Title of Invention

A PROCESS FOR REDUCING FREE FATTY ACID PRESENT IN AN ANHYDROUS LIQUID ANIMAL FAT

Abstract The present invention relates to a process for reducing free fatty acids (FF A) present in an anhydrous liquid animal fat, consisting essentially of pure lipid materials essentially without protein, to form a processed animal fat which comprises the steps of reacting: (a) providing a reaction mixture of the free fatty acids in the liquid animal fat with a water solution of an alkali metal hydroxide selected from the group consisting of potassium hydroxide, sodium hydroxide and mixtures thereof at an elevated temperature with mixing so that the FF A present in the liquid animal fat forms a soluble fatty acid salt (SF AS) ; (b) reacting the SF AS with an alkaline earth metal salt so that the SF AS forms an insoluble fatty acid salt (IF AS) in the reaction mixture simultaneously with or after step (a); and (c) separating the IF AS from the reaction mixture to form the processed animal fat.
Full Text

METHODS TO REDUCE FREE FATTY ACIDS AND CHOLESTEROL IN
ANHYDROUS ANIMAL FAT
BACKGROUND OF THE INVENTION (1) Field of the Invention
The invention relates to a process for the reduction of free fatty acids (FFA) and preferably, cholesterol and melting point in animal fats, particularly anhydrous milkfat. The process uses β-cyclodextrin and an aqueous liquid formula consisting of alkali metal hydroxide (Na or K) as a neutralizing agent, alkaline earth metal (Ca or Mg salts) as fatty acid acceptors, and preferably low melting point vegetable oils. In particular, the present invention relates to a process wherein a mixture of animal fats with the liquid formula with mild heating is used to precipitate the FFA, to decrease the melting point, and to clathrate the cholesterol with the 3-cyclodextrin and then the mixture is centrifuged to remove the insoluble salts of fatty acids and clathrate. The invention particularly addresses the problem of selectively removing the FFA from anhydrous milkfat without precipitating the lipid materials (the anhydrous milkfat) or damaging the fine volatile flavor components of anhydrous milkfat, which are the lactones.
r
(2) Description of the Prior Art
It has long been known, that very high serum cholesterol levels, high blood pressure, and an abnormal electrocardiogram (EKG) are important contributing factors to heart attacks. It is important to note that these factors become apparent long bts of smoking, obesity, lack of exercise are observed.efore the effec The importance of serum cholesterol levels has been strengthened over the years, and one of the most

consistent findings in cardiovascular studies is that high levels of plasma cholesterol are associated with atherosclerosis and enhanced risk of coronary heart disease (CHD)• This effect usually is mediated through the plasma low density lipoproteins (IDL) , which are the most atherogenic lipoproteins (Grundy, S. M., Am. J. Clin. Nutr, 45:1168 (1987)).
The major causes of high serum cholesterol levels are genetic disorders, heterozygous familial hypercholesterolemia (FH), and the habitual diet high in saturated fat-calories-cholesterol.
Health experts and physicians generally agree that the dietary management is the initial step in the treatment of hypercholesterolemia and hyperlipidemia. This applies even when later drug therapy is required. Changes in diet, serum cholesterol and CHD in immigrant populations have provided convincing evidence that diet plays a maj or role (Dyerberg, J., Nutrition Review 44(4):125 (1986)).
Although the consumption of cholesterol does not seem to be a major factor in CHD, Khosla, P. , and K, C. Hayes, Biochim Biophys Acta 1210:13 (1993) reported that excessive intake of dietary cholesterol exerts a synergistic effect on the metabolism of C16:0-rich fats, causing them to be hypercholesterolemic. In the absence of dietary cholesterol and in individuals with normal lipoprotein profiles, C16:0 does not ordinarily raise total plasma cholesterol concentration or LDL (Hayes, K. C., Food Technology Journal 50(4):92-97 (1996). Further, it has been reported that oxides of cholesterol are toxic and. cause degeneration of aortic smooth muscle cells in tissue culture and may lead to the development of atherosclerosis.
Milkfat is stable to oxidation and possesses a uniquely pleasing flavor not found in other fats. Milkfat has received most attention because of its commercial importance. It confers distinctive

