AU5787101A - Method and arrangement for processing cocoa mass; resulting products - Google Patents

Description

AUSTRALIA

Patents Act COMPLETE SPECIFICATION

(ORIGINAL)

Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority Related Art: 0 00 00 0 0.

Name of Applicant: Cargill, Incorporated Actual Inventor(s): lan C Purtle, Todd W Gusek Address for Service: PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Invention Title: METHOD AND ARRANGEMENT FOR PROCESSING COCOA MASS; RESULTING PRODUCTS Our Ref 649935 POF Code: 1415/229462 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): 1A METHOD AND ARRANGEMENT FOR PROCESSING COCOA MASS; RESULTING PRODUCTS This application is a divisional of Australian Patent Application 61436/98 (733327) the entire content of which is incorporated herein by reference.

Field of the Invention The present invention relates to processing of cocoa. It particularly concerns processing cocoa mass to generate separated cocoa powder and cocoa butter, both at desirable quality levels and in desirable yields.

Background of the Invention Cocoa beans may be processed into cocoa butter and cocoa powder.

Cocoa butter represents a portion of the fat content isolated from the cocoa beans. The cocoa powder represents remaining solids, after processing to recover cocoa butter.

Cocoa butters are widely utilized food additives. For example, cocoa butter is used in the production of chocolate. Cocoa powder is also used as a food additive for flavor and color, for example, to produce chocolate flavored milk, cake mixes and brownie mixes.

In general, cocoa beans are harvested in tropical countries. Beans from different regions do provide somewhat different tastes of characteristics. For example, for chocolate, many European manufacturers prefer beans from Ghana and Nigeria (Ivory Coast) because of their flavor. For top quality •chocolate, South American, West Indian and other so-called flavor beans are often used. The pressing industry may select beans containing fat with higher melting points, such as those obtained from Malaysia. Regardless of the source, the same general processing techniques have been used.

In typical processing, the cocoa beans are harvested within a husk.

Typically, the beans are dried in the fields, and dehusked. The beans are then W:6skakinspedes~dlv 733327.doc WO 98/34496 PCT[US98/02106 2 subjected to various forms of heating, for example to intense infrared treatment, to pop the shells and in some instances for microbiological control. The shelled beans are generally referred to as cocoa nibs. The nibs are separated from the shells, for processing.

In typical processing operations, the nibs are roasted and in some instances subjected to dutching (alkali treatment or alkalization). The nibs are then ground, :ften with significant generation of heat.

The grinding is generally done to provide a fineness in the mass such that there will be no grittiness felt in the mouth, when eating resulting products containing the cocoa powder. The grinding is normally carried out in a series of mills; for example, pre-grinding to a size of less than 300 microns using a harmmer mill, blade mill, disc mill or ball mill, followed by fine grinding using a triple disc mill or staged agitator ball mills. In general, sufficient grinding is conducted so that the resulting cocoa S 20 powder, after separation of the cocoa butter, will have a parzicle size of less than I wz. retained on a 200 micron sieve and less than 30% retained on a 30 micron sieve. typical average particle size would be between 2 microns and 20 microns.

Some manufacturers do not grind the nibs sufficiently to achieve this fineness, but rather engage in further refinement with later processing steps.

In general, the mass which results from grinding of the nibs is referred to as "cocoa mass" or "cocoa 1iquor". At room temperature, it is a thick solid mass; however, when heated above the melting point of the fat it forms a viscous, flowable slurry. Typical cocoa liauors contain about 50-58% fat and 42-50% powder (or remaining solids), by weight. The moisture content of cocoa liquor is generally at a maximum of about The pH is typically within a range of 5.2-6.0. The WO 98/34496 PCT/US98/02106 3 shell content, by weight, is generally no more than about 1.75%. The fat content of cocoa liquor is that portion generally referred to as "cocoa butter", after it has been separated from a remainder of the mass.

In general, about 30% of the world cocoa bean crop is converted into cocoa mass in a country where it is grown. This material is sometimes referred to as "original" liquor ormass. In later processing, such mass is not necessarily used alone, but sometimes is blended with mass or liquor from other sources.

In conventional "press" processing, cocoa liquor is mechanically pressed, to physically "squeeze." a ortion of the fat out. In some instances the mass may be washed, to modify flavor or color. Generally up to about 80-85% of the fat content (of the 50-58%) can be removed from the cocoa mass, by mechanical pressing.

This typically leaves a cake comprising about 10-20% butter (often 11-12%), by weight, the remaining comprising cocoa powder. Cocoa powder with a fat 20 content of about 10% or below is often referred to as low-fat cocoa powder. The fat which is isolated by mechanical pressing is typically called "press butter".

The time and pressure it takes to remove the fat by pressing, to generate isolated press butter, 25 increases substantially when the process is practiced to reduce the residue cake from about 20% fat content to about 11% fat content or lower. To reduce the fat content from 20% to about 10% may require twice as long of a processing (pressing) operation, as to reduce to 20%. Indeed, it may not be practical or even possible to get to less than about 5-9% fat, by weight, in the resulting cocoa cake, by conventional pressing techniques.

According to one report, whole cocoa beans have been processed without previous deshelling by continuous expeller techniques. The expeller cake and WO 98/34496 PCTIUS98/0206 4 various resulting cocoa waste materials would then apparently be defatted by means of solvent extraction.

The defatted residues from such a process, however, would be unlikely to be useful as food products, since they would contain large particles, such as shells and miscellaneous ditrious associated with the shells, which provide an unpleasant feel to the product. The isolated fat from such sources (which may include fats from portions of the cocoa bean other than just nibs) would also likely be of inferior quality.

Herein the term "cocoa butter" will be used to refer to the fat which is isolated from cocoa mass, during a separation process. Cocoa butter, which primarily comprises triglycerides of acids such as oleic acid, palmitic acid, and stearic acid, is a relatively valuable vegetable oil commodity. It is somewhat unique among vegetable oils, because of the combination cf its taste, mouth feel and melt characteristics. These, ir.

part, result from crystalline forms of some of its 2C constituents, which provide for a sharp melting point just below body temperature. Also, the heat required to melt the crystals in cocoa butter results in a characteristic "cooling" sensation in the mouth, a :"highly desired quality of cocoa butters when used as food additives.

.The remaining mass resulting from pressing of the cocoa mass, is referred to herein as "cocoa cake".

As indicated above, with conventional press processing, the cocoa cake comprises about 10-20% cocoa butter, by weight. Again, this represents the (practical) maximum extent to which typical, conventional, mechanical pressing operations can remove cocoa fat from the cocoa liquor.

Typically, the resulting cocoa cake (after butter recovery) also comprises a useful commodity. It is generally ground into a powder and packaged for a WO 98/34496 PCTUS98/02106 variety of uses. For example, cocoa powder made in this manner is used as a flavorant (and for color) in such materials as cake mixes, frostings, cookies, chocolate and drink mixes.

Conversion of the cocoa cake to the cocoa powder is no trivial matter. Due to the fat content, typically 10% or greater, the cocoa cake after pressing will be a clumped-together mass. To convert it to a powder, it must be cooled sufficiently and maintained sufficiently cool, while it is broken up; and, in some instances it must be.further ground and sieved, again without generation of sufficient heat to reclump, due to the fat content. In general it must be maintained below about 27-30°C, or the fat content will tend to melt and generate clumping.

Cocoa beans have been processed by pressing generally in the manner described above for many decades. As indicated, the two principal commodities obtained are: the cocoa butter isolated from the 20 pressing steps; and, the cocoa powder, typically containing about 10-2C, cocoa fat by weight In some applications, the fat content (10-20%) of the cocoa powder has been found undesirable. These are applications in which it is desired that the 25 ultimate food product which is manufactured contain relatively low amounts of various added fats or oils.

In recent years, then, processes of reducing the fat content of cocoa powder have been examined. In general, fat-free cocoa powders, cocoa powders containing no more than about 0.5% by weight cocoa butter, have Sbeen generated by extracting the cocoa powder obtained after pressing, via a supercritical carbon dioxide extraction. The supercritical extraction reduces the residual fat content of the cocoa powder, leaving the powder defatted.

6 U.S. Patent No. 5,405,633 (Heidlas et al.) discloses a process for the extraction of fats and oils from natural products such as plant, animal or microbial starting materials. According to the disclosure, the extraction is performed using liquid propane at a cressure between 10 to 30 bar and 100 to 550C.

?CT A=clication Publication No. WO 94/15483 (Franke) discloses a solvent extraction process which includes contacting a carbonaceous material with a normally caseous solvent within an extraction zone that is maintained at temperatures and pressures that cause :he solvenr to remain a liquid during the extraction.

Preferred solvents include propane, iso-butane, and mixtures thereof.

E? Patent 0 711 508 (Heidlas et al.) discloses a crocess for extracting natural aromas from natural substances containing fat and oil using compressed casses. The disclosed process entails two steps: (1) extracting the natural substance with liquid propane and/or butane at a temperature 70°C and a pressure of 599 bar; and subsequently extracting the natural substance using compressed carbon dioxide at a temperature 500C and a pressure between 70 and 500 car.

