The content of the invention
To solve the problem of prior art is present, the present invention provides a kind of method that liquor seasoning product are obtained from yellow water.
The present invention is achieved in that a kind of yellow water concentrate, and the preparation method of the yellow water concentrate includes following step
Suddenly:
Step one, 100 parts of liquor tailings of ethanol content 42% are put into destilling tower, distill out 44.7 parts of high ethano contents
Edible alcohol;
Step 2, takes 97 parts of yellow waters, 3 parts of concentration liquor tailings according to volume parts, is put into destilling tower and distills after mixing, rise
Temperature, which is steamed, stops distillation after 9.5 parts of cuts;Then aeration head is put into cut, be passed through it is ozonation aerated, when observing cut
In yellow disappear after stop aeration, cut after decolouring is yellow water concentrate;
Step 3, the yellow water concentrate of acquisition need to be put into closed container, be placed in shady place preservation.
Another object of the present invention is to provide a kind of white wine of liquid modulated by the yellow water concentrate.
Another object of the present invention is to provide a kind of white spirit by solid state method modulated by the yellow water concentrate.
Another object of the present invention is to provide a kind of liquor seasoning product prepared by the yellow water concentrate, the white wine
The preparation method of flavouring comprises the following steps:
100 portions of yellow water concentrates are added azeotropy rectification column according to volume parts, steam 4 kinds of low boiler cuts by the first step
After (acetaldehyde, binary azeotropic natural methanoic acid ethyl ester, binary azeotropic natural acetic acid ethyl ester and methanol), by azeotropy rectification column tower reactor
Liquid is released, and is transported to the reaction and rectification device with magnetic agitation of next procedure;
124.61g food-grades are added in second step, every liter of binary azeotropic natural methanoic acid ethyl ester that azeotropic distillation is obtained
CaCl2, the CH in binary azeotrope3OH and CaCl2Form crystalloid material:CaCl2·4CH3OH, then removes crystallization through distillation
Thing CaCl2·4CH3After OH, pure natural methanoic acid ethyl ester is obtained after collecting cut;
325.80g food-grades are added in 3rd step, every liter of binary azeotropic natural acetic acid ethyl ester that azeotropic distillation is obtained
CaCl2, the CH in binary azeotrope3OH and CaCl2Form crystalloid material:CaCl2·4CH3OH, then removes crystallization through distillation
Thing CaCl2·4CH3After OH, pure natural acetic acid ethyl ester is obtained after collecting cut;
4th step, according to volume parts, is disposably input to band magnetic force by 98.4324 parts of tower reactor kettle liquid after azeotropic distillation
In the tower reactor of the reaction and rectification device of stirring, 100 portions of yellow water concentrates are also surplus 98.4324 parts in tower reactor after azeotropic distillation, then
Take 6 parts of superpower solid acids to add in tower reactor, carry out esterification, obtain synthesis of natural ethyl acetate binary mixture and be transported to conjunction
Into the reception device of natural ethyl acetate binary mixture.Further reaction, obtains the mixed solution of 5 kinds of esters, i.e. esterifying liquid.
In 5th step, 6 kinds of materials derived above in addition to methanol, liquor seasoning product are referred to as.
Further, the first step includes:When azeotropic distillation starts, heater switch is opened, treats that bottom temperature reaches 40 DEG C
When, open tower body insulation circuit;When tower top temperature reaches 20.8 DEG C, overhead vapours is flowed out after overhead condenser is condensed
Cut flow to the receiving tank of acetaldehyde, when cut starts to reduce, when tower top temperature is stepped up, illustrate that crude aldehyde has steamed;This
When, by the valve transfer of cut effuser to methanol and the position of Ethyl formate receiving tank, then when adjusting bottom temperature to 65 DEG C,
It is again turned on tower body insulation circuit;When tower top temperature reaches 51 DEG C, overhead vapours is flowed out after overhead condenser is condensed
Cut flow to the receiving tank of methanol and Ethyl formate, when cut starts to reduce, when tower top temperature is stepped up, illustrate natural first
Acetoacetic ester has steamed;Now, then by behind the position of the valve transfer of cut effuser to methanol and ethyl acetate receiving tank, then by tower
When kettle temperature degree is adjusted to 70 DEG C, tower body insulation circuit is again turned on, when tower top temperature is increased to 62.3 DEG C, overhead vapours warp
The receiving tank that the cut flowed out after overhead condenser condensation flows to methanol and ethyl acetate is crossed, when cut starts reduction, tower top
When temperature is stepped up, illustrate that natural acetic acid ethyl ester has steamed;Then by the valve transfer of cut effuser to methanol receiving tank
Position, when tower top temperature is increased to 64.7 DEG C, the cut that overhead vapours is flowed out after overhead condenser is condensed flows to first
Alcohol receiving tank, when flowing out without cut goes out at this temperature, illustrates that methanol has steamed, and stops azeotropic distillation.
Further, in the 4th step esterification equation:
Further, 244.8827g food is added in the polynary azeotropic mixture of every liter of synthesis of natural ethyl acetate
Level CaO, obtains synthesis of natural ethyl acetate binary mixture.
Another object of the present invention is to provide white wine tune prepared by a kind of preparation method using the liquor seasoning product
The white wine of liquid of taste product modulation.
Another object of the present invention is to provide white wine tune prepared by a kind of preparation method using the liquor seasoning product
The white spirit by solid state method of taste product modulation.
