WO2025250412A1 - Non-alkalized cocoa powders and methods for producing the same using a cold plasma technique - Google Patents

Abstract

Methods of producing cocoa products with the use of cold plasma are described. The cocoa products are produced without use of an alkalizing agent or the use of an alkalizing step. Non-alkalized cocoa products are described that have an L value lower than the cocoa material that have not been treated with cold plasma. Food and beverage compositions comprising the cocoa products are also disclosed.

Description

NON-ALKALIZED COCOA POWDERS AND METHODS FOR PRODUCING THE SAME USING A COLD PLASMA TECHNIQUE

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of EP Application No. 24179015.3, filed May 30, 2024, which is incorporated by reference herein in its entirety.

BACKGROUND

[0002] Cocoa beans are a highly sought-after commodity. Processed to produce cocoa butter, cocoa mass, and cocoa powder, they are used in the manufacture of chocolate, confectionery products (including baked goods such as cookies and cakes), and beverages. Cocoa bean processing typically involves a series of well-established steps designed to enhance the sensory and color profiles of the final cocoa products. These include fermentation, de-hulling, and roasting of the cocoa beans. A de-hulled, cracked cocoa bean is called a cocoa nib. Nibs are crushed and/or milled to produce cocoa liquor (or “cocoa mass”) which, in turn, may be pressed to extract cocoa butter, leaving a substantially defatted cocoa cake (or “press-cake”). The cake can then be more finely ground to produce cocoa powder.

[0003] The color and flavor of cocoa powder is adjusted through alkalization. Typical alkalization methods are described in United States Patent Nos. 4,435,436, 4,784,866 and 5,009,917, and in European Patent No. 2068641. They usually involve heating cocoa nibs (or powder) in the presence of an alkalizing agent such as sodium hydroxide or potash, and result in alkalized (or “dutched”) cocoa powders with darker or more intense colors, less acidic flavors and improved water solubility when compared to their non-alkalized equivalents. These darker colors are considered highly desirable and there has therefore been a trend in the industry for more and more intense alkalization, including the production of so-called “black” cocoa powders. In addition, different alkalization conditions (temperature, alkalizing agent content, reaction time and pressure) can also be used to change the hue of the product, and in particularly the redness.

[0004] Unfortunately, stronger alkalization can have a detrimental impact on flavor, producing astringent, overly bitter or chemical taste profiles. What’s more, the production of black cocoa powders may require the use of undesirable chemicals (such as iron saccharate or ammonium carbonate) that create safety, environmental and regulatory risks. There has therefore been a push to develop dark cocoa powders that have improved flavor profiles and that do not rely on the use of harmful chemicals or over-alkalization. [0005] The color of cocoa powders can be described using the Hunter color coordinate scale or CIE 1976 (CIELAB) color system which uses three coordinates (or values) to define a powder’s color profile. The L coordinate represents lightness and can assume values between 0 (for black) and 100 (for white). The L value for non-alkalized cocoa powders is about 20 or more; between 12 and 20 for slightly alkalized powders; and between 6 and 12 for highly alkalized powders using a wet method of L-value measurement. Cocoa powders described as “black” cocoa powders will typically have an L value of 6 or less.

[0006] Nevertheless, there remains a need in the industry for a method of producing nonalkalized (natural) cocoa powder without the use of undesirable chemicals and with improved flavor and color profiles.

SUMMARY

[0007] The disclosure provides a method for producing a cocoa product, comprising the steps of hydrating a cocoa material with at least 50g of an aqueous composition/lOOg of the cocoa material to form a moistened cocoa material, wherein the cocoa material has not been alkalized and wherein the cocoa material comprises less than 20wt% of fat. The method further includes treating the moistened cocoa material with cold plasma (CP), wherein the cold plasma comprises reactive species generated by ionization of one or more gases and wherein the cocoa material is treated with the CP for at most 15 minutes. The cocoa material may be cocoa powder. The cocoa material may be hydrated at an amount of at least 80g of the water/lOOg of the cocoa material, preferably at about 100g of the water/lOOg of the cocoa material. The aqueous composition may include tap water, plasma activated water or combinations thereof. The one or more gases may include argon, helium, nitrogen, oxygen, air, compressed air and combinations thereof, preferably the one or more gases comprises compressed air. The reactive species may include ozone and/or nitrogen containing free radicals. The cocoa product may comprise an L-value less than the starting cocoa material. The treating the cocoa material may include applying power to generate the reactive species in the cold plasma, preferably the power is between 0.1 and lOOkW and wherein the frequency of the applied power is between 30 KHz and 50 KHz. A nozzle may discharge the cold plasma directed to the cocoa material, wherein the distance from the nozzle to the cocoa material is between 1cm and 10 cm. The cocoa material may be treated with the cold plasm for a duration of at most 10 minutes, preferably between 15 seconds and about 5 minutes. The treated cocoa product may have a L-value of less than 19, preferably less than 18. The amount of hydration may be increased to decrease the L value of the cocoa product. The intensity of the treating may be increased to increase the “a” value. The intensity of the treating may be increased by increasing the power applied to generate the cold plasma, decreasing the distance between the nozzle and the cocoa material, increasing the duration of the treating, increasing the number of reactive species in the cold plasma and combinations thereof.

[0008] The present disclosure provides a dark cocoa product with a decrease in L-value compared to the natural cocoa powder. The decrease in L-value is a result of the treatment with a cold plasma process.

[0009] The present disclosure provides compositions containing dark cocoa product obtained by, or obtainable by, the process of any one of the preceding claims.

[0010] The present disclosure also provides a method for producing a cocoa product, comprising the steps of: treating an aqueous composition comprising water with cold plasma to generate an activated aqueous composition comprising activated water, wherein the activated water comprises reactive species generated by ionization of one or more gases; and hydrating a cocoa material with at least 50g of the activated aqueous composition/lOOg of the cocoa material to form a moistened cocoa material, wherein the cocoa material has not been alkalized and wherein the cocoa material comprises less than 20wt% of fat.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011] The drawings illustrate generally, by way of example, but not by way of limitation, various aspects discussed herein.

