CA1104411A - Process for preparing decaffeinated coffee - Google Patents
Process for preparing decaffeinated coffeeInfo
- Publication number
- CA1104411A CA1104411A CA300,116A CA300116A CA1104411A CA 1104411 A CA1104411 A CA 1104411A CA 300116 A CA300116 A CA 300116A CA 1104411 A CA1104411 A CA 1104411A
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- Prior art keywords
- extract
- caffeine
- coffee
- water
- solvent
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Classifications
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23F—COFFEE; TEA; THEIR SUBSTITUTES; MANUFACTURE, PREPARATION, OR INFUSION THEREOF
- A23F5/00—Coffee; Coffee substitutes; Preparations thereof
- A23F5/20—Reducing or removing alkaloid content; Preparations produced thereby; Extracts or infusions thereof
- A23F5/22—Reducing or removing alkaloid content from coffee extract
- A23F5/226—Reducing or removing alkaloid content from coffee extract by extraction with selective solvents
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23F—COFFEE; TEA; THEIR SUBSTITUTES; MANUFACTURE, PREPARATION, OR INFUSION THEREOF
- A23F5/00—Coffee; Coffee substitutes; Preparations thereof
- A23F5/46—Coffee flavour; Coffee oil; Flavouring of coffee or coffee extract
- A23F5/48—Isolation or recuperation of coffee flavour or coffee oil
- A23F5/50—Isolation or recuperation of coffee flavour or coffee oil from coffee extract
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Tea And Coffee (AREA)
Abstract
PROCESS FOR PREPARING DECAFFEINATED COFFEE
Gregory L. Bolt and Dennis R. Grubbs ABSTRACT
A process for preparing a soluble decaffeinated coffee of improved flavor and aroma is described. The process comprises the steps of forming an aqueous extract of roast and ground coffee, decaffeinating the extract by contact with a water-immiscible organic solvent for caffeine, and separating the decaffeinated aqueous coffee extract from the caffeine-laden water-immiscible organic solvent. The coffee extract is improved in its flavor and aroma by incorporation of certain flavorful compounds separated from the caffeine-laden organic solvent. Caffeine is partitioned from the organic solvent by contact with water and the resulting organic solvent and its content of flavorful compounds is incorporated into the coffee extract.
Gregory L. Bolt and Dennis R. Grubbs ABSTRACT
A process for preparing a soluble decaffeinated coffee of improved flavor and aroma is described. The process comprises the steps of forming an aqueous extract of roast and ground coffee, decaffeinating the extract by contact with a water-immiscible organic solvent for caffeine, and separating the decaffeinated aqueous coffee extract from the caffeine-laden water-immiscible organic solvent. The coffee extract is improved in its flavor and aroma by incorporation of certain flavorful compounds separated from the caffeine-laden organic solvent. Caffeine is partitioned from the organic solvent by contact with water and the resulting organic solvent and its content of flavorful compounds is incorporated into the coffee extract.
Description
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, . ~ 15 BACKGROUND OF THE INVENTION
This invention relates to a process for preparing a ' ~ ' decaffeinated coffee extract. More'particuiarly, it relates to '~ a process for the preparation of a decaffeinated coffee extract of the soluble or instant type.
, Numerous metho,ds for the decaffeination of,coffee have been desc~ibed in the art.' For example, U.S. Reissue Patent 13,261, ' issued September 1, 1908 to ~eyer et al., describes a process involv ' ing direct contact between green coffee and a solvent for caffeine.
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~loistened green coffee beans are contacted with an or~anic solvent, residual solvent is removed from the green beans, and the decaffeinated beans are roasted for preparation of a coffee extract and product therefrom. Another approach to decaffeina-tion of coffee has involved the formation of an aqueous extract ofgreen coffee solubles followed by a liquid/liquid decaffeination operation utilizing an organic solvent. This method is described in detail in U.S. Patent 2,309,092, issued January 26, 1943 to ' Berry et al.
10Green bean decaffeination methods, while effective to remove caffeine from the coffee beans, involve the handling of large amounts of coffee and solvent materials and require the ; utilization of expensive equipment and facilities. Moreover, the decaffeination and desolventizing steps employed in green bean decaffeination methods are slow operations tending to reduce process efficiency.
Certain of the economic considerations and processing inefficiencies of green bean decaffeination methods have been overcome by resort to liquid/liquid decaffeination of roast and ground coffee extract. Extract decaffeination methods are rela-tively fast in operation and require less capital equipment and expense than green bean decaffeination methods. Examples of extract decaffeination methods are described in U.S. Patent
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, . ~ 15 BACKGROUND OF THE INVENTION
This invention relates to a process for preparing a ' ~ ' decaffeinated coffee extract. More'particuiarly, it relates to '~ a process for the preparation of a decaffeinated coffee extract of the soluble or instant type.
, Numerous metho,ds for the decaffeination of,coffee have been desc~ibed in the art.' For example, U.S. Reissue Patent 13,261, ' issued September 1, 1908 to ~eyer et al., describes a process involv ' ing direct contact between green coffee and a solvent for caffeine.
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~loistened green coffee beans are contacted with an or~anic solvent, residual solvent is removed from the green beans, and the decaffeinated beans are roasted for preparation of a coffee extract and product therefrom. Another approach to decaffeina-tion of coffee has involved the formation of an aqueous extract ofgreen coffee solubles followed by a liquid/liquid decaffeination operation utilizing an organic solvent. This method is described in detail in U.S. Patent 2,309,092, issued January 26, 1943 to ' Berry et al.
10Green bean decaffeination methods, while effective to remove caffeine from the coffee beans, involve the handling of large amounts of coffee and solvent materials and require the ; utilization of expensive equipment and facilities. Moreover, the decaffeination and desolventizing steps employed in green bean decaffeination methods are slow operations tending to reduce process efficiency.
