WO2008059220A1

WO2008059220A1 - Method of preparing non-hydrogenated emulsifiers

Info

Publication number: WO2008059220A1
Application number: PCT/GB2007/004315
Authority: WO
Inventors: Allan Torben Bech; Paul Wassell; Marianne Hornholt
Original assignee: Danisco A/S
Priority date: 2006-11-13
Filing date: 2007-11-13
Publication date: 2008-05-22
Also published as: GB0622580D0

Abstract

The present invention provides a method of preparing a non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprising: (i) an interesterification step comprising a polyol compound and a non-hydrogenated triglyceride, wherein the triglyceride has an iodine value of less than 9 and substantially no trans carbon-carbon double bonds. The present invention also provides a non- hydrogenated emulsifier having substantially no trans carbon-carbon double bonds, and foodstuffs and compositions containing such an emulsifier and uses of such an emulsifier.

Description

METHOD OF PREPARING NON-HYDROGENATED EMULSIFIERS

The present invention relates to a method of preparing a non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds. The present invention also relates to a non-hydrogenated emulsifier, foodstuffs containing the emulsifier and uses of the emulsifier.

Medical experts have suggested that trans fatty acids (that is fatty acids containing trans isomers of carbon-carbon double bonds) may contribute to problems with the human circulatory system. In particular, evidence suggests that consumption of trans fatty acids may raise low-density lipoprotein cholesterol levels, and lower high-density lipoprotein cholesterol levels, which can contribute to causing arteries to become clogged and increasing the risk of a stroke and of developing heart disease.

As discussed in WO 2006/029139 trans fatty acids may be formed during hydrogenation or partially hydrogenation processes that have been commonly used in the preparation of food product formulations.

As a result of these health concerns, research has been carried out to develop new processes and products that reduce the amounts of trans fatty acids in foods. In general, this research has focussed on processes that produce low trans fat blends and compositions. For example, WO 2006/029139 teaches a fat composition which contains low levels of trans fats, and includes a mixture of palm kernel oil and palm oil. It also teaches the use of this fat composition in a confectionary composition.

EP 1159877 discloses a margarine and spread fat blend containing a trans free hard structural fat. This structural fat is made from selectively fractionated non-hydrogenated palm oil fraction which is interesterified with dry fractionated non-hydrogenated palm kernel fraction.

However, trans fatty acid residues may be present in food ingredients other than fat compositions. In particular, fatty acid residues are present in emulsifiers. Hence, there is a need for further research in this area.

The present invention alleviates the problems of the prior art. In one aspect the present invention provides a method of preparing a non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprising: (i) an interesterification step comprising a polyol compound and a non-hydrogenated triglyceride, wherein the triglyceride has an iodine value of less than 9 and substantially no trans carbon-carbon double bonds.

In another aspect, the present invention provides a non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprising: (a) mono-fatty acid esters of a polyol compound; and/or

(b) di-fatty acid esters of a polyol compound; and/or

(c) carboxylic acid esters of (a) and/or (b), wherein the carboxylic acid esters are selected from acetic acid esters, citric acid esters, lactic acid esters and diacetyltartaric acid esters; wherein the fatty acids are derived from a triglyceride having an iodine value of less than 9 and substantially no trans carbon-carbon double bonds.

In another aspect, the present invention provides a foodstuff or food ingredient comprising a non-hydrogenated emulsifier of the present invention.

In another aspect, the present invention provides a use of a non-hydrogenated emulsifier according to the present invention in a foodstuff or food ingredient selected from a bakery product, bread improver, chocolate, chocolate spread, dairy product, fat based confectionary filling, fat based icing, frozen dairy product, low-fat spread, margarine, frying margarine, peanut butter, salad dressing, shortening, tahina, soluble food or drink powders, vegetable ghee and whipped food product.

In another aspect, the present invention provides a use of a non-hydrogenated emulsifier according to the present invention to prepare a food grade emulsion, foam, dispersion, or an anhydrous based lipid preparation.

In another aspect, the present invention provides a composition comprising: (r) a non-hydrogenated palm stearine triglyceride having substantially no trans carbon- carbon double bonds with an iodine value of 15 or less; and (s) a non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprising:

(a) mono-fatty acid esters of a polyol compound; and/or

(b) di-fatty acid esters of a polyol compound; and/or (c) carboxylic acid esters of (a) and/or (b), wherein the carboxylic acid esters are selected from acetic acid esters, citric acid esters, lactic acid esters and diacetyltartaric acid esters; wherein the fatty acids are derived from a triglyceride having an iodine value of less than 9 and substantially no trans carbon-carbon double bonds.

In another aspect, the present invention provides an emulsifier composition comprising: (x) a non-hydrogenated palm stearine monoglyceride and/or palm stearine diglyceride having substantially no trans carbon-carbon double bonds with an iodine value of 15 or less; and

(y) a non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprising:

(a) mono-fatty acid esters of a polyol compound; and/or

Further aspects of the invention are defined in the claims.

Polyol compound

A polyol compound is a compound comprising two or more hydroxy! groups.

Preferably the polyol compound is selected from a glycol compound and a glycerol compound.

Preferably the polyol compound is selected from a glycol compound and glycerol. Preferably the polyol compound is a glycol compound. Preferably the glycol compound is propylene glycol.

Preferably the polyol compound is a glycerol compound. Preferably the glycerol compound is selected from glycerol and a polyglycerol.

Preferably the polyol compound is selected from propylene glycol, glycerol and a polyglycerol.

Preferably the polyol compound is glycerol.

Preferably the glycerol compound is a polyglycerol. Preferably the polyglycerol has from 2 to 10 glycerol units in the polyglycerol chain.

Preferably the polyglycerol is selected from 1 ,1'-diglycerol, 1 ,2'-diglycerol and 1,1,1'- triglycerol.

Further method features

Preferably the interesterification step (i) is carried out in the presence of an alkaline catalyst. Suitable alkaline catalysts may be selected from potassium hydroxide, sodium hydroxide and sodium methoxide.

Preferably the method comprising the further step of isolating monoglycerides from the product of step (i).

Preferably, the monoglycerides are isolated by distillation.

Preferably the method comprising the further step:

(ii) of esterification of the product of step (i) with a reagent selected from acetylating reagents; lactic acid; citric acid; tartaric acid, acetic acid and acetic anhydride; and diacetylated tartaric acid anhydride and acetic acid. Acetylation may be carried out with any suitable acetylating agent. Preferably the acetylating reagent is selected from acetic acid, acetyl chloride, acetyl bromide, acetyl iodide, acetyl fluoride, N-acetyl imidazole and acetic anhydride.

Preferably the acetylating reagent is selected from acetyl chloride and acetic anhydride.

Preferably the acetylating reagent is acetic anhydride.

Preferably the interesterification step (i) further comprises triacetin.

Preferably the further step: (ii) of esterification of the product of step (i) is carried out in the presence of a tertiary amine. Suitable tertiary amines which can be used may be selected from triethylamine, tributylamine, diisopropylethylamine, pyridine, A- dimethylaminopyridine and mixtures thereof.

The further step: (ii) of esterification of the product of step (i) may be carried out in an inert solvent. Preferably the solvent is selected from chlorinated hydrocarbons, such as chloroform and dichloromethane; ethers, such as diethyl ether and tetrahydrofuran; low molecular weight esters, such as ethyl acetate and butyl acetate; low molecular weight aliphatic ketones, such as acetone and methyl ethyl ketone; tertiary amides, such as N,N-dimethyl formamide and N-methylpyrridone; acetonitrile; and mixtures thereof.