The method that liquor seasoning product are obtained from yellow water that the present invention is provided, is analyzed through chromatography of gases:Influenceed in yellow water white
38 kinds of organic chemical compositions of wine taste, have been detected 21 kinds (except ethanol and methanol), wherein steaming in yellow water concentrate
Extracting rate has 19 kinds more than 50%, and steam rate has 15 kinds more than 80%.Wherein, exchange sobriety body local flavor and play important work
Acetaldehyde, acetal, the organic acid of ethyl hexanoate and synthesizing ester:Acetic acid, propionic acid, butyric acid, valeric acid, caproic acid steam rate more
More than 90% is up to, some acid is even as high as 100%.More the good news is the concentration of ethyl hexanoate and ethyl acetate is respectively reached
:1966.2mg/L and 3251.8mg/L, its content has reached the level of top grade aromatic Chinese spirit.In addition, three big acid are for oneself
The concentration of acid, acetic acid and butyric acid is even more to respectively reach:84904.3mg/L (percentage by weight is about:10.05%),
67039.3mg/L (percentage by weight is about:7.94%) and 29056.6mg/L (percentage by weight is about:3.44%), all reach
The easy quick concentration for occurring catalytic esterification.Due in this yellow water concentrate not only the content of two big esters reached it is excellent
The requirement of level aromatic Chinese spirit, the content of particularly three big acid is even more the 119-175 of three big acid contents in common aromatic Chinese spirit
Again (representative of common aromatic Chinese spirit is used as using the base liquor in table 1).In addition, ethanol in the yellow water concentrate, water and various having
Machine thing (except ethanol) total content is respectively:549.1g/L (69.5 degree), 45.7g/L and 249.7g/L.In liquor seasoning product
In whole producing process, though esterification be also the acid produced by pure natural fermentation and the ester that ethanol is waste (this with
The method that the caproic acids produced using chemical method most now produce ethyl hexanoate for raw material and ethanol esterification is different), Qi Tabu
Rapid is entirely physical method, thus with liquor seasoning product produced by the present invention be safe and producing process in will not bring into and appoint
The natural product of what chemicals (is traditionally that the ester that raw material esterification is produced is referred to as closing with acid and ethanol made from fermentation method
Into natural esters), so the liquor seasoning product that are obtained by raw material of yellow water of the present invention are including synthesis of natural esters and other naturally have
Machine thing, closer to natural product during for concocted white spirit, it is easier to be esthetically acceptable to the consumers.100 portions of yellow water concentrates are by altogether
Boiling distillation, reactive distillation have obtained following rare natural materials:Crude aldehyde:0.2885 part;Natural methanoic acid ethyl ester:0.1196
Part;Natural acetic acid ethyl ester:0.3605 part;Natural methanol:0.4496 part;Binary azeotropic synthesis of natural ethyl acetate (ethanol and second
Acetoacetic ester):15.8870 parts, wherein the number containing pure synthesis of natural ethyl acetate is:10.5126 parts;Esterifying liquid:74.6997
Part.Wherein contain pure 15.7595 parts of synthesis of natural ethyl hexanoate, containing total 27.2514 parts of ester (the volume number of ester simply adds up).
5 kinds of natural liquor seasoning product can be made by raw material of yellow water concentrate by the present invention:Acetaldehyde, Ethyl formate, acetic acid
Ethyl ester, binary azeotropic ethyl acetate and esterifying liquid.Sobriety body local flavor plays an important role third is exchanged in the esterifying liquid of the present invention
Acetoacetic ester, ethyl butyrate, ethyl valerate, the content of ethyl lactate and ethyl hexanoate are up to respectively:19036.2mg/L、
46511.1mg/L, 1461.2mg/L, 39769.6mg/L and 137107.3mg/L;Ethyl hexanoate content is that common Luzhou-flavor is white
113 times of wine content.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The application principle of the present invention is explained in detail below in conjunction with the accompanying drawings.
As shown in figure 1, the method provided in an embodiment of the present invention that liquor seasoning product are obtained from yellow water comprises the following steps:
S101:100 parts of liquor tailings of ethanol content 42% are put into destilling tower, the food of 44.7 parts of high ethano contents is distilled out
Use alcohol;
S102:97 parts of yellow waters, 3 parts of concentration liquor tailings are taken according to volume parts, is put into destilling tower and distills after being mixed, rise
High-temperature, which is steamed, stops distillation after 9.5 parts of cuts;Then aeration head is put into cut, is passed through ozonation aerated, evaporated when observing
Yellow in point stops aeration, the cut hereinafter referred to as yellow water concentrate after decolouring after disappearing;The yellow water concentrate of acquisition need to be put
Enter in closed container, be placed in shady place preservation;
S103:100 portions of (volume parts) yellow water concentrates are added into azeotropy rectification column, steamed after the lower boiling cut in part
(acetaldehyde, binary azeotropic natural methanoic acid ethyl ester, binary azeotropic natural acetic acid ethyl ester and methanol), then will be remained in azeotropy rectification column tower reactor
Remaining liquid is released, and is transported to the reaction and rectification device with magnetic agitation of next procedure;
S104:Appropriate food-grade CaCl is added in obtained binary azeotropic natural methanoic acid ethyl ester2, in binary azeotrope
CH3OH and CaCl2Form crystalloid material:CaCl2·4CH3OH, then removes crystal CaCl through distillation2·4CH3After OH,
Pure natural methanoic acid ethyl ester can be obtained after collecting cut;
S105:Appropriate food-grade CaCl is added in obtained binary azeotropic natural acetic acid ethyl ester2, in binary azeotrope
CH3OH and CaCl2Form crystalloid material:CaCl2·4CH3OH, then removes crystallization CaCl through distillation2·4CH3After OH, collect
Pure natural acetic acid ethyl ester can be obtained after cut;
S106:98.4324 parts of tower reactor kettle liquid after azeotropic distillation is disposably input to the reactive distillation with magnetic agitation
In the tower reactor of device (100 portions of yellow water concentrates also remain 98.4324 parts after azeotropic distillation in tower reactor), then take 6 parts of superpower solids
Acid is added in tower reactor, is carried out esterification, is obtained the mixed solution of synthesis of natural ethyl acetate binary mixture and 5 kinds of esters, i.e.,
Esterifying liquid.
The application principle of the present invention is further described with reference to specific embodiment.
1 production method and technique
The distillation and concentration of 1.1 liquor tailings
100 parts of liquor tailings of ethanol content 42% are put into destilling tower, the edible wine of 44.7 parts of high ethano contents is distilled out
The organic matter of many influence liquor flavors is distilled together with second alcohol and water formation binary or polynary azeotropic mixture in essence, wherein liquor tailing
Out, the azeotropic mixture referred to as concentrates liquor tailing below.The alcoholic strength and various organic chemical compositions concentrated in liquor tailing is as shown in table 2
(data of the various chemical compositions in this table are being averaged for the gas chromatographic analysis result of three distillation gained cuts of liquor tailing of the same race
Value).