Certain of the economic considerations and processing inefficiencies of green bean decaffeination methods have been overcome by resort to liquid/liquid decaffeination of roast and ground coffee extract. Extract decaffeination methods are rela-tively fast in operation and require less capital equipment and expense than green bean decaffeination methods. Examples of extract decaffeination methods are described in U.S. Patent
2,472,121 (issued June 7, 1949 to Ornfelt); U.S. Patent 2,472,881 (lssued June 14, 1949 to Bender); and U.S. Patent 2,933,395 (issued April 19, 1960 to Adler et al.). In general, these methods involve the preparation of an extract of roast and ground coffee and decaffeination of the extract by utilization of a water-immiscible organic solvent for caffeine. The resulting decaf-
3~ feinated extract, separated from the caffeine-laden organic solvent, can be utillzed in the preparation of a soluble coffee in conventional manner.
while extract decaf~eination methods per-Jni~
certain ~conomlc aind practical limitations of green ~ean decaf-feination methods to be overcome, extract decaffeination methods are attended by the same problems of flavor quality as exist in the case of decaffeination methods in general. Thus, it has been generally appreciated that decaffeinated coffee products tend to lack the flavor and aroma qualities of their non-decaffeinated counterparts. The tendency of decaffeinated coffee ' products to be diminished with respect to flavor and aroma principles that contribute materially to cup aroma and flavor has heen attributed for the most part to the tendency of caffeine solvents to remove certain desirable non-caffeine constituents of coffee.
It is an object of the present invention to provide a process for the decaffeination of coffee.
It is another object of the invention to provide an economical and efficient process for preparin~ a decaffeinated coffee extract.
Still another object of the invention is to provide a process for the preparation of a coffee extract deprived of its caffeine content while retaining to the extent practicable its non-caffeine constituents.
These and other objects of the invention will become apparent from the detailed description provided hereinafter.
SUMM~RY OF THE INVENTION
The present invention is based in part upon the dis-covery that important non-caffeine flavor and aroma constituents normally removed from an aqueous coffee extract in the course of liquid/liquid decaffeination can be efficiently recovered and restored to the coffee extract with the result that an extract ~1~44~
having improved flavor and aroma characteristics is obtained.
Thus, the recovery and restoration to a coffee extract of these important coffee and aroma principles can be effectively utilized in extract decaffeination methods. These methods generally comprise the steps of forming an aqueous extract of roast and ground coffee, decaffeinating the extract by contact with a water-immiscible organic solvent for caffeine, and separating the decaffeinated aqueous coffee extract from the caffeine-containing water-immiscible organic solvent. It has been found that desirable flavor and aroma principles can be effectively recovered by partitioning the caffeine content of the water-immiscible organic solvent into water. The resulting organic solvent and its content of flavor and aroma principles can thereafter be restored to the coffee extract.
The extract can then be desolventized and dried in a conventional manner to a soluble coffee product having improved flavor and aroma characteristics.
More particularly, the present invention resides in a process for preparing a decaffeinated coffee, which comprises the steps of:
(1) decaffeinating an aqueous roast and ground coffee extract by contact with a water-immiscible organic solvent for caffeine;
(2) separating the decaffeinated aqueous coffee extract from the caffeine-containing water-immiscible organic solvent;
(3) concentrating the caffeine-containing water-immiscible solvent to a solids content of from about 1~ to about 10% by weight;
while extract decaf~eination methods per-Jni~
certain ~conomlc aind practical limitations of green ~ean decaf-feination methods to be overcome, extract decaffeination methods are attended by the same problems of flavor quality as exist in the case of decaffeination methods in general. Thus, it has been generally appreciated that decaffeinated coffee products tend to lack the flavor and aroma qualities of their non-decaffeinated counterparts. The tendency of decaffeinated coffee ' products to be diminished with respect to flavor and aroma principles that contribute materially to cup aroma and flavor has heen attributed for the most part to the tendency of caffeine solvents to remove certain desirable non-caffeine constituents of coffee.
It is an object of the present invention to provide a process for the decaffeination of coffee.
It is another object of the invention to provide an economical and efficient process for preparin~ a decaffeinated coffee extract.
Still another object of the invention is to provide a process for the preparation of a coffee extract deprived of its caffeine content while retaining to the extent practicable its non-caffeine constituents.
These and other objects of the invention will become apparent from the detailed description provided hereinafter.
SUMM~RY OF THE INVENTION
The present invention is based in part upon the dis-covery that important non-caffeine flavor and aroma constituents normally removed from an aqueous coffee extract in the course of liquid/liquid decaffeination can be efficiently recovered and restored to the coffee extract with the result that an extract ~1~44~
having improved flavor and aroma characteristics is obtained.
Thus, the recovery and restoration to a coffee extract of these important coffee and aroma principles can be effectively utilized in extract decaffeination methods. These methods generally comprise the steps of forming an aqueous extract of roast and ground coffee, decaffeinating the extract by contact with a water-immiscible organic solvent for caffeine, and separating the decaffeinated aqueous coffee extract from the caffeine-containing water-immiscible organic solvent. It has been found that desirable flavor and aroma principles can be effectively recovered by partitioning the caffeine content of the water-immiscible organic solvent into water. The resulting organic solvent and its content of flavor and aroma principles can thereafter be restored to the coffee extract.
The extract can then be desolventized and dried in a conventional manner to a soluble coffee product having improved flavor and aroma characteristics.
More particularly, the present invention resides in a process for preparing a decaffeinated coffee, which comprises the steps of:
(1) decaffeinating an aqueous roast and ground coffee extract by contact with a water-immiscible organic solvent for caffeine;
(2) separating the decaffeinated aqueous coffee extract from the caffeine-containing water-immiscible organic solvent;
(3) concentrating the caffeine-containing water-immiscible solvent to a solids content of from about 1~ to about 10% by weight;
(4) contacting the concentrated caffeine-containing water-immiscible organic solvent with an amount of water sufficient to partition caffeine into the aqueous phase;
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(5) recovering the water-immiscible organic solvent containing flavor and aroma constituents;
(6) incorporating said water-immiscible organic solvent and flavor and aroma constituents into the decaffeinated roast and ground coffee extract; and
(7) desolventizing the decaffeinated coffee extract to form a desolventized extract.
DETAILED DESCRIE'TION OF THE IN~IENTION
By the process of the present invention, an aqueous extract of roast and ground coffee is subjected to a liquid/
liquid extraction with an organic water-immiscible caffeine solvent. A resulting caffeine-laden solvent is separated from the decaffeinated coffee extract and is subjected to a recovery process whereby certain desirable flavor and aroma principles in the organic solvent are retained after partitioning of a caffeine content of the organic solvent into water.
The aqueous coffee extract can be prepared in conven-tional manner from roast and ground coffee beans. Coffee beans are roasted and yround to a suitable state of subdivision for extraction by any of a number of known methods. Counter-current extraction -4a-l:lQ4~11 methods can conveniently be employed, and examples of such methods are described in, for example, U.S. Patent 3,700,463 (issued October 24, lg72 to Bolt et al.), and U.S. Patent 3,700,466 (issued October 24, 1972 to Bergeron et al.). The extract will normally have a concentration of soluble coffee solids in ' the range of from about 15% to 35%, although extracts having a lesser or greater concentration of such coffee solids can be employed.