-3 patent No. 742,537 (Chayen) discloses a process for recovering fat from raw materials by subjecting the raw material to a high speed series of repeated intense impacts delivered through a liquid medium. The liquid metidum is inert to the raw material and is not a solvent for any substantial part of the residue of the raw material after removal of the fatty material, including liquid hydrocarbons such as hexane. The process is conducted at usual atmospheric temperatures (from 0°C to 38

C

S

7 "New Fat Solvent System", International Food Manufacture, 13(4) :18 (1996) discloses a liquefied gassolvent extraction process invented by CF Systems Corp which can be used to separate chocolate liquor into cocoa butter and fat-free cocoa powder. The extraction process is performed in heated, stirred extraction vessels where the food product is mixed with a liquefied gas solvent such as propane.

Heidlas, "Propane Extraction in Food Processing", Food Marketing and Technology, 8(6):38-43 (1994) discloses the use of compressed propane pressure of 20 bar and a temperature of 50 0 C) to extract lipophilic material from food products such as dried egg yolk and roasted cocoa.

U.S. Patent No. 3,923,847 (Roselius et al.) discloses a process for extracting cocoa butter using a supercritical gas such as carbon dioxide.

DE Parent No. 41 39 817 (Wilke) discloses a process for obtaining cocoa butter and cocoa powder from cocoa 20 mass by coining the cocoa granules with a washing fluid water) to form an emulsion which is subsequently centrifuged at 27,000 to 30,000 rpm to divide the emulsion into three fractions: the fat; the washing fluid; and the residue slurry 25 the fat free dry mass of the cocoa bean).

PCT Acolication Publication No. WO 95/03708 (Girsh) discloses a process for reducing the allergenicity of .2 foods by treatment with a supercritical fluid, such as supercritical carbon dioxide.

Summary of the Invention Techniques for processing cocoa mass are described. In general, the techniques concern processing cocoa mass in a manner including steps of: extracting cocoa mass with solvent to provide a solvent phase containing dissolved cocoa fat and a residual solids phase comprising defatted cocoa solids; and, separating the solvent phase containing the dissolved cocoa fat from the solids phase. The process can be conducted in multiple stages of extraction/separation, with a final separation before isolation of product(s).

In one aspect the present invention provides a continuous process for treating cocoa mass; said process comprising steps of: providing a cocoa mass containing: 10% or greater cocoa fat, by weight; and, (ii) cocoa powder; mixing the cocoa mass. with a solvent to form a slurry, the solvent comprising at least 75% by weight saturated hydrocarbon with a molecular weight of no more than separating the slurry into a separator system; and separating the slurry into a solvent phase containing dissolved cocoa fat and a solids phase containing defatted cocoa solids.

20 In a further aspect the present invention provides a continuous process of treating cocoa mass; said process comprising steps of: providing a cocoa mass containing: at least 45% by wt., fat content; and, (ii) cocoa powder; mixing the cocoa mass with a solvent which contains at least 75% by wt.

solvent selected from saturated hydrocarbons having a molecular weight of no greater than about 75 to provide a slurry of cocoa mass dissolved in the solvent and undissolved cocoa solids; transferring the slurry to a separator system; 30 separating the slurry into a solvent phase containing dissolved cocoa fat and a solids phase containing defatted cocoa solids.

W~\oWKPN1*Spo6436.dDC In an even further aspect the present invention provides a continuous process of treating cocoa mass; said process comprising the steps of: providing a cocoa mass containing; at least 10% by wt., fat content; and, (ii) cocoa powder; mixing the cocoa mass with a solvent which contains at least 90% by wt.

solvent selected from saturated hydrocarbons having a molecular weight of no greater than about 75 to provide a slurry of cocoa mass dissolved in the solvent and undissolved cocoa solids; transferring the slurry to a separator system; separating the slurry into a solvent phase containing dissolved cocoa fat and a solids phase containing defatted cocoa solids.

A variety of separation techniques can be applied. Certain preferred ones are described below.

Is In general, processing according to the present invention will be conducted under a pressure sufficient to allow for the solvent to be substantially in the liquid phase, while the process is conducted above the melting point of the cocoa fat.

This will typically comprise processing at a temperature within a range of about 40-90 0 C, and a pressure within a range of about 16 psia to about 580 psia, 20 depending on the particular solvent chosen. For example, when butane is used, the pressure will typically be within a range of about 50 psia to about 200 psia.

Although a variety of solvents may be used, in general it is foreseen that solvent or solvent mixtures selected from propane(s), butane(s) and/or pentane(s) will be preferred. With respect to quality of isolated butter, from the extraction/separation, the most preferred solvent identified thus far, as indicated by the experiments below, is butane. Although various isomers can (in some S 4instances) be used, generally the linear alkanes (n-propane, n-butane, n-pentane) are preferred.

W:'.fWoaoUSPfiai6143dMc Q2rAAOL rrr~ r ~r V .J 7,jDiU r I i1u yaIuz IU Techniques according to the present invention can be readily applied to achieve, by extraction, removal of at least 95%, by weight, of all cocoa fat in the cocoa mass extracted. Indeed, they can be practiced to achieve extraction of at least 99% by weight, of all cocoa fat, in the cocoa mass, in many instances. In general, this requires appropriate amounts, or extent, of extraction. In some instances multiple stage extractions will be used to accomplish this. In at 1C least some instances, such an extent of fat recovery can be achieved whether the fat content of the mass extracted is relatively high, greater than (for example, 50-58%) or relatively low, 20-45% (perhaps due to some preprocessing).

In general, cocoa powders (or isolazed solids) resulting from preferred practices of the present invention will contain no more than about 21, and typically no more than about 1I, cocoa fat, by weight.

Fat contents of less than by wt., are achievable.

20 These latter cocoa powders may be especially useful in preparing focd products to be desiqr.ated as "fait-ree" under the KLEA (Nutritional Labelinc Education Ac) In general, when multi-staae extractions are conducted, it is typically preferable to conac: tne most defatted cake with the freshest solvent. That is, the preferred multi-stage extractions are ccr.curted in a somewhat countercurrent fashion or torm. Preferred processes will be conducted in such a manner that the fat is extracted relatively efficiently, for example through control of conditions, and relative amounts of solvent and solid phase, such that a concentration of fat in the solvent phase after a step (for example, including multiple stages) of extraction is at least preferably at least 25%, and most preferably at least 35%, by weight.

6 WO 98/34496 PCTIUS98/02106 11 In general, preferred processes according to the present invention will involve extractions at pressures greater than atmosphere, typically about psia to 200 psia (for butane) or 50 psia to 400 psia (for propane).

According to the present invention, preferred products are provided. These may comprise, in part, good quality (or better) cocoa butter achieved by the techniques; and, desirable cocoa powder products.

Brief Description of the Drawings Fig. 1 is a schematic process flow diagram of a first process embodiment according to the present invention; and, Fig. 2 is a schematic process flow diagram cf a second process embodiment according to the present invention.

Detailed Description S"i* I. Some Drawbacks to Conventional Cocoa Processing As indicated above, in general many cocoa nib processing methods (to isolate high quality cocoa butter Sand cocoa powder) applied in the past have involved a step of mechanically pressing the cocoa mass, to generate cake and separated butter. While various 25 designs of equipment have been developed for this, in general the equipment has been constructed to operate at high pressures, on the order of about 6000-8000 psi.

This has generally required relatively expensive, highmaintenance equipment.

Also, a pressing operation is typically a batch operation. As such, processing using a pressing operation is relatively slow. As indicated above, the rate is greatly affected by the extent to which the fat is to be removed from the cocoa mass. Efforts to obtain WO 98/34496 PCT/US98/02106 12 high cocoa butter yield, greater amounts of fat removal, require substantially greater amounts of time in the press. At some point, a practical limit is reached at which further fat removal cannot be readily accomplished. In many systems, this is at a fat content of about 11%. It may, in some instances, be as low as 9-10%. !Different varieties of cocoa plants generate beans of different propensities with respect to pressing.) During the pressing operation, the resulting cake becomes relatively hot, typically about 80-1100C.

Cocoa processing has therefore generally required a step of warehousing the cake for a day or so, or use of heat removal systems, to cool the cake down sufficiently for further processing to be undertaken. A reason is that when the cake is hot, the residual fat melts and causes the cake zo clump severely.

In general, the desirable cocoa or chocolate flavor and/or color, resulting from use of the cocoa S 20 powder, stems from the nonfat components of the cocoa powder. That is, the portion of the cocoa powder, i.e., 10-201 by weight, which comprises cocoa fat is not, generally, essential to the operation of the cocoa powder as a desirable food additive for cocoa flavor and/or color. However, the fat content represents an inconvenience due to its weight and physical characteristics. Also, it may provide undesired nutritional characteristics.

Supercritical extractions of press cake with

CO

2 to reduce fat content in the cake, are undesirable, especially on a large scale, because relatively expensive high pressure equipment is needed, and large amounts of CO 2 are required. In addition, the relatively low solubility of fat in CO 2 (typically on the order of a few percent or less by weight), reduces substantially the desirability of the process. Also, CO 2 extractions 13 (in practice) should be operated on a powder (not a liquor) because the high surface area is needed for a practical extraction. Thus, in general the physical chara:reristics of cocoa mass, coupled with the low solven-cy of COz, severely limits mass transfer of cocoa fats into the solvent phase and the utility of CO; extrar-ions.

II. Some Desired Characteristics for Cocoa Processing.

Due to the relative value of cocoa butter, by comparison to cocoa powder, it is desirable to recover as much of the fat content of a cocoa mass, as cocoa butter, as is reasonably and cost-effectively feasible.

However, as indicated hereinbelow, the preferred chara=:eristics of cocoa butter are such that while isola-ion of the cocoa butter is desirable, it must be contr:lled in a manner which results in a cocoa butter of certain preferred physical and chemical chara:zeristics quality).

