CN1015065B

CN1015065B - Degradation and catalytic aging method for white spirits

Info

Publication number: CN1015065B
Application number: CN 86107576
Authority: CN
Inventors: 董为毅; 张怀彬; 高峰; 李赫恒
Original assignee: Nankai University
Current assignee: Nankai University
Priority date: 1986-11-06
Filing date: 1986-11-06
Publication date: 1991-12-11
Also published as: CN86107576A

Abstract

The present invention belongs to a processing technology of spirits. Basic spirits which are newly brewed are stored for half a year to one year(ageing) to remove unpleasant odor before the basic spirits are drunk. Methods of distillation, freezing filtration and adsorption are used for reducing alcohol content of spirits and eliminating impurities, and the methods have defects which are difficult to overcome. In the present invention, basic spirits pass through an adsorption column (which contains treated ZSM-5 zeolite), and therefore, dual purposes of catalytic aging and no turbidity during lowering the alcohol content of the basic spirits are achieved.

Description

Degradation and catalytic aging method for white spirits

The invention belongs to the working method of liquor.

Liquor is the human traditional beverages of very liking.But, the liquor that distillery is brewageed, general concentration is all than higher, and pungency is big when drinking, and the harm people's is healthy, so liquor degree of falling is present important topic.The local flavor of low alcohol depends primarily on the local flavor of former wine, therefore the base liquor made of eo-acid must be through the storage (aging) of half a year to one year, to remove its evil assorted smell, and then degree of falling processing, therefore must spend the long time and take bigger production site.

Degree of falling problem about liquor, because the existence of some high-grade aliphatic ester in the liquor,, have a strong impact on colours of wine and quality when thin up in liquor milky dregs will occur during to certain dilution, in order to solve muddy problem, be to adopt following method at present:

1. redistillation method

Though this method solves haze problem, make the flavour substances loss of wine more, and consumption of heat energy is bigger.

2. frozen filtration

This method needs a high chilling unit of cover and a filter at low temperature room, thereby facility investment is big, the productive expense height.

3. absorption method

Used sorbent material has Mierocrystalline cellulose, diatomite, starch, gac etc. at present.This method adsorption time is longer, needs a cover filter plant, and needs filter at low temperature sometimes.

4. resin method

This method is that the liquor with high density flows through a kind of macroporous adsorbent resin by certain flow rate, and then dilute with water.This method technology is simple, easy to operate, and cost is low, is that muddy method is gone in industrial low alcohol preferably at present.

The objective of the invention is to seek a kind of treatment process of liquor, this method can make muddy and catalytic aging carries out simultaneously.

In order to achieve the above object, we adopt a kind of multi-functional zeolite adsorbents, and this sorbent material can optionally adsorb the high-grade aliphatic ester in the liquor, also can remove some the evil assorted smell in the basic white spirits simultaneously.The main raw material of this sorbent material is the ZSM-5 zeolite, its silica alumina ratio (SiO ₂/ Al ₂O ₃) can in 30～80, select arbitrarily,, tradable positively charged ion has K ⁺, Na ⁺, NH ⁺ ₄, Ga ⁺⁺, Mg ⁺⁺, Ag ⁺, H ⁺Deng, these ions carry out ion-exchange by solution such as its halogenide, nitrate, vitriol, phosphoric acid salt, mineral acids and obtain.When making basic white spirits (Sorghum vulgare Pers. Wine of for example newly brewageing, sweet potato wine, corn wine, big rice wine etc.) flow through the adsorption column that this sorbent material is housed, then can receive the double effects of muddy and catalytic aging with certain flow rate.

The liquor dilutable water that uses this sorbent treatment to cross becomes 38 ° limpid transparent liquor, through still having muddy appearance in freezing 24 hours at subzero 5 ℃; The low alcohol that the present invention makes is tasted through the wine taster of brewery, thinks that this wine is significantly sweet, coordinates, do not have the assorted smell (seeing Table 1,2,3) of heresy in the basic white spirits; Through certificate of analysis, be used for the wine that sorbent treatment crosses, its physical and chemical index sees Table 4, as known from Table 4, all reductions of harmful lead tolerance.This low alcohol is deposited after 1 year and is tasted with the liquor contrast of natural aging, and its local flavor is identical; This sorbent material do not have smell, nontoxic, and water insoluble and various organic solvent, its adsorption efficiency height, per hour the per kilogram sorbent material can be handled liquor 6-12 kilogram, and can operate continuously; This sorbent material can be regenerated by heat-treating methods, uses repeatedly.

Below we illustrate implementing method of the present invention.

