DE2233812B2 - Process for the tartar stabilization of wine, grape must and grape juice using electrodialysis - Google Patents

Description

This invention relates to a method for the tartar stabilization of wine, grape must and Grape juice using electrodialysis.

During or after the fermentation of grapes, the wine contains potassium bitartrate, also known as tartar, in crystalline form. The vulgar term "Weinstein" was already known in ancient times.

Potassium and tartaric acid are already contained in the juice of the ripe grapes. The deposition of Potassium bitartrate in wine is mainly caused by the formation of ethanol during fermentation, because Weinstein is much less soluble in ethanol than in water. Also the lowering of the temperature when the wine is stored in the cellar and the biological acidity decrease contributes to the separation of tartar at. The latter causes a pH increase that is in the range below pH 3 (at this pH value Kegt the minimum solubility of tartar) and to a reduction in the solubility of tartar • leads. Conversely, the pH value of the wine decreases when tartaric acid precipitates, provided that it was previously below pH 3.5. A change in the pH value can also be the cause of the mixing process of two wines that are individually stable to tartar, a separation of tartar occurs.

Potassium bitartrate and calcium tartrate easily form The same problems as occur with wine and sparkling wine also with grape juice. The grape juice usually contains so much tartaric acid and potassium that Weinstein is excreted, albeit with grape juice mostly over a longer period of time.

Since consumers demand wines, sparkling wines and grape juices without crystalline precipitates, in the cellar economy tartar-unstable drinks are chilled in order to accelerate the elimination of the tartar. In general, the wine is kept in an insulated cooling tank until it is close to its freezing point cooled and stirred for several days at this temperature.

If the costs of setting up cooling systems are avoided, the wine can also get through Carbonated snow can be cooled by means of the so-called Weinstein cold fining. The cooling remains but an expensive measure.

Besides the potassium, calcium and tartaric acid content, the alcohol content and pH are essential for the The crystallization of wine is crucial. In scientific work, curves for the solution equilibria have been drawn up from which it can be seen whether the wine is tartar-stable, when it is and when not yet. When on If the above factors determine that the wine is unstable, it must be refrigerated. Frequently but when cooling it is found that despite long-term cooling it no longer contains tartar ruled out. This leads to the conclusion that other factors besides those mentioned also influence the elimination influenced by tartar.

It was recommended, if the tartar deposits were not deposited, by cooling the wine through Stirring or pumping or inoculating it by adding tartar crystals. Despite Such measures, it happens that the wine still excretes tartar after bottling, so it is not tartar-stable.

Through research it has been found that the delay in excretion of tartar precedes mainly caused by polymeric and colloidal substances and that condensed polyphenols especially have an inhibiting effect on crystallization.

The cooling of the wine for the purpose of tartar stabilization does not always lead to the desired result Success; it is unsafe and costly. From the knowledge that polymeric substances the

oversaturated solutions. The excretion of these salts 50 Delays the excretion of tartar or completely

* The wine therefore takes several months to complete. The excretion of tartar from the Supersaturated solutions are particularly noticeable unpleasantly when the wine, like the consumer It is expected and desired for consumer wines, bottled early Will. Consumers reject wines with such selections in wine, although they are harmless to health, generally out of ignorance of the Operations.

In sparkling wine, where the increase in the ethanol content during the second fermentation causes instability (Tendency to deposit) the dissolved tartar can increase again, this has the unpleasant result, that the carbon dioxide can easily be released from the separated crystals of the tartar and then when the bottle is opened it suddenly becomes free.

one has tried to prevent it. To stabilize wines against the crystallization of tartar by adding polymeric substances. It has been known since 1956 to add small amounts of polymeric esters of tartaric acid, obtainable by heating tartaric acid to 170 ^{° C., to wine for this purpose.} After adding to wines, sparkling wines and grape juices, tartar excretion is usually prevented for about 9 months.

