JP2021001317A - Method for producing aromatic liquid and aromatic liquid - Google Patents

Abstract

To provide a convenient production method for an aromatic liquid having a green aroma.SOLUTION: A method for producing an aromatic liquid includes the steps of: heating a lipid containing at least one selected from the group consisting of oleic acid peroxide and palmitoleic acid peroxide, in aqueous liquid to produce a C6-10 linear saturated aliphatic aldehyde; and recovering the linear saturated aliphatic aldehyde.SELECTED DRAWING: None

Description

The present invention relates to an aromatic liquid, and more particularly to an aromatic liquid having a green aroma.

Aoba aldehyde (that is, unsaturated aldehyde (2E) -hexenal) is known as a component that produces an aroma generally called a green scent (Non-Patent Documents 1 and 2). This green leaf aldehyde is contained in vegetables and fruits as a component constituting a "grass-like" or "leaf-like" aroma in the aroma of food.

Among the characteristic scents recognized in high-quality Scotch whiskey, there is a "green" scent, which is a major classification of aroma (innermost) in the flavor wheel used to specifically express the aroma of whiskey. "Green / Grassy" is described as the ring), and "Herbal, Leafy" is described as the middle classification (intermediate ring) (Non-Patent Document 3). ..

Non-Patent Document 4 describes E, Z-2,6-nonenal, as a result of analyzing malt whiskey using multidimensional gas chromatography-mass spectrometer / orfactometry (MDGC-MS-O). It is described that E-2-nonenal, 1-octen-3-ol, 4-heptene-1-ol and nonane-2-ol contribute to the green aroma.

Whiskey does not contain green leaf aldehyde. Nevertheless, there are products that feature a green scent. Green leaf aldehydes are characterized by a refreshing green scent, while the sensual "green scent" of whiskey has a fresh or dry grassy scent. The mechanism by which green scent is produced in whiskey has not been elucidated.

Patent Document 1 relates to a product having a green scent, a method for obtaining the product, and an alcoholic beverage containing the same. Patent Document 1 describes a method for obtaining a product having a green scent, which is characterized by allowing lipoxygenase to act on unsaturated fatty acids in a medium, the product, and an alcoholic beverage containing the same. In Patent Document 1, a sensory test was actually performed on whiskey and shochu by adding a solution having a green scent. As a result, when the flavor changes the taste of distilled liquor and a green scent is felt, it is said to have an advantage in that the taste is sweet and the taste is improved.

However, the method for producing a product having a green aroma in Patent Document 1 requires complicated work such as preparing an appropriate medium, preparing aspergillus as an enzyme source, pre-culturing, and performing an enzyme reaction. .. Therefore, the production efficiency of products with green aroma is very low and the cost of implementation is high.

In Patent Document 1, whiskey and shochu having a green scent are produced by adding the produced green scented distillate to commercially available shochu or shochu. That is, the product having a green aroma of Patent Document 1 is used as a fragrance. On the other hand, distilled liquors such as whiskey are often prohibited from using additives such as flavors during their production (Non-Patent Document 3). As described above, the product having the green aroma of Patent Document 1 has a narrow application target and is not practical.

As for whiskey, it has not yet been clarified how to manufacture it to enhance its green aroma.

Japanese Unexamined Patent Publication No. 2005-21055

Akikazu Hatanaka, "Scent of Plant Origin", FFI Journal, No. 168, 1996, pp. 5-22 Akikazu Hatanaka, "After the 5th Anniversary Symposium" Why Humans Are Refreshed by the Green Scent! ", FFI Journal, No. 198, 2002, pp. 45-55. Charles W. Bamforce and Robert E. Ward, "The Oxford Handbook of Food Fermentations", Oxford University Press, 2014, pp. 238-241 Akira Wanikawa et al., "Identification of green note compounds in malt whiskey using multimetric gas chromatography", Flavor Fragr. J. , 2002, No. 17, pp. 207-211 Hiroshi Kaneko et al., "Yeast Lipids", Journal of the Japan Oil Chemists' Society, Vol. 20, No. 10, 1971, pp. 687-694.