As can be seen from Table 2:100 parts of (volume parts) liquor tailings of ethanol content 42% are put into destilling tower, are distilled out
The polynary azeotropic mixture (cut) of 44.7 parts of high ethano contents is concentration liquor tailing, through gas chromatographic analysis:White wine wind is influenceed in liquor tailing
42 kinds of organic chemical compositions of taste, have been detected 21 kinds (except ethanol and methanol), wherein steam rate exists in concentration liquor tailing
More than 50% has 19 kinds, and steam rate has 15 kinds more than 80%, particularly exchange what sobriety body local flavor played an important role
Acetaldehyde, acetal, the organic acid of ethyl hexanoate and synthesizing ester:Acetic acid, propionic acid, butyric acid, valeric acid, the steam rate of caproic acid are even more high
Up to more than 90%, the sour steam rate having is even as high as 100%.
The distillation and concentration of the important chemical composition of liquor flavor is influenceed in 1.2 yellow waters
97 parts of yellow waters, 3 parts of concentration liquor tailings (volume parts) are taken, distillation in destilling tower is put into after being mixed and (why
It is in order to improve the ethanol content of yellow water, to there is the organic matter formation binary in enough ethanol and yellow water to add concentration liquor tailing
Or polynary azeotropic mixture is steamed together), rise temperature steams to stop distilling after 9.5 parts of cuts and (only controls to steam the amount of cut
Control vapo(u)rizing temperature).Then aeration head is put into cut, be passed through it is ozonation aerated, when observe the yellow in cut disappear after
Stop aeration, the cut hereinafter referred to as yellow water concentrate after decolouring.The various organic chemical compositions contained in yellow water concentrate are such as
Shown in table 3 (after the data of the various chemical compositions in this table are yellow water and the mixing of liquor tailing ratio of the same race, the gas of three distillation fractions
The average value of analysis of hplc result).
As can be seen from Table 3:After 97 parts of yellow waters and 3 parts of concentration liquor tailing mixing, it is put into destilling tower and distills out 9.5 parts of second
The polynary azeotropic mixture (cut) of alcohol content 69.5% (volume parts), is analyzed through chromatography of gases:Liquor flavor is influenceed in yellow water
38 kinds of organic chemical compositions, have been detected 21 kinds (except ethanol and methanol), wherein steam rate exists in yellow water concentrate
More than 50% has 19 kinds, and steam rate has 15 kinds more than 80%.Wherein, the second that sobriety body local flavor plays an important role is exchanged
Aldehyde, acetal, the organic acid of ethyl hexanoate and synthesizing ester:Acetic acid, propionic acid, butyric acid, valeric acid, the steam rate of caproic acid are more up to
More than 90%, some acid is even as high as 100%.More the good news is the concentration of ethyl hexanoate and ethyl acetate is respectively reached:
1966.2mg/L and 3251.8mg/L, its content has reached the level of top grade aromatic Chinese spirit.In addition, three big acid are caproic acid, second
The concentration of acid and butyric acid is even more to respectively reach:84904.3mg/L (percentage by weight is about:10.05%), 67039.3mg/L
(percentage by weight is about:7.94%) and 29056.6mg/L (percentage by weight is about:3.44%), all reached easily quick
Occurs the concentration of catalytic esterification.Because not only the content of three big esters has reached that top grade Luzhou-flavor is white in this yellow water concentrate
The content of the big acid of the requirement of wine, particularly three is even more 119-175 times of three big acid contents in common aromatic Chinese spirit (with table 1
Base liquor as common aromatic Chinese spirit representative).In addition, in the yellow water concentrate ethanol, water and various organic matters (ethanol is removed
Total content is respectively outside):549.1g/L (69.5 degree), 45.7g/L and 249.7g/L.Second in next every liter of yellow water concentrate
The mol ratio of alcohol and the molal quantity and ethanol and acid of main several linear saturated fatty acids is as shown in table 4 below:
In addition, the yellow water concentrate obtained with above method need to be put into closed container, being placed in shady place preservation (prevents
The lower boiling organic matter such as acetaldehyde evaporates at normal temperatures), in case underneath with.
1.3 the purposes of yellow water concentrate
The yellow water concentrate obtained through above method can have three below in terms of purposes:
1.3.1 white wine of liquid is blent
Can be directly as liquor seasoning product, you can by the yellow water concentrate for blending to white wine of liquid 1% or so
Method, not only makes in white wine of liquid the concentration of three big acid reach the concentration of common solid-state method aromatic Chinese spirit, and to liquid
The organic chemical composition of the influence liquor flavor contained in 21 kinds of white spirit by solid state method is with the addition of in state method white wine, and then makes liquid phase process
The local flavor of white wine also tends to white spirit by solid state method, while can also increase the degree of recognition of white wine of liquid, expands its consumer group.
1.3.2 the quality of white spirit by solid state method is improved
Blent into white spirit by solid state method 1% or so yellow water concentrate, can not only improve in white wine three big acid (caproic acid,
Acetic acid and butyric acid) concentration provide material base for follow-up liquor aging (contents of three big acid increase by more than 1 times).Meanwhile,
The concentration of the organic chemical composition of 21 kinds of influence liquor flavors can also be further improved, and then reaches raising white wine quality, shadow
Ring the purpose of liquor flavor.
1.3.3 produce or concentrate the esters and other materials needed for liquor seasoning product
Yellow water concentrate is alternatively arranged as producing the raw material of the esters such as ethyl hexanoate, ethyl acetate and ethyl butyrate, also simultaneously
Other liquor seasoning materials can be distilled out.