properties on dairy products that affect processing. Milkfat is a good source of essential fatty acids and it contains a high proportion of short chain fatty acids which contributes to its ease of digestibility (Kennedy, J,, Food Technol. 11:76 (1991)). Moreover, milkfat contains conjugated linoleic acids (CIA) recognized for their potential ability to inhibit cancer (Yeong et al., J, Agric- Food Chem, 37:75-81 (1989)), CLA are unusual because they are abundant in products from rtiminant animals. They are formed during the process of biohydrogenation of polyunsaturated fatty acids (POFA) in the rumen of cows and subsequently find their way into milk (Gurr, M. I •, Advanced Dairy Chemistry, Lipids, P. F* Fox (ed,)/ P. 349, Chapman & Hall, London (1994)), One epidemiological study compared dietary habits in rural Finland which has one-quarter the incidence of colon cancer compared with larban Copenhagen, Denmark (MacLennan, R., et al., Am, J. Clin, Nutr. 3l:S239 (1978)* The community with a low
*
incidence of colon cancer consumed more potatoes and whole milk than the high incidence group and ate less white bread and meat- Milkfat has a high proportion of saturated fatty acids, mainly C16:0 (26,3 %), and cholesterol (0.2-0,4 %) which has resulted in its decreasing consumption. This is because of the perception that the milkfat is bad for the diet.
Among most of the natural fats, milkfat is the most varied in its chemical characteristics and functional property. The melting point of milkfat increases with increasing saturation and chain length of its fatty acids components (Walstra, P,, et al,. Advanced Dairy Chemistry, Lipids (P. F, Fox (ed) Chapter 5, pp. 179-212 Chapman & Hall, London (1994)). The melting point of milkfat is also affected by the positioning of the fatty acid residues over the glycerol molecule (Walstra et al., IBID). In its native form, milkfat does not always suit various food formulations.

For example, the wide melting range or milkrat, -40 to 40°C (Walstra et al. , IBID), makes it difficult to produce spreadable butter at refrigeration temperature which is considered by many modern consumers to be an undesirable attribute. Therefore, new fields of use of milkfat are constrained due to its limited functionality (pourability and spreadability)•
An optimum fat cannot always be obtained from nature. Animal fats, when viewed in their native state, have limited use. But they can become an economic asset when viewed as a raw material to produce fats with desirable health characteristics.
The fats and oils industry is looking at new techniques to alter the fat molecules. The biggest challenge is to reconcile the functional needs with the nutritional concerns. In terms of physical and nutritional performance, interesterificaton of milkfat or milkf at/vegetable oils is a useful technique to achieve a desired softening point. Interesterification of milkfat alters the distribution of fatty acids in the triacylglycerol and thus, changes its physical properties such as melting behavior, crystallization, and plasticity. Christophe, A. M., et al.. Arch. Int. Physiol. Biochem 86:413 (1978) have shown that interesterification of milkfat with chemical catalysts reduces its potency to raise the blood serum cholesterol in human. Interesterified milkfat appears to be more rapidly hydrolyzed by pancreatic lipases in vitro than native milkfat (Christophe, A. M., et al., Arch Int. Physiol. Biochim. 89:B156 (1981)).
Interesrification can be accomplished by heating the fat or a blend of fat and oil in the presence of a chemical catalyst at relatively low temperature (50°C) for 30 minutes (Eckey,, E. W. Ind. and Eng. Chem. 40:1183 (1948)). Catalysts are commonly used to allow the reaction to be completed in a short time at lower temperatures. Alkali metals and alkali metal