The coffee extract can be devolatilized prior to the liquid/liquid extraction operation. For example, the coffee extr~c can be devolatilized by flashing-off volatiles at subatmospheric pressure or by passing an inert gas such as carbon dioxide, nitro-gen, or steam through the coffee extract. The coffee volatiles are condensed for later addition to the coffee extract, kno~7n as the add-back process. The ernployment of a devolatilization step, whereby the volatiles are condensed in a suitably chilled conden-ser for add-back to the coffee extract, constitutes a preferred practice from the standpoint of optimizing flavor of the ultimate coffee product and minimizing the possibly adverse affect of opera-ting conditions upon the volatile components of the coffee extract.
A preferred devolatilization step involves the stripping of vola-tiles from the coffee extract ~ ith the aid of steam.
If desired, the coffee extract can be concentrated prior to the liquid/liquid decaffeination operation. For example, the 25 extxact can be concentrated into the range of about 30% to about 4596 coffee solids prior to the decaffeination step.
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The roast and ground coffee extract can be decaf-- feinated by a number of methods. The decaffeination operation involves a liquid/liquid extraction whereby contact of the aqueous extract with a liquid water-immiscible organic solvent 5 effects substantial removal of the caffein~- content of the ' coffee extract. Any of a variety of water-immiscible organic caffeine solvents can be employed. Examples include hydrocarbon solvents such as benzene and toluene, halogenated hydrocarbons, such a~ chloroform, methylene chloride, dichloroethylene, trichloro-ethylene, difluoromonochloromethane, and l,l,l-trichloroethane.
Other suitable water-immiscible organic solvents for caffeine include ethyl acetate and benzyl alcohol. It will be appreciated that preferred solvents will include those which are effective to remove caffeine from the extract while removing as small an amount of non-caffeine coffee solids as practicable and leaving as little residue of solvent in the ultimate coffee product.
The liquid/liquid extraction is preferably performed while using as low a solvent to extract ratio as is practicable. The employment of low solvent to extract ratios permits removal of the caffeine content from the coffee extract while minimizing the ` amount of non-caffeine solids removed from the extract. Thus, by controlling the amount of organic solvent contacted with the coffee extract, the extraction of coffee solids having solvent-to-water distribution coefficients smaller than caffeine is mini-mized. Employment of high ratios of solvent to extract results in the increased removal along with caffeine of coffee solids having solvent to water distribution coefficients smaller than caffeine.
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When the caffeine-laden solvent is thereafter contacted with water to partition the caffeine content from the organic solvent, such coffee solids tend to partition along with the caffeine with the result that such solids do not remain with the organic sol-vent for restoration to the coffee extract. A ratio of water-immiscible organic solvent to coffee extract in the range of from about 0.3:1 to about 10:1 can be employed. The particular ratio employed will depend upon the particular solvent selected for the ' extract decaffeination. For example, where the solvent is 10 methylene chloride, a preferred ratio will be from 0.5:1 to 1:1.
The liquid/liquid decaffeination operation can be con-ducted in a batch or continuous operation, although a continuous countercurrent liquid/liquid extraction of caffeine will be pre-ferred. Liquidjliquid extraction techniques are well known and 15 generally involve continuous contacting of extract with the water-immiscible organic caffeine solvent. The contact can be suitably conducted in an elongated column. For example, where a solvent heavier than the aqueous extract is employed, the aqueous extract can be sprayed into the lower end of an elongated column containing 20 the caffeine solvent. The coffee extract is allowed to travel upwardly in a manner countercurrent to the solvent and the decaf-feinated extract is removed continuously from the top of the decaffeination column. Such a method is described in detail in U.S. Patent 2,933,395 (issued April 19, 1960 to Adler et al.l.
25 Other methods for effecting the liquid/liquid extraction can be employed. For example, the coffee extract can be contacted with the caffeine solvent by passing the extract and the organic solvent in countercurrent fashion into a packed columnar bed comprising an elongated tower fitted with Pall rings, Raschig 30 rings or the like.
' Pre~erred apparatus foL conducting the liquid/liquid decaffeination comprises such liq~lid/liquid contacting devices as the ~otary-disk Contactor, the"Oldshue-Rushto~' column, or the "~ork-Scheibel~column. It will be appreciated that the feasibility of the employment of low ratios of solvent to extract will depend in part upon the nature of the solvent employed, the concen- ~
tration of the coffee extract, and the efficiency or mass transfer -capability of the liquid/liquid contacting equipment. Thus, it will be preferred to employ a liquid/liquid contacting device which provides the mechanical agitation and turbulence necessary for maximization of mass transfer. For this reason, a preferred type of liquid/liquid contactor is the Rotary-disk Contactor.
It has been found that such a device will permit efficient decaf-feination at low solvent-to-extract ratios, e.g., less than 1:1. The Rotary-disk Contactor and other suitable liquid/liquid contacting devices are described in detail in Perry's Chemical Engineers' Handboo~, McGraw-~ill Book Company, 4th Edition, Section 21, pp. 23-35.
The decaffeinated extract is separated from the caffeine-laden solvent in known manner. Normally the separation will be the result of continuous removal of countercurrent coffee extract and solvent streams from the liquid/liquid contactor. The sepa-rated caffeine-laden solvent is thereafter treated for recovery of flavor and aroma principles.
The water-immiscible organic caffeine-laden solvent is treated for separation of the caffeine therefrom. This is accom-plished by contacting the caffeine-laden solvent with an amount of water sufficient to remove or partition the caffeine from the organic phase into the aqueous phase. Substantially complete removal F partition of caffeine from the organic solvent is * Trademark __ _ _ ** Trademark n q~
realized. The amount of water employed will vary with the parti-cular nature of the solvent. Generally, an amount of water pro-viding a ratio of water to caffeine-laden solvent of from about 0.5:1 to about 10:1 ~Jill be sufficient to effect the partition-ing of caffeine into an aqueous phase. A preferred ratio in thecase of methylene chloride solvent is from 5:1 to 6:1.
Preferably, the caffeine-laden solvent will be concentrated prior to caffeine removal so as to minimize the amount of caffeine-laden solvent which must be handled and contacted with water for 10 the caffeine removal. In addition, concentration of the caffeine-laden solvent permits maximization of mass transfer and reduces capital equipment requirements. Concentration can be effected by flashing of the organic solvent, hy the use of conventional thin-film evaporators or the like. For 15 economy of operation, evaporated solvent will be condensed for re-use in further liquid/liquid decaffeination. The concentrated caffeine-laden solvent will preferably be concentrated such that the solids content comprlses from about 1% to about 10% by weight of the caffeine-laden solvent.