Also, cocoa powder contains many components respcnsible for its desirable flavor and color. It is preferred that cocoa processing be conducted in a manner such -hat undesirable modifications in the cocoa powder, with respect to those, are not made. For discussions of the complex compositions of cocoa powder see: Hashim, et al., "Extraction and determination of methy-pyrazines in cocoa beans using coupled steam distillation-microdistillator", Food Research International, Vol. 27, p. 537-544 (1994); Ghizzoni, C. et al., "Composition of Volatile Fraction of Indus-rial Chocolate", Italian Food and Beverage Technology, March 1995, p. 3-13; and, Keme, T., "Heat Treatment of Cocoa--Problems and Controlling", The Manufacturing Confectioner, June 1994, p. 101-108.

WO 98/34496 PCTfUS98/02106 14 It is also preferred to provide a low fat, and preferably fat-free, cocoa powder. These would be powders with a fat content of less than more preferably less than 1% and most preferably no more than (and indeed, less than) by wt.

It is preferred to develop processing in which, after the cocoa nib grinding process, the cocoa mass: is not, again, heated to above about 900C; is not treated with agents which will substantially modify the desirable characteristics of either the separated cocoa butter or the residual cocoa powder; and, is not treated with agents that leave or cause a significant residue in the products.

Another preference is for a process which generates solids, from the separation step, in a form that: does not require substantial periods of precooling prior to storage; does not require substantial processing (grinding, etc. beyond simple break-up and sifting) to provide for a fine powder; and, is storage stable, does not reclumo substantially upon exposure to the types of temperatures encountered in storage and shipment.

These and other preferred characteristics and benefits are readily achievable with certain of the preferred techniques described herein.

III. General Characteristics of Processing According to .the Present Invention.

According to the present invention, a solvent extraction process is applied to cocoa mass, in order to provide for isolation of separated cocoa butter and *...*cocoa powder therefrom. Preferably the extraction is conducted with a relatively low molecular weight no more than 75 molecular weight-mw) hydrocarbon, or mixture of hydrocarbons. For example, propane(s), butane(s) and pentane(s) or mixtures thereof, can be WO 98/34496 PCTfUS98/02106 used. Either linear or branched forms of those hydrocarbons are useable; however, the linear hydrocarbons are preferred. Preferably, the solvent is one in which the cocoa fats are soluble at least up to 10% by weight, more preferably at least 20%, and most preferably considerably more. Preferably saturated, unsubstituted alkanes are used. n-Butane is preferred, although n-propane is also desirable. The process may be conducted in a continuous or flow-through manner.

In some applications, a step of mechanical pressing or other preprocessing of the cocoa mass can be completely avoided. That is, cocoa fat is extracted directly from a cocoa mass, without any step of pressing of the mass. Advantages which result from this include: final yield of cocoa butter (based on fat content cf the mass) being increased over pressing techniques, because the extraction approach can be operated to provide for a higher amount of isolation of cocoa fat from cocoa mass than is practical with mechanical pressing techniques; avoidance of the substantial heazing, associated with pressing; avoidance of pressing equipment; and, attainment of a low-fat, easy to handle, cocoa cake or powder. Techniques 23 according to the present invention can be applied to S: 25 remove 95% or more, and in many instances 99% or more, of the fat content of the cocoa.mass. Thus, a recovery of 95% (indeed 99%) or more of cocoa butter during the extraction is feasible; and, a cocoa powder containing 2% or less (indeed, 1% or even 0.5% or less if desired) 30 by weight fat is readily achievable.

In spite of the fact that an extraction (rather than simply mechanical processing) is conducted, the resulting isolated cocoa butter has been found to be desirable as a potential cocoa butter commodity. It demonstrates appropriate melting point characteristics, texture characteristics, etc., desirable for use in food processing. Indeed, depending on the source of cocoa beans, it can be isolated as a relatively high quality cocoa butter, as discussed below.

In general, the quality of cocoa butter obtainable with techniques according to the present invention, involving extraction, at lest matches the quality of butter that can be isolated from the same cocoa mass material using pressing techniques, even though its selected yield may be higher. Thus, if a pressing technique to a 10-12% cake, conducted on a selected source of cocoa mass, results in a butter having a specifically defined d/q value of 3% (d/q and 3 are discussed hereinbelow), practice of techniques according to the present invention involving separation of the fat by extraction will, if practiced on cocoa mass from the same source, typically provide a separated butter of at least the same d/q and/or 3% values; and typically similar or better overall quality.

In addition, in spite of the fact that the cocoa mass is treated with an organic solvent for extraction, the resulting cocoa powder is found to possess desirable taste, mouth feel and related characteristics, to be useful and desirable as a food additive.

Throughout the description and claims of the specification the word "comprise" and variations of the word, such as "comprising" and "comprises", is not intended to exclude other additives, components, integers or steps.

20 Herein, the term "cocoa mass" is used to refer to a mixture of cocoa fat and solids. A "cocoa mass", for example, would be ground cocoa nibs, before later °°o.o processing, whether dutched or not. The term "cocoa liquor" is used herein to refer to cocoa mass which results from grinding cocoa nibs (whether dutched or not) but which has not been modified with respect to its fat content (typically or greater). Thus, as the terms are used herein, a "cocoa liquor" is one type of "cocoa mass". The term "cocoa mass" is also intended to include within its scope the result of modifying cocoa liquor, for example compositions which have been ('ANU D-z%11 %Sy~ Scdacr b143odm WO 98/34496 PCT/US98/02106 17 modified by the addition of further cocoa butter or similar materials thereto. In addition, techniques according to the present invention can be applied on cocoa mass which has already been mechanically pressed (or otherwise modified perhaps by centrifugation), for example to a fat content of 20%-30% or greater.

Such a hybrid process (using both mechanical pressing (or centrifugation) and extraction for fat removal) may be desirable, in some instances, for reasons discussed generally below.

One reason that the preferred solvents are low molecular weight no greater than 75 mw) nonpolar alkane solvents is that it has been found that such solvents readily extract the fat content, without extracting flavor compounds desirable in the powder.

Preferably the solvent used in the extraction is one which can be easily separated from: the extracted butter; and, 12) the recovered solids (powder).

Preferably the solvent is also one that can be readily recovered. Most preferably, the solvent is a category I solvent approved by The Council of the European Committees (June 13, 1988 Council Directive) for use in food processing. Food grade propanes and butanes generally meet all of the above stated preferences. The amount of solvent is preferably chosen such that, before isolation of the cocoa butter, the separated solvent phase will comprise at least 10%, preferably at least and more preferably at least 35%, by wt., cocoa fat.

This can be achieved with the preferred solvents 30 identified.

Although not necessarily preferred, alternative solvent systems are possible. Mixed solvents, for example, may be useful in some instances.

In general, however, it is foreseen that preferably at least 90%, by wt., (typically 95-100%) of the solvent used will comorise a saturated, unsubstituted, WO 98/34496 PCTfUS98/02106F~ 18 hydrocarbon or hydrocarbon (alkane) mixture comprising either butane, propane or a mixture thereof. Again, the straight chain hydrocarbons (n-propane, n-butane) will be preferred, and will preferably comprise at least by wt. (typically 95-100%), of the unsubstituted, saturated, alkane component or mixture. These solvent definitions are intended to allow for the presence of those contaminants (or other components) typically found in food grade propane and butane solvents. That is, such solvents may, in most instances, be used without further purification.

Although it is foreseeable that in some instances polar additives in the solvent mixture may be desirable, in general for processing to achieve both desirable cocoa butter produc:s and desirable cocoa powder products, polar solvents will be avoided. This is because polar solvents may tend to modify the characteristics of the powder, by extracting polar components therefrom. Of course this latter could also result in a modification of the isolated cocoa butter.

It is foreseen that ether solvents, or mixtures of ethers and alkanes, may be usable to effect a desirable extraction. However, in general, ether solvents are not desirable in food processing operations.

Preferably the extraction will be performed a. at, or with the solids maintained at, a temperature above the melting point of the fat, above about 350C, but less than 900C. Operation above the melting point of the fat is desirable, to obtain high solubility (and miscibility) of the cocoa fat in the liquid solvent and to provide a desirable reduction in viscosity of the mixture. At about 900C or higher, undesirable heat effects in the products and excessive pressure requirements, may result.

WO 98/34496 PCTIUS98/02106 19 In general, it has been found that the cocoa fat is completely miscible in the liquid solvent (alkane), provided the temperature is not too close to the critical temperature. For propane, this would limit the upper extraction temperature to about 700C. For solvents such as butane, the preferred upper temperature, about 900C, is, again, generally controlled by the heat sensitivity of the resulting products.

The operating pressure during the extraction should generally be at least equal to the vapor pressure of the mix system, in order to prevent boiling. For purposes of system design, one can use the vapor pressure of the pure solvent(s) at the temperatures of interest, as an indicator of the appropriate operating pressure.

Table I below reports: the vapor pressure at 54°C; the critical temperature; and, the critical pressure for some of the solvents of interest.

TABLE I SVapor Pressure Critical Critical Solvent 54°C (psia) Temp. Pressure (psia) n-propa.e 280 97 617 n-butane 80 153 530 n-pentane 30 197 484 In general, extractions according to the present invention can be operated in a number of stages.

25 Typically, it is expected that they will be conducted with two to five stages, with the specific choice being based on net cost versus benefit. In general, increasing the number of stages allows a more concentrated solution of fat to be obtained, reducing operating costs.