[0012] FIGs. 1A and IB show the effect on the L-value with addition of water and CP application time, respectively.

[0013] FIGs. 2A and 2B show the effect on a/b value with addition of water and CP application time, respectively.

DETAILED DESCRIPTION

[0014] Reference will now be made in detail to certain aspects of the disclosed subject matter, examples of which are illustrated in part in the accompanying drawings. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter.

[0015] This disclosure relates to a cocoa product and a process for producing the cocoa product using cold plasma (CP). The cocoa products are produced without the use of alkalizing agents or alkalization. The use of alkalizing agents or alkalizing agents can lead to an undesirable flavor and/or sensory feel. However, the alkalization of the cocoa materials is generally conducted to generate the desirable darker cocoa products. Alkalization is also often performed to increase the dispersibility of the powder in aqueous products such as drinkable chocolate as well to increase the pH and avoid quality issues in certain products (for example, curdling of chocolate milk).

[0016] The term “cocoa product” as used herein may refer to any product derived from the cocoa bean including, in particular, cocoa nibs, cocoa liquor (or cocoa mass), cocoa cake, and cocoa powder. In one aspect, the cocoa product is a cocoa powder. The cocoa powder may be of any type known to the skilled person. For instance, it may be a high-fat cocoa powder, with more than 12%, typically about 20-25%, cocoa butter by weight; a standard cocoa powder, with 10- 12% cocoa butter by weight; or a low-fat or fat-free cocoa powder, with less than 10% cocoa butter or less than 2% cocoa butter by weight, respectively. Preferably, the cocoa powder is a standard, low fat, or fat-free cocoa powder with about 10-12wt% of fat or less.

[0017] In some embodiments, the cocoa product is a cocoa powder, preferably a dark cocoa powder. The term “dark” used to describe the cocoa products of the present invention refers to the color of the cocoa product. In particular, it refers to the L value of the cocoa product as defined by the Hunter color coordinate scale or CIE 1976 (CIELAB) color system. The L-values as used herein are determined using a wet method measuring protocol as described below in Examples. A dark cocoa product will thus be a cocoa product with an L value that is preferably less than 20 when the L-value is measured using a wet method, preferably less than 18, more preferably less than 16, more preferably less than 14, more preferably less than 12, more preferably less than 10, for example between 2 and 20, preferably between 3 and 18, more preferably between 4 and 16, more preferably between 5 and 14, more preferably between 6 and 12, more preferably between 7 and 10, for instance, about 8. Advantageously, the method of the present invention may be used to produce so-called “black” cocoa products, having an L value of 20 or lower.

Cocoa Material

[0018] The cocoa product of the present invention will be described in more detail below. It can be obtained from an initial or starting cocoa material and applying a method as described herein to the starting cocoa material. The starting cocoa material may be selected from cocoa beans, cocoa nibs, cocoa liquor (or cocoa mass), cocoa cake, cocoa powder (including for example in agglomerated or pelletized form), and mixtures or two or more thereof. It may be (or may be derived from) cocoa beans of any type and any origin which may have undergone any one or more processing steps prior to the method of the present invention. For example, it may be (or may be derived from) cocoa beans with any degree of fermentation (including under-fermented and unfermented beans) which may have been sterilized or not and/or roasted or not.

[0019] In one aspect, the cocoa material can be a cocoa powder. Preferably, the starting material is a cocoa powder that has not been treated with alkali or an alkalizing agent. Advantageously, the cocoa material will be a natural cocoa material. A natural cocoa material is one that has not been treated with alkali or an alkalizing agent.

[0020] In one aspect, the starting cocoa material is a natural cocoa powder. By natural, it is meant that the cocoa material has not been alkalized or has been exposed to an alkali agent in the processing to form the cocoa powder. In one aspect, the starting cocoa material may be derived from roasted cocoa material, e.g., roasted cocoa nibs. Preferably, the starting cocoa material is a natural cocoa powder comprising less than 30wt% of fat, or preferably less than 20wt% of fat, or preferably less than 15wt% fat, or preferably between about 10-12wt% fat. The starting cocoa material is the cocoa material remaining after pressing of the cocoa mass (liquor) to separate the cocoa powder and the cocoa butter.

Method of Producing a Cocoa Product

[0021] The method for producing the cocoa product described herein includes a cold plasma process. Preferably, the method does not include the use of alkali or alkalizing agents in the method of producing the cocoa product.

[0022] In one aspect, the method of the present invention comprises: a. hydrating a starting cocoa material, preferably the cocoa material is a cocoa powder; and b. treating the cocoa material with cold plasma, wherein the cold plasma comprises reactive species generated by an ionization of one or more gases.

[0023] In another aspect, the method of the present invention comprises: a. treating water with cold plasma to generate activated water, wherein the activated water comprises reactive species generated by ionization of one or more gases; and b. hydrating a cocoa material with at least 50g of the activated water/lOOg of the cocoa material to form a moistened cocoa material, wherein the cocoa material has not been alkalized and wherein the cocoa material comprises less than 20wt% of fat.

A, Hydrating the Cocoa Material [0024] In one aspect, the starting cocoa material is hydrated with an aqueous composition, preferably with water, prior to treating with cold plasma. Advantageously, it had been found that alkalization may be avoided entirely in the disclosed method herein. As such, the method of the present invention preferably may not include any alkalizing agents and/or an alkalization step. As such, the cocoa material will preferably not be hydrated with an alkali solution. Instead, it will preferably be hydrated with a non-alkali aqueous composition, e.g., water and/or steam, without the presence of any alkalizing agents. The cocoa material may be hydrated with an acidic solution with a pH of less than 7.

[0025] In one aspect, the cocoa material may be hydrated with an alkaline solution having a pH of greater than 7, wherein the amount of alkali that is used can be less when used in conjunction with CP treatment of the starting cocoa material than with conventional alkalization of cocoa material without the use of CP treatment.