The present invention solves the above-mentioned conventional problems, and an object of the present invention is to provide a method for producing an aromatic liquid having a green aroma, which is easy to operate and has excellent practicality.

The present inventors have discovered that a linear saturated aliphatic aldehyde, particularly a linear saturated aliphatic aldehyde having 6 to 10 carbon atoms, contributes to the green aroma of whiskey, and is particularly convenient and particularly in whiskey production. We have found a highly practical method for adding green scent.

The present invention produces a linear saturated aliphatic aldehyde having 6 to 10 carbon atoms by heating a lipid containing at least one selected from the group consisting of oleic acid peroxide and palmitoleic acid peroxide in an aqueous solution. And the step of recovering the linear saturated aliphatic aldehyde;
Provided is a method for producing an aromatic liquid including.

In one embodiment, heating of the lipid is carried out in a substantially anoxic environment.

In one embodiment, heating of the lipid is performed by distilling an aqueous solution containing the lipid.

In one form, the aqueous solution that heats the lipid is mash.

In one form, the lipid is added to the mash after fermentation is complete.

In one form, the fragrance is an alcoholic beverage.

In one form, the fragrance is a distilled liquor.

The present invention also provides an aromatic liquid produced by the method for producing an aromatic liquid according to any one of the above.

The present invention also provides an aromatic liquid having a green aroma containing 1-hexanal, 1-octanal and 1-nonanal.

In one form, the green aroma of the fragrance liquid further contains 1-heptanal and 1-decanal.

Further, the present invention is a step of adding a lipid containing at least one selected from the group consisting of oleic acid peroxide and palmitoleic acid peroxide to the mash after fermentation;
A step of producing a linear saturated aliphatic aldehyde having 6 to 10 carbon atoms by distilling the fat-containing sardine; and a step of recovering the linear saturated aliphatic aldehyde;
Provided is a method for producing distilled liquor including.

Further, the present invention is a step of adding a lipid containing at least one selected from the group consisting of oleic acid peroxide and palmitoleic acid peroxide to the mash after fermentation;
A step of producing a linear saturated aliphatic aldehyde having 6 to 10 carbon atoms by distilling the fat-containing sardine; and a step of recovering the linear saturated aliphatic aldehyde;
Provided is a method for increasing the green aroma of distilled liquor including.

The method for producing an aromatic liquid having a green aroma of the present invention can be incorporated into a general manufacturing process for distilled liquor, and is easy to operate. Further, in the method of the present invention, an aromatic liquid having a green aroma can be produced as a spice or as a distilled liquor. Therefore, the present invention has a wide range of applications and is excellent in practicality.

In the method of the present invention, a predetermined lipid peroxide is thermally decomposed to produce a linear saturated aliphatic aldehyde having 6 to 10 carbon atoms. It suffices if any one of the linear saturated aliphatic aldehydes having 6 to 10 carbon atoms is produced. In a preferred embodiment, all linear saturated aliphatic aldehydes having 6, 8 and 9 carbon atoms are produced. In a more preferred form, all linear saturated aliphatic aldehydes having 6 to 10 carbon atoms are produced.

The linear saturated aliphatic aldehyde having 6 to 10 carbon atoms is preferably 1-hexanal, 1-heptanal, 1-octanal, 1-nonanal and 1-decanal, respectively. At least one aldehyde selected from the group consisting of 1-hexanal, 1-heptanal, 1-octanal, 1-nonanal and 1-decanal may be hereinafter referred to as "green aldehyde".

Yeast has many lipids in the cells. Table 1 of Non-Patent Document 5, page 689 describes the composition of yeast membrane lipid constituent fatty acids. Some of them are shown below.