The partitioning of caffeine from the caffeine-laden solvent can be achieved by any effective contact of water with the caffeine-laden solvent. The caffeine-laden solvent can ~e introdu ed in a countercurr2nt manncr into a colu~n containing water. As in the case of the liquid/liquid 25 deca~feination operation, the separation of caffeine from the caffeine-laden solvent can be facilitated by the use of other conventional liquid~liquid contacting devices. A preferred device is a continuous countercurrent extractor such as a Rotary-disk Contactor. This device permits intimate contact between 30 water and the caffelne-laden solvent and efficient recovery of aqueous and organic phases.
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The amount of aroma and Llavor principles restored to the coffee extract will depend upon the amount present in the organic solvent as the result of the extract decaffeination operation. It will be appreciated that the advantages achieved 5 by restoration to a coffee extract of such principles will depend upon the nature of the coffee e~tract and the selectivity of the caffeine solvent used in the decaffeination operation. For example, ethyl acetate will remove from a coffee extract, in addition to caffeine, an appreciable content of aroma and flavor 1~ principles, relative to a more selective solvent such as metllylene chloride. Accordingly, the benefits of the process of the inven-tion will be most advantageous and the greatest contribu-tion realized where relatively non-selective solvents are employed.
The process of the invention, thus, makes more feasible the use of such solvents for the decaffeination of coffee.
The removal of caffeine from the caffeine-laden solvent results in the recovery in the solvent of certain flavor -and aroma principles. These principles, when restored to the decaffeinated coffee extract, permit the preparation of a decaf-feinated coffee extract having as much of the aroma and flavor principles as is practicable. Thus, the extract when dried in a conventional manner to a soluble or instant coffee product, pro-vides a product having improved flavor and aroma properties.
While the precise chemical nature of the recovered flavor and aroma principles is not entirely unAerstoorl, they are com.~rised of numerous flavorful and aromatic principles resulting from roasting and extraction or hydrolysis of coffee. The flavor and aroma principles, although water-soluble, have a greater affinity than caffeine for the organic solvent as is apparent from the recover~ of such principles in the organic phase and recovery of caffeine in the aqueous phase.
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The flavor and aroma principles recov~red by th~
process of the invention are incorporated into the decaffeinated coffee extract prior to conventional drying thereof. The production of a soluble coffee powder from a decaffeinated coffee extract will be preceded by a solvent-stripping operation whereby residual solvent can be removed from the coffee extract. The flavor and aroma principles in the organic solvent can be added to the decaffeinated extract prior to the removal of residual solvent therefrom. Thus, the decaf-1'~ feinated aqueous extract and the added solvent with flavor andaroma principles can be treated for simultaneous removal of solvent. Preferably, the solvent will be stripped from the decaf-feinated extract by passing the extract over a heated evaporating surface under reduced pressure or by stripping with steam.
lS Conventional thin-film evaporation devices can be used for this purpose. Other methods for volatilizing and recovering residual solvent can, however, be employed.
Ater stripping of residual solvent, con~ensed vola-tiles from the coffee extract obtained prior to the decaffeination thereof, if any, can be added to the extract. The resulting extract is then dried to a soluble coffee powder, e.g., by spray-drying or freeze-drying, with or without a prior concentration stép.
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The invention is illustrated in the following specific e~amples which are given by way of example only and not as limiting the invention. All pcrcen~agcs and ratios expressed in the specification and clai.-.ls are by weight.
EXAMPI.E I
An aqueous coffee extract having a solubles content of 20% is prepared by conventional countercurrent extraction of roast and ground coffee. The coffee extract is subjected to a devolatilization step by contacting the extract with steam (0.1 lb. of steam/lb. of extract~ in a packed column maintained at a vacuum of 21 inches of mercury. The steam-stripped volatiles .~ -.1.1- .
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are condensed, and the condensate is stored at less than 50F
for subsequent reincorporation into the coffee extract.
The stripped, i.e., devolatilized, coffee extract is introduced as the dispersed phase into the bottom of a con-tinuous countercurrent extractor (a Rotary-disk Contactor).
The decaffeination solvent, methylene chloride, is introduced at the top of the extractor as the continuous phase. A solvent ratio of 1.0 lb. of solvent/lb. of coffee extract is used at a-temperature of 9QF, and caffeine removal of 98% is achieved.
The decaffeinated extract containing dissolved and entrained solvent is withdrawn from the top of the extractor. The decaf-feination solvent containing caffeine and flavor and aroma constituents is withdrawn from the bottom of the extractor.
The decaffeination solvent containing caffeine and flavor and aroma constituents is evaporated to a solids concen-tration of about 5% by weight. The concentrated solvent is then introduced as the dispersed phase into the top of a second continuous countercurrent extractor (another Rotary-disk Contactor) with water as the continuous phase. A water-to-solvent ratio of 5.0 is used at a temperature of 70F and a caffeine removal of 99% i5 achieved. The decaffeinated concentrated solvent stream containing the flavor and aroma constituents is withdrawn from the bottom of the extractor and added to the decaffeinated coffee extract. The resulting extract is then desolventized by steam-stripping in another packed column maintained at a vacuum of 21 inches mercury and using 0.1 lb. of steam/lb. of extract. The residual solvent level in the decaffeinated coffee extract is reduced ~o less than 1 ppm on a solids basis. The decaffeinated coffee extract is then concentrated to 63~ solubles by vacuum evaporation. The condensate of steam-stripped volatiles is added to the coffee extract, and the extract is spray-dried to a 97 decaffeinated soluble coffee powder.
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The resulting product is si~nificantly stronger and has a more flavorful, balanced flavor than would a corresponding product made without recovery of flavor and aroma constituents from the caffeine-laden solvcnt and restoration thereof to the decaffeinated coffee extract.
- EXAM~LE II
An aqueous coffee extract having a solubles content of 20% is prepared by conventional countercurrent extraction of roast and ground coffee. The coffee extract is subjected to a devolatilization step by contacting the extract with steam (0.1 lb. of steam/lb. of extract) in a packed column maintained at a vacuum of 21 inches of mercury. The steam-stripped volatiles are condensed, and the condensate is stored at less than 50F
for subsequent reincorporation into the coffee extract.
