Augmentation of cocoa butter

Abstract

A method and system of augment cocoa butter compositions includes removal of free fatty acids and phospholipid augmentation. Phospholipid augmentation may include removal of more polar phospholipids such as lyso-phosphatidylcholine (LPC) and phosphatidylinositol (PI) and enrichment of less polar phospholipids such as phosphatidylcholine (PC) and phosphatidylethanolamine (PE) and may be facilitated by acid washing and the use of phospholipases.

Description

Patent Application Attorney Docket No. 58566.24WO01AUGMENTATION OF COCOA BUTTER CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U.S. Provisional Application No. 63 / 727,805 filed December 4, 2024, entitled “Augmentation of Cocoa Butter,” the disclosure of which is hereby incorporated by reference in its entirety.FIELD OF THE DISCLOSURE

[0002] The present disclosure relates to a method and system of augment cocoa butter compositions. More particularly, the disclosure relates to removal of free fatty acids and / or phospholipid augmentation of cocoa butter.BACKGROUND

[0003] High free fatty acid (FFA) concentrations in cocoa butter are detrimental to the performance of cocoa butter in chocolate manufacture and application. This negative effect is at least observed in the solid fat content (SFC) of cocoa butter in equilibrium at different temperatures (see FIG. 1). High FFA content also lowers shelf-life stability with the tendency of the material to go rancid. Negative attributes are also observed with the SFC content during static crystallization over time (see FIGS. 2 and 3). In FIGS. 2 and 3, the Feed cocoa butter is natural Ivory Coast cocoa butter having a FFA content of 2.01 wt%, the 160C CB is cocoa butter deodorized at 160 °C having a FFA content of 0.96 wt%, and the 200C CB is cocoa butter deodorized at 200 °C having a FFA content of 0.07 wt%. Static crystallization is accelerated and increased in the lower FFA content materials.

[0004] Additionally, phospholipids (gums) are present in cocoa butter. It is believed that certain phospholipid components can produce negative effects on the cocoa butter properties. It is further believed that certain of these phospholipid compounds produce positive effects on the cocoa butter properties.

[0005] Different phospholipids create different types of micelles when they crystallize in the presence of cocoa butter. The less polar phospholipids, phosphatidylcholine (PC) and phosphatidylethanolamine (PE) are believed to form micelles with the polar regions on the inside of the micelle. The non-polar tails are on the outside of the micelle. These non-polar tails are able to interact with the triacylglycerides (TAG) present in the cocoa butter creatingPatent Application Attorney Docket No. 58566.24WO01a faster crystallization event and harder cocoa butter which is believed to have better heat stability and allow larger amounts of milk fat to be used in chocolate formulations.

[0006] The more polar phospholipids, lyso-phosphatidylcholine (LPC) and phosphatidylinositol (PI) are believed to form micelles with the polar regions on the outside of the micelle. These polar regions on the outside of the micelle do not interact as well with the TAG present in the cocoa butter. This makes for a slower crystallization event producing softer cocoa butter which is believed to have poorer heat stability and more easily penetrated by larger amounts of milk fat to be used in chocolate formulations.

[0007] Small concentrations of phospholipids present in raw butter have been shown to be disproportionately present in the first crystals that form during the crystallization of cocoa butter. The proportion of phospholipids (PL) found in the early to crystallize seed crystals is 12 times their concentration in the bulk liquid. The proportion of glycolipids found in the early to crystallize seed crystals is 16 times their concentration in the bulk liquid (see Table 1 below). The melting point of these early -to-form crystals is significantly higher than the bulk crystals normally found in cocoa butter.

[0008] TABLE 1Composition (% ) Sample Melting Point (*C) TAG PL Glycalipids Cocoa butter 32-34 96.2 0.4 0.9 Dynamic crystallizationSeed crystal 34-37 92.1 2.0 2.6 Static crystallizationSeed crystal 55-62 87.7 4.0 6.0 Seed crystal 62-72 82.2 6.6 11.1 Source: Dimick, 1999.

[0009] Selective removal of the more polar phospholipids, namely, lyso-phosphatidylcholine (LPC) and phosphatidylinositol (PI), may produce a superior cocoa butter for chocolate formulations. As such, there remains a need for an effective process for removal of FFA and augmentation of phospholipids in cocoa butter compositions.BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Various embodiments of the present disclosure will be understood more fully from the detailed description given below and from the accompanying drawings. In thePatent Application Attorney Docket No. 58566.24WO01drawings, like reference numbers may indicate identical or functionally similar elements. Embodiments are described in detail hereinafter with reference to the accompanying figures, in which:

[0011] FIG. 1 is a graph depicting solid fat content of cocoa butter as a function of FFA content.

[0012] FIG. 2 is a graph depicting solid fat content of cocoa butter as a function of time during static crystallization at 22 °C.

[0013] FIG. 3 is a graph depicting solid fat content of cocoa butter as a function of time during static crystallization at 20 °C.

[0014] FIG. 4 is a schematic diagram showing cocoa butter purification system according to an embodiment of the present disclosure.

[0015] FIG. 5 is a schematic diagram showing cocoa butter purification system according to an embodiment of the present disclosure.

[0016] FIG. 6 is a schematic process diagram showing phospholipases for use in vegetable oil processing and the resultant products.

[0017] FIG. 7 is a schematic chemical reaction using acyltransferase to convert phospholipids.DETAILED DESCRIPTION

[0018] The following disclosure provides many different embodiments or examples. Specific examples of components and arrangements are described below to simplify the present disclosure. These are, of course, merely examples and are not intended to be limiting. In addition, the present disclosure may repeat reference numerals and / or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and / or configurations discussed.

