.55 It is clear that palm oil – which is free of trans fats – offers a direct way of obtaining the solid content needed to give margarine its consistency. The spreadability changes quite rapidly with temperature. WHAT IS THE RIGHT CONSISTENCY? The desired consistency of margarines and spreads can be defined as being spreadable at the temperature of use. It is good between 15ºC and 25ºC. and interesterifying it with a proportion of liquid oil. apply it to a slice of bread and spread it. A second factor is that the solid fat must be in small crystals. and the margarine flows until the pushing stops. It transformed during storage to the beta form.Then the liquid component takes over. Problems arose in Canada when margarine was formulated with hydrogenated rapeseed oil. such as soybean or rapeseed.This can be measured with simple equipment and used to compare the spreadability of different products.The network is rigid enough so that the product looks solid but is easily disturbed when ‘pushed’. Margarines have a physical behaviour in between that of liquids – which flow when poured – and solids.This is normally more expensive. . the local produce. Chapter 4). giving an unsatisfactory appearance and a gritty feel on the palate (Figure 6).The margarine manufacturer can improve this. this requires the beta prime polymorphic form (Figure 3. ‘Spreadability’ means we can cut a portion of margarine from a block or out of a tub. This three-dimensional network holds the liquid oil component and also the emulsified aqueous phase. They have an internal structure that consists of a network of very small crystals of the solid triglycerides. It may be said that the spreadability of butter is not ideal. See Figure 5 for SFC curves of various products. A second way is to prepare fully hydrogenated oil.

56 .

Apart from the first. HISTORIC MARGARINE FORMULAE Table 1 gives a number of published formulae.57 The reason for the transformation is that the canola oil contains almost solely fatty acids of 18 carbon atoms. When the margarine was reformulated using a proportion of palm oil (with palmitic acid of 16 carbon atoms) the change to the beta form was made difficult due to the diversity of chain lengths. Experimental formulae that have satisfactory characteristics and are free of trans fats have been developed in the laboratories of MPOB (Table 2). and the product was stable in the prime form. the formulae all contain trans fats from the hydrogenated component. .

but now it is carried out within a scraped surface heat exchanger (Figure 7) and then a second cylinder – the ‘worker unit’ – where fat is intensely mixed (Figures 8 and 9). the product is ready for packing. usually into 250gm or 500gm packs or plastic containers. Improved margarine processing Mege Mouries’ original process was soon improved. their imports of palm oil and stearin have increased. margarines in Europe are substantially free of trans fats and that there have been big reductions also in the USA. At the same time.58 While manufacturers do not generally reveal the blend formulae in use. analyses show that today.e.The fully crystallised fat was rested for a time and packed.The partly crystallised mass was scraped off into an open trough fitted into a rotating shaft fitted with beater arms. .The margarine emulsion was pumped in a thin layer onto a rotating drum. today. Crystallisation in the desired small crystals was initiated. This processing is today essentially unaltered. which was chilled internally with ice water or a refrigerant.The second column gives the price calculated for the fat component (i. After a period in a resting tube. the nutritional element). Table 3 gives prices of products on the shelves of a London supermarket.

59 .

During World War II. butter very quickly develops an off-flavour mainly due to hydrolytic breakdown of the glycerides at the high ambient temperature. It may be noted that Denmark has the highest per capita consumption of margarines and spreads. Figure 10 shows world production data for margarines and spreads. VANASPATI In the Indian subcontinent.60 Production and consumption Margarine production has shown continuous growth. This is because its important dairy industry exports much of the production. It has therefore been traditional to market ‘butterfat ghee’. with some increase in rate during and after World War I. Consumption in some Western countries is listed in Table 4. the high quality of the product was recognised and when rationing was relaxed. This is made by melting butter and boiling off the water layer. The slower increase from about 1960 was due to the lower fat content of the increasing market for reduced fat spreads. production went up. . A desirable flavour develops.

61 In 1930 Hindustan Lever developed vanaspati as a vegetable oil-based alternative. some butter flavour was added and the appearance of butterfat ghee was imitated. with a little free oil remaining. In order to find acceptance among consumers. up to 1-2mm across. When the melted butterfat cools slowly. . it cr ystallises in rather coarse grains.

The market for vanaspati in Pakistan is 1. Similar products are used in the Middle East and Egypt.7 million tonnes. . and by expatriate Indian populations in other countries. A suitable product was obtained by partial hydrogenation directed towards the production of trans fats in preference to saturated acids.62 Figure 11 is a photograph of the crystals in a thin layer of vanaspati. This appearance is regarded as important by the consumer and therefore had to be achieved in the alternative product. Most of these countries rely on imported oils for a large part of their consumption. Government regulations initially required the melting point to be no higher than 37-38ºC but subsequently the range was widened to 41ºC. while the world market was estimated at 5-6 million tonnes in 2009.

However. However. as consciousness of the adverse effects of trans fats spread. At present the formulations used in Pakistan are varied. Due to the high summer temperatures a firmer product is required (Table 6). it forms small crystals and a high proportion of liquid oil. more than 50% for Iran and 27% for Pakistan. a lower trans fats value of 3. or by interesterification.7% was reported in Pakistan.63 Formulation Palm oil has the desired melting point for vanaspati. More recently. In the 1980s. adverse comments appeared in the press in April 2009 about analyses of products in the market with 23-24% trans fats. when vanaspati was largely based on hydrogenated vegetable oils. to be reduced further with time. . Iran introduced a limit of 20%. as palm oil became available. the trans fats content was high with a figure of 53% for India. A better appearance can be obtained with a blend containing some hydrogenated oil. Some satisfactory experimental formulae with zero trans fats are shown in Table 5. when crystallised slowly. In India.

. The warm blends are filled into large tins. typically 28lb.64 The processing of vanaspati is very simple. and placed in a temperature controlled store at 21-22ºC until cold.

contains mainly fatty acids with 16 or 18 carbon atoms. Figure 1 shows how the production and export of the two oils have developed over 20 years. however. like most vegetable oils.The yield of palm kernel oil (PKO) is about 10% of the oil derived from the flesh. The volume of coconut oil has.65 CHAPTER 7: THE LAURIC OILS The oil palm is the only crop yielding two different types of oil. There is a striking difference. Palm oil.These two are often described as lauric oils. PKO typically contains 48% lauric acid with only 12 carbon atoms and another 9-10% of fatty acids with shorter chain length. . The availability of PKO has grown in line with the increase in palm oil supplies. The only similar oil available commercially is coconut oil. The most interesting feature of the two oils is the substantially different make-up of the fatty acids. remained about static.

so it must be extracted on site from the nut for economies of transport. The exception is babassu oil – a few thousand tonnes have occasionally appeared in the market. It has been estimated that 1-2 million tonnes of oil per year are not being utilised.Worldwide. . and some have been exploited by the native populations for their oil content. Oleochemical demand The content of medium and short chain length fatty acids renders the lauric oils of great interest to the oleochemical industry. it is encased in a thick and extremely hard shell.66 The oil palm and coconut palm are members of a large family of some 3.000 species. Attempts to commercialise some of these kernel oils have failed. However. The babassu is a large palm of the Amazon forest and it grows in dense natural stands. and this is probably true of all the palm family. which presents a technical challenge. Table 1 shows the fatty acid composition of the lauric oils – note the contrast with palm oil.The kernel forms only 10% of the fruit. A commercial evaluation of the oil has indicated that its properties are intermediate between PKO and coconut oil and that it would serve similar applications. Chemical analyses of kernel oils from a number of these species show that they are all lauric oils. Several hundred of them are native to the Amazon basin in South America. it uses up to half of the lauric oil supplies.