Triglyceride

Preferably the triglyceride is prepared by selective fractionation and/or winterisation and/or solvent extraction of an edible fat or oil.

Preferably the edible fat or oil is crystallised and/or condensed at controlled temperatures and fractionated to provide a stearin fraction, removing the olein fraction. Preferably this stearin fraction is further fractionated one or more times to provide a non-hydrogenated triglyceride with the desired iodine value and substantially no trans carbon-carbon double bonds.

Preferably the selective fractionation is dry fractionation. Preferably the proportion of fatty acid residues in the triglyceride comprising 12 carbon atoms or less is less than 40%; preferably less than 35%, less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 5%.

Preferably the proportion of fatty acid residues in the triglyceride comprising 14 carbon atoms or more is at least 40%; preferably at least 50%, at least 55%, at least 60%, at least 70%, at least 80%, at least 90%.

Preferably the proportion of fatty acid residues in the triglyceride comprising 16 carbon atoms or more is at least 40%; preferably at least 50%, at least 55%, at least 60%, at least 70%, at least 80%, at least 90%.

Preferably the proportion of fatty acid residues in the triglyceride comprising 18 carbon atoms or more is at least 40%; preferably at least 50%, at least 55%, at least 60%, at least 70%, at least 80%, at least 90%.

Preferably the proportion of fatty acid residues in the triglyceride comprising 20 carbon atoms or more is at least 40%; preferably at least 50%, at least 55%, at least 60%, at least 70%, at least 80%, at least 90%.

Preferably the proportion of fatty acid residues in the triglyceride comprising 22 carbon atoms or more is at least 40%; preferably at least 50%, at least 55%, at least 60%, at least 70%, at least 80%, at least 90%.

Preferably the proportion of fatty acid residues in the triglyceride comprising from 12 to 24 carbon atoms is at least 90%.

In a further aspect, preferably the proportion of fatty acid residues in the triglyceride comprising from 14 to 24 carbon atoms is at least 60%, preferably at least 70%, at least 80%, at least 90%.

In a further aspect, preferably the proportion of fatty acid residues in the triglyceride comprising from 16 to 24 carbon atoms is at least 60%, preferably at least 70%, at least 80%, at least 90%. In a further aspect, preferably the proportion of fatty acid residues in the triglyceride comprising from 18 to 24 carbon atoms is at least 60%, preferably at least 70%, at least 80%, at least 90%.

In a further aspect, preferably the proportion of fatty acid residues in the triglyceride comprising from 20 to 24 carbon atoms is at least 60%, preferably at least 70%, at least 80%, at least 90%.

In a further aspect, preferably the proportion of fatty acid residues in the triglyceride comprising from 22 to 24 carbon atoms is at least 60%, preferably at least 70%, at least 80%, at least 90%.

The triglyceride is derived from a fat or oil selected from alfalfa oil, allanblackia seed oil, apricot kernal oil, argane oil, artemisia oil, Australian golden jajoba oil, avocado butter, avocado oil, babassu oil, baobab oil, blackcurrant seed oil, borage (starflower) oil, brazil nut oil, butter oil, camellia oil, canola oil, carrot oil, cashew nut oil, caster oil, chaulmoogra oil, cherry pit oil, chia oil, cocoa butter, coconut oil, coffee oil, corn oil, coriander oil, cotton seed oil, evening primrose oil, foraha oil, gold of pleasure oil, grape seed oil, hazelnut oil, hemp oil, hyptis oil, illipe butter, juniper berry oil, kenaf oil, kiwi seed oil, kokum butter, kukui nut oil, linseed oil, macadamia nut oil, mango seed oil, manketti nut oil, manoi, marigold oil, marula oil, meadowfoam seed oil, neem oil, nigali oil, olive oil, orchid oil, oyster nut oil, palm oil, passionflower oil, peach kernel oil, peanut oil, pentadesma butter, perilla oil, pine nut oil, pistachio nut oil, poppy seed oil, pumpkin seed oil, rapeseed oil, rice bran oil, rose hips oil, safflower oil, St, John's wort oil, sal butter, seabuckthorn oil, sesame oil, shikonin seed oil, shea butter, sisymbrium irio oil, soybean oil, sunflower oil, sweet almond oil, tamanu oil, wallnut oil, watermelon seed oil, wheatgerm oil and wild borage oil.

Preferably the triglyceride is derived from an edible fat or oil selected from allanblackia seed oil, babassu oil, butter oil, canola oil, coconut oil, cotton seed oil, foraha oil, kokum butter, palm oil, pentadesma butter, rapeseed oil, rice bran oil, sal butter and shea butter.

Preferably the triglyceride is derived from an edible fat or oil selected from allanblackia seed oil, butter oil, canola oil, cotton seed oil, foraha oil, kokum butter, palm oil, pentadesma butter, rapeseed oil, rice bran oil, sal butter and shea butter. Preferably the triglyceride is derived from palm oil.

Preferably the triglyceride has a melting point of at least 40 ⁰C; preferably at least 45 ⁰C; at least 50 ⁰C; at least 55 ⁰C; at least 60 ⁰C; at least 65 ⁰C; at least 70 ⁰C; at least 75 ⁰C; at least 80 "C; at least 85 ⁰C; at least 90 ⁰C; at least 95 ⁰C; at least 100 ⁰C.

Emulsifier

Preferably the emulsifier comprises mono-fatty acid esters and di-fatty acid esters of a polyol compound selected from propylene glycol, glycerol and a polyglycerol.

Preferably the emulsifier comprises mono-fatty acid esters and di-fatty acid esters of glycerol.

Preferably the emulsifier comprises mono-fatty acid esters of glycerol.

Preferably the emulsifier comprises di-fatty acid esters of glycerol.

In another aspect, the emulsifier comprises: (c) carboxylic acid esters of (a) mono-fatty acid esters of a polyol compound, and/or acid esters of (b) di-fatty acid esters of a polyol compound; wherein the carboxylic acid esters are selected from acetic acid esters, citric acid esters, lactic acid esters and diacetyltartaric acid esters.

Preferably where the emulsifier comprises (c), the polyol is glycerol.

Thus, for example, where (c) is an acetic acid ester of (a) mono-fatty acid esters of glycerol, the compound has the formula:

wherein one of the R groups is a fatty acid residue (e.g. -C(O)-(CH₂)i₄-CH₃); a second of the R groups is an acetic acid ester residue (i.e. -C(O)CH₃); and the third R group is either a hydrogen, or an acetic acid residue.

In another aspect, the present invention provides a non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprising (d) monoglycerides and/or (e) diglycerides and/or (f) carboxylic acid esters of monoglycerides and/or (g) carboxylic acid esters of diglycerides; wherein the carboxylic acid esters are selected from acetic acid esters, citric acid esters, lactic acid esters and diacetyltartaric acid esters; wherein the fatty acids of the monoglycerides and/or diglycerides are derived from a triglyceride having an iodine value of less than 9 and substantially no trans carbon- carbon double bonds.

Preferably the emulsifier comprises mono- and diglycerides.

Preferably the emulsifier comprises monoglycerides.

Preferably the emulsifier comprises diglycerides.

Preferably the proportion of fatty acid residues in the emulsifier comprising 12 carbon atoms or less is less than 40%; preferably less than 35%, less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 5%.

