CA1290612C - Solid essential oil flavor composition and method of manufacture - Google Patents
Solid essential oil flavor composition and method of manufactureInfo
- Publication number
- CA1290612C CA1290612C CA000503795A CA503795A CA1290612C CA 1290612 C CA1290612 C CA 1290612C CA 000503795 A CA000503795 A CA 000503795A CA 503795 A CA503795 A CA 503795A CA 1290612 C CA1290612 C CA 1290612C
- Authority
- CA
- Canada
- Prior art keywords
- essential oil
- flavor
- aqueous mixture
- solid
- extruded
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Seasonings (AREA)
Abstract
Solid Essential Oil Flavor Composition and Method of Manufacture Abstract A solid essential oil flavor composition having a high essential oil content and a process for preparing the product are disclosed, the process involving preparation of a heated or cooked aqueous mixture of a surfar and starch hydrolystate together with an emulsifier. A selected essential oil or other oil-soluble flavor is combined and blended with a mixture in a closed vessel under controlled pressure conditions to form a homogeneous melt, the melt being extruded into a relatively cool solvent, dried and combined with a selected anticaking agent to produce the stable, relatively non-hygoscopic particulate flavor composition of the invention. The selected quantity of essential oil flavor blended into the homogeneous melt being sufficient to yield about 12 to 35% by weight of essential oil in the encapsulated solid particulate composition. During the process, encapsulation efficienty is maintained preferably at or above about 60%, more preferably above about 70% and most preferably above about 75 to 80%. Also, the cook temperature for the process is preferably maintained at or below a maximum of about 126° C.
Description
~0~12 .
Description Solid cssential Oil Flavor Composition and Method of .~anufacture Background of the Invention The present invention relates to a S process for producing a solid essential oil flavor composition and the product of the process and more particularly to such a process resulting in a product in the form of a stable, extruded, solid essential oil flavor composition.
ld , .
- 15 In order to preserve the aroma and flavor of various essential oils and make them available for use in consumer products such as beverages and the like, the prior art h~s developed a n~mber of techniques for oroducing solid essential oil compositions. These compositions permit combination of the essential oils into various products such as beverages to which it is desirable to impart the aroma and
Description Solid cssential Oil Flavor Composition and Method of .~anufacture Background of the Invention The present invention relates to a S process for producing a solid essential oil flavor composition and the product of the process and more particularly to such a process resulting in a product in the form of a stable, extruded, solid essential oil flavor composition.
ld , .
- 15 In order to preserve the aroma and flavor of various essential oils and make them available for use in consumer products such as beverages and the like, the prior art h~s developed a n~mber of techniques for oroducing solid essential oil compositions. These compositions permit combination of the essential oils into various products such as beverages to which it is desirable to impart the aroma and
2--flavor of the oil. Such techniques have been found to be particularly useful and desirable, for example, in connection with essential oils of various citrus fruits while being equally useful with essential oils from other sources. Citrus fruit, for example, are characterized by essential oils having particularly desirable characteristics of aroma and flavor which are useful not only in beverage products but in various food products as lD well.
The prior art in this regard is believed to be best exemplified by a number of U. S. patents which are hereinafter discussed in greater detail. These references include U. S.
Patents 2,809,895 and 3,041,180 issued respectively on October 15, 1975 and June 2~, 1962 to H. E. Swisher under assignment to the assignee of the present invention. The references also include U. S. Patent 3,704,137 issued Novem~er 28, 1972 to Beck and U. S. Patent 4,271,202 issued June 2, 1981 to Giel.
Turning now to these references, the earlier Swisher patent disclosed a process for forming solid essential oil flavoring composition particles wherein an essential oil was emulsified in hot corn syrup solids (42 DE) glycerine solution, cooled, ground, rinsed with a solvent and dried. The flavoring composition retained the aroma and flavor of the oils within the particles while making them available for release in various consumer products such as beverages and other food products.
The second Swisher patent disclosed an improved process and solid essential oil flavoring 9~6~
~ --3--.
composition wherein glycerine and corn syrup solids ~42 DE) were formed into an aqueous, semiplastic mass which was then combined with the essential oil by means of an emulsifier, the resulting combination being extruded into a cold solvent to form an extruded solid wherein the essential oil was encapsulated by khe glycerine and corn syrup solids combination. This extruded solid was then dried and an antica~ing agent added, yielding an extruded particulate solid having an extended shelf life while facilitating its combination with beverage or other food products to release the aroma and~or flavor of the oil.
The Beck patent related to a similar process and product as summarized above for the second Swisher patent, except that the process and product included a simple sugar and hydrolyzed cereal solids ~less than 20 DE) with pyrogenic ~o silica as an anticakin~ agent.
The Giel patent related to a spray-drying process for forming solid flavoring ` material capable of including high percentages of flavoring oil per total particulate unit of weight. Because of the high oil content possible, such spray-dried products found wide use in a number of beverages and other foods. However, it was also found that spray-dried flavors typically exhibit a relatively limited shelf life. In addition, the high temperatures necessarily involved during spray-drying processes have been found to impair the flavor and aroma of various heat-sensitive oil flavors, such as those in citrus fruit. Furthermore, solids formed by ï;~9c~6~2 .. ..
spray-drying commonly exhibit hygroscopic characteristics making them difficult to handle and store~
As noted above, spray dried oil flavors have been used in the production of various beverages and foods where it is desirable to take advantage of their high oil content. At the sarne time, extruded essential oil solids of the type covere~ by the second Swisher and Beck patents have also found a substantial market, particularly where it is desirable to take advantage of the better preserved aroma and flavor of the oil.
However, as was noted in the Beck patent, the process for forming such extruded essential oil flavor compositions has heretofore been considered to have a practical maximum essential oil content of about 12~ in the extruded particles. This - limitation has at times prevented or limited the use of extruded flavor compositions in certain products where high oil content is desirable.
A number of patents issued to T. H.
Schultz, either alone or with other inventors, including U. S. 2,856,291; 2,857,281; U. S.
2,899,313; U. S. 2,919,989; U. S. 2,929,72~ and U. S. 2,929,723. Certain of these patents related to processes for encapsulating essential oils in generally the same manner as the Beck patent noted above. In Schultz et al U. S. 2,857,281, reference was made generally to use of an essential oil or flavoring agent "to furnish about from 5 to 25% thereof in the emulsion.~ However, in the speci~ic discloses and examples provided in the Schultz et al patent as well as in the other patents where Schultz wàs an inventor, xesulting ~0~2 .
oil percentages in encapsulated form were far - below the practical limit of 12~ noted above and initially stated in the Beck patent.
Accordingly, there remains a need for a process making possible the formation of stable, extruded, solid essential oil or flavor compositions having a relatively high percentage - of essential oil encapsulated therein, preferably at least in excess of the practical limit of 12%.
as stated in the Beck patent.
.Summary of the Invention It is therefore an object of the invention to provide an improved process for forming an extruded, solid, essential oil flavor composition and a product of such process while . overcoming one or more problems of the type summarized above.
It is a further object of the invention to provide such a process for producing a 20 resulting product characterized by a ~elatively high essential oi~ or oil-soluble flavor content completely encapsulated within the extruded particulate solids.
. It is an even further object of the invention to provide such a process for producing a resulting produc' charac~erized by a relatively ~ , .high essential oil or oil-soluble flavor content : completely en~apsulated within the extruded particulate solids.
~ 30 It is an even further object of the invention to provide such a process for forming a resulting product in the form of a stable, melt-based and extruded, solid essential oil 1%9C)6~
flavor composition characterized by about 12 to 35% by weight of essential oil in substantially completely encapsulated form within the extruded solids. A somewhat hi~her percentage of the essential oil or oil-soluble flavor is initially added in the process to accommodate oil losses, for example, during emulsification and solvent washing of the product.
. It is a related object of the invention to provide such a process for forming a resulting product in the form of a stable, melt-based and extrude~, solid essential oil flavor composition - wherein a selected quantity of essential oil is combined and blended with an aqueous mixture of a sugar, starch hydrolysate and selected emulsifier and at least preferably about 60% by weight, more preferably 70~ by weight and most preferably about 75 to 80% by weight of the selected quantity of essential oil is present in encapsulated form within the resulting particulate essential oil composition Although, as noted above, the solid essential oil flavor composition of the invention ~s preferably characterized generally by about 12 to 35% by weight of essential oil in substantially completely encapsulated form, the present invention more preferably contemplates the solid : , essential oil flavor composition as being characterized by about 14 to 30% by weight of essential oil in substantially completely encapsulated form within the extruded solids.
In accordance with the present invention, it has been found that such a process and product are possible by first forming an . , .
9~;12 aqueous mixture of a sugar and starch hydrolysate in combination with a suitable emulsifier, the aqueous mixture and emulsifier is combined and blended with a selected quantity of an essential S oil or oil-soluble flavor in a closed vessel to form a homogeneous melt under controlled pressure conditions substantially greater than atmospheric pressure.
It is an even further object of the invention to provide such a process and product of the process wherein the blending step is carried out in a closed vessel pressurized within the range of from about 7 to 50 pounds per square inch ~psi) or more.
It is yet a further related object of the invention to cook the aqueous mixture of the sugar and starch hydrolysate preferably to a maximum temperature of about 126~ C before the aqueous mixture and a selected emulsifier are combined and blended with the essential oil in a closed vessel as described above. More preferably, the aqueous mixture is heated to a maximum temperature of about 124 C and most preferably to a temperature in the range of about 1~2 to 124 C generally under atmospheric ~ressure conditions. These temperatures are especially applicable where the essential oil comprises at least about 28% by weight of the combination just prior to emulsification.