. anionic and nonionic detergents. The steep melting curve of PKO in comparison with palm oil should be noted. This is even more marked in palm kernel stearin (PKSt). lubricants. surface active agents. as shown in Figure 4. Chapter 6. the formation of fatty acid compounds such as esters.000 tonnes in 1986. Margarines and spreads Another feature of PKO behaviour of particular value in margarine formulations is its formation of eutectic mixtures with palm oil. Functionally. fabric softeners. Other technical uses require. fatty alcohols. FOOD USES OF PKO The solid fat content curves for PKO products are shown in Figure 3. The rapid development of the oleochemical industry in Malaysia is indirectly illustrated by figures for domestic disappearance of 53. foods with a high content of PKO give rise to a pleasant cooling sensation on the tongue due to heat being rapidly abstracted as the oil melts. A good soap formula consists of 7580% tallow.41million tonnes in 2009. Further chemical modification is often required to reach end products with a long list of applications in a variety of industries. When eaten. most of which was converted into chemical products for export.67 The demand from both the food and oleochemical industries means that lauric oils usually fetch a premium over other vegetable oils. palm oil or palm stearin and 20-25% lauric oil. the shor ter chain fatty acids impar t good foaming while the long chain fatty acids give the foam persistence. as a first step. The foam suspends par ticles of dir t and is impor tant for a good cleansing action. This may be noted in biscuits with a cream filling. Chapter 6. mineral processing aids and corrosion inhibitors. as has been practised since the time of the ancient Egyptians. Probably the biggest chemical use of lauric oils is in soap making. rising to 1. in whipped cream and some confectionary products.The list includes personal care products. a variety of nitrogen compounds and metal soaps.

low acidity and oxidation. These include clean flavour. Refined PKO has no difficulty in meeting these specifications.These products are required to have a long shelf life. There are long-standing recommendations from the International Dairy Federation for the specifications of the oils to be used. therefore. The product may be marketed in cans or as UHT processed in tetrapak cartons. A large part of cheese flavour is derived from the short chain fatty acids in butterfat. In some products. Some ‘filled’ milk products are used as a powder – for example. There is a limited market for cheese made with vegetable oil. which have an inadequate supply of fresh milk. This blend has a similar solid fat content to butter but is cheaper. A satisfactory mozzarella cheese can be made using a blend of 70% palm kernel olein (PKOL) with 30% PO. impor t skimmed milk powder and make recombined ‘filled’ milk with locally available vegetable oil. 40% coconut or PKO and 10% rapeseed oil. better performance can be achieved with a ‘tailor-made’ fat blend. Danish-type cheeses have been made using a blend of 50% palm oil. . coffee ‘whitener’ and coffee ‘creamer’ used in drinks dispensers and provided in sachets in restaurants or fast-food outlets. 4. Mozzarella cheese is an important ingredient in pizzas. PKO is a very suitable component for ice cream and is widely used. 2. Countries like Malaysia. fully hydrogenated PKO (with zero trans fats) is preferred. and low levels of trace metals and impurities. There is less risk of deterioration during transport of skimmed milk powder than of full cream milk powder. 3. The fatty acids of PKOL help to develop the desirable flavour.68 Dairy products PKO is the preferred replacement for butterfat in various dairy products because: 1. Filled milk is cheaper.

who are unable to digest ordinary fats. PKOL blended with palm olein is useful for shallow pan frying. MCTs are made by first fractionating the fatty acid components of PKO and then re-synthesising those of the shor ter chain lengths into triglycerides. the warm fluid filling is deposited mechanically on one biscuit and the second biscuit is placed on top. but not deep fat frying. . The high stability to oxidation of the blend is important.69 Frying PKO and PKOL are suitable for frying. As PKO crystallises very rapidly.This is a dietary product used for people with a metabolic problem. A major area of use for PKO – and one where considerable added value can be obtained – is in fats for confectionery use. because the mixture tends to foam. Dietary product A special use of PKO is in the manufacture of medium chain triglycerides (MCT). the timing of the process must be judged so that there is still enough liquid to ‘glue’ on the second biscuit. In the manufacturing process.This is discussed in Chapter 8. A particular use is for frying nuts intended for snack foods or in bakery products. where two biscuits are sandwiched with a layer of PKO-sugar mixture. It finds applications as spray oil for certain types of biscuit such as cream crackers. A blend of 80-90% of capric (10 carbons) and 10-20 % of caprylic (8 carbons) is preferred. PKO is used in other types of biscuits such as Bourbon Creams. The high stability of PKO also makes it suitable for the ‘popping’ of popcorn. The purpose is to provide an attractive shiny appearance and to act as a moisture barrier so that the crackers remain crisp. Biscuits A blend containing 40% PKOL with palm olein forms a eutectic mixture similar to that described for PKO with palm oil.

Later they are roasted and ground. Chocolate bars.70 CHAPTER 8: CONFECTIONERY FATS Palm oil and palm kernel oil (PKO) are. valuable ingredients in confectionery products. The chocolate bar requires extra fat over and above the natural fat content of the bean. Ancient pottery vessels found in southern Mexico. The appearance. It has an attractive. whereas the flavour is derived mainly from the cocoa solids. When analysed. the fat of the cocoa bean. releasing its complex flavour. The flavour is developed in two stages. Research has shown that this drink was in use more than 3. were developed in the 18th century.500 years ago. in different ways. It became a luxury item favoured by the aristocracy. When the Spaniards arrived in America in the 16th century they found the Aztecs were making a popular drink called 'chocolatl' from powdered roasted cocoa beans. The best starting point to understand the special character required in confectionery fats is cocoa butter. The added fat is obtained by pressing roasted cocoa beans. the residues were found to contain theobromine. It melts rapidly in the mouth. texture and melting behaviour depend on the properties of the fat. After harvest the beans are allowed to ferment naturally for 2-3 days before being dried. smooth but shiny appearance. as we know them. CHARACTERISTICS OF CHOCOLATE Chocolate has a number of attributes valued by the consumer. where the cocoa tree is native. with Fry of Bristol being a pioneer. . an important substance specific to the cocoa bean. resulting in the cocoa mass used in chocolate. The Spaniards introduced the bean and its use as a drink to Europe. leaving a cocoa powder with a much reduced fat content. contained brown residues. Recipes also contained maize and flavouring like chilli or vanilla. The chocolate bar has a firm solid texture and breaks cleanly when a bite is taken.

The chocolate is softened and loses its desirable crispness. but Table 1 shows a typical example of plain chocolate and the composition of the roasted ground bean (cocoa mass). there is interest in the use of alternative fats which must not. There are two possibilities: firstly to replace some or all of the added cocoa butter in chocolate. however.71 The formulae for chocolate vary quite widely between manufacturers. albeit in different proportions. In the European Union (EU) the amount of vegetable fat that may be added is restricted to 5% of the end product. However.They form eutectics. and secondly to make a more economical product using an alternative fat with cocoa powder.at the time of writing. Cocoa butter The composition of cocoa butter is very simple (Table 2). Unfortunately the lauric oils are not compatible with cocoa butter. it is 21/2 times the price of palm oil.The fatty acids are also the major components of palm oil. Therefore. as is evident from the solid fat content (SFC) curves shown in Figure 1. Each approach has limitations. early attempts to make confectionery fat from palm oil were unsuccessful. similar to that formed with palm oil. alter the physical appearance and melting behaviour of the chocolate. Cocoa butter is much more expensive than other vegetable fats . . The concept of chocolate is protected legally in many countries. The properties of PKO products are quite similar to those of cocoa butter.