The stripped, i.e., devolatilized, coffee extract is introduced as the dispersed phase into the top of a continuous countercurrent extractor (a Rotary-disk Contactor). The decaf-feination solvent, ethyl acetate, is introduced at the bottom of the extractor as the continuous phase. A solvent ratio of 1.3 lbs. of solvent/lb. of coffee extract is used at a tempera-ture of 140~ F. and caffeine removal of 98% is achieved. The decaffeinated extract containing dissolved and entrained solvent is withdrawn from the ~ottom of the extractor. The decaffeination solvent containi~g caffeine and flavor and aroma constituents is withdrawn from the top of the extractor.
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The decaffeination solv~nt containing caffeine and flavor and aroma constituents is evaporated to a solids concen-tration of about 1.5~ by weight. The concentrated solvent is then introduced as the dispersed phase into the bottom of a 5 second continuous countercurrent extractor (:another Rotary- :
dis.k Contractorl with water as the continuous phase. A water~
to-solvent ratio.~of ~7 is used at a temperature of 70 F. and a caffeine removal of ~g% i.s ach.ieved. The decaffeinated con-centrated solvent stre.am containing the flavor and aroma con~ ;
st~.tuti.ons is. withdrawn from the top of the extractor and added to th.e.decafeinate.d coffee extract, The resulting extract is then desolventized ~y steam-stripping in another packed column maintaine.d at a vacuum of 21 inches mercury and using 0.1 1~.
of steam~lb-~ of extract. The residual solvent level in the de.caffeinate.d coffee extract is reduced to less than 1 ppm on a solids ~.asis, The de.caffe~.nated coffee. extract is then con-centrated to ~3% solu~les ~.y vacuum evaporation, The condensate of steam-stripped volatiles is added to the coffee extract, and the extract ~s spray~drl:ed to a g7~ decaffeinated soluble coffee 20. po~der, Th.e resulti.ng product is significantly stronger and has a more ~lavorful, ~alanced flavor than ~ould a corresponding product made without recovery of flavor and aroma constituents from the caffeine~laden solvent and restoration thereof to the deca~einated coffee extract, , , ~14~
DETAILED DESCRIE'TION OF THE IN~IENTION
By the process of the present invention, an aqueous extract of roast and ground coffee is subjected to a liquid/
liquid extraction with an organic water-immiscible caffeine solvent. A resulting caffeine-laden solvent is separated from the decaffeinated coffee extract and is subjected to a recovery process whereby certain desirable flavor and aroma principles in the organic solvent are retained after partitioning of a caffeine content of the organic solvent into water.
The aqueous coffee extract can be prepared in conven-tional manner from roast and ground coffee beans. Coffee beans are roasted and yround to a suitable state of subdivision for extraction by any of a number of known methods. Counter-current extraction -4a-l:lQ4~11 methods can conveniently be employed, and examples of such methods are described in, for example, U.S. Patent 3,700,463 (issued October 24, lg72 to Bolt et al.), and U.S. Patent 3,700,466 (issued October 24, 1972 to Bergeron et al.). The extract will normally have a concentration of soluble coffee solids in ' the range of from about 15% to 35%, although extracts having a lesser or greater concentration of such coffee solids can be employed.
The coffee extract can be devolatilized prior to the liquid/liquid extraction operation. For example, the coffee extr~c can be devolatilized by flashing-off volatiles at subatmospheric pressure or by passing an inert gas such as carbon dioxide, nitro-gen, or steam through the coffee extract. The coffee volatiles are condensed for later addition to the coffee extract, kno~7n as the add-back process. The ernployment of a devolatilization step, whereby the volatiles are condensed in a suitably chilled conden-ser for add-back to the coffee extract, constitutes a preferred practice from the standpoint of optimizing flavor of the ultimate coffee product and minimizing the possibly adverse affect of opera-ting conditions upon the volatile components of the coffee extract.
A preferred devolatilization step involves the stripping of vola-tiles from the coffee extract ~ ith the aid of steam.
If desired, the coffee extract can be concentrated prior to the liquid/liquid decaffeination operation. For example, the 25 extxact can be concentrated into the range of about 30% to about 4596 coffee solids prior to the decaffeination step.
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11~4~
The roast and ground coffee extract can be decaf-- feinated by a number of methods. The decaffeination operation involves a liquid/liquid extraction whereby contact of the aqueous extract with a liquid water-immiscible organic solvent 5 effects substantial removal of the caffein~- content of the ' coffee extract. Any of a variety of water-immiscible organic caffeine solvents can be employed. Examples include hydrocarbon solvents such as benzene and toluene, halogenated hydrocarbons, such a~ chloroform, methylene chloride, dichloroethylene, trichloro-ethylene, difluoromonochloromethane, and l,l,l-trichloroethane.
Other suitable water-immiscible organic solvents for caffeine include ethyl acetate and benzyl alcohol. It will be appreciated that preferred solvents will include those which are effective to remove caffeine from the extract while removing as small an amount of non-caffeine coffee solids as practicable and leaving as little residue of solvent in the ultimate coffee product.
The liquid/liquid extraction is preferably performed while using as low a solvent to extract ratio as is practicable. The employment of low solvent to extract ratios permits removal of the caffeine content from the coffee extract while minimizing the ` amount of non-caffeine solids removed from the extract. Thus, by controlling the amount of organic solvent contacted with the coffee extract, the extraction of coffee solids having solvent-to-water distribution coefficients smaller than caffeine is mini-mized. Employment of high ratios of solvent to extract results in the increased removal along with caffeine of coffee solids having solvent to water distribution coefficients smaller than caffeine.
,A
11~44~
When the caffeine-laden solvent is thereafter contacted with water to partition the caffeine content from the organic solvent, such coffee solids tend to partition along with the caffeine with the result that such solids do not remain with the organic sol-vent for restoration to the coffee extract. A ratio of water-immiscible organic solvent to coffee extract in the range of from about 0.3:1 to about 10:1 can be employed. The particular ratio employed will depend upon the particular solvent selected for the ' extract decaffeination. For example, where the solvent is 10 methylene chloride, a preferred ratio will be from 0.5:1 to 1:1.
The liquid/liquid decaffeination operation can be con-ducted in a batch or continuous operation, although a continuous countercurrent liquid/liquid extraction of caffeine will be pre-ferred. Liquidjliquid extraction techniques are well known and 15 generally involve continuous contacting of extract with the water-immiscible organic caffeine solvent. The contact can be suitably conducted in an elongated column. For example, where a solvent heavier than the aqueous extract is employed, the aqueous extract can be sprayed into the lower end of an elongated column containing 20 the caffeine solvent. The coffee extract is allowed to travel upwardly in a manner countercurrent to the solvent and the decaf-feinated extract is removed continuously from the top of the decaffeination column. Such a method is described in detail in U.S. Patent 2,933,395 (issued April 19, 1960 to Adler et al.l.