[0019] The present disclosure relates to the chemical refining of cocoa butter. In some embodiments, one or more microchannel fiber reactors may be used to facilitate high aspect ratio reaction channels in which diffusion rates and mass transfer between oleaginous and aqueous solutions are accelerated. The microchannel fiber reactor may be fabricated via the uniform vertical suspension of micron-sized stainless-steel fiber enclosed in a cylindrical reactor shell (see, e.g., U. S. Patent Nos. 7,618,544 and 11,198,107, each of which is hereby incorporated by reference in its entirety). In other embodiments, the cocoa butter andPatent Application Attorney Docket No. 58566.24WO01reactants described below may be contacted using a stirred pot or similar device. That is, in each instance where a fiber reactor is mentioned below, a stirred pot or similar device may be optionally substituted.

[0020] Referring to FIG. 4, a system 100 for refining cocoa butter includes a cocoa butter supply 102 containing the cocoa butter to be processed. The cocoa butter includes a mixture of triglycerides, FFA, phospholipids, and other minor contaminants. In some embodiments, the cocoa butter may include about 0.5 to about 8 wt%, about 1 to about 5 wt%, or about 2 to about 4 wt% of FFA.

[0021] In some embodiments, the cocoa butter supply 102 may include an agitation mechanism 102a, such as a stirrer. In some embodiments, the cocoa butter supply 102 may be maintained at or above a melting point of the cocoa butter (e.g., at least 25 °C, at least 30 °C, at least 35 °C, or at least 40 °C). In some embodiments, the entire system 100 may be maintained at or above a melting point of the cocoa butter. The cocoa butter is transported from the cocoa butter supply 102 via line 104 to a first reactor 110, which may be a microchannel fiber reactor.

[0022] An aqueous reactant solution or extraction solution (“reactant solution”) is simultaneously supplied to the first reactor 110 via line 106 from a reactant supply 105. The higher polarity phospholipids contained in the cocoa butter are more acidic than the lower polarity phospholipids. Selectively removing the higher polarity phospholipids may be achieved by intentionally altering the pH of the reactant solution such the pH is sufficiently high solubilize the “bad” phospholipids while leaving behind the “good” phospholipids. Calculations show that highly alkaline solution, particularly pH of 12+ (after FFA neutralization), may remove lyso-phosphatidylcholine (LPC). Further, at pH of 13+ (after FFA neutralization), the reactant solution may remove phosphatidylinositol (PI). At these pH ranges phosphatidylcholine (PC) and phosphatidylethanolamine (PE) have poor water solubility and are expected to remain in the cocoa butter.

[0023] Additionally, these “sparingly soluble” phospholipids (LPC, PI, PC, and PE) may be washed into water even at lower pH. For the removal of FFAs into water, a pH of 12 is not necessary and significantly lower pH may be used. In addition, a buffered solution that has a controllable pH, as opposed to a strong base (e.g., NaOH), can precisely ionize FFAs to make them soluble at lower pH ranges in order to more selectively wash FFAs away from the cocoa butter without bringing as much phospholipid into the aqueous phase. Further, the ratioPatent Application Attorney Docket No. 58566.24WO01of water to cocoa butter used can alter the amount of ‘'sparingly soluble” species into the water phase from the butter phase.

[0024] LPC has a chemical structure shown by chemical formula 1 below, wherein FFA is a free fatty acid chain:(X,0. FFARo b©

[0025] (1)

[0026] The solubility values for LPC are shown in Table 2 below:

[0027] TABLE 2LogSpH LPC mol weight M / L g / L % cone 0 -5.7 544 1.995E-06 0.0011 0.000% 1 -6.7 544 1.995E-07 0.0001 0.000% 2 -7.3 544 5.012E-08 0.0000 0.000% 3 -7.5 544 3.162E-08 0.0000 0.000% 4 -7.5 544 3.162E-08 0.0000 0.000% 5 -7.5 544 3.162E-08 0.0000 0.000% 6 -7.5 544 3.162E-08 0.0000 0.000% 7 -7.5 544 3.162E-08 0.0000 0.000% 8 -7.5 544 3.162E-08 0.0000 0.000% 9 -7.2 544 6.31E-08 0.0000 0.000% 10 -6.6 544 2.512E-07 0.0001 0.000% 11 -5.7 544 1.995E-06 0.0011 0.000% 12 -4.7 544 1.995E-05 0.0109 0.001% 13 -3.6 544 0.0002512 0.1366 0.014%14 -2.15 544 0.0070795 3.8512 0.385%

[0028] PI has a chemical structure shown by chemical formula 2 below-, wherein each FFA is a free fatty acid chain:Patent Application Attorney Docket No. 58566.24WO01FFA FFA

[0029] (2)

[0030] The solubility values for PI are shown in Table 3 below:

[0031] TABLE 3LogS PH PI mol weight M / L g / L % cone 0 -14 868 IE-14 8.68E-12 0.000% 1 -13.8 868 1.585E-14 1.376E-11 0.000% 2 -13.5 868 3.162E-14 2.745E-11 0.000% 3 -12.4 868 3.981E-13 3.456E-10 0.000% 4 -11.7 868 1.995E-12 1.732E-09 0.000% 5 -10.7 868 1E-10.7 8.68E-105 0.000% 6 -9.7 868 1.995E-10 1.732E-07 0.000% 7 -8.7 868 1.995E-09 1.732E-06 0.000% 8 -7.7 868 1.995E-08 1.732E-05 0.000% 9 -6.7 868 1.995E-07 0.0001732 0.000% 10 -5.7 868 1.995E-06 0.0017319 0.000% 11 -4.7 868 1.995E-05 0.0173189 0.002% 12 -3.5 868 0.0003162 0.2744857 0.027% 13 -1.7 868 0.0199526 17.318877 1.732%14 0 868 1 868 86.800%