This proved to be an essential feature of a compatible fat.72 In 1956. O = oleic acid . in other words. This achievement required first a detailed knowledge of the triglycerides present in cocoa butter. 1 P = palmitic acid. and StOSt (28%). These glycerides are symmetrical. with the unsaturated oleic acid placed on the glycerol molecule in the middle position between the two saturated fatty acids. Typically three major components1 made up 85% of the fat: POP (18%). POSt (39%). researchers at Unilever obtained a patent for a cocoa butter equivalent (CBE) fat. a fat that can be mixed with cocoa butter in any proportion without changing its hardness or melting behaviour. St = stearic acid.

POP 29% and POSt 5%.73 The fatty acids are of similar chain length and identical structure. but blends are available that are completely compatible with cocoa butter (Table 4). Palm oil contains two of these glycerides in useful concentration.e. it needs to be blended with another fat rich in StOSt.The trees do not flower every year and the harvest of nuts can vary from nil to 50. PMF is miscible with cocoa butter but has a lower melting point and. A number of seeds from tropical trees have a suitable fat. all the seed fats listed in Table 3 (except PMF) present some difficulty. in some cases the desired component has to be concentrated by fractionation. i. together with cocoa butter. to match its characteristics. Attempts . resulting in the characteristic sharp melting behaviour of cocoa butter. 11% POSt and 2% StOSt.000 tonnes. They can be concentrated by a partial crystallisation and filtration to separate the higher melting portion and a second crystallisation at a lower temperature to remove the more unsaturated portion. Illipe nuts are obtained from tall forest trees growing in remote parts of Borneo. In terms of availability.Their content of the important glycerides is shown in Table 3. Seed fats It is not possible to prepare blends which exactly match the main glycerides of cocoa butter. The resulting palm mid-fraction (PMF) forms about 20% of the original palm oil and contains typically 57% POP.

while Malaysian cocoa butter is the hardest.the Brazilian product is softest. but includes some undesirable components and the oil is difficult to refine. Furthermore.74 to grow them in plantations have not succeeded. Hardness at room temperature is a highly desirable characteristic. Supplies of kokum fat are small. such as kokum fat. so kernel collection is only feasible from those that are industrially processed. It is possible to improve the behaviour of Brazilian cocoa butter by using a CBE rich in the StOSt glyceride. Improving chocolate behaviour Since the price of CBE fats is often half or less than that of cocoa butter.The warmer part of the tree produced significantly harder fat. This was proved by a very elegant experiment. such additions represent a worthwhile saving and can help improve the behaviour of the chocolate. they grow in rainforests and the harvest is gathered from the ground. Legislation varies elsewhere. but its high content of StOSt is valuable. Sal nuts are collected from forest trees in India. The EU legal definition of chocolate permits the addition of vegetable fat from the list shown in Table 3 at a level of 5% of the finished product. so a varying degree of biodegradation occurs. Most mangoes are consumed as fresh fruit. in which heating was provided to raise the temperature of half of a tree by a few degrees during the period of fruit formation.The oil content is 44-55%. Shea nuts are also gathered from the ground in the rainforests of West Africa. equivalent to about 15% of the fat content. provided the melting at mouth temperature is still rapid. Cocoa butter from different sources shows some variability . . At least some of this variability is due to climatic conditions.

It can go into six different arrangements of the glycerides in the crystals. with constant stirring until it thickens. with increasing melting points (Table 5). Subsequently the remaining crystals act as nuclei to induce recrystallisation in Form V. During the crystallising process. which is characterised by larger crystals. Transition to Form VI.The butterfat softens the texture of the chocolate. a mixture of the forms develops. All the added cocoa butter can be replaced by CBE or. CRYSTALLISING OF CHOCOLATE Molten chocolate is a suspension of the solid ingredients in liquefied fat.75 The formula of dark chocolate (Table 1) can be modified by using 7 parts of cocoa butter and 5 parts of CBE as the added fat. They are described as super coatings. Butterfat contents of 5-20% or even higher are used in different quality products. leads to some fat crystals appearing on the surface of the chocolate.To obtain the shiny solid surface. the less stable forms melt. a special method of crystallising the fat is used. It is then carefully warmed a few degrees and allowed to set. can be induced by temperature fluctuations during storage. A large part of today's market for chocolate is for milk chocolate. The desired form giving a shiny surface is Form V. By selecting a CBE fat such as Blend 4 or 5 in Table 4. to go further. Products containing more than 5% CBE may no longer be called chocolate. giving it a grey appearance called 'chocolate bloom'. which is the most stable form. a low-fat cocoa powder (containing 11% cocoa butter) can be used in place of cocoa mass together with a higher level of CBE.The chocolate is cooled slowly. By reheating the mass to just below the melting point of Form V. its crystallising behaviour is very complex. in which usually there is less cocoa and a large part of the overall flavour is given by the milk solids and fat. . While this is harmless. As the Form VI develops further the chocolate loses its smooth texture and becomes gritty on the palate. a firmer product is obtained. it is unattractive and consumers may think it indicates mould. Although the glyceride composition of cocoa butter is very simple. Formation of Form VI. The science behind this process is fascinating.

At the thousand-fold magnification used. The last section shows the crystals of bloom on a bar of chocolate.76 Figure 2 shows electron micrographs of all six forms. the difference between Forms V and VI is dramatic. clearly of Form VI. .

but its melting point (28°C) is too low for a direct replacement of cocoa butter in chocolate.5%. Because PKO products cause an unacceptable softening of the chocolate.5% is cocoa butter contributed by the cocoa powder. Contamination can be introduced by an ingredient such as milk powder or as a result of poor hygiene. PKO products can develop off flavours if a fat splitting enzyme (lipase) . Other CBRs Fats with a suitable sharp melting behaviour can be made by partial hydrogenation of oil . Hydrogenated stearin (having virtually zero trans fats) is also suitable for chocolates.The stearin prepared from PKO has a solid content profile very close to cocoa butter. of which 1. The total fat content is 32.derived from contamination by yeast or mould .The lipase splits off some fatty acids and the short chain acids characteristic of PKO have a strong soapy flavour. they can be used only if the cocoa butter content is 5% or less of the product. especially in hot climates. Figure 1 shows the SFC curves of cocoa butter and various PKO products.77 CONFECTIONERY FATS FROM PKO PKO has the rapid melting characteristics required in a confectionery fat. A typical formula using palm kernel stearin (PKSt) as a cocoa butter replacer (CBR) is shown in Table 6.This drawback does not arise when a non-lauric confectionery fat is used. Figure 3 shows chocolate made with hydrogenated PKSt. Precautions need to be taken by testing ingredients and ensuring good hygiene.is present. This means using a low-fat cocoa powder.

They are handled at a low temperature (below -10°C) from manufacture to retail sale. However. withdrawing it and. and must set immediately before being packed. the lower melting eutectic being an advantage here.78 high in oleic acid. A true chocolate is very brittle under these conditions and often flakes off.The manufacturing process involves dipping the ice cream into the coating. For stick confections a PKO or coconut oil blend with liquid oil may be used. It is necessary to use a catalyst and hydrogenation conditions that maximise the formation of trans-oleic (elaidic) acid. although other fats are also used. Palm olein is a good starting material. in some cases. Suitable fat blends are specially formulated according to the method of use. it does not fit in well with current recommendations to minimise trans fats in foods. A typical product has about 18% trans fats and only a small increase in the saturated stearic acid. applying a layer of crushed nuts or crisp biscuit crumbs. For bars a palm oil-PKO blend can be used. Coatings for ice cream Ice cream bars and lollies (stick confectionery) coated in chocolate are very popular. . The oil blend is subtly adjusted to the timing of the process.The coating must be 'tacky' to permit adhesion of the layer.

