GB2416107A

GB2416107A - Roasting food products

Info

Publication number: GB2416107A
Application number: GB0415863A
Authority: GB
Inventors: Henricus J J Van Der Meer
Original assignee: Cargill Inc
Current assignee: Cargill Inc
Priority date: 2004-07-15
Filing date: 2004-07-15
Publication date: 2006-01-18
Also published as: GB0415863D0

Abstract

A process for the roasting of food products comprises; grinding the food product, thus reducing and homogenising particle size of the food product, shaping the ground food product to form shaped agglomerated food product and roasting the shaped agglomerated food product. The process is more economic from a process technology point of view and the obtained roasted food products, in particular cocoa powder and liquor made thereof, have improved colour and taste at a low acrylamide content.

Description

Process for the Roasting of Food Products The invention relates to a

process for the roasting of food products, in particular cocoa, and to roasted food products obtainable with said process. In particular, the invention relates to a process for the manufacture of cocoa liquor, cocoa powder and cocoa butter and to cocoa liquor, cocoa powder and cocoa butter obtainable in the process according to the invention and their use in the manufacture of chocolate products.

Food products often are roasted to improve the taste and the colour. Food product that are roasted for example are cocoa, coffee, nuts, grains, soy, herbs, spices, bakery products, starch, maize products, potato products, meat, fish, fruit or raisins. It is believed that during roasting at elevated temperature reactions occur, the so-called Maillard reactions, in which reducing sugars and amino acids react causing the development of a characteristic taste and odour profile.

A well-known example of a roasted food product is cocoa. Cocoa is the main and essential ingredient for making chocolate and cocoa powder used in various consumer products to provide a chocolate taste. As described in US 5635183, for the production of cocoa powder the cocoa nibs are often treated with a solution containing a base, typically an alkali solution, to provide a more attractive, brighter and more intense red colour. This process is called alkalising. After alkalising, the cocoa nibs are dried and subsequently roasted to develop a more attractive odour and taste profile. The roasted cocoa nibs are subsequently ground at elevated temperatures to release the cocoa butter contained in the cocoa nibs, producing cocoa liquor. The cocoa powder is obtained by separating the cocoa butter from the cocoa liquor, for example by pressing and/or extraction. The cocoa powder can be used to provide a chocolate taste to consumer products. The cocoa butter can be added together with sugar and milk solids to cocoa liquor to manufacture chocolate.

A disadvantage of the processes of the prior art for the roasting of food products, in particular also of cocoa, is that a relatively long time and relatively high temperatures are required to achieve an attractive taste and odour profile. Apart from the long process disadvantage it has been found that a long exposure to high temperatures during roasting also leads to the formation of acrylamides, which are suspected of being carcinogenic. A further disadvantage of the prior art cocoa roasting processes is that over-roasting adversely affects the quality of the cocoa butter, in particular when the cocoa nibs are alkalised before roasting. Lithe solidification characteristics of chocolate, e.g. the speed of crystallization, decreases if cocoa butter is used from cocoa nibs with a high level of roasting. Further; over-roasting leads to a high level of degradation products and impurities. A reduced crystallization speed implies poorer mould release properties and reduced production capacity in serial production of shaped chocolate articles such asEaster bunnies.

Also, in other food products a delicate balance exists between the aim to on the one hand improve the taste by roasting and on the other hand try andkeep acrylamide content as low as possible.

It is the object of the present invention to provide a process for the roasting of food products, in particular of cocoa, which does not have the above-mentioned disadvantages.

In particular, the object of the invention Is to provide a roasting process resulting in lower acrylamide levels in the roasted end product, in particular, in case of cocoa roasting, in the obtained cocoa powder and cocoa liquor. A further object of the invention is to provide a roasting process that is simpler, more economic and attractive from a process technical point of view. Further, as there is a continuous desire to improve the taste and attractiveness of the food products, it is an object of the invention to provide a roasting process resulting in food products having a consistently better taste and odour profile and a more attractive colour.

According to the invention there is provided a process for the roasting of food product comprising: grinding the food product, thus reducing and homogenizing particle size of the food product; and shaping the ground food product to form shaped agglomerated food product and roasting the shaped agglomerated food product.