[0026] The aqueous composition may include at least 90wt% of water, or at least 95wt% water, or at least 96wt% water, or at least 97wt% water, or at least 98wt% water, or at least 99wt% water. In one aspect, the aqueous composition can include 99.9wt% water, or 100wt% water.

[0027] In one aspect, the aqueous composition includes water. The water can be, for example, tap water, cold plasma-activated water, treated water, e.g., demineralized water, plasma activated solution or any combinations thereof. The aqueous composition may be about pH 7 or less. The process will be described with the use of tap water as the aqueous composition, but it will be understood that other aqueous compositions may be used and are within the scope of this description.

[0028] In one aspect, the amount of aqueous composition, preferably water, added to the cocoa material can be at least 50g of water/lOOg cocoa material, or preferably at least 80g of water/lOOg cocoa material, or preferably at least 100g of water/lOOg cocoa material.

[0029] In one aspect, the amount of aqueous composition, preferably water, added to the cocoa material can be more than 5.0g of water/lOOg cocoa material, or preferably more than 10g of water/lOOg cocoa material, or preferably more than 20g of water/lOOg cocoa material, or preferably more than about 30g of water/lOOg cocoa material.

[0030] The amount of aqueous composition, preferably water, added to the cocoa material can be between about 50 g of water/lOOg cocoa material and 150g of water/lOOg cocoa material, or preferably between 50g of water/lOOg cocoa material and 125g of water/lOOg cocoa material, or preferably between 50g of water/lOOg cocoa material and 100 g of water/lOOg cocoa material, or preferably between about 80g of water/lOOg cocoa material and 110g of water/lOOg cocoa material, or preferably about 100g of water/lOOg cocoa material.

[0031 ] The ratio of water to cocoa powder by weight is at least 0.5 : 1 , or at least 1 :1. The ratio of water to cocoa powder is between 0.5: 1 to about 2: 1, or preferably between 0.8: 1 and about 1.2:1, or preferably about 1 : 1.

[0032] The cocoa material is placed in a vessel to carry out the process described herein. A variety of vessels may be used. Preferably, the vessel is a beaker/tank/mixing bowl and/or a continuous mixer. Exemplary vessels are disclosed in the Examples below.

[0033] The cocoa material may be hydrated by any of the means known in the art. The cocoa material, for example, may be hydrated by pouring water into a vessel with the cocoa material, spraying the water or steam onto the cocoa material in a vessel under agitation, or by use of any industrial “preconditioner” such as those in cereal pasta or extruded semi-finished snacks (pellet) production. Other means of hydrating the cocoa material are also within the scope of this description. In one aspect, the aqueous composition is poured into the starting cocoa material and mixed to form a moistened/wet composition. The moistened cocoa material can include a moisture content of at least 20wt%, or at least 25wt%, or at least 30wt%, or at least 35wt%, or at least 40wt%, or at least 45wt%, or at least 50wt% based on the weight of the moistened cocoa material. The moistened cocoa material can include a moisture content between about 20wt% and about 60wt%, or between 20wt% and 55wt%, or between 20wt% and 50wt%, or between 25wt% and

60wt%, or between 25wt% and 55wt%, or between 25wt% and 50wt%, or between 30wt% and

60wt%, or between 30wt% and 55wt%, or between 30wt% and 50wt%, or between 30wt% and

45wt%, or between 30 wt% and 40wt%, or between 35wt% and 60wt%, or 35wt% and 55wt%, or between 35wt% and 50wt%, or between 35wt% and 40wt%, or between 40wt% and 60wt%, or between 40wt% and 50wt%.

[0034] The cocoa material may be hydrated with the aqueous composition at a temperature between 10°C and 100°C, or preferably between 20°C and about 80°C, or preferably between 20°C and about 60°C, or preferably between 20°C and about 40°C, or preferably between 20°C and about 30°C, or preferably between 20°C and 25°C. Preferably, the hydration of the cocoa material is performed at ambient temperature.

[0035] In one aspect, the aqueous composition and the cocoa powder are combined to form a moistened starting cocoa material. The moistened cocoa material could be a slurry and/or a paste of the starting cocoa material. The moistened cocoa material has a wet sand/pasty consistency. The cocoa material may be combined, for example by manual or mechanical stirring of the cocoa material or by agitation, shaking of the vessel or in a fluidized bed. Preferably, the cocoa material is a homogeneously moistened cocoa material.

[0036] After hydration, the cocoa material may be, optionally, allowed to equilibrate with the water. Preferably the cocoa material is allowed to equilibrate for at least about 1 minute, or at least about 5 minutes before application of the cold plasma. Longer times are also within the scope of this method. Preferably, the equilibration is performed in a manner such that evaporation of the liquid is minimized or negligible over the equilibration time.

[0037] In one aspect, the cocoa material may, optionally, be pre-heated prior to hydration and/or during hydration. The preheating may increase the a/b value of the cocoa product after the CP treatment. The starting cocoa material may be preheated to between about 30°C and about 100°C, or between about 50°C and about 100°C, or between about 80°C and about 100°C. The preheating may be conducted for at least about 5 minutes, or at least about 15 minutes, or at least about 30 minutes.

[0038] In one aspect, the starting cocoa material is hydrated with an activated aqueous composition, preferably the activated aqueous composition comprises activated water. The activated water is treated with cold plasma as described herein prior to hydration of the cocoa material. The cocoa material may then be hydrated with the activated aqueous composition. The activated water includes the reactive species generated by cold plasma treatment. Advantageously, it had been found that alkalization may also be avoided entirely in the disclosed method herein.

B, Treatment of Cocoa Material with Cold Plasma

[0039] The process of the present invention comprises treating the cocoa material with cold plasma. Preferably, the cocoa material is hydrated, as described above, prior to contact with cold plasma, or more preferably, cocoa material is a moistened cocoa material when contacted with the cold plasma.