[0032] PC has a chemical structure shown by chemical formula 3 below, wherein each FFA is a free fatty acid chain:Patent Application Attorney Docket No. 58566.24WO01

[0033] (3)

[0034] The solubility values for PC are shown in Table 4 below:

[0035] TABLE 4LogSpH PC mol weight M / L g / L % cone 0 -12.5 794 3.162E-13 2.511E-10 0.000% 1 -14 794 IE-14 7.94E-12 0.000% 2 -14.5 794 3.162E-15 2.511E-12 0.000% 3 -14.6 794 2.512E-15 1.994E-12 0.000% 4 -14.6 794 2.512E-15 1.994E-12 0.000% 5 -14.6 794 2.512E-15 1.994E-12 0.000% 6 -14.6 794 2.512E-15 1.994E-12 0.000% 7 -14.6 794 2.512E-15 1.994E-12 0.000% 8 -14.6 794 2.512E-15 1.994E-12 0.000% 9 -14.5 794 3.162E-15 2.511E-12 0.000% 10 -14 794 IE-14 7.94E-12 0.000% 11 -12.5 794 3.162E-13 2.511E-10 0.000% 12 -11.2 794 6.31E-12 5.01E-09 0.000% 13 -10.5 794 3.162E-11 2.511E-08 0.000%14 -9.5 794 3.162E-10 2.511E-07 0.000%

[0036] PE has a chemical structure shown by chemical formula 4 below, wherein each FFA is a free fatty acid chain:

[0037] (4)Patent Application Attorney Docket No. 58566.24WO01

[0038] The solubility values for PE are shown in Table 5 below:

[0039] TABLE 5LogSpH PE mol weight M / L g / L % conc 0 -13 749 IE-13 7.49E-11 0.000% 1 -13.8 749 1.585E-14 1.187E-11 0.000% 2 -14.5 749 3.162E-15 2.369E-12 0.000% 3 -14.8 749 1.585E-15 1.187E-12 0.000% 4 -14.8 749 1.585E-15 1.187E-12 0.000% 5 -14.8 749 1.585E-15 1.187E-12 0.000% 6 -14.8 749 1.585E-15 1.187E-12 0.000% 7 -14.8 749 1.585E-15 1.187E-12 0.000% 8 -14.8 749 1.585E-15 1.187E-12 0.000% 9 -14.8 749 1.585E-15 1.187E-12 0.000% 10 -14.8 749 1.585E-15 1.187E-12 0.000% 11 -13.8 749 1.585E-14 1.187E-11 0.000% 12 -12.3 749 5.012E-13 3.754E-10 0.000% 13 -11.8 749 1.585E-12 1.187E-09 0.000% 14-11 749 IE-11 7.49E-09 0.000%

[0040] The solubility values for Cl 8 free fatty acid are shown in Table 6 below:

[0041] TABLE 6C18 free fatty acidLogSpH C18:l FFA mol weight M / L g / L % cone 0 -8 284 0.00000001 0.00000284 0.000%1 -8 284 0.00000001 0.00000284 0.000%2 -8 284 0.00000001 0.00000284 0.000%3 -8 284 0.00000001 0.00000284 0.000%4 -8 284 0.00000001 0.00000284 0.000%5 -7.5 284 3.1623E-08 8.9809E-06 0.000%6 -6.8 284 1.5849E-07 4.5011E-05 0.000%7 -5.8 284 1.5849E-06 0.00045011 0.000%8 -4.8 284 1.5849E-05 0.0045011 0.000%9 -3.8 284 0.00015849 0.04501097 0.005% 10 -2.8 284 0.00158489 0.45010967 0.045% 11 -1.8 284 0.01584893 4.50109667 0.450% 12 -0.8 284 0.15848932 45.0109667 4.501% 13 0 284 1 284 28.400%14 0 284 1 284 28.400%Patent Application Attorney Docket No. 58566.24WO01

[0042] From the foregoing solubilities, it has been found that using a pH of between approximately 10 and 11 will create soluble FFA but not create soluble phospholipid compounds. Running a process at a pH high enough to solubilize FFA contaminants can produce a cocoa butter material with low FFA but the full complement of natural phospholipids.

[0043] In the system 100, the cocoa butter reacts with reactant solution in the first reactor 110- which controllably contact the reactants with minimal perturbations in concentration, temperature, and flow under continuous operations-to form reaction products. The reaction products are collected in a first separator 110a of the first reactor 110, wherein the reaction products include a first raffinate including the cocoa butter having a first impurity removed therefrom and a first aqueous effluent including the reactant solution and the first impurity. The first impurity may include, e.g., FFA, phospholipids, or a combination of impurities. The aqueous reactant solution (in some embodiments having a high pH) readily separates from the oleaginous triglycerides of the cocoa butter by natural phase separation after exiting the microchannel reactor wherein the higher density aqueous phase concentrates in the bottom of a first separator 110a. The first aqueous effluent is removed from the first separator 110a via line 114 into an aqueous effluent tank 160. which may include a recycling system to separate the water, the first impurity, and / or the reactant for further use. The lower density neutralized cocoa butter raffinate (first raffinate) may be continuously collected from the top of the first separator 110a and directed via line 112 to a second reactor 120, which may be a microchannel fiber reactor.