Example 1

100 gram ZSM-5 zeolites are joined in 1000 milliliters the round-bottomed flask, add the HCl solution of 500 milliliters of 0.3N, 90 ℃ of exchanges 1 hour down, the elimination mother liquor is washed till no chlorine, in 120 ℃ of bakings down, obtains the NaHZSM-5 zeolite.To the hydro-halloysite of this zeolite adding 15%, get 20～40 purpose particles after the moulding, in 550 ℃ of roastings 3 hours, promptly obtain the NaHZSM-5 zeolite adsorbents.

Utilize above-mentioned similar methods, use other mineral acid or inorganic salt, can make have, H ⁺Respectively with K ⁺, Ga ⁺⁺, Mg ⁺⁺, Ag ⁺The cation adsorbent of combination.

Example 2

The jowar Daqu is crossed the adsorption column that the sorbent material that 10 grams make from example 1 is housed with 60 milliliters velocity flow per hour.Wine after the processing is tasted through the wine taster of brewery, and its result is as shown in table 1: about the wine thin up to 38 after handling ℃, in subzero 5 ℃ down freezing 48 hours still be water white transparency.

Example 3

Sweet potato wine is flow through the adsorption column that the sorbent material that 10 grams make with example 1 method is housed with 60 milliliters flow velocity per hour, and the wine after the processing is through trial test, result such as table 2:

With the liquor thin up to 38 handled ℃, in subzero 5 ℃ down freezing 24 hours still be water white transparency.

Example 4

Exhausted sorbent material in the example 2 in 550 ℃ of following roastings 3 hours, is crossed sorbent material after the regeneration with jowar yeast wine with 60 milliliters velocity flow per hour then.Wine after the processing experiment showed, that through tasting with degree of falling its quality is identical with the wine of crossing with the sorbent treatment that newly makes.

Example 5

Wheat bran wine is crossed the adsorption column that the sorbent material that 5 grams make with example 1 method is housed with 60 milliliters velocity flow per hour, trial test the results are shown in Table 3, degree of falling experiment is with example 3, its result still is a water white transparency, and, prove that by analysis the liquor of treated mistake compares with the basis, its lead tolerance reduces (seeing Table 4) greatly.

Table 1

Wine title outward appearance fragrance taste

Base wine water white transparency has evil assorted flavor, assorted flavor is arranged, peppery, numb mouth,

Smelly slightly bitterness, flavor are greatly

Can better sweet, the wine body coordination of inlet of degree of falling wine water white transparency fragrance

Tail is clean

Table 2

Wine title outward appearance fragrance flavor

Base wine water white transparency melon is done the bigger inlet Ma Zui of flavor, assorted flavor is big, tail is bitter

Only

Can degree of falling wine water white transparency fragrance better sweet, the little acid of inlet,

Tail is clean

Table 3

Wine title outward appearance fragrance flavor

The denseer inlet of the base limpid transparent foul smell of wine is sweet, perfume (or spice) is not outstanding,

Tail is cleaner

Can the thin puckery fragrance of the limpid transparent fragrance of degree of falling wine denseer, inlet is sweet,

Tail remainder perfume (or spice)

Table 4

The total aldehyde potato spirit of wine title total acid and ester methyl alcohol lead content

g/100ml g/100ml g/100ml g/100ml g/ml （PPb）

Base wine 0.159 0.311 0.0227 0.075＜0.04 23.52

Can degree of falling wine 0.154 0.304 0.0225 0.075＜0.04 11.43

Claims

1, a kind of muddy method not taking place can make the basic white spirits catalytic aging and make it be diluted to low alcohol the time, it is characterized in that making basic white spirits to flow through with 60 milliliters flow velocity per hour silica alumina ratio (SiO is housed ₂/ Al ₂O ₃) be 30～80, contain H ⁺Respectively with K ⁺, Na ⁺, NH ⁺ ₄, Ga ⁺⁺, Mg ⁺⁺, Ag ⁺The adsorption column of the cationic ZSM-5 zeolite adsorbents of combination, it is the K of 0.3N that wherein said ZSM-5 zeolite adsorbents is to use a kind of concentration ⁺, Na ⁺, NH ⁺ ₄, Ga ⁺⁺, Mg ⁺⁺, Ag ⁺Halogenide, nitrate, vitriol, phosphoric acid salt, or working concentration is HCl, the H of 0.3N ₂SO ₄, HNO ₃, H ₃PO ₄Solution carries out ion-exchange to the ZSM-5 zeolite under 90 ℃, make with the hydro-halloysite moulding then.