DE2233812C3 - Process for the tartar stabilization of wine, grape must and grape juice using the electrical - Google Patents

Description

fertilize, ζ, e.g. from calcium carbonate, to precipitate, as happens in the case of deacidification, which is generally known in cellar technology. CaO, Ca (CH) ₂ or calcium salts of organic acids can also be added.

The use of anion exchangers to remove tartaric acid is also known. They have been used in various countries since 1949, just like CaCO _{; l} , for general deacidification of wines. However, since they prefer to exchange polybasic acids, this treatment mainly removes phosphoric acid, sulfuric acid and tartaric acid from the wine.

In practice, the concentration of potassium can currently only be reduced by means of cation exchangers' 5 will. By treating a wine with cation exchangers, potassium becomes more or less selectively removed from the wine. For the reduction of the potassium concentration, it does not matter whether that is Potassium ion by a hydrogen ion or by another cation, such as. B. sodium, is exchanged. About preventing the excretion of tartar by removing potassium with the help of potassium ion exchangers Numerous papers have been published and patents registered and granted.

Overall, the extensive literature on the treatment of wines with cation exchangers shows that the excretion of tartar can be prevented with certainty in this way. aside from that other improvements can be made.

In the sparkling wine industry in particular, there has been a large-scale transition to that for production to make certain wines of sparkling wines tartar-stable by treatment with ion exchangers do.

Despite the fact that the method can be carried out simply and safely, it has a major disadvantage in this respect when the wine comes into contact with substances, their nutritional harmlessness or unloxicity has not yet been determined. * °

It is also possible that the ion exchangers are monomeric, oligomeric or polymeric Substances are released into the wine and remain in it, so that the consumption under certain circumstances Consumes nutritionally not harmless * 5 or toxic substances. That has Legislators prompted the use of ion exchangers for the treatment of food and To prohibit luxury foods as a matter of principle. The producers of wines and sparkling wines are thereby Got in great embarrassment and would have to go to the old, technical and described above economically unsatisfactory processes decline, if not one that works without ion exchangers, useful, safe and economically satisfactory method for tartaric stabilization is being developed.

It is known that electrodialysis can be used to desalinate whey ("Deutsche Milchwirtschaft", Hildesheim 48/1971, p. 2158 and 2161/2162 and 49/1971, p. 2204/2205). Also for desalination of Electrodialysis is already being used for seawater and brackish water applied.

Also in the field of the treatment of radioactively contaminated wastewater in the area of weak specific Activities with an average ion content of the wastewater of <10 ° DH should be carried out by electrodialysis be applicable while they are higher specific activity for the treatment of radioactive wastewater is still too uneconomical due to the mechanical instability of the membranes ("radioactive waste", May 1967, Volume 27 - Preparation, Storage, Disposal -, Author: S. J. B. K r a w c ζ y η s k i, Verlag Karl Thiemig KG, Munich).

Other known fields of application of electrodialysis are the recovery of catalysts, the had gone into solution, processing of dilute acids, cleaning of chemical and pharmaceutical products Products and purification of certain by-products in the sugar industry.

In Chemical Abstracts, Vol. 55, 12758, i (1961) on a work by Motoo Kagami (EuII. Res. Inst. Fenn. Yamanashi Univ., No. January 6, 1959) reported. Kagami uses electrodialysis of wine with ion-selective membranes for the purpose the increase of the pH value, the decrease of titratable acid and of cations, of which Fe, Cu, Ca and Mg (but not K) can be mentioned.

According to the publication by Chemical Abstracts, Vol. 40, 3222, 9 (1946) Lambcrto P a r ο η ε 11 ο (Annuar, sta *. Spec. Viticolu enol. Conegliano 10, 123-49 (1941) is the acidity of wine, must and by means of electrodialysis other fruit juices decreased.

According to FR-PS 13 16 502, the pH value of fruit juices by means of electrodialysis is also used modified by membranes selective for anions and cations.

The DE-PS 6 19 191 describes a method for reducing the acidity of waves and musts or other fruit juices, which consists in the electrodialysis liquid to be deacidified subject.

The subject of FR-PS 7 11 300 is a method for improving alcoholic beverages with the aim of Obtain products that are similar to those naturally aged. The liquids undergo electrolysis between two electrodes, separated or not separated by a membrane. In addition, catalysts such. B. Salts occr Oxides of metals of different oxidation levels, such as iron, nickel, manganese, titanium, etc. added will.

The present invention is based on the object of a technically easy and safe to carry out, compared to the known methods for tartar stabilization and improved in nutritional physiology Respect to create harmless process for wine instability.

This object was achieved according to the invention in such a way that the tartar stabilization using the electrodialysis was carried out in such a way that the rinsing liquids in the anode and Cathode compartment Wine, grape must or grape juice with different tartaric acid and potassium content is used will.

With this method, in contrast to the known fields of application of electrodialysis, none Extraction and suction of the wine, but a Weinstcinstabilisiemng be achieved.

The method is carried out in such a way that the wine to be treated, grape must or grape juice for electrodialysis through a dialysis chamber and that one in the anode and cathode compartment as Rinsing liquids used for wine, grape must or grape juice.