alkylates are effective low-temperature catalysts, with sodium methoxide being the most used. Directed interesterification, where the fat is heated just below its melting point, is a useful technique to remove the saturated fatty acids from the fat as crystallized trisattirated glycerides precipitates (Eckey, E, W., Ind. and Eng. Chem. 40:1183 (1948)) and therefore, improving its nutritional properties (saturated:unsaturated fatty acids ratio) . Eckey was able to remove 19% trisaturated glycerides from cottonseed oil, which contains 25% saturated fatty acids. Directed interesterification had been commonly used in the industry to improve the quality of lard (Hawley, H. K., and G, W* Holman, J. Am, Oil Chem. Soc. 33:29 (195i5)).
Nevertheless, interesterif ication has not yet been applied to the milkfat industry, since its feasibility is restricted by the fact that it is often deleterious to milkfat .flavor, refining and deodorization to remove milkfat FFA (Frede, 1991; Bulletin of the International Dairy Federation No 260/1991)• FFAs consume the catalyst or inactivate the active catalyst once it is formed. Sreenivasan, B., J. Am. Oil Soc, 55:796 (1978) reported that an acid value (A.V,) of 0,1 is able to poison 0.1 lb of sodium methoxide per 1000 lbs of oil. Thus, removing the FFA from anhydrous milkfat is an important step, before interesterification. Moreover, FFAs are more prone to oxidation than esterified fatty acids and hence can predispose milkfat to oxidative rancidity characterized by off-flavor described as "bitter".
U.S. Patent-No. 5,382,442 to perlman et al. (1995) describes a blending process to increase the oxidative stability of vegetable or fish oils and animal fats. The fat blends consist of vegetable or fish oil and cholesterol reduced animal fats which comprises about 2 parts and about 9 parts linoleic acid per 1 part myristic acid.

Refining and deodorization of fats and oils. are very commonly used techniques in the fat and oil industry to remove FFA, Alkali refining, used by the vast majority of European and American refiners (Braae, B., J. Am. oil Chem. Soc 53:353 (1976); Carr, R.A., J, Am. Oil Chem. Soc, 53:347 (1976)), consists of heating the fat or oil to 75 - 90°C then treating it with a concentrated caustic solution of sodium hydroxides, 12 to 18o Be', depending on the type of oil (cotton, soybean, corn, palm, safflower, peanut) for 30 seconds (Short-Mix process) or 0.2 seconds with 28o Be' sodium hydroxide (Ultra-Short-Mix process). Using these processes for milkfat is very detrimental to the lactones, the major milkfat flavor components. Lactones (y or 5) are cyclic esters of y or 5 - hydroxy acid which in the presence of concentrated caustic solution are rapidly hydrolyzed to give the open chain salt of hydroxy acids. consequently, the prior-art processes, short reaction time, high concentration caustic solution, and high temperature cannot be applied ro milkfat.
Deodorization, very commonly used in the fats and oils industry, consists of blowing steam through hot oil at 200° to 275°C under a high vacuum (3 - 10 torr) . The deodorization process removes simultaneously the FFAs, fat soluble vitamins (A, E, D, K), monoglycerides, sterols, and some pigments such as caratenoids. As he term implies, deodorization strips off the aroma and flavors of fats and oils resulting in a bland finished product which is viewed as extremely undesirable for milkfat. Therefore, refining . by using concentrated alkali metal hydroxide and deodorization of milkfat reduces the FFA losing the volatile fine milkfat flavor, the aroma, and the vitamins content. This puts milkfat in the same class as other cheap raw materials-
U.S. Patent No. 3,560,219 to Attebery describes the use of metal salts under alkaline:





of supercritical carbon dioxide is a major drawback in cholesterol reduction, since some triacylglycerols were extracted along with cholesterol which can disrupt the normal aromatic balance of milkfat.
Vacuum steam distillation.
Vacuum steam distillation for deacidification and deodorization of oils has been practiced in Europe for many years. The technique consists of blowing superheated steam through hot oil at 200°-275°C under high vacuum. General Mills, Inc. (Minneapolis, USA) has disclosed a vacuum steam distillation process for simultaneous cholesterol reduction and deacidification of butter oil (Marschner and Fine, U. S . Patent No • 4,804,555 1989). The cholesterol removal achieved by this technique was 90%, with a 95% yield. The major drawback of this technique is that the heated steam strips off the volatile flavor components of milkfat along with cholesterol and FFA. The loss of the fine butter flavor puts milkfat in the same class as other cheap fats.
Complex formation.
This technique is used to reduce the cholesterol in milk and dairy products by complexing the cholesterol and its esters with a complexing agent such as (3-cyclodextrin (3-CD) .
Cyclodextrins are cyclic oligosaccharides obtained by enzymatic degradation of starch. They consist of six, seven, or eight glucose monomers arranged in a donut shaped ring, which are denoted alpha, beta or gamma cyclodextrin, respectively, β-CD are not. hygroscopic and contain is. 6% "moisture at 30°C and 86% relative humidity (RH) (Szejtli, j., et al. Inclusion Compound 3:331 (1984))• Cyclodextrins are water soluble due to the location of free hydroxy 1 groups on the external rim of the molecule (Szejtli, J., et al, Inclusion Compound 3:331 (1984)). Solubility is a function of temperature. The higher the temperature

the higher the solubility. The solubility of 3-CD increases from 0,8% at 0.5°C to 39.7% at 90°C. The internal cavity which is hydrophobic allows the cyclodextrins to complex molecules such as aromatic alcohols, fatty acids and their esters and cholesterol• β-CD has been used to reduce cholesterol in milkfat for several reasons:
1 - The relative size and geometry of the β-CD
internal cavity allowed good complexing with free and
esterified cholesterol;
2 - The realization of industrial scale production
of 3-CD;
3 - The intensive research on toxicity of β-CD
during the past decade, has assured its safety as a food
ingredient.
Currently, cyclodextrins are used: (i) to control volatility of agricultural compounds which control . pathogens, insects, and weeds; (2) in pharmaceutical products (drugs, .vitamins), fragrance, and skin care lotions to improve stability by means of encapsulation; and (3) to enhance color, odor, and flavor stability in beverages and processed foods (Szejtli, J., Inclusion Compound 3:311 (1984)),
The most important parameters that determine whether a given molecule can form complexes are its hydrophobicity, relative size and geometry in relation to the cyclodextrin cavity (Szejtli, J., Inclusion Compound 3:331 (1984))• When dissolved in water, the cyclodextrin molecules are able to accommodate smaller guest molecules, or functional groups of molecules less hydrophilic than water in their internal cavities (Szejtli, J., Inclusion Compound 3:331 (1984)). In aqueous solution, the slightly apolar cyclodextrin cavity is occupied by water molecules, an energetically unfavored process (polar-apolar interaction). These water molecules are therefore readily substituted by appropriate guest molecules "such as cholesterol or FFA











for percent FFA reduction (Y2) of AMP.
Figure 16 is a flow diagram showing a process for removing cholesterol FFA and decreasing the melting point of other anhydrous animal fat (AMF) . The liquid formula consists of distilled water, corn oil, KOH and CaCl2. The mole ratio of KOH:FFA is 1:1. The mole ratio of CaCl2:FFA is 5:1. The water to corn oil weight ratio is 11.5:1.5.
DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention provides a process which
reduces FFA, and preferzibly, melting point and
cholesterol in anhydrous milkfat using an aqueous liquid
formula and β-cyclodextrin. The aqueous liquid formula
consists of a mixture of an alkali metal hydroxide (Na,
K), alkaline earth metal (ca and Mg) , and low melting
point vegetable oils. The liquid formula is
specifically designed to achieve the objectives in a
single operation which gives the present invention many
advantages over the prior art processes. The process
titrates and selectively precipitates FFA in anhydrous
milkfat using very dilute concentrations (0.023 to
0.058%) of alkali metal hydroxide (Na or K) and calcium
or magnesium salts as fatty acceptors under very mild
experimental conditions to protect milkfat flavor.
Also, the process uses stoichiometric amounts of alkali
metal hydroxide with respect to the free fatty acids
present in milkfat to selectively remove the free fatty
acids without precipitating or damaging the milkfat per
se. The process uses alkaline earth metals to diminish
the losses of milkfat and get a better yield and higher
cholesterol reduction. The process reduces FFA based on
relatively long reaction time and low temperature which
are effective in preserving the milkfat flavor lactones .
The process simultaneously reduces cholesterol, melting
point and FFA in anhydrous milkfat using β-CD as a
complexing agent for the cholesterol. The process
significantly reduces cholesterol, FFA and melting point