A still further related object of the invention is to carry out the heating step whereby the resulting particulate essential oil composition has a relatively higher water content, preferably at least about 5% by weight.
.
.. ~ .
. ~ ~,'' .. .
. , . :
9~6~
In connection with the present invention, the term ~sugar" is intended to include simple sugars such as sucrose, lactose, levulose, dextrose, fructose and maltose, as well as polyols such as glycerin and even other sweetners having generally similar characteristics. Similarly, the term ~starch hydrolysate" is intended to include all hydrolyzed starches, both hydrolyzed cereal solids of about 20 DE or less and corn syrup solids of about 20 DE or higher. The term "emulsifier" is used herein to indicate any emulsifier which is satisfactory for use particularly in combination with the selected flavoring oil. Specific examples of suitable emulsifiers are set forth within the following detailed description. In addition, the term "essential oil" is intended to include other oil - soluble flavors which are capable of incorporation in the process and product-of the present invention.
Additional objects and advantages of the invention are made apparent in the following description having reference to the accompanying drawings.
Brief Description of the Drawings FIGURE l is a block-type flow sheet including steps of the process of the present invention and for forming the product of that process.
FIGURE 2 is a graphic representation of the effect of increased pressure on encapsulation of the essential oil flavoring within the product of the process.
~90~1~
.
Descxiption of the Preferred ~mbodiments As noted above, the present invention - relates to a process for forming or preparing a stable, melt-based and extruded solid essential oil flavor composition in particulate form as well as the product of the proc:ess. Generally, the process comprises the steps of (1) heating to a suitable cook temperature an a~ueous mixture of a sugar and a starch hydrolysate together with a selected emulsifier, the cook temperature being approximately the boiling point of the aqueous mixture, 12) blending a selected quantity of an essential oil flavor with the aqueous mixture to form a homogeneous melt, (3) extruding the 1~ homogeneous melt into a relatively cool liguid solvent to form extruded solids of selected size and shape, and ~4) drying the particles and blending with a selected antica~ing agent to produce a stable and relatively non~hygroscopic composition in particulate form. The process is improved by the present invention in that the step of blending or emulsifying the essential oil with the aqueous mixture is carried out in a closed vessel and the quantity of essen~ial oil flavor added to the homogeneous melt is preferably selected to provide about 12 to 35% by weight and more preferably about 14 to 30~ by weight of essential oil flavor in completely encapsulated form within the particulate oil composition.
The present invention further contemplates a process and product of the process wherein preferably at least about 60~ by weight, more preferably at least about 70% by weight and ~90~12 . --1 o--most preferably at least about 75 to 8C~ by weight of a selected quantity of e~sential oil combined and blended with the aqueous mixture is present in encapsulated ~orm within the resulting particulate essential oil composition.
~ The invention also contemplates that the sugar and starch hydrolysate, either together with or pxior to combination of the selected emulsifier therein, is preferably heated to a maximum temperature of about 126 C in order to minimize flavor deterioration of the essential oil flavor and also to facilitate encapsulation according to the present invention. More pxeferably, the heating temperature is limited to a maximum of about 12~ C and most preferably, th~
aqueous mixture is heated to a temperature in the range of about 122 to 124 C generally under atmospheric pressure conditions. These reduced temperatures zre of greatest value when the 2~ essential oil comprises at least about 28% by weight of the combination.
These temperature limits are discussed in connection with the present invention in greater detail below. In addition to minimizing deterioration of flavor and other undesirable characteristics of the essential oil which commonly result at higher temperatures, the reduced cook temperature is also believed to permit a relatively increased amount of water to remain in the melt prior to extrusion. It is theorized that this additional water assists in stabili2ing and facilitating emulsification and encapsulation of the higher guantities of essential oil within the particulate solid in accordance with the process of the present invention. Preferably, the invention contemplates that the solid resulting from the,process of the present invention comprise at least about 5~ by w~ter.
At the same time, the above temperature conditions for the heating step are preferably stated as maximums at least within the broad and preferred ranges since a number of variations in the process may be carried out for accomplishing similar results under even further reduced temperatures. For example, it has been found that a lower cook temperature may be used where a lower DE rated sugar or sweetener is employed. For example, if a 10 DE sweetener were employed in place of the 20 DE sweetener described below in connection with a number of examples, it would be possible to urther reduce the cook temperature in accordance with the present invention.
Similarly, it would also be possible to reduce the cook temperature while otherwise achieving the objects of the present invention by either employing a greater degree of agitation during the cooking process in order to facilitate removal of excess water therefrom or by carrying out the cooking process under vaeuum conditions for the same purpose.
The second Swisher patent, and the Beck patent referred to above discussed in substantial detail the manner in which a homogeneous melt can be formed from an aqueous mixture of a sugar and starch hydrolysate together with a separate flavor component to form an extruded solid capable of being dried in the manner summarized above. Those ... .. .
6~LZ
.
references also discussed the manner in which such a homogeneous melt can be extruded into a cool liquid solvent to form particle of selected shape and size as well as the selection of a suitable ~nticaking agent for combination with the extruded solid particles in order to maintain them in a more ~table condition. Accordingly, those references are incorporated herein as though set forth in full with respect to the particular 1~ features referred to above.
Referring now to the drawings and particularly to FIGURE 1, a selected sugar and starch hydrolysate are mixed together as indicated at 12. The mixture is then agitated in order to 1~ uniformly mix together the sugar and starch hydrolysate. As noted above, the sugar may be any of the simple sugars such as sucrose, levulose, dextrose, fructose or maltose, as well as a polyol such as glycerine or other similar sweeteners.
Any preferred sugar or sweetner may be used for any of a variety of reasons, such as to achieve improved flavor of the resulting product and/or to reduce hygroscopcity of the product. The mixture 12 is then heated to a coo~ temperature preferably 2i approximating its boiling point as indicated at 14. A suitable cook temperature ~or such mixtures including most sugars extends across a range of approximately 110 to 130~ C. For example, with the sugar beiny sucrose and the starch hydrolysate being 20 DE corn syrup, the boiling point of the mixture is approximately 125-130 C and the mixture is preferably heated to a temperature within that range.
/ ~ ~
I
90~12 An emulsifying agent is preferablyadded to the a~ueous mixture 12 after the heating step. Within FIGURE l, addition of the emulsifying agent is indicated at 16; The emulsifier is selected to facilitate emulsification or dispersion of essential oil described below into the mixture 14. Selection of the particular emulsifier and the quantity of the emulsifier added to the agueous mixture 14 is one of the important features of the present invention permit~ing from 12 to 35~ of a selected essential ` oil to be encapsulated within the final extruded product. Suitable emulsifiers for use within the present invention include sulfoacetate of mono-and diglycerides as well as polyglycerol esters and lecithin. Polyqlycerol esters suitable for use within the present invention are available, ~or example, under the trademark identification DREWPOL 6-2-S available from California Fats &
Oils, Richmond, California. Generally, the polyglycerol esters have been found satisfactory within the present invention for the lower end o~
the specified range.
One preferred emulsifier for emulsifying and encapsulating up to 35~ essential oil within the final extruded product is a sulfoacetate of mono- and diglycerides containing . 1% by weight water and available under the trademark identification EMARGOL KL available from the Witco Company. Emulsifiers such as those referred to above are added to the molten mixture 14 in the amount of approximately 0.5 to 5% by weight of the aqueous mixture. However, it is to ~e noted that the amount of emulsifier used in l~g()~2 -such an application can vary depending upon other factors. Accordingly, the above noted range is set forth only as a general indication in connection with the present invention~
Another emulsifier which has been found to be particularly satis~actory in terms of the present invention bu~ possibly less preferred than the EMARGOL XL product rleferred to above is lecithin, available for example from Ross & Rowe under the trademark ~ELKIN TS.
Examples employing both of the emulsifiers noted above are set forth below.
An essential oil or other oil-soluble flavor contemplated for combination with the mixture 14 and emulsifier 16 is generally indicated at 18 and may be an essential oil, for example, of a citrus fruit contemplated for use in bever~ge or other food products.
The addition of a small amount of an oil-soluble heat-stable antioxidant ~indicated at 20 in FIGU~E 1) such as 4-methyl-2, 6-ditertiary butyl phenol or butylated hydroxyanisole is optional. Generally, from about 0.05 to about 0.5~ by weight of the antioxidant, based on the weight of the essential oil, is sufficient.
The essential oil 18, alone or in com~ination with the antioxidant 20, is then added to the a~ueous mixture 14 and emulsifier 16 in a vessel 22. In accordance with the pr~sent invention, it is particularly important that the vessel 22 be closed during blending of the essential oil 18 with the cooked aqueous mixture 14 and emulsifier 16. It has been found that the carrying out of this blending or emulsification ~90~Z
step in a closed vessel is essential to insure uniform and consistent encapsulation of relatively large quantities of essential oil within the solid product.
The closed vessel 22 is charged with gas, preferably an inert gas such as nitrogen or carbon dioxide, for example, to maximize encapsulation of the oil or flavor. Even more preferably, the vessel 22 is pressurized after addition of the inert gas to a pressure from about 7 to 50 psi. In FIGU~E 1, addition of the inert gas is generally indicated at 24. Pressurization and its effects within the closed vessel 22 are described in greater detail below with further 1~ reference to the graph of FIGURE 2.