Initially these contribute to the desirable taste of the cooked food. Virtually all the oil is absorbed by the food. over time. In the case of the shallow pan. which develops a brown crust and an attractive flavour. Inevitably. Frying in the kitchen may be done in a shallow pan or in a deep pan. while snack foods such as potato crisps and instant noodles are manufactured in large continuous frying baths.79 CHAPTER 9: FRYING OILS Palm oil and palm olein are widely used for frying because they are economic and effective. it is of primary importance for every business to understand the competition it faces. means that the food itself does not get above 100°C except for the surface layer. .This chapter describes the development of alternative oils in the context of the technical requirements for satisfactory frying oil. some oxidation of the oil takes place. However. Although the oven temperature is well above 100°C.This is true even in oven baking. some chemical changes take place in the oil. When the quality of the food is affected. turned over and cooked on the other side. Similarly during frying. a little oil is used. which is carried out with the oil heated to a temperature of 170180°C. Clearly this has an important effect on the economics of use. A small proportion is absorbed and the rest is kept for re-use. over time. However. are best cooked fully immersed in a deep pan full of oil.The food is cooked on one side. the food itself gets no hotter than about 100°C except on its surface. the used oil has to be discarded and replaced. Some kinds of food. for example potato chips or French fries. Eventually some polymerisation occurs. the viscosity becomes higher and more oil is absorbed into the food. such as meat joints and cake batter. The resulting changes produce an unpleasant taste as the oil has become rancid. the high moisture content of food. Deep pans are used in fast-food restaurants everywhere. occurring mainly at the unsaturated double bonds of the fatty acid chains. Most cooking processes are carried out at the boiling point of water (100°C).

Linoleic acid (2 double bonds) oxidises 10 times more rapidly than oleic acid (1 double bond). The temperature must be controlled. many countries have published nutritional guidelines for their populations. so maintaining quality.are highly stable to oxidation. It is estimated that globally some 10 million tonnes of palm oil and palm olein are used annually in restaurants. the antioxidants. In addition palm oil and olein are relatively rich in protective antioxidants especially the Vitamin E tocotrienols. The fatty acid composition of palm olein is shown in Table 1 on page 81.There is broad agreement among developed countries that fat intake should be no more than 30% of total energy (current fat consumption in the West is about 35-37% of energy). It has a very low level of the sensitive linolenic acid and a moderate level of linoleic acid. • The second is the choice of frying oil. but is often questioned with regard to its nutritional benefits. oil is absorbed by the food product and therefore removed from the pan. It is replaced by fresh oil. During frying. Clearly a high rate of oil turnover is desirable. The other main components . The susceptibility of an unsaturated fatty acid to oxidation increases with the number of double bonds in the chain. while linolenic acid (3 double bonds) oxidises at least 20 times more rapidly than oleic. . especially in terms of blood cholesterol modulation. Nutritional guidelines The high content of the saturated palmitic acid undoubtedly contributes to the stability of palm oil in frying. which inhibit the action of oxygen on the unsaturated bonds.palmitic and oleic acids . fast-food outlets and industrial deep-fat fryers.There is also substantial domestic use.80 Two main factors control the useful life of frying oil: • The first is good practice in its use. With increasing understanding of the association between diet and health. the equipment kept clean and the correct oil level maintained. These good properties have been recognised.Vegetable oils all contain some minor components. Therefore oils with more than 3% linolenic acid are not regarded as suitable for deep-fat frying.

for example soybean oil (SFA 15%) and rapeseed oil (SFA 7%).81 Within that 30% it is recommended generally that saturated fatty acids (SFA) should be no more than 10% of total energy intake. . Some commodity oils fit this specification quite well. However they also have high levels of PUFA. with polyunsaturated (PUFA) at 7-10% and monounsaturated (MUFA) at 10% or more. The recommended level of SFA refers to the total amount of fat consumed. and especially of linolenic acid (>7%) and therefore lack stability at the frying temperature. plant breeding programmes for these oils and others have been undertaken to develop frying oil with a fatty acid composition that could confer higher stability. As a result. Competitive marketing considerations have led to a desire for the lowest possible SFA content in oils used for frying.

a good fried flavour needs about 10% while higher levels can lead to off flavours due to oxidation • Saturated acids below 15% • Oleic acid 65-70%. palm olein of higher unsaturation . in their current form. We will now review results of these breeding programmes and of any practical frying results reported in using the modified oils. it is possible to obtain palm olein with unsaturated fatty acid content (mostly oleic) in excess of 62% of its composition. are excellent frying fats.obtained through multiple fractionation .is becoming increasingly available. given the desire for higher oleic varieties and efforts to reduce saturates content. Through process innovations. especially through hybrid selection or genetic modification. can be higher More precisely: • Saturated acids 10-15% • Oleic acid 65-75% • Linoleic acid 15-20% (I would suggest 10-15% at most) • Linolenic acid 1-2% Palm oil and palm olein. has demonstrated the potential to develop palm olein with a fatty acid composition that mirrors olive oil. . Advanced research. Such a composition would be competitive against the new varieties of frying oils described next. MODIFIED OILS Several modified oils have been produced using conventional plant breeding techniques and tested in frying trials. The following requirements need to be met: • Linolenic acid less than 3%. However.82 Ideal specifications It would be instructive to first draft a specification for frying oil that meets as far as possible the current nutritional and technical optima. as low as possible • Linoleic acid .

In contrast. Palm olein was used in the trials as the reference oil. when the crop is an annual one. the seed can be used for further breeding. The conclusion was that the HOSO was as good as palm olein for both the French fries and potato crisps. but adequate for retail purposes. it is possible by the use of greenhouses and artificial lighting to produce three generations per year.The composition of the oils used is shown in the first three columns of Table 1. the replanting of a large area would require some years compared to an annual crop. Sunflower oil A thorough collaborative project was carried out from 1994-1996 between different research centres in the European Union to test the frying properties of High Oleic Sunflower Oil (HOSFO).83 Modern analytical techniques enable a single seed to be sampled and its fatty acid composition to be determined while the seed remains viable. Furthermore. The storage life of the potato crisps was shorter than when palm olein was used. The oils were used to prepare.The last column shows the composition of Nusun. furthermore.The products were submitted to extensive analytical tests and to tasting tests before and after storage. an equivalent product in the USA. potato crisps and pre-fried frozen French fries. on an industrial scale. the analysis reveals an interesting variation from the standard composition. the oil palm requires 3-5 years before the oil from a new plant becomes available for testing and. Rapid progress can be made towards a new product. If therefore. .

0%. a significant premium accompanies HOSO. The oil with raised oleic and low linolenic acid gave very good results. either replacing palm olein or used in a blend with it. In one trial. No production figures are available for high oleic rapeseed oil. Rapeseed oil A high oleic rapeseed oil has been developed by the Dow chemical company.8% performed better than one with 2. . Its composition in comparison with typical commercial oil is shown in Table 2. Small-scale frying trials were conducted with bread cubes. The conclusion. Consumption figures for the high oleic oils are not available in Europe but in the USA. The most important feature of the Natreon composition is the reduction in the highly-sensitive linolenic acid.This result provides good evidence for the recommendation for a minimal content of linolenic acid. French fries or tortilla chips.000 tonnes/year of the equivalent Nusun is currently in use. The potatoes still had acceptable taste after the oil had been used for 66 hours. Significantly better flavour and storage performance were reported for the oils with the lowest linolenic acid content.The oil was compared in domestic scale deep-fat frying of potatoes with HOSO and palm olein. The only production figure reported for Asoyia was about 10. Soybean oil Experimental quantities of soybean oil with various modified compositions have been produced (Table 3). oil with 0.The modified oils all performed better than the standard oil. but it is in commercial use. potato crisps.84 Today HOSO is increasingly used for snack food frying in Europe. 200.000 tonnes in 2009. However. under the name Natreon. after a number of analytical tests and tasting of both the used oils and the French fries. curtailing its use for many low-cost foods. was that the three oils were comparable.

