OA20203A - Process for the manufacture of edible water-in-oil emulsion. - Google Patents
Process for the manufacture of edible water-in-oil emulsion. Download PDFInfo
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- OA20203A OA20203A OA1201600436 OA20203A OA 20203 A OA20203 A OA 20203A OA 1201600436 OA1201600436 OA 1201600436 OA 20203 A OA20203 A OA 20203A
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- fat
- oil
- water
- hardstock
- liquid
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Abstract
Process for the manufacture of a non-pourable edible water-in-oil emulsion comprising at least 50 wt. % of total fat, comprising the following steps : a. providing 5 to 90 wt. % of hardstock fat, based on the weight of total fat, in liquid form; b. providing a liquid mixture of water and oil, wherein the mixture has a temperature below the melting point of the hardstock fat; c. mixing the hardstock fat in liquid form with the liquid mixture of water and oil; wherein the temperature of the mixture provided at step 'c' is below the melting point of the hardstock fat, and wherein the amount of trans unsaturated fatty acid is less than 5 wt. %, based on the weight of total fat.
Description
Process for the manufacture of edible water-in-oil émulsion
Field of the invention
The présent invention is directed to a process for the manufacture of non-pourable edible waterin-oil émulsions. In addition the invention is directed to the émulsions obtainable by said process. These products are characterized by having improved properties, such as stability and firmness. Furthermore the invention is directed to the use of such émulsions for baking to provide baked goods with improved texture.
Background ofthe invention
Edible water-in-oil émulsions, which comprise a continuous fat phase and a dispersed aqueous phase, are well known in the art and include for example margarine.
The fat phase of margarine and similar water-in-oil émulsions is typically a mixture of liquid oil (i.e. fat that is liquid at ambient température) and fat which is solid at ambient températures. The solid fat, also called structuring fat or hardstock fat, serves to structure the fat phase and helps to stabilize the aqueous phase (e.g. in the form of droplets) by forming a fat crystal network. Ideally the structuring fat has such properties that it melts or dissolves at mouth température otherwise the product may hâve a heavy and/or waxy mouthfeel.
Margarine is generally defined as a composition containing at least 80 wt. % fat and about 20 wt. % aqueous phase. In contrast, émulsions containing less than 80 wt. % fat are generally called spreads. Nowadays the terms margarine and spread are sometimes used interchangeably although in some countries the commercial use of the term margarine is subject to certain regulatory requirements. For the purpose of the présent invention the terms margarine and spread will be used interchangeably.
In the market place margarine is generally sold as one of three principal types of water-in-oil émulsion:
• hard or stick margarine (also referred to as wrappers);
• (typically softer) tub margarine; and • liquid or pourable margarine.
Wrapper margarines and tub margarines are non-pourable and generally contain a higher amount of hardstock fat than liquid or pourable margarines.
The general process for the manufacture of water-in-oil émulsions, using the votator or churn process, encompasses the following steps:
1. Mixing of the liquid oil, the hardstock fat and if présent the water-phase at a température at which the hardstock fat is definitely liquid;
2. cooling of the mixture under high shear to induce crystallization of the hardstock fat to create an émulsion;
3. formation of a fat crystal network to stabilize the resulting émulsion and give the product some degree of firmness;
4. modification of the crystal network to produce the desired firmness, confer plasticity and reduce the water droplet size.
These steps are usually conducted in a process that involves apparatus that allow heating, cooling and mechanical working of the ingrédients, such as the churn process or the votator process. The churn process and the votator process are described in the Ullmans Encyclopedia, Fifth Edition, Volume A 16, pages 156-158.
High-fat (e.g. above 50 % fat) non-pourable water-in-oil émulsions (e.g. wrapper and tub margarines) are commonly used in the préparation of foods, such as for baking, frying and cooking (e.g. to make gravy). For example, the use of such high-fat émulsions in baking general improves the aération of the dough (or batter) and improves the moist feel of the final backed product. Furthermore, the hardstock fat (crystals) provide additional structure and stability to the dough and backed product.
A common problem in the use of such high-fat non-pourable émulsions in baking is that the texture ofthe baked products can be suboptimal. In particular, when used in amounts as generally specified by recipes (e.g. to make cake), the baked product often has a texture which is less soft than is désirable.
US5,178,897 relates to water-in-oil émulsion composition for bakery capable of giving a product soft texture and good meltability in the mouth. This is achieved by a water-in-oil émulsion comprising from 0.1 to 2.0 wt. % of trans-unsaturated monoglyceride; and further comprising a sizing agent.
High-fat non-pourable émulsions need to hâve a certain firmness (also called hardness), and a good stability (e.g. small and stable water-droplet size). For example, wrapper margarines should also be able to withstand a certain amount of pressure to enable stacking at the manufacturing site, during transport, storage or présentation in the shop. For example, high-fat tub margarinesoften hâve an irregular upper surface as the product tends to congeal very rapidly when it is filled into the tub. Consumers nowadays hâve corne to expect such surface undulations upon opening ofthe tub as an indication of freshness. Therefore, also tub margarines need to hâve a certain firmness to retain (surface) shape during storage and transport.
Thus it is désirable that high-fat non-pourable émulsions, such as tub margarines and wrappers, are sufficiently firm at storage conditions, in particular at réfrigération conditions. On the other hand during use at ambient températures it is désirable that the high fat non-pourable émulsions are sufficiently soft to enable easy processing. For example, when used for baking an essentiel step is the kneading of dough to mix ingrédients. For easy dough kneading, especially if done by hand, it is important that the high-fat émulsion sufficiently softens at ambient températures. Thus preferably such émulsions soften considerably after being take from the fridge and are warmed to ambient températures.
Stability is another important attribute of good quality high-fat non-pourable émulsions. For example, oil and/or water-phase séparation during storage or use should be avoided. An indication of stability is that the average water-droplet size is small, that the variance in droplet size is small; and that these remain so during storage. A small and stable droplet size is also important to maintain microbiological stability.
Nowadays health conscious consumers desire high-fat non-pourable émulsions to hâve reduced amounts of saturated fatty acids (SAFAs). SAFAs typically contribute to the overail solids content and stability. Reducing the amount of SAFA of in émulsion typically adversely impacts firmness and stability. Thus there is a need for high-fat émulsions which are sufficiently firm (at storage conditions) and/or stable, while having a reduced amount of SAFA.