*4 0@* 6 4r Sc 46 5 0 WO 98/34496 PCT/US98/02106 Herein when reference is made to steps of: "extracting cocoa mass with a solvent"; and, "separating" a solvent phase from a solid phase, the intent is to refer to an extraction process which may be either one stage or multi-stage. When the process is multi-stage, the step of "extracting" could well comprise multiple steps of extraction/separation, due to the various stages. The "final" or "last" step of "separating" when used in this context, will generally refer to the separation which occurs after the last stage of extraction, the "separating" step or step of separation prior to isolation of fat and/or powder.

Table II below shows the calculated mass flows, and concentration of fat in solvent, for various numbers of theoretical stages in system based on 8,820 ibs./hour of cocoa liquor. The mass flows will hold for any of the preferred solvents. It is generally believed that any liquefied hydrocarbon, at a temperature above the melting point of fat and at least 30°C below the critical temperature of the hydrocarbon, is capable of *o*o dissolvin. the fat concentrations indicated in the Table.

S

o" Table II 0 0 0S S Three Four One Stage Two Staqes Stages Staaes Solvent 260,000 21,800 9,500 6,400 Rate (Ibs./hr.) Fat Cone. 1.8 23 40 53 (wt. In general, when cocoa liquor is prepared using conventional processing techniques, the solids of the cocoa liquor will have been ground to a mean particle size of about 7-10 microns. This is a relatively fine particle size. While it helps ensure rapid extraction, such a fine particle size can make WO 98/34496 PCTIS98/02106 21 separation of the solid phase from the extracted phase somewhat difficult.

In general, herein when reference is made to preferred steps of "separation" or "separating" to separate solids in solvent phase, prior to isolation of butter and/or powder, what is generally meant is a separation such that no more than about by wt., solids content is found within the separated solvent phase. Sometimes the percent by weight of solids carried in the separated solvent phase will be substantially less than this. However, because some of the solids are extremely fine, it is expected that typically some will still be found in the solvent phase after separation. These can generally be reduced to whatever level is desired, by fil:ration/clarificaticr.

techniques operated on either: the solvent/fa- phasC prior to removal of the solvent; or, the isolated butter, after solvent has been removed. 1. general, such a filtration/clarification operation should be 20 conducted sufficiently for the final isolated cocoa butter et be of the desired clarity, ex:ture, etc.

In general, any separation technique which can accommodate the level of separation identified above, on the materials involved, is usable. It is foreseen that simple mixer/settler technology approaches, at least using conventional equipment, will generally not be preferred. This is because the solids phase resulting from mixing solvent and cocoa mass (which has previously been ground) will be sufficiently fine that settlino will not be a fully desirable technique of separation.

Thus, it is foreseen that preferred separation systems, with presently available equipment, will generally be one of two types: decanter/centrifuge or hydrocyclone systems; or, mixer/filter systems. In a detailed description below in connection with Fig. 1, a specific example using a decanter/centrifuge system is WO 98/34496 PCTIUS98/02106 22 described. In connection with Fig. 2, a specific example illustrating a mixer/filter system is provided.

IV. Process Flow Diagrams for Typical Systems.

Attention is now directed to Fig. 1. In Fig. 1, a process flow diagram is illustrated, showing processing of cocoa mass according to one of many possible applications of the present invention.

Referring to Fig. 1, a cocoa mass feed into the system is illustrated at reference numeral 1. It is anticipated that in typical processing, the cocoa mass in feed I will comprise the result of grinding cocoa nibs, and will contain about 54% fat (50-58%) and 46% powder by weight. This feed could comprise, for example, cocoa nib material which has beer. cround in a conventional manner, but has not beer pressed for mechanical removal of cocoa butter; it may comprise cocoa liquor as the term is defined herein. Of course the material may be the result cf a dutchina 20 process, but there is no requirement cf :.is.

IT is foreseen that cocoa as-- iu. ln. e could o* alternately comprise: mixtures of unpressed cocoa liquor with other material; or, cocoa mass which has beer mechanically pressed (or centrifuged) for some 0 25 removal of cocoa butter therefrom. Inaeed, in some instances, techniques described here.r; culd be applied to remove cocoa fat from a cocoa cake that has resulted from conventional mechanical pressing.

Referring to Fig. 1, cocoa mass at line 1 is 30 shown directed into a tank 2. In tank 2, the cocoa mass is mixed and maintained liquefied. A steam circulation heating coil is indicated at 3, for application of heat to maintain the cocoa mass above the melting point of the cocoa fat. (The melting point for typical cocoa fats is around 27-330C.) It is foreseen that typical cocoa masses will preferably be heated to temperatures WO 98/34496 PCT/~S98/02106 23 within the range of 40-800C, in tank 2, for convenient processing.

Referring still to Fig. 1, cocoa mass is shown directed through line 4 into mixing tank 5. In addizion, solvent is directed into mixing tank through line 6. The resulting solvent/cocoa mass mixture is shown removed from mixing tank 5 via line 7.

For the system shown in Fig. 1, the solvent/cocoa mass slurry of line 7 is directed into a separator system or arrangement 10 for secaration of the solid and liquid phases. A separa:or 10 may comprise, for example, a horizontal decanter centrifuge operated to separate the slurry into two phases comprising: a hydrocarbon solvent phase containing dissolved fat; and, a powder (solids) phase co prising resulting (or residual, cocoa solids with reduced fat content. The powder phase (solids phase) is shown removed from separator 10 via line 15, and the solvent phase is shown removed from separator 10 via line 16. The solvent 20 phase is directed via line 16 into storace tank 17.

Storage tank 17 is provided with a steam heating coil 18 to maintain solubility of the fat (butter The solvent/fat is shown directed outwardly from tank 17 through line 19 into solvent separator 20. The solvent 25 separator may comprise, for example, an evaporator, with the resulting butter (non-volatiies) shown drawn off in line 21, to storage. The solvent is removed from the solvent evaporator via line 22, and is directed into solvent storage tank 23, for recycling into the extraction. (Of course a condenser, not shown, in line 22 may be used.) If desired, either before introduction into the solvent separator, or after, the material may be clarified, for removal of small amounts of solids therein. This would typically be accomplished by circulating the material through a clarifying filter.

WO 98/34496 PCT/IUS98/02106 24 Referring still to Fig. 1, the powder or solids phase of line 15 is shown directed into heated mixer 30. Solvent from tank 23 is directed, via line 24, into mixer 30, to conduct another stage of extraction. The resulting slurry is directed through line 31 into separator 32. The solid phase or powder phase from the separator 32 is removed via line 33; and, the solvent phase is shown removed via line 34. The solvent via line 34 is then directed into mixer 5 via line 6, for conduct of the first extraction stage described above. Separator 32 may also comprise a horizontal decanter centrifuge similar to separator Herein the first extraction to which solids directed in the system are subjected, will be referred to as the "first stage" of extraction. For the system shown ir. Fi:. 1, this would be the extraction which occurs as a result cf mixing in mixer 5, with the concomitant separation in separator 1C. The next stage or second stage is the extraction which results from 20 mixing nr, mixer 30, with follow-up separation at separator 32. The last time solvent is mixed with a soli; phiase, for extraction, will generally be referred to herein as the "final" or "last" stage of extraction.

For the system shown in Fig. 1, this would comprise the oo* 25 mixing that occurs in mixer 30, with follow-up separation at separator 32.

The powder (solids) phase via line 33 is directed into a surge tank 40. From the tank 40, it is directed into a solvent evaporator 41, with the 30 devolatilized powder product removed at line 42, and the collected volatiles directed via line 43 through compressor/condenser and into solvent tank 23. An advantage to the use of low molecular weight alkane solvents, such as propane and butane, is that the solids can be readily desolventized without application of steam to them. Typically good solvent removal will WO 98/34496 PCTfUS98/02106 merely require some agitation with reduction in pressure, and in some instances heat, to flash off residual solvent. It is noted that in some facilities it will be desirable not to reduce the pressure, for solvent recovery, any more than is necessary to adequately desolventize, in order to facilitate solvent recovery.

Processing according to the present techniques is oarticularly advantageous with respect to the nature of the powder obtained. The powder is obtained in a relatively fine form. If it clumps somewhat, it can be easily broken and sifted, to produce a high quality, low fat, readily handleable, flowable, powder. Due to the low fat content resulting from the extraction, it is not a very temperature-sensitive material. That is, under ordinary storage temperatures, conveyance temperatures and use temperatures, it does not as undesirably reclump, etc. as powders containing 101 or more fat.

Also, because it is obtained in a fine, or readily 20 sifted, form from the extraction, grinding or ctner rigorous mechanical manipulations of the material may not be reauired.

In the following paragraphs, operation of the process ir Fig. I will be further described, in 25 connection with one possible set of flow parameters. In particular, cocoa liquor, comprising 54 fat and 467 powder, by weight, would be pumped as a liquid at 54 0

C

to the first mixing vessel. Approximately 8,820 lbs./hour of the liquor would be mixed with 21,750 lbs./hour of liquefied hydrocarbon phase (for example, butane solvent with some oil (or fat) therein) obtained as an output of second stage extraction, via line 6.

The hydrocarbon would be expected to include about 400 lbs. of fat/hour, resulting from extraction in the second stage. The mixing vessel 5 would be selected to 26 have a volume sufficient to provide for a residence time of about 2-10 minutes.