It was found that with the process according to the invention food products can be obtained with a much better and more intense taste and a more attractive colour, whereas on the other hand the acrylamide content is lower. In particular, cocoa powder could be obtained with a better taste and brighter and more intense red colour, which scored substantially better in consumer tasting tests by panels and had a lower acrylamide content. The shaped agglomerated food product particles showed homogeneous roasting properties and afforded easy bulk handling and low dust formation.

Although the food product can be ground and shaped in separate process steps it is in view of process economy preferred that the food product is ground and shaped in one operational step. It was found that good results can be obtained also when grinding and shaping is done in one operational step in, for example, a pelletiser or an extruder.

l S In pelletising or extrusion the shaped agglomerated food product particles have a cylindrical shape preferably having a diameter of between 1 and 5 millimetres. The particle size of the food product in the shaped agglomerated particles is considerably reduced. Preferably, the average particle size of the food product in the shaped agglomerated particle is less than 50%, preferably less than 30%, more preferably less than 20% and most preferably less than 10% of the average particle size of the food product before grinding. Accordingly, a lower shaped particle diameter is preferred in view of obtaining improved roasting properties according to the invention. A higher particle diameter is however preferred in view of obtaining sufficient particle strength and good particle handling properties. Preferably, the particle diameter is between 2 and 4 mm. The length of the shaped agglomerated particles typically is between 3 and 10 mm. The ratio of length over diameter of the shaped particles is preferably between one and eight, more preferably between one and five in view of sufficient particle strength and bulk handling properties.

It was found that the roasting properties in the process according to the invention are favourably influenced when the shaped agglomerated food product particles have a relatively high porosity. On the other hand high porosity also implies low shaped particle strength. It was found that a good particle strength and excellent roasting properties could be obtained in the process for roasting cocoa according to the invention if the cocoa particles are shaped in a die having cylindrical holes with a compression (defined as the ratio of the length over the diameter of the hole) of between 3 and 30, preferably between and 25, most preferably between 7 and 15.

In a preferred embodiment the food product is ground and shaped in one operational step in a pelletiser having a die with holes having a compression of between 5 and 25 and a diameter of between 2 and 4 mm. It is further preferred that the holes in the die have a conically shaped entry opening, preferably over at least 0.5 mm at an angle with the holes' cylindrical axis of between 30 and 75 degrees. The advantage is that the retention periodof the food product in the pelletiser is reduced, higher throughput is achieved and the risk of releasing enclosed fat during grinding is reduced.

To improve the grinding and shaping process it is preferred that the food product is wetted with a processing aid, preferably water. In case the food product is a fat containing food product, in particular nuts or cocoa beans or nibs, the food product is wetted with water up to a water content of at least 5 wt /O. The temperature during the grinding and shaping is preferably below 100 C. It was found that cocoa nibs, after wetting with water, could be ground and reduced in size without substantial releasing the cocoa butter contained in the nibs. This was surprising because the cocoa nibs contain about 50 wt % cocoa butter contained in micro-cells of the bean and, on grinding, these micro-cells normally quickly release the cocoa butter, turning the ground nibs into a pasty viscous cocoa liquor mass. In case the food product is fat containing like nuts or cocoa nibs, the food product is wetted with an amount of water allowing sufficient time to make the hard parts of the bean flexible and to prevent temperatures from rismg to high during grinding, thus preventing the release of the cocoa butter during grinding. The required amount of water depends on the type of food product, the process conditions and the process equipment and can be established by routine experimentation using the guidelines described above. For cocoa nibs the water content at which this effect is obtained is at least about 5 wt %. Preferably, the water content in the wetted cocoa nibs is between 10 and 75 wt %, more preferably at least 12 wt %, most preferably at least 15 or even at least 20 wt %. It is preferred that in the process according to the invention the water content is equal to or less than the maximum amount of water than can be absorbed. This maximum amount usually is about 50 wt % for cocoa nibs. The advantage is that no water separation step is required, no ingredients are lost and no wastewater is generated.