1.4 extract by raw material of yellow water concentrate, produce liquor seasoning product
1.4.1 the extraction of acetaldehyde, methanol and natural methanoic acid ethyl ester and ethyl acetate
100 portions of (volume parts) yellow water concentrates are added into azeotropy rectification column, when rectifying starts, heater switch are opened,
It is careful not to make electric current excessive, in order to avoid equipment is acutely heated and damaged suddenly, when bottom temperature reaches 40 DEG C, opens tower body
Thermal circuit (insulation electric current can not be excessive).When tower top temperature reaches 20.8 DEG C or so, (boiling point of acetaldehyde is:20.8 DEG C),
The cut that overhead vapours is flowed out after overhead condenser is condensed flows to the receiving tank of acetaldehyde, when cut starts reduction, tower top
When temperature is stepped up, illustrate that crude aldehyde has steamed substantially;Now, by the valve transfer of cut effuser to methanol and formic acid
The position of ethyl ester receiving tank, then when adjusting bottom temperature to 65 DEG C or so, it is again turned on tower body insulation circuit.When tower top temperature reaches
To (the boiling point of methanol at 51 DEG C:64.7℃;The azeotropic point of methanol and Ethyl formate:51 DEG C, azeotropic composition:16%, 84%;First
The azeotropic point of alcohol and ethyl acetate:62.3 DEG C, azeotropic composition:44%, 56%;The azeotropic point of ethanol and Ethyl formate:54.23
DEG C, azeotropic composition:2.66%, 97.34%), the cut that overhead vapours is flowed out after overhead condenser is condensed mainly first
The azeotropic mixture of alcohol and natural methanoic acid ethyl ester, when cut starts to reduce, when tower top temperature is stepped up, has illustrated natural methanoic acid ethyl ester
Substantially steamed;Now, then by the position of the valve transfer of cut effuser to methanol and ethyl acetate receiving tank, then by tower reactor temperature
When degree is adjusted to 70 DEG C or so, tower body insulation circuit is again turned on, when tower top temperature is increased to 62.3 DEG C or so, overhead vapours
The cut flowed out by overhead condenser is mainly the azeotropic mixture of methanol and natural acetic acid ethyl ester, subtracts when cut is started again at
It is few, when tower top temperature is stepped up, illustrate that natural acetic acid ethyl ester has steamed substantially;Then the valve transfer of cut effuser is arrived
The position of methanol the receiving tank, (boiling point of methanol when tower top temperature is increased to 64.7 DEG C:64.7 DEG C), now overhead vapours passes through
The cut mainly methanol that flows out after overhead condenser condensation, when cut starts again at reduction, when tower top temperature is stepped up,
Illustrate that methanol has steamed substantially.Now stop distillation, the liquid in azeotropy rectification column tower reactor is released, and be transported to next procedure
The reaction and rectification device with magnetic agitation.
Above overhead is as follows through gas chromatographic detection and volume metering result respectively:
1) when tower top temperature is increased to 20.8 DEG C or so, the overhead that acetaldehyde receiving tank is obtained is:Acetaldehyde.Its is total
Volume parts be about:0.2885 part (total number before yellow water concentrate azeotropic distillation is 100 parts), through adjusting yellow water concentrate
In the 2259.8mg/L acetaldehyde that contains all steamed substantially, i.e., can be dense from 100 parts of yellow waters by azeotropic distillation above
Rectifying goes out 0.2885 part of high-purity natural acetaldehyde in contracting liquid;
2) when tower top temperature is increased to 51 DEG C or so, the tower top azeotropic mixture that methanol and Ethyl formate receiving tank are obtained is:
The binary azeotrope of methanol and Ethyl formate.The volume parts of the azeotropic mixture of methanol and Ethyl formate are:0.1460 part (yellow water is dense
Total number before contracting liquid azeotropic distillation is 100 parts), wherein methanol, the mass content of Ethyl formate are respectively:15.99% He
84.01%, the proportionate relationship of the methanol and Ethyl formate with《Some conventional industrial solvent azeotropic mixture data》Described in one book
Azeotropic mixture proportion of composing is very close.Pass through azeotropic distillation above, rectifying can go out from 100 portions of yellow water concentrates
The Ethyl formate binary azeotrope of 0.1460 part of Ethyl formate content 84.01%, the two-component fractionation azeotropic mixture hereinafter referred to as binary
Azeotropic natural methanoic acid ethyl ester.Ethyl formate through adjusting the 1099.2mg/L contained in yellow water concentrate is all steamed change substantially
Into Ethyl formate and the binary azeotrope of methanol;
3) when tower top temperature is increased to 62.3 DEG C or so, the tower top azeotropic mixture that methanol and ethyl acetate receiving tank are obtained
For:The binary azeotrope of methanol and ethyl acetate.The volume parts of the azeotropic mixture of methanol and ethyl acetate are:0.6834 part (yellow
Total number before concentrated liquid azeotropic distillation is 100 parts), wherein methanol, the mass content of ethyl acetate are respectively:44.02%
With 55.98%, the proportionate relationship of the methanol and ethyl acetate with《Some conventional industrial solvent azeotropic mixture data》Described in one book
Azeotropic mixture proportion of composing be sufficiently close to.Pass through azeotropic distillation above, rectifying can go out from 100 portions of yellow water concentrates
The natural acetic acid ethyl ester of 0.6834 part of ethyl acetate content 55.98%, the natural second of the binary azeotrope hereinafter referred to as binary azeotropic
Acetoacetic ester.Become acetic acid second through adjusting the 3251.8mg/L contained in yellow water concentrate ethyl acetate and all being steamed substantially
The binary azeotrope of ester and methanol.
4) when tower top temperature is increased to 64.7 DEG C or so, the overhead that methanol receiving tank is obtained is:Methanol.Its body
Accumulating number is about:0.4496 part (including the methanol that Ethyl formate, ethyl acetate azeotropic are steamed amounts to 0.7990 part, yellow water concentration
Total number before liquid azeotropic distillation is 100 parts), the methanol through adjusting the 6326.1mg/L contained in yellow water concentrate is substantially complete
Portion steams (including Ethyl formate, ethyl acetate azeotropic steam methanol), i.e., can be from 100 parts by azeotropic distillation above
Rectifying goes out 0.4496 part of high purity methanol in yellow water concentrate.
In summary, 100 portions of yellow water concentrates pass through above-mentioned azeotropic distillation, and rectifying has gone out following material:0.2885 part
High-purity acetaldehyde, the binary azeotropic natural methanoic acid ethyl ester of 0.1460 part of Ethyl formate content 84.01%, 0.6834 part of acetic acid second
The binary azeotropic natural acetic acid ethyl ester of ester content 55.98% and 0.4496 part of high purity methanol, are amounted to from 100 portions of yellow water concentrates
In steamed 1.5675 parts of cuts.
Note:Equivalent to 100 portions yellow water concentrates have been concentrated to 98.4324 parts, and the composition contained inside it is all concentrated.