Decanoic acid (C10): <1%
Lauric acid (C12): <1%
Myristic acid (C14): 3 ± 0.6%
Palmitic acid (C16: 0): 7 ± 0.5%
Palmitoleic acid (C16: 1): 53 ± 1%
Stearic acid (C18: 0): 2 ± 0.5%
Oleic acid (C18: 1): 35 ± 1%

Among these lipids, unsaturated fatty acids are easily converted to lipid peroxides upon contact with oxygen. For example, when the oleic acid solution comes into contact with oxygen, a part or all of the oleic acid contained in the oleic acid solution is changed to an oleic acid peroxide which is a lipid peroxide. The same applies to the palmitoleic acid solution.

As the unsaturated fatty acid in contact with oxygen, from the viewpoint of increasing the intensity of the green aroma produced, for example, one containing an oxidative unsaturated fatty acid in an amount of 3% by weight or more can be used. The unsaturated fatty acid in contact with oxygen may preferably contain an oxidative unsaturated fatty acid in an amount of 7-40% by weight, more preferably 10-30% by weight.

The conditions under which palmitoleic acid and oleic acid are brought into contact with oxygen are not particularly limited as long as they are at least partially oxidized. For example, these may be stored in contact with the atmosphere at room temperature. When the product is stored in a normal temperature environment, the storage period is, for example, about 5 days or more, preferably about 10 to 300 days, and more preferably about 20 to 100 days.

Lipid peroxides or lipids that can be used as a source thereof are as follows. Palmitoleic acid peroxide, oleic acid peroxide, lipid containing one or both of them, palmitoleic acid solution containing palmitoleic acid peroxide, oleic acid solution containing oleic acid peroxide, or a mixture thereof. Hereinafter, these are collectively referred to as "oleic acid peroxide, etc." Among the oleic acid peroxides and the like, preferable are oleic acid peroxide, lipid containing oleic acid peroxide, and oleic acid solution containing oleic acid peroxide.

In the method of the present invention, the oleic acid peroxide or the like is contained in an aqueous solution and heated. The amount of oleic acid peroxide or the like used is appropriately determined in consideration of the degree of green aroma to be produced. Generally, the amount of oleic acid peroxide or the like is 0.1 μl to 1 ml, preferably 1 to 500 μl, more preferably 5 to 250 μl, and further preferably 10 to 100 μl with respect to 1 liter of the aqueous solution.

An aqueous solution is a substance that contains water and exhibits fluidity. The aqueous solution blocks oleic acid peroxide and the like from oxygen and functions as a medium for transferring heat to the oleic acid peroxide and the like. The aqueous solution may be water, an aqueous solution, or an inhomogeneous mixture containing solids. The aqueous solution may contain alcohol. When the oleic acid peroxide or the like is heated in an aqueous solution, the lipid peroxide is heated in an oxygen-free environment, so that the efficiency of the decomposition reaction is improved.

The heating temperature is sufficient as long as the lipid peroxide decomposes. The heating temperature is preferably the temperature up to the boiling point of the aqueous solution. From the viewpoint of decomposition efficiency, the heating temperature is preferably 70 ° C. or higher, more preferably 80 to 110 ° C., and even more preferably 90 to 100 ° C. when heated at normal pressure. When heating under reduced pressure, it is desirable to heat at 40 to 70 ° C. Heating of the oleic acid peroxide or the like may be performed by distilling an aqueous liquid containing the oleic acid peroxide or the like.

For example, when the fragrance liquid is distilled liquor, mash can be used as the aqueous liquid. Specific examples of the distilled liquor, which is an aromatic liquid, include whiskey, shochu, brandy, and spirits such as gin, vodka, and rum. The distilled liquor, which is an aromatic liquid, is particularly preferably whiskey. Among the characteristic scents found in high-quality Scotch whiskey is the "green" scent, which makes the green scent useful for the production of highly palatable whiskey.