GB1327511 discloses a process for the préparation of low-calorie spreads by mixing a first liquid which consists of a fat phase containing crystallisable material at a température of at least 28 degrees Celsius, with a second liquid substantially free from crystallisable material at a température of at most 8 degrees Celsius. It was found that the stability and hardness (at low and ambient températures) of the high fat émulsions made according to GB1327511 leaves to be desired.
EP 1688044 discloses a process to make a butter-like dairy spread, wherein an edible vegetable fat is mixed at a température below 22°C with at least butter and a taste ingrédient.
Alternatives to the votator or churn process for the manufacture of margarines are known which involve the use of fat powder comprising hardstock fat (i.e. pre-crystallized fat) (WO 2005/014158). However, it was observed that use of fat powder (containing pre-crystallized hardstock) may give rise to problems when used for the manufacture of high-fat non-pourable émulsions. Such products typically require a relatively high amount of hardstock fat. In particular it was found that the liquid oil slurry, when comprising a relatively large amount of hardstock fat in the form of fat powder, can become very viscous and difficult to handle (e.g. mix and/or pump). Furthermore the use of micronized fat powder comprising hardstock fat may hâve other disadvantageous as well. For example when used on factory scale the fat powder can lead to problems such as dustiness and the (large) space requirementforthe machinery. In particular, large scale hoppers and micronisation equipment which are used to make fat powder can generally take up a large amount of space in the factory.
In fact it is desired to provide a process for the manufacture of high-fat non-pourable water-in-oil émulsion which is simple, and preferably requires less (factory) equipment.
It is therefore an object of the présent invention to provide high-fat non-pourable water-in-oil émulsion (e.g. tub margarine, wrapper margarine) which has:
• an improved firmness, and/or • has an improved stability, and/or • can be used in baking to provide improved organoleptic properties to the baked product, and/or when compared to émulsions made with prior art processes;
• while preferably comprising a low amount of SAFAs and/or solids; and/or • while preferably made using a reduced amount of micronized fat powder.
In particular, it is an object ofthe présent invention to provide high-fat non-pourable water-in-oil émulsion which has:
• an increased firmness at low températures while having a reduced firmness at ambient températures, and/or • good softening from réfrigération to ambient température, and/or • has a reduced average water-droplet size (or size distribution), and/or • can be used in baking to provide improved softness to the baked product; when compared to émulsions made with prior art processes;
• while preferably comprising a low amount of SAFAs and/or solids; and/or • while preferably made using little or no micronized fat powder.
Summary of the invention
It was found that one or more of these objectives are achieved by a process for the manufacture of a non-pourable edible water-in-oil émulsion comprising at least 50 wt. % of total fat, comprising the following steps:
a. providing 5 to 90 wt. % of hardstock fat, based on the weight of total fat, in liquid form;
b. providing a liquid mixture of water and oil, wherein the mixture has a température below the melting point of the hardstock fat;
c. mixing the hardstock fat in liquid form with the liquid mixture of water and oil; wherein the température of the mixture provided at step ‘c’ (i.e. comprising hardstock fat, water and oil) is below the melting point of the hardstock fat, and wherein the amount of trans unsaturated fatty acid is less than 5 wt. %, based on the weight of total fat.
For example, wrapper products made by the process according to the invention show improved stability and firmness compared to wrappers having the same composition but not made with the process according to the invention. Furthermore, itwas observed that when making nonpourable émulsions according to the invention less equipment is required. For example, generally a votator process to manufacture wrappers involves one or more A-units, C-units and B-units. The C and B-unit are necessary to further treat the mixed émulsion before packing (e.g. to allow further working and hardening before packing). It was found that the in the process according to the invention the use of B-units and/or C-units could be omitted before wrapping, while still resulting in good quality products.
Without being bound by theory it is believed that low levels of trans fatty acids (trans FAs) used in the présent process, and the mixing of the relatively hot hardstock fat with a relatively cold liquid mixture of water and oil (e.g. versus mixing with only oil or water) allows more rapid crystallization. The rapid crystallization of the hardstock fat, at the moment water-droplets are dispersed in the oil phase, is believed to be important in providing the improved high-fat émulsions according to the invention. However, the exact underlying structural différences of the émulsion made according to the invention and not made according to the invention are not known in detail.
Therefore in a second aspect the invention relates to a non-pourable edible water-in-oil émulsion obtainable according to the process of the invention.
Surprisingly, it was further observed that when a high-fat non-pourable émulsion according to the invention is used for baking, the resulting baked products, such as cakes, show improved organoleptic properties. In particular, they hâve a softer texture compared to cakes made using e.g. prior art (votator) wrapper products.
Thus the invention relates in a third aspect to the use of the non-pourable émulsion according to the invention in baking to improve the organoleptic properties of bakery products.
Detailed description
Weight percentage (wt. %) is based on the total weight of the product unless otherwise stated. It will be appreciated that the total weight amount of ingrédients will not exceed 100 wt. % based on total weight of the product.
The terms ‘fat’ and Oil’ are used interchangeably. Where applicable the prefix ‘liquid’ or ‘solid’ is added to indicate if the fat or oil is liquid or solid at ambient température as understood by the person skilled in the art. Ambient température is considered to be a température of about 20 degrees Celsius. Hardstock fat refers to a fat that is solid at ambient température as understood by the person skilled in the art. The terms ‘hardstock fat’, ‘structuring fat’ or ‘hardstock’ are used interchangeably.
The terms ‘liquid hardstock fat’ and ‘hardstock fat in liquid form’ are used interchangeably. The terms ‘water’ and ‘water-phase’ are used interchangeably.
Non-pourable water-in-oil émulsions according to the invention encompass solid or semi-solid émulsions such as wrapper- and tub margarines. Preferably the non-pourable water-in-oil émulsions according to the invention are tub or wrapper margarines, and more preferably are wrapper margarines. The non-pourable émulsions according to the invention are non-pourable at réfrigération conditions (e.g. 4 degrees Celsius) and preferably also at ambient conditions. Preferably the non-pourable edible émulsion according to the invention has a Stevens value (measured at 5 degrees Celsius, after storage at 5 degrees Celsius for 1 week) of from 300 to 2000, more preferably from 400 to 1500, even more preferably from 550 to 1200 and stiil even more preferably from 600 to 900. This Stevens value is preferably measured using a Stevens penetrometer (Brookfield LFRA Texture Analyser (LFRA 1500), ex Brookfield Engineering Labs, UK) equipped with a stainless Steel probe with a diameter of 4.4 mm and operated in “normal” mode. The probe is pushed into the product at a speed of 2 mm/s, a trigger force of 5 gram from a distance of 10 mm. The force required is read from the digital display and is expressed in grams.