The slurry stream, taken from the outlet of the mixinc vessel 5 via line 7, would be separated into -wo phases in the horizontal decanter centrifuge tank.

Other types of centrifuges may also be useful, as described in Perry's Chemical Engineer's Handbook, 6th Ed. (1984), pp. 19-89 to 19-103. Equipment suppliers could include Bird Machine Co. (South Walpole, !assachuse-ts), Westfalia (Oelde, Germany); and Alfa- Laval (Warminster, Pennsylvania). The separated liquid phase, containing about 19,905 lbs./hour of solvent and 4,722 Ibs./hour of fat, would be directed to the fat recovery via line 16. The solid phase, containing 4,057 lbs./hour cf cocoa solids and about 1,847 lbs./hour of solvent (and 440 lbs./hour of fat) is discharged from the secarator 10 via line 15 into the second mixing vessel 30, where it would be contacted with 22,150 Sbs./hour of solvent from the solvent working tank 23.

20 The time and temperature of mixing in the second mixing vessel 30 would be analogous to the first mixing vessel.

The outlet of the second mixing tank 30 would be directed to the second horizontal decanter centrifuge 32, where it would be separated into a liquid phase (fed zo the first mixing vessel as described earlier) and a solids-rich phase, containing about 4,057 lbs./hour powder, 2,240 lbs./hour solvent and 40 lbs./hour butter.

The operating pressure of the system would be about 80 psia when the solvent is butane. The solids 30 chase would be passed to a lower pressure system, where the solvent is vaporized and collected by recompression or cooling. The recovered powder would contain less than 1% fat.

In the fat recovery section, to which the fats would be directed via line 16, dissolved fat would be WO 98/34496 PCTIS98/02106 27 sent to a lower pressure section for solvent recovery.

For butane, suitable conditions would be a first stage solvent recovery at about 50 psia, with a condenser temperature of about 38 0 C and a bottoms temperature of about 105°C. At those conditions, the solvent content of the fat phase would be reduced to about 10 wt.

percent, while allowing recovery of the solvent by vaporization/condensation. The remaining solvent would be stripped and recovered under vacuum. The recovered fat could be deodorized in a conventional manner, for example by steam deodorization (short contact) and given a final filtration for clarity. In some instances the solvent removal step and deodorization step could be combined.

Optionally, the mass could be first centrifuged to remove as much fat as possible, reducing the solvern requirements. A second alternative would be to use prepressed mass, which also has a lower fat content than cocoa liquor and thereby uses less solvent.

S 20 This latter may be a particularly desirable approach for implementation in presently existing cocoa processing plants.

In particular, conventional processing plants generally comprise the result of substantial investments in pressing equipment. When such plants are combined with techniques according to the present application, in a hybrid process, the presses could still be used to some extent, for processing to remove some butter and to reduce cocoa mass content to some 30 selected value, perhaps selected to be somewhere in the range of 15 to 45% (for example, 20-40%) fat, by weight.

This could be conducted relatively rapidly, with conventional pressing equipment, for increased throughput. Further isolation of fat (as butter), and reduction in fat content of the resulting powder, would then be conducted with a follow-up extraction process.

WO 98/34496 PCTfUS98/02106 28 It is foreseen that in some instances this would be much more advantageous than the present practice of attempting to press the mass until the fat content of the resulting solids is reduced to below 20% (by wt.), especially when the reduction is to below about Attention is now directed to Fig. 2. In Fig.

2, a possible alternate filtration system is described.

In the system of Fig. 2, cocoa mass would be pumped to a first mixing vessel 60, via line 61. In mixing vessel 1C 60, the cocoa mass would be combined with solvent directed thereto via line 62. The resulting slurry would be removed from mixer 60 via line 63. It would be directed into a pressurized, contained, belt filter system indicated generally at 65. In belt filter system 65, the slurry would be deposited onto belt 66. The primary liquid collected would be the product stream shown drawn off at 67. A fresh solvent wash would be directed in at lines 68, with removal at line 69.

Defatted solid cocoa powder; discharge would be as indicated generally az 70, with removal being via **outlet 7".

The solvent wash removed via line 69 is shown cycled via line 75 for recycling into to mixer 60 via line 62. The fat-enriched solvent drawn off via line 67 25 can be directed into butter recovery processing, similar to that shown for line 16, Fig. It could be directed S into a clarifier, not shown. Clarified solvent would then be directed to butter recovery. Back wash from the filter wculd be recirculated to line 62.

S 30 The discharge via line 71 can be directed to powder (solids) processing similar to that described for the process in Fig. 1, through line 33.

The arrangement shown in Fig. 2 may be viewed as a multi-stage extraction arrangement, with a first stage indicated as occurring in mixer 60, with separation at line 67, and with the following stages WO 98134496 PCTIUS98/0106 29 occurring as a result of spray 68 and material draw-off at 69 and 71.

It is foreseen that the system of Fig. 2 could be operated, for example, on cocoa mass comprising 54% fat and 46% powder pumped into mixing vessel 60 at 54 0

C.

Approximately 8,820 lbs./hour of the liquor would be mixed with about 8,300 lbs./hour of solvent obtained from the filter cake washing via line 69. It is anticipated that the system could be constructed so that such solvent would contain on average about 800 lbs./hour of fat.

The system could be configured so that the primary liquid collected at line 67 in a product stream would comprise about 4,723 Ibs./hour of fat and 8,120 lbs./hour of solvent. As the cake moves down the belt, it would be washed with fresh aliquots of solvent, totaling about 8,82C lbs./hour.

It is foreseen that with such a system, after draining, the cake would still have a liquid content of 20 about 10-20 wt. percent. After sclvent recovery, the desolventized powder would contain less than 1 wt.

percent fat.

If a system according to Fig. 2 were used, it is foreseen that the pressure inside the belt filtration 25 system 65 will be maintained at a pressure high enough that the solvent after passing through the filter is still at a pressure sufficient to prevent boiling. With butane, for example, the container vessel would be at about 120 psi with a 35 psi pressure drop across the 30 belt, leaving the solvent collection trays at 85 psia.

V. Products.

As indicated above, according to the techniques described herein, cocoa mass is processed to generate two isolated and desirable products: cocoa butter; and, cocoa powder.

WO 98/34496 PCTIUS98/02106 In general, when preferred processes according to the present invention are practiced, a cocoa powder yield of 97% or greater from the cocoa mass extracted, can be obtained having: a fat content of less than 2%, by wt. for or even if desired); a particle size of 0.1/i to 40j; and, a mean particle size of about 6 -10P. This material will be found to have a desirable cocoa flavor, mouth feel, color, etc., for use as a food additive.

The cocoa butter isolated is also generally desirable. The principal component of cocoa butter is a trigiyceride which consists of a backbone of glycerol esterified with three fatty acids, in particular, palmitic oleic and stearic (ST) acids.

The :ype of acid positioned az each of the three available sites in the triglyceride molecule is important. These are generally designated in a shorthand form of triglyceride nomenclature, with POST being different from PSTO, although the cons:ituent 20 acids in both of these triglycerides would be one-third palmitic, one-third oleic and one-third stearic.

The triglyceride POST belongs to the group of triglycerides that are typically called symmetrical monounsaturated, referred to as "SOS triglycerides", where refers to a saturated acid residues and to oleic acid. Such "SOS triclycerides" comprise about (by wt.) of the triglycerides in cocoa butter.

The melting behavior of the fat (cocoa butter) is critical to its behavior in chocolate formulations.

*e 30 It is believed that it is affected substantially by the presence of "SOS triglycerides" in the butter. In very broad terms, for example, SOS triglycerides are solid at room temperature, whereas SOO triglycerides are more liquid at roo. temperature.

WO 98/34496 WO 9834496PCT/US98OZ 106 Inl Table III below, from Industrial Chocolate Manufacture and Use, 2d Ed., ed. by S. T. Beckett, p.

246, Blac*k-ie Academic Professional, Glasgow (1993) is provided :he triglyceride composition of conventional cocoa buzzers from various sources. In Table from the same Source, some solid fat contents are provided.

Table III Triglyceride composition of cocoa butters Brazili Ghana Malaysia (Ivory 'Coast) SSS 1.0 1.4 2. 3 SOS 63.7 -76.8 84.0 SSO 0.3 0.4 SLiS 8.9 6.9 6.8 300 8 .4 .1 000 8.0 .11.3 S =sat~urat-ed i-atty acidis (mainiy- palmitic and stearic); 0 o-leic acid; Li=lincle'Lc acid Table IV 15 Solid fat contents* (by pNMR) cocoa butters Temperazzure (OC) '10F) Brazil Ghana Malaysia (68) 66.3 76.2) 8 1 .2 25 (17 60.1 70.4 76.2 30 (8H) 36 .9 45.1 54.8 32.5 (90) 6.6 13.3 9 7 35 (937) 2.0 0. 0 0.0 *9 9e .9 9 9 9 9 9 99 9 9 999w *Tempered at 260C (790F) content measurement.

for 40hi orior to solicj rat It is significant that the cocoa processing according to the present invention does not appear to WO 9834496 PCT/US98/02106 32 result in any negative impact on the butter, by comoarison to conventional processing. Thus, if an appropriate quality cocoa nib is used, for cocoa butter production, techniques according to the present invention can be applied to obtain a butter of good (or preferred) quality.