Referring to FIG~RE 2, encapsulation of substantially increased quantities of essential oils or other oil-soluble flavors is illustrated as being possible with pressurization in the vessel 22 generally from about 7 to about 100 psi.
Destabilization of the resulting product sometimes occurs with higher pressures at or above approximately 100 psi. Best results are obtained with the closed vessel 22 if pressure is maintained within the approximate range of 7-50 psi.
In this regard, a pressure of about 7 psi is developed from vapor pressure alone resulting from combination of the essential oil 18 with the molten mixture 14 and emulsifier 16 within the closed vessel. In such an event, the vessel 22 is initially charged either with air or an inert gas at atmospheric pressure.
~Z~9~6~-~
--lo--Referring to FIGURE 2, the upper limit of S0 psi for pressurization of the vessel 22 is not a precise limit. In some applications, it is possible to pressurize the vessel substantially 5 above 50 psi and even above 100 psi without causing destabilization. ~owever, since the amount of essential oil capable of encapsulation within the final extruded product tends to diminish when pressure is increased above 50 psi, that pressure has been selected as the generally preferred upper limit for pressurization of the vessel 22.
Mixing of the essential oil 18, aqueous mixture 14 and emulsifier 16 in the closed vessel 22 under pressure is continued until those components are uniformly mixed and emulsified to result in a homogeneous melt of the type also discussed in the Beck and Swisher references, for example. Generally, the homogeneous ~elt is ~efined as having a plastic condition suitable for forming a solid product in the manner defined below with an amphorous character for achieving high stability over an extended period of time.
The homogeneous melt from the vessel 22 is then extruded under pressure, using either gas or mechanical pressure, for example, into a cold organic solvent such as isopropanol to form the melt into extruded filaments.
Extrusion is carried out in an extruder 26 having die openings of a si~e selected in accordance with the size and shape desired for the - resulting particles. For example, where small particles are desired for use in beverage or food products, the homogeneous melt from the vessel 22 1~906~2 -17~
is extruded through openings (not shown) having diameters, for example, of about l/32 inch.
Extruded filaments of the homogeneous melt pass from the extruder 26 into a cold cold organic solvent, such as isopropanol at about -20 C, as generally indicated at 28. The function of the isopropanol or other solvent is two-fold. Initially, it acts as a coolant to rapidly solidify the extruded shapes of homogeneous melt. Secondly, it removes any essential oil on the surface of the extruded solids which would otherwise be susceptible to oxidation. -The extruded filaments are preferably broken up into small rod-like particles while within the solvent 28 in order to permit removal of any essential oil exposed on the smaller or separated particles. For example, the f ilaments can be divided by impact action of an agitator ~o impeller ~not shown) to produce a desired particle size and shape.
Following the solvent washing step 28, the particles from the extruded filaments are then screened or centrifuged at 30 to remQve the organic solvent. The solvent is transferred to a holding tank 32 and may be returned to the washing step 28 if desired.
The particles from the separation step 30 are dried in a vacuum oven 33 and blended with a suitable anticaking agent 36. The partlcles are then screened by passage over a succession of sizing screens (not shown) and packaged, preferably in a dehumidified room, as indicated at 39~
l~g()~
1~-The anticaking agent, as gen~rally indicated at 36, is added to the particles after drying to facilitate their urther handling and to prevent the particles from sticking together. The S anticaking agent is preferably silica, introduced either before or after the particles are treated - in the oven 33.
The process described above may be used for preparing extruded solids containing essential oils froln various sources. In particular, the process of the invention is contemplated for use in conjunction with various citrus fruits such as oranges, grapefruit, lemons, etc. However, it will be apparent that the process of the invention is also useful with other essential oil or oil-soluble flavors, either for use in beverages or food products.
The product of the process described above is novelly characterized as a stable, melt based and extruded, solid essential oil composition in particulate form. The particles are of a solid amorphous character with a shape determined by the extruder 26 and further divided, for example, by impact breaking at 28. The particles consist of a sugar and starch hydrolysate as defined above, a selected emulsifier and a selected essential oil flavor.
The essential oil flavor preferably forms about 12 to 35%, more preferably about 15 to 30%, by weight of the particles while being present therein completely encapsulated form.
The preceding process is particularly adapted for assuring reproducible production of particles having a high oil content as defined .. . .. .
~9~z above. ~he process is also particularly adapted for forming about 12 to 35% by weight of the particles with the essential oil flavor being present therein in completely encapsulated form.
S The following examples of various embodiments of the invention are presented to further illustrate and exemplify but not to limit the scope of the invention.
Exam~le 1 6025 grams of 20 DE corn syrup (70%
- solids), 4125 grams sugar and 200 grams EMARGOL RL
were mixed in a steam jacketed stainless steel vessel. The vessel was fitted with a thermometer and an agitator-assembly produced by C. E. Howard Company, Los Angeles, California and having a flat bladed turbine type agitator about 4 1/2 inches in diameter. After heating to 130 during an initial cook, 2200 grams of cold-pressed orange oil were added to the vessel. The vessel was immediately closed. After 5 minutes mixing with the aqitator, the pressure inside the vessel had increased to 7 psi. During mixing, the cold-pressed orange oil lowered the temperature of the aqueous mixture below its cooking temperature, for example, to about 125 C. After mixing was complete, nitrogen was added to pressurize the vessel to 30 psi and the melt was extruded through a plate with 0.030 inch diameter holes into 19 liters of cold (-20~ C) isopropanol to solidify the filaments.
After impact breaking of the filaments, the excess isopropanol was removed on a vacuum screen and the material was dried for 3 hours in a vacuum oven ~50D C, 27 in. Hg YacUUm). After addition of 2% silica as an anticaking agent, the product contained 16.7% by weight flavor.
Example 2 6025 grams of 20 DE corn syrup ~70~
solids), 4125 grams sugar and 200 grams EMARGOL KL
were mixed in a steam jacketed stainless steel vessel. The vessel was fitted with an agitator and thermometer as in Example 1. After heating to 130 C in an initial cook, 2200 grams of cold-pressed orange oil were added to the vessel.
The vessel was immediately closed and pressurized to 50 psi with nitrogen. After S minutes mixing and agitation, the melt was extruded throuqh a plate with 0.030 inch diameter holes into 19 l; liters of cold (-20 C) isopropanol to solidify the filaments. The excess isopropanol was removed on a vacuum screen and the material was dried for
The prior art in this regard is believed to be best exemplified by a number of U. S. patents which are hereinafter discussed in greater detail. These references include U. S.
Patents 2,809,895 and 3,041,180 issued respectively on October 15, 1975 and June 2~, 1962 to H. E. Swisher under assignment to the assignee of the present invention. The references also include U. S. Patent 3,704,137 issued Novem~er 28, 1972 to Beck and U. S. Patent 4,271,202 issued June 2, 1981 to Giel.
Turning now to these references, the earlier Swisher patent disclosed a process for forming solid essential oil flavoring composition particles wherein an essential oil was emulsified in hot corn syrup solids (42 DE) glycerine solution, cooled, ground, rinsed with a solvent and dried. The flavoring composition retained the aroma and flavor of the oils within the particles while making them available for release in various consumer products such as beverages and other food products.
The second Swisher patent disclosed an improved process and solid essential oil flavoring 9~6~
~ --3--.
composition wherein glycerine and corn syrup solids ~42 DE) were formed into an aqueous, semiplastic mass which was then combined with the essential oil by means of an emulsifier, the resulting combination being extruded into a cold solvent to form an extruded solid wherein the essential oil was encapsulated by khe glycerine and corn syrup solids combination. This extruded solid was then dried and an antica~ing agent added, yielding an extruded particulate solid having an extended shelf life while facilitating its combination with beverage or other food products to release the aroma and~or flavor of the oil.
The Beck patent related to a similar process and product as summarized above for the second Swisher patent, except that the process and product included a simple sugar and hydrolyzed cereal solids ~less than 20 DE) with pyrogenic ~o silica as an anticakin~ agent.
The Giel patent related to a spray-drying process for forming solid flavoring ` material capable of including high percentages of flavoring oil per total particulate unit of weight. Because of the high oil content possible, such spray-dried products found wide use in a number of beverages and other foods. However, it was also found that spray-dried flavors typically exhibit a relatively limited shelf life. In addition, the high temperatures necessarily involved during spray-drying processes have been found to impair the flavor and aroma of various heat-sensitive oil flavors, such as those in citrus fruit. Furthermore, solids formed by ï;~9c~6~2 .. ..
spray-drying commonly exhibit hygroscopic characteristics making them difficult to handle and store~
As noted above, spray dried oil flavors have been used in the production of various beverages and foods where it is desirable to take advantage of their high oil content. At the sarne time, extruded essential oil solids of the type covere~ by the second Swisher and Beck patents have also found a substantial market, particularly where it is desirable to take advantage of the better preserved aroma and flavor of the oil.
However, as was noted in the Beck patent, the process for forming such extruded essential oil flavor compositions has heretofore been considered to have a practical maximum essential oil content of about 12~ in the extruded particles. This - limitation has at times prevented or limited the use of extruded flavor compositions in certain products where high oil content is desirable.
A number of patents issued to T. H.
Schultz, either alone or with other inventors, including U. S. 2,856,291; 2,857,281; U. S.