Preferably the proportion of fatty acid residues in the emulsifier comprising 14 carbon atoms or more is at least 40%; preferably at least 50%, at least 55%, at least 60%, at least 70%, at least 80%, at least 90%.

Preferably the proportion of fatty acid residues in the emulsifier comprising 16 carbon atoms or more is at least 40%; preferably at least 50%, at least 55%, at least 60%, at least 70%, at least 80%, at least 90%.

Preferably the proportion of fatty acid residues in the emulsifier comprising 18 carbon atoms or more is at least 40%; preferably at least 50%, at least 55%, at least 60%, at least 70%, at least 80%, at least 90%. Preferably the proportion of fatty acid residues in the emulsifier comprising 20 carbon atoms or more is at least 40%; preferably at least 50%, at least 55%, at least 60%, at least 70%, at least 80%, at least 90%.

Preferably the proportion of fatty acid residues in the emulsifier comprising 22 carbon atoms or more is at least 40%; preferably at least 50%, at least 55%, at least 60%, at least 70%, at least 80%, at least 90%.

Preferably the proportion of fatty acid residues in the emulsifier comprising from 12 to 24 carbon atoms is at least 90%.

In a further aspect, preferably the proportion of fatty acid residues in the emulsifier comprising from 14 to 24 carbon atoms is at least 60%, preferably at least 70%, at least 80%, at least 90%.

In a further aspect, preferably the proportion of fatty acid residues in the emulsifier comprising from 16 to 24 carbon atoms is at least 60%, preferably at least 70%, at least 80%, at least 90%.

In a further aspect, preferably the proportion of fatty acid residues in the emulsifier comprising from 18 to 24 carbon atoms is at least 60%, preferably at least 70%, at least 80%, at least 90%.

In a further aspect, preferably the proportion of fatty acid residues in the emulsifier comprising from 20 to 24 carbon atoms is at least 60%, preferably at least 70%, at least 80%, at least 90%.

In a further aspect, preferably the proportion of fatty acid residues in the emulsifier comprising from 22 to 24 carbon atoms is at least 60%, preferably at least 70%, at least 80%, at least 90%.

Preferably the non-hydrogenated emulsifier is an emulsifier obtainable or obtained by the method of the present invention. Preferably the emulsifier has a melting point of at least 40 °C; preferably at least 45 ⁰C; at least 50 ⁰C; at least 55 ⁰C; at least 60 ⁰C; at least 65 ⁰C; at least 70 ⁰C; at least 75 ⁰C; at least 80 °C; at least 85 ⁰C; at least 90 ⁰C; at least 95 ⁰C; at least 100 ⁰C.

Foodstuffs or food ingredients

Preferably the foodstuff or food ingredient selected from a bakery product, bread improver, chocolate, chocolate spread, dairy product, fat based confectionary filling, fat based icing, frozen dairy product, low-fat spread, margarine, frying margarine peanut butter, salad dressing, shortening, tahina, soluble food or drink powders, vegetable ghee

( and whipped food product.

Preferably the foodstuff or food ingredient is a bakery product, and the non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprises (d) monoglycerides and/or (e) diglycerides; wherein the fatty acids are derived from a triglyceride having an iodine value of less than 9 and substantially no trans carbon-carbon double bonds.

Preferably, the bakery product may be selected from cake, cream bakery product, and puff pastry bakery product.

Preferably the soluble food or drink powders is a wetting agent for powdered milk instantisation.

Preferably the foodstuff or food ingredient is a dairy product, and the non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprises (d) monoglycerides and/or (e) diglycerides; wherein the fatty acids are derived from a triglyceride having an iodine value of less than 9 and substantially no trans carbon-carbon double bonds.

Preferably the foodstuff or food ingredient is a dairy product, and the non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprises (f) carboxylic acid esters of monoglycerides and/or (g) carboxylic acid esters of diglycerides; wherein the carboxylic acid esters are lactic acid esters; wherein the fatty acids of the monoglycerides and/or diglycerides are derived from a triglyceride having an iodine value of less than 9 and substantially no trans carbon- carbon double bonds.

Preferably the dairy product is selected from ice cream and mousse. More preferably the dairy product is mousse. The mousse may be a low-fat (2% fat or less) or a standard-fat mousse (5% fat or more). Most preferably, the dairy product is a low fat mousse.

Preferably the foodstuff or food ingredient is a low fat spread or a margarine, and the non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprises (d) monoglycerides and/or (e) diglycerides; wherein the fatty acids are derived from a triglyceride having an iodine value of less than 9 and substantially no trans carbon-carbon double bonds.

Preferably the foodstuff or food ingredient is a topping powder, and the non- hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprises (f) carboxylic acid esters of monoglycerides and/or (g) carboxylic acid esters of diglycerides; wherein the carboxylic acid esters are acetic acid esters; wherein the fatty acids of the monoglycerides and/or diglycerides are derived from a triglyceride having an iodine value of less than 9 and substantially no trans carbon- carbon double bonds.

Composition

More preferably the non-hydrogenated emulsifier (s) is (a) mono-fatty acid ester of a polyol compound. Preferably the polyol compound is glycerol. Most preferably the non- hydrogenated emulsifier (s) is a monoglyceride.

Preferably the ratio of the palm stearine triglyceride (r) to the emulsifier (s) ranges from 30:70 to 70:30. Preferably the ratio ranges from 40:60 to 60:40. Preferably the ratio is about 50:50.

Emulsifier Composition More preferably the non-hydrogenated emulsifier (y) is (a) mono-fatty acid ester of a polyo! compound. Preferably the polyol compound is glycerol. Most preferably the non- hydrogenated emulsifier (y) is a monoglyceride.

Preferably the ratio of the palm stearine monoglycerides and/or palm stearine diglycerides (x) to the non-hydrogenated emulsifier (y) ranges from 30:70 to 70:30. Preferably the ratio ranges from 40:60 to 60:40. Preferably the ratio is about 50:50.

Further aspects

In another aspect, the invention provides the use of a non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprising (d) monoglycerides and/or (e) diglycerides; wherein the fatty acids are derived from a triglyceride having an iodine value of less than 9 and substantially no trans carbon-carbon double bonds; in a bakery product.

Preferably, the bakery product may be selected from a cake, a cream bakery product, and puff pastry bakery product.

In another aspect, the invention provides the use of a non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprising (d) monoglycerides and/or (e) diglycerides; wherein the fatty acids are derived from a triglyceride having an iodine value of less than 9 and substantially no trans carbon-carbon double bonds; in a low fat spread or a margarine.

In another aspect, the invention provides the use of a non-hydrogenated ^emulsifier having substantially no trans carbon-carbon double bonds comprising (d) monoglycerides and/or (e) diglycerides; wherein the fatty acids are derived from a triglyceride having an iodine value of less than 9 and substantially no trans carbon-carbon double bonds; in a dairy product.

Preferably the dairy product is selected from ice cream and mousse. In another aspect, the present invention provides the use of a non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprising (f) acid esters of monoglycerides and/or (g) acid esters of diglycerides; wherein the acid esters are lactic acid esters; wherein the fatty acids of the monoglycerides and/or diglycerides are derived from a triglyceride having an iodine value of less than 9 and substantially no trans carbon- carbon double bonds; in a dairy product.