1.4.2 the purifying of Ethyl formate and ethyl acetate
1) in Ethyl formate methanol removal
Appropriate food-grade CaCl is added in the binary azeotropic natural methanoic acid ethyl ester obtained in 1.4.12, in binary azeotrope
CH3OH and CaCl2Form crystalloid material:CaCl2·4CH3OH, then removes crystal CaCl through distillation2·4CH3OH
Afterwards, pure natural methanoic acid ethyl ester, specific CaCl are obtained after collecting cut2Addition can be calculated according to following method:
Because the mass content of methanol, Ethyl formate is respectively:15.99% and 84.01%, the ratio of methanol and Ethyl formate
It is respectively 0.7918kg/L and 0.919kg/L (average) again, then the proportion of binary azeotropic natural methanoic acid ethyl ester is:
0.7918 × 15.99%+0.919 × 84.01%=0.8987kg/L;
The amount containing methanol is in so every liter binary azeotropic natural methanoic acid ethyl ester:
0.8987kg/L × 15.99%=0.1437kg/L=143.7g/L;
If needing to add CaCl in every liter of binary azeotropic natural methanoic acid ethyl ester2Amount be x, then:
The ÷ 128=124.61g/L of x=143.7 × 111;
That is need to add CaCl in every liter of binary azeotropic natural methanoic acid ethyl ester2Amount be:124.61g (to ensure
Whole remove of methanol can make CaCl2Amount it is suitably excessive).Secondly, 0.1460 part of binary azeotropic natural methanoic acid ethyl ester is gone
Except can obtain pure natural 0.1196 part of Ethyl formate after methanol, i.e., 100 portions yellow water concentrates are through rectifying, except can be obtained after methanol
0.1196 part of high-purity natural Ethyl formate.This high-purity natural Ethyl formate need to load closed container, and be stored in shady and cool, dry
In dry, draughty storehouse in case underneath with.
2) in ethyl acetate methanol removal
Appropriate food-grade CaCl is added in the binary azeotropic natural acetic acid ethyl ester obtained in 1.4.12, in binary azeotrope
CH3OH and CaCl2Form crystalloid material:CaCl2·4CH3OH, then removes crystal CaCl through distillation2·4CH3OH
Afterwards, pure natural acetic acid ethyl ester, specific CaCl are obtained after collecting cut2Addition can be calculated according to following method:
Because the mass content of methanol, ethyl acetate is respectively:44.02% and 55.98%, the ratio of methanol and ethyl acetate
It is respectively 0.7918kg/L and 0.902kg/L again, then the proportion of binary azeotropic natural acetic acid ethyl ester is:
0.7918 × 44.02%+0.902 × 55.98%=0.8535kg/L;
The amount containing methanol is in so every liter binary azeotropic natural acetic acid ethyl ester:
0.8535kg/L × 44.02%=0.3757kg/L=375.7g/L;
If needing to add CaCl in every liter of binary azeotropic natural methanoic acid ethyl ester2Amount be y, then:
The ÷ 128=325.80g/L of y=375.7 × 111;
That is need to add CaCl in every liter of binary azeotropic natural acetic acid ethyl ester2Amount be:325.80g (to ensure
Whole remove of methanol can make CaCl2Amount it is suitably excessive).Secondly, 0.6834 part of binary azeotropic natural acetic acid ethyl ester is gone
Except can obtain pure natural 0.3605 part of ethyl acetate after methanol, i.e., 100 portions yellow water concentrates through azeotropic distillation, can be with except after methanol
Obtain 0.3605 part of high-purity natural ethyl acetate.This high-purity natural ethyl acetate need to load closed container, and be stored in the moon
In cool, dry, draughty storehouse in case underneath with.
1.4.3 the Ester such as ethyl acetate, ethyl propionate, ethyl butyrate and ethyl hexanoate is produced
As shown in Table 4:The mol ratio of ethanol and acetic acid, propionic acid, butyric acid, valeric acid, caproic acid is respectively in yellow water concentrate:
10.6762:1、68.3815:1、36.1398:1、304.0536:1 and 16.3072:1, the mol ratio of ethanol and total acid is about 5:1
(ratio of the tower reactor kettle liquid after azeotropic distillation is basically unchanged).That is the esterification inside the tower reactor kettle liquid after azeotropic distillation
Reaction is the excessive esterification of ethanol.
98.4324 parts of tower reactor kettle liquid after 1.4.1 azeotropic distillations is disposably input to the reactive distillation with magnetic agitation
In the tower reactor of device (100 portions of yellow water concentrates also remain 98.4324 parts after 1.4.1 azeotropic distillation in tower reactor), then take 6 parts
Superpower solid acid is added in tower reactor, is then opened magnetic stirring apparatus and heater switch, is careful not to make electric current excessive, in order to avoid equipment
Acutely it is heated and damages suddenly, when bottom temperature being increased into 80 DEG C under infinite reflux state, opens (the insulation of tower body insulation circuit
Electric current can not be excessive), and continue to be kept for infinite reflux certain time, so that esterification is fully carried out.Magnetic agitation is noted simultaneously
The rotating speed of device makes solid acid be suspended in yellow water concentrate just.Within this time, higher concentration in reactor
With ethanol following esterification occurs for several linear saturated fatty acids:
When reacting progress more than, every the content of acetic acid in the tower reactor kettle liquid of monitoring in 2 hours, and monitoring time is recorded
Several and total reaction time (when under the same conditions from now on, repeating the reaction, can be used as esterification using the reaction time
(4) time of balance is reached).When front and rear 2 adjacent testing results are almost unchanged, illustrate that acetic acid content tends to be steady in tower reactor
Fixed, esterification (4) has basically reached reaction poised state, and infinite reflux now is changed into reflux ratio is 2 reflux state, and controls
Tower top temperature≤70.4 DEG C (wherein, the azeotropic point of ethanol, water and ethyl acetate processed:70.23 DEG C, azeotropic, which is constituted, is:8.4%th,
9.0%th, 82.6%;The azeotropic point of water and ethyl acetate:70.4 DEG C, azeotropic, which is constituted, is:6.1%th, 93.9%), thus to be anti-
Product-ethyl acetate, water and small part reactant ethanol formation binary or polynary azeotropic mixture is answered to create condition.I.e. in this tower top
At a temperature of, the part water and whole ethyl acetate and part ethanol that acetic acid and ethanol esterification are generated can be formed azeotropic mixture from
Tower top is steamed, so that above esterification (5-8) can be promoted further to carry out to the right.The condensed device condensation of cut that tower top is steamed
Afterwards, synthesis of natural ethyl acetate receiving tank is flowed to, when tower top almost flows out without effluent, is illustrated in tower reactor again without acetic acid
Ethyl ester is generated.The cut (azeotropic mixture) is through gas chromatographic detection, and the percentage by weight of its ethanol, water and ethyl acetate is respectively:
7.56%th, 8.71% and 83.73%, the volume total number of the cut is:10.9132 parts.Wherein, ethanol, water and ethyl acetate
Each volume parts are respectively:0.9411 part, 0.8554 part and 9.1167 parts.The composition result of above cut with《Some are commonly used
Industrial solvent azeotropic mixture data》Described in one book:" the ternary azeotropic composition and water and acetic acid second of ethanol, water and ethyl acetate
The binary azeotropic composition of ester " is all otherwise varied.Thereby it is considered that the cut is neither simple ternary azeotrope nor simple
Binary azeotrope, it should be the mixture of ternary azeotrope and binary azeotrope, the cut is referred to as below:Synthesis of natural acetic acid second
The polynary azeotropic mixture of ester (when tower top temperature can not be controlled accurately, may also evaporate in the polynary azeotropic mixture containing 71.8 DEG C
Point:The binary azeotrope of ethyl acetate and ethanol).