25 Other methods for effecting the liquid/liquid extraction can be employed. For example, the coffee extract can be contacted with the caffeine solvent by passing the extract and the organic solvent in countercurrent fashion into a packed columnar bed comprising an elongated tower fitted with Pall rings, Raschig 30 rings or the like.
' Pre~erred apparatus foL conducting the liquid/liquid decaffeination comprises such liq~lid/liquid contacting devices as the ~otary-disk Contactor, the"Oldshue-Rushto~' column, or the "~ork-Scheibel~column. It will be appreciated that the feasibility of the employment of low ratios of solvent to extract will depend in part upon the nature of the solvent employed, the concen- ~
tration of the coffee extract, and the efficiency or mass transfer -capability of the liquid/liquid contacting equipment. Thus, it will be preferred to employ a liquid/liquid contacting device which provides the mechanical agitation and turbulence necessary for maximization of mass transfer. For this reason, a preferred type of liquid/liquid contactor is the Rotary-disk Contactor.
It has been found that such a device will permit efficient decaf-feination at low solvent-to-extract ratios, e.g., less than 1:1. The Rotary-disk Contactor and other suitable liquid/liquid contacting devices are described in detail in Perry's Chemical Engineers' Handboo~, McGraw-~ill Book Company, 4th Edition, Section 21, pp. 23-35.
The decaffeinated extract is separated from the caffeine-laden solvent in known manner. Normally the separation will be the result of continuous removal of countercurrent coffee extract and solvent streams from the liquid/liquid contactor. The sepa-rated caffeine-laden solvent is thereafter treated for recovery of flavor and aroma principles.
The water-immiscible organic caffeine-laden solvent is treated for separation of the caffeine therefrom. This is accom-plished by contacting the caffeine-laden solvent with an amount of water sufficient to remove or partition the caffeine from the organic phase into the aqueous phase. Substantially complete removal F partition of caffeine from the organic solvent is * Trademark __ _ _ ** Trademark n q~
realized. The amount of water employed will vary with the parti-cular nature of the solvent. Generally, an amount of water pro-viding a ratio of water to caffeine-laden solvent of from about 0.5:1 to about 10:1 ~Jill be sufficient to effect the partition-ing of caffeine into an aqueous phase. A preferred ratio in thecase of methylene chloride solvent is from 5:1 to 6:1.
Preferably, the caffeine-laden solvent will be concentrated prior to caffeine removal so as to minimize the amount of caffeine-laden solvent which must be handled and contacted with water for 10 the caffeine removal. In addition, concentration of the caffeine-laden solvent permits maximization of mass transfer and reduces capital equipment requirements. Concentration can be effected by flashing of the organic solvent, hy the use of conventional thin-film evaporators or the like. For 15 economy of operation, evaporated solvent will be condensed for re-use in further liquid/liquid decaffeination. The concentrated caffeine-laden solvent will preferably be concentrated such that the solids content comprlses from about 1% to about 10% by weight of the caffeine-laden solvent.
The partitioning of caffeine from the caffeine-laden solvent can be achieved by any effective contact of water with the caffeine-laden solvent. The caffeine-laden solvent can ~e introdu ed in a countercurr2nt manncr into a colu~n containing water. As in the case of the liquid/liquid 25 deca~feination operation, the separation of caffeine from the caffeine-laden solvent can be facilitated by the use of other conventional liquid~liquid contacting devices. A preferred device is a continuous countercurrent extractor such as a Rotary-disk Contactor. This device permits intimate contact between 30 water and the caffelne-laden solvent and efficient recovery of aqueous and organic phases.
_g_ -` 11(34~
The amount of aroma and Llavor principles restored to the coffee extract will depend upon the amount present in the organic solvent as the result of the extract decaffeination operation. It will be appreciated that the advantages achieved 5 by restoration to a coffee extract of such principles will depend upon the nature of the coffee e~tract and the selectivity of the caffeine solvent used in the decaffeination operation. For example, ethyl acetate will remove from a coffee extract, in addition to caffeine, an appreciable content of aroma and flavor 1~ principles, relative to a more selective solvent such as metllylene chloride. Accordingly, the benefits of the process of the inven-tion will be most advantageous and the greatest contribu-tion realized where relatively non-selective solvents are employed.
The process of the invention, thus, makes more feasible the use of such solvents for the decaffeination of coffee.
The removal of caffeine from the caffeine-laden solvent results in the recovery in the solvent of certain flavor -and aroma principles. These principles, when restored to the decaffeinated coffee extract, permit the preparation of a decaf-feinated coffee extract having as much of the aroma and flavor principles as is practicable. Thus, the extract when dried in a conventional manner to a soluble or instant coffee product, pro-vides a product having improved flavor and aroma properties.
While the precise chemical nature of the recovered flavor and aroma principles is not entirely unAerstoorl, they are com.~rised of numerous flavorful and aromatic principles resulting from roasting and extraction or hydrolysis of coffee. The flavor and aroma principles, although water-soluble, have a greater affinity than caffeine for the organic solvent as is apparent from the recover~ of such principles in the organic phase and recovery of caffeine in the aqueous phase.
11~'4~
The flavor and aroma principles recov~red by th~
process of the invention are incorporated into the decaffeinated coffee extract prior to conventional drying thereof. The production of a soluble coffee powder from a decaffeinated coffee extract will be preceded by a solvent-stripping operation whereby residual solvent can be removed from the coffee extract. The flavor and aroma principles in the organic solvent can be added to the decaffeinated extract prior to the removal of residual solvent therefrom. Thus, the decaf-1'~ feinated aqueous extract and the added solvent with flavor andaroma principles can be treated for simultaneous removal of solvent. Preferably, the solvent will be stripped from the decaf-feinated extract by passing the extract over a heated evaporating surface under reduced pressure or by stripping with steam.
lS Conventional thin-film evaporation devices can be used for this purpose. Other methods for volatilizing and recovering residual solvent can, however, be employed.
Ater stripping of residual solvent, con~ensed vola-tiles from the coffee extract obtained prior to the decaffeination thereof, if any, can be added to the extract. The resulting extract is then dried to a soluble coffee powder, e.g., by spray-drying or freeze-drying, with or without a prior concentration stép.