In the experimental section below, some definitions are provided for functional or performance characterizations of cocoa butters (used by buyers of cocoa burter as a commodity). In general, d/q values are an indication of the hardness of the butter. Higher values indicate harder butters with faster setting tir.es. Buyers of cocoa butter(s) for use in food orccessing will typically have a preferred d/q for their przoess or final product. With the techniques described herein, these preferences can readily be accommodated.

Indeed, techniques according to the present invention can be readily applied to obtain butters exhibiting d/q values, as defined, within the range identified as 20 satisfactory, within the range identified as very good, cr within the range defined as exceptional, depending S. uron the cocoa mass selected. As the experiments show, preliminary indications are that in some instances d/q values greater than 0.18 or even greater than 0.20 are obtainable.

Higher beta values are associated with a 0 higher propensity for the butter to crystallize.

Techniques according to the present invention can be utilized to provide butters with percent P values of S 30 or higher.

The above indicates that: conventional "prime press butters" can be replaced with cocoa butters isolated according to the present invention, in many follow-up food processing operations; and, the extraction techniques can be used to provide a cocoa butter of a predictable quality (and at least as good a WO 98/34496 PCT/US98/02106 33 quality as could have been obtained from the same raw material by pressing). Thus, prime press butter can be readily and completely eliminated from a recipe calling therefor, and can be replaced wi:h an extracted cocoa butter according to the present invention.

It is noted that residual solvent levels of ppm or less, preferably 3 ppm or less (and indeed, sometimes 1 ppm or less), will be preferred for both cocoa butters and cocoa powders. These levels can be readily obtained by the techniques described herein.

VI. Recipes As indicated above, techniques according to the present invention are utilized to isolate: cocoa butter; and, low fat, even "fat-free", cocoa powder, from a cocoa mass. The cocoa burrers may be utilized to replace cocoa butters in otherwise conventional recipes, to advantage. The cocoa powders can also be utilized to replace cocoa powders in conventional recipes.

20 Referring first to the cocoa powders, it is noted that cocoa powders isolated according to the present invention generally have a lighter appearance than conventional 10/12 powders 10%-12% fat by weight).

The lighter color is generally a result of the lower fat 25 content. The powders isolated after extraction, however, are generally acceptable, even in recipes calling for 10/12 powder, since the taste, texture and color characteristics desirable of the powder are not negatively affected by the removal of the fat-content by 30 the extraction techniques described herein. Indeed, generally flavor impact is noticed to be enhanced as a result of the loss of the fat content; and, the powder material may be easier to handle, again due to the fact that it does not clump when it becomes warm. Also, in general, the color difference is not observed once the powder is mixed into a food product.

34 Thus, cocoa powders having a fat content of 1% or less, especially 0.5% or less, when prepared according to the present invention, can be used in applications well beyond simply low fat applications.

They nay be desirably utilized to replace powders in almost any application.

In this section, some general recipes using materials according to the present invention are provided. From these recipes, broad applications of materials made according to the present invention will be used. For a general discussion of food processing using cocoa butter and/or cocoa powder, see: Industrial Chocolate Manufacture and Use, 2d Ed., ed. by S.T.

Becket:, Blackie Academic and Professional, London, Chapter 15 (1993).

nmany instances, stable ingredients (or seleczed stable ingredients) of the formulations can be blended and sold as premix, for use to make the products recited.

2 A. Milk Chocolate.

Milk chocolates generally include a blend of: sugar; cocoa butter; milk solids (for example, milk powder); chocolate liquor; lecithin; and vanillin. A 25 typical milk chocolate formulation, by weight, is as follows: Typical Milk Chocolate Sugar 51.3 Cocoa butter 20.1 Whole milk powder 15.1 Chocolate liquor 13.0 Lecithin 0.45 Vanillin 0.05 100.00% WO 98/34496 PCTIUS98/02106 It is foreseen that cocoa butters according to the present invention can be used to replace the cocoa butter component, in such typical milk chocolate formulations.

B. Semisweet Chocolate.

A typical semisweet chocolate is a blending of the following materials: sugar; chocolate liquor; cocoa butter; lecithin; and vanillin. The followina table gives a typical semisweet chocolate formulation, by weight: Typical Semisweet Chocolate Sugar 50.3 Chocolate licuor 38.3 Cocoa butter 10.9 Lecithin 0.45 Vanillin 0.05 100.00% It is foreseen that cocoa butter isolated 15 according to the present invention can be utilized to replace cocoa butter in such a formulation.

C. Cocoa Confectionary.

A typical cocoa confectionary comprises a blend of: sugar; partially hydrogenated vegetable oil; 10/12 cocoa powder; milk; whey powder; lecithin; and vanillin. A formulation for a typical cocoa confecticnary, by weight, is as follows: WO 98/34496 PTU9IZO PCTIUS98/02106 Typical Cocoa Confectionary Sugar 4.

Part-ially hydrogenated 2.

veoetable oil (cottonseed, soybean) Cocoa powder nat. 10/12 Norn-fat dry milk7.

Whey powder6.

Lecithin 04 98.0 0.05 100. 00% is foreseer. that a cocoa oowder pDrepared according t-o the present invention, including less than _W 2% by weicht fat, and indeed ir Some inst.ances no mcre than 0.5% by wegt can be used -1-c replace the cocoa powder of such a confectionary. irn some instances, a minor lessening in the presence the powaer by weiaht, in the formulation, may be do-a:-o ne 1t0 reduction of' fat content ant, as resul,*, re.-nnnement of the cocoa flavor. This will cirrl ~trc taste.

a D. Chocolate Ice Cream.

a a a.

a a a. a 15 Chocolate ice cream generally =Trises a.

blend of: cream; mill.; whey; su-car zrcI~ud :r syrup; cocoa powder (221/24% fat, fLor exaM.e-,; anCJ water. A typical fformulation for a chocolate ice cream product., using 22/24 AIristocratTll cocoa powder as the 20 cocoa ingredient, is listed below: WO 98/34496 PCTTJS98OZ 106 Typical Chocolate Ice Cream using Gerkens 22/24 Aristocrat

M

Cocoa Powder Cream 22 Skim milk powder 8 Whey powder 2 Sugar cane liquid 21 (BRIX .6734) Corn syrup 36DE1 (BRIX St-abilizers 22/24 Aristocrat'" Water 42 100 @0OqS*

S.

*0

S

.5

S.

SOSS

*5 S S

S

S

S

*5*5 S S

S

S S *5 5 It is foreseen -:hat t*-e hioher fat 22/'24 AristocratT- powder (Wilbur Chocolate Lititz, pennsylvania) can be replaced with a cocoa powder isolated according to the present invention, even one having less than 2% by weight fa,: therein. Some reduction in the cocoa powder presence of the formu.lat:Ofl may be desirable, since powders according to 10 the preser.: invention nrovide focr enhanced flavor imoact, due to the reduction in fat content. This will.

primarily be a matter of tast-e.

E. Chocolate Milk.

is A chocolate milk f~ormulation generally comorises, in addition to thie x.rilk, a blend of: fat; MSNF; sucrose; cocoa powder; stabilizer; and vanillin.

A typical formula for a chocolat-e milk formulation, disregarding milk content, wou-"c- be as follows: WO 98/34496 PCTIUS98/02106 38 Typical Chocolate Milk Formulation Fat 1-3 MSN.F' 0.5-1 Sucrose 7-9 Cocoa 1-3 Stat-ilizer 0.2 Vani-llin 0.02-0.05 ~milLk solids, non-fLat It i's foreseen that a cocoa powder according to the ipresent inverntion can- replace he Conventional cocoa usec in such r'ormulations. Again, since higher flavor imoact w:ill result, due the lesser fat content, slight-ly lower amounts c: cocoa powder may be des-'rabe in :ormulat -_ons. This will Primarily be a matter o'f taste.

F. Chocolate Frosting.

Typical chocolaze frosting formulations :0Comprise a blend of: suaar; sn.-c'rten_ng; water; cocoa 1 powder; salt; and vanillin. formula for such a formulation, by weight, would-- be as -follows: *000, Typical Chocolate Frosting Formulation 004Sugar 45-60 0Shortening 10-20 to*Water 10-20 Cocoa powder 4.5-6.0 salt trace 000Vaniilin. trace 100.00% It is f1oreseen that a cocoa powder according to the present invention, containing 2% or less, and even 0.3% or less, by weight, fat, can be used to WO 98/34496 PCT/US98/02106 replace the cocoa powder in such formulations. In some instances, a slight reduction in the amount of cocoa powder presence may be desirable, since cocoa powders according to the present invention are generally enhanced with respect to cocoa flavor, by comparison to conventional powders, due to reduction in fat content.

This latter will primarily be a matter of test.

G. Chocolate Syrup.

0 A chocolate syrup formulation generally comprises a blend of: cocoa powder; sugar; water; salt; and vanilla. Some typical formulae for a chocolate svrup formulation would be as follows: Chocolate Syrup Formula I Los. Medium Dutch cocoa powder 35 lbs. Granulated sugar 8 lbs. Corn syrup solids 15 lbs. Water 1 oz. K-Sorbate 1 oz. Salt 1 oz. Vanilla 1 oz. Stabilizer 0 00 0.

0 0090 Typically the materials in Formula I would be blended and used as follows: 1. Blend all dry ingredients except preservative(s) and vanilla.

2. Heat water to about 1600F, add dry ingredients from #1 agitating continuously. After all the powder is wet, increase heat to about 180- 200 0 F and hold about 15 minutes. Turn off heat and start cooling.