Other substances known to delay the deposition of tartar are gummy rubble and polymeric phosphates.

Another way of preventing the excretion of tartar from beverages that are unstable

prevent is to remove the tartaric acid, potassium, or both from them. One way that To change the concentration of tartaric acid is to change the tartaric acid e.g. B. by adding calcium carbonate

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According to the novel method for tartar stabilization according to the invention, the same applies to the treatment with ion exchangers, the concentration of potassium and tartrate ions is reduced, but without the Wine comes into contact with any nutritionally unsound substances.

The advantage of the new process over the use of ion exchangers, which is forbidden is that the producers of wine and sparkling wines are now an economically satisfactory Process for tartar stabilization is available so that they are not forced to to go back to the old, technically and economically unsatisfactory processes described above.

The course of the process and the devices required for it are shown schematically in the figures shown:

Like A b b. 1 shows, the wine, grape must or grape juice to be treated is passed through a dialysis chamber D , which is delimited on both sides by one or more nutritionally harmless semipermeable membranes 1 permeable to potassium and tartrations and thus separated from the surrounding rinsing liquid. To the left of the dialysis chamber D is located in the A b b. 1 to 3 anode compartment A with anode 2, while the cathode compartment KA with cathode 3 is arranged on the right. The electrodes 2 and 3 are bathed in a conductive liquid. The numbers 4 represent pumps and the numbers 5 represent gas separators (Tables IA and 1 B).

A b b. 2 shows the implementation of the method in which wine, grape must or grape juice is passed through the anode compartment A as the rinsing liquid, while any wine is passed as the rinsing liquid in the cathode compartment KA (Table HA).

According to A b b. 3, wine, grape must or grape juice is passed through the cathode chamber KA as the rinsing liquid. Any wine can be used as the rinsing liquid in the anode compartment A (Table HB).

In the schematic A b b. 1 to 3, K stands for potassium ion, HT for tartrate ion, H ₂ for hydrogen and O ₂ for oxygen.

If a direct current voltage of up to about 80 V is applied to the electrodes, this will migrate Potassium ion through the membrane to cathode 3 and the acid ion through the membrane to anode 2. For the deposition of 0.406 mg of potassium requires 1 amp. The current strength depends on it the amount of potassium to be deposited. The task of the electrolytic rinsing solution is that in ionic form remove any substances present and the gases produced when the ions are discharged at the electrodes. The flow of the wine through the dialysis chamber and the rinsing liquid through the anode and cathode spaces can be designed continuously. Voltage, amperage and flow rate are now regulated in such a way that the concentration of potassium and acid in the wine is reduced to such an extent that that the wine can be considered tartar-stabilized. It has been found that it is convenient to use the To lower the potassium content of the wine, grape must or grape juice so much that it still contains about 450 mg of potassium per liter remain. Experience has shown that wine and juices are stable when this concentration The amount of potassium falls below this level, i.e. if there is less than 1 to 4 g potassium / l.

Since the rinsing liquids wine, grape must and grape juice in the anode and cathode compartments unite have the same or approximately the same osmotic pressure as is present in the wine to be treated one can use semipermeable membranes which are inexpensive and readily available commercially. if there would have to be no adjustment of the osmotic pressure in the anode and cathode compartments Membranes are used that only allow the migration of anions or cations, but the ίο Exclude the passage of water. Experience has shown that such membranes are difficult to manufacture and therefore expensive. If the membranes only have traces of water as a result of the osmotic pressure drop let through, an undesirable dilution of the wine or juice occurs.