Appropriate food-grade CaO is added into the polynary azeotropic mixture of synthesis of natural ethyl acetate derived above, should
H in polynary azeotropic mixture2O and CaO is formed respectively:Ca(OH)2Precipitation, i.e.,:
CaO+H2O=Ca (OH)2↓ (9)
Then the polynary azeotropic mixture for forming precipitation is distilled, its cut is the mixture of ethanol and ethyl acetate.
The mixture of the ethanol and ethyl acetate hereinafter referred to as synthesis of natural ethyl acetate binary mixture, specific CaO addition
It can be calculated according to following method:
Because the weight content of ethanol, water and ethyl acetate is respectively:7.56%th, 8.71% and 83.73%, ethanol, water
Proportion with ethyl acetate is respectively 0.789kg/L, 1kg/L and 0.902kg/L, then the polynary azeotropic of synthesis of natural ethyl acetate is mixed
The proportion of compound is:
0.789 × 7.56%+1 × 8.71%+0.902 × 83.73%=0.9020kg/L
Water content is in the polynary azeotropic mixture of so every liter synthesis of natural ethyl acetate:
0.9020kg/L × 8.71%=0.0786kg/L=78.6g/L
If the water in the polynary azeotropic mixture of every liter of synthesis of natural ethyl acetate reacts the amount for needing to add CaO with CaO
For z, then:
Then:The ÷ 18=244.8827g of z=56.08 × 78.6
That is added in the polynary azeotropic mixture of every liter of synthesis of natural ethyl acetate:244.8827g, could with it is many
Water in first azeotropic mixture reacts generation Ca (OH) completely2Precipitation (for the water in azeotropic mixture is removed as far as possible,
The CaO amount of being actually added into should be 101% of theoretical amount or so).Secondly, 10.9132 parts of synthesis of natural ethyl acetate
Polynary azeotropic mixture go water removal after can obtain 9.1167 parts of synthesis of natural ethyl acetate binary mixture, i.e., 100 parts yellow waters
Concentrate is under heating and solid acid catalysis, and acetic acid therein generates 9.1167 parts of ethyl acetate (warp with ethanol esterification
Adjust the acetic acid 83.6% contained in yellow water concentrate and be converted into ethyl acetate), the ethyl acetate forms polynary with water and ethanol
Azeotropic mixture, can obtain 10.0578 parts of synthesis of natural ethyl acetate binary mixture after azeotropic mixture water removal.
In addition, when tower top temperature can not be controlled accurately, also may be used in the polynary azeotropic mixture of synthesis of natural ethyl acetate
71.8 DEG C of cut (because less reason of the temperature difference between 70.4 DEG C and 71.8 DEG C) can be contained:The two of ethyl acetate and ethanol
First azeotropic mixture, but this had not both interfered with the water removal principle of the above, did not interfered with the concentration of ethanol in reactor yet, because under
Face can also by synthesis of natural ethyl acetate binary mixture derived above, then residual titration reactor, even if therefore ethyl acetate and
The binary azeotrope of ethanol can take part ethanol out of, as residual titration causes ethanol to be supplemented in time.
The synthesis of natural ethyl acetate binary mixture obtained through above step is transported to synthesis of natural ethyl acetate binary
(ethyl acetate traditionally generated by tunning acetic acid and ethanol esterification is referred to as synthesis of natural to the reception device of mixture
Ethyl acetate).It is mainly ethyl acetate and a small amount of ethanol in the reception device.Then, in order to will in esterification (4)-(8) it is raw
Into water and original yellow water concentrate in the whole discharge reaction systems of intrinsic water, then will more than remove water after obtained synthesis of natural
Ethyl acetate binary mixture is at the uniform velocity instilled in tower reactor.So with the progress of reaction, on the one hand, synthesis of natural ethyl acetate two
First mixture constantly instills tower reactor, on the other hand, and the polynary azeotropic mixture of synthesis of natural ethyl acetate also can be steamed continuously, acetic acid
Ethyl ester all can gradually take water intrinsic in the water generated in esterification and former reaction system outside reaction system out of (again
The secondary polynary azeotropic mixture of the synthesis of natural ethyl acetate steamed needs to remove moisture removal in time with reference to method described above, in case even
Continuous dropwise addition is used).When synthesis of natural ethyl acetate binary mixture starts to instill, because not only the water generated in esterification
Take out of, the water not being carried over also that also as early as possible generate original water in reaction system and acetic acid with ethanol esterification
Take out of, so instilling speed needs soon.Due to original water in the water and system of generation in esterification (4)-(8) and
When reaction system is taken out of by ethyl acetate, so as to promote esterification (5)-(8) to carry out to the right to greatest extent.Work as tower top temperature
When maintaining≤70.4 DEG C, when being continued to flow out again almost without cut, illustrate that esterification (5)-(8) have basically reached reaction flat
Weighing apparatus state.Then disposably put into remaining synthesis of natural ethyl acetate binary mixture is added dropwise in tower reactor, at this moment tower top
Temperature can gradually rise.When tower top temperature is increased to 71.8 DEG C, the cut that tower top flows out under this tower top temperature is ethyl acetate
With the binary azeotrope of ethanol, continued to flow out after certain time when without cut, when tower top temperature is raised once again, stop stirring and
Heating, and filter out tower reactor kettle liquid, the tower reactor kettle liquid hereinafter referred to as esterifying liquid, the solid acid catalyst filtered out can be with Reusability.
Secondly, synthesis of natural ethyl acetate binary mixture is added dropwise into reactor, on the one hand can be water in time from anti-
Answer in system and take out of, promote esterification (5)-(8) to carry out to the right, other impurity will not be brought into reaction system again;It is another
Ethyl acetate can be evaporated the ethanol taken out of and is supplemented in reaction system by aspect again, to ensure ethanol and acid in reaction system
Big mol ratio.