_ _, , . . ,__ _ , .
The invention is illustrated in the following specific e~amples which are given by way of example only and not as limiting the invention. All pcrcen~agcs and ratios expressed in the specification and clai.-.ls are by weight.
EXAMPI.E I
An aqueous coffee extract having a solubles content of 20% is prepared by conventional countercurrent extraction of roast and ground coffee. The coffee extract is subjected to a devolatilization step by contacting the extract with steam (0.1 lb. of steam/lb. of extract~ in a packed column maintained at a vacuum of 21 inches of mercury. The steam-stripped volatiles .~ -.1.1- .
4~ `
are condensed, and the condensate is stored at less than 50F
for subsequent reincorporation into the coffee extract.
The stripped, i.e., devolatilized, coffee extract is introduced as the dispersed phase into the bottom of a con-tinuous countercurrent extractor (a Rotary-disk Contactor).
The decaffeination solvent, methylene chloride, is introduced at the top of the extractor as the continuous phase. A solvent ratio of 1.0 lb. of solvent/lb. of coffee extract is used at a-temperature of 9QF, and caffeine removal of 98% is achieved.
The decaffeinated extract containing dissolved and entrained solvent is withdrawn from the top of the extractor. The decaf-feination solvent containing caffeine and flavor and aroma constituents is withdrawn from the bottom of the extractor.
The decaffeination solvent containing caffeine and flavor and aroma constituents is evaporated to a solids concen-tration of about 5% by weight. The concentrated solvent is then introduced as the dispersed phase into the top of a second continuous countercurrent extractor (another Rotary-disk Contactor) with water as the continuous phase. A water-to-solvent ratio of 5.0 is used at a temperature of 70F and a caffeine removal of 99% i5 achieved. The decaffeinated concentrated solvent stream containing the flavor and aroma constituents is withdrawn from the bottom of the extractor and added to the decaffeinated coffee extract. The resulting extract is then desolventized by steam-stripping in another packed column maintained at a vacuum of 21 inches mercury and using 0.1 lb. of steam/lb. of extract. The residual solvent level in the decaffeinated coffee extract is reduced ~o less than 1 ppm on a solids basis. The decaffeinated coffee extract is then concentrated to 63~ solubles by vacuum evaporation. The condensate of steam-stripped volatiles is added to the coffee extract, and the extract is spray-dried to a 97 decaffeinated soluble coffee powder.
' ql~
The resulting product is si~nificantly stronger and has a more flavorful, balanced flavor than would a corresponding product made without recovery of flavor and aroma constituents from the caffeine-laden solvcnt and restoration thereof to the decaffeinated coffee extract.
- EXAM~LE II
An aqueous coffee extract having a solubles content of 20% is prepared by conventional countercurrent extraction of roast and ground coffee. The coffee extract is subjected to a devolatilization step by contacting the extract with steam (0.1 lb. of steam/lb. of extract) in a packed column maintained at a vacuum of 21 inches of mercury. The steam-stripped volatiles are condensed, and the condensate is stored at less than 50F
for subsequent reincorporation into the coffee extract.
The stripped, i.e., devolatilized, coffee extract is introduced as the dispersed phase into the top of a continuous countercurrent extractor (a Rotary-disk Contactor). The decaf-feination solvent, ethyl acetate, is introduced at the bottom of the extractor as the continuous phase. A solvent ratio of 1.3 lbs. of solvent/lb. of coffee extract is used at a tempera-ture of 140~ F. and caffeine removal of 98% is achieved. The decaffeinated extract containing dissolved and entrained solvent is withdrawn from the ~ottom of the extractor. The decaffeination solvent containi~g caffeine and flavor and aroma constituents is withdrawn from the top of the extractor.
` . ~` 11~4q1~
The decaffeination solv~nt containing caffeine and flavor and aroma constituents is evaporated to a solids concen-tration of about 1.5~ by weight. The concentrated solvent is then introduced as the dispersed phase into the bottom of a 5 second continuous countercurrent extractor (:another Rotary- :
dis.k Contractorl with water as the continuous phase. A water~
to-solvent ratio.~of ~7 is used at a temperature of 70 F. and a caffeine removal of ~g% i.s ach.ieved. The decaffeinated con-centrated solvent stre.am containing the flavor and aroma con~ ;
st~.tuti.ons is. withdrawn from the top of the extractor and added to th.e.decafeinate.d coffee extract, The resulting extract is then desolventized ~y steam-stripping in another packed column maintaine.d at a vacuum of 21 inches mercury and using 0.1 1~.
of steam~lb-~ of extract. The residual solvent level in the de.caffeinate.d coffee extract is reduced to less than 1 ppm on a solids ~.asis, The de.caffe~.nated coffee. extract is then con-centrated to ~3% solu~les ~.y vacuum evaporation, The condensate of steam-stripped volatiles is added to the coffee extract, and the extract ~s spray~drl:ed to a g7~ decaffeinated soluble coffee 20. po~der, Th.e resulti.ng product is significantly stronger and has a more ~lavorful, ~alanced flavor than ~ould a corresponding product made without recovery of flavor and aroma constituents from the caffeine~laden solvent and restoration thereof to the deca~einated coffee extract, , , ~14~
Claims (8)
1. A process for preparing a decaffeinated coffee, which comprises the steps of:
(1) decaffeinating an aqueous roast and ground coffee extract by contact with a water-immiscible organic solvent for caffeine;
(2) separating the decaffeinated aqueous coffee extract from the caffeine-containing water-immiscible organic solvent;
(3) concentrating the caffeine-containing water-immiscible solvent to a solids content of from about 1% to about 10% by weight;
(4) contacting the concentrated caffeine-containing water-immiscible organic solvent with an amount of water sufficient to partition caffeine into the aqueous phase;
(5) recovering the water-immiscible organic solvent containing flavor and aroma constituents;
(6) incorporating said water-immiscible organic solvent and flavor and aroma constituents into the decaffeinated roast and ground coffee extract; and (7) desolventizing the decaffeinated coffee extract to form a desolventized extract.
(1) decaffeinating an aqueous roast and ground coffee extract by contact with a water-immiscible organic solvent for caffeine;
(2) separating the decaffeinated aqueous coffee extract from the caffeine-containing water-immiscible organic solvent;
(3) concentrating the caffeine-containing water-immiscible solvent to a solids content of from about 1% to about 10% by weight;
(4) contacting the concentrated caffeine-containing water-immiscible organic solvent with an amount of water sufficient to partition caffeine into the aqueous phase;
(5) recovering the water-immiscible organic solvent containing flavor and aroma constituents;
(6) incorporating said water-immiscible organic solvent and flavor and aroma constituents into the decaffeinated roast and ground coffee extract; and (7) desolventizing the decaffeinated coffee extract to form a desolventized extract.