[0040] “Cold plasma” or “CP” as used herein includes a partially ionized gas comprising ions, electrons, ultraviolet photons and reactive neutrals such as radicals, excited and/or ground-state molecules. Cold plasma also referred to as non-thermal plasma (near the ambient temperature of 30°C-60°C), can be generated whether in both vacuum and atmospheric pressure conditions by applying energy to a neutral gas or a mixture of gases, which causes the ionization and the formation of active components. Cold plasma can be generated when a gas is in the vicinity of a strong electric field. Generation of cold plasma is known in the art can described, for example, in Shashi K Pankaj et al., Current Opinion in Food Sci, Vol. 16, 2017, Pages 49-52 and in Food Eng. Rev. Rao et al., 2023; 15: 86—112, incorporated herein by reference. [0041] The method comprises contacting the hydrated cocoa material with cold plasma generated by ionization of one or more gases. The one or more gases can include, for example, oxygen, nitrogen, argon, helium, carbon dioxide and/or combinations thereof. In one aspect, the gases include oxygen and nitrogen, air, compressed (dry) air and the like.

[0042] The ionization of the gases can generate reactive species that interact with the cocoa material, preferably hydrated cocoa material. Without being bound by theory, it is thought that hydration of the cocoa material enhances the mobility of the reactive species in the ionized gas or gas mixture and increases the interactions between the reactive species and the cocoa material. A variety of reactive species may be generated and depend on the gas and/or gases that are ionized. In one aspect, the reactive species can include ozone and/or nitrogen containing free radicals. The reactive species can also include HsO+, O+, O-~, OH , N2+), molecular species (03 (ozone), H2O2), and reactive radicals (O«, OH«, NO The amounts and/or concentration of the reactive species generated can depend on the different gas types and mixtures thereof, the configuration of the plasma reactor, the relative humidity. The amounts of the reactive species may also vary depending on the operating conditions such as power input, the extent of the treatment, gas pressure, and application method.

[0043] The reactive species can be transferred to the sample directly or indirectly, as well as by means of plasma-activated solutions (PAS), such as water. In the direct exposure method, the cocoa material is exposed to the plasma discharge itself, and interactions between the cocoa material and the reactive species can be maximized.

[0044] Indirect exposure can include the transfer of produced plasma via the flow of the feed gas onto the surface, so the treatment surface can be separated from plasma-generating electrodes. Indirect exposure can also include plasma-activated aqueous compositions, e.g., plasma activated water, wherein the water is independently treated with cold plasma to generate activated plasma activated water. The plasma activated water can subsequently be used for hydration of the cocoa materials and described in the formulations herein.

[0045] In one aspect, the starting cocoa material is hydrated with an activated aqueous composition, preferably the activated aqueous composition comprises activated water. The activated water is treated with cold plasma as described herein prior to hydration of the cocoa material. The cocoa material may then be hydrated with the activated aqueous composition. The activated water includes the reactive species generated by cold plasma treatment. Advantageously, it had been found that alkalization may also be avoided entirely in the disclosed method herein. [0046] The method can include tuning of a variety of operational conditions. By “tuning” it is meant that the parameters for conducting the CP treatment are adjusted and/or varied to obtain the desired cocoa product profile. Tuning parameters can include adjusting the type of ionized gas or gas mixtures, flow rate of the gas or gas mixtures. Tuning parameters can also include varying or adjusting the operational conditions of the treatments. The operational conditions can influence the effectiveness of the CP treatment. Operational conditions can be related to a power supply such as voltage and frequency. Operational conditions can also include exposure time, distance from the nozzle to the cocoa material and temperature of application. The power input used to generate the cold plasma can vary. Generally, an increase in power input produces electrons with higher density and can result in an increase in the concentration of reactive species and plasma activity.

[0047] In one aspect, the method includes tuning the CP treatment by varying the concentrations of the gases in a mixture of gases. In one aspect, the mixture of gases can include oxygen and nitrogen. The percentage of oxygen in the gas mixture can be between about 0wt% and 100wt%, or preferably between 10wt% and 80wt%, or preferably between 10wt% and 50wt%, or preferably between 10wt% and 30wt%, or preferably between 20wt% and 25wt%, or preferably between 22wt% and 24wt% in the mixture of gases. The percentage of nitrogen in the gas mixture can be between about 0wt% and 100wt%, or preferably between 20wt% and 90wt%, or preferably between 50wt% and 90wt%, or preferably between 70wt% and 80wt%, or preferably between 70wt% and 78wt%, or preferably between 74wt% and 76wt% in the mixture of gases.

[0048] In one aspect, the flow rate of the gas can be between about 20 liters/min (1/min) and about 80 1/min, or preferably between about 30 1/min and about 70 1/min, or preferably between about 30 1/min and about 60 1/min, or preferably between about 35 1/min and about 55 1/min. In one aspect, the velocity of the gas can be between about 5 meters/sec (m/sec) and about 25 m/sec, or preferably between about lOm/sec and about 20 m/sec, or preferably between about 10 m/sec and about 15 m/sec. The diameter of the nozzle can vary and can be between about 0.5 cm and about 1.5 cm, or between about 0.7 cm and about 1.2cm, or between about 0.8 cm and about 1.0 cm, or about 0.9cm.

[0049] In one aspect, the method includes tuning the CP treatment by varying the power applied for ionization of the gas and/or gases in the gas flow to generate the reactive species. The power applied to the gas flow can vary between O.lkW and about 100 kW, or preferably between O. lkW and 50 kW, or preferably between O.lkW and 30 kW, or preferably between O. lkW and 10 kW, or preferably between O.lkW and 5 kW, or preferably between O.lkW and 2 kW, or preferably between 0.5kW and 1.5 kW, or preferably about 1 kW.

[0050] In one aspect, the method includes tuning the CP treatment by varying the voltage applied for ionization of the gas and/or gases in the gas flow to generate the reactive species. The voltage applied to the gas flow can vary between O.lkV and about 100 kV, or preferably between IkV and 50 kV, or preferably between 5 kV and 30 kV, or preferably between 5 kV and 20 kV, or preferably about 10 kV.