In another aspect, the present invention provides the use of a non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprising (f) acid esters of monoglycerides and/or (g) acid esters of diglycerides; wherein the acid esters are acetic acid esters; wherein the fatty acids of the monoglycerides and/or diglycerides are derived from a triglyceride having an iodine value of less than 9 and substantially no trans carbon- carbon double bonds; in a toping powder.

Iodine Values

Preferably the triglyceride has an iodine value of less than 8, less than 7, less than 6, less than 5, less than 4, less than 3, less than 2.

Preferably the non-hydrogenated emulsifier has an iodine value of less than 8, less than 7, less than 6, less than 5, less than 4, less than 3, less than 2.

Other features

The term substantially no trans carbon-carbon double bonds means that the fatty acid residues comprise less that 5% trans; preferably less than 3% trans; preferably less than 2% trans; preferably less than 1 % trans; preferably less than 0.7% trans; preferably less than 0.5% trans; preferably less than 0.4% trans; preferably less than 0.3% trans; preferably less than 0.2% trans.

The trans content may be measured using Gas Chromatography. A suitable method is American Oil Chemists' Society (AOCS) Method Ce 1f-96.

The present invention will now be described in further detail by way of example only with reference to the accompanying figures in which:-

Figure 1 shows with the melting profiles for samples 1 to 4 as detailed in table 8;

Figure 2 shows cream density as a function of emulsifier and whipping time;

Figure 3 shows cross sections of croissants, where the numbers correlates to the experimental no of table 22; Figure 4 shows cross sections of puff pastry, where the numbers correlates to the experimental no of table 22;

Figure 5 shows volume and cross section of puff pastry made with puff pastry margarine with DIMODAN NH 100 (1) and distilled monoglyceride based on Margo 8;

Figure 6 shows the rate of crystallisation results in the commercial filling fat AKOCREM M (also known as ACOCREAM); and

Figure 7 shows the impact of different emulsifiers on rate of crystallisation in a fat blend consisting of 20% interesterified fat (PK4lnes) and rapeseed oil.

The present invention will now be described in further detail by way of example only.

EXAMPLES

Unless stated otherwise, all starting materials were obtained from Danisco AJS.

General Method

1) A triglyceride is melted, and glycerol compound (and optionally a catalyst, typically an alkaline catalyst) is charged to a reactor. The proportion of monoglycerides in the mono-diglyceride mixture will depend on the proportions of triglyceride and glycerol used. Table 1 indicates suitable proportions of triglyceride and glycerol that may be used.

Table 1

2) The temperature in the reactor is brought to the reaction temperature of between 240- 255°C.

3) The reaction mixture is reacted at the reaction temperature until the reaction mixture becomes clear, and thereafter a further 30 minutes.

4) If a catalyst has been used, the reaction mixture is neutralized with phosphoric acid.

5) The reaction mixture is cooled to about 9O⁰C.

6) A deodorisation setup is prepared and the reaction mixture is deodorized at 140⁰C, at <0.5mmHg for 30 minutes.

7) The reaction mixture is filtered through a diatomaceous filter earth to give a product mono-diglyceride. Suitable diatomaceous filter earth include kieselguhr or celite.

8) Optionally, the product mono-diglyceride is then distilled on a short path column in order to provide a distilled monoglyceride.

Example 1 The triglyceride Margo 8 was obtained from Premium Vegetable Oils, Malaysia.

The fatty acid content of this triglyceride is shown in Table 2, the triglyceride had a melting point of 61.1⁰C and an iodine value of 6.5 (see Table 3).

Table 2

The triglyceride was reacted with glycerol in accordance with the general method to provide a distilled monoglyceride with the properties shown in Table 3.

Table 3

Values calculated by gas chromatography (GC) unless marked by *. For values marked by * the data obtained via GC, and the fatty acid composition (FAC) of the sample, are used to calculate the value using standard formulas in accordance with the literature methods given below.

Standard Method Of Calculating The Iodine Value

The iodine value is a measure of the unsaturation of fats and oils, and is expressed in terms of the number of grams of iodine absorbed per 100 grams of the sample (% iodine absorbed). The method is applicable to all animal fats, oils and products derived from these not containing conjugated systems.

Reaction:

C=C + ICI / \ 44-

Cl

ICI cr

2 S₂O₃- 2 r S₄O₆-

Reagents:

Chloroform, p. a.

Wijs Reagent

15% potassium iodide: 150 g of potassium iodide is dissolved and diluted to 1000 ml with deionised water (Reagents) 30% acetic acid: 300 ml of acetic acid is diluted to 1000 ml with deionised water

(Reagents)

1% starch indicator (Indicator)

0.1 N Sodium thiosulphate (Volumetric solution)

Apparatus:

500 ml Erlenmeyer flask T 24/40 glass stoppered 25 ml dispenser (e.g. Brand)

50 ml burette, preferable piston burette (e.g. Metrohm equipment) 20 ml repeater pipette

Magnetic stirrer with Teflon coated magnet.

Method:

1) Weigh accurately into a 500 ml Erienmeyer flask the indicated amount of sample, stopper the flask. The sample and glassware must be completely dry.

Table 4

2) Dissolve the sample in chloroform (20 ml). However, if the expected iodine value is less than 2 dissolve the sample in chloroform (50 ml), and also use 50 ml for blanks.

3) Prepare 2 blanks simultaneously with each group of samples. The blanks should be prepared in an analogous way to the samples.

4) Add with dispenser Wijs reagent (25.00 ml) and stopper the flask and place in the dark for from 30 minutes to 60 minutes. 5) Add 15% potassium iodide (20 ml) and deionised water(100 ml). However, when the iodine values are less than 2 and for polysorbates, replace deionised water (100 ml) with 30% acetic acid (100 ml).

6) Shake gently, place on magnetic stirrer and titrate at once with 0.1 N sodium thiosulphate until the yellow colour has almost disappeared.

7) Add 1% starch indicator (1 to 2 ml) and continue the titration until the blue starch colour has just disappeared. The inflexion point has been reached when the sample is colourless for at least 30 seconds.

8) The iodine value may be calculated as follows:

_* i _A- _w . (B -S) x Ct x N x12.69 Iodine Value =

W

Where:

B = ml 0.1 N sodium thiosulphate used for blank A = ml 0.1 N sodium thiosulphate used for sample N = Normality of 0.1 N sodium thiosulphate Ct = Temperature correction factor W = Weight of sample in grams

* To make sure that there is an excess of Wijs reagent the following must be fulfilled:

S (ml for sample) _> B (ml for blank)

The temperature correction factor Ct is as shown in Table 4

Table 5

Repeatability and accuracy

Table 6

r (95%) two blanks should not differ more than 0.09 ml. r (99%) two blanks should not differ more than 0.12 ml.

Literature: AOCS Cd 1-25; TR 2710; IUPAC Standard method 2.205; DGF- Einheitsmetoden, C-V 11 d

The saponification value may be determined using (AOCS) Method Cd 3-25. IUPAC sixth ed.

The acid value may be determined using Food Chemical Codex (FCC) method 2, p. 902, 2^nd edition.

British Standard, p. 684, 1956. Food Chemical Codex III, p.166.

The colour number, red and yellow values may be determined using AOCS Cc 13e-92.

The melting point may be determined using AOCS Cc 3-25; FCC page 842-843; Ph. Nordica Vol. 1963, page 69.