3. When temperature is about 100-110 0 F, add preservative and vanilla.

WO 98/344%6PTU9/20 PCTIUS98/02106 4. Homogenize, can and cool.

Chocolate Syrup Formula II lbs. 10-1-2% Medium Dutch cocoa powder lbs. Granulated suaar lbs. Corn syrup 31 lbs. Water 1 oz. K-Sorbate 1 oz. Sal.: OZ. Vanilla 1 oz. Stabilizer Typically the materials in For-rula would be and used as follows: S. end all drv incredients e:xce=: K-Sorbat=.

Hea-- ;water to about add Cr-y :"naredients from agitating corntlnuously. Rfter all t:he powder is wet, increase heat to about 160- 10 200*F while aqi :at~inq and hold about minutes. TurnL off_ heat: and start cooling.

tr:addi.na corn syrup while az-,:ta: ing. Wh en tem~erature is about 100-110'F. add preservati.ve and vani'la.

154. Homogenize, can and cool.

Chocolate Syrup Formula III 325 lbs. Water 100 lbs. Medium Dutch cocoa 4 43_ lbs. Sugar 230 lbs. invert sugar 1 lb. Salt 0.3 lbs. Vanillin Typically the materials in For-mula ILII would be blended and used as follows: WO 98/34496 PCTfUS98/02106 41 1. As water is being agitated and heated, add the cocoa mixed with some of the sugar and then the salt and the rest of the sugar. Heat to 1800F.

2. Add the invert sugar syrup.

3. Cook to 2200-2250F.

4. Turn off heat and add vanillin.

Homcgenize, can and cool.

It is foreseen that a cocoa powder according to the present invention can replace the conventional cocoa used in such formulations. Again, since higher flavor impact will result, due to the lesser fat content, slightly lower amounts of cocoa powder may be desirable in the formulations. This latter will orimarilv be a matter of taste.

H. Chocolate Cake.

A chocolate cake formulation generally 2C comcrises a blend of: shortening; sugar; eggs; vanilla; flour; bakinc soda; salt; cocoa; and sour milk. A typical formula for a chocolate cake formulation would be as follows:

E.

Typical Chocolate Cake Formulation Measure- Batch ment Size 1 9"x13" or 9"x13" cr Batch two 8" two 8" Size 2 Ingredient round Formula round 8" round Shcrtening 1/2 cup 6.73 95.4 g 47.70 g Sucar 1-3/4 cup 25.96 368.11 a 184.05 g Eggs 1 3.35 47.5 g 23.75 g Vanilla 1 tsp. 0.16 2.25 a 1.125 g Flour 2-1/2 cup 27.17 385.25 c 192.62 g Baking 2 tsp. 0.49 7.00 3..50 g soda Salt 1/2 tsp. 0.16 2.25 g 1.125 g Cocoa 6 Tbsp. 2.77 39.26 g 19.63 g cowder Sour milk* 2 cups 33.21 471.00 g 235.50 g Total 100 1418.02 g 709.01 g *4 Tbsp. vinegar milk to 2 cups sour milk WO 98/34496 PCTIUS98/02106 Typically the materials would be blended and used as follows: 1. Preheat oven to 350 0

F.

52. Cream together shortening and sugar on low speed.

3. Add egg and vanilla, beat 2 minutes on medium speed.

4. Blend flour, baking soda, salt, and cocoa and sift.

Add dry ingredients to creamed ingredients alternating with sour milk.

6. Pour inzo greased pan.

7. Bake 30-40 minutes or until done.

8. Cool or wire rack.

tis foreseen that a cocoa powder accordinc to the oresent invention can replace the conventional cocoa used in such formulations. Again, since higher flavor mrpact will result, due to the lesser fat contenL, slightly lower amounts of cocoa powder may be desirable in the formulations. This latter will primarily be a matter of taste.

25 I. Chocolate Brownies.

A chocolate brownie formulation generally comprises a blend of: butter; sugar; vanilla; eggs; cocoa; flour; and salt. A typical formula for a chocolate brownie formulation would be as follows:

S

S

9 S. S

S-

PCT[US98OZ106 WO 98/34496 Typical Chocolate Brownie Formulation Batch Batch Ingredient Measure- Size 1 Size 2 ment Formula 9"x1311 8 Ix8f/ Butter 1/2 cup 11.97 113.00 g 56.50 g Sugar 2: cups 44.56 420.70 g 210.35 g Vanilla 1 tsp. 0.24 2.25 g 1 125 g Eggs 4 2 0 12 190.00 g 95.0O g Cocoa (see batch 6.67 63.00 g 31.50 g powder columns) Flour I Cup 16.32 154.10 g 77.05 g Salt _1/4 -Sp. 0.12 .12-5 g 0.56 a Total 100 944.20 q 472.10 a Typically the materials used as follows: 1. ?rehea': oven to 25 2. Melt butter.

3. Add cocoa, beaz un would be blended and 00 F.

til we-- blended on low

S

p speed.- 4. Beat ecas and salt toother.

10 ,.Ad sugar and a~l ao ct 6. Add egg and sugar u*te-f cocoa mixture and blend on Low speed.

7. Adid flour and blend or. low: speed.

S. ?our int-o greased par.

is 9. Bake 25 minutr-es.

It is foreseen that a *:ocza =:crdino to the oresen-t invention can reclace t:he convent. onal cocoa used in such formulations. Again, since higher f1 lavor impact will result, due to the lesser fatL content, sligh-tly lower amounts of cocoa powder may be desirable in the formu_-lations. This latter will primarily be a matter of: taste.

44

EXPERIMENTAL

Summary of Methods Natural African cocoa liquor and dutched (alkalized. cocoa liquor (in drop form, from Wilbur Chocolate of Lititz, Pennsylvania) were processed batchwise -sing liquefied propane. Natural African liquor was also processed batchwise with liquefied butane. The cocoa butter content of the liquors, before orocessing, was around 54%.

The butane and propane extractions were conducted i- two steps, using solvent to feed ratios of 2:1, at a zemperature of 125 0 F and reactor pressures around 100 ?si for butane, and 200 psi for propane. The contact time of solvent and liquor was approximately minutes for each stage. The extracted butter and fatr--e solids streams were desolventized by holding the materials at 150°F and atmospheric pressure for one hour.

:he cocoa butter isolates were analyzed using IOCC cooling/solidification method 110, and differential scanning calorimetry (DSC). Solvent-extracted fat-free powders were analyzed for residual fat, residual solvent, particle size distribution (Coulter counter), pH, color and flavor.

IOCC Cooling Method This method (published in "Analytical Methods of the Office International du Cacao et du Chocolat" (1988), Bicggio, Switzerland) involves analysis of the behavior of cocoa butter while cooling and thus serves as an important predictor of cocoa butter behavior in applications. The latent heat of triglyceride crystallization is measured during solidification of the finished product. A sample of cocoa butter is thermally conditioned, placed into a Shukoff flask and cooled in a 0 C water bath. The temperature of the butter is recorded over time. The rise in temoerature (AT) reflects the latent heat of crystallization over time interval Cooling curves yield d/q values which represent the ratio AT/A,. The total ti.me for crystallization is also important, because the latent heat of crystallization melts some of the cocoa butter mass. The more time required to recrystallize, the softer the butter and the more difficult it is to process. In general, higher d/q values indicate harder butters. Ivcry Coast butters typically exhibit d/q values in the range of 0.10-0.18 values.

Differential Scanning Calorimetry (DSC) With this method, one analyzes the amcunt of crystal polymorphism and/or self-fra:tionation in cocoa butter. Cocoa butter is conditioned and slowly melted in a DSC using a pre-programmed heating profile. Heat flow (enthalpy AH) is measured at a given temperature.

Peaks of heat flow within a DSC curve depict melting of zriglyceride crystals. By definition, P and P' crystals occur in narrow regions of the temperature continuum.

Integratic- of their respective peaks allows one to quantify the total which is expressed as a 25 percentage of the total butter The other significant crystal types are a and y. Higher %P values indicate faster rates of crystallization.

For the measurements reported herein, a proprietary variation of the method reported in Lebensmwiss. Tech-.nol. (1982), Vol. 15, pp. 195-198 by Merken, Vaeck Dewulf was used. The published method cited is adequate.

Total P-crystal is largely influenced by country of origin. Press butters typically fall in the range of 15-60. Butters isolated with the techniques WO 98/34496 PCT/US98/02106 46 described herein typically fall within the range of p values.

Particle Size Analysis Coulter The Coulter LS 230 (available from Coulter Corp., Miami, Elorida) determines the size distribution of cocoa particles. Actual size is measured with a laser defraction analyzer based on Fraunhofer's theory of light diffraction. Particle sizes under 0.4 microns 1C are determined by polarization intensity differential scattering. Samples of cocoa are mixed with 2-propanol and sor.icated to break up agglomerates. Laser scans produce a defraction pattern, and the particle "size" of the sample is the value at the 8Cth percen:ile.

Sieve Residues The sieve residue wet method gives the percentage of cocoa powder that passes through a 200 mesh (75.uL screen. Cocoa powder is suspended in hot 20 water, sieved and passed through the screen. Residue is dried with acetone, defatted with petroleur-.

ether, redried and finally weighed.

RESULTS

25 Cocoa Butter Propane- and butane-ex=racted cocoa butters exhibited cooling curve and DSC characteristics equivalen- to, or better than, acceptable African (Ivory Coast) press butters.