in animal fats, within a commercially feasible amount of
time,
Materials and Methods
Commercial grades of unsalted butter, beef tallow and lard were obtained from a local food store. The unsalted butter was converted into anhydrous milk at (AMF) by melting at 55oC, centrifuging at 5000 x g for 10 minutes at room temperature and filtering the top fat layer through Whatman No, 1 filter paper. The AWF was stored at -20oC for future use.

PROCESSES DEVELOPMENT Process for Removal of FFA.
A preferred process for removal of FFA from anhydrous milkfat (AMF) is outlined in Figure 1. This process is based on a relatively long reaction time, a low concentration alkali solution and low temperature (40° to 50°C) • This is in contrast of the prior art process (used for cottonseed, corn, peanut, soybean and palm oil) which uses concentrated alkali solution {12 to 28° Be'), high temperatures (75-95°), and short reaction time (0,2 to 30 seconds). The rational for each step is described below. The refining solution in the process herein is a key control factor for a successful refining. The refining solution consists of an aqueous mixture of alkali metal hydroxide (Na or K) and Ca or Mg chloride.








at room temperature. The FFA reduced lard was recovered in the upper Supernatant phase• The FFA content of the refined lard was 0.02%* The FFA reduction achieved was 83.60%.
The process for reducing PPA in animal fats is based on the use of an alkali metal hydroxide as a neutralizing agent and Ca or Mg salts as fatty acceptors. The concept of this process is to use a dilute refining solution, low temperature and relatively long reaction times. The process has a number of attributes which results in considerable practical advantages over the prior art processes used for oil refining. The process is efficient and reduced the FFA in AMF to 0.02% in a single stop without the need for deodorization, in contrast to the prior art processes. The mild experimental conditions used in this process do not damage the fine flavor components of AMF, the lactones. Process for Removal of FFA and Cholesterol.
The process developed to reduce cholesterol and FFA in AMF is outlined in Figure 8.
EXAMPLE 11
10 (g) AMF containing 0.395% cholesterol and 0.293% FFA were mixed with 10 mL refining solution (0.0583% KOH and 0.763% CaCl2) at 1000 rpm until the temperature reached 50°C. At 50°C, 650 mg 3-cyclodextrin β-cyclodextrin:cholesterol mole ratio 5.58) were added to the mixture while mixing at the same rate for 10 more minutes. The resultant soaps and β-cyclodextrin:cholesterol = complexes were immediately centrifuged at 8700 x g for 10 minutes at room temperature. The reduced cholesterol and FFA in AMF were recovered in the upper supernatant phase. The cholesterol and FFA reduction achieved was 54 and 92%, respectively,
COMPARATIVE EXAMPLE 12
10 (g) AMF containing 0.395% cholesterol and