2,899,313; U. S. 2,919,989; U. S. 2,929,72~ and U. S. 2,929,723. Certain of these patents related to processes for encapsulating essential oils in generally the same manner as the Beck patent noted above. In Schultz et al U. S. 2,857,281, reference was made generally to use of an essential oil or flavoring agent "to furnish about from 5 to 25% thereof in the emulsion.~ However, in the speci~ic discloses and examples provided in the Schultz et al patent as well as in the other patents where Schultz wàs an inventor, xesulting ~0~2 .
oil percentages in encapsulated form were far - below the practical limit of 12~ noted above and initially stated in the Beck patent.
Accordingly, there remains a need for a process making possible the formation of stable, extruded, solid essential oil or flavor compositions having a relatively high percentage - of essential oil encapsulated therein, preferably at least in excess of the practical limit of 12%.
as stated in the Beck patent.
.Summary of the Invention It is therefore an object of the invention to provide an improved process for forming an extruded, solid, essential oil flavor composition and a product of such process while . overcoming one or more problems of the type summarized above.
It is a further object of the invention to provide such a process for producing a 20 resulting product characterized by a ~elatively high essential oi~ or oil-soluble flavor content completely encapsulated within the extruded particulate solids.
. It is an even further object of the invention to provide such a process for producing a resulting produc' charac~erized by a relatively ~ , .high essential oil or oil-soluble flavor content : completely en~apsulated within the extruded particulate solids.
~ 30 It is an even further object of the invention to provide such a process for forming a resulting product in the form of a stable, melt-based and extruded, solid essential oil 1%9C)6~
flavor composition characterized by about 12 to 35% by weight of essential oil in substantially completely encapsulated form within the extruded solids. A somewhat hi~her percentage of the essential oil or oil-soluble flavor is initially added in the process to accommodate oil losses, for example, during emulsification and solvent washing of the product.
. It is a related object of the invention to provide such a process for forming a resulting product in the form of a stable, melt-based and extrude~, solid essential oil flavor composition - wherein a selected quantity of essential oil is combined and blended with an aqueous mixture of a sugar, starch hydrolysate and selected emulsifier and at least preferably about 60% by weight, more preferably 70~ by weight and most preferably about 75 to 80% by weight of the selected quantity of essential oil is present in encapsulated form within the resulting particulate essential oil composition Although, as noted above, the solid essential oil flavor composition of the invention ~s preferably characterized generally by about 12 to 35% by weight of essential oil in substantially completely encapsulated form, the present invention more preferably contemplates the solid : , essential oil flavor composition as being characterized by about 14 to 30% by weight of essential oil in substantially completely encapsulated form within the extruded solids.
In accordance with the present invention, it has been found that such a process and product are possible by first forming an . , .
9~;12 aqueous mixture of a sugar and starch hydrolysate in combination with a suitable emulsifier, the aqueous mixture and emulsifier is combined and blended with a selected quantity of an essential S oil or oil-soluble flavor in a closed vessel to form a homogeneous melt under controlled pressure conditions substantially greater than atmospheric pressure.
It is an even further object of the invention to provide such a process and product of the process wherein the blending step is carried out in a closed vessel pressurized within the range of from about 7 to 50 pounds per square inch ~psi) or more.
It is yet a further related object of the invention to cook the aqueous mixture of the sugar and starch hydrolysate preferably to a maximum temperature of about 126~ C before the aqueous mixture and a selected emulsifier are combined and blended with the essential oil in a closed vessel as described above. More preferably, the aqueous mixture is heated to a maximum temperature of about 124 C and most preferably to a temperature in the range of about 1~2 to 124 C generally under atmospheric ~ressure conditions. These temperatures are especially applicable where the essential oil comprises at least about 28% by weight of the combination just prior to emulsification.
A still further related object of the invention is to carry out the heating step whereby the resulting particulate essential oil composition has a relatively higher water content, preferably at least about 5% by weight.
.
.. ~ .
. ~ ~,'' .. .
. , . :
9~6~
In connection with the present invention, the term ~sugar" is intended to include simple sugars such as sucrose, lactose, levulose, dextrose, fructose and maltose, as well as polyols such as glycerin and even other sweetners having generally similar characteristics. Similarly, the term ~starch hydrolysate" is intended to include all hydrolyzed starches, both hydrolyzed cereal solids of about 20 DE or less and corn syrup solids of about 20 DE or higher. The term "emulsifier" is used herein to indicate any emulsifier which is satisfactory for use particularly in combination with the selected flavoring oil. Specific examples of suitable emulsifiers are set forth within the following detailed description. In addition, the term "essential oil" is intended to include other oil - soluble flavors which are capable of incorporation in the process and product-of the present invention.
Additional objects and advantages of the invention are made apparent in the following description having reference to the accompanying drawings.
Brief Description of the Drawings FIGURE l is a block-type flow sheet including steps of the process of the present invention and for forming the product of that process.
FIGURE 2 is a graphic representation of the effect of increased pressure on encapsulation of the essential oil flavoring within the product of the process.
~90~1~
.
Descxiption of the Preferred ~mbodiments As noted above, the present invention - relates to a process for forming or preparing a stable, melt-based and extruded solid essential oil flavor composition in particulate form as well as the product of the proc:ess. Generally, the process comprises the steps of (1) heating to a suitable cook temperature an a~ueous mixture of a sugar and a starch hydrolysate together with a selected emulsifier, the cook temperature being approximately the boiling point of the aqueous mixture, 12) blending a selected quantity of an essential oil flavor with the aqueous mixture to form a homogeneous melt, (3) extruding the 1~ homogeneous melt into a relatively cool liguid solvent to form extruded solids of selected size and shape, and ~4) drying the particles and blending with a selected antica~ing agent to produce a stable and relatively non~hygroscopic composition in particulate form. The process is improved by the present invention in that the step of blending or emulsifying the essential oil with the aqueous mixture is carried out in a closed vessel and the quantity of essen~ial oil flavor added to the homogeneous melt is preferably selected to provide about 12 to 35% by weight and more preferably about 14 to 30~ by weight of essential oil flavor in completely encapsulated form within the particulate oil composition.
The present invention further contemplates a process and product of the process wherein preferably at least about 60~ by weight, more preferably at least about 70% by weight and ~90~12 . --1 o--most preferably at least about 75 to 8C~ by weight of a selected quantity of e~sential oil combined and blended with the aqueous mixture is present in encapsulated ~orm within the resulting particulate essential oil composition.
~ The invention also contemplates that the sugar and starch hydrolysate, either together with or pxior to combination of the selected emulsifier therein, is preferably heated to a maximum temperature of about 126 C in order to minimize flavor deterioration of the essential oil flavor and also to facilitate encapsulation according to the present invention. More pxeferably, the heating temperature is limited to a maximum of about 12~ C and most preferably, th~
aqueous mixture is heated to a temperature in the range of about 122 to 124 C generally under atmospheric pressure conditions. These reduced temperatures zre of greatest value when the 2~ essential oil comprises at least about 28% by weight of the combination.
These temperature limits are discussed in connection with the present invention in greater detail below. In addition to minimizing deterioration of flavor and other undesirable characteristics of the essential oil which commonly result at higher temperatures, the reduced cook temperature is also believed to permit a relatively increased amount of water to remain in the melt prior to extrusion. It is theorized that this additional water assists in stabili2ing and facilitating emulsification and encapsulation of the higher guantities of essential oil within the particulate solid in accordance with the process of the present invention. Preferably, the invention contemplates that the solid resulting from the,process of the present invention comprise at least about 5~ by w~ter.
At the same time, the above temperature conditions for the heating step are preferably stated as maximums at least within the broad and preferred ranges since a number of variations in the process may be carried out for accomplishing similar results under even further reduced temperatures. For example, it has been found that a lower cook temperature may be used where a lower DE rated sugar or sweetener is employed. For example, if a 10 DE sweetener were employed in place of the 20 DE sweetener described below in connection with a number of examples, it would be possible to urther reduce the cook temperature in accordance with the present invention.
Similarly, it would also be possible to reduce the cook temperature while otherwise achieving the objects of the present invention by either employing a greater degree of agitation during the cooking process in order to facilitate removal of excess water therefrom or by carrying out the cooking process under vaeuum conditions for the same purpose.
The second Swisher patent, and the Beck patent referred to above discussed in substantial detail the manner in which a homogeneous melt can be formed from an aqueous mixture of a sugar and starch hydrolysate together with a separate flavor component to form an extruded solid capable of being dried in the manner summarized above. Those ... .. .
6~LZ
.
references also discussed the manner in which such a homogeneous melt can be extruded into a cool liquid solvent to form particle of selected shape and size as well as the selection of a suitable ~nticaking agent for combination with the extruded solid particles in order to maintain them in a more ~table condition. Accordingly, those references are incorporated herein as though set forth in full with respect to the particular 1~ features referred to above.
Referring now to the drawings and particularly to FIGURE 1, a selected sugar and starch hydrolysate are mixed together as indicated at 12. The mixture is then agitated in order to 1~ uniformly mix together the sugar and starch hydrolysate. As noted above, the sugar may be any of the simple sugars such as sucrose, levulose, dextrose, fructose or maltose, as well as a polyol such as glycerine or other similar sweeteners.
Any preferred sugar or sweetner may be used for any of a variety of reasons, such as to achieve improved flavor of the resulting product and/or to reduce hygroscopcity of the product. The mixture 12 is then heated to a coo~ temperature preferably 2i approximating its boiling point as indicated at 14. A suitable cook temperature ~or such mixtures including most sugars extends across a range of approximately 110 to 130~ C. For example, with the sugar beiny sucrose and the starch hydrolysate being 20 DE corn syrup, the boiling point of the mixture is approximately 125-130 C and the mixture is preferably heated to a temperature within that range.