The results of using electrodialysis to stabilize wine tartar, Grape musts and grape juices are surprising. One can first achieve the effect that as with The natural deposition of tartar reduces the concentration of potassium and tartaric acid so far is that no more tartar excretion takes place. The procedure therefore corresponds to the accelerated one Elimination of tartar as it is achieved by the expensive and lengthy cooling process, but it is much cheaper and quicker to carry out. Opposite the procedure for treatment of wines and musts with ion exchangers, the new process has, in addition to those already described above Results have the special advantage that the wines retain their natural taste. If potassium is exchanged for hydrogen ions during treatment with ion exchangers, you get wines with such a sour taste. that they are no longer edible. When potassium Replacing it with sodium results in wines with an unnaturally high sodium content. Man receives a wine that is completely different from its natural composition. With Wines treated with ion exchangers are analytically recognizable without difficulty, especially when Potassium is exchanged for sodium. This is the case with the wines treated with the new method not the case, since their composition corresponds to that, for example, after the tartar stabilization by cooling. But it could not be foreseen that electrodialytic treatment So by removing the potassium and tartaric acid ions in such a simple, cost-saving way Tartaric stabilization would be achieved in a quick manner.

The new process for tartar stabilization can be carried out continuously and discontinuously will.

As semipermeable membranes for the present process, membranes made of polymers, ζ. Β from polyolefins, chlorinated polyolefins, polyamides and polysaccharides, such as cellulose acetate or cellu loose ethyl ether, is used.

The results are shown in the following tables of embodiments with different zi stabilizing wines and grape musts and mi strongly and slightly different wines around grape musts as rinsing liquids in the anode Cathode room shown with the numbers of wine and grape musts before and after the treatment as well as the wines and musts that have been used as rinsing liquids.

IA (Fig. 1) To be stabilized Wine Wine used as a rinsing liquid after leaving Content of before the after before entering the rinsing circuit treatment treatment the rinsing circuit 930 mg / 1 835 mg / 1 730 mg / 1 835 mg / 1 2320 mg / 1 potassium 2100 mg / 1 1900 mg / 1 2100 mg / 1 2490 mg / 1 Tartaric acid 2500 mg / 1 2500 mg / 1 2500 mg / 1 1710 mg / 1 Malic acid 1700 mg / 1 1750 mg / 1 1700 mg / 1 670 mg 1 Lactic acid 700 mg / 1 600 mg / 1 700 mg / 1 145 mg / 1 fl. acid 128 mg / 1 112 mg / 1 128 mg / 1 5 mg / 1 total sulphurous acid 5 mg / 1 3 mg / 1 5 mg / 1 520 mg / 1 free sulphurous acid 414 mg / l 315 mg / 1 414 mg / 1 182 mg / 1 Potassium sulfate 172 mg / 1 163 mg / 1 172 mg / 1 8020 mg / 1 phosphate 7800 mg / 1 7500 mg / 1 7800 mg / 1 2520 mg / 1 Total acid 2140 mg / 1 1780 mg / 1 2140 mg / 1 32.2 ml η NaO ash 28.3 ml n NaOH 24.3 ml η NaOH 28.3 ml η NaOH 75.6 g / l Ash alkalinity 75.9 g / l 75.3 g / l 75.9 g / l 24.1 g / l alcohol 22.2 g / l 20.1 g / l 22.2 g / l 1.5 g / l Total extract 1.5 g / l 1.6 g / l 1.5 g / l sugar

IB (A b b. 1)

Content of

Wine to be stabilized

before the
treatment

after
treatment

Wine used as rinsing liquid before entering the rinsing circuit

after leaving the rinsing circuit

potassium

Tartaric acid

Malic acid

Lactic acid

fl. acid

total sulphurous acid

free sulphurous acid

Potassium sulfate

phosphate

Total acid c

ash

Ash alkalinity

alcohol

Total tract

sugar

1220 mg / 1 2800 mg / 1 3800 mg / 1

700 mg / l

450 mg / 1

243 mg / 1 45 mg / l

690 mg / 1

198 mg / 1 6900 mg / 1 1800 mg / I 18 ml η NaOH 85.9 g / l
21.4 g / l

1.7 g / l

815 mg / 1 1800 mg / 1 3700 mg / 1

480 mg / 1

390 mg / l

172 mg / I 35 mg / I

390 mg / l

147 mg / I 6800 mg / 1 1300 mg / 1 13 ml η NaOH 85.3 g / l
19.9 p / l

1.7 g / l

612 mg / 1 1120 mg / 1 2100 mg / 1 1520 mg / I 520 mg / 1 178 mg / I 35 mg / 1 570 mg / 1