In addition, why being to prevent the stirring of other manner from causing ethanol to explode using magnetic agitation.Secondly stir
Purpose have two:First, the yellow water concentrate thermally equivalent in water-bath can be made;2nd, solid acid catalyst can be made to be suspended in all the time
In yellow water concentrate, it is ensured that solid acid catalyst can keep uniformly contacting with the yellow water concentrate in tower reactor, so that catalyst is sent out
Wave the catalytic action of maximum.
Why solid super strong acid as catalyst is used, one is that can reduce equipment corrosion and environmental pollution;Two be because
Solid superacid as catalyst activity is high, be not required to pretreatment, and be easy to reclaim, can Reusability;Three be because after the completion of esterification
Solid acid is easily separated with ester, and without any residual, and liquid acid (refers mainly to H2SO4) when making catalyst, not only ester with acid not
Good separation, and accessory substance is more, and post processing is cumbersome, particularly the by-product sulfuric ester and ether poisonous to human body, to doing food flavor
It is very unfavorable that (at present, explicit order is forbidden to use H in Liquor-making industry2SO4Make catalyst), while causing mental handicape to consumer
(because the ester that the present invention is generated is mainly used in adjusting the local flavor of white wine).
The overhead fraction (at 71.8 DEG C) and esterifying liquid (tower reactor kettle liquid) that above process is obtained are through volume metering and gas phase color
Analysis of spectrum is understood:
1) when tower top temperature is at 71.8 DEG C, obtained overhead fraction is the binary azeotrope of ethyl acetate and ethanol, warp
Volume metering, its volume parts is:15.8870 parts, wherein ethyl acetate accounts for 10.5126 parts, and ethanol accounts for 5.3743 parts, and (yellow water is dense
Total number before the distillation of contracting liquid is 100 parts, and the conversion ratio through adjusting final acetic acid reaches:96.4%), ethanol, ethyl acetate
Mass content be respectively:30.9% and 69.1%, the proportionate relationship of the ethanol and ethyl acetate with《Some conventional industrial solvents
Azeotropic mixture data》Azeotropic mixture proportion of composing described in one book is relatively.I.e. 100 portions yellow water concentrates are final through catalytic esterification
It can obtain:The ethyl acetate of 15.8870 parts of ethyl acetate contents 69.1% and the binary azeotrope of ethanol, the binary azeotropic
Thing hereinafter referred to as binary azeotropic synthesis of natural ethyl acetate.
2) esterifying liquid (tower reactor kettle liquid) is through volume metering, and its volume fraction is up to:(74.6997 yellow water concentrate steams part
Total number before evaporating is 100 parts), the esterifying liquid is through gas chromatographic analysis, wherein ethanol, ethyl propionate, ethyl butyrate, valeric acid second
The mass content of ester, ethyl lactate and ethyl hexanoate is respectively:65.7%th, 2.3%, 5.7%, 0.2%, 4.8% and
16.7%, the percentage by weight of this 5 kinds of esters of the above is amounted to:29.7% (esterification generation ester with it is original in yellow water concentrate
Ester sum).Through adjusting, ethyl propionate in the esterifying liquid, ethyl butyrate, ethyl valerate, the body of ethyl lactate and ethyl hexanoate
Fraction is accounted for respectively:2.1389 parts, 5.3247 parts, 0.1672 part, 3.8611 parts and 15.7595 parts, the body of this 5 kinds of esters of the above
Fraction is amounted to:27.2514 part (including it is obtained above:0.1196 part of natural methanoic acid ethyl ester, 0.3605 part of natural acetic acid second
Including ester and 10.5126 parts of synthesis of natural ethyl acetate, the total volume fraction that can obtain ester is:38.2441 part).Acetic acid, third
Acid, butyric acid, the conversion rate of esterification of valeric acid and caproic acid are respectively:96.4% (final conversion ratio), 79.9%, 89.9%, 21.4%
With 95.3%.From the point of view of the conversion ratio of acid, except valeric acid because in reaction substrate concentration it is too low, its conversion rate of esterification less than outside 22%,
Acetic acid is also because when taking place esterification, the reason for the presence of reaction system reclaimed water, and conversion ratio when it starts also only has
83.6%, with the removal of the carry out reaction system reclaimed water of reaction, its conversion ratio is further increased to 96.4%.
Integrated survey above esterification, illustrates the proper temperature of the esterification setting of the present invention, chooses process route
Rationally, the solid acid catalysis excellent effect used.The specific of various organic matters contains in the esterifying liquid drawn through gas chromatographic analysis
Amount is as shown in table 5.
As can be seen from Table 5:The organic chemical composition containing 38 kinds of influence liquor flavors in yellow water is removed in the esterifying liquid
In 19 kinds (except ethanol) outside, also containing higher concentration influence liquor flavor ethyl propionate, particularly exchange sobriety body
The content of ethyl propionate, ethyl butyrate, ethyl valerate, ethyl lactate and ethyl hexanoate that local flavor plays an important role is high respectively
Reach:19036.2mg/L, 46511.1mg/L, 1461.2mg/L, 39769.6mg/L and 137107.3mg/L.In addition, more gratifying
Be that consumption is maximum in bent wine class essence, while the content for being also the ethyl hexanoate of the main body spices of aromatic Chinese spirit is even more high
Reach:137107.3mg/L, its content is 113 times of common aromatic Chinese spirit content and (is used as common Luzhou-flavor using the base liquor in table 1
The representative of white wine), the amount of the ethyl hexanoate contained in esterifying liquid is 3.4475 times of ethyl lactate (to regulation ethyl lactate and oneself
The ratio of acetoacetic ester is of great benefit to).
In summary, 100 portions of yellow water concentrates have obtained following rare natural materials by azeotropic distillation, reactive distillation:
1) crude aldehyde:0.2885 part.
2) natural methanoic acid ethyl ester:0.1196 part
3) natural acetic acid ethyl ester:0.3605 part
4) natural methanol:0.4496 part
5) binary azeotropic synthesis of natural ethyl acetate (ethanol and ethyl acetate):15.8870 parts, wherein containing pure synthesis of natural
The number of ethyl acetate is:10.5126 parts.