In a preferred embodiment the wetted cocoa nibs are heated (cooked) to a temperature above 50 C to accelerate the absorption of water in the hard cell parts of the cocoa nibs and, in particular in case the cocoa nibs are to be alkalised, to speed up the alkalisation reaction. The heating can be done by adding heated water or alkali solution, by a double heated jacket or by supplying hot steam direct into the product mix. Preferably, the temperature is at least 70 C, more preferably at least 80 C and most preferably at least 90 C to effect simultaneous sterilization of the cocoa nibs. The time required to reach sufficient water absorption by the cocoa nibs depends on the amount of water and the temperature and can be easily determined by the skilled man having regard to the above teaching. Typically, the time is at least 0.5 h, preferably at least 0.75 h, more preferably at least l h. The optimum process conditions for grinding and shaping a food product differ for different food products. As described above, fat containing food product needs a substantial amount of water to prevent the release of the fat on grinding. Food products with a low fat content like spices, coffee, starch etc only need a low amount of water to give the ground food product a pasty consistency required for shaping and obtaining a strong agglomerated particle. In these cases optionally processing aids, for example polysaccharides, starches or other binder materials, are added instead of or in addition to water to facilitate shaping and to obtain sufficiently strong shaped particles. The skilled person can determine on the basis of the above considerations for each food product the optimum in the balance betwocn sufficient shaped particle strength on the one hand and sufficient particle porosity on the other hand.

A further advantage of the process according to the invention is that effective roasting of the shaped agglomerated particles can be obtained at moderate temperature conditions and even when the roasting is performed in the presence of a substantial amount of water.

A great advantage of this is that a very low acrylamide content can be achieved, whereas on the other hand the food product does have the desired attractive taste and odour profile. A further advantage is that this obviates the necessity of a separate drying step before the roasting step, which is a process economic advantage. Therefore, in a preferred embodiment of the process according to the invention the shaped agglomerated food lO product particles are simultaneously dried during roasting and the process does not contain a separate drying step before the roasting step.

The shaped agglomerated food product particles are roasted in the presence of water to prevent formation of acrylamide. It was found that water also delays or prevents the development of a taste and odour profile, so the amount of water is critical in this respect and for each food product and each process the temperature and duration of roasting and the amount of water during the roasting must be chosen in view of on the one hand obtaining sufficient taste and odour development and on the other hand preventing acrylamide formation. It is preferred that the process according to the invention, comprises prior determination of a water activity value of the food product that is required to achieve the desired roasting results for the food product, then roasting the food product by contacting the shaped agglomerated food product with water or water vapour at elevated temperatures between 80 and 260 C and adjusting the partial water vapour pressure at a value substantially equal to the determined water activity value.

For obtaining roasted shaped agglomerated cocoa particles having a low acrylamide content it is preferred that the water content at any time during the roasting is at least 0.5 w% and the water activity value is at least 0.05. Then water content is preferably at least 1, more preferably at least 1.5 and even more preferably at least 1.75 and most preferably at least 2 wt %. The water activity value is preferably at least 0. 1, more preferably at least 0.15, most preferably at least 0.2. Ideally, the water content at any time during the roasting is at least 1 w% and the water activity value is at least 0.1. In view of the same objective to achieve a low acrylamide content, it is further preferred that the temperature of the roasting is between 70 and 135 C, preferably between 80 and 120 C, more preferably between 90 and 110 C. It was found that despite these low roasting temperatures of the shaped agglomerated cocoa particles an acceptable or excellent roasted product can be achieved.

As described above cocoa nibs are often alkalised to improve the brightness and intensity of the red colour of the cocoa powder. Accordingly, in one embodiment of the process of the invention the cocoa nibs or shaped agglomerated cocoa particles are contacted with a base for alkalising the cocoa. It is preferred that the base is added with the water in the wetting of the cocoa nibs before grinding and shaping. In this way a good mixing, contacting and impregnation of the cocoa nibs with the base is achieved resulting in improved cocoa powder properties as will be described in more detail below. The shaped agglomerated cocoa particles containing a base after the wetting are preferably kept at a temperature between 50 and 120 C for a time sufficient to at least partially complete the alkalising reaction and are subsequently roasted at a higher temperature between 80 and 160 C. It was found that a higher quality cocoa butter could be obtained in case the alkalising reaction is performed at a lower temperature than the roasting temperature. It is preferred that substantially all base has reacted and the alkalising reaction is as complete as possible before raising the temperature for roasting.

The invention also relates to shaped agglomerated cocoa particles obtainable by a process according to the invention, in particular to shaped agglomerated cocoa particles having a cylindrical shape with a diameter of between 2 to 5 mm and a length of between 3 and 10 mm. The invention also relates to the use of shaped agglomerated cocoa particles comprising ground and agglomerated cocoa nibs, preferably pelletised particles, in a process for the manufacture of cocoa liquor, cocoa powder and/or cocoa butter.