170 mg / I 3800 mg / I 2200 mg / 1 21 ml η NaOH 92.3 g / l 19.8 g / l 2.4 g / l

1018 mg / 1 2100 mg / 1 2550 mg / 1 1620 mg / l

590 mg / 1

250 mg / 1 44 mg / 1

850 mg / 1

212 mg / I 3650 mg / I 2650 mg / 1 15 ml η NaOH 91.7 g / l 21.2 g / l

2.3 g / l

509 52:

IL A (A b b. 2)
Content of

potassium

Tartaric acid

Malic acid

Lactic acid

fl. acid

total sulphurous acid

free sulphurous acid

Potassium sulfate

phosphate

Total acid

ash

Ash alkalinity

alcohol

Total extract

sugar

Grape must to be stabilized

before treatment

1420 mg / 1

3500 mg / 1

4200 mg / 1

200 mg / 1

210 mg / 1

280 mg / 1 147 mg / 1 7200 mg / 1 2680 mg / 1 27 ml n NaOH> 5g / l 156 g / l 132 g / l after the
treatment

1008 mg / 1

2450 mg / 1 mg / 1

mg / 1

mg / 1

mg / 1
mg / 1
mg / 1
mg / 1
ml η NaOH
> 5g / l
g / l
g / l

10

Grape must used as rinsing liquid in the anode compartment

before entering the rinsing circuit

980 mg / 1

mg / 1

mg / 1

160 mg / 1

200 mg / 1

250 mg / 1 158 mg / 1 4020 mg / 1 2020 mg / 1 21 ml η NaOH> 5g / l 180 g / l 158 g / l

after leaving the rinsing circuit

965 mg / 1

2880 mg / 1

4010 mg / 1

165 mg / 1

220 mg / 1

260 mg / 1

160 mg / 1 5200 mg / 1 2140 mg / 1 24 ml η NaOH

> 5g / l

179 g / l

158 g / l

As a rinsing liquid in the cathode compartment

Grape must to be stabilized

potassium

Tartaric acid

Malic acid

Lactic acid

fl. acid

total sulphurous acid free sulphurous acid

Potassium sulfate

phosphate

Total acid

ash

Ash alkalinity

alcohol

Total extract

sugar

before treatment

1380 mg / 1

2700 mg / 1

3400 mg / 1

180 mg / 1

150 mg / 1

240 mg / 1

190 mg / l

5400 mg / 1

2620 mg / 1

28 ml η NaOH

5 g / l

175 g / l

151 g / l according to dei
treatment

mg / 1

mg / 1

mg / 1

mg / 1

mg / 1

mg / 1

mg / 1
mg / 1
mg / 1
ml η NaOH

g / l
g / l
g / l

before entering the rinsing circuit

940 mg / 1

4200 mg / 1

5200 mg / 1

210 mg / 1

170 mg / 1

180 mg / l

175 mg / 1

9800 mg / l

2100 mg / l

21 ml η NaOH

5 g / l

142 g / l

120 g / l

after exiting the rinsing circuit

1300 mg / l

3900 mg / l

4900 mg / l

210 mg / l

180 mg / l

170 mg / l

172 mg / l

8900 mg / l

2540 mg / l

24 mg η NaO

5 g / l

143 g / l

123 g / l

For this purpose 3 sheets of drawings

Claims (1)

Claim: Process for the tartar stabilization of wine, grape must and grape juice using electrodialysis, characterized in that that as rinsing liquids in the anode and cathode compartment wine, grape must or grape • aft different tartaric acid and potassium contents can be used.