6) esterifying liquid:74.6997 parts.Wherein contain pure 15.7595 parts of synthesis of natural ethyl hexanoate, containing total 27.2514 parts of ester
(the volume number of ester simply adds up).
The purposes of the 2 liquor seasoning product obtained through azeotropic distillation and reactive distillation
Removed in 6 kinds of " natural " materials being obtained through above step of the present invention natural methanol because it is harmful cannot function as it is white
Outside the flavouring of wine, remaining 5 kinds of material is all excellent liquor seasoning product, be numerous distillery's dream product in the hope of, while being also
Rare natural liquor seasoning product not to be had even for 1000 pieces of gold.Below for convenience, other 5 kinds of materials in addition to methanol are referred to as white
Wine condiment.
2.1 white wine of liquid are blent
Liquid phase process, by blending the method for appropriate esterifying liquid into white wine of liquid, can be made according to the requirement of bartender
Increase the organic chemical composition of influence liquor flavor intrinsic in 19 kinds of white spirit by solid state method in white wine, and then make white wine of liquid
Local flavor also tends to white spirit by solid state method, while can also increase the degree of recognition of white wine of liquid, expands its consumer group.In addition, can
To add other 4 kinds of liquor seasoning product in liquor seasoning product in addition to esterifying liquid in right amount according to the requirement of bartender, liquid phase process is white
The wine of wine, which is known from experience, becomes more plentiful.
2.2 improve the quality of white spirit by solid state method
Blent into solid state process base liquor 0.8% esterifying liquid, i.e., 1 part esterifying liquid can blend 125 parts of white wine, with table 1
Base liquor as common aromatic Chinese spirit representative.The content of various chemical substances such as table 6 in top grade wine after being blent through esterifying liquid
It is shown.
The content of various chemical substances in the top grade wine after 0.8% esterifying liquid is blent in the solid state process base liquor of table 6
It can see by table 6:Before blending, the content of its ethyl lactate and ethyl hexanoate is respectively:1299.9mg/L and
1146.7mg/L, its content is respectively reached after blending:1607.7mg/L and 2234.4mg/L, its ethyl lactate:Ethyl hexanoate
Proportionate relationship also by:1.1336:1 is changed into:0.7195:1 (and the requirement of top grade aromatic Chinese spirit ethyl hexanoate exists:1200-
Between 2800mg/L, ethyl lactate:The ratio of ethyl hexanoate is in 0.6-0.8:Between 1).Blending more than can not only make
Common white spirit reaches concentration requirement of the top grade aromatic Chinese spirit to ethyl hexanoate, can more increase substantially ethyl propionate, butyric acid second
The concentration of ester and ethyl valerate, can also turn down the ratio of ethyl lactate and ethyl hexanoate, make ethyl lactate:The ratio of ethyl hexanoate
Drop to 0.6-0.8:Between 1 (in general white spirit by solid state method, the concentration of ethyl lactate is typically larger than ethyl hexanoate), in addition, in vain
In 48 kinds of materials of the influence liquor flavor contained in wine, the concentration for having 19 kinds obtains different degrees of raising.Particularly propionic acid
The concentration of ethyl ester, ethyl butyrate and ethyl hexanoate is increased substantially.Make white wine reach " soft aroma and, sweet natural, acid
Ester harmony, taste are clean, sticky suitable " style.Meanwhile, because 97 parts of yellow waters can concentrate 9.5 portions of yellow water concentrates, often
100 portions of yellow water concentrates can produce 74.6997 parts of esterifying liquids, and 1 part of esterifying liquid can blend 125 parts of base liquors as top grade wine,
So 9.14 parts of common base liquors can be blent into top grade aromatic Chinese spirit by the esterifying liquid that 1 part of yellow water is produced, therefore yellow water has
Value is recycled well.Furthermore, it is possible to be added in right amount in liquor seasoning product in addition to esterifying liquid according to the requirement of bartender
Other 4 kinds of liquor seasoning product, wine, which is known from experience, becomes more plentiful.
3 provide spices for other food industry
Natural methanoic acid ethyl ester derived above and ethyl acetate can be added to gourmet food as senior natural condiment containing
To change the fragrance of food in (including high quality wine).In addition, the further rectifying of esterifying liquid can also obtain 5 kinds of esters and ethanol
The azeotropic mixture of azeotropic mixture, i.e. ethyl propionate, ethyl butyrate, ethyl valerate, ethyl lactate, ethyl hexanoate respectively with ethanol, then
Copy the method described in 1.4.2 to remove the ethanol in azeotropic mixture, 5 kinds of pure natural esters can be obtained, this 5 kinds of pure natural esters are foods
Product industry is important flavouring, and the seasoning aspect used in white wine can make bartender be more prone to manipulate addition.
On the one hand, because the primary raw material yellow water used in the present invention be fermented grain fermented in pit production wine when association form,
It may be said that yellow water is the twin brothers of white spirit by solid state method;On the other hand, because the present invention is concentrating the yellow water being made concentration with yellow water
Liquid is raw material, is extracted or during esterification produces liquor seasoning product, although added in following steps into extract
Food-grade CaCl2, CaO or solid acid, but the process of the present invention also ensure that CaCl2, CaO and solid acid will not bring into
In end article liquor seasoning product.
1) it with the addition of CaCl during the removal of the methanol in the binary azeotrope of natural methanoic acid ethyl ester and ethyl acetate2;
2) the polynary azeotropic mixture of ethanol, water, acetic acid and ethyl acetate with the addition of CaO when removing water removal and acetic acid;
3) solid acid is added during esterification and makees catalyst.
Also as in the whole producing process of liquor seasoning product, even if esterification is also to be produced by pure natural fermentation
(this is esterified with ethanol as raw material using the caproic acid that chemical method is produced with the overwhelming majority now and produced for acid and ester that ethanol be waste
The method of white wine main body spices ethyl hexanoate is different), other steps are entirely physical method, therefore use white wine produced by the present invention
Flavouring be safe and producing process in will not bring into any chemicals natural product (traditionally with fermentation method be made
Acid and ethanol be that the ester produced of raw material esterification is referred to as synthesis of natural ester), so what the present invention was obtained by raw material of yellow water
Liquor seasoning product include synthesis of natural esters and other natural organic matters, closer to natural product during for concocted white spirit, more
Easily it is esthetically acceptable to the consumers.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modifications, equivalent substitutions and improvements made within refreshing and principle etc., should be included in the scope of the protection.