[0044] Next, if necessary or desired, a second aqueous reaction solution, such as water or a pH adjust solution, is simultaneously supplied from aqueous tank 107 via line 116 to the second reactor 120. The aqueous solution thereby washes the first raffinate in the second reactor 120 and the resulting second wash products are collected in a second separator 120a. The second wash products include a second raffinate including the first raffinate having a second impurity removed therefrom (which may be of the same kind or different from the first impurity ) and a second aqueous effluent including the aqueous solution and the second impurity. The second aqueous effluent is removed from the second separator 120a via line 124 to the aqueous effluent tank 160. The second raffinate is directed via line 122 to a third reactor 130, which may be a microchannel fiber reactor.

[0045] Next, if necessary or desired, an aqueous reaction solution is simultaneously supplied from the aqueous tank 107 via line 126 to the third reactor 130. In somePatent Application Attorney Docket No. 58566.24WO01embodiments, the aqueous reaction solution may be different from that in tank 107 and may be separately supplied. The aqueous solution thereby washes the second raffinate in the third reactor 130 and the resulting third wash products are collected in a third separator 130a. The third wash products include a third raffinate including the second raffinate having a third impurity removed therefrom (which may be of the same kind or different from the first and / or second impurity) and a third aqueous effluent including the aqueous solution and the third impurity. The third aqueous effluent is removed from the third separator 130a via line 134 to the aqueous effluent tank 160. The third raffinate is directed via line 132 to a fourth reactor 140, which may be a microchannel fiber reactor.

[0046] Next, if necessary or desired, an aqueous reaction solution is simultaneously supplied from the aqueous tank 107 via line 136 to the fourth reactor 140. In some embodiments, the aqueous reaction solution may be different from that in tank 107 and may be separately supplied. The aqueous solution thereby washes the third raffinate in the fourth reactor 140 and the resulting fourth wash products are collected in a fourth separator 140a. The fourth wash products include a fourth raffinate including the third raffinate having a fourth impurity removed therefrom (which may be of the same kind or different from the first, second, and / or third impurity) and a fourth aqueous effluent including the aqueous solution and the fourth impurity. The fourth aqueous effluent is removed from the fourth separator 140a via line 144 to the aqueous effluent tank 160. The fourth raffinate is directed via line 142 to pure cocoa butter tank 150.

[0047] Although the system 100 described above includes four reactors, any number of reactors may be used. In some embodiments, any of the reactors may differ from one or more of the other reactors in terms of temperature, types of fibers, length, diameter, and / or packing density. See U.S. Patent No. 11,198,107. Further, as described above, any one or more of the reactors may be replaced by a stirred pot or similar device.

[0048] In some embodiments, the reaction products and / or wash products do not include any solids. That is, the impurities removed from the cocoa butter at each stage may remain dissolved in the aqueous phase and removed with the liquid (aqueous effluent).

[0049] In some embodiments, the reactant solution in supply 105 and / or the second aqueous reaction solution in aqueous tank 107 has a pH of at least 7, at least 8, at least 9. at least 10, at least 11, at least 12, or at least 13. In some embodiments, the reactant solution and / or the second aqueous reaction solution comprises a hydroxide base, such as NaOH or KOH. In some embodiments, the reactant solution and / or the second aqueous reactionPatent Application Attorney Docket No. 58566.24WO01solution is a buffered solution having a pH of 6 to 8. In some embodiments, the first wash in the first reactor 110 is with the buffered solution in order to neutralize and remove FFA. Thereafter, the first raffinate may be treated with an aqueous solution having elevated pH described above to remove one or more phospholipids. This configuration allows for selective ability to remove FFAs from cocoa butter while leaving behind phospholipids with a slightly alkaline wash using controlled pH buffer, for example pH 6 to 8.

[0050] In some embodiments, a ratio of reactant solution and / or the second aqueous reaction solution to cocoa butter (or raffinate) is from 5:1 to 1:5, about 5:1, about 2:1, or about 1:1.

[0051] Turning to FIG. 5, a system 200 for refining cocoa butter is shown. Unless indicated otherwise, components of the system 200 may be the same as those described for system 100 above. The system 200 includes cocoa butter supply 202 containing the cocoa butter to be processed. In some embodiments, the cocoa butter supply 202 may include an agitation mechanism 202a, such as a stirrer. In some embodiments, the cocoa butter supply 202 may be maintained at or above a melting point of the cocoa butter as described above. In some embodiments, the entire system 200 may be maintained at or above a melting point of the cocoa butter. The cocoa butter is transported from the cocoa butter supply 202 via line 204 to a first reactor 210, which may be a microchannel fiber reactor.

[0052] An aqueous reactant solution is simultaneously supplied to the first reactor 210 via line 206 from a reactant supply 205. The reactant solution may be as described above. The cocoa butter reacts with reactant solution in the first reactor 210 to produce reaction products. The reaction products are collected in a first separator 210a of the first reactor, wherein the reaction products include a first raffinate including the cocoa butter having a first impurity removed therefrom and a first aqueous effluent including the reactant solution and the first impurity. The first impurity may include, e.g., FFA, phospholipids, or a combination of impurities. The first aqueous effluent is removed from the first separator 210a via line 214 into an aqueous effluent tank 260, which may include a recycling system to separate the water, the first impurity, and / or the reactant for further use. The first raffinate is directed via line 212 to a second reactor 220, which may be a microchannel fiber reactor.