[0051 ] In one aspect, the method includes tuning the CP treatment by varying the frequency of the power applied for ionization of the gas and/or gases in the gas flow to generate the reactive species. The frequency applied to the gas flow can vary between 1 kHz and about 100 kHz, or preferably between 1kHz and 50kHz, or preferably between 10kHz and 50kHz, or preferably between 20kHz and 50kHz, or preferably between 30kHz and 50kHz, or preferably about 40kHz. [0052] In one aspect, the method includes tuning the CP treatment by varying the distance from the nozzle to the sample of cocoa material. The distance can vary between 0.1 cm and about 20 cm, or preferably between 0.1cm and 10cm, or preferably between 0.1 cm and 10 cm, or preferably about 7cm. Without being bound by theory, it is thought that shorter the distance, the better the performance. However, there are practical material handling limitations to how close the powder can be placed on the electrodes.

[0053] In one aspect, the method includes tuning the CP treatment by varying the exposure time or duration of the cocoa material to the reactive species in the ionized gases. The time can vary between 10 seconds and about 20 minutes, or preferably between 15 seconds and 15 min., or preferably between 15 sec and 10 min, or preferably between 15 sec and 5 min.

[0054] The cold plasma treatment of the cocoa material may be conducted at atmospheric pressure or under vacuum. Preferably, the cold plasma treatment of the cocoa material is conducted at atmospheric pressure.

[0055] The temperature at the initiation of the cold plasma treatment of the cocoa material may be between 10°C and 100°C, or preferably between 15°C and about 80°C, or preferably between 15°C and about 60°C, or preferably between 15°C and about 40°C, or preferably between 15°C and about 30°C. The temperature of the cocoa material can increase during the cold plasma treatment. The temperature of the cocoa material during conduction of the cold plasma treatment can be between 10°C and 150°C, or preferably between 15°C and about 90°C, or preferably between 15°C and about 80°C. [0056] The method can include treating the cocoa material in a batch process, a continuous process or a combination thereof. In one aspect, the cocoa material is treated with CP in a batch process.

[0057] The cocoa material may be agitated during the cold plasma treatment, for example by manual or mechanical stirring of the cocoa material or by agitation or shaking of the vessel. In one aspect, the cocoa material is homogeneous with continuous stirring during the cold plasma treatment process. The cocoa material may also be made homogenous by the use of fluidized bed. [0058] The cocoa material will preferably be in continuous or substantially continuous contact with the reactive species throughout the CP treatment, or for a substantial portion thereof.

[0059] In one aspect, the method includes treating the cocoa material with CP treatment for decreasing the L-value of the treated product, wherein the method excludes treating the cocoa material with any other step(s) or processes that decrease the L-value of the cocoa. In other words, the method for decreasing the L-value of the cocoa product consists essentially of the CP treatment.

[0060] In one aspect, the method comprises processing cocoa material, preferably cocoa nibs and/or cocoa beans. The method comprises milling the cocoa material, wherein the cocoa material is not alkalized to produce a non-alkalized cocoa liquor. The method further comprises pressing the non-alkalized cocoa liquor to generate non-alkalized cocoa powder and non-alkalized cocoa butter. The method further comprises using the non-alkalized cocoa powder in any of the methods described herein.

[0061] The non-alkalized cocoa butter may be further processed by conventional further refining, as needed. Advantageously, the non-alkalized cocoa butter is not degraded due to lack of exposure to alkalizing conditions and/or alkalizing agents.

[0062] After completion of the CP treatment steps, and removal of any residual excess aqueous composition, the CP treated cocoa product may be recovered. Alternatively, the cocoa material may be subjected to one or more further processing steps.

Further Processing

[0063] Optional further processing steps include drying and/or milling the cocoa material.

[0064] Preferably, after completion of the CP treatment and any other processing steps, the cocoa material is dried, preferably by vacuum drying. The vacuum drying may be conducted at a pressure of less than 1 bar, preferably less than 0.5 bar, preferably less than 0.0 bar, more preferably less than -0.5 bar, more preferably about -0.8 bar. The cocoa material may be dried for a duration of at least 10 minutes, preferably at least 15 minutes, more preferably at least 20 minutes. The cocoa material may be stirred during drying at a rate of at least 5 rpm, preferably at least 10 rpm, more preferably at least 15 rpm, more preferably at least 20 rpm. The moisture content of the cocoa material after the reactor is preferably reduced to 35% or less, more preferably to 30% or less, more preferably to 29% or less, more preferably to 28% or less, more preferably to 27% or less, more preferably to 26% or less. The moisture content of the cocoa material after the roasting is preferably reduced to 5% or less, more preferably to 4% or less, more preferably to 3% or less, more preferably between 2% and 3%. All moistures contents are presented as % w/w. [0065] Drying can also be achieved using other techniques known in the art. This may include simple air drying at ambient temperature, drying at elevated temperatures, for example at temperatures above 105°C.

[0066] The cocoa material may also be milled and/or ground. For instance, it may be subjected to one or more milling and/or grinding steps to reduce its particle size. Advantageously, the cocoa material will be milled and/or ground to a particle size of less than 100pm, more preferably to less than 50pm, more preferably to less than 40pm. For example, the cocoa material may be milled to 20-40pm.

[0067] Other possible processing steps will be well known to a person skilled in the art, and will readily be adapted depending on the nature of the starting cocoa material and the desired end product. For instance, if the cocoa material comprises cocoa beans/and or cocoa nibs and the desired end product is a cocoa powder, the process of the present invention may also comprise a pressing step (to separate cocoa solids from cocoa butter) and one or more optional milling/grinding steps (to further reduce the particle size of the cocoa solids).

[0068] Preferably, cocoa powder will be used as the starting material for the method of the present invention. They will be CP treated, as described above.

[0069] Thus, for example, the method of the present invention may include the following steps: hydrating the cocoa material, such as cocoa powder, treating the cocoa material with a CP treatment process, wherein the process includes tuning the CP treatment to generate a cocoa product with the desired L value and/or “a/b” ratio. The process may include optionally drying the cocoa material. The process includes recovering a cocoa product, preferably a dark cocoa powder with a desirable sensory profile.