As noted above, cooling curves by IOCC reflect the rate of crystallization of molten cocoa butter triglycerides. In general, short crystallization times are preferred and correspond to higher d/q values. By way of reference, d/q values (of cocoa butter) between 0.10-0.13 are generally considered satisfactory, 0.13- WO 98/34496 PCT/US98/02106 47 0.17 are generally considered very good; and values of >0.17 are considered exceptional. Pure prime press butters of Ivory Coast origin (commercially available) rarely exceed 0.175.

The cocoa butter resulting from extracting African natural cocoa liquor using propane yielded a d/q value of C.16 (very good). The butter recovered from dutched liquor using propane gave a d/q value of 0.15 (also very good). Cocoa butter extracted from African natural liquor using butane yielded an unprecedented d/q value of 0.21.

Differential scanning calorimetry provides information on crystal structure of cocoa butter triclycerides. For African press butters, %R values of 30.0 or greater are considered good. The propaneextracted African natural liquor and dutched liquor produced butters with 29.7 and 33.4%p, respectively.

*Butane-extracted African natural liquor yielded a butter with 40.0%P. While the cooling curve and DSC tests n analyze different attributes, the values for the butaneextracted butter are directionally consistent insofar as predicting butter functionality.

All of the butter extracts tested had residual solvent levels under 5 ppm. Indeed, they were less 25 than 1 ppm.

The Fat-Free Cocoa Powder Propane and butane extraction of the natural and dutched liquors produced cocoa powders with zero no greater than residual fat and less than opm residual (indeed, less than 1 ppm) solvent.

Residual fat content was determined using three methods: soxhlet extraction; supercritical fluid extraction with carbon dioxide; and NMR. The NMR method was found to be less accurate in quantifying low levels of residual fat.

WO 98/34496 PCT/US98/02106 48 Residual propane and butane solvent (head space recovery) were analyzed by gas chromatography.

The fat-free powders resulting from the processes tested exhibited particle size distributions identical to standard cocoa powders. The latter contained 10-12% fat after liquor is pressed and the resultant cake milled and classified. Particle sizes ranged between 45 microns on the high end to 0.1i on the low end, with a mean size of E.2p and a median size of 6.6. The fat-free powders match the size specifications for standard 10/12% fat powders in that of the particles were smaller than approximately 1 2 .5p and greater than 99.5% of the same material passed through 200 mesh screen (particles <75i). Particle size was found to have been contr lled during grinding of the nibs to form liquors, so the particle size was maintained downstream irrespe:tive of the butter extraction (solvent vs. press).

The of the tested fat--free- ;citur! .l )wder resultinc from the crocessino accordir.: t the resent invention was 5.6 (10% slurry in water and the fatfree dutched powder had a pH of 7.0. The color of the fat-free powders was somewhat lighter than their counterparts that contain 10-12 fat, when made via S 25 conventional processing. The apparent dcisparity is related to the interaction of light with :at, and it •disappears when the materials are suspended in water or blended in a confection or batter at equivalent levels of nonfat solids. The fat-free powders resulting from processing according to the present invention had comparable bitterness and astringency flavor characteristics to standard powders, when the products were adjusted for fat content. A trained sensory panel reported the flavor differences between the fat-free powders made by processing according to the present WO 98134496 pCTIUS98/021O 6 49 invention, and their standard counterparts containing 10-12% fat as "negligible". The differences were within the range of typical product variability versus production batohes.

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Claims (34)

1. A continuous process for treating cocoa mass; said process comprising steps of: providing a cocoa mass containing: 10% or greater cocoa fat, by weight; and, (ii) cocoa powder; mixing the cocoa mass with a solvent to form a slurry, the solvent comprising at least 75% by weight saturated hydrocarbon with a molecular .g......weight.of nQmore_tha-_ transferring the slurry to a separator system; and separating the slurry into a solvent phase containing dissolved cocoa fat and a solids phase containing defatted cocoa solids. 15

2. A continuous process according to claim 1 wherein said step of providing comprises providing cocoa mass comprising at least 30% by wt., cocoa fat.

S3. A continuous process according to claim 1 wherein said step of providing comprises providing cocoa mass comprising at least 45% by wt., cocoa fat.

4. A continuous process according to any one of claims 1-3 wherein the cocoa fat remaining in the cocoa solids is no greater than 1% by wt. 25

5. A continuous process according to any one of claims 1-4 wherein the cocoa fat remaining in the cocoa solids is no greater than 0.5% by wt.

6. A continuous process according to any one of claims 1-5 wherein said step of mixing is conducted at a temperature at or above the melting point of cocoa fat, but less than

7. A continuous process according to any one of claims 1-6 wherein said solvent comprises at least 90% by wt. hydrocarbon having a molecular weight of no more than W:vniijNrc ptcc61436.doc 51

8. A continuous process according to any one of claims 1-7 wherein said solvent comprises at least 90% by wt. propane, butane, pentane, or a mixture thereof.

9. A continuous process according to any one of claims 1-8 wherein the solvent comprises linear hydrocarbon.

A continuous process according to any one of claims 1-8 wherein the sovent comprises branched.hydrocarbon

11. A continuous process according to any one of claims 1-10 wherein said step of mixing is conducted under a pressure of greater than atmospheric. 15is

12. A continuous process according to any one of claims 1-11 wherein said i step of mixing is conducted under a pressure within the range of 16-580 psia.

13. A continuous process according to any one of claims 1-12 wherein said cocoa butter product has a residual solvent content of no greater than 5 ppm.

14. A process according to any one of claims 1-12 wherein said cocoa butter product has a residual solvent pressure of no greater than 3 ppm.

A continuous process according to any one of claims 1-14 wherein said 25 step of separating is selected from: a decanter/centrifuge process; a hydrocyclone process; a filtration process; and any combination thereof.

16. A continuous process according to any one of claims 1-15 wherein said step of separating comprises directing the slurry of cocoa mass and liquid solvent onto a moving belt filter of a moving belt filter system. W:lo N pCSpal%61436.doc 52

17. A continuous process according to claim 15 or claim 16 wherein the step of separating comprises at least one step of washing, separating, or drying, or a combination thereof.

18. A continuous process according to claim 17 wherein said step of washing includes at least two washing stages.

19. A continuous process according to any one of claims 17 or 18 wherein said step of washing comprises a countercurrent wash.

A continuous process according to any one of claims 1-19 wherein said step of mixing comprises mixing cocoa mass which has, prior to said mixing, been subjected to processing for removal of cocoa fat therefrom. 5

21. A continuous process according to any one of claims 1-19 wherein said step of mixing comprises mixing cocoa mass which has, prior to said mixing, been subjected to mechanical pressing for removal of cocoa fat therefrom.

22. A continuous process according to any one of claims 1-19 wherein said 20 step of mixing comprises mixing cocoa mass which has not, prior to said mixing, been subjected to processing for removal of cocoa fat therefrom.

23. A continuous process according to any one of claims 1-19 wherein said step of mixing comprises mixing cocoa mass which has not, prior to said mixing, been subjected to mechanical pressing for removal of cocoa fat therefrom. g4 4

24. A continuous process according to any one of claims 1-23 wherein said cocoa mass is a dutched material.

25. A continuous process according to any one of claim 1-23 wherein said cocoa mass is not a dutched material. W:%fimV4KrQepiid 61436-d 53

26. A cocoa powder product isolated according to the process of any one of claims 1-25.

27. A cocoa butter product isolated according to the process of any one of. claims 1-25.

28. Use of the cocoa powder product of claim 26 in a cocoa powder containing food product.

29.. The use according to claim 28 wherein the cocoa powder containing food product is selected from: cocoa confectionery; chocolate ice cream; chocolate milk; chocolate frosting; chocolate syrup; chocolate cake; chocolate brownies; and mixes or partial mixes for preparing: cocoa confectionary, chocolate ice cream, chocolate milk, chocolate frosting, chocolate syrup, chocolate cake and chocolate 15 brownies.

30. Use of the cocoa butter product of claim 28 in a cocoa butter containing food product. 20

31. The use according to claim 30 wherein the coca butter product is a chocolate food product. S S. S S S. *505 S. 5 955555 S .5S S. S S *SS. 55S0 *S 55 5 0

32. steps A continuous process of treating cocoa mass; said process comprising of: 25 providing a cocoa mass containing: at least 45% by wt., fat content; and, (ii) cocoa powder; mixing the cocoa mass with a solvent which contains at least 75% by wt. solvent selected from saturated hydrocarbons having a molecular weight of no greater than about 75 to provide a slurry of cocoa mass dissolved in the solvent and undissolved cocoa solids; transferring the slurry to a separator system; separating the slurry into a solvent phase containing dissolved cocoa fat and a solids phase containing defatted cocoa solids. W:rioa\NpKI\Specics61436.doc -54-

33. A continuous process of treating cocoa mass; said process comprising the steps of: providing a cocoa mass containing; at least 10% by wt., fat content; and, (ii) cocoa powder; mixing the cocoa mass with a solvent which contains at least 90% by wt. solvent selected from saturated hydrocarbons having a molecular weight of no greater than about 75 to provide a slurry of cocoa mass dissolved in the solvent and undissolved cocoa solids; transferring the slurry to a separator system; separating the slurry into a solvent phase containing dissolved cocoa fat and a solids phase containing defatted cocoa solids.

34. A continuous process according to claim 1, 32 or 33 substantially as 15 hereinbefore described with reference to any of the examples. *f Attorneys for: CARGILL, INCORPORATED 0 0 O 5550 W:\ciskankspedciesiv 733327.doc