A PROCESS FOR REMOVING CHLOROGENIC ACID COMPOUNDS AND CAFFEINE FROM COFFEE, AND ROASTED COFFEE OBTAINABLE BY THIS PROCESS

Abstract: This invention relates to a process for removing caffeine and substances that are potentially detrimental to health from green coffee, which comprises subjecting the green coffee in the form of beans or in reduced form to extraction, using an organic solvent having a boiling point under atmospheric pressure of not more than 150°C and water, in such a way that after equilibrium has been reached or substantially reached between the coffee and the external phase of the extraction liquid this external phase is homogeneous, subjecting the thus treated coffee to a stream treatment, drying and optionally roasting the same. In order to remove substances that are potentially detrimental to health from the coffee, this invention is characterized in that extraction is carried out by co-using an acid in an amount sufficient to remove chlorogenic com­ pounds from the coffee.

Description: A process for removing caffeine and substances that are potentially detrimental to health from coffee. This invention relates to a process for preparing mild decaffeinated coffee by removing caffeine and substances that are potentially deterimental to health from green coffee, which comprises subjecting the green coffee in the form of beans or in reduced form to extraction, using an organic solvent having a boiling point of not more than 1500C under atmospheric pressure and water, in such a way that after equilibrium has been reached or substantially reached between the coffee and the external phase of the extraction liquid, this external phase is homogeneous, subjecting the thus treated coffee to steam treatment, drying and optionally roasting the same. It is known that coffee contains different components which large groups of consumers feel are irritating to the gastrointestinal tract or otherwise deleterious. One of such components is caffeine which is contained in coffee spread throughout the whole bean. Many processes for decaffeinating coffee are known. In general, caffeine is made diffusible by allowing coffee to absorb water, and caffeine is removed by extraction with an organic solvent, often dichloromethane, in which the caffeine is properly soluble, but in which other coffee ingredients are soluble as poorly as possible in order to minimize decrease in weight and quality of the coffee. After extraction the coffee is treated with steam to remove residual solvent. The organic solvent may be water-immiscible or limitedly watermiscible Applicants' laid-open European application 101,135 discloses a process for decaffeinating dry coffee with a mixture of water and an organic solvent of the last-mentioned type. As regards the decaffeination, reference is made to US patent 4,256,774 for a further discussion of the prior art. The irritation of the gastrointestinal tract caused with certain people by the consumption of coffee is ascribed to substances contained for the major part in the wax layer surrounding the green coffee beans. Some researchers believe that these substances are carboxyl5-hydroxy tryptamides (C5HT). Anyhow, these C5HT are used as indicators of the presence of the wax layer which would have to be removed in order to decrease the irritating effect of the coffee. Processes are known in which attempts are made to remove this wax layer by treating dry green coffee with an organic solvent followed by a steam treatment of the thus treated coffee to remove solvent residues. In the decaffeination of coffee by extraction with an organic solvent the wax layer will in general also dissolve so that decaffeinated coffee shows not only a decreased caffeine content, but also a decreased C5HT content. Yet it appears that such coffee causes undesirable effects with certain people. There are strong indications that chlorogenic acid compounds, particularly the caffeic acid moiety and/or ferulic acid moiety of chlorogenic acid compounds occurring in coffee play an important role for that matter. It has hitherto not been possible to remove caffeine and chlorogenic acid compounds from green coffee simultaneously and in a sufficient degree. This is caused by the fact that caffeine is substantially nonpolar, and the chlorogenic acid compounds are highly polar so that these substances behave very differently with respect to solvents. Caffeine is properly suitable in many organic solvents, which is much less the case with the chlorogenic acid compounds. The use of much water to dissolve the chlorogenic acid compounds in a sufficient degree would cause an unacceptable loss of other, properly watersoluble coffee ingredients, e.g., all types of sugars. The object of this invention is to prepare "mild" coffee by simultaneous removal of caffeine, the wax layer and chlorogenic acid compounds, particularly the caffeic acid moiety and/or ferulic acid moiety thereof, from green coffee. Surprisingly, it has been found that this object may be achieved by additional use of an acid in the extraction liquid for the extracti-.of the green coffee. Consequently, this invention relates to a process for removing caffeine and substances that are potentionally detrimental to health from green coffee, which comprises subjecting the green coffee in the form of beans or in reduced form to extraction, using an organic solvent having a boiling point under atmospheric pressure of not more than 1500C and water, in such a way that after equilibrium has been reached or substantially reached between the coffee and the external phase of the extraction liquid this external phase is homogeneous, subjecting the thus treated