/ ~ ~
I
90~12 An emulsifying agent is preferablyadded to the a~ueous mixture 12 after the heating step. Within FIGURE l, addition of the emulsifying agent is indicated at 16; The emulsifier is selected to facilitate emulsification or dispersion of essential oil described below into the mixture 14. Selection of the particular emulsifier and the quantity of the emulsifier added to the agueous mixture 14 is one of the important features of the present invention permit~ing from 12 to 35~ of a selected essential ` oil to be encapsulated within the final extruded product. Suitable emulsifiers for use within the present invention include sulfoacetate of mono-and diglycerides as well as polyglycerol esters and lecithin. Polyqlycerol esters suitable for use within the present invention are available, ~or example, under the trademark identification DREWPOL 6-2-S available from California Fats &
Oils, Richmond, California. Generally, the polyglycerol esters have been found satisfactory within the present invention for the lower end o~
the specified range.
One preferred emulsifier for emulsifying and encapsulating up to 35~ essential oil within the final extruded product is a sulfoacetate of mono- and diglycerides containing . 1% by weight water and available under the trademark identification EMARGOL KL available from the Witco Company. Emulsifiers such as those referred to above are added to the molten mixture 14 in the amount of approximately 0.5 to 5% by weight of the aqueous mixture. However, it is to ~e noted that the amount of emulsifier used in l~g()~2 -such an application can vary depending upon other factors. Accordingly, the above noted range is set forth only as a general indication in connection with the present invention~
Another emulsifier which has been found to be particularly satis~actory in terms of the present invention bu~ possibly less preferred than the EMARGOL XL product rleferred to above is lecithin, available for example from Ross & Rowe under the trademark ~ELKIN TS.
Examples employing both of the emulsifiers noted above are set forth below.
An essential oil or other oil-soluble flavor contemplated for combination with the mixture 14 and emulsifier 16 is generally indicated at 18 and may be an essential oil, for example, of a citrus fruit contemplated for use in bever~ge or other food products.
The addition of a small amount of an oil-soluble heat-stable antioxidant ~indicated at 20 in FIGU~E 1) such as 4-methyl-2, 6-ditertiary butyl phenol or butylated hydroxyanisole is optional. Generally, from about 0.05 to about 0.5~ by weight of the antioxidant, based on the weight of the essential oil, is sufficient.
The essential oil 18, alone or in com~ination with the antioxidant 20, is then added to the a~ueous mixture 14 and emulsifier 16 in a vessel 22. In accordance with the pr~sent invention, it is particularly important that the vessel 22 be closed during blending of the essential oil 18 with the cooked aqueous mixture 14 and emulsifier 16. It has been found that the carrying out of this blending or emulsification ~90~Z
step in a closed vessel is essential to insure uniform and consistent encapsulation of relatively large quantities of essential oil within the solid product.
The closed vessel 22 is charged with gas, preferably an inert gas such as nitrogen or carbon dioxide, for example, to maximize encapsulation of the oil or flavor. Even more preferably, the vessel 22 is pressurized after addition of the inert gas to a pressure from about 7 to 50 psi. In FIGU~E 1, addition of the inert gas is generally indicated at 24. Pressurization and its effects within the closed vessel 22 are described in greater detail below with further 1~ reference to the graph of FIGURE 2.
Referring to FIG~RE 2, encapsulation of substantially increased quantities of essential oils or other oil-soluble flavors is illustrated as being possible with pressurization in the vessel 22 generally from about 7 to about 100 psi.
Destabilization of the resulting product sometimes occurs with higher pressures at or above approximately 100 psi. Best results are obtained with the closed vessel 22 if pressure is maintained within the approximate range of 7-50 psi.
In this regard, a pressure of about 7 psi is developed from vapor pressure alone resulting from combination of the essential oil 18 with the molten mixture 14 and emulsifier 16 within the closed vessel. In such an event, the vessel 22 is initially charged either with air or an inert gas at atmospheric pressure.
~Z~9~6~-~
--lo--Referring to FIGURE 2, the upper limit of S0 psi for pressurization of the vessel 22 is not a precise limit. In some applications, it is possible to pressurize the vessel substantially 5 above 50 psi and even above 100 psi without causing destabilization. ~owever, since the amount of essential oil capable of encapsulation within the final extruded product tends to diminish when pressure is increased above 50 psi, that pressure has been selected as the generally preferred upper limit for pressurization of the vessel 22.
Mixing of the essential oil 18, aqueous mixture 14 and emulsifier 16 in the closed vessel 22 under pressure is continued until those components are uniformly mixed and emulsified to result in a homogeneous melt of the type also discussed in the Beck and Swisher references, for example. Generally, the homogeneous ~elt is ~efined as having a plastic condition suitable for forming a solid product in the manner defined below with an amphorous character for achieving high stability over an extended period of time.
The homogeneous melt from the vessel 22 is then extruded under pressure, using either gas or mechanical pressure, for example, into a cold organic solvent such as isopropanol to form the melt into extruded filaments.
Extrusion is carried out in an extruder 26 having die openings of a si~e selected in accordance with the size and shape desired for the - resulting particles. For example, where small particles are desired for use in beverage or food products, the homogeneous melt from the vessel 22 1~906~2 -17~
is extruded through openings (not shown) having diameters, for example, of about l/32 inch.
Extruded filaments of the homogeneous melt pass from the extruder 26 into a cold cold organic solvent, such as isopropanol at about -20 C, as generally indicated at 28. The function of the isopropanol or other solvent is two-fold. Initially, it acts as a coolant to rapidly solidify the extruded shapes of homogeneous melt. Secondly, it removes any essential oil on the surface of the extruded solids which would otherwise be susceptible to oxidation. -The extruded filaments are preferably broken up into small rod-like particles while within the solvent 28 in order to permit removal of any essential oil exposed on the smaller or separated particles. For example, the f ilaments can be divided by impact action of an agitator ~o impeller ~not shown) to produce a desired particle size and shape.
Following the solvent washing step 28, the particles from the extruded filaments are then screened or centrifuged at 30 to remQve the organic solvent. The solvent is transferred to a holding tank 32 and may be returned to the washing step 28 if desired.
The particles from the separation step 30 are dried in a vacuum oven 33 and blended with a suitable anticaking agent 36. The partlcles are then screened by passage over a succession of sizing screens (not shown) and packaged, preferably in a dehumidified room, as indicated at 39~
l~g()~
1~-The anticaking agent, as gen~rally indicated at 36, is added to the particles after drying to facilitate their urther handling and to prevent the particles from sticking together. The S anticaking agent is preferably silica, introduced either before or after the particles are treated - in the oven 33.
The process described above may be used for preparing extruded solids containing essential oils froln various sources. In particular, the process of the invention is contemplated for use in conjunction with various citrus fruits such as oranges, grapefruit, lemons, etc. However, it will be apparent that the process of the invention is also useful with other essential oil or oil-soluble flavors, either for use in beverages or food products.
The product of the process described above is novelly characterized as a stable, melt based and extruded, solid essential oil composition in particulate form. The particles are of a solid amorphous character with a shape determined by the extruder 26 and further divided, for example, by impact breaking at 28. The particles consist of a sugar and starch hydrolysate as defined above, a selected emulsifier and a selected essential oil flavor.
The essential oil flavor preferably forms about 12 to 35%, more preferably about 15 to 30%, by weight of the particles while being present therein completely encapsulated form.
The preceding process is particularly adapted for assuring reproducible production of particles having a high oil content as defined .. . .. .
~9~z above. ~he process is also particularly adapted for forming about 12 to 35% by weight of the particles with the essential oil flavor being present therein in completely encapsulated form.
S The following examples of various embodiments of the invention are presented to further illustrate and exemplify but not to limit the scope of the invention.
Exam~le 1 6025 grams of 20 DE corn syrup (70%
- solids), 4125 grams sugar and 200 grams EMARGOL RL
were mixed in a steam jacketed stainless steel vessel. The vessel was fitted with a thermometer and an agitator-assembly produced by C. E. Howard Company, Los Angeles, California and having a flat bladed turbine type agitator about 4 1/2 inches in diameter. After heating to 130 during an initial cook, 2200 grams of cold-pressed orange oil were added to the vessel. The vessel was immediately closed. After 5 minutes mixing with the aqitator, the pressure inside the vessel had increased to 7 psi. During mixing, the cold-pressed orange oil lowered the temperature of the aqueous mixture below its cooking temperature, for example, to about 125 C. After mixing was complete, nitrogen was added to pressurize the vessel to 30 psi and the melt was extruded through a plate with 0.030 inch diameter holes into 19 liters of cold (-20~ C) isopropanol to solidify the filaments.
After impact breaking of the filaments, the excess isopropanol was removed on a vacuum screen and the material was dried for 3 hours in a vacuum oven ~50D C, 27 in. Hg YacUUm). After addition of 2% silica as an anticaking agent, the product contained 16.7% by weight flavor.
Example 2 6025 grams of 20 DE corn syrup ~70~
solids), 4125 grams sugar and 200 grams EMARGOL KL
were mixed in a steam jacketed stainless steel vessel. The vessel was fitted with an agitator and thermometer as in Example 1. After heating to 130 C in an initial cook, 2200 grams of cold-pressed orange oil were added to the vessel.