Fat as used in the présent invention refers to edible triglycéride based fat as understood by the person skilled in the art. The terms ‘triacylglycerols’, ‘TAGs’, and ‘triglycérides’ are used interchangeably; they refer to esters of glyceroî and three fatty acids. The fatty acid (moieties) of the TAGs may vary in length. The length of a fatty acid is commonly indicated by their carbon number. The fatty acid (moieties) may be saturated, monounsaturated or polyunsaturated.
Process to manufacture non-pourable edible water-in-oil émulsion
In a first aspect the invention relates to a process for the manufacture of a non-pourable edible water-in-oil émulsion comprising at least 50 wt. % of total fat, comprising the following steps:
a. providing 5 to 90 wt. % of hardstock fat, based on the weight of total fat, in liquid form;
b. providing a liquid mixture of water and oil, wherein the mixture has a température below the melting point of the hardstock fat;
c. mixing the hardstock fat in liquid form with the liquid mixture of water and oil; wherein the température ofthe mixture provided at step ‘c’ (i.e. comprising harstock fat, water and oil) is below the melting point of the hardstock fat, and wherein the amount of trans unsaturated fatty acid is less than 5 wt. %, based on the weight of total fat.
step ‘a’ - providing the hardstock fat in liquid form
The process according to the invention comprises the step ‘a’ of providing hardstock fat in liquid form. This is to be understood as providing hardstock fat in liquid form. The hardstock fat provided at step ‘a’ should be in liquid form upon contact (i.e. just before) with the liquid mixture of water and oil at step ‘c’. After contact at step ‘c’ the hardstock fat is allowed to (fully) crystallize. Preferably the hardstock fat is provided in liquid form at step ‘a’ by sufficiently heating the hardstock fat (e.g. above its melting point). The melting point of hardstock fat is in large part determined by its triglycéride composition. The melting point of common hardstock fats is known by the skilled person or can be determined by a simple testing (e.g. by controlled heating of a hardstock fat sample. Preferably the température of the hardstock fat in liquid form provided at step ‘a’ is at least 25 degrees Celsius, more preferably from 27 to 80 degrees Celsius, even more preferably from 30 to 70 degrees Celsius, still even more preferably from 35 to 60 degrees Celsius and still even more preferably from 38 to 50 degrees Celsius.
It was observed that conditions which favor fast crystallization of the hardstock fat upon mixing with the émulsion at step ‘c’ of the process of the invention, further improve the quality of the émulsions made. This was observed to lead to émulsions with improved firmness, stability and organoleptic properties of the baked products. Fast cooling of the hardstock fat can be achieved by providing liquid hardstock fat at step ‘a’ with a température which is close to its melting point (i.e. not raised too far above its melting point).
Preferably the liquid hardstock fat provided at step ‘a’ has a température which is at least above the melting point of the hardstock fat, but preferably not more than at most 15 degrees Celsius, more preferably at most 10 degrees Celsius, even more preferably at most 8 degrees Celsius and still even more preferably at most 5 degrees Celsius above the melting point of the hardstock fat.
step ‘b’ - providing the liquid mixture of water and oil
Providing the liquid mixture of water and oil provided at step ‘b’, is to be understood as providing a mixture of liquid oil and liquid water upon contact with the hardstock fat in liquid form at step ‘c’. For example, a process wherein the liquid oil, liquid water and hardstock fat in liquid form enter a mixing device as three separate streams, and meet for the first time within the (running) mixing chamber is encompassed by the présent invention. However, preferably the liquid mixture of water and oil is provided at step ‘b’ in the form of a pre-mix and more preferably as a liquid water-in-oil émulsion before contact with the hardstock fat in liquid form. A water-in-oil émulsion comprising a dispersed water-phase and a continuous oil phase can be provided from a water-phase and liquid oil using techniques known in the art. These techniques typically involve suitable agitation and commonly the use of water-in-oil promoting additives, such as certain emulsifiers.
Typically fat soluble emulsifiers are used in the manufacture of water-in-oil émulsions. The Hydrophilic-Lipophilic Balance (HLB) of an emulsifier is a measure of the degree to which it is hydrophilic or lipophilie. The HLB value is a parameter which is describing the solubility ofthe surfactant. The HLB value is a concept introduced by Griffin in 1950 as a measure of the hydrophilicity or lipophilicity of nonionic surfactants. It can be determined experimentally by the phénol titration method of Marszall; see Parfumerie, Kosmetik, Vol. 60, 1979, pp. 444-448; and Rompp, Chemistry Lexicon, 8th Edition 1983, p. 1750. An emulsifier having an HLB value of 8 or lower is usually classified as being a water-in-oil promoting emulsifier and as fat soluble. Said preferred liquid water-in-oil émulsion provided at step ‘b’ may be a coarse émulsion, but more preferably has a D3.3 of at most 100 pm, even more preferably of at most 75 pm, still even more preferably of at most 50 pm and still even more preferably of at most 25 pm.
The température ofthe liquid mixture of water and oil provided at step ‘b’ should be below the melting point of the hardstock fat. Hereby is meant that the liquid mixture of water and oil should hâve a température below the melting point of the hardstock fat upon (i.e. just before) contact with the liquid hardstock at step ‘c’. After contact the température of the mixture of water, oil and hardstock fat as a whole should not increase above the melting point ofthe hardstock fat. Optionally cooling can be applied to control the température of the mixture (of hardstock fat, water and liquid oil) at step ‘c’.
As mentioned, conditions which favor fast crystallization of the hardstock fat upon mixing with the liquid mixture of water and oil at step ‘c’ improve the quality of the non-pourable émulsions made. Faster crystallization rates of the hardstock fat at step ‘c’ can be achieved by providing the liquid mixture of water and oil at step ‘b’ with a température further below the melting point of the hardstock fat. However, preferably for easy of processing, the température of the liquid mixture of water and oil at step ‘b’ is above the freezing point of water. Preferably the température ofthe liquid mixture of water and oil provided at step ‘b’ is from 1 to 20 degrees Celsius, more preferably from 2 to 15 degrees Celsius, even more preferably from 3 to 10 degrees Celsius, and still even more preferably from 4 to 8 degrees Celsius.