Moromi is an intermediate raw material for alcoholic beverages made by fermenting starch raw material, jiuqu, water, and yeast. The mash containing oleic acid peroxide or the like is preferably in a state in which fermentation has been completed. When oleic acid peroxide or the like is added to mash that has not been fermented, the amount of lipid peroxide may decrease due to the metabolic action of yeast.

Distillation of mash to which oleic acid peroxide or the like is added may be carried out under the conditions normally performed when distilling mash when producing distilled liquor. When the distilled liquor is malt whiskey, the distillation of mash, that is, the initial distillation, is usually carried out by maintaining the distillation temperature for 5 to 8 hours, although it depends on the capacity of the container. The distillation temperature of mash is generally 70 to 100 ° C.

In the distillation step, the air in the distiller is discharged to the outside of the system by the heated steam, and the distillation process becomes substantially oxygen-free.

The thermal decomposition of the lipid peroxide produces a linear saturated aliphatic aldehyde having 6 to 10 carbon atoms, and further heating in an anoxic environment enhances the production of the linear saturated aliphatic aldehyde. The produced linear saturated aliphatic aldehyde having 6 to 10 carbon atoms is volatile and may be released from the aqueous solution. In such a case, the released linear saturated aliphatic aldehyde having 6 to 10 carbon atoms is brought into contact with a medium for dissolving them, dissolved and recovered. Water, an aqueous alcohol solution, or the like is used as a medium for dissolving the linear saturated aliphatic aldehyde having 6 to 10 carbon atoms. When the aqueous liquid is distilled, the linear saturated aliphatic aldehyde having 6 to 10 carbon atoms is recovered in a state of being contained in the reflux liquid.

The solution in which the recovered linear saturated aliphatic aldehyde having 6 to 10 carbon atoms is dissolved is an aromatic liquid having a green scent. The fragrance is used as is, or adjusted to a concentration that gives a more suitable green aroma, for example as a distilled liquor or flavor. The distilled liquor of the present invention can be used alone or appropriately mixed with liquors to produce a distilled liquor having a green scent, an alcoholic beverage, or the like. The distilled liquor of the present invention has an enhanced green aroma. The fragrance of the present invention can be appropriately mixed with predetermined components such as drinking water, sweeteners, alcohols, pigments, and carbonic acids to produce soft drinks and alcoholic beverages having a green scent.

[Example 1]
It was investigated whether green aldehyde was produced when oleic acid peroxide was present during distillation. A test group was set in which the oleic acid reagent, which had been stored at room temperature for 10 months, was added immediately before the initial distillation.

The whiskey mash was fermented for 3 days by a conventional method, and the first and main mashes were carried out. As a test group, 100 μl of oleic acid reagent was added to 4 L of mash at the time of initial distillation, and the whole amount was distilled twice with a 5 L volume distiller to obtain a distillate. The concentrations of linear saturated aldehydes (1-hexanal, 1-heptanal, 1-octanal, 1-nonanal, 1-decanal) in the obtained distillate were analyzed. The results are shown in Table 3.

<1-hexanal analysis method>
(1) Sample collection 2.5 ml of ultrapure water and 0.5 ml of distillation solution were collected in a headspace vial, 75 μL of 63% EtOH water and 50 μl of internal standard solution (1-pentanal 2 ppm) were added and used for measurement.
The standard solution (STD) (1-hexanal 1.64ppm) is used after mixing with 2.5 ml of ultrapure water and 0.5 ml of 63% EtOH water. To prepare a calibration curve, add 25 μl, 50 μl, and 75 μl. I prepared it.