[0053] An aqueous solution, such as water, is simultaneously supplied from aqueous tank 207 via line 216 to the second reactor 220. The aqueous solution thereby washes the first raffinate in the second reactor 220 and the resulting second wash products are collected in a second separator 220a. The second wash products include a first purified cocoa butter (a topPatent Application Attorney Docket No. 58566.24WO01layer) which may be removed from the second separator via line 228 to a first pure cocoa butter tank 250a. The second wash products further include a second raffinate (a middle layer) including the first raffinate having a second impurity removed therefrom (which may be of the same kind or different from the first impurity) and a second aqueous effluent (bottom layer) including the aqueous solution and the second impurity. The second aqueous effluent is removed from the second separator 220a via line 224 to the aqueous effluent tank 260. The second raffinate is directed via line 222 to a third reactor 230, which may be a microchannel fiber reactor.

[0054] An aqueous solution is simultaneously supplied from the aqueous tank 207 via line 226 to the third reactor 230. The aqueous solution thereby washes the second raffinate in the third reactor 230 and the resulting third wash products are collected in a third separator 230a. The third wash products include a second purified cocoa butter including the second raffinate having a third impurity removed therefrom (which may be of the same kind or different from the first and / or second impurity) and a third aqueous effluent including the aqueous solution and the third impurity. The third aqueous effluent is removed from the third separator 230a via line 234 to the aqueous effluent tank 260. The second purified cocoa butter is directed via line 238 to a second pure cocoa butter tank 250b, wherein the second purified cocoa butter comprises a distinct composition from the first purified cocoa butter.

[0055] Although the system 200 described above includes three reactors, any number of reactors may be used. In some embodiments, any of the reactors may differ from one or more of the other reactors in terms of temperature, types of fibers, length, diameter, and / or packing density. See U.S. Patent No. 11,198,107. Further, as described above, any one or more of the reactors may be replaced by a stirred pot or similar device.

[0056] It has also been found that using a high enough pH to wash FFA and one or more phospholipids into the wash water will concentrate those compounds into the wash water. Given the selective pH solubility of the compounds, for example, once the wash water has accumulated the compounds, a second pass through a wash process can be accomplished whereby the FFA compounds stay in the aqueous phase, but one or more phospholipid species lose solubility in water and will tend to dissolve into an oil layer. This method enables the tailoring of the concentration of certain phospholipids into any number of desired water insoluble materials, for example TAG rich cocoa butter. As such, in some embodiments, the aqueous effluent from any of the wash processes may be recycled through a reactor or stirred pot with fresh unprocessed cocoa butter in order to reintroduce one orPatent Application Attorney Docket No. 58566.24WO01more phospholipids from the aqueous effluent back into the cocoa butter and concentrate that component in the cocoa butter.

[0057] Additionally, food grade lecithin is a rich source of phospholipids, including PI and PE. This material is also lower priced than cocoa butter. Lecithin can be derived from a number of crops such as soya, sunflower, or canola. The major components of commercial soybean-derived lecithin are 33-35 wt% soybean oil, 20-21 wt% PI, 19-21 wt% PC, 8-20 wt% PE, 5-11 wt% of other phosphatides, 5 wt% free carbohydrates, 2-5 wt% sterols, and 1 wt% moisture. Adding lecithin into raw cocoa butter and then performing the selective refining processes described herein will allow the desired phospholipids to be increased above the concentration normally found in cocoa butter. This technique allows tailoring of cocoa butter with low-cost ingredients to produce higher quality cocoa butter.

[0058] Yet another source of phospholipids that may be used to supplement cocoa butter is toll manufacturers. That is, some toll manufacturers that process, for example, cocoa butter use a process wherein the phospholipids are removed from the raw cocoa butter prior to stripping FFA content to yield the refined cocoa butter. The removed phospholipids may be recycled using the processes described herein.

[0059] Using the processes above, the addition of phosphatidylcholine (PC) and phosphatidyl ethanolamine (PE) components to CB may increase the desirability of the butter. Additionally, the mixing of one or both of these components into the cocoa butter can be facilitated by using a microchannel fiber reactor as a mixing device using the methods described herein.

[0060] In some embodiments, the reactant solution and / or aqueous solution in the system 100 or 200 may include one or more enzymes. Enzymes for the hydrolysis of phospholipids are commercially available. Chemical formula 5 below shows the general structure for a number of phospholipids:Patent Application Attorney Docket No. 58566.24WO01

[0061] (5)

[0062] In formula 5, R1 and R2 are fatty acid chains and X is H (phosphatidic acid, PA), choline (PC), ethanolamine (PE), serine (phosphatidylserine, PS), or inositol (PI). There are three main classes of phospholipase enzymes. PLA1 cleaves the terminal fatty acid from the glycerol backbone (from C1 of the glycerol backbone, i.e., the fatty acid comprising R1 in formula 5). PLA2 cleaves the middle fatty acid from the glycerol backbone (from C2 of the glycerol backbone, i.e., the fatty acid comprising R2). PLC cleaves the phospholipid at the phosphate group (from C3 of the glycerol backbone). FIG. 6 illustrates the functions of PLA1, PLA2, and PLC. Other phospholipases include PLB, which cleaves both fatty' acids from the glycerol backbone, and PLD. which cleaves the functional group from the phosphate group (X in formula 5 above). Acy transferase (AT) removes fatty acids from phospholipids and attaches the free fattv acid to natural sterols in the raw material.

[0063] These enzymes can therefore be used to cleave fatty acids from phospholipids (PL) to form free fatty acids (FFA) and to re-esterify a portion of said FFA to sterols. In some embodiments, it has been found that 0.036 wt% of FFA is formed for every 0.1 wt% of PL converted to a lyso-phospholipid (LL), and each 0.1 wt% of free sterols is able to re-esterify with 0.065 wt% of FFA. An example of this process is depicted in FIG. 7. By transferring the liberated fatty acids to a sterol, the amount of butter loss may be minimized as the new molecule will likely be kept within the refined cocoa butter.