Preferably at least 75 wt. %, more preferably at least 85 wt. %, even more preferably at least 95 wt. % and still even more preferably at least 99 wt. % of the liquid oil and water, based on the total (combined) amount of liquid oil and water, is provided at step ‘b’.
Step ‘c’ - mixing the hardstock fat in liquid form with the liquid mixture of water and oil At step ‘c’ of the process according to the invention, liquid hardstock fat is brought into contact with the liquid mixture of water and oil. As mentioned conditions which favor fast crystallization of the hardstock fat at step ‘c’ improve the quality of the émulsion products made. Fast crystallization rates can be further improved by mixing conditions which favor efficient heat exchange between the hardstock fat and the liquid mixture of water and oil. This can be achieved by fine (and fast) mixing (e.g. dispersion/homogenization) ofthe hardstock fat with the liquid mixture of water and oil to provide a large hardstock fat surface area for température exchange.
Preferably upon contact at step ‘c’ the liquid hardstock fat is essentially instantaneously mixed (e.g. to homogenization) with the liquid mixture of water and oil. Essentially instantaneous mixing of the hardstock fat with the liquid mixture of water and oil can be for example achieved by use of a mixing device having more than one inlet leading into the mixing chamber. In such a device one inlet can allow entry of the hardstock fat in liquid form and a second the entry of the liquid mixture of water and oil. Such a device can for example enable the liquid hardstock fat and the liquid mixture of water and oil to contact within an (actively running) mixing chamber and be essentially instantaneously mixed (to homogenization).
Many mixing devices known in the art of émulsion (e.g. margarine) making are suitable for use in the process according to the invention, and e.g. also allow streams of material to enter the mixing device via separate inlets. Preferably the one or more mixing devices used in the process according to the invention are in-line mixing devices suitable for continuous production of water-in-oil émulsions; and more preferably are high-shear mixing devices as understood by the person skilled in the of margarine making. Typically the process of mixing can lead to an increase in température of the mixture. During mixing at step ‘c’ the température of the mixing materiais should not rise above the melting point of the hardstock fat. Optionally cooling can be applied to control the température ofthe mixture during mixing.
Examples of suitable mixing devices are pin stirrers (sometimes called C-units) and fluid dynamic mixers (sometimes called FDM mixers). Preferably the mixing device used in the process according to the invention is a FDM mixer and more preferably an FDM mixer as are described in WO02/038263.
It was found that high-fat non-pourable émulsions of further improved quality (e.g. hardness, stability and organoleptic quality of baked goods) can be achieved by use of a FDM mixer which preferably opérâtes at one, more preferably more, of the following operating conditions/configurations:
• Preferably the FDM mixer opérâtes above 500 rpm, more preferably from 750 to 4000 rpm, even more preferably from 1000 to 3500 rpm and still even more preferably from 1500 to 2500 rpm.
• Preferably the FDM mixer opérâtes at a rotor tip speed of from 5 to 25 meters per second, more preferably from 7 to 20 meters per second and even more preferably from 10 to 15 meters per second.
• Preferably the FDM mixer opérâtes (and is suitably configured) such that a mixing number (i.e. number of cavity-cavity interactions during résidence time) is achieved from 5000 to 20000, more preferably from 7500 to 17500 and even more preferably from 10000 to 15000.
Conventional (prior art) wrappers and/or tub margarines are generally made using the votator process. Therein the hardstock fat, water and oil are typically treated by one or more A-units (i.e. surface scrapped heat exchangers), C-units (i.e. pin stirrers) and B-units before packing (e.g. in a wrapper). The B-unit, which is also known as a resting tube, typically has a relatively large volume and sieves plates as certain positions in the tube. The B-unit allows the émulsion to further harden before packaging.
Surprisingly it was found that in the process according to the invention, further treatment (i.e. after (high-shear) mixing) by one or more additional C-units and/or B-units to achieve sufficient product quality (e.g. hardness before packing) can be omitted. For example, (high-shear) mixing by a FDM was found to be sufficient to provide good quality products and allow packing in a tub or wrapper. To improve ease of packing, in particular for wrapper margarines, preferably the exit-temperature ofthe product leaving the (high shear) mixing device is at most 15 degrees
Celsius, more preferably at most 12 degrees Celsius, even more preferably at most 10 degrees Celsius and still even more preferably at most 8 degrees Celsius.
The option to omit further treatment by C-, and/or B-units to provide good quality products results in faster processing times, a reduced energy requirement, lower line pressure and reduced factory space requirement and generally leads to a more simple process. Preferably the process according to the invention does not comprise B-unit or C-unit treatment and more preferably does not comprise C-unit and B-unit treatment.
Hardstock fat
The non-pourable water-in-oil émulsion according to the invention comprises from 5 to 90 wt. % of hardstock fat, based on total fat. The hardstock fat may be a single fat or a mixture of different fats. The hardstock fat may be of vegetable, animal or marine origin. The hardstock fat may comprise conventional oils and fats which may be of both animal and vegetable origin. Examples of sources of conventional oils and fats include coconut oil, palm kernel oil, palm oil, marine oils, lard, tallowfat, butter fat, soybean oil, safflower oil, cotton seed oil, rapeseed oil, poppy seed oil, corn oil, sunflower oil, olive oil, algae oil and blends thereof. For the purpose of this invention, algae oils are considered vegetable oils. Preferably at least 50 wt. % of the hardstock fat, based on total amount of hardstock fat, is of vegetable origin, more preferably at least 80 wt. % and even more preferably the hardstock fat essentially consists of hardstock fat of vegetable origin. Preferably the hardstock fat comprises or essentially consists of fat derived from palm fat, allanblackia, pentadesma, shea butter, coconut oil, soybean oil, rapeseed oil, dairy fat or any combination thereof.
The hardstock fat may be modified fat, such as fat which is produced by fractionation, hydrogénation and/or interesterification. In particular fractionation and hydrogénation can be used to alter the melting profile and N-line profile of a fat. Preferably the hardstock fat according to the invention does not contain partially hydrogenated fats and more preferably contains no partially- or fully hydrogenated fats. Preferably the émulsion according to the invention comprises only natural hardstock fats.