(2) Analytical condition device: Agilent HS7697A, GC6890N, MS5973
Headspace condition: Loop size 3ml
Temperature (oven 60 ° C, loop 80 ° C, transfer line 120 ° C)
Vial equilibration time 10 min
Loop equilibration time 0.01 min
Injection time 1min
Injection conditions: pulsed split (20: 1), 250 kPa, gas saver 30 ml / min (2 min)
Injection temperature: 150 ℃
Column: VF-WAXms (Varian) 1 μm × 0.25 mm I.D. × 30 m
Column flow rate: 1.2 ml / min (He, constant flow mode)
Heating conditions: 40 ° C (10 min) → 10 ° C / min → 240 ° C (1 min)
MS conditions: Temperature (transfer line 230 ° C, ion source 230 ° C, quadrupole 150 ° C)

[Table 1]

<1-heptanal, 1-octanal, 1-nonanal, 1-decanal analysis method>
(1) Pretreatment 5 ml of distillate was collected in a 50 ml centrifuge tube, 20 μl of IS (Octanal-d16 100 ppm) was added, and 20 ml of ultrapure water was added for dilution.
The standard solution (STD) (50 ppm for each component) is used after mixing with 20 ml of ultrapure water, 5 ml of 63% EtOH water, and 20 μl of IS, but 3 types of 10 μl, 20 μl, and 30 μl are added to prepare a calibration curve. ..
These test solutions were loaded on a solid-phase column (Oasis HLB 3cc, 60 mg manufactured by Waters) conditioned with ethyl acetate, methanol, and ultrapure water, and passed through at about 1 drop / sec. After passing the test solution, it was washed with 10 ml of ultrapure water and sucked and dried for about 5 minutes. After drying, remove the solid phase, wash the flow path with acetone, dry it, set a dehydration cartridge (GL Science Inertsep Slim-J DRY), attach the adsorbed solid phase on it, and quantify with 6 ml of ethyl acetate. It was eluted in a test tube. The eluate was concentrated to 0.5 ml or less by nitrogen purging, and the volume was adjusted to 1 ml with ethyl acetate and subjected to GC / MS.

(2) Analytical condition device: Agilent GC6890N, MS5973
Injection conditions: pulsed split (20: 1), 250kPa, gas saver 20ml / min (2min)
Temperature 210 ° C, injection volume 1 μl
Column: Inert Pure WAX (GL Science) 0.25 μm × 0.25 mm I.D. × 30 m
Column flow rate: 1.2 ml / min (He, constant flow mode)
Heating conditions: 40 ° C (3min) → 8 ° C / min → 120 ° C (2min) → 12 ° C / min → 230 ° C (10min)
MS conditions: Temperature (transfer line 230 ° C, ion source 230 ° C, quadrupole 150 ° C)

[Table 2]

tr：痕跡量が検出された。 [Table 3]
Green aldehyde analysis result of model whiskey

tr: Trace amount was detected.

The results in Table 3 show that the presence of oleic acid peroxide during distillation produces green aldehyde.

(Sensory evaluation of whiskey)
The whiskey produced was sensorimetrically evaluated by seven panelists specializing in distilled liquor. The score was the average of 5 of the 7 panels, excluding the upper and lower ones.

[Table 4]
Overall evaluation criteria

[Table 5]
Green aroma evaluation criteria

[Table 6]
Sensory evaluation result

[Example 2]
It was investigated whether green aldehyde was produced when palmitoleic acid peroxide was present during distillation. The palmitoleic acid reagent stored in a refrigerator was heated at 37 ° C. for 7 days, and a test group was set in which the palmitoleic acid reagent was added immediately before the initial distillation.

A distillate was obtained in the same manner as in Example 1 except that the above-heated palmitoleic acid reagent was used instead of the oleic acid reagent stored at room temperature, and the concentration of linear saturated aldehyde in the obtained distillate was analyzed. , Sensory evaluation was performed. The results are shown in Tables 7 and 8.

tr：痕跡量が検出された。 [Table 7]
Green aldehyde analysis result of model whiskey

tr: Trace amount was detected.

The results in Table 7 show that the presence of palmitoleic acid peroxide during distillation produces green aldehyde.

[Table 8]
Sensory evaluation result

[Reference example]
The oleic acid reagent and palmitoleic acid reagent immediately after opening were heated under the following conditions and forcibly oxidized, and how the purity of each fatty acid changed by heating was measured.