[0070] Advantageously, dark cocoa products may be recovered from the process of the present invention, without the use of alkalizing agents. Accordingly, the process of the present invention does not include an alkalization step, or the addition or use of any alkalizing agents.

Cocoa Products [0071] The present invention also provides cocoa products, preferably dark cocoa products, obtained by, or obtainable by, a process as described herein. Cocoa products of the present invention will advantageously have a desirable color profile. The color of cocoa powders can be expressed using the Hunter color coordinate scale or CIE 1976 (CIELAB) color system which uses three coordinates (or values) to define a powder’s color profile. The L-values are based on the wet method determination described in the Examples below. The L coordinate represents lightness and can assume values between 0 (for black) and 100 (for white); the a value represents the red/green component (a>0); and the b value represents the yellow/blue component (b>0). The quotient of “a” over “b” represents the redness of the product. Further information on the CIELAB color system can be found, for example, in “Defining and Communicating Color: The CIELAB System” (2013 - Sappi Fine Paper North America) and an example of how to measure the “L", “a” and “b” values is described under Methodology below.

[0072] Cocoa products obtainable by the method of the present invention advantageously have a darker color than the corresponding starting cocoa material. Preferably, they will also have a darker color than a cocoa product obtained from the same starting material but without the cold plasma process of the present method. For example, cocoa products obtained by the method of the present invention will be darker than cocoa products obtained from the same starting material and processed in the same way except for the omission of the cold plasma process.

[0073] As used herein, the term “darker” refers to a product having a lower L value than the product to which it is being compared. Preferably, the darker product will have an L value at least 1 point lower, even more preferably at least 2 points lower, than the product to which it is being compared.

[0074] Advantageously, cocoa products obtainable by the method of the present invention will be “dark” cocoa products, that is cocoa products with an L value of less than 20, preferably less than 18, more preferably less than 16, more preferably less than 14, more preferably less than 12, more preferably less than 10, for example between 4 and 20, preferably between 5 and 18, more preferably between 6 and 16, more preferably between 8 and 14, such as 8-13 or 8-12 or 8-11 or 8-10.

[0075] Preferably, the “a” value of the cocoa products obtainable according to the method of the present invention will be in the range of 1.0 to 12.0, preferably 2.0 to 11.0, more preferably 3.0 to 10.0. For example, powders obtainable according to the present invention, with L values below 20, will typically have an “a” value of 3.0 to 6.0, preferably of 4.0 to 5.0; and powders with L values from 10 to 18 will typically have an “a” value of 8.0 to 10.0, preferably of 8.5 to 9.5. [0076] The “b” value of the cocoa products obtainable according to the method of the present invention will preferably be in the range of 1.0 to 10, more preferably 2.0 to 9.0, more preferably 3.0 to 8.0. For example, powders obtainable according to the present invention, with L values below 20, will typically have a “b” value of 1.0 to 5.0, preferably of 2.0 to 4.0; and powders with L values from 10 to 18 will typically have a “b” value of 5.0 to 9.0, preferably of 6.0 to 8.0.

[0077] Normally, to produce cocoa powders like those of the present invention, the degree of alkalization required results in a high pH and an alkaline flavor profile. Advantageously, with the method of the present invention, it is possible to produce cocoa powders with much lower alkalinity (since no alkalization is required) and therefore with improved flavor relative to alkalized cocoa powders of equivalent darkness. Thus, the cocoa products of the present invention will advantageously have a pH that is lower than a corresponding product made from the same starting material and with the same L value but obtained by traditional alkalization techniques. The cocoa products of the present invention preferably have a pH of 9.0 or less, more preferably of 8.0 or less, more preferably of 7.0 or less, more preferably of 6.0 or less, for example between 3.0 and 9.0, preferably between 3.0 and 8.0, more preferably between 3.0 and 7.0, more preferably between 4.0 and 6.0, for example between 4.5 and 6.0 or between 4.5 and 5.5. This results in improved taste relative to highly alkalized cocoa products.

[0078] In one aspect, the present invention therefore provides cocoa products, such as cocoa powders, which have an L value of less than 20; a ratio of a/b greater than 1, and a pH of less than 7.0. Advantageously, the cocoa products of the present invention are natural cocoa products. A natural cocoa product is one that has not be treated with alkali or alkalizing agents. Thus, the present invention preferably provides natural cocoa products which have an L value of less than 20; a ratio of a/b greater than 1, and a pH of less than 7.0.

[0079] In one aspect, the present invention therefore provides cocoa products, such as cocoa powders, which have a desirable low ash content. The increase in ash content of the cocoa product is negligible compared to the ash content of alkalized cocoa powder.

[0080] In one aspect, the present invention therefore provides cocoa products, such as cocoa powders, which have reduced acidic fractions. The reduction in the acidic fractions can be due to the CP treatment.

[0081 ] Conventional complementary ingredients can be included with the samples to be tested if desired. For example, a cocoa powder sample may be mixed with sweetening agents such as natural sweeteners (including, for example, sugars such as sucrose, sugar alcohols such as xylitol, sorbitol, erythritol), artificial sweeteners (such as, for example, saccharin and aspartame, sodium cyclamate, and mixtures of sodium cyclamate and saccharin). Other examples include acesulfame- k, alitame, and sucralose. Mixtures can be used. Milk powders also can be used (including fullfat, semi-skimmed or fat-free milk powders). Other examples of complementary ingredients include vitamins, trehalose, colors, flavors, and bulking agents. The powder mixtures may then be dissolved in a solvent such as water or milk. Complementary ingredients can be selected to be compatible with the solvent.

[0082] In one aspect, the present invention also provides non-alkalized cocoa liquor and/or non-alkalized cocoa butter. The non-alkalized liquor and/or butter can have improved taste compared to cocoa liquor and/or cocoa butter derived from alkalized cocoa materials. The butter can have reduced darkening or flavor deterioration due to lack of exposure to alkali agents.