[0064] The addition of phospholipase into the mixing procedure of water plus cocoa butter may be enhanced with the use of a fiber reactor, such as that described above. The emulsion layers created by this process give good evidence that the fiber reactor intimately mixes the water and oil together and would also be expected to mix enzyme solution in with equal efficacy. When emulsions layers are formed, these layers can be separated from the oil and aqueous phases and treated by, for example, additional washes to separate the oil andPatent Application Attorney Docket No. 58566.24WO01water components; the oil components may then be reintroduced to the cocoa butter. In some embodiments, the addition of phospholipase can be done in a first wash or a second wash where the pH is low enough for enzyme stability. If the pH is adjusted with a buffer in the neutralization fiber reactor, the enzyme could likely be added at that vessel as a very high pH (12+) could be avoided.

[0065] In some embodiments, different combinations of enzymes within the same system may be used to further tailor the cocoa butter product for yield and / or quantity of production. In some embodiments, enzymes may be used to add a FFA to water insoluble species of phospholipids. For example, adding a fatty acid to LPC to create phosphatidylcholine would convert a “bad” phospholipid into a “good” phospholipid.

[0066] The process and system disclosed herein may provide selective addition of phosphatidylethanolamine and / or phosphatidylcholine to increase the desirability of the cocoa butter. A fiber reactor may be employed to enhance this process. These techniques may increase the cocoa butter in most desired phospholipids above the natural concentration thereby creating cocoa butter with unusually good characteristics. Further, tailor creation of cocoa butter by the controlled addition of phospholipids before processing may yield finished cocoa butter enriched in the most desired phospholipids. The current disclosure also enables creation of specialty cocoa butters with high melting point and the ability to tolerate increased low-cost components, such as cow’s milk fat, in the formulation of chocolates. The total cost of formulation of chocolates may be reduced because of the ability to include higher concentrations of low-cost components and lower concentrations of cocoa butter.

[0067] As disclosed above, the system and process described herein enable selective removal of phosphatidylinositol from cocoa butter with an alkaline wash at pH 12+, selective removal lyso-phosphatidylcholine from cocoa butter with an alkaline wash at pH 13+, and / or selective removal of both phosphatidylinositol and lyso-phosphatidylcholine with an alkaline wash at pH 13+. Again, this provides improved cocoa butter quality due to the removal of polar phospholipids phosphatidylinositol and / or lyso-phosphatidylcholine. Moreover, the concentration of desired phospholipids, phosphatidylcholine and phosphatidylethanolamine, may be increased through selective removal of more polar phospholipids. These methods may also modify crystallization properties and polymorph characteristics of the cocoa butter through selective removal of certain phospholipids.

[0068] Also disclosed herein is the selective ability to remove lyso-phosphatidylcholine from cocoa butter with the assistance of enzymatic hydrolysis with an alkaline wash at pHPatent Application Attorney Docket No. 58566.24WO0113+, the selective ability to remove phosphatidylinositol from cocoa butter with the assistance of enzymatic hydrolysis with an alkaline wash at pH 12+, modification of crystallization properties and polymorph characteristics through selective removal of certain phospholipids, and reduction in loss of finished cocoa butter mass from phospholipid removal by use of acyltransferase enzyme activity.

[0069] The system and methods described herein may also be applied to natural oils other than cocoa butter. That is, in some embodiments, the cocoa butter supply 102, 202 may be replace with a natural oil supply in order to provide tailored creation of specific phospholipid enriched natural oils and natural oils enriched in compounds that have different water solubilities at different pH ranges such that they are mostly water insoluble at a given pH range and mostly water soluble at another given pH range.EXAMPLES

[0070] Example 1: Removing FFA and leaving behind phospholipids

[0071] A pH controlled aqueous phase at between, for example, pH 10 to pH 11 is mixed with a crude cocoa butter liquid. Sufficient contact time is provided between the aqueous phase and the cocoa butter phase. This contact time can be done with a variety of procedures, for example a stirred tank or a fiber conduit reactor.

[0072] The aqueous phase is allowed to separate from the hydrophobic phase. The FFA will be dissolved in the aqueous phase and the hydrophobic cocoa butter phase will contain the phospholipids, TAG, MAG, DAG and other natural water insoluble components.

[0073] Example 2, Removing FFA and phosphatidylinositol from cocoa butter

[0074] A pH controlled aqueous phase at betw een, for example, pH 12 to pH 12.5 is mixed with a crude cocoa butter liquid in a first fiber reactor. The phases are allowed to separate and an emulsion rich layer, if present, is removed. The emulsion rich layer is passed through a second fiber reactor adding pH 8 or lower buffered water.

[0075] Sufficient contact time between the aqueous phase and the cocoa butter phase is provided. This contact time can be done with a variety of procedures, for example a stirred tank, for a second example a fiber conduit reactor. In some embodiments, this step may be facilitated by mixing a controlled amount of enzyme directly into the water layer in the separator on the water wash fiber reactor. The enzyme should hydrolyze material dissolved within the water. As the phosphatidylinositol concentration drops due to hydrolysisPatent Application Attorney Docket No. 58566.24WO01additional phosphatidylinositol should dissolve from the oil phase into the water phase. The use of enzy me can reduce the amount of water required in the process.

[0076] The aqueous phase is allowed to separate from the hydrophobic phase. The FFA and phosphatidylinositol will be dissolved in the aqueous phase and the hydrophobic cocoa butter phase will contain the remaining phospholipids (little to no phosphatidylinositol), TAG, MAG, DAG and other natural water insoluble components.