Example 2 All emulsifiers are prepared according to European Food Emulsifiers and Manufacturers Association (EFEMA) guidelines. The acetem samples were prepared according to EFEMA guideline e472a and in accordance with industry standards. A number of preparative methods are known and are discussed in "Emulsifiers in Food Technology" Edited by Robert J. Whitehurst (2004) Blackwell Publishing Ltd. Suitable methods include those disclosed in US RE28.737.

Acetem 38-00 is an Acetem compound based on fully hydrogenated palm oil prepared to provide a comparision. Acetem 38-8 is an Acetem prepared from the Margo 8 starting material. Acetem 38-15 is prepared from a fractionated palm stearine with an iodine value of 15.

Fractionated palm stearine with an iodine value of 15 is commercially available from a number of manufacturers including Loders Crooklaan B.V., The Netherlands; and Premium Vegetable Oils, Malaysia.

Acetem was tested in a topping powder formulation. The results are:

Table 7

The gel strength of the jelly was tested using a Boucher Electronic Jelly Tester.

ACETEM 35-8 shows the best results, based on the jelly results.

Example 3

All emulsifiers are prepared according to European Food Emulsifiers and Manufacturers

Association (EFEMA) guidelines. The monoglycerides and mono- diglycerides were prepared according to EFEMA guideline e4721 and in accordance with industry standard. These emulsifiers may be prepared in accordance with the General Method. Also, a number of preparative methods are known and are discussed in "Emulsifiers in Food Technology" Edited by Robert J. Whitehurst (2004) Blackwell Publishing Ltd.

A non-hydrogenated mono- diglycerides version of GRINDSTED^® Mono-Di 60 based on the Margo 8 starting material was tested in the ice cream application.

This non-hydrogenated mono-diglycerides, marked as Lot Nr2482/037 in the following tables, was used in samples 2 and 3. Ice cream with following recipes were made on lab freezer lncotech CMF 100 freezer. Samples 1 and 2 were based on partially hydrogenated coconut oil and samples 3 and 4 on butter oil (anhydrous milk fat - AMF).

Table 8

The ingredients were handled according to the following established procedure:

1. Melt the fat and the emulsifiers together at approx. 5O⁰C

2. Mix liquid ingredients at 20-22⁰C 3. Mix dry ingredients 4. Add flavouring and colouring

6. Add the fat and increase temperature to 70⁰C

7. Homogenise at 78°C/175 bar

8. Pasteurise at 84°C/30 seconds 9. Cool to 5⁰C

10. Ageing for at least 4 hours

11. Measure viscosity

12. Freeze with 100% overrun and drawing temperature of -5.5⁰C

13. Fill 14. Overnight freezing in hardening tunnel at -3O⁰C 15. Store at -25⁰C

Analyses of the ice cream

The following analyses were performed on the ice cream:

Mix viscosity

The viscosity was determined by measuring the outlet time from a GRINDSTED® standard pipette in seconds.

Meltdown determination

The melting rate of the ice cream(drip rate) was measured as follows:

APPARATUS

• Freezer (-18⁰C)

• Cabinet with analytical balances (accuracy: +/-0.1g) linked to a computer for data registration and handling

• Wire netting made of stainless steel wire (0.9mm thick) with square holes of 5.0mm

• Temperature controlled room (2O⁰C +/-1°C)

• 500ml glass beaker PROCEDURE

A rectangular piece of ice cream (125cc, dimension: approx. 100mm x 50mm x 25mm), which has been tempered to approx. -18°C for a minimum of 24 hours, is weighed and placed on wire netting. The room, in which the melting process takes place, is kept at a constant temperature of 20°C +/-1⁰C. The wire netting is placed above a 500ml glass beaker placed on an analytical balance.

The analytical balances are linked to a computer which registers the weight of the ice cream in the beaker every 2 minutes and calculates the percentage of melted ice cream as a function of time. After 120 minutes a graph of the melting behaviour can be plotted.

The time elapsed before the first drop of liquid is released from the product is also recorded.

CALCULATION

(a/b) x 100 = melted ice cream after Tmin a = weight of melted ice cream sample after T minutes b = weight of ice cream sample before melting

Solvent Extractable Fat (SEF)

The SEF was determination as follows:

Extraction Agent Heptane

Cylinder rotary speed 15 revolutions / 30rpm 25g ice cream mix + 3 x 30ml heptane in a 100ml cylinder glass

Apparatus

Balance weight ±0.01 g Rotator 30rpm 100ml cylinder glass, 2.9cm x 26.5cm + lid Tripod Pipette

100ml conical flask + pumice dried 60 min at 105⁰C Sandbath Incubator 105⁰C 30ml dosimeter

PROCEDURE

Weigh 25.Og frozen ice cream directly into 100ml cylinder glasses. Thaw the ice cream samples (approx. 2 hours) and fill 30ml heptane into each cylinder glass. Close the lid carefully and place the cylinder glasses on the rotator. Rotate 15 times at 30rpm. Wait for a couple of minutes to avoid mix on the surface, then rotate 10 times. Let the samples stand for approx. 60 minutes for separation. Lever the heptane phase into a 100ml conical flask which has been dried for 1 hour in an incubator at 105⁰C together with 1 pumice and then weighed. Evaporate the heptane phase in a sandbath. Repeat the procedure twice more, without, however, including the last 10 revolutions. After the final evaporation, dry the conical flasks in the incubator at 105⁰C for 4 hours.

CALCULATION Gramme SEF:^wflask + fat - ^wflask Per cent SEF: « (100) (100)

(25.O) (X) X: fat percentage in ice cream sample

Sensorial evaluation was carried out by an experienced panel of experts.

Results

No difficulties were observed in preparing a mix, or in freezing samples, that comprised the experimental samples of mono-di-glycerides according to the described procedure.

The viscosity of mixes containing experimental mono-diglycerides, samples 2 and 3 were slightly higher than the viscosity of corresponding mixes with CREMODAN® Mono-Di 60Veg (samples 1 and 4). The numbers are depicted in the table:

Table 9

Solvent Extractable Fat (SEF) Value and Melting Rate

The detected SEF values correlate well with the melting profiles (see Figure 1 ) - quicker melting samples of ice cream (sample 3 and 4) had smaller SEF value (see table below). The melting rate of ice cream samples which contain experimental sample of mono- diglycerides (2 and 3) were slower than the melting rate of the samples containing CREMODAN® Mono-Di 60 Veg (1 and 4) (see Figure 1).

The ice cream samples which are based on hydrogenated coconut oil (sample 2) and on anhydrous milk fat (sample 3) and contain experimental samples of mono-diglycerides, had a higher SEF value than the corresponding samples with commercial CREMODAN® Mono-Di 60Veg (samples 1 and 4).

Table 10

The sensorial evaluation panel observed that ice cream samples containing experimental mono- diglycerides were slightly creamer and warmer when consumed than the corresponding samples prepared with commercial CREMODAN® Mono-Di 60 Veg.

Conclusion

The tested non-hydrogenated mono-diglycerides with an iodine value of 8 can be used in ice cream production. Surprisingly, the tested mono- diglycerides appear to be provide improved sensorial performance in comparison with the corresponding samples prepared with commercial CREMODAN® Mono-Di 60 Veg.

Example 4 All emulsifiers are prepared according to European Food Emulsifiers and Manufacturers Association (EFEMA) guidelines. The Lactem samples were prepared according to EFEMA guideline e472b and in accordance with industry standard. A number of preparative methods are known and are discussed in "Emulsifiers in Food Technology" Edited by Robert J. Whitehurst (2004) Blackwell Publishing Ltd.