Food and Beverage Compositions

[0083] The cocoa products of the present invention or obtained according to the method of the present invention, can be used on their own or mixed with other cocoa products to produce food and beverage compositions with tailored color and flavor profiles. Advantageously, they can also be used to decrease costs, since smaller quantities can be used to achieve the same color impact as larger quantities of standard cocoa products. Thus, the present invention also provides food and beverage compositions comprising a cocoa product, or obtainable by a method, as described herein. These may include, by way of illustration only, milk, dark, and white chocolate and compound compositions (for use, amongst others, in confectionary, as bars, in truffles and pralines, or as inclusions, coatings, or fillings), drinking chocolate, flavored milks (dairy and nondairy), flavored syrups, bakery products (such as cakes, cookies and pies), diet bars and meal substitutes, sports and infant nutrition, ice-cream products, dairy products, puddings, mousses, sauces, and breakfast cereals. Methods of manufacturing these food and beverage compositions are also part of the present invention.

[0084] Representative features of the present invention are set out in the following clauses, which stand alone or may be combined, in any combination, with one or more features disclosed in the text of the specification.

[0085] The present invention is as set out in the following clauses:

[0086] Clause 1 : A process for producing a cocoa product, comprising the steps of: a. hydrating a cocoa material with at least 50g of an aqueous composition/ 100g of the cocoa material to form a moistened cocoa material, wherein the cocoa material has not been alkalized and wherein the cocoa material comprises less than 20wt% of fat; and b. treating the moistened cocoa material with cold plasma (CP), wherein the cold plasma comprises reactive species generated by ionization of one or more gases and wherein the cocoa material is treated with the CP for at most 15 minutes.

[0087] Clause 2: The process according to clause 1 wherein the cocoa material of step (a) is cocoa powder.

[0088] Clause 3 : The process according to any one of the preceding clauses, wherein the cocoa material is hydrated at an amount of at least 80g of the water/lOOg of the cocoa material, preferably at about 100g of the water/lOOg of the cocoa material.

[0089] Clause 4: The process according to any one of the preceding clauses, wherein the aqueous composition comprises tap water, plasma activated water or combinations thereof.

[0090] Clause 5: The process according to any one of the preceding clauses, wherein the one or more gases comprises argon, helium, nitrogen, oxygen, air, compressed air and combinations thereof, preferably the one or more gases comprises compressed air.

[0091] Clause 6: The process according to any one of the preceding clauses, wherein the reactive species comprise ozone and/or nitrogen containing free radicals.

[0092] Clause 7 : The process according to any one of the preceding clauses, wherein the cocoa product comprises a L-value less than the starting cocoa material.

[0093] Clause 8: The process according to any one of the preceding clauses, wherein the treating the cocoa material comprises applying power to generate the reactive species in the cold plasma, preferably the power is between 0.1 and lOOkW and wherein the frequency of the applied power is between 30 KHz and 50 KHz.

[0094] Clause 9: The process according to any one of the preceding clauses, wherein a nozzle discharges the cold plasma directed to the cocoa material, wherein the distance from the nozzle to the cocoa material is between 1cm and 10 cm.

[0095] Clause 10: The process according to any one of the preceding clauses, wherein the cocoa material is treated with the cold plasm for a duration of at most 10 minutes, preferably between 15 seconds and about 5 minutes.

[0096] Clause 11 : The process according to any one of the preceding clauses, wherein the treated cocoa product has a L-value of less than 19, preferably less than 18.

[0097] Clause 12: The process according to any one of the preceding clauses, wherein the amount of hydration is increased to decrease the L value of the cocoa product.

[0098] Clause 13: The process according to any one of the preceding clauses, wherein the intensity of the treating is increased to increase the “a” value. [0099] Clause 14: The process according to any one of the preceding clauses, wherein the intensity of the treating is increased by increasing the power applied to generate the cold plasma, decreasing the distance between the nozzle and the cocoa material, increasing the duration of the treating, increasing the number of reactive species in the cold plasma and combinations thereof. [0100] Clause 15: A dark cocoa product obtained by, or obtainable by, the process of any one of the preceding clauses.

[0101] Clause 16: A process for producing a cocoa product, comprising the steps of: a. treating an aqueous composition comprising water with cold plasma to generate an activated aqueous composition comprising activated water, wherein the activated water comprises reactive species generated by ionization of one or more gases; and b. hydrating a cocoa material with at least 50g of the activated aqueous composition/lOOg of the cocoa material to form a moistened cocoa material, wherein the cocoa material has not been alkalized and wherein the cocoa material comprises less than 20wt% of fat.

[0102] The invention is further described in detail by reference to the following experimental examples. These examples are provided for purposes of illustration only and are not intended to be limiting unless otherwise specified. Thus, the invention should in no way be construed as being limited to the following examples, but rather should be construed to encompass any and all variations which become evident as a result of the teaching provided herein.

EXAMPLES

Example 1- Use of cold plasma on cocoa material

Methods and Materials:

[0103] Colour Measurement method

[0104] All color values measured in the below examples were measured according to the following methodology.

[0105] A, Wet Method: 5,00 ± 0,01 gram cocoa powder was measured in a 100 ml beaker; 15,0 ml tap water of minimal 50 °C was added to the cocoa powder; the solution was directly stirred until a homogeneous slurry was obtained without lumps; the contents of the 100 ml beaker were then cooled to room temperature by letting it rest for 15 minutes; the contents of the beaker were then stirred again and the slurry without lumps was poured into the optically neutral petri dish making sure that the entire petri dish is covered; the petri dish was placed in the middle of the measuring opening and immediately the color value was measured using a “Hunter Lab ColorFlex EZ” colorimeter, with measurement settings: Illuminant C, 2° standard observer. The L, a and b- values were measured on the calibrated color meter - the Hunter L value are recorded to 2 decimal, the a and b values to 2 decimals and the a/b value is calculated and recorded to 2 decimals. Note: after calibration of the color meter, the reference sample was measured first to check matrix fluctuations, followed by non-reference samples.

[0106] B, Dry Method: 5,00 ± 0,01 gram cocoa powder was measured and placed into an optically neutral petri dish making sure that the entire petri dish is covered; the petri dish was placed in the middle of the measuring opening and immediately the color value was measured as described above for the wet method.