An important considération in selecting hardstock fat and liquid oil is that the level of trans FA of the fat blend as a whole should not exceed 5 wt. %. Thus the hardstock fat may hâve trans FA content which exceeds 5 %, based on the weight of the hardstock fat, when mixed with suitable amounts of oil/fat which hâve little or no trans FA. As such the fat blend as a whole would still adhéré to the trans FA content of less than 5 wt. % as specified by the invention.
It is observed that a further réduction of the trans FA content of the hardstock fat leads to émulsions according to the invention of further improved quality. Therefore, preferably the hardstock fat according to the invention comprises at most 10 wt. %, more preferably at most 7 wt. %, even more preferably at most 5 wt. %, still even more preferably at most 3 wt. % and still even more preferably at most 2.5 wt. % of trans FA’s based on the total weight of the hardstock fat.
Preferably the émulsion according to the invention comprises from 10 to 70 wt. %, more preferably from 15 to 60 wt. %, even more preferably from 20 to 50 wt. % and still even more preferably 25 to 40 wt. % of hardstock fat, based on the weight of total fat.
Preferably the hardstock fat according to the invention has a solid fat content N10 from 45 to 100 (i.e. a 45 to 100 wt. % of solid fat at 10 degrees Celsius), N20 from 20 to 95 and N35 from 2 to 60; and more preferably has a solid fat content N10 from 50 to 85, N20 from 25 to 70 and N35 from 5 to 40.
Preferably the fat blend according to the invention has an N-line: N10 of 15 to 100; N20 of 5 to 70, N30 of 0 to 50; preferably has an N-line: N10 of 15 to 75; N20 of 10 to 50; N30 of 2 to 30; more preferably an N-line: N10 of 20 to 40; N20 of 15 to 30; N30 of 5 to 10.
It was found that use of such N-lines for the hardstock fat and the fat-blend respectively lead to émulsions according to the invention having further improved quality.
Liquid oil
The liquid mixture of water and oil provided at step ‘b’ ofthe process comprises liquid oil (i.e. as understood by the skilled person at ambient température). The liquid oil of the wrapper product according to the invention may be a single oil or a mixture of different oils. Preferably at least 50 wt. % of the oil, based on total amount of oil, more preferably at least 80 wt. % and even more preferably essentially the oil; is oil of vegetable origin. The liquid oil fraction preferably comprises unmodified vegetable oil such as soybean oil, sunflower oil, linseed oil, low erucic rapeseed oil (Canola), corn oil (maize oil), olive oil, algae oil and blends of vegetable oils. For the purpose of this invention algae oil is considered vegetable oil.
Preferably the liquid oil according to the invention comprises less than 2 wt. %, more preferably less than 1.5 wt. %, even more preferably less than 1.0 wt. % and still even more preferably less than 0.5 wt. % of trans FA’s based on the total weight of the liquid oil.
Preferably the émulsion according to the invention comprises from 10 to 95 wt. %, preferably from 30 to 90 wt. %, more preferably from 40 to 80 wt. % and even more preferably from 50 to 75 wt. % of liquid oil, based on the weight of total fat.
Preferably both the hardstock fat as well as the liquid oil consists essentially of vegetable fat and oil.
Water-phase
The water (i.e. water-phase) is prepared according to the standard way in accordance with the chosen ingrédients as understood by the person skilled in the art. The water-phase of the émulsion may suitably contain a variety of food grade ingrédients, such as salts, vitamins and minerais, preservatives, flavors, and emulsifiers. The water-phase may also comprise gelling and/or thickening agents like for example starches, vegetable gums, pectin and gelling proteins suitable for such use like gelatin.
Preferably the émulsion according to the invention comprises from 1 to 50 wt. %, more preferably from 5 to 40 wt. %, even more preferably from 10 to 30 wt. % and still even more preferably from 15 to 25 wt. % of water-phase.
Non-pourable edible water-in-oil émulsion
In a second aspect the invention relates to a non-pourable edible water-in-oil émulsion obtainable by the process according to the invention. The émulsion according to the invention is characterized by having novel properties such as an improved firmness, stability and organoleptic properties of bakery products made with the émulsion. In particular it was observed that cakes made with the émulsions according to the invention were softer compared to cakes made with votator-made wrapper products. This was the case even though both émulsions (e.g. wrappers) had the same composition (e.g. same fat blend, water-phase). The structural basis, which underlies these new properties of the émulsions according to the invention are not known.
The émulsions according to the invention are further characterized by an improved stability as shown by a small and stable droplets size (as expressed in D3.3). This is apparent, in particular when compared to e.g. wrappers which are made according to the same general process steps, but having a trans FA level which exceeds 5 wt. %, based on total fat.
The non-pourable émulsions according to the invention hâve good firmness and shape retaining properties at réfrigération conditions (e.g. 4 degrees Celsius). However, as mentioned, in particular for convenience during use (e.g. in baking when making dough), but also for improved organoleptic qualities; it is désirable that non-pourable (e.g. solid or semi-solid) émulsion substantially soften at températures of 25-35 degrees Celsius. Surprisingly, the émulsion products according to the invention hâve greater hardness/firmness at 5 degrees Celsius, but greater softness at 25 degrees Celsius; when compared to products (e.g. wrappers) having a trans FA level exceeding 5 wt. % based on total fat. This effect is observed even when the hardness/firmness levels as measured in Stevens value are adjusted by the amounts of solids. Thus at réfrigération température surprisingly émulsions according to the invention show a greater firmness value per amount of solids, compared to émulsions not according not the invention. In contrast, at températures of 25 degrees Celsius surprisingly émulsions according to the invention show a lower firmness value per amount of solids, compared to émulsions not according to the invention. Therefore the émulsions according to the invention also show a greater softening between réfrigération températures (e.g. 4 degrees Celsius) to ambient températures or to 25 degrees Celsius. Further reducing the total amount of trans FAs further improves the properties of the émulsions according to the invention. Preferably the amount of trans unsaturated fatty acid is less than 3 wt. %, more preferably less than 2 wt. %, even more preferably less than 1.5 wt. % and still even more preferably less than 1.0 wt. %, based on the weight of total fat.
Preferably the non-pourable émulsion according to the invention has a Stevens value (as measured at 5 degrees Celsius) divided (7’) by the solids content (as measured at 5 degrees Celsius; i.e. ‘N5’) of at least 50, preferably at least 55, more preferably at least 60, even more preferably at least 65 and still even more preferably at least 70.
Preferably the émulsion according to the invention a Stevens value at 25 degrees Celsius of at most 125 and more preferably at most 100.