0.293% FFA were mixed with 10 mL distilled water at 1000
rpm until the' temperature reached 50°C. At 50°C, 650 mg
β-cyclodextrin (β-cyclodextrin: cholesterol mole ratio
5,58) were added to the mixture while mixing at the same
rate for 10 more minutes. The resultant β-
cyclodextrin: cholesterol and β-cyclodextrin: FFA
complexes were immediately centrifuged at 8700 x g for 10 minutes at room temperature. The reduced cholesterol and FFA in AMF were recovered in the upper supernatant phase. The cholesterol and FFA reduction achieved was 54 and 49.65%/ respectively. This experiment shows the importance of the refining solution in improving the reduction of FFA in AMF, since the reduction was increased by 42.35%. Moreover, the refining solution did not affect the formation of complexes between cholesterol and β-cyclodextrin, since the cholesterol reduction remained unchanged.
EXAMPLE 13
When many factors and interactions affect
desired responses, response surface methodology (RSM) is
an effective tool for optimizing the process (Hunter,
19 59) . Thus, the optimization of the combined effects
of the independent variables (KOHrFFA mole ratio,
Cacl2:FFA mole ratio, mixing time, β-
cyclodextrin:cholesterol mole ratio, and mixing rate) on
cholesterol and FFA reduction was accomplished using
response surface methodology. Two responses were
measured: cholesterol reduction % (Yi) was defined as
the ratio of the total amount of cholesterol in the
sample to the total amount of cholesterol in the controJ.
multiplied by 100;' FFA reduction ,% (Y2) was defined at
the ratio of the total amount of FFA in the sample to
the total amount of FFA in the control multiplied by
100, Based on preliminary experiments, the five
independent variables, shown in Table 1, were KOH:FFA mole ratio, CaCl2:FFA mole ratio, mixing time, (3-cyclodextrin:cholesterol mole ratio, mixing rate. The

other important independent variables were held fixed: temperature and centrifugation (8700 x g, 10 min, room temperature) . The experimental design adopted was a 5 factor, 5 level central composite (John L, Gill, Design and Analysis of Experiments in the Animal and Medical Science. Volume (2), Chapter 9, Michigan State University (1993) )• The coded values of the independent variables were -2 (lowest level), -1,0 (medium level), 1,0 and 2 (highest level) • For each independent variable studied, the central value (0) was chosen according to the preliminary study as described in Figure 8• The complete design shown in Table 2 consisted of 32 experimental points which included six (6) replications of the center (0, 0, 0, 0, 0),
Table 1- Variables and their levels for central composite design used in the process optimization





order, quadratic and tyo factor interaction terms.













mole ratio tested is shown in Table 2. Mixing time
The cholesterol reduction Y1 was strongly dependent on the mixing time. The positive slope B3-=10.76 indicated that cholesterol reduction increased with increased mixing time at any β-cyclodextrin: cholesterol mole ratio or any mixing rate (Figures 12 and 13) • The range of- mixing time examined is show in Table 2. β-cyclodextrin:cholesterol mole ratio
Theoretically one mole of β-cyclodextrin will complex one mole of compound (Szejtli, J., Inclusion Compound 3:331 (1984))• Some larger molecular weight compounds may complex with more then one cyclodextrin molecule (Szjetli 1984, IBID) . The range of (5-cyclodextrin: cholesterol mole ratio tested is shown in Table 2. The cholesterol reduction was strongly dependent on the b-cyclodextrin:cholesterol mole ratio. The positive slope B4=4.97 indicated that cholesterol reduction increased with increased β-cyclodextrin:cholesterol mole ratio (Figure 14).
Mixing rate
The mixing rate is an important factor to assure contact between β-cyclodextrin and cholesterol, stabilize the oil-in-water emulsion. As soon as the temperature reached 50°C/ β-cyclodextrin was added and mixed for 10 minutes using a LIGHTNIN LAB MASTER (MS) Mixer Model L1U03 and an impeller type AlOO (dia 1")* The cholesterol reduction was strongly dependent on the mixing rate/ The positive slope 65=30.44 strongly indicated that cholesterol - reduction increased with increased mixing rate at any 3-cyclodextrin:cholesterol mole ratio. The shape of the response surface (Figure 14) was characteristic of the strong interaction between β-cyclodextrin: cholesterol mole ratio and the mixing rate. The range of mixing rates tested is shown in Table 2,



micelles and minimize the flocculation of the β-cyclodextrin on the electronegatively charged micelles surface, and therefore better cholesterol reduction (18 and 19 of Table 1); (4) synergistically increase the reduction of FFA in conjunction with KOH; and (5) saturate the medium with cations and thus improve the FFA reduction by prohibiting the occurrence of the following reaction.