[0107] Raw material: Cocoa powder- The cocoa powder was from cocoa beans grown in Wes Africa having a blend of Ivory Coast and Ghana beans. Cocoa material was a natural cocoa powder with about 10-12% fat.

[0108] Cold plasma method:

[0109] Type of apparatus: Custom made atmospheric jet plasma system capable of the following specifications.

Distance from Nozzle: 7cm

Voltage: 10 KV

Frequency: 40 KHz

Power: 600W

Ionized gas: Dry air

Gas flow rate: 10-15 m/s is the gas velocity Flow rate is in between 36-54 1/min.

Jet Nozzle diameter: 0.9 cm.

[0110] Starting material: 10-12% fat Natural cocoa powder (same lot for all cells)

[0111] Description: For each cell or run (including controls), 10g of natural cocoa powder was used. The cocoa powder was uniform, i.e., with no agglomerates.

[0112] Analysis:

[0113] All cells well be analyzed for color using a wet method.

[0114] Table 1 below shows the contents of the cells with or without CP.

[0115] Experimental matrix: Table 1

¹ Air dried to standard moisture, to demonstrate color differences are not due to hydration, but the combination of hydration and cold plasma application.

[0116] FIGs. 1 A and IB use the dry color measurement method and are the result of a general linear model analysis, meaning the effect of water content and CP application have been separated. This allows the reader to observe the effect of the amount of water addition (FIG. lA/left) irrespective of the cold plasma application time used, and vice versa in FIG. IB/right. In other words, the effect of each variable has been separated. Similarly, FIGs. 2A and 2B show the effect of the amount of water addition and CP application time on the a/b values.

[0117] FIGs. 1 A and IB show that increasing the water addition rate (expressed as % of solids, so 100% addition rate = 1 : 1 powder: water ratio), reduces the L value (becomes darker). The decrease in L-value occurs after 15 seconds of CP. FIGs. 2A and 2B show a small effect on redness with moisture increase, but a leveling out of the effect with CP application time. The trends are opposite to L, suggesting that darkness and redness being somewhat independent (moisture affects L only). A drop in L-value can be selected by adding moisture independently from the redness.

[0118] In this document, the terms “a,” “an,” or “the” are used to include one or more than one unless the context clearly dictates otherwise. The term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. All publications, patents, and patent documents referred to in this document are incorporated by reference herein in their entirety, as though individually incorporated by reference. In the event of inconsistent usages between this document and those documents so incorporated by reference, the usage in the incorporated reference should be considered supplementary to that of this document; for irreconcilable inconsistencies, the usage in this document controls.

[0119] Values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range were explicitly recited. For example, a range of “about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement “about X to Y” has the same meaning as “about X to about Y,” unless indicated otherwise. Likewise, the statement “about X, Y, or about Z” has the same meaning as “about X, about Y, or about Z,” unless indicated otherwise.

[0120] Unless expressly stated, ppm (parts per million), percentage, and ratios are on a by weight basis. Percentage on a by weight basis is also referred to as wt% or % (wt) below.

Claims

CLAIMS What is claimed is:

1. A process for producing a cocoa product, comprising the steps of: a. hydrating a starting cocoa material with at least 50g of an aqueous composition/lOOg of the starting cocoa material to form a moistened cocoa material, wherein the starting cocoa material has not been alkalized and wherein the starting cocoa material comprises less than 25wt% of fat, the aqueous composition comprising at least 90wt% of water; and b. treating the moistened cocoa material with cold plasma (CP), wherein the cold plasma comprises reactive species generated by ionization of one or more gases and wherein the moistened cocoa material is treated with the CP for between 15 seconds and 15 minutes.

2. The process according to claim 1 wherein the starting cocoa material is cocoa powder.

3. The process according to any one of the preceding claims, wherein the aqueous composition is water, and wherein the moistened cocoa material comprises at least 50g of the water/lOOg of the starting cocoa material, preferably about 80g of the water/lOOg of the starting cocoa material.

4. The process according to any one of the preceding claims, wherein the aqueous composition comprises tap water, plasma activated water or combinations thereof.

5. The process according to any one of the preceding claims, wherein the one or more gases comprises argon, helium, nitrogen, oxygen, air, compressed air and combinations thereof, preferably the one or more gases comprises compressed air.

6. The process according to any one of the preceding claims, wherein the reactive species comprise ozone and/or nitrogen containing free radicals.

7. The process according to any one of the preceding claims, wherein the cocoa product comprises a L-value less than the starting cocoa material.

8. The process according to any one of the preceding claims, wherein the treating the cocoa material comprises applying power to generate the reactive species in the cold plasma, preferably the power is between 0.1 and lOOkW and wherein the frequency of the applied power is between 30 KHz and 50 KHz.

9. The process according to any one of the preceding claims, wherein a nozzle discharges the cold plasma directed to the cocoa material, wherein the distance from the nozzle to the cocoa material is between 1cm and 10 cm.

10. The process according to any one of the preceding claims, wherein the cocoa material is treated with the cold plasma for a duration of at most 10 minutes, preferably between 15 seconds and about 5 minutes.

11. The process according to any one of the preceding claims, wherein the treated cocoa product has a L-value of less than 19, preferably less than 18.

12. The process according to any one of the preceding claims, wherein the amount of hydration is increased to decrease the L value of the cocoa product.

13. The process according to any one of the preceding claims, wherein the intensity of the treating is increased to increase the “a” value.

14. The process according to any one of the preceding claims, wherein the intensity of the treating is increased by increasing the power applied to generate the cold plasma, decreasing the distance between the nozzle and the cocoa material, increasing the duration of the treating, increasing the number of reactive species in the cold plasma and combinations thereof.

15. A cocoa product obtained by, or obtainable by, the process of any one of the preceding claims, wherein the cocoa product comprises an L value of less than 20, a ratio of a/b greater than 1, and a pH of less than 9.0, preferably a pH of less than 8.0.