Preferably the émulsion according to the invention comprises from 60 to 95 wt. %, preferably from 70 to 90 wt. % and more preferably from 75 to 85 wt. % of total fat.
Use ofthe non-pourable edible water-in-oil émulsion
As mentioned the émulsions according to the invention can be used in the préparation of baking to provide bakery products with improved organoleptic properties. This is in particular apparent when compared to e.g. wrapper products (having the same overall composition) but made according to a conventional votator process. Thus in a third aspect the invention relates to the use of non-pourable émulsions according to the invention in baking to improve the organoleptic properties of bakery products, more preferably to improve the softness of the bakery products and even more preferably to improve the softness of cakes.
Preferred aspects of the invention disclosed herein in the context of one or two aspect(s) of the invention (e.g. the first (process), second (product) or third aspect (use)) are also applicable to the other aspect(s) as well, mutatis mutandis.
For example the preferred levels of trans unsaturated fatty acid of the fat blend specified for the finished product apply also to the fat blend used in the process according to the invention make the product, as well as to the fat blend of the products when used according to the invention.
The invention is now illustrated by the following non limiting examples.
Examples
Softness measurements of cakes
The softness of cakes was measured by texture profile analysis. Texture profile analysis was carried out by a compression test on 3 cm thick cake slices using a TA.XT_Plus texture analyzer (Stable Micro Systems, UK) equipped with a 25 mm diameter cylindrical plastic probe. Samples were compressed maximally after 2 sec and 11 sec with a pénétration speed 5 mm/s of and a pénétration depth of 10 mm. Softness (or hardness) was determined as the peak force of the first compression of the cake slice.
Solid Fat Content (SFC) measurements of fat
The solid fat content (SFC) in this description and claims is expressed as N-value, as defined in Fette, Seifen Anstrichmittel 80 180-186 (1978). The stabilization profile applied is heating to a température of 80 degrees Celsius, keeping the oil for at least 10 minutes at 60 degrees Celsius or higher, keeping the oil for 1 hour at 0 degrees Celsius and then 30 minutes at the measuring température.
Stevens value
Stevens values indicates a products hardness or firmness. The Stevens value was measured with a Stevens penetrometer (Brookfield LFRA Texture Analyser (LFRA 1500), ex Brookfield Engineering Labs, UK) equipped with a stainless Steel probe with a diameter of 4.4 mm and operated in “normal” mode. The probe is pushed into the product at a speed of 2 mm/s, a trigger force of 5 gram from a distance of 10 mm. The force required is read from the digital display and is expressed in grams. The température at which the Stevens value is determined at 5 degrees Celsius unless otherwise indicated.
In case of very soft products a 6.35 mm diameter probe was used to measure the Stevens hardness. The Stevens value measured with the 4.4 mm probe and the 6.35 mm probe could be compared by multiplying the 6.35 mm probe values by a factor of 2.
Water droplet size distribution of spreads (D3.3 measurement)
The normal terminology for Nuclear Magnetic Résonance (NMR) is used throughout this method. On the basis of this method the parameters D3.3 and exp(o) of a lognormal water droplet size distribution can be determined. The D3.3 is the volume weighted mean droplet diameter and σ (i.e. eAsigma) is the standard déviation ofthe logarithm ofthe droplet diameter.
The NMR signal (écho height) ofthe protons of the water in a water-in-oil émulsion are measured using a sequence of 4 radio frequency puises in the presence (écho height E) and absence (écho height E*) of two magnetic field gradient puises as a function of the gradient power. The oil protons are suppressed in the first part of the sequence by a relaxation filter. The ratio (R=E/E*) reflects the extent of restriction of the translational mobility of the water molécules inthe water droplets and thereby is a measure ofthe water droplet size. By a mathematical procedure, which uses the log-normal droplet size distribution, the parameters of the water droplet size distribution D3.3 (volume weighed géométrie mean diameter) and σ (distribution width) are calculated.
A Bruker magnet with a field of 0.47 Tesla (20 MHz proton frequency) with an air gap of 25 mm is used (NMR Spectrometer Bruker Minispec MQ20 Grad, ex Bruker Optik GmbH, DE).
Production of hiqh-fat non-pourable water-in-oil émulsions
In order to examine the impact of trans FA’s content of the fat blend on the quality of nonpourable émulsions, we hâve made and compared two types of wrapper products. Wrappers of Composition A comprised a low trans hardstock (inES48), wrappers of Composition B comprised a high trans hardstock (PO45). Although the inES48 and PO45 hardstocks different in amount of trans FAs, we hâve aimed to keep them as much the same in other aspects. For example, these hardstocks hâve an almost identical N-line profile, which is generally considered an important characteristic of wrapper hardstock fats.
The Experiments 1 to 4 relate to wrappers with Composition A, which are wrappers according to the invention. The Comparatives 1-3 relate to wrappers with Composition B, which are wrappers not according to the invention Table 1.
Table 1. Composition of wrapper products with composition A and B. Numbers represent parts by weight.
Composition A | Composition B | |
Sunflower oil | 45.5 | 45.5 |
Canola oil | 12.4 | 12.4 |
1 inES48 | 25 | - |
2PO45 | - | 25 |
3Dimodan HP | 0.2 | 0.2 |
4 Bolée ZT | 0.4 | 0.4 |
Beta carotène (1%) | Trace | trace |
Water | 16.5 | 16.5 |
Trans FA (on total fat) | 0.5 | 7.0 |
1 inES48 (hardstock): interesterified mixture of 65% dry fractionated palm oil stearin with an lodine Value of 14 and 35% palm kernel oil. inES48 comprises 1.7 wt. % of trans FAs based on the hardstock.
2 PO45 (hardstock): palm oil partially hydrogenated up to a slip melting point of 45 degrees Celsius. PO45 comprises 23 wt. % of trans FAs based on the hardstock.
3Dimodan HP: molecularly distilled mono-/diglyceride mixture derived from fully hardened palm oil (90% monoglyceride) (Supplier: Danisco, Denmark).
4 Bolée ZT (Supplier: Unimills B.V., the Netherlands) is a lecithin-based emulsifier
Production of Examples 1 to 4 and Comparatives 1 to 3
Hardstock fat in liquid form was prepared by melting and stirring the hardstock fat at 40 degrees Celsius (in a 200 liter thermostated stainless steel vessel, equipped with a rotor with stirrer blades operating at about 20 rotations per minute). To the liquid hardstock fat (either inES48 or PO45) dimodan HP and part of the Bolée ZT were added. (These emulsifiers were first predissolved by heating to 80 degrees Celsius in a small amount of oil.)