The excess of cations are provided by the Ca salt and not by the caustic solution due to the detrimental effect of the excess hydroxyl group on the yield and the flavor* The range of CaCl2:FFA mole ratio examined is shown in Table 2. The effect of calcium chloride on FFA reduction was predicted by the β-cyclodextrins present in the medium, since 3-cyclodextrins themselves can reduce FFA.
Mixing rate
The mixing rate is an important factor to
assure contact between the solutes of the refining
solution and FFA. The mixing rate used within the
experimental domain had a slight effect on the FFA
reduction (Figure 15). The positive slope 85=5.28 (Table
5) indicated that FFA reduction increased with increased
mixing rate. The range of mixing rates tested is shown
in Table 2.
EXAMPLE 14
The model for Y1 showed that the higher the β--
cyclodextrin:c;holesterol mole ratio, mixing time, and
mixing rate, the higher the cholesterol reduction. The
joint effect of these 3 independent variables used in
#4 and #26 OF Table 2, reduced AMF cholesterol by 77.30%
and 73,70%,respectively. Further optimization of these
treatments can improve the cholesterol reduction. The
amount of β-cyclodextrin used in experiment #4 of Table
2 is higher than the amount used in experiment #26.

Taking into account the cost-effectiveness of the process, the further optimization was performed on experiment #2 6 of Table 2. #26 was optimized with regard to mixing time, since increasing the amount of β--cyclodextrin is not economically feasible and the use of higher mixing rates can increase the viscosity of the medium which causes yield problems during centrifugation. Taking into consideration the two responses studied, it was found that the reduction of cholesterol can be further improved by increasing the mixing time. In fact, the theoretical mathematical model for cholesterol reduction showed that the cholesterol could be completely removed at about 30 to 35 minutes of mixing time.
The main objectives of the present invention are to reduce the cholesterol, free fatty acids, and melting point in animal fats in one single operation, to produce a healthy fat that is spreadable at refrigeration temperatures. These obj ectives can be accomplished by using the final optimized process outlined in Figure 16*
EXAMPLE 15
10 (g) AMF containing 0.283% cholesterol and 0,3% FFA were mixed at 1400 rpm with 10, 13, 16, 22, 30 (g) "liquid formula" having a water to corn oil weight, ratio of 10:0, 11.5:1.5, 13:3, 16:6 and 20:10, respectively, until the temperature reached 50oC. The "liquid formula" used for all the experiments consists of KOH, CaCl2f dH2O and corn oil. The ratios of the
different components are as follows: KOH:FF.A mole ratio 1:1 {fixed ratio), FFA:CaCl2 mole ratio 1:5 (fixed ratio) and variable weight ratios of H20:corn oil as described above. At 50oC, 650 mg β-cyclodextrin were added to the mixture while mixing at the same rate (1400 rpm) for 30 more minutes. The resultant soaps and β-cyclodextrin:cholesterol complexes were immediately centrifuged at 8700 X g for 10 minutes at room





capital equipment. It requires only heating and mixing followed by centrifugation.
The processed animal fat without the FFA or cholesterol can be homogenized in low fat or fat,free milk to reconstitute a whole milk. This product can be used for making cheese or ice cream •
It is intended that the foregoing description be only illustrative of the present invention and the present invention be limited only by the hereinafter appended claims.