The invention further also relates to a process for the manufacture of cocoa liquor, wherein the obtained roasted shaped agglomerated cocoa particles are subjected to grinding at elevated temperature to release the cocoa butter. The invention further relates to cocoa liquor obtainable through the process according to the invention. The cocoa liquor is a viscous pasty substance used as a basic ingredient for the manufacture of chocolate. The cocoa liquor can also be further processed by extraction and/or pressing to separate the cocoa butter and cocoa powder. The temperature may be raised just by the mechanical fraction or grinding of the process. For the production of cocoa powder the cocoa nibs are preferably alkalised. As described above, the alkalising generally has the disadvantage of a lower quality cocoa butter. Lower quality implies that the cocoa butter has a higher impurity level and, more importantly, has a lower erystallisation speed, expressed as a lower Q value. The Q value is defined as the slope or tangent of the erystallisation peak in a cooling curve (in a measurement of temperature as a function of time determined according to standard method ICA no 31 (former 1OCCC no 110, 1988).

An advantage of the present invention is that even in ease of alkalising the cocoa nibs, a good quality cocoa butter is obtained. Preferably, in the process of the invention the decrease in Q value caused by alkalising is less than 0.03 C per minute, more preferably less than 0.02 C per minute and most preferably less than 0.01 C per minute.

In particular, the invention relates to shaped agglomerated cocoa particles or cocoa liquor, wherein the acrylamide content is below 350 parts per billion (ppb), preferably below 200 ppb, more preferably below 140 ppb, even more preferably below 120 ppb and most preferably below 75 ppb. The invention further relates to cocoa butter obtainable according to the process of the invention from alkalised shaped agglomerated cocoa particles, wherein the cocoa butter has a Q value of at least 0.15 C /min, more preferably at least 0.2 C /min, even more preferably at least 0.25 C /mint In particular, the cocoa butter according to the invention has a Q value of less than 50 %, preferably less than 20 % below the Q value of natural cocoa butter obtainable in the same process without alkalisation.

The cocoa powder obtained in the process according to the invention involving an alkalisation step has an excellent quality both in terms of attractive colour and taste as well as low acrylamide content. The colour is expressed as the Oetker value. A high Oetker value correlates highly with a high consumer quality appreciation and is determined by measuring the colour of the Cocoa powder in a Hunter colour analyser, determining colour characteristic values L, a and b from the measurement in a known standard way and determining the Oetker value according to the formula: Oether value = a - 0.2 x (L + 29.7). Preferably, the cocoa powder according to the invention has an Oetker value of at least 1.0, more preferably at least l. l, even more preferably at least 1.2 and most preferably at least 1.3. The cocoa powder has an acryl amide content below 350 parts per billion (ppb), but is preferably below 200 ppb, more preferably below 150 ppb, even more preferably below 125 ppb and most preferably below 1 10 ppb.

The invention further relates to the use of the shaped cocoa agglomerated particles, cocoa liquor, cocoa powder or cocoa butter according to the invention for the manufacture of chocolate products and to chocolate products comprising cocoa powder, cocoa butter or cocoa liquor according to the invention.

The invention will be illustrated by the following examples without however bemg limited thereto.

In the experiments cocoa nibs were used from fermented African cocoa beans (40 wt % Ivory Coast, 30 wt % Nigeria, 30 wt% Cameroon). For the alkalisation an alkali solution was prepared of potassium carbonate and sodium hydroxide in a 1:1 ratio with a strength of 6.25 Be at 20 C. 2 weight parts of cocoa nibs were mixed with I weight part of alkali solution and precooked by heating coming from direct steam injection in the product mix.

The water content in the wetted nibs will be around 33 wt%. The wetted cocoa nibs were mixed for 45 minutes at a temperature 96-99 C to completely absorb the alkali solution and to simultaneously sterilise the mixture.

- Comparative experiment A: The wetted cocoa nibs were cooled down to 80 C with cold air and stored for three hours at this temperature to complete the alkalsation reaction. The wetted cocoa nibs were subsequently dried and roasted with hot air of 180 C to a water content of between 0.5 and 1.5 % ( The water activity was 0.05). The temperature of the cocoa nibs during roasting was between 80 C (at the start of the drying/roasting) and 125 C at the end of the roasting process, i.e. when it had developed the right flavour.