In a separate vessel a water-in-oil émulsion (W/O émulsion) was made by mixing, the water, sunflower oil, the remainder ofthe Bolée ZT and the Beta carotène (in a separate 200 liter thermostated stainless steel vessel, equipped with a rotor with stirrer blades operating at about 40 rotations per minute). (The Bolée ZT was first pre-dissolved by heating to 80 degrees Celsius in a small amount of oil.) The liquid W/O émulsion was cooled to 6 degrees Celsius.
The streams of liquid hardstock fat (40 degrees Celsius) and liquid W/O émulsion (6 degrees Celsius) were combined and mixed using a fluid dynamic mixer (FDM mixer) according to WO02/38263 having the following spécifications: the FDM comprised of a concentric rotor-stator system with 4 rows of indentations or cavities machined into the rotor and stator surfaces with a total volume of 0.083 liter. The cavities in the rotor and stator are generally spherical segments which are open on both vertical and horizontal faces. The rotor and stator are based on a stepped conical form so that the diameter of the cône increases from inlet to outlet (about 50 up to 150 mm). The mixer is commercially available from Maelstrom (http://www.maelstromapt.com/product-dc50/). The FDM was equipped with two séparâtes inlets for feeding the hardstock fat in liquid form and the liquid W/O émulsion. Thereby the liquid hardstock fat en the liquid W/O émulsion were instantaneously mixed upon contact, as they met in the running FDM mixing chamber. The FDM was operated according to the conditions as described in Table 2. In particular the effect of throughputs rates and rotation speeds of the FDM were also evaluated on wrapper product quality.
The finished mixed product (comprising hardstock, oil and water) was packaged in a wrapper to provide a wrapper product.
Results
After the wrappers were made according to the processing conditions as described, the 10 wrappers were stored at 5 degrees Celsius for one week. After said week the Stevens value, spreadibility, average droplet size and solids content were measured (Table 3). Next wrappers were stored for an additional two days at 25 degrees Celsius after which the wrappers were measured again (Table 4).
Table 2. processing conditions of Examples 1 to 4 and Comparatives 1 to 3.
Sample | Composition | Throughput kg/h | Rotation speed (rpm) |
Ex. 1 | A | 200 | 1800 |
Ex. 2 | A | 200 | 2300 |
Ex. 3 | A | 200 | 2800 |
Ex. 4 | A | 300 | 2800 |
Comp. 1 | B | 200 | 1800 |
Comp. 2 | B | 200 | 2300 |
Comp. 3 | B | 200 | 2800 |
Table 3. Analysis of Examples 1 to 4 and Comparatives 1 to 3, stored 1 week at 5 degrees Celsius.
Sample | Stevens | Solids | S/N | D3.3 | eAsigma |
Ex. 1 | 805 | 21.8 | 73.8 | 5.75 | 1.87 |
Ex. 2 | 868 | 22.1 | 78.6 | 4.20 | 1.83 |
Ex. 3 | 688 | 22.3 | 61.8 | 3.06 | 1.77 |
Ex. 4 | 634 | 21.1 | 60.0 | 2.88 | 1.67 |
Comp. 1 | 528 | 21.6 | 48.8 | 6.52 | 1.88 |
Comp. 2 | 547 | 20.9 | 52.3 | 4.89 | 1.65 |
Comp. 3 | 548 | 20.6 | 53.3 | 4.39 | 1.84 |
The results of Table 3 show that when stored at 5 degrees Celsius the wrappers made according to the invention (Examples 1 to 4) hâve smaller droplet size and a higher Stevens value (also when adjusted for solids content; i.e. higher S/N value). This when compared to wrappers not according to the invention (Comparatives 1 to 3). For ail wrappers, the size distribution (eAsigma) was acceptable (e.g. below 2.0). Table 3 further shows that the best results were obtained at FDM operating in the range of 1500 to 2500 rpm. Finally, it was observed that use of higher throughput conditions (e.g. 300 kg/hour) lead to wrapper products which had a very smooth appearance (more so than at any of the other processing conditions).
Table 4. Analysis Examples 1 to 4 and Comparatives 1 to 3, stored 1 week at 5 degrees Celsius, followed by 2 days at 25 degrees Celsius.
Sample | Stevens | Solids | S/N |
Ex. 1 | 109 | 11.8 | 9.3 |
Ex. 2 | 122 | 12.0 | 10.2 |
Ex. 3 | 41 | 11.9 | 3.5 |
Ex. 4 | 40 | 11.7 | 3.4 |
Comp.1 | 121 | 12.6 | 9.6 |
Comp. 2 | 150 | 13.1 | 11.5 |
Comp. 3 | 157 | 12.6 | 12.5 |
Table 5. Analysis Examples 1 to 4 and Comparatives 1 to 3, stored 1 week at 5 degrees 15 Celsius, followed by 2 days at 25 degrees Celsius.
Sample | 1softening |
Ex. 1 | 7.9 |
Ex. 2 | 7.7 |
Ex. 3 | 17.7 |
Ex. 4 | 17.6 |
Comp.1 | 5.1 |
Comp. 2 | 4.5 |
Comp. 3 | 4.3 |
1softening = S/N value of table 3 divided by S/N value of Table 4.
The wrappers were measured again (Table 4) after storing an additional two days at 25 degrees Celsius. Wrapper products according to the invention (Examples 1 to 4) were substantially softer than wrapper products not according to the invention (Comparatives 1 to 3). This is very surprising since the wrapper products according to the invention were initially harder (higher Stevens value and S/N) at 5 degrees Celsius than the wrappers not according to the invention (see Table 3). To highlight this ‘softening’, in Table 5 under the S/N value, measured after storage for 1 week at 5 degrees Celsius (Table 3) is divided by the S/N value as measured after two additional days at 25 degrees Celsius (Table 4). Clearly, this ‘softening factor’ is a factor 2 to 3 times higher for wrappers according to the invention (Examples 1 to 4) versus for wrappers not according to the invention (Comparatives 1 to 3). To conclude wrappers according to the invention show improved and excellent softening at working températures, which is bénéficiai for use in baking.
Bakery performance
Wrapper products were made according to the composition set out in Table 6:
Table 6. Composition of wrapper products used for Example 5 and Comparative 4. Numbers represent parts by weight.