The vessel was immediately closed and pressurized to 50 psi with nitrogen. After S minutes mixing and agitation, the melt was extruded throuqh a plate with 0.030 inch diameter holes into 19 l; liters of cold (-20 C) isopropanol to solidify the filaments. The excess isopropanol was removed on a vacuum screen and the material was dried for
3 hours in a vacuum over (50 C, 27 in Hg.
vacuum). After blending in 2~ silica, the product contained 20.7% by weight flavor.
~xam~le 3 6025 grams of 20 DE corn syrup ~703 solids), 4125 grams sugar and 450 grams EM~RGOL KL
were mixed in a steam jacketed stainless steel 2~ vessel. The vessel was fitted with an agitator and thermometer again as in Example 1. After heating to 130 C in an initial cook, 2500 grams of cold-pressed orange oil were added to the vessel. The vessel was immediately closed and pressurized to 50 psi with nitrogen. The melt was then extruded through a plate with 0.030 inch diameter holes into 19 liters of cold (-20 C) ~L~6~Z
isopropanol to solidify the filaments. The excess isopropanol was removed on a vacuum screen and the material was dried or 3 hours in a vacuum oven (50~ C, 27 in. Hg. vacuum). After blending in 2%
silica, the product conta-ined 19.8~ by weight flavor.
.. . ..
ExamDle 4 The steps of Example 3 were repea~ed except that the vessel was pressurized to 100 psi with nitrogen. Upon extrusion of the xesulting product, the solids were found to be destahilized as indicated at 38 in FIG~RE 2. Thus, Example 4 represents instability of the resulting product upon pressurization to about 100 psi.
The steps of Examples 1-3 are also capable of reproduction with other essential oils, for example, from citrus fruit other than oranqes or other oil-soluble flavors.
In addition, the steps of Example 1 were repeated with a number of other combinations of essential oil and emulsifier as typified below in Table I. Table I summarizes Examples 1-4 and illustrates additional Examples 5-8 carried out with the same steps and amounts described above for Example 1 except where different amounts of various components are indicated in Table I. As noted above, about 7 psi pressure was developed within the vessel 22 for each of these examples by vapor pressure of the components being mixed therein. At the same time, the temperature in the vessel was reduced from the initial cook temperature primarily by addition of the essential oil to the cooked aqueous mixture.
96~61Z
co 8 ~
N ~ ,~ ,J ~! C
I ' o ~o oo ~
o o r~ n <~
~ 3 ~
~ ~ . ~ 1` ~ a~
u~ Lr O ~
~ ~ . 8 ~ G ,~
N
~ I' ul a~ I` O ~ C~ ~
~1 C dP
~1 ct7 o-'o ~
~ ~ O U~ O ' ~1 U~
H t~
~_I O o ~ ~ ~_ I` H ,~
t~ O
~ 0 ~ b ~
1~30612, -~3-The information set forth in Table I is . .
summarized as follows. Initially, for Examples 5-8, the processing steps described in connection with Example 1 were again followed including the s identity and ~eight oE sugar and starch hydrolysate. The amount of E~ARGOL KL and flavor or essential oil is set fc)rth in Table I for each of the examples. Also, the identity of the flavor or essential oil for each of the examples is ld indicated in the footnotes to Table I.
Thereater, the initial emulsifier content and flavor or essential oil content are set forth as percentages. These values were calculated based - on the total weight of the product prior to extrusion. Accordingly, the percentages are based on a total weight of the sugar, starch hydrolysate, emulsifier and flavor assuming loss of all but about 5~ of the water from the corn syrup or starch hydrolysate. Encapsulation efficiency, referred to in the note following Table I, was determined directly from the values for initial flavor content and encapsulated flavor. For example, encapsulation efficiency for Example 1 was determined by dividing 16.7 by 20.1 and multiplying by 100 to result in encapsulation efficiency of about 83.1%.
Information set forth below for ,. additional examples was determined in the same manner described immediately above. It is again noted that, for each of the examples, all but about 5% by weight of the water from the starch hydrolysate was removed during the initial cooking step.
,~. .. , , . ~
~6~2 -2~-Abbreviated data for Examples 9-13 is set forth in Table II to demonstrate the efect of coo~ temperature on encapsuLation efficiency. The examples set forth in Table II were carried out in the same pilot plant reactor used for each of Examples 1-8. At the same time, each of Examples 9-13 was carried out according to the specific steps set forth in connection with Example 6. The only variation for Examples 9-13 was the heating or cooking temperature to which the aqueous mix was heated during the initial cook.
qA3LE II
Encapsulation Efficiency vs. Cook Te~perature OilEncapsulation Cook mple No. caDsulatedEfficienc~le~perature, C
9 20.5 63.5 118 22.9 70.9 122 11 21.1 65.3 126 12 19.3 59.8 130 13 19.2 - 59.4 134 N'ote: In each of Examples 9-13, 6025 grams of 20 DE
oorn syrup ~70% solids), 4125 gra,~s sugar and 240 grams EM~RGO~ KL were mixed in a steam jacketed stailless steel vessel fitted with an agitator and thermometer as descri'ked for preceding examples. ~le mixture was then heated to a cook te~perature as set forth a'bove in Table II. Thereafter, 4200 grams of cold-pressed orange oil was added, the vessel i,nmediately closed and agitation commenoed. A pressure of about 7 psi developed after about five nunutes of agitation m e resulting melt was then extruded through a plate wit'n 0.030 inch openings into 19 liters of cold (-20 C) isopropanol. The solidified filaments ~ere im3act broken as described a'~ove, excess isopropanol ren~ved b~ vacu~m, the material dried and blen~ed with 2~ by ~eight silica. ~esulting encapsulating efficienc~ for examples 9-13 is set forth in Table II.
. . .
~9[:)6~2 The data of Table II is set forth : independently o~ the rest of the examples 9-13 - were all run at about the same time with the same lots or batches of emulsifier, essential oil, etc.
Accordingly, Table II is believed to very clearly ~emonstrate a trend according to the present invention in terms of encapsulation efficiency 2S
determined by the cook temperature.
At the same time, Examples 9-13 lG represent a relatively limited number of temperatures in the range between 118 C and 135 C. Table III sets forth a larger number of examples run in a similar manner as the examples of Table II but at different times and possibly with different lots of emulsifier, essential oil, etc. Although the examples of Table III were run in different equipment from those Table II, they are believed sufficiently similar so that Tables II and III taken together tend to establish the ~0 same trend, referred to above in connection with Table II alone, as to the effect of cook temperature on encapsulation efficiency according to the invention.
~ Table III, below, sets forth Examples 14-39 which were also carried out in a similar manner as described above for Examples 9-13 of Table II. The examples of Table III were run ln a large scale plant reactor rather than the pilot plant reactor used in Table II. However, results in Tables II and III are believed to be clearly capable of corre9ation to further demonstrate consistency for the process of the present invention.
~29;~6~;~
&~ :
, t) ~1 r~ o a~ o 1-- 1~ o L~ ~ ., ~ .
~ 'O ~ a~ ~ ~ ~ ~ ~1 ~ ~P O O O O ~
. .
a ~ O CO O ~ ~ ~ U~ ~ O ~ O ~3 0 H 1:~ ~
O ~ Ih u~ U~
a ~D ~ 00 CO C~ CO CO CO ~O ~ a~ ~ o o .
o~ O O O G~ O O G~ o o o .
`::
lZgO6~2 ,, ~
,~ a~ ~ o cl~ 1-- ~ ~ s~ ~r ~ t~ er dP ~ o u~ ~ O ~ ~ O~
~ ~3 .. , ,~ ~a~ o co ,~ o ~
~ ~ ~ N 1~1 I~J ~1 ~ t`J ~ r~l _1 Q~
~ ~ ~ ~ ~`:1 N ~`1 ~I ~ ~ ~ r~
H
~P Q) tJ~
h ~1 ~J Q O a~ O O C~ O a~ O~ CO
.
~ o~ o~ o ~ ~ r~
..,,.: , :
' ' ' ,; ~
,, , g It may also be seen in connection with Table III that unacceptable encapsulation efficiency resulted particularly in connection with Examples 26, 27, 38 and 39. Each of these examples included a generally high cook temperature varying from about 130 to about 134 C. In addition, those same examples included relatively high initial essential oil contents ranging from about 30.2 to about 32.9~ b weight.
Accordingly, Table III is believed to even further emphasize the importance of cook temperature in accordance with the present invention.
~ able IV, below, sets forth yet an additional series of Examples 40-42, each carried out using lecithin as an emulsifier.
~906~LZ
o' ~
~ o~
3 ~ a~ ~
~ . ..
.~
dQ rl ~ CO CO ~
o y ~ . ~
.~
~ o ~o ~
..... - ~
,, O ~.~ ~ ~ ~D , .
N N CO
,~ .C ~
~ ~ ~ ~ a~ ~r O ~I N
1~ ' .
: `
Table IV illustrates the ut~lity of the present invention including lecithin as an emulsifier. In each of Examples 40-42 of Table IV, lecithin available from Ross & Rowe under the tradename YELXIN TS was employed.
Table IV in particular demonstrates that lecithin was quite effective as an emulsifier where the essential oil WclS initially present in an amount of about 22~ by weight. With an ini~ial essential oil percentage of about 28, for example, it is particularly important to employ a lower cook temperature of no more than about 1~6 C and preferably no more than about 123 to 124 C in order to achieve effective encapsulation efficiency.
Further Discussion of Prior Art In order to further illustrate advantages of the present invention, ~able V sets forth Examples 43-51 only for the purpose of 20 representinq the ~rior art for pur~oses of com~arison. Examples 43-51 were conducted in essentially the same manner as Examples 9-13 of Table II ~ut with the vessel remaining open during mixing of the essential oil with the aqueous mix.