coffee to a steam treatment, drying and optionally roasting the same, which process is characterized in that extraction is carried out by co-using an acid in an amount sufficient to remove chlorogenic compounds from the coffee. Preferably, such amounts of organic solvent, water and acid are used that the external phase of the extraction liquid being in equilibrium with the coffee contains 65-99.48 by weight of solvent, O.5-15% by weight of water, and 0.1-25% by weight of acid. Surprisingly, it has appeared that by using the process according to this invention not only the substances are removed that are potentially detrimental to health, but also the caffeine removal efficiency increases. In addition, the selective removal of the dicaffeoylquinic acid compounds may effect an improvement in quality of the coffee in view of the negative influence on the quality suggested for these compounds (0. Ohiolpehai, G. Brumen and M.N. Clifford 10th ASIC Colloquium, Salvador de Bahia 1982, p. 177). As the various substances used in the extraction are absorbed by the green coffee in a different degree, it will be necessary tp attune the employed amounts of organic solvent, water and acid thereto. The composition of the extraction liquid and the extraction conditions, particularly the extraction temperature, should be selected in such a way that after equilibrium has been reached between the coffee and the external phase of the extraction liquid this external phase is homogeneous. By the external phase of the extraction liquid is meant the portion of the extraction liquid that is outside the green coffee during extraction. The amounts of organic solvent, water and acid in the extraction liquid should be selected in relation to the mutual miscibility of these liquids in such a way that at a practically available extraction temperature the external phase of the extraction liquid is homogeneous. For a selected organic solvent suitable mixing ratios with water and acid and a suitable extraction temperature can be determined by means of simple tests. In the extraction liquids used according to the invention a phase separation may occur owing to the separation of an aqueous phase from the organic solvent. This is particularly the case if the solvent is highly nonpolar, or if a lot of water is used. Phase separation results in that the efficiency of the extraction substantially deteriorates. Consequently the ratios of the different-substances should be selected in such a way that the external phase of the extraction liquid is homogeneous. Of course, it is PoSsible that solid particles are present in this external phase. The concept "equilibrium", as used in this context, is concerned with the absorption of the extraction liquid by the green coffee. Equilibrium has been reached as soon as the content of organic solyent, water and acid in the coffee, on the one hand, and the mutual ratio of these substances in the external phase, on the other hand, both remain constant or substantially constant. In the process according to this invention green coffee1 which has been moistened previously to such an extent that the caffeine is diffusible, or dry green coffee may be started from. In the latter case so much additional water should be used in the extraction as would have been required for previously moistening the coffee. By "moistening" is meant here a treatment with water or steam such that the coffee contains in total 20 50% by weight of water. On the other hand, it is also possible to start from coffee moistenedò such an extent that it is not necessary to supply any water to the extraction. The water contained in the coffee then diffuses, when equilibrium has been reached, partly from the coffee to the external liquid phase. In principle, any organic solvent in which caffeine is sufficiently soluble can be used in the extraction liquid. Examples of such solvents are dichloromethane, trichloroethylene and ethyl acetate. Preferably, however, as disclosed in applicants' British patent 1,527,667, an organic solvent is selected which naturally-occurs in roasted coffee and is preferably contained therein in such an amount that a not unduly long steam time is sufficient to remove the solvent residues from the coffee to such an extent that after roasting a normal content of the solvent is found in the coffee. Examples of such solvents are methyl ethyl ketone, acetone and methyl acetate. Besides, any acid can be used in the extraction liquid in principle. However; the effect has proved to be better, in proportion as the acid is better dissociable. Consequently, use is preferably made of an acid having a pKa value of less than 5. If it is desired that the roasted coffee contains no residues of the acid, use is preferably made of an acid which volatilizes or is decomposed to volatile products in the process of steaming, drying and/or roasting the coffee. It is also possible to use an acid, the acid residue of which naturally occurs in roasted coffee. Examples of acids satisfying one of these conditions or both conditions are formic acid, acetic acid, citric acid, malic acid, hydrochloric acid, sulfuric acid, and phosphoric acid. The amount of acid in the external phase of the extraction liquid is co-determined by the acidity of the acid. Particularly when stronger acids are used, smaller amounts will suffice. It should be noted that French patent publication 2363995 discloses a process for decaffeinating green coffee with benzyl alcohol. In order to reduce the viscosity thereof, there may be used a second organic compound selected from a long enumeration also mentioning acetic acid. Benzyl alcohol has a boiling point