Ingrédients | amount |
Rapeseed oil | 42.2 |
1 inES48 | 17.4 |
aDimodan HP | 0.1 |
4 Bolée ZT | 0.2 |
Sodium chloride | 0.3 |
Potassium sorbate | 0.05 |
Butter milk powder | 0.5 |
Beta carotène (1%) | Trace |
Flavours | Trace |
Water | 39.0 |
1 inES48 (hardstock): interesterified mixture of 65% dry fractionated palm oil stearin with an lodine Value of 14 and 35% palm kernel oil.
3 Dimodan HP: molecularly distilled mono-/diglyceride mixture derived from fully hardened palm oil (90% monoglyceride) (Supplier: Danisco, Denmark).
4 Bolée ZT (Supplier: Unimills B.V., the Netherlands) is a lecithin-based emulsifier
Production of Example 5
Example 5 (according to the invention) was made according to the following conditions:
The liquid hardstock was prepared as described for Example 1, except that ail of the emulsifier was dissolved in the liquid hardstock. The water phase was prepared by mixing the ingrédients into the water at pasteurization température, followed by pH adjustment at about 60 degrees Celsius and subsequently by an inline cooling in a tubular heat exchanger to obtain about 5 degrees Celsius at the inline junction point with the cold oil phase in case of the spreads production process. The oil phase was prepared by adding the flavors and beta-carotene and cool down the oil phase in the tank to about 5 degrees Celsius.
The streams of liquid oil, water and liquid hardstock were combined at a flow rate of 63.8 kg/h, 60 kg/h and 26.4 kg/h respectively in the FDM as described above. The températures of the liquid oil, water and liquid hardstock were 10.7, 4.6 and 43 degrees Celsius respectively. The FDM was operated at 2000 rpm. After mixing with the FDM the mixtures were packaged and stored at 5 degrees Celsius.
After 1 week at 5 degrees Celsius the products of Example 5 had a hardness of about 370 gram at 5 degrees Celsius and a solids content of 15.1%, resulting in an S/N ratio of about 49. After said week of storage the average droplet size was 5.7 (as measured in D3.3) with an e-sigma of 2.15.
Production of Comparative 4
Comparative 4 (not according to the invention) was made according to the general votator process having the following conditions. The fat blend was prepared by blending the oil and the hardstock fat at about 70 degrees Celsius in a 200 liter stainless Steel feed tank equipped with a rotor with stirrer blades operating at about 40 rotations per minute. The emulsifier and Lecithin were added (pre-heated in a magnetron to about 80 degrees Celsius). Next the flavors and beta-carotene solution were added followed by water phase. This water and oil premix was kept at a holding température of about 65°C.
The premix was processed (throughput about 100 kg/h) in an ACAAB sequence of A-, C, and Bunits to provide the final émulsion. The A-units (sometimes called scraped surface heat exchangers) had an internai volume of about 0.1 liter and were operated at 1000 rpm. The Cunit which was used had an internai volume of about 3 liter. The B-unit used was configured as a hollow tube of about 1.5 meter length with an internai diameter of 8 cm.
After 1 week at 5 degrees Celsius the products of Comparative 4 had a hardness of about 190 gram at 5 degrees Celsius and a solids content of 16.8%, resuiting in an S/N ratio of about 23. After said week of storage the average droplet size was 2.3 (as measured in D3.3) with an esigma of 3.3.
The wrappers according to Example 5 and Comparative 4 were subsequently used to bake cakes: AH cakes were prepared with 150 g wrapper product, 150 g eggs, 150 g flour, 150 g sugar, 6 g baking powder. Cake préparation consisted of the following steps:
1. Cream margarine with sugar for 3 min with a hand mixer
2. While mixing for 1 min add egg slowly to cream
3. Add flour and mix for 0.5 min
4. Bake for 70 min at 150 °C
The cake baking was done in triplicate (cakes A, B and C)
Results
The softness of the cakes made with the wrapper Example 5 and Comparative 4 was measured (Table 7).
Table 7. Softness measurements of cakes
Softness | Cake A | Cake B | Cake C | Average |
Example 5 | 750 | 729 | 711 | 730 |
Comparative 4 | 912 | 920 | 940 | 923 |
As can be clearly see from Table 7, cakes made with émulsions according to the (process of the) invention (Example 5) results in much softer cakes than if made with émulsions not according to the invention (Comparative 4).
À-S'
Claims (9)
- Claims1. Process for the manufacture of a non-pourable edible water-in-oil émulsion comprising at least 50 wt. % of total fat, comprising the following steps:a. providing 5 to 90 wt. % of hardstock fat, based on the weight of total fat, in liquid form;b. providing a liquid mixture of water and oil, wherein the mixture has a température below the melting point of the hardstock fat;c. mixing the hardstock fat in liquid form with the liquid mixture of water and oil; wherein the température of the mixture provided at step ‘c’ is below the melting point of the hardstock fat, and wherein the amount of trans unsaturated fatty acid is less than 5 wt. %, based on the weight of total fat.
- 2. Process according to claim 1, wherein the température of the hardstock fat in liquid form provided at step ‘a’ is at least 25 degrees Celsius.
- 3. Process according to claim 1 or claim 2, wherein the température of the liquid mixture of water and oil provided at step ‘b’ is from 1 to 20 degrees Celsius.
- 4. Process according to any one of claims 1 to 3, wherein step ‘c’ is performed in a fluid dynamic mixer operating above 500 rpm.
- 5. Process according to any one of claim 1 to 4, wherein the amount of trans unsaturated fatty acid of the hardstock fat is at most 10 wt. %, based on the weight of hardstock fat.
- 6. Process according to any one of claims 1 to 5, wherein the émulsion comprises from 10 to 70 wt. % of hardstock fat, based on the weight of total fat.
- 7. Process according to any one of claims 1 to 6, wherein the fat blend on total fat has an N-line: N10 of 15 to 100; N20 of5to 70, N30 ofOto 50.
- 8. Process according to any one of claims 1 to 7 wherein the émulsion comprises from 10 to 95 wt. % of liquid oil, based on the weight of total fat.
- 9. Process according to any one of claims 1 to 8 wherein the émulsion comprises from 1 to 50 wt. % of water-phase.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP14169109.7 | 2014-05-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
OA20203A true OA20203A (en) | 2022-03-18 |
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