.
~ .
0~;12 g ~1 .
0 ~
O ~ o ~ ' ~ . ~ 0 ~o CO ~` ~ ~9 O ~ ~ co ~ c~ ~r ~ o ~ o dP 0 U~ ~ O ~ O ~ ~ i o -cq 0 ~ ~D ~D ~ ~D ~ U~ C~ CO ~
~4 ,~
o Z ~ ~ ~ r- co ~ o ,~
,, , ~ ~ .
~ 9~ 2 Examples 43-51 are believed, by contrast, to demonstrate further adv~ntages of the present invention. A cursory review of Table V
indicates some high encapsulation efficiencies S achieved even with an open mixing vessel, in particular, Examples 43, 45 and 47. ~owever, it is especially important to note that the initial amount of essential oil employed in each of Examples 43-Sl.was very lo~ compared to that in Examples 1-42.
Even with the advantage of lower initial oil content, encapsulation efficiency was not repeatable even for the limited purpose of ~ccomplishing uniform encapsulation with oil content in the range of about 12 to 15%. ~or example, note that whereas Example 43 resulted n encapsulation efficiency of 90%, substantially identical Example 44 resulted only in encapsulation efficiency of 66% with an oil :20 content in encapsulated form of only 10.8%. The other examples of Table V demonstrate similar inconsistent results and thus are believed to further assist in emphasizing the novel features of the present invention.
In view of the preceding description and Examples 1-42, other modifications of the process and resulting product of the present invention, in addition to those noted above, will be apparent to those skilled in the art.
Accordingly, the scope of the present invention is defined only by the following appended claims.
vacuum). After blending in 2~ silica, the product contained 20.7% by weight flavor.
~xam~le 3 6025 grams of 20 DE corn syrup ~703 solids), 4125 grams sugar and 450 grams EM~RGOL KL
were mixed in a steam jacketed stainless steel 2~ vessel. The vessel was fitted with an agitator and thermometer again as in Example 1. After heating to 130 C in an initial cook, 2500 grams of cold-pressed orange oil were added to the vessel. The vessel was immediately closed and pressurized to 50 psi with nitrogen. The melt was then extruded through a plate with 0.030 inch diameter holes into 19 liters of cold (-20 C) ~L~6~Z
isopropanol to solidify the filaments. The excess isopropanol was removed on a vacuum screen and the material was dried or 3 hours in a vacuum oven (50~ C, 27 in. Hg. vacuum). After blending in 2%
silica, the product conta-ined 19.8~ by weight flavor.
.. . ..
ExamDle 4 The steps of Example 3 were repea~ed except that the vessel was pressurized to 100 psi with nitrogen. Upon extrusion of the xesulting product, the solids were found to be destahilized as indicated at 38 in FIG~RE 2. Thus, Example 4 represents instability of the resulting product upon pressurization to about 100 psi.
The steps of Examples 1-3 are also capable of reproduction with other essential oils, for example, from citrus fruit other than oranqes or other oil-soluble flavors.
In addition, the steps of Example 1 were repeated with a number of other combinations of essential oil and emulsifier as typified below in Table I. Table I summarizes Examples 1-4 and illustrates additional Examples 5-8 carried out with the same steps and amounts described above for Example 1 except where different amounts of various components are indicated in Table I. As noted above, about 7 psi pressure was developed within the vessel 22 for each of these examples by vapor pressure of the components being mixed therein. At the same time, the temperature in the vessel was reduced from the initial cook temperature primarily by addition of the essential oil to the cooked aqueous mixture.
96~61Z
co 8 ~
N ~ ,~ ,J ~! C
I ' o ~o oo ~
o o r~ n <~
~ 3 ~
~ ~ . ~ 1` ~ a~
u~ Lr O ~
~ ~ . 8 ~ G ,~
N
~ I' ul a~ I` O ~ C~ ~
~1 C dP
~1 ct7 o-'o ~
~ ~ O U~ O ' ~1 U~
H t~
~_I O o ~ ~ ~_ I` H ,~
t~ O
~ 0 ~ b ~
1~30612, -~3-The information set forth in Table I is . .
summarized as follows. Initially, for Examples 5-8, the processing steps described in connection with Example 1 were again followed including the s identity and ~eight oE sugar and starch hydrolysate. The amount of E~ARGOL KL and flavor or essential oil is set fc)rth in Table I for each of the examples. Also, the identity of the flavor or essential oil for each of the examples is ld indicated in the footnotes to Table I.
Thereater, the initial emulsifier content and flavor or essential oil content are set forth as percentages. These values were calculated based - on the total weight of the product prior to extrusion. Accordingly, the percentages are based on a total weight of the sugar, starch hydrolysate, emulsifier and flavor assuming loss of all but about 5~ of the water from the corn syrup or starch hydrolysate. Encapsulation efficiency, referred to in the note following Table I, was determined directly from the values for initial flavor content and encapsulated flavor. For example, encapsulation efficiency for Example 1 was determined by dividing 16.7 by 20.1 and multiplying by 100 to result in encapsulation efficiency of about 83.1%.
Information set forth below for ,. additional examples was determined in the same manner described immediately above. It is again noted that, for each of the examples, all but about 5% by weight of the water from the starch hydrolysate was removed during the initial cooking step.
,~. .. , , . ~
~6~2 -2~-Abbreviated data for Examples 9-13 is set forth in Table II to demonstrate the efect of coo~ temperature on encapsuLation efficiency. The examples set forth in Table II were carried out in the same pilot plant reactor used for each of Examples 1-8. At the same time, each of Examples 9-13 was carried out according to the specific steps set forth in connection with Example 6. The only variation for Examples 9-13 was the heating or cooking temperature to which the aqueous mix was heated during the initial cook.
qA3LE II
Encapsulation Efficiency vs. Cook Te~perature OilEncapsulation Cook mple No. caDsulatedEfficienc~le~perature, C
9 20.5 63.5 118 22.9 70.9 122 11 21.1 65.3 126 12 19.3 59.8 130 13 19.2 - 59.4 134 N'ote: In each of Examples 9-13, 6025 grams of 20 DE
oorn syrup ~70% solids), 4125 gra,~s sugar and 240 grams EM~RGO~ KL were mixed in a steam jacketed stailless steel vessel fitted with an agitator and thermometer as descri'ked for preceding examples. ~le mixture was then heated to a cook te~perature as set forth a'bove in Table II. Thereafter, 4200 grams of cold-pressed orange oil was added, the vessel i,nmediately closed and agitation commenoed. A pressure of about 7 psi developed after about five nunutes of agitation m e resulting melt was then extruded through a plate wit'n 0.030 inch openings into 19 liters of cold (-20 C) isopropanol. The solidified filaments ~ere im3act broken as described a'~ove, excess isopropanol ren~ved b~ vacu~m, the material dried and blen~ed with 2~ by ~eight silica. ~esulting encapsulating efficienc~ for examples 9-13 is set forth in Table II.
. . .
~9[:)6~2 The data of Table II is set forth : independently o~ the rest of the examples 9-13 - were all run at about the same time with the same lots or batches of emulsifier, essential oil, etc.
Accordingly, Table II is believed to very clearly ~emonstrate a trend according to the present invention in terms of encapsulation efficiency 2S
determined by the cook temperature.
At the same time, Examples 9-13 lG represent a relatively limited number of temperatures in the range between 118 C and 135 C. Table III sets forth a larger number of examples run in a similar manner as the examples of Table II but at different times and possibly with different lots of emulsifier, essential oil, etc. Although the examples of Table III were run in different equipment from those Table II, they are believed sufficiently similar so that Tables II and III taken together tend to establish the ~0 same trend, referred to above in connection with Table II alone, as to the effect of cook temperature on encapsulation efficiency according to the invention.
~ Table III, below, sets forth Examples 14-39 which were also carried out in a similar manner as described above for Examples 9-13 of Table II. The examples of Table III were run ln a large scale plant reactor rather than the pilot plant reactor used in Table II. However, results in Tables II and III are believed to be clearly capable of corre9ation to further demonstrate consistency for the process of the present invention.
~29;~6~;~
&~ :
, t) ~1 r~ o a~ o 1-- 1~ o L~ ~ ., ~ .
~ 'O ~ a~ ~ ~ ~ ~ ~1 ~ ~P O O O O ~
. .
a ~ O CO O ~ ~ ~ U~ ~ O ~ O ~3 0 H 1:~ ~
O ~ Ih u~ U~
a ~D ~ 00 CO C~ CO CO CO ~O ~ a~ ~ o o .
o~ O O O G~ O O G~ o o o .
`::
lZgO6~2 ,, ~
,~ a~ ~ o cl~ 1-- ~ ~ s~ ~r ~ t~ er dP ~ o u~ ~ O ~ ~ O~
~ ~3 .. , ,~ ~a~ o co ,~ o ~
~ ~ ~ N 1~1 I~J ~1 ~ t`J ~ r~l _1 Q~
~ ~ ~ ~ ~`:1 N ~`1 ~I ~ ~ ~ r~
H
~P Q) tJ~
h ~1 ~J Q O a~ O O C~ O a~ O~ CO
.
~ o~ o~ o ~ ~ r~
..,,.: , :
' ' ' ,; ~
,, , g It may also be seen in connection with Table III that unacceptable encapsulation efficiency resulted particularly in connection with Examples 26, 27, 38 and 39. Each of these examples included a generally high cook temperature varying from about 130 to about 134 C. In addition, those same examples included relatively high initial essential oil contents ranging from about 30.2 to about 32.9~ b weight.