-Examples 1 and 2:

The wetted cocoa nibs were fed to a pelletiser to grind and shape them to pellets of 3 mm wide and 5 mm long. A UMT ring pelletiser was used, with a matrix having 3 mm holes and 30 mm length and having a capacity 3000 kg/in. The temperature of the cocoa nibs in the pelletiser during pelletising was about 80 C. The temperature of the shaped agglomerated cocoa particles after pelletising was also about 80 C. The shaped agglomerated cocoa particles were subsequently simultaneously dried and roasted with hot air of 180 C to a water content between 1.75 and 2.5% which means a water activity value of 0.1 - 015. Roasting was stopped when the pellets reached a temperature of 105- 1 10 C at the point where the right flavour was developed. The temperature of the shaped agglomerated cocoa particles during roasting was between 80 C (at the start) and 1 10 C (at the finish).

After the roasting step the roasted cocoa nibs of Comparative experiment A and the roasted shaped agglomerated cocoa particles of Examples 1 and 2 were ground to produce cocoa liquor and subsequently pressed to separate the cocoa butter and the cocoa powder. The obtained cocoa liquor and cocoa powder were characterized by measuring the colour characteristics L, a and b in a Hunter colour analyser according to a modified method applicable for cocoa. Light reflection of cocoa liquor is measured in liquid form at a temp of 50 C in a suitable transparent sample holder. Light reflection of cocoa powder is measured in the same way by making liquid slurry of 1 part cocoa powder and 3 parts water. The Oetker value was derived from the colour measurements as described above.

The cocoa butter was ana]ysed by determining the Q value from the tangent of the crystallization peak in a cooling curve obtained by measuring the temperature of a cocoa butter sample as a function of time on cooling according to method ICA no 31 (former IOCCC no. 1 10, 1988).

The acrylamide content of the cocoa powder was measured using liquid chromatography connected with double mass spectrometry.

The measurement results are listed in Table 1. The measurements show that the cocoa liquor and the cocoa powder according to the invention have a much lower acrylamide content whereas on the other hand the products have a more attractive and intense red colour (higher a/b) and a brighter red colour (higher Oetker value). The cocoa butter obtained in the process according to the invention has a higher Q value indicating that it has a higher crystallization rate.

Table 1:

Comparative Example 1 Example 2 experiment A Cocoa liquor 8.9 9.1 A 5.8 6. 3 6.1 3.7 3.8 3.5 a/b 1.58 1.64 1.74 Cocoa butter Q-value 0.15 0.18 0.18 Cocoa powder 13.3 13.9 14 9.5 10.1 10 5.8 6.1 6.1 Oetker 0.9 1.4 1.3 a/b 1.63 1.65 1.65 Acrylamide 320 115 1 23 (ppb) is

Claims

Claims 1. Process for the roasting of food product comprising: grinding

the food product, thus reducing and homogenising particle size of the food product; shaping the ground food product to form shaped agglomerated food product; and roasting the shaped agglomerated food product.
2. A process according to claim 1, wherein the food product is chosen from the IO group of cocoa, coffee, nuts, grains, soy, herbs, spices, bakery products, starch, maize products, potato products, meat, fish, fruit or raisins.
3. A process according to claim I or 2, wherein the food product is ground and shaped in one operational step in a pelletiser or an extruder.
4. A process according to claims 1 to 3, wherein the shaped agglomerate food product particles have a cylindrical shape with a diameter of between 1 and
5 mm and wherein the average particle size of the food product is reduced with at least 50 /O.