A suitable preparative procedure is as follows:

Distilled mono-and diglyceride (11 g), were reacted with a 88 % by weight lactic acid in water (3 g) in a 50 mL three necked reaction flask with mechanical agitation. The reaction was carried out at up to 21O⁰C and a pressure of 5 kPa for 3 hours. The resulting reaction mixture was washed with water at 90 ⁰C (5 g x 2). The washed product was deodorized with live steam at 160⁰C and a pressure of 10 Pa for 30 min to provide a Lactem.

A comparison was carried out between standard GRINDSTED® LACTEM P22 (available from Danisco A/S) and a non-hardened versions of this emulsifer (designated Lactem P22 NH). This comparison was carried out in a mousse product.

One non-hardened version is designated Lactem P22 NH (8) and is prepared from Margo 8. The second non-hardened version is designated Lactem P22 NH (15) and is prepared from Fractionated palm stearine with an iodine value of 15.

Analytical Methods

The functionality of P22 NH based on a non hardened Lactem was compared to standard P22 in a chocolate mousse. The Lactems were evaluated in 2 different mousse systems, standard fat (7%) and low fat (2%) types.

All samples were analysed with regards to whippability (% overrun, OR), firmness (force, g which was analysed on the mousses produced on a MONDO mixer) and for sensorial response (evaluated by from 3 to 5 judges).

Textural Analysis TA-XT 2 Plus texture analyzer was used with the following settings:

Table 11

Sensory Characteristics

From 3 to 5 judges evaluated the products 2 days after production. The samples were evaluated after being whipped to 100% OR on a MONDO mixer.

Formulation & Processing

The first trials involved Lactem P22 NH (8) prepared from Margo 8. Subsequent trials also involved Lactem P22 (15) prepared from palm stearine

All the mousses were produced batch wise with a pasteurisation process.

Recipe and Formulation,

Ingredients Standard, % Low fat, %

Skim Milk 67-67.1 82.5-82 .7 Cream (38% fat) 15.8 - Sucrose 12 12 Cocoa Powder 3 3

Na Caseinate 0.5 0.5

Gelatine S 250 1.1 1.1

Lactem _^ 0.5-0.6 0.7-0.9

Total 100 100

Tat 7 <ϊ

Table 12: Mousse Formulations, Standard and Low Fat Chocolate Mousse

Process:

• Mix all dry ingredients

• Heat cream/milk to 2O⁰C and mix with dry ingredients, continue heating to 75°C.

• homogenization

• Heat to 85°C for 5min. • Cooling to approx. 10⁰C and age for 0.5-1 hour in ice water bath

• Whip on Mondo mixer (1200 rpm, 100% OR)

• Fill & store at 5⁰C

Results

Two separate sets of trials were run which are shown in tables 14-17. For the first set of trials (tables 14 and 16) OR was not measured and a sample with the Lactem P22 NH (15) was not included.

Standard fat (7%):

Samples for the mix were whipped on a Hobart mixer for measurements of overrun (OR). Those results are given in Table 13 below. Sample 1 is the reference with Lactem P22 as the whipping agent.

Table 13: Overrun of product obtained after whipping for 300 seconds in a Hobart and sensorial evaluation, standard fat chocolate mousse

The results in table 14 are a replication of the results found in table 13 plus additional trials with a non-hardened Lactem P22 with a higher iodine value, as well as samples with low dosage of emulsifier.

The firmness results in table 13 indicate that the non-hardened sample is more firm than the reference. However this was not detected sensorial where the samples gave comparable results.

Table 14. Overrun of product obtained after whipping for 300 seconds in a Hobart and sensorial evaluation, standard fat. Low fat (1.5%):

Two separate sets of trials were run which are shown in tables 15 and 16.

Table 15 : Overrun of product obtained after whipping for 300 seconds in a Hobart and sensorial evaluation, low fat chocolate mousse

The results in Table 15 show that the non-hardened lactem actually has a positive effect on the firmness and creaminess of the low fat mousse. It is also clear from observation of the samples that sample 4 has a lighter colour than sample 3, indicating a better air distribution in the sample.

Table 16 Overrun of product obtained after whipping for 300 seconds in a Hobart and sensorial evaluation, low fat chocolate mousse

The results in table 16 are a replication of the results found in table 16 plus additional trials with a non-hardened Lactem P22 with a higher iodine value, as well as samples with low dosage of emulsifier.

The results shown that overrun and sensorial properties is affected by the dosage of emulsifier, in particular, when looking at the reference samples P22 (samples 22 and 26) where the overrun is decreased and the sample is more fluffy. The firmness seems to increase with lower dosage of emulsifier.

Discussion & Conclusion

The results indicate that the standard fat samples using non-hardened lactem provided comparable results with regard to overrun, firmness and sensorial properties to the samples prepared with the standard P22.

With low fat mousses, the non-hardened lactem surprisingly shows increased firmness, increased ability to be whipped (as shown by a higher overrun) and increased creaminess compared to standard P22.

The results also show that it is possible to use lower dosages of the non-hydrogenated P22 as compared to standard P22 and still achieve this increased functionality.

The non-hydrogenated lactem P22 can be used as an alternative to standard P22, and in some applications (such as low fat mousse) provides increased functionality.

Example 5

Test of Margo 8 based emulsifiers in Oil &Fat applications In Oils & Fats a distilled monoglyceride and a citric acid ester based on Margo 8 have been tested in retail spread, cake and cream margarine, puff pastry margarine and in frying margarine to see how the choice of raw material influenced the application.

Furthermore both distilled monoglycerides and mono-diglycerides based on Margo 8 were tested for their ability to promote crystallisation in a static (as opposed to the dynamic conditions experienced on a margarine production line) crystallisation test.

All emulsifiers are prepared according to European Food Emulsifiers and Manufacturers Association (EFEMA) guidelines. The monoglycerides and mono- diglycerides were prepared according to EFEMA guideline e4721 and in accordance with industry standard. The Citrems were prepared according to EFEMA guideline e472c and in accordance with industry standard. A number of preparative methods are known and are discussed in "Emulsifiers in Food Technology" Edited by Robert J. Whitehurst (2004) Blackwell Publishing Ltd. Suitable methods include those disclosed in US 4,071 ,544.

The applications will be dealt with separately in the following Examples.

Example 6

Retail Spread

In retail spread a distilled monoglyceride based on Margo 8 was tested in 80% table margarine and 60% fat spread against the standard product DIMODAN HP based on fully hardened palm and DIMODAN NH 100. Recipes can be seen in Table 17

Table 17 Test of distilled monoglycerides in 80% margarine and 60% fat spread

Procedure

Retail Spread

Perfector

Mixing procedures Water phase:

1. Mix tap water (10°-20°C), potassium sorbate, EDTA, and salt on stirring device for approx. 1 min.

2. Adjust pH with citric acid or NAOH

3. Add flavour just before running the Perfector

Fat phase:

1. Weigh out emulsifier, beta carotene (2% solution) and oil/fat in the same container

2. Heat to 80° C

3. Stir the fat phase until mixed well

4. Cool the fat phase to 5O⁰C 5. Add flavour just before running the Perfector Emulsion: Add the water phase to the fat phase while stirring

Table 18 The margarine and spread samples were evaluated sensorial for mouth feel (with focus on creaminess) and meltdown and their ability to spread was evaluated by a standard spread test using a spreading knife and a piece of cardboard.