[Table 9]

(Method of measuring fatty acid purity)
<Pretreatment>
The sample was dissolved in ethanol to prepare a standard stock solution, from which a small amount was taken and diluted with ethyl acetate / methanol (9: 1). Trimethylsilyldiazomethane was added to the obtained diluted solution, and the mixture was allowed to stand at room temperature to methyl esterify the fatty acid.

<GCMS analysis conditions>
Column: Inertpure WAX (manufactured by GL Science) 30m x 0.25mm I.D., 0.25μm
(WAX column)
Injection port temperature: 230 ° C
Injection method: pulsed split (20: 1)
Column flow rate: 1.2 ml / min
Oven temperature: 130 ℃ (2min) → 5 ℃ / min → 220 ℃ (0min) → 12 ℃ / min → 230 ℃ (12min)
Transfer line temperature: 230 ℃
MS condition: SIM

[Table 10]

In the GCMS chromatograph, assuming that the peak area corresponding to the fatty acid before heating is 100, the percentage of the peak area corresponding to the fatty acid after heating is the ratio of the fatty acid not oxidized by heating, that is, after heating. It is considered to be the purity of fatty acids. The results are shown in Tables 11 and 12.

[Table 11]
Purity of oleic acid after heating

[Table 12]
Purity of palmitoleic acid after heating

The palmitoleic acid peroxide used in Example 2 is palmitoleic acid heated under the condition corresponding to the heating condition 1. It was confirmed that such palmitoleic acid had a purity of 97%. From this, it was shown that the presence of a fatty acid peroxide having a fatty acid purity of 97% or less during distillation produces a green aroma.

Claims (13)

A step of producing a linear saturated aliphatic aldehyde having 6 to 10 carbon atoms by heating a lipid containing at least one selected from the group consisting of oleic acid peroxide and palmitoleic acid peroxide in an aqueous solution; Step of recovering the linear saturated aliphatic aldehyde;
A method for producing an aromatic liquid including. The method for producing an aromatic liquid according to claim 1, wherein the heating of the lipid is performed in a substantially oxygen-free environment. The method for producing an aromatic liquid according to claim 1 or 2, wherein the heating of the lipid is performed by distilling an aqueous liquid containing the lipid. The method for producing an aromatic liquid according to any one of claims 1 to 3, wherein the aqueous liquid for heating the lipid is mash. The method for producing an aromatic liquid according to claim 4, wherein the lipid is added to the mash after fermentation. The method for producing an aromatic liquid according to any one of claims 1 to 5, wherein the lipid comprises at least one selected from the group consisting of an oleic acid peroxide and a palmitoleic acid peroxide. The method for producing an aromatic liquid according to any one of claims 1 to 6, wherein the aromatic liquid is an alcoholic beverage. The method for producing an aromatic liquid according to any one of claims 1 to 7, wherein the aromatic liquid is distilled liquor. An aromatic liquid produced by the method for producing an aromatic liquid according to any one of claims 1 to 8. An aromatic liquid having a green aroma containing 1-hexanal, 1-octanal and 1-nonanal. The aromatic liquid having a green aroma according to claim 10, further containing 1-heptanal and 1-decanal. A step of incorporating a lipid containing at least one selected from the group consisting of oleic acid peroxide and palmitoleic acid peroxide into the mash after fermentation;
A step of producing a linear saturated aliphatic aldehyde having 6 to 10 carbon atoms by distilling the fat-containing sardine; and a step of recovering the linear saturated aliphatic aldehyde;
A method for producing distilled liquor including. A step of incorporating a lipid containing at least one selected from the group consisting of oleic acid peroxide and palmitoleic acid peroxide into the mash after fermentation;
A step of producing a linear saturated aliphatic aldehyde having 6 to 10 carbon atoms by distilling the fat-containing sardine; and a step of recovering the linear saturated aliphatic aldehyde;
A method of increasing the green aroma of distilled liquor, including.