[0077] Example 3, Removing FFA and phosphatidylinositol and lyso-phosphatidyl choline from cocoa butter

[0078] A pH controlled aqueous phase at between, for example, pH 13 or higher is mixed wi th a crude cocoa butter liquid in a first fiber reactor. The phases are allowed to separate and an emulsion rich layer, if present, is removed. The emulsion rich layer is passed through a second fiber reactor adding pH 8 or lower buffered water.

[0079] Sufficient contact time between the aqueous phase and the cocoa butter phase is provided. This contact time can be done with a variety of procedures, for example a stirred tank, for a second example a fiber conduit reactor. In some embodiments, this step may be facilitated by mixing a controlled amount of enzyme directly into the water layer in the separator on the water wash fiber reactor. The enzy me should hydrolyze material dissolved within the water. As the phosphatidylinositol and lyso-phosphatidylcholine concentrations drop due to hydrolysis additional phosphatidylinositol and lyso-phosphatidylcholine should dissolve from the oil phase into the water phase. The use of enzyme can reduce the amount of water required in the process.

[0080] The aqueous phase is allowed to separate from the hydrophobic phase. The FFA and phosphatidylinositol and lyso-phosphatidylcholine will be dissolved in the aqueous phase and the hydrophobic cocoa butter phase will contain the remaining phospholipids (little to no phosphatidylinositol or lyso-phosphatidylcholine), TAG, MAG, DAG and other natural water insoluble components.

[0081] Example 4, Removing FFA from cocoa butter while enriching cocoa butter in phosphatidylinositol

[0082] A pH controlled aqueous phase at between, for example, pH 12 to pH 12.5 is mixed with a crude cocoa butter liquid. Sufficient contact time between the aqueous phasePatent Application Attorney Docket No. 58566.24WO01and the cocoa butter phase is provided. This contact time can be done with a variety of procedures, for example a stirred tank, for a second example a fiber conduit reactor.

[0083] The aqueous phase is allowed to separate from the hydrophobic phase. The FFA and phosphatidylinositol will be dissolved in the aqueous phase and the hydrophobic cocoa butter phase will contain the remaining phospholipids (little to no phosphatidylinositol), TAG, MAG, DAG and other natural water insoluble components.

[0084] The aqueous phase is separated from the hydrophobic phase and transfer into different vessels. The pH of the aqueous phase is adjusted to pH 10 to 11. This will cause the phosphatidylinositol to lose solubility in the aqueous phase.

[0085] The material from the previous step is mixed with fresh cocoa butter. Sufficient mixing and contact time is provided. This contact time can be done with a variety of procedures, for example a stirred tank, for a second example a fiber conduit reactor.

[0086] The aqueous phase is allowed to separate from the hydrophobic phase. The phosphatidylinositol will now be dissolved in the cocoa butter phase along with all the original phospholipids, TAG, MAG. DAG and other natural water insoluble components. The aqueous phase will contain FFA dissolved in water. The cocoa butter leaving this step will now be enriched in phosphatidylinositol and depleted in FFAs.

[0087] Example 5, Removing FFA from cocoa butter while enriching cocoa butter in phosphatidylinositol and lyso-phosphatidylcholine

[0088] A pH controlled aqueous phase at between, for example, pH 13 or higher is mixed with a crude cocoa butter liquid.

[0089] Sufficient contact time between the aqueous phase and the cocoa butter phase is provided. This contact time can be done with a variety of procedures, for example a stirred tank, for a second example a fiber conduit reactor.

[0090] The aqueous phase is allowed to separate from the hydrophobic phase. The FFA and phosphatidylinositol and lyso-phosphatidylcholine will be dissolved in the aqueous phase and the hydrophobic cocoa butter phase will contain the remaining phospholipids (little to no phosphatidylinositol or lyso-phosphatidylcholine), TAG, MAG, DAG and other natural water insoluble components.Patent Application Attorney Docket No. 58566.24WO01

[0091] The aqueous phase is separated from the hydrophobic phase and transferred into different vessels. The pH of the aqueous phase is adjusted to pH 10 to 11. This will cause the phosphatidylinositol and lyso-phosphatidylcholine to lose solubility in the aqueous phase.

[0092] The material from previous step is mixed with fresh cocoa butter. Sufficient mixing and contact time is provided. This contact time can be done with a variety of procedures, for example a stirred tank, for a second example a fiber conduit reactor.

[0093] The aqueous phase is allowed to separate from the hydrophobic phase. The phosphatidylinositol and lyso-phosphatidylcholine will now be dissolved in the cocoa butter phase along with all the original phospholipids, TAG, MAG, DAG and other natural water insoluble components. The aqueous phase will contain FFA dissolved in water. The cocoa butter leaving this step will now be enriched in phosphatidylinositol and lyso-phosphatidylcholine and depleted in FFAs.

[0094] Example 6: Selective enrichment of oils in phospholipids

[0095] A pH controlled aqueous phase at a pH sufficient to increase water solubility of desired component is mixed with oil containing that component.

[0096] Sufficient contact time between the aqueous phase and the natural oil phase is provided to effect dissolution of newly water-soluble components. This contact time can be done with a variety of procedures, for example a stirred tank, for a second example a fiber conduit reactor.

[0097] The aqueous phase is allowed to separate from the hydrophobic phase. The newly water-soluble compounds will be dissolved in the aqueous phase and the hydrophobic species will contain the remaining water insoluble components.