Results

The results of the evaluations can be found in table 19

A: Meltdown: +++ Excellent, ++ Good, - Poor B: Mouthfeel: +++ Excellent, ++ Good, + Acceptable C: Spreadability: +++ Excellent

Table 19: Results from the sensory analysis and the spread test

Comments

It was in general difficult to distinguish between samples within the 3 series. The 60% spreads made with 0.75% emulsifier were all clearly over emulsified with no release of flavour nor salt, a very poor meltdown and a texture close to rubbery.

Conclusion

In retail spreads (60%) and 80% margarine good functionality can be obtained using a distilled monoglyceride based on Margo 8. The functionality is comparable to both DIMODAN® HP and DIMODAN NH 100, but according to current understanding provides improved health benefits.

Example 6

Cake & Cream Margarine

^' The distilled monoglyceride based on Margo 8 was tested in a typical cake & cream recipe as can be seen in table 20. It was tested against the fully hardened DIMODAN® HP and the non hydrogenated DIMODAN® NH 100

Table 20: Test of distilled monoglycerides in cake and cream margarine

Procedure

Cake & cream Margarine

Perfector

Mixing procedures and process conditions:

Water phase:

1. Mix tap water (10°-20°C), potassium sorbate, EDTA, salt and protein on stirring device for approx. 1 min.

2. Adjust pH with citric acid or NAOH Fat phase:

1. Weigh out emulsifier, beta carotene (2% solution) and oil/fat in the same container 2. Heat to 80° C 3. Stir the fat phase until mixed well

4. Cool the fat phase to 55°C

5. Add flavour just before running the Perfector

Emulsion: Add the water phase to the fat phase while stirring

Table 21

Results

Figure 2 shows cream density as a function of emulsifier and whipping time As can be seen from figure 2 the distilled monoglyceride based on Margo 8 performs similar to DIMODAN NH 100 with a tendency of a foam collapse after 15 min of whipping. DIMODAN HP gives creams with lighter density and with increased air incorporation compared to distilled monoglyceride based on Margo 8 and DIMODAN NH 100

Example 7

Puff Pastry Margarine

80% puff pastry margarine was produced with distilled monoglyceride based on Margo 8, DIMODAN HP, DIMODAN NH 100 and GRINDSTED® PS 404.

The recipe can be found in table 22.

Table 22: Test of distilled monoglycerides in puff pastry margarine

Procedure

Cake & Cream Margarine

Perfector

Mixing procedures:

Water phase:

2. Adjust pH with citric acid or NAOH

Fat phase:

2. Heat to 80° C

3. Stir the fat phase until mixed well 4. Cool the fat phase to 6O⁰C

5. Add flavour just before running the Perfector

Emulsion:

Add the water phase to the fat phase while stirring

Table 23

To test the puff pastry margarines performance puff pastry and croissants were baked.

Results

Initially differences in volume were seen between samples 11 & 12 and samples 13 &14 with the former giving better volume. Within the sample pairs no differences were seen on volume nor layer definition.

Figure 3: Cross sections of croissants. The numbers correlates to the experimental no of table 22.

Figure 4: Cross sections of puff pastry. The numbers correlates to the experimental no of table 22.

However as the margarines were tested in two different types of dough, the margarines experienced different temperature profiles during the dough handling which might have affected the volume. It was therefore decided to repeat samples 12 (DIMODAN® NH 100) and sample 13 (Distilled monoglyceride based on Margo 8) in puff pastry where the differences in volume are more easily observed.

The new set up for puff pastry margarine can be seen in table 24:

Table 24: Test of distilled monoglycerides on Margo 8 and DIMODAN NH 100 in puff pastry margarine Puff pastry was made of the two margarines - and this time no differences in volume were noted. This is illustrated in Figure 5.

Figure 5: Volume and cross section of puff pastry made with puff pastry margarine with DIMODAN NH 100 (1) and distilled monoglyceride based on Margo 8.

Conclusion

Based on the above results it was concluded that all tested emulsifiers performed equally well in the application, that is that DIMODAN HP and distilled monoglyceride based on Margo 8 performed on par in this test.

Example 8

Frying Margarine - solid and liquid

Citric acid esters are typically used in frying margarine to reduce the spattering generated by the frying process. Typically GRINDSTED® CITREM 2-IN-1 or GRINDSTED® CITREM SP 70 are recommended for the use in frying margarine.

CITREM 30-40 (citric acid ester based on Margo 8) was tested against GRINDSTED® CITREM 2-IN-1 and GRINDSTED® CITREM SP 70 in both solid and liquid frying margarine according to Table 25 and Table 27:

Table 25: Solid frying Margarine

Procedure

Frying Margarine

Perfector

Mixing procedures:

Water phase:

2. Adjust pH with citric acid or NAOH

Fat phase:

2. Heat to 80° C 3. Stir the fat phase until mixed well 4. Cool the fat phase to 55°C 5. Add flavour just before running the Perfector

Emulsion: Add the water phase to the fat phase while stirring

Table 26

Table 27: Liquid frying Margarine

Procedure

Liquid Margarine

Perfector

Mixing procedures:

Water phase:

2. Adjust pH with citric acid or NAOH 3. Add flavour just before running the Perfector Fat phase:

2. Heat to 8O⁰C 3. Stir fat phase until mixed well

4. Cool fat phase to 60⁰C

5. Add flavour just before running the Perfector

Emulsion:

Add water phase to fat phase while stirring

Fill the margarine into steel containers and leave to rest for 2 hours, then stir for 10 minutes

Table 28

Methods

It is well known that frying results depends very much on the frying method and the frying pan employed. Open Pan Frying

A fixed amount of margarine is added to a preheated hot frying pan on a hot plate surrounded by brown paper. The spattering is measured when the margarine is no longer spattering as the amount of fat stains on the brown paper, the numbers as stated below:

5) None 4) Very little 3) Some 2) A good deal 1) A lot 0) Excessive

The higher the number the better the result.

The samples were in this method fried four times in total over two 2 days.

Refined frying method

This method was based on the open pan method, but is more refined in terms of reducing the experimental variance The scale employed is 10-0 with 10 being no spattering and 0 being excessive spattering

Using this method the samples were fried twice on the same day.

Results

Table 29 gives the average spattering values for the both solid and liquid margarine (along with the standard deviation). The spattering is here defined as spattering created during the evaporation of the water phase of the margarine, also sometimes called the primary spattering, i.e. the spattering that takes place before food stuff is added to the pan.

Table 29: Spattering results of solid and liquid margarine

In solid margarine, CITREM 30-40 provides comparable performance to CITREM 2-IN-1 and CITREM SP 70 when fried using the open pan method. Using the refined method CITREM 30-40 performs better than SP 70 and on par with CITREM 2-IN-1.

In liquid margarine CITREM 30-40 also gives better results when using the refined method compared to CITREMSP 70 and is on par or even better than CITREM 2-IN-1.

Example 9

DIMODAN NH 100 is sometimes known as GRINDSTED® CRYSTALLIZER NH 105 and is commercially available from Danisco A/S.

AKOCREM M (also known as ACOCREAM) is commercially available from AAK Aarhus Karlshamn.

Rate of Crystallisation Tests

Rate of crystallisation tests were performed to investigate the effect of distilled monoglyceridβs and mono-diglycerides on the crystallisation speed.