WE CLAIM
A process for reducing free fatty acids (FFA) present in an anhydrous liquid animal fat, consisting essentially of pure lipid materials essentially without protein, to form a processed animal fat which comprises the steps of reacting:
(a) providing a reaction mixture of the free fatty acids in the liquid animal fat with a water solution of an alkali metal hydroxide selected from the group consisting of potassium hydroxide, sodium hydroxide and mixtures thereof at an elevated temperature with mixing so that the FFA present in the liquid animal fat forms a soluble fatty acid salt (SFAS);
(b)' reacting the SFAS with an alkaline earth metal salt so that the SFAS forms an insoluble fatty acid salt (IFAS) in the reaction mixture simultaneously with or after step (a); and
(c) separating the IFAS from the reaction mixture to form the processed animal fat.
-2-
The process of Claim 1 wherein in addition the animal fat is mixed with β-cyclodextrin to remove cholesterol present in the animal fat.
-3-The process of Claim-1 wherein in addition the animal fat is mixed with β-cyclodextrin after steps (a) and (b) and prior to separating the IFAS.

-4-The process of any one of Claims. 1, 2 or 3 wherein the base is potassium hydroxide.
-5-The process of any one of Claims 1, 2 or 3 wherein the alkaline earth metal salt is calcium chloride.
-6-The process of any one of Claims 1, 2 or 3 wherein the base is potassium hydroxide, the mole ratio of potassium hydroxide to FFA is between 0,5 to 5 to 1, the alkaline earth metal salt is calcium chloride and the mole ratio of CaCl2 to FFA is between about 0.25 and 10 to 1.
The process of any one of Claims 1, 2 or 3 wherein the temperature is between about 0o - 55oc.
-8-The process of any one of Claims l, 2 or 3 wherein the mole ratio of base to FFA is between about 0.5 and 5.
-9-The process of any one of Claims 1, 2 or 3 wherein the mixing in sTep (a) is for between 5 and 35 minutes,
-10-The process of any one of Claims 1, 2 or 3 wherein the IFAS are separated by centrifugation.



-15-The method of any one of Claims 1, 2 or 3 wherein the mixing in step (a) is by a multi-bladed mixer at 200 to 1800 rpm.
-16-The process of Claim 2 wherein the mole ratio of cyclodextrin to cholesterol is between about 4.7 and 6.4 to 1,
-17-The process of Claim 1 wherein in addition the animal fat is mixed with a cyclodextrin to remove cholesterol present in the animal fat and wherein the IFAS and the cholesterol and cyclodextrin are separated by centrifugation.
-18-The process of any one of Claims 1, 2 or 3 wherein the base is potassium hydroxide, the mole ratio of potassium hydroxide to FFA is between 0,5 to 5 to 1, the alkaline earth metal salt is calcium chloride, the mole ratio of CaCl2 to FFA is between about 0.25 and 10 to 1, the temperature is between about 0° ~ 55°C , the mole ratio of base to FFA is between about 0,5 and 5, the mixing is for between 5 and 35 minutes, the IFAS are separated by centrifugation, and a vegetable oil is provided in the reaction mixture as a liquid and wherein β-cyclodextrin is also mixed with the animal fat to remove cholesterol simultaneously with the IFAS during the centrifugation, and the mole ratio of 3-cyclodextrin to cholesterol is between 4,72 and 6.4 to 1.

19. A process for reducing free fatty acids (FFA) present in an anhydrous liquid animal fat substantially as herein described with reference to the accompanying drawings.
Dated this 7 day of June 2001


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Patent Number 212338
Indian Patent Application Number IN/PCT/2001/789/CHE
PG Journal Number 07/2008
Publication Date 15-Feb-2008
Grant Date 03-Dec-2007
Date of Filing 07-Jun-2001
Name of Patentee AZIZ CHAFIC AWAD
Applicant Address 1524F Spartan Village, East Lansing, MI 48823,
Inventors:
# Inventor's Name Inventor's Address
1 AZIZ CHAFIC AWAD 1524F Spartan Village East Lansing, MI 48823,
PCT International Classification Number A23C 15/04
PCT International Application Number PCT/US99/29207
PCT International Filing date 1999-12-09
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 09/208,960 1998-12-10 U.S.A.