[0098] The aqueous phase is separated from the hydrophobic phase and transfer into different vessels. The pH of the aqueous phase is adjusted to pH 10 to 11. This will cause FFAs to stay in solution but phospholipids to become insoluble in the aqueous phase.

[0099] The material from the previous step is mixed with oil to be enriched in the newly insoluble components. Sufficient mixing and contact time is provided. This contact time can be done w ith a variety of procedures, for example a stirred tank, for a second example a fiber conduit reactor.

[0100] The aqueous phase is allow ed to separate from the hydrophobic phase. The newly water insoluble compounds due to pH shift will now be dissolved in the oil phase along withPatent Application Attorney Docket No. 58566.24WO01all the original phospholipids, TAG, MAG, DAG and other natural water insoluble components. The aqueous phase will contain FFA dissolved in water. The oil leaving this step will now be enriched in the newly insoluble compounds and depleted in FFAs.

[0101] Example 7, Increasing desired PLs in cocoa butter by removing FFA from cocoa butter while enriching cocoa butter in phosphatidylinositol and lyso-phosphatidylcholine

[0102] A source of complex phospholipids is added into raw cocoa butter. Sources can be soy lecithin or cocoa butter lecithin (byproduct of standard correction butter process).

[0103] A pH controlled aqueous phase at between, for example, pH 13 or higher is mixed with the PL spiked crude cocoa butter liquid.

[0104] Sufficient contact time between the aqueous phase and the cocoa butter phase is provided. This contact time can be done with a variety of procedures, for example a stirred tank, for a second example a fiber conduit reactor.

[0105] The aqueous phase is allowed to separate from the hydrophobic phase. The FFA and phosphatidylinositol and lyso-phosphatidylcholine will be dissolved in the aqueous phase and the hydrophobic cocoa butter phase will contain the remaining phospholipids (little to no phosphatidylinositol or lyso-phosphatidylcholine), TAG, MAG, DAG and other natural water insoluble components.

[0106] The aqueous phase is separated from the hydrophobic phase and transferred into different vessels. The pH of the aqueous phase is adjusted to pH 10 to 11. This will cause the phosphatidylinositol and lyso-phosphatidylcholine to lose solubility' in the aqueous phase.

[0107] The material from the previous step is mixed with fresh cocoa butter. Sufficient mixing and contact time is provided. This contact time can be done with a variety' of procedures, for example a stirred tank, for a second example a fiber conduit reactor.

[0108] The aqueous phase is allowed to separate from the hydrophobic phase. The phosphatidylinositol and lyso-phosphatidylcholine will now be dissolved in the cocoa butter phase along with all the original phospholipids, TAG, MAG, DAG and other natural water insoluble components. The aqueous phase will contain FFA dissolved in water. The cocoa butter leaving this step will now be enriched in phosphatidylinositol and lyso-phosphatidylcholine and depleted in FFAs.

[0109] Although various embodiments have been shown and described, the disclosure is not limited to such embodiments and will be understood to include all modifications andPatent Application Attorney Docket No. 58566.24WO01variations as would be apparent to one of ordinary skill in the art. Therefore, it should be understood that the disclosure is not intended to be limited to the particular forms disclosed; rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the disclosure as defined by the appended claims.

Claims

Patent Application Attorney Docket No. 58566.24WO01CLAIMSWhat is claimed is:

1. A method comprising:mixing an aqueous solution having a pH of at least 10 and a crude cocoa butter liquid comprising free fatty acids (FFA) to product reaction products, wherein the reaction products comprise an aqueous phase comprising the FFA and a hydrophobic phase comprising the crude cocoa butter liquid having the FFA removed therefrom;separating the aqueous phase from the hydrophobic phase.

2. The method of claim 1, wherein the mixing step comprises contacting the aqueous solution and the crude cocoa butter liquid comprises simultaneously introducing the aqueous solution and the crude cocoa butter liquid into a conduit having a plurality of fibers disposed therein.

3. The method of claim 1, wherein the aqueous solution has a pH of 12 to 12.5;wherein the crude cocoa butter liquid comprises phosphatidylinositol; and wherein the aqueous phase further comprises the phosphatidylinositol.

4. The method of claim 3, wherein the mixing step further comprises mixing a phospholipase with the aqueous solution and the crude cocoa butter liquid.

5. The method of claim 1, wherein the aqueous solution has a pH of 13 or higher;wherein the crude cocoa butter liquid comprises phosphatidylinositol and lyso- phosphatidylcholine; andwherein the aqueous phase further comprises the phosphatidylinositol and lyso- phosphatidylcholine.

6. The method of claim 3, further comprisingadjusting a pH of the aqueous phase to 10-11;mixing the pH adjusted aqueous phase with a second crude cocoa butter liquid to produce second reaction products comprising a second aqueous phase and a secondPatent Application Attorney Docket No. 58566.24WO01hydrophobic phase comprising the second crude cocoa butter liquid and the phosphatidylinositol from the pH adjusted aqueous phase; andseparating the second aqueous phase from the second hydrophobic phase.

7. The method of claim 5, further comprisingadjusting a pH of the aqueous phase to 10-11;mixing the pH adjusted aqueous phase with a second crude cocoa butter liquid to produce second reaction products comprising a second aqueous phase and a second hydrophobic phase comprising the second crude cocoa butter liquid and the phosphatidylinositol and lyso-phosphatidylcholine from the pH adjusted aqueous phase; andseparating the second aqueous phase from the second hydrophobic phase.

8. The method of claim 7, further comprising mixing the crude cocoa butter liquid with soya lecithin or cocoa butter lecithin prior to mixing with the aqueous solution.

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