of 2050C and is therefore not suitable for the present process. Owing to the high boiling point it is hard to remove this benzyl alcohol from the treated coffee. Preferably, according to the present invention, use is made of organic solvents having a boiling point which is not higher than the boiling point of water. The lower limit for the boiling point is not critical, but compounds having a boiling point of less than OOC are preferably not used for practical reasons (necessity of very low extraction temperature or pressure apparatuses). The process according to this invention can be carried out batchwise or continuously, e.g., in an extraction battery or in a conveyor-belt extractor. By using the process according to this invention caffeine, the wax layer and chlorogenic acid compounds are removed from green coffee simultaneously. The principal chlorogenic acid compounds occurring in coffee are monocaffeoyl monoferoyl-, and dicaffeoylquinic acid compounds. The chlorogenic acid compounds which seem to be most detrimental to health are the dicaffeoyl- and monoferoylquinic acid compounds. This is explained by the fact that owing to the presence of two caffeic acid groups per molecule the dicaffeoylquinic acid compounds contribute to the formation of phenolic decomposition products during roasting of the coffee more considerably than the other chlorogenic acid subgroups, and that ferulic acid acts on the bile more strongly than the other chlorogenic acid subgroups. It its exactly the monoferoyl- and dicaffeoylquinic acid compounds that are preferentially removed from the green coff-ee by using the process according to this invention. According to this invention the extracted coffee is treated with steam and is then dried. This drying step may be immediately followed by the roasting step. It is also possible, however, to roast the dried coffee only at a later stage, if desired in another place. This invention therefore relates not only to the preparation of roasted coffee but also to the preparation of unroasted coffee. The present invention further relates to roasted or unroasted coffee obtained by using the process according to this invention. Surprisingly it has further been found that as a result of the addition of acid not only the abovementioned chlorogenic acids are co-extracted, but also the extraction of caffeine is improved-by a more favourable distribution coefficient, as shown in the following table. DISTRIBUTION COEFFICIENT Organic Methyl ethyl Ethyl Dichlorosolvent ketone acetate methane Acetic acid (g/l external 0 0 0 phase extractant (at 70 C) (at 70 C) (at 37 C) O (C0.5) 1.5 (65)* 2.4 (39)* 1.3 (2)* 8.5 1.4 (69) 12.0 2.1 (44) 16.0 1.1 (4) 21.0 1.3 (72) 31.0 1.9 (50) 33.5 1.2 (75) 47.0 , 1.0 (6) 51.7 1.9 (51) 84.4 1.0 (8) 104.6 0.9 (18) 161.3 0.9 (22) * Indicated in parentheses is the water concentration in the external phase of the extractant (in g/l). The distribution coefficient is the equilibrium concentration of caffeine in the coffee divided by that in the extract expressed as g caffeine/kg dry coffee divided by g caffeine/l extract. These distribution coefficients were determined by allowing aliquots of green coffee (optionally moistened) organic solvent, acid and, if required, water to come to equilibrium with each other overnight at the indicated temperature. If after equilibrium had been reached the external phase of the extractant was a homogeneous (i.e. single) liquid phase, then the equilibrium concentrations of water, acid and the relevant dissolved substances were measured and the distribution coefficient was calculated therefrom in the manner as indicated above. The immediate result of this more favourable distribution coefficient is that with the same amount of extractant a higher degree of caffeine extraction is reached, in other words, that less extractant is required for obtaining complete decaffeination of the coffee. This effect will be illustrated by the following examples. EXAMPLE I. In an extraction battery with six extraction sections portions of 1 kg Robusta coffee having a moisture content of approximately 10% by weight were extracted, for 8 hours, with an extraction liquid consisting of a mixture of methyl ethyl ketone (MEK), water (H20) and acetic acid (HAc), which contained 72 g H20 and 21 g HAc per liter. Portions of 1 kg coffee were supplied to the first section of the battery, as well as, spread over the residence time of one portion in the first section, 0.16 kg of a mixture of HAc and 20 in a weight ratio of 1:15. From the first section, 2.1 1 extract was withdrawn per portion of coffee, said extract containing, per liter, 72 g H20 and 21 g HAc, as well as the extracted caffeine and chlorogenic acid compounds. Portions of 2.3 kg fresh extraction liquid were supplied to the last section of the battery. The extracted coffee was obtained from the last section. The extracted coffee was steamed to remove solvent, then dried to its original moisture content, and roasted in the conventional manner. Of the original green coffee and of the dried (not yet roasted) extracted coffee, the contents of caffeine, chlorogenic acid compounds and C5HT were determined. Of the roasted extracted coffee the HAc content was determined. For comparative purposes the test described was repeated, but without HAc in the extraction liquid. The same analyses were carried out. The results are listed in the following table, in which the contents are indicated in g/kg dry matter. Before After extraction with extraction MEK + H2O MEK + H 20 + HAc Caffeine 22 0.9 0.5 Chlorbgenic acid compounds -monocaffeoylquinic acids 75 72 64 -monoferoylquinic acids 16 13.5 6.9 -dicaffeoylquinic acids 17 12 7.3 Carboxr 5-hydroxy- 0.8 o .1 (o .1 tryptamides The roasted products from both tests contained substantially equal amounts of HAc. These results show that the presence of HAc in the extraction liquid leads to a preferential increase in the extraction of monoferoylquinic acids (from 16% removal to 57% removal) and of dicaffeoylquinic acids (from 29% removal to 578 removal). The quality of the roasted product of the thus extracted green coffee was judged by professional testers as upgraded in comparison with the unextracted roasted product. EXAMPLE II. In an extraction battery with 6 extraction sections Robusta coffee was extracted countercurrently with an extraction liquid consisting of ethyl acetate, water (50 g/l) and acetic acid (31 g/l) for 9 hours at 700C. Portions of 1.35 kg moistened coffee were supplied to the first section of the battery. This moistened coffee was moistened with steam and/or water in an otherwise known manner to a moisture content of 33%. From the first section 3.0 1 extract perportion of coffee were withdrawn, said extract containing per liter 50 g water and 31 g acetic acid, as well as the extracted caffeine and chlorogenic acid compounds. 3.6 1 fresh extraction liquid per portion of coffee were supplied to the last section of the battery. The portions of extracted coffee were also obtained from this section. The extracted coffee was steamed to remove solvent residues and then dried to its original moisture content-(+ 10%). A sample of the thus obtained extracted coffee was analyzed, and the remaining part was roasted in the conventional manner. For comparative purposes the test described was repeated under equal conditions and in equal amounts, but now without acetic acid in the extraction liquid. The analysis results of the crude coffee and of both extracted green coffees are listed in the following table (indicated in g/kg dry matter). Before After extraction with extraction EtAc + H20 EtAc + H2O + HAc Caffeine 22 1.2 0.5 Chlorogenic acid compounds: -monocaffeoyl quinic acids 75 74.2 69.6 monoferoylquinic acids 16 15.0 10.4 -dicaffeoylquinic acids 17 15.6 11.1 Carboxy-5-hydroxytryptamides 0.8 t0.1 (0.1 By addition of acetic acid (31 g/l) to the extractant, under otherwise equal extraction conditions, the extraction of monoferoylquinic acids and decaffeoylquinic acids increases from respectively 6 and 8% to 35% of the-amounts originally contained in the green coffee. After roasting samples of both the unextracted and the two extracted coffees contain an acetic acid content normal to roasted Robusta coffee W4 g/kg). When testing brews of these roasted coffees, experts judged the quality of the coffee extracted with EtAc + H20 + HAc as upgraded. EXAMPLE III. The process of Example II was repeated, using dichloromethane as the organic solvent. When 161 g/l acetic acid was used in the external phase, the distribution coefficient of the monoferoylquinic acids was 35, while in the absence of acetic acid no extraction of these compounds took place. EXAMPLE IV. Example III was repeated using instead of acetic acid a series of other acids, namely,¯formic acid, citric acid, malic acid, hydrochloric acid, sulfuric acid and phosphoric acid. Comparable results are obtained. A repetition of Examples I and II with these acids gives comparable results

Claims: CLAIMS 1. A process for removing caffeine and substances that are potentially detrimental to health from green coffee, which comprises subjecting the green coffee in the form of beans or in reduced form to extraction, using an organic solvent having a boiling point under atmospheric pressure of not more than 1500C and water, in such a way that after equilibrium has been reached or substantially reached between the coffee and the external phase of the extraction liquid this external phase is homogeneous, subjecting the thus treated coffee to a steam treatment, drying and optionally roasting the same, characterized in that extraction is carried out by co-using -an acid in an amount sufficient to remove chlorogenic compounds from the coffee. 2. A process according to claim 1, characterized by using such amounts of organic solvent, water and acid that said homogeneous external phase contains 65-99.48 of solvent, 0.5-15% by weight of water, and 0.1-25% by weight of acid. 3. A process according to claim 1 or 2, characterized by using an acid having a pKa value of less than 5. 4. A process according to claims 1-3, characterized by using an acid which volatilizes or is decomposed to volatile products when the extracted coffee is steamed, dried and/or roasted. 5. A process according to claims 1- 3, characterized by using an acid having an acid residue naturally occurring in roasted coffee. 6. A process according to claims 3-5, characterized by using formic acid, acetic acid, citric acid, malic acid, hydrochloric acid, sulfuric acid, phosphoric acid or a mixture of two or more thereof. 7. A process according to claims 1-6, characterized by using an organic solvent naturally occurring in roasted coffee or a mixture of such solvents. 8. A process according to claims 1-7, characterized by using as the organic solvent methyl ethyl ketone, acetone, methyl acetate, ethyl acetate, dichloromethane, trichloroethylene or a mixture of two or more thereof. 9. A process according to claim 1, substantially as described in and illustrated by the examples. 10. Coffee obtained by using the process according to claims 1-9.

Inventors: VAN DER STEGEN, GERRIT HUBERT DIRK
Applicants: DOUWE EGBERTS KONINKLIJKE TABAKSFABRIEK- KOFFIEBRANDERIJEN-THEEHANDEL N.V.
Application year: 1985
Main classification: A23F5
IPC codes: A23F5