one with still too much linolenic acid and the other with high linoleic acid content.Their compositions are given in Table 4. the saturated long chain acids arachidic (0. Neither of the modified linseed oils is good for frying.5% oleic acid and 52-56% linoleic acid.5%) and lignoceric (1. 17. One strain has been produced in Australia with 77% oleic acid. Standard oil typically has 53% oleic acid and 27% linoleic acid and.5%). with 20. some cultivars of peanuts are being grown commercially in the USA in which oleic acid content is increased and the linoleic acid decreased. Other oils Modified oils have been produced from three other commercial oilseed crops but are not yet commercialised as far as can be ascertained.Their nutritional implications at high levels of consumption are still unclear. Cottonseed oil Standard cottonseed oil contains 28% saturated acids (mostly palmitic). in addition. Behenic and arachidic acids are unique fatty acids occurring in peanut oil. However. The modified corn oil and safflower oil fit the ideal specifications for frying oil. The modified oil is more stable to oxidation but the linoleic acid content is too low for optimum 'fried' flavour development. 22 and 24 carbon chains respectively.0%). the increase being mainly at the expense of the linoleic acid content. High oleic cultivars have 76-81% oleic acid and only 3-5% linoleic acid. . The oil is more suitable for frying.85 Peanut oil Peanut oil has long had the reputation of being excellent as frying oil for snack foods. behenic (2.

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It may be concluded, therefore, that palm oil and palm olein will meet growing competition from other oils, despite higher cost.The latter have the advantage that they can be grown in a wide range of temperate climates. One practical way of improving the properties of palm olein has been demonstrated in a project carried out at the Malaysian Palm Oil Board. A good quality palm olein was interesterified with methyl oleate.The product was fractionated to give a new olein with Iodine Value of 81 and a cloud point of -1.5C. The oil had oleic acid (60.5), linoleic acid (16.0%) and saturated acids (22.6%), quite comparable with the liquid oils. Blended oils Blended oils provide the best cost-benefit opportunity to produce frying oil with optimised fatty acid composition. Such blends can be made with two or more commodity oils. Work has been reported from Iran on two-component blends of palm olein with rapeseed (canola) oil, olive oil and corn oil, and on three-component blends of canola/palm olein/olive and canola/palm olein/corn oil. In each case canola was 75% of the blend. The frying performance of the blends was superior to that of canola, especially the 3-component blends. In India coconut oil was blended with sesame or palm olein. The latter had the better frying performance. In most cases, it has been demonstrated that palm oil and/or palm olein could be one of the major components, blended with any of the commodity seed oils that are otherwise limited in their usefulness for use as frying fats. The palm oil component significantly improves the keeping properties of the blends and the proportions can be adjusted to give the desired clarity during storage.

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CHAPTER 10: LOW TRANS FATS FORMULAE
It is useful to bring together the low trans fats formulae proposed earlier, with new published studies relating to a wide range of food products. The product formulae that will be discussed have met the laboratory test for functionality and in some instances have been adopted for manufacture. However, they may well require minor modification for specific market requirements. In any case, they should properly be submitted to a test market, as would normally be done for any new product. The physical characteristics of palm oil products are shown in Figure 2, Chapter 6 with those of butterfat for comparison. It is apparent that palm oil products are suitable as major components of food fats. Palm stearin is an ideal high melting component (of zero trans fats content) to provide consistency in place of hydrogenated oils. The process of interesterification is often the best way to incorporate palm stearin in a blend with other oils. By the use of high temperature and a catalyst, the fatty acids become detached from the glycerol backbone of the fat molecule and re-attached in a random manner. For example, if palm stearin is reacted together with a suitable proportion of soybean oil, a semi-solid fat results with a consistency similar to butter.The change in physical behaviour is illustrated in Figures 1 and 2 on page 87, which relate to a practical application using palm stearin and palm kernel olein.

BAKERY SHORTENINGS
1. The Malaysian Palm Oil Board (MPOB) has processed on a pilot scale a number of zero trans fats shortenings. In each case, the performance was assessed by comparison in a standard cake-baking test with a high quality commercial shortening. Some trans-free shortening formulae are given in Table 3, Chapter 4. 2. Workers in Denmark have published formulae for a conventional and a liquid shortening for cakes (Table 1).

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3. Belgian workers have proposed an interesterified blend of 30 parts soybean oil with 70 parts of palm stearin (melting point 55.5°C, Iodine Value 34.8) as a basis for margarine and also shortenings. 4. American workers have been accustomed to formulating mainly with various grades of hydrogenated soybean oil, which result in high trans fats content. Several methods for reduced or zero trans fats products have now been proposed: • The use of a hard stock of 50% fully hydrogenated (therefore zero trans) soybean oil interesterified with 50% soybean oil: When this hard stock was blended with an equal quantity of soybean oil, the resulting shortening had a solid content profile close to commercial products. However, no practical baking tests have been reported. • Blends with suitable proper ties for a baker y shor tening were obtained by interesterifying 15 parts fully hydrogenated soybean oil with rapeseed oil and palm stearin (melting point 53.7°C) in various proportions. • 71% rapeseed oil and 29% stearic acid were interesterified: 52 parts of this were blended with 33 parts palm mid-fraction and 15 parts cottonseed oil.This blend was made into margarine which was comparable with two products in the market.

soybean.89 • Partly hydrogenated oils were prepared by a special process which gave lower trans fats content. Figure 1 shows the SFC . Some hydrogenation was done with a conventional nickel catalyst. Canadian workers interesterified 40% palm stearin with 60% palm kernel olein. the product had trans fats content of 2% or less. 5. alternatively 80% soybean oil interesterified with 20% fully hydrogenated soybean oil: The products are diluted with 20 parts soybean oil for tub margarine. safflower and sunflower oils were used.When blended with soybean oil to get a solid fat content (SFC) suitable for spreads and also shortenings.These are both the less valued products of the respective fractionations. followed by a second step using a special platinum catalyst. Canola. • 25% fully hydrogenated soybean oil interesterified with 75% palm oil.

90 profile before .The country's labelling regulations only require a declaration of the range of trans fats content. which would give poor eating properties. It was made from partially hydrogenated groundnut oil and cooled so that it crystallised in large granules with little free oil.This approach is now being adopted very widely. An approach similar to the Canadian example has been to interesterify palm stearin with palm kernel oil. Similar blends using interesterification also have the right properties.and Figure 2 after . has been eliminated. In one case. 6. The MPOB has published some suitable formulae. A high level of palm oil in vanaspati can substantively reduce or even eliminate trans fats. In recent years the market for spreadable fats has moved strongly towards reduced-fat spreads.The undesirable long 'tail' of the blend. MARGARINE AND SPREADS Some trans-free margarine formulae are given in Table 2. . little palm oil is used in vanaspati. VANASPATI Vanaspati was developed in India in 1930 as a substitute for butterfat ghee. For soft blends suitable for plastic tubs the range of 25-50% palm oil with 75-50% sunflower oil is suitable. In India.3% and 23. For packets. we indicated that the practical approach to obtaining low and zero trans products is by incorporating either palm stearin or fully hydrogenated liquid oil. Pakistan and Iran in the 1980s indicated a high trans fats content of 30-50%. Chapter 6.7% trans fats in two popular brands. Analyses from India. These results received adverse comment in the Indian press.interesterification. formulae within the range of 80-75% palm oil. to simulate the character of butterfat ghee. A recent analytical survey revealed levels of 23. often coupled with interesterification. 8-33% is declared which is not very helpful to the consumer. In Chapter 1. 10-15% sunflower oil and10-0% palm kernel oil are recommended.