S. A process according to claim 4, wherein the length of the shaped agglomerate food product particles is between 3 and 10 mm.
6. A process according to claims I to 5, wherein the food product is shaped in a die having cylindrical holes with a compression (defined as the ratio of the length over the diameter of the hole) of between 3 and 30.
7. A process according to claims I to 6, wherein the food product is ground and shaped in one operational step in a pelletiser having a die with holes having a compression of between 5 and 25 and a diameter of between 2 and 4 mm.
8. A process according to claims 1 to 7, wherein the holes in the die have a conically shaped entry opening, preferably over at least 0.5 mm at an angle with the holes' cylindrical axis of between 30 and 75 degrees.
9. A process according to claims I to 8, wherein the food product is wetted with a processing aid.
10. A process according to claims I to 9, wherein the food product is a fat containing food product, in particular nuts or cocoa beans or nibs and wherein the food product is wetted with at least 5 wt % water (relative to the total weight of food product and water).
II.A process according to claims I to 10, wherein the temperature during the grinding and shaping is below 100 C.
12. A process according to claims 1 to 11, comprising determining a water activity value of the shaped agglomerated food product particles that is required to achieve the desired roasting results for the food product and roasting the shaped agglomerated food product particles by contacting with water or water vapour at an elevated temperature of between 80 and 260 C and adjusting the partial water vapour pressure at a value substantially equal to the determined water activity value.
13. A process according to claims I to 12, wherein the food product is cocoa nibs and wherein the cocoa nibs are wetted with water up to a water content of at least 5 wt % before grinding and are roasted at a temperature between 80 and 160 C.
14. A process according to claim 13, wherein the water content of the wetted cocoa nibs is between 10 and 75 wt %.
15. A process according to claims 13 or 14, wherein the water content in the wetted cocoa nibs is equal to or less than the maximum amount of water that can be physically absorbed by the cocoa nibs.
16. A process according to any one of claims 13 to 15, wherein the shaped agglomerate food product particles are simultaneously dried during roasting.
17. A process according to claims 13 to 16, wherein the shaped agglomerated cocoa particles are roasted at a temperature between 80 and 1 20 C.
18. A process according to any one of claims 13 to 17, wherein the water content at any time during the roasting is at least 0.5 w% and the water activity value is at least 0.2.
19. A process according to any one of claims 13 to 18, wherein the agglomerate cocoa particles are contacted with a base for alkalising the cocoa.
20. A process according to claim 19, wherein the base is added with the water in the wetting of the cocoa before grinding and shaping.
21. A process according to claim 19 or 20, wherein the shaped agglomerate cocoa particles containing a base are kept after the wetting at a temperature between 50 and 120 C for a time sufficient to at least partially complete the alkalising reaction and are subsequently roasted at a higher temperature between 80 and 1 60 C.
22. A process for the manufacture of cocoa liquor for the manufacture of cocoa powder, cocoa butter or chocolate products, wherein the roasted shaped agglomerate cocoa particles obtained in the process according to any one of claims 13 to 21 are subjected to grinding at an elevated temperature to release the cocoa butter.
23. A process according to claim 22, wherein the cocoa butter is separated from the cocoa liquor and wherein the decrease in Q value of the cocoa butter caused by alkalising is less than 0.02 C per minute.
24. Shaped agglomerate food product particles obtainable by a process according to any one of claims 1 to 21.
25. Shaped agglomerate food product particles according to claim 24, wherein the 10particles have a cylindrical shape with a diameter of between 2 to 5 mm and a length of between 3 and 10 mm.
26. Shaped agglomerate food product particles comprising ground and agglomerated food product, preferably pelletised, for use in a roasting process.
27. Shaped agglomerate food product particles according to claims 24 to 26, wherein the acrylamide content is below 350 parts per billion (ppb).
28. Cocoa liquor obtainable according to process of claim 22.
29. Cocoa butter obtainable according to the process according to claims 13 to 23, wherein the cocoa butter has a Q value of less than 20% below the Q value of natural cocoa butter obtainable in the same process without alkalisation.
30. Cocoa butter according to claim 29, wherein the decrease in Q value of the cocoa butter is less than 50% of the decrease in Q value of the cocoa nibs.
31. Cocoa powder obtainable according to any one of claims 13 to 23, wherein the Oetker value is at least 1.0, wherein the Oetker value is determined by measuring the colour of the Cocoa powder in a Hunter colour analyser, determining colour characteristic values L, a and b from the measurement and determining the Oetker value according to the formula: Oetker value = a - 0.2 x (L + 29.7)
32. Cocoa powder according to claim 31, wherein the acrylamide content is below 200 parts per billion (ppb).
33. Use of the shaped cocoa agglomerate particles, cocoa liquor, cocoa powder or cocoa butter according to any one of claims 23 to 27 for the manufacture of chocolate products.
34. Chocolate products comprising cocoa powder, cocoa butter or cocoa liquor according to any one of claims 23 to 27.