2. The process of Claim 1 wherein caffeine is partitioned from said caffeine-containing water-immiscible organic solvent by contacting water and said solvent at a weight ratio of water to caffeine-containing solvent of about 0.5:1 to about 10:1.
Claim 3. The process of Claim 2 wherein the water-immiscible organic solvent is methylene chloride and the weight ratio is from 5:1 to 6:1.
4. The process of Claim 3 further comprising the step of drying the desolventized extract to form a soluble decaffeinated coffee powder.
5. The process of Claim 1 wherein the water-immiscible solvent is ethyl acetate.
6. The process of Claim 2 wherein prior to decaffeinating the aqueous extract of roast and ground coffee, the process further comprises the steps of devolatilizing the aqueous extract of roast and ground coffee; collecting the devolatilized volatiles, and then subsequent to the desolventiz-ing of the decaffeinated roast and ground coffee extract to form a desolventized extract, and adding the collected volatiles to the desolventized extract.
7. The process of Claim 6 wherein said water-immiscible organic solvent is ethyl acetate.
8. The process of Claim 7 further comprising the step of drying the desolventized extract to form a soluble decaffeinated coffee powder.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US78324677A | 1977-03-31 | 1977-03-31 | |
| US783,246 | 1977-03-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1104411A true CA1104411A (en) | 1981-07-07 |
Family
ID=25128630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA300,116A Expired CA1104411A (en) | 1977-03-31 | 1978-03-30 | Process for preparing decaffeinated coffee |
Country Status (19)
| Country | Link |
|---|---|
| JP (1) | JPS542380A (en) |
| AT (1) | AT365045B (en) |
| AU (1) | AU514860B2 (en) |
| BE (1) | BE865488A (en) |
| CA (1) | CA1104411A (en) |
| CH (1) | CH634467A5 (en) |
| DE (1) | DE2813147A1 (en) |
| DK (1) | DK145678A (en) |
| ES (1) | ES468369A1 (en) |
| FI (1) | FI63326C (en) |
| FR (1) | FR2385336A1 (en) |
| GB (1) | GB1596587A (en) |
| GR (1) | GR63558B (en) |
| IE (1) | IE46702B1 (en) |
| IT (1) | IT7848639A0 (en) |
| LU (1) | LU79346A1 (en) |
| NL (1) | NL7803436A (en) |
| NO (1) | NO147364C (en) |
| SE (1) | SE7803587L (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4352829A (en) | 1981-03-05 | 1982-10-05 | The Procter & Gamble Company | Coffee extraction process |
| US4409253A (en) | 1981-03-05 | 1983-10-11 | The Procter & Gamble Company | Recovery of noncaffeine solubles in an extract decaffeination process |
| EP0086526A3 (en) * | 1982-02-16 | 1984-10-03 | The Procter & Gamble Company | Process for steaming coffee |
| US4505940A (en) * | 1984-03-29 | 1985-03-19 | General Foods Corporation | Non-caffeine solids recovery process |
| US6544576B2 (en) * | 2000-12-21 | 2003-04-08 | Kraft Foods Holdings, Inc. | Coffee beverage preparation aroma system |
| AU2013403581C1 (en) * | 2013-10-21 | 2018-06-07 | Demus S.P.A. | Process for removing caffeine from green coffee and plant for implementing the process |
-
1978
- 1978-03-25 DE DE19782813147 patent/DE2813147A1/en not_active Withdrawn
- 1978-03-28 GR GR55813A patent/GR63558B/en unknown
- 1978-03-29 AT AT0220678A patent/AT365045B/en not_active IP Right Cessation
- 1978-03-29 IT IT7848639A patent/IT7848639A0/en unknown
- 1978-03-30 NO NO781111A patent/NO147364C/en unknown
- 1978-03-30 FI FI780964A patent/FI63326C/en not_active IP Right Cessation
- 1978-03-30 BE BE186399A patent/BE865488A/en unknown
- 1978-03-30 SE SE7803587A patent/SE7803587L/en unknown
- 1978-03-30 CA CA300,116A patent/CA1104411A/en not_active Expired
- 1978-03-30 CH CH339278A patent/CH634467A5/en not_active IP Right Cessation
- 1978-03-30 AU AU34608/78A patent/AU514860B2/en not_active Expired
- 1978-03-30 ES ES468369A patent/ES468369A1/en not_active Expired
- 1978-03-30 GB GB12458/78A patent/GB1596587A/en not_active Expired
- 1978-03-30 FR FR7809270A patent/FR2385336A1/en not_active Withdrawn
- 1978-03-31 IE IE639/78A patent/IE46702B1/en unknown
- 1978-03-31 LU LU79346A patent/LU79346A1/en unknown
- 1978-03-31 JP JP3801478A patent/JPS542380A/en active Pending
- 1978-03-31 NL NL7803436A patent/NL7803436A/en not_active Application Discontinuation
- 1978-03-31 DK DK145678A patent/DK145678A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ATA220678A (en) | 1981-05-15 |
| SE7803587L (en) | 1978-10-01 |
| DE2813147A1 (en) | 1978-10-12 |
| AT365045B (en) | 1981-12-10 |
| IT7848639A0 (en) | 1978-03-29 |
| LU79346A1 (en) | 1978-11-03 |
| IE780639L (en) | 1978-09-30 |
| IE46702B1 (en) | 1983-08-24 |
| NO147364C (en) | 1983-03-30 |
| JPS542380A (en) | 1979-01-09 |
| NL7803436A (en) | 1978-10-03 |
| GB1596587A (en) | 1981-08-26 |
| CH634467A5 (en) | 1983-02-15 |
| NO147364B (en) | 1982-12-20 |
| NO781111L (en) | 1978-10-03 |
| AU514860B2 (en) | 1981-03-05 |
| AU3460878A (en) | 1979-10-04 |
| BE865488A (en) | 1978-10-02 |
| FI780964A (en) | 1978-10-01 |
| ES468369A1 (en) | 1978-12-16 |
| FR2385336A1 (en) | 1978-10-27 |
| GR63558B (en) | 1979-11-17 |
| FI63326C (en) | 1983-06-10 |
| FI63326B (en) | 1983-02-28 |
| DK145678A (en) | 1978-10-01 |
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