The test was performed in 3 different fat blends:

- AKOCREM M a commercial transfree filling fat

- 75% rapeseed oil and 25% interesterified fat

In AKOCREM M the following emulsifiers were tested: - 1 % GRINDSTED® CRYSTALLIZER 100

- 1 % and 1.5% DIMODAN® HP 1% and 1.5% distilled monoglyceride based on Margo 8 1 % and 1.5% mono-diglceride based on Margo 8

- 1 % and 1.5% DIMODAN® NH 100

In the blend of rapeseed oil and interesterified fat the following emulsifiers were tested for their ability to promote crystallisation:

- 1 % and 1.5% DIMODAN® HP

1 % and 1.5% distilled monoglyceride based on Margo 8 1 % and 1.5% mono-diglceride based on Margo 8

The tests were conducted by melting the fat to 85⁰C and then adding the emulsifier. When the emulsifier was properly melted the fat/em ulsifier blend was measured into NMR tubes and allowed to solidify. Prior to the analysis the NMR tubes were placed at 85°C to ensure complete neutralisation of the crystal history by the complete melting of the fat/emulsifier blend for at least one hour.

The measurements of rate of crystallisation were done using a Bruker Minispec NMS 120 low field pulsed NMR spectrometer. First reading of the solid fat content (SFC) was done at 8O⁰C, after which the sample was placed in a 2O⁰C water bath. Subsequent measurements were done every minute for 20 minutes. Rate of crystallisation describes the crystal formation in the fat.

Results

In general the rate of crystallisation increases with the dosage of emulsifier.

Figure 6 shows the rate of crystallisation results in the commercial filling fat AKOCREM M.

From the curve it can be seen that 1% GRINDSTED® CRYSTALLIZER 100 has the biggest impact on crystallisation.

1.5% distilled monoglyceride based on Margo 8 provides a faster crystallisation rate than

DIMODAN® NH 100 and is almost comparable to DIMODAN® HP. At 1% dosage the distilled monoglyceride is situated between DIMODAN NH 100 and DIMODAN HP and the differences between DIMODAN HP and the distilled monoglyceride based on Margo 8 is bigger.

For the mono-diglyceride based on Margo 8 increasing the dosage form 1 % to 1.5% provides only a small effect, giving a slightly slower rate of crystallisation compared to 1% distilled monoglyceride based on Margo 8.

It is interesting that in the rate of crystallisation test the distilled monoglyceride based on Margo 8 provides similar results to DIMODAN HP in a dosage of 1.5%.

As can bee seen in Figure 7 mono-diglyceride based on Margo 8 apparently does not influence the rate of crystallisation compared to the pure fat blend. The distilled monoglyceride based on Margo 8 at 1% does not promote crystallisation quite as strongly as does DIMODAN® HP; however, it is broadly comparable. At 1.5% the distilled monoglyceride based on Margo 8 appears to be stronger in the crystallisation promotion at certain parts of the crystallisation as compared to 1.5% DIMODAN HP.

Conclusion on the rate of crystallisation test

Distilled monoglyceride based on Margo 8 appears to provide similar crystallisation promotion results to DIMODAN HP, especially at the higher dosage of 1.5%. It provides better crystallisation promotion results than DIMODAN NH 100.

All publications mentioned in the above specification are herein incorporated by reference. Various modifications and variations of the described methods and system of the invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in connection with specific preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in chemistry or related fields are intended to be within the scope of the following claims

Claims

1. A method of preparing a non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprising: (i) an interesterification step comprising a polyol compound and a non-hydrogenated triglyceride, wherein the triglyceride has an iodine value of less than 9 and substantially no trans carbon-carbon double bonds.

2. A method according to claim 1 wherein the triglyceride has an iodine value of less than 7.

3. A method according to any of the preceding claims wherein the triglyceride has an iodine value of less than 5.

4. A method according to any of the preceding claims wherein the polyol compound is selected from propylene glycol, glycerol and a polyglycerol.

5. A method according to any of the preceding claims wherein the polyol compound is glycerol.

6. A method according to claim 5 comprising the further step of isolating monoglycerides from the product of step (i).

7. A method according to any of the preceding claims comprising the further step: (ii) of esterification of the product of step (i) comprising using a reagent selected from acetylating reagents; lactic acid; citric acid; tartaric acid, acetic acid and acetic anhydride; and diacetylated tartaric acid anhydride and acetic acid.

8. A method according to claim 7 wherein the acetylating reagent is selected from acetic acid, acetyl chloride, acetyl bromide, acetyl iodide, acetyl fluoride, N-acetyl imidazole and acetic anhydride.

9. A method according to claim 5 wherein the interesterification step (i) further comprises triacetin.

10. A method according to any of the preceding claims wherein the triglyceride is prepared by selective fractionation and/or winterisation and/or solvent extraction of an edible fat or oil.

11. A method according to any of the preceding claims wherein the proportion of fatty acid residues in the triglyceride comprising 14 carbon atoms or more is at least 60%.

12. A method according to any of the preceding claims wherein the proportion of fatty acid residues in the triglyceride comprising from 12 to 24 carbon atoms is at least 90%.

13. A method according to any of the preceding claims wherein the triglyceride is derived from an edible fat or oil selected from allanblackia seed oil, butter oil, canola oil, cotton seed oil, foraha oil, kokum butter, palm oil, pentadesma butter, rapeseed oil, rice bran oil, sal butter and shea butter.

14. A non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprising:

(a) mono-fatty acid esters of a polyol compound; and/or

15. A non-hydrogenated emulsifier according to claim 14 wherein the polyol compound is selected from propylene glycol, glycerol and a polyglycerol.

16. A non-hydrogenated emulsifier obtainable or obtained by any one of claims 1 to 13.

17. A foodstuff or food ingredient comprising a non-hydrogenated emulsifier according to any one of claims 14 to 16.

18. A foodstuff or food ingredient according to claim 17 wherein the foodstuff or food ingredient is selected from a bakery product, bread improver, chocolate, chocolate spread, dairy product, fat based confectionary filling, fat based icing, frozen dairy product, low-fat spread, margarine, frying margarine, peanut butter, salad dressing, shortening, tahina, soluble food or drink powders, vegetable ghee and whipped food product.

19. A dairy product according to claim 18 wherein the dairy product is ice cream.

20. Use of a non-hydrogenated emulsifier according to any one of claims 14 to 16 in a foodstuff or a food ingredient selected from a bakery product, bread improver, chocolate spread, dairy product, fat based confectionary filling, fat based icing, low-fat spread, margarine, frying margarine, peanut butter, shortening, tahina and vegetable ghee

21. Use of a non-hydrogenated emulsifier according to any one of claims 14 to 16 to prepare a food grade emulsion, foam, dispersion, or an anhydrous based lipid preparation.

22. A composition comprising:

(r) a non-hydrogenated palm stearine triglyceride having substantially no trans carbon- carbon double bonds with an iodine value of 15 or less; and

(s) a non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprising:

(a) mono-fatty acid esters of a polyol compound; and/or

23. An emulsifier composition comprising:

(x) a non-hydrogenated palm stearine monoglyceride and/or palm stearine diglyceride having substantially no trans carbon-carbon double bonds with an iodine value of 15 or less; and (y) a non-hydrogenated emulsifier having substantially no trans carbon-carbon double bonds comprising:

(a) mono-fatty acid esters of a polyol compound; and/or

24. A method substantially as hereinbefore described with reference to any one of the examples.