Accordingly, Table III is believed to even further emphasize the importance of cook temperature in accordance with the present invention.
~ able IV, below, sets forth yet an additional series of Examples 40-42, each carried out using lecithin as an emulsifier.
~906~LZ
o' ~
~ o~
3 ~ a~ ~
~ . ..
.~
dQ rl ~ CO CO ~
o y ~ . ~
.~
~ o ~o ~
..... - ~
,, O ~.~ ~ ~ ~D , .
N N CO
,~ .C ~
~ ~ ~ ~ a~ ~r O ~I N
1~ ' .
: `
Table IV illustrates the ut~lity of the present invention including lecithin as an emulsifier. In each of Examples 40-42 of Table IV, lecithin available from Ross & Rowe under the tradename YELXIN TS was employed.
Table IV in particular demonstrates that lecithin was quite effective as an emulsifier where the essential oil WclS initially present in an amount of about 22~ by weight. With an ini~ial essential oil percentage of about 28, for example, it is particularly important to employ a lower cook temperature of no more than about 1~6 C and preferably no more than about 123 to 124 C in order to achieve effective encapsulation efficiency.
Further Discussion of Prior Art In order to further illustrate advantages of the present invention, ~able V sets forth Examples 43-51 only for the purpose of 20 representinq the ~rior art for pur~oses of com~arison. Examples 43-51 were conducted in essentially the same manner as Examples 9-13 of Table II ~ut with the vessel remaining open during mixing of the essential oil with the aqueous mix.
.
~ .
0~;12 g ~1 .
0 ~
O ~ o ~ ' ~ . ~ 0 ~o CO ~` ~ ~9 O ~ ~ co ~ c~ ~r ~ o ~ o dP 0 U~ ~ O ~ O ~ ~ i o -cq 0 ~ ~D ~D ~ ~D ~ U~ C~ CO ~
~4 ,~
o Z ~ ~ ~ r- co ~ o ,~
,, , ~ ~ .
~ 9~ 2 Examples 43-51 are believed, by contrast, to demonstrate further adv~ntages of the present invention. A cursory review of Table V
indicates some high encapsulation efficiencies S achieved even with an open mixing vessel, in particular, Examples 43, 45 and 47. ~owever, it is especially important to note that the initial amount of essential oil employed in each of Examples 43-Sl.was very lo~ compared to that in Examples 1-42.
Even with the advantage of lower initial oil content, encapsulation efficiency was not repeatable even for the limited purpose of ~ccomplishing uniform encapsulation with oil content in the range of about 12 to 15%. ~or example, note that whereas Example 43 resulted n encapsulation efficiency of 90%, substantially identical Example 44 resulted only in encapsulation efficiency of 66% with an oil :20 content in encapsulated form of only 10.8%. The other examples of Table V demonstrate similar inconsistent results and thus are believed to further assist in emphasizing the novel features of the present invention.
In view of the preceding description and Examples 1-42, other modifications of the process and resulting product of the present invention, in addition to those noted above, will be apparent to those skilled in the art.
Accordingly, the scope of the present invention is defined only by the following appended claims.
Claims (18)
1. In a process for preparing a stable, melt-based, extruded, solid essential oil flavor composition in a process where an aqueous mixture of a sugar, a starch hydrolysate and a selected emulsifier is heated to about the melting point of the aqueous mixture, an essential oil flavor is combined and blended with the aqueous mixture to form a homogeneous melt and the homogeneous melt is extruded into a relatively cool solvent to form a solid extruded material which is dried and combined with an anticaking agent to produce a resulting stable and relatively non-hygroscopic particulate essential oil composition, the improvement comprising carrying out the step of combining and blending of the essential oil flavor with the aqueous mixture by agitating the essential oil flavor and aqueous mixture together in a closed vessel in order to form the homogeneous melt under controlled pressure conditions greater than atmospheric pressure, and selecting a quantity of the essential oil flavor for combination and blending with the aqueous mixture, the selected quantity of essential oil flavor being sufficient to provide about 12 to 35% by weight of the essential oil flavor in encapsulated form within the particulate essential oil composition.
2. The improved process of Claim 1 further comprising the step of developing a pressure in the range of about 7 to 50 psi in the closed vessel during the step of combining and blending the essential oil flavor with the aqueous mixture by agitation in the closed vessel.
3. The improved process of Claim 2 wherein the emulsifier is selected from the class consisting of sulfoacetates of mono- and diglycerides, polyglycerol esters and lecithin.
4. The improved process of Claim 1 wherein at least about 60% by weight of the selected quantity of essential oil combined and blended with the aqueous mixture is present in encapsulated form within the resulting particulate essential oil composition.
5. The improved process of Claim 4 wherein at least about 70% by weight of the selected quantity of essential oil combined and blended with the aqueous mixture is present in encapsulated form within the resulting particulate essential oil composition.
6. The improved process of Claim 5 wherein at least about 75 to 80% by weight of the selected quantity of essential oil combined and blended with the aqueous mixture is present in encapsulated form within the resulting particulate essential oil composition.
7. The improved process of Claim 1 wherein the step of heating the aqueous mixture of the sugar, starch hydrolysate and selected emulsifier is limited to a maximum temperature of about 126° C.
8. The improved process of Claim 7 wherein the step of heating the aqueous mixture of the sugar, starch hydrolysate and selected emulsifier is limited to a maximum temperature of about 124° C.
9. The improved process of Claim 7 wherein the step of heating the aqueous mixture of the sugar, starch hydrolysate and selected emulsifier is carried out generally under atmospheric pressure conditions and at a temperature in the range of about 122 to 124° C.
10. The improved process of Claim 1 wherein the step of hearing the aqueous mixture of the sugar, starch hydrolysate and selected emulsifier is carried out in a manner to limit water loss from the mixture whereby the resulting particulate essential oil composition has relatively higher water content.
11. The improved process of Claim 10 wherein the resulting particulate essential oil composition comprises at least about 5% by weight water.
12. The improved process of Claim 1 wherein the essential oil flavor is an oil of a citrus fruit.
13. A stable, melt-based and extruded solid essential oil composition in particulate form produced by the process of Claim 1 and comprising solid amorphous particles of extruded shape, the particles consisting of a sugar, starch hydrolysate, selected emulsifier, selected essential oil flavor and water, the essential oil flavor forming about 12 to 35% by weight of the particles in substantially completely encapsulated form.
14. The extruded solid essential oil composition of Claim 13 wherein the emulsifier is selected from the class consisting of sulfoacetates of mono- and diglycerides, polyglycerol esters and lecithin.
15. The extruded solid essential oil composition of Claim 13 wherein the essential oil flavor forms about 14 to 30% by weight of the particles in substantially completely encapsulated form.
16. The extruded solid essential oil composition of Claim 15 wherein the solid amphorous particles comprise at least about 5% by weight water.
17. The extruded solid essential oil composition of Claim 13 wherein the solid amphorous particles comprise at least about 5% by weight water.
18. The extruded solid essential oil composition of Claim 13 wherein the essential oil flavor is an oil of a citrus fruit.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/754,105 US4610890A (en) | 1984-07-16 | 1985-07-12 | Preparation of solid essential oil flavor composition |
| US754,105 | 1985-07-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1290612C true CA1290612C (en) | 1991-10-15 |
Family
ID=25033511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000503795A Expired - Lifetime CA1290612C (en) | 1985-07-12 | 1986-03-11 | Solid essential oil flavor composition and method of manufacture |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1290612C (en) |
-
1986
- 1986-03-11 CA CA000503795A patent/CA1290612C/en not_active Expired - Lifetime
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4707367A (en) | Solid essential oil flavor composition | |
| US4610890A (en) | Preparation of solid essential oil flavor composition | |
| US5202147A (en) | Peanut butter and a method for its production | |
| US4096281A (en) | Method and composition for producing flavored popcorn | |
| EP0673605A1 (en) | Hydrogenated starch hydrolysate based flavoring materials in the form of particles and use of same | |
| US5264238A (en) | Method for manufacturing snack foods | |
| US3961091A (en) | Process for producing flavored popcorn | |
| US2976159A (en) | Fibrous fruit product and process | |
| US3953615A (en) | Hydration drying of coffee, tea, or juice concentrate by means of anhydrous dextrose | |
| JP2708869B2 (en) | Method for producing transparent edible film | |
| US4902526A (en) | Process for preparing high-fat soybean milk | |
| US4423085A (en) | Cocrystallized sugar-nut product | |
| US3199988A (en) | Process for making a whippable composition | |
| US4491597A (en) | Candy bar | |
| EP0461605A1 (en) | Method for manufacturing snack foods | |
| EP1505078B1 (en) | Method of modifying gum arabic | |
| CA1290612C (en) | Solid essential oil flavor composition and method of manufacture | |
| US4499112A (en) | Process for forming solid juice composition and product of the process | |
| US4888186A (en) | Method for producing flavored popcorn | |
| EP0082459B1 (en) | Preparation of flavorant capsules | |
| JPH1169963A (en) | Solid-like cooking auxiliary food | |
| US3239359A (en) | Process of making a baked edible citrus peel product | |
| EP0462838B2 (en) | Flavour oil and process for producing the same | |
| JPH06141814A (en) | Red potato powder | |
| JPS592253B2 (en) | How to make yokan with mozuku |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry | ||
| MKEX | Expiry |
Effective date: 20081015 |