Experience has shown that palm oil has the necessary properties to ensure satisfactory adhesion of sugar. INDUSTRIAL FRYING Industrial frying in restaurants and snack food factories requires oil with good resistance to high temperature.91 Indian workers have proposed two trans-free blends incorporating palm-based products (Table 2). therefore. palm oil provides the required high temperature stability naturally. Low and zero trans fats vanaspati formulae currently in use in Pakistan are detailed in Chapter 6.The cooked product is given a sugar coating. hydrogenated oil is often specified by the manufacturers of large-scale equipment. Annually. . Partly hydrogenated oils have been widely used in preference to liquid oils. A particular application is in doughnut frying. The granular crystals desired are readily obtained in interesterified blends. and inevitably there is a significant content of trans fats. If liquid oil is used the coating falls off. as shown in Table 3. at least 10 million tonnes are used worldwide. As an alternative.

One refiner in the USA specialises in supplying palm-based products to the domestic industry. The user only has to mix in water and roll out the dough. Pastry mix The product consists of a flour-and-fat mix packed as a free flowing powder for home use. providing a low trans fats option.This is now often replaced by a similar quantity of a hard grade of palm stearin (zero trans fats). While commercial concerns do not usually reveal their formulae beyond the legal labelling requirements. By chilling the fat and the flour and using an appropriate mixing machine.92 MINOR USES OF PALM OIL Peanut butter To prevent oil separation during storage of peanut butter. it is clear from the many reports of development work that reformulation with palm-based products is a favoured practice towards low trans fats content. . Dried soups The fat traditionally used in dried soup powders was beef fat. manufacturers add about 2% of partly hydrogenated vegetable oil.These are mainly but not exclusively based on palm-based products. where long-term storage is required. Hydrogenated vegetable oil has been replaced by palm oil or palm oil blended with 10-15% palm stearin. This was changed to partly hydrogenated vegetable oil to avoid the cholesterol content and achieve good storage life. a free flowing powder is obtained. Europe and Malaysia offer blends of suitable hard stock or finished product. Adverse publicity in the USA from 1986 onwards had reduced palm oil use in foods to near zero at one time. This is borne out by the high levels of palm-based imports by Europe and increasing intake by the USA. For those who do not have the resources to formulate trans-free products from scratch. a number of suppliers in the USA. Palm oil is now the preferred (zero trans fats) ingredient. partly hydrogenated palm oil is used (melting point 40-42°C).

Comments were made to the effect: 'Why do you want to do that? We already have plenty of capacity'. At the time that Malaysia first ventured into the oleochemical industry in the late 1970s the industry was mainly located in the USA.17 million tonnes of oleochemical products in 2009 (Table 2). but the oleochemicals have advantages. for example.They are from renewable resources and are much more easily biodegradable and therefore environmentally friendly. The oleochemicals market has been growing at 2-3% a year. This chapter describes the most important chemical steps to higher value products. In many products there is direct competition from petrochemicals. Nonetheless the Malaysian industry grew with encouragement from the government and has taken a significant share of the world market. 1 1 The author acknowledges the collaboration of Prof RJ Hamilton in the preparation of this chapter.These assets have become much more important in recent years. exported 2. Malaysia's exports to key destinations are shown in Table 1. Malaysia. and lists some of the many applications of palm-based oleochemicals.93 CHAPTER 11: PALM-BASED OLEOCHEMICALS The production of chemicals from palm oil and palm kernel oil (PKO) is attractive because the great variety of end products has much higher added value than the commodity oils themselves. .Western Europe and Japan. It is estimated that 14% of all oils and fats are available for non-food use.

Soap was most likely the first oleochemical made by man. Splitting was first achieved with the use of alkali.This primitive process is still carried on in remote Nigerian villages (Figures 1 to 3). using wood ash from a bonfire as the source of alkali. resulting in the formation of soap and glycerol.94 THE BEGINNING The 'splitting' of oils has been described as the 'gateway' to oleochemicals. .

95 Soap is a worldwide commodity for personal and laundry use. Good quality toilet soap is formulated with 75-80% of palm stearin or tallow and 20-25% of PKO or coconut oil.The .

. as outlined in Scheme 1. In the industry today. The glycerol is separated and concentrated. Alternatively they are further processed. while the shorter chain acids of the lauric oils impart good lathering and detergency. forming a valuable by-product. with Malaysia having supplied 381. The fatty acids may then be distilled to various levels of purity and marketed as such.448 tonnes in 2009. The world market for soap is over 10 million tonnes a year. fats are split very efficiently using a catalyst with water under high pressure (50-60 kg/cm2) and temperatures around 260°C (Figure 4).96 long chain fatty acids give foam stability.

Long chain alcohols have also been used to form an impervious layer to reduce evaporation from water reservoirs in hot climates. paper and plastics industries. used in shampoos and washing-up liquids. cadmium and lead stearates are used in the rubber. Calcium stearate is used in cattle feed. copper-chromium oxide). among others. Fatty alcohols A fatty acid can be directly hydrogenated to give a fatty alcohol. hydrogen at pressure (200kg/cm2) and a temperature of 300°C. Zinc.97 Fatty acids The saturated fatty acids can be made into different metal soaps. The reaction requires a catalyst (for example. Alternatively the methyl esters may be hydrogenated. The fatty alcohols are the first step towards an important group of synthetic detergents. Effectively the acidic group -COOH at the end of the fatty acid chain is changed into the -CH2OH group of the alcohol. .

) (1) is hydrogenated stepwise to give first the intermediate The nitrile R-CH=NH (2). All three bonds of the . The further reactions are shown in Scheme 2. If intermediate (2) is reacted with (4) we make a tertiary amine (5). and again to give R-CH2-NH2 (3) This is a primary amine.98 NITROGEN COMPOUNDS The starting point for a range of nitrogen compounds is the formation of a fatty acid nitrile by heating the acid with ammonia to 300°C with a catalyst such as zinc oxide or alumina. the aldimine. (It should be noted that the nitrogen atom has 3 bonds available for combination. Alternatively the intermediate (2) can be reacted with the primary amine (3) to give the secondary amine (4). whereas the carbon atom has 4.

for example. this time using an alkyl chloride or an alkyl bromide. Further reaction. gives quaternary ammonium salts (6) and (7). the reagent used in the final reaction has 14 carbon atoms and is obtained from PKO.The finely milled ore is dispersed in a solution of the quaternary and air is vigorously blown through. R represents a hydrocarbon chain which can be of different lengths. In product (7). In formulae (6) and (7). . A quaternary is used for concentrating minerals by ore flotation. distearyl dimethyl ammonium chloride. is used in hair conditioners and fabric softeners. Another quaternary. Product (7) is used as a disinfectant in the food industry.99 nitrogen atom have now reacted with alkyl groups. in breweries and in hospitals.

Fatty amides are water-proofing agents. Amine oxides are components of cosmetics and detergents.The products form water-in-oil or oil-in-water emulsions depending on the length of the chain (Scheme 3).can be transformed into tetrazoles with antiviral activity. bubble baths and in heavy-duty cleaning agents. . Primar y amines can be 'ethoxylated' by reaction with ethylene oxide Ethylene oxide chains can be built up to various lengths. and so separated from the unwanted waste.100 The ore particles are suspended in the stable foam that forms. Other amines are used as corrosion inhibitors. Biologically active fatty acid derivatives • Methyl epoxystearate. as anti-static agents in textile manufacture.see (1) in Scheme 2 . • Fatty nitriles . as release agents in rubber mouldings and as additives in lubricants. made by oxidising methyl oleate. can be transformed in a series of reactions to give aziridine. Betaines are derivatives of amino acids that occur widely in nature. Synthetic betaines are used in shampoos. which acts as an anti-tumour agent.

Their efficiency as detergents is as good as that of the petroleum derived linear alkyl benzene sulphonates (LAS).101 Palm fatty acids for candles Candles with good performance are obtained when double-pressed stearic acid is blended with paraffin wax in the ratio of 70:30. . However the SME are much more biodegradable than LAS. Sulphonated methyl esters as a detergent The methyl esters of palm stearin are fully hydrogenated and then sulphonated with sulphur trioxide (SO 3 ) to give sulphonated methyl esters (SME).

At the time of writing. mainly Vitamin E and carotenes. (an alcohol with many -OH groups) with an isocyanate. egg and gravy stains. Polyurethane foam Polyurethane is obtained by reacting a 'polyol'. . Polyurethane foam can be made with flexible. The world market is estimated to exceed 10 million tonnes per annum. the purification of the esters also yields valuable by-products. Research at the Malaysian Palm Oil Board developed a process for making a polyol based on palm oil and using it in polyurethane foam. built a pilot plant (Figure 7) and carried out extensive tests on road vehicles to prove the effectiveness of palm oil for this application. European directives require industry to move towards the incorporation of increasing levels of bio-diesel into the fuel offered to motorists at the pump. In the USA. Bio-diesel has been promoted in the European Union with the objective of reducing greenhouse gas emissions and to provide a new market for farmers who grow rapeseed. Bio-diesel The transformation of a triglyceride into the methyl esters used as bio-diesel is achieved at moderate temperature with dry methyl alcohol and an alkali catalyst. and in construction. World production of bio-diesel was projected at 3.The price structure of vegetable oils has made the import of palm bio-diesel attractive and also the import of palm oil for transformation in Europe. the level in the UK is 3.The latter is obtained by introducing the functional group N=C=O into toluene. with the Asia-Pacific region absorbing one-fifth of this. whereas LAS are not compatible.25%.926 million gallons in 2009 and is estimated to increase rapidly.102 Furthermore SME are compatible with the proteolytic enzymes often added to washing powders to remove milk. semi-rigid or rigid characteristics and finds many uses in furniture. In the case of palm oil. bio-diesel production from soybean oil has become significant.The Palm Oil Research Institute of Malaysia started a project on bio-diesel in the 1980s. SME based on palm fatty acids are now in manufacture. insulation of roofs and pipework.The process has been patented.

lipstick and eye make-up.These esters are sourced from PKO.103 USES OF OTHER FATTY ACID ESTERS Esters of medium chain fatty acids with medium chain alcohols have various uses.The following mixture is used: . A particularly interesting use of fatty acids from PKO is in the synthesis of medium chain triglycerides (MCT). while isopropyl myristate is used in hair conditioners. Myristyl myristate is a component of cosmetics. Glyceryl monolaurate is used in oil-in-water emulsions.

poly hydroxyl alkanoate (PHA).104 The MCT have special nutritional proper ties. razor handles and bottles. They are then transpor ted as the free acids in the por tal blood stream and rapidly digested. one of which produces 'sophorolipids' of potential use in cosmetics and detergents. . Other organisms produce a polymer. Glycerol A consequence of the production of bio-diesel is a greatly increased supply of glycerol. Cosmetic applications Products from palm oil and PKO are used in some cosmetic items (Examples 1 and 2). has uses in golf tees. They are impor tant food sources for patients who have difficulty in digesting normal fats. A project at a US Department of Agriculture laboratory uses glycerol as feed stock for selected micro-organisms. which has the following uses: • As a component of alkyd resins used in paints • In glyceryl monomethacrylate. Depending on the bacterial strain used PHA. which is polymerised and used in solar panels. Owing to their rapid metabolism MCT have been proposed as energy sources in the diet of athletes. They are broken down in the digestive system more rapidly than fats of longer chain length. which is biodegradable. of leather and textile processing aids • As a humectant to keep tobacco moist and also as a minor ingredient of cakes and in 'scoopable' ice cream • In the explosive nitro glycerine Potential new uses are the subject of research in a number of laboratories. etc • In other polymers used by dentists • In formulations of cleaners and polishes.

105 Example 1 Example 2 The ingredient list for a skin cream includes: • Isopropyl palmitate • Triple pressed stearic acid • Glyceryl monostearate • Medium chain triglycerides • Glycerol .

Because it is impractical to physically weigh a shipment of several hundred tonnes of oil.The term 'litre weight in air' is self-explanatory.This is the Relative Density. Accurate temperature measurement is made by the surveyor when sampling the tank.To obtain the weight in the tank.00068 per degree centigrade (it is 0. Density The density of the oil is of great commercial importance because it is required for the determination of the weight of oil in shore. The sampler should not be exposed to extreme ambient temperatures during this measurement. the volume of oil is measured in tanks that have been calibrated.and ship's-tanks.00071 for the lauric oils) and therefore an error of 1°C represents 340kg of oil.Then samples are drawn at three levels and their temperature taken with an accurate mercury-in-glass thermometer. The sampling device is first warmed by filling and emptying it.This chapter gives definitions of some physical properties and discusses their practical importance. He must make sure the tank contents are fully liquid. For practical use in determining the weight of oil in a ship's tank or a storage tank.The empty head space in the tank (the ullage) is measured and the volume of oil obtained from a calibration chart previously prepared for the tank. . quite a significant amount. with no solid fats at the bottom.The measurement of the density is carried out in the laboratory and corrected to the actual temperature of oil in the tank. we need to know the volume.The weight is then calculated by multiplying by the apparent density. the Apparent Density is used. The formal definition is the weight of a volume of the oil at a defined temperature divided by the weight of the same volume of water at 4˚C.106 CHAPTER 12: OILS AND FATS PROPERTIES The physical properties of oils and fats are basic in relation to their practical use. The change in density for most oils is 0.The chosen temperature is 4˚C because water has its maximum density at that temperature.

and a 1-inch cell for the stronger coloured crude oils. Colour The colour of oils enters into trading specifications. yellow or orange colours.0 in a 51/4-inch cell. The oil colour is matched by using a suitable combination of the graded glasses.When measuring red. Refined palm oil is usually specified at a maximum Lovibond Red of 3. A 51/4-inch cell is used for refined oil. Most refined vegetable oils have a near-white colour. Note the undesirable use of a copper or brass implement. Oil colour is generally given in terms of 'Lovibond red and yellow'. yellow or blue of increasing intensity to standardise the colour of his production. Copper is a powerful catalyst for oxidation of oils. The oil in a glass cell of a standard size is placed in an enclosed box fitted with illumination.107 Figure 1 shows a temperature measurement being made on top of a shore tank. only the red and yellow glasses are needed. He devised a system of pieces of glass coloured in red.The standards and the trade specifications for the colour of oils use the Lovibond scale. Mr Lovibond was a brewer in the English country town of Salisbury in the 18th century. .

Experience shows that poor quality CPO is difficult . this time in the infra-red part of the spectrum.The SFC is much more informative about the character of a fat than the slip melting point. It is particularly useful for describing hydrogenated fats and different grades of palm stearin and palm kernel stearin.and palm oil.with a rapid change from hard solid to liquid . It is called the Deterioration of Bleachability Index or DOBI.0. Slip melting point The melting point of solid fats is a basic characteristic used in specifications. Some laboratories use an empirical bleaching test to decide what treatment is needed in the factory. is shown in Figure 3. Another measurement of absorption.The difficulty is not due to carotene residues. These are partly removed with the use of bleaching earth and partly destroyed at high temperature during refining. but to colour formed due to deterioration of the oil.to bleach to the specified colour of 3. It consists of measurements of colour in a spectrophotometer at two wavelengths in the ultraviolet part of the spectrum. Carotene is gradually destroyed by oxidation. One of these measures the carotene level. An instrumental method for determining the melting point was developed by the MPOB (Figure 2). provides a measure of the trans fats content.or in extreme cases.The ratio of the two is a sensitive measure of the quality of CPO and is simple and rapid.The conventional method for obtaining the melting point is described in Chapter 2. where the change is much more gradual.108 The strong colour of crude palm oil (CPO) is due to its content of various carotenoids (pro-Vitamin A). impossible . Solid fat content (SFC) The relationship of the SFC with temperature has been used in earlier chapters. .The second measures the increase in oxidation products of the fatty acids. An example of the marked difference between palm kernel oil . A science-based measure to define bleachability of palm oil was developed by the Malaysian Palm Oil Board (MPOB) and is now part of the buying specification for CPO.

The solid part of the fat responds .109 The method of measurement most widely used depends on the response of a sample to a magnetic field (the Nuclear Magnetic Resonance).

To determine the cloud point. By measuring the fat brought to a range of temperatures. A proportion of about 30% of palm olein is suitable. a tube of the oil is placed in a refrigerated bath and the oil temperature measured at which cloudiness is first observed.The test indicates the ability of the oil to remain clear when kept in a domestic refrigerator. The cold test involves placing a sample in an ice water bath. Cloud Point and Cold Test These two empirical measurements are used to characterise liquid oils. the familiar curves can be prepared. but these are still inferior to the more unsaturated oils. the new olein matches the characteristics of liquid oils. Standard palm olein fails to pass these tests. Double fractionation gives improved results. Both tests relate to the consumer's wish for a salad or cooking oil to be sparkling clear. Recently reported research shows that. An oil that remains clear for 51/2 hours passes the test. after interesterification of palm olein with methyl oleate. .110 differently from the liquid part. Such blends are already being marketed. An acceptable cloud point can be obtained by blending palm olein with liquid oil as shown in Figure 4.

The temperature is measured while observing the steady evolution of smoke from oil being heated in an open vessel. particularly fatty acids. . Smaller more volatile molecules.111 Smoke Point The smoke point is of interest in oils to be used for frying. other breakdown products also affect the smoke point. in addition to free fatty acids. The lauric oils have a lower smoke point because of their content of the more volatile medium and short chain acids. shows the effect of adding fatty acids to refined oil. Curve 1. taken from a text book. A high smoke point limit is often specified for frying oils since it indicates a longer life in use. lower the smoke point and these increase during usage. Curve 3 was obtained in the MPOB laboratories on used frying oils. A high smoke point is a desirable characteristic. Curve 2 was obtained in the same way but using a lauric oil. Figure 5 shows three curves for the smoke point obtained on oils containing increasing levels of free fatty acids. It shows that.

Polymorphism The desirability of the small crystals of the beta prime (β') formed in shortenings and margarines has been discussed in earlier chapters.This is the combustion point. On further heating the gases will support the flame. Over-heated frying pans are a major cause of domestic fires.The vessel is fitted with a thermometer pocket and a stirrer.112 Flash Point and Combustion Point As the oil continues to be heated. and are also a problem in restaurants. the alpha (α) form is first obtained. The term polymorphism is applied to the existence of a triglyceride in several crystal forms. When a molten pure triglyceride is cooled quickly.The temperature at which the evolving gases momentarily light up is the flash point. The flash point and combustion point are measured by heating the oil in a small closed vessel with a sliding door at the top (Figure 6). are not at a dangerous level. which have a very low flash point. the door is momentarily opened while a flame is applied to the opening. During heating. smoke evolution increases until the gases can catch light and support combustion. A modified apparatus is used for solvent-extracted oils to test that any solvent residues. If .

Each triglyceride molecule looks like a chair. they are stacked vertically. as it were. The same behaviour applies to the mixture of triglycerides that is a natural fat.This is the final and stable form. In the α form. with two fatty acids facing one way and the third in the opposite direction. Figure 8 shows the disposition of the α. β' and β forms of tristearin.113 this is gently warmed it melts.The fatty acids are attached to the glycerol molecule. On further gentle heating. which forms the seat of the chair. The fatty acid chains are in zig-zag form. the β' form melts and re-solidifies in the beta (β) form. with adjacent . but solidifies again to give the β' form. The reason for this behaviour is that the rather long fatty acid chains have difficulty in packing together in the tidy structure that is a crystal. they are stacked somewhat more tightly at an angle to the vertical. In the β' form.

The different arrangement of the three forms is also evident when we look at the arrangement of the glycerides end on. . where the middle chains zig-zag at right angles to the plane of the paper. This is indicated in the diagram. whereas in the most stable beta form. the layers are aligned at alternate angles.114 chains at right angles. in cross-section (Figure 9). their position is rather random. In the β' form. the fatty acids are all aligned. In the β form. they all face in the same direction and are closer together. In the α form.

115 Figure 10 shows how the layers of glycerides build up into a crystal. . The example shows the most stable form of trilaurin with the 12-carbon lauric acid chains.

116

The distance between the glycerides within the layer and the distance between the layers are measured by means of x-ray diffraction. A narrow beam of x-rays is deflected at angles determined by the spacing between the glycerides.The measurements tell us that the glycerides in the α form have the most freedom of movement, while those in the β form have the least. The melting points of the three polymorphic forms of some simple glycerides are given in Table 1. The crystallisation behaviour of cocoa butter is more complex than that of other fats. It has six polymorphic forms, of which four are unstable and readily transform into the more stable form V that is required. The main glycerides contain two saturated and one oleic acid. The final most stable arrangement arrived at is shown in Figure 11, where tristearin is compared with 2-oleodistearin. The bend at the double bond of oleic acid is accommodated in the crystal by aligning with an oleic acid from the adjacent 2-oleodistearin. So, instead of the dimension of a layer being roughly the length of two fatty acids chains, it is the length of 3. The melting points of the six polymorphs of cocoa butter are shown in Table 5, Chapter 8. Refractive Index The speed of light is lower when it is passing through a medium, such as glass, water or other liquid, than it is in vacuum. As a result a ray of light is bent at an angle in the medium.The ratio of the speed of light in a vacuum to that in the medium is the refractive index

117

(RI) of the medium. It is also the ratio of the sine of the angle of incidence to the sine of the angle of refraction.The RI varies with the temperature. The measurement is made in a refractometer where the sample is placed between glass prisms, which are maintained at a constant temperature by water circulated through a jacket. The RI varies somewhat depending on the wavelength of light and this is conveniently controlled in the laboratory by using a sodium lamp, which has a strong yellow line called the D line in its spectrum.

118 The RI also varies with the chain length of the fatty acids and their unsaturation and it therefore has some value as an identity characteristic. It is listed in Codex Alimentarius and other standard specifications, though for identification purposes it is somewhat outdated. However, it is used for control of the hydrogenation process. The measurement is very rapid and can be easily carried out close to the plant in the factory, or a continuously recording refractometer can be fitted on the hydrogenation vessel. A change of 0.00116 in the RI is equivalent to 10 units of Iodine Value, and the accuracy of measurement enables a change of one unit of Iodine Value to be observed.This is sufficient for most purposes. It may be noted incidentally that, due to the need to minimise trans fats, hydrogenation is much less practised than it was. Hydrogenation is now often used to saturate all double bonds, so producing a zero trans fat which is then used by interesterification with oils to produce consistent fats.