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 procedure and the necessary Devices are shown schematically in the figures:

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 anode compartment A with anode 2 in FIGS. 1 to 3, while the cathode compartment KA with cathode 3 is arranged on the right. The electrodes 2 and 3 are bathed in wine, grape must or grape juice. The numbers 4 represent pumps and the numbers S represent gas separators (Tables IA and IB).

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

After A h 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 II B).

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. The strength of the current depends on the amount of potassium to be deposited. The electrolytic rinse solution has the task of the substances present in ion form and those during the discharge of the ions to dissipate gases generated at the electrodes. The flow of wine through the dialysis chamber and the flushing liquid through the anode and cathode compartments can be made continuous will. Voltage, amperage and flow rate are now regulated in such a way that the concentration in the wine potassium and acid are so low that the wine can be considered tartar-stabilized. It has been found that it is useful to check the potassium content of the wine, grape must or grape juice lower it to the point where about 450 mg of potassium per liter remain. According to experience wine and juices are stable when the potassium concentration falls below this, i.e. when less than 1 to 4 g of tartaric acid are present.

As the rinsing liquid is wine. Grape must and grape juice in the anode and cathode compartments the same oiler have 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 no adjustment of the osmolic pressure in the anode and cathode compartment were available, membranes would have to be used, which only allow the migration of anions or cations, but the

ίο Exclude the passage of water. Such membranes Experience has shown that they are difficult to manufacture and therefore expensive. If the membranes as a result of osmotic pressure drop also only traces of water let through, there is an undesirable dilution of the wine or juice.

The results of the application of electrodialysis to the tartaric stabilization of wines Grape musts and grape juices are superfluous One can first achieve the effect that like be The natural separation of tartaric acid so low the concentration of potassium and tartaric acid is that there is no excretion of tartar flour. The procedure therefore corresponds to the accelerated one Excretion of tartar as it is caused by this expensive and lengthy cooling processes are achieved but can be carried out much cheaper and faster. Compared to the process for the production of wines and musts with ion exchangers In addition to the results already described above, the new method has the particular advantage that the wines retain their natural ".icM-hniack." When potassium is exchanged for hydrogen ions during treatment with ion exchangers you get wines with such a sour taste that they are no longer palatable. When Kaliurr Replacing it with sodium results in cries with an unnaturally high sodium content. Mar receives a wine that is completely different from its natural composition. Mil Wines treated with ion exchangers can be recognized analytically without any difficulties, especially if no Potassium is exchanged for sodium. This is the case with wines treated with the new process not the case, since their composition corresponds more closely to that according to the tartar stability ization by cooling is present. But it could not be foreseen that by electrodialytic handling treatment, i.e. by removing the potassium and tartaric acid ions, in such a simple, cost-saving process and a quick way to achieve a tartar stabilization would be achieved.

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

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

The following tables show the results of exemplary embodiments with different zi stabilizing wines and grape musts and with strongly and slightly different wines un < Grape musts as rinsing fluids in the anode and cathode compartment shown with the key figures of the Weim and grape musts before and after the treatment as well as the wines and musts used as rinsing liquid eggs have been used.

IA (Λ fig. 1) Wine to be stabilized after As a rinsing liquid used wine Content of before the treatment before entering after leaving treatment 730 mg / 1 the rinsing circuit the rinsing circuit 835 mg / 1 1900 mg / 1 835 mg / 1 930 mg / 1 potassium 2100 mg / 1 2500 mg / 1 2100 mg / 1 2320 mg / 1 Tartaric acid 2500 mg / 1 1750 mg / 1 2500 mg / 1 2490 mg / 1 Malic acid 1700 mg / 1 600 mg / 1 1700 mg / 1 1710 mg / 1 Lactic acid 700 mg / l 112 mg / i 700 mg / 1 670 mg I. fl. acid 128 mg / 1 3 mg / 1 128 mg / 1 145 mg / 1 total sulphurous acid 5 mg / 1 515 mg / 1 5 mg / 1 5 mg / 1 free sulphurous acid 414 mg / 1 163 mg /! 414 mg / 1 520 mg / 1 Potassium sulfate 172 mg / 1 7500 mg / 1 172 mg / 1 182 mg / 1 Phosphnt 7800 mg / 1 1780 mg / 1 7800 mg / 1 8020 mg / 1 Total acid 2140 mg / 1 24.3 ml η NaOH 2140 mg / 1 2520 mg / 1 ash 28.3 ml n NaOH 75.3 g / l 28.3 ml η NaOH 32.2 ml η NaOH Ash alkalinity 75.9 g / l 20.1 g / l 75.9 g / l 75.6 g / l alcohol 22.2 g / l 1.6 g / l 22.2 g / l 24.1 g / l whole extract 1.5 g / l 1.5 g / l 1.5 g / l Zi: ker

IB (Fig. 1) To be stabilized Wine As a rinsing liquid used wine Content of before the after before entering after leaving treatment treatment the flush cycle the flush cycle 1220 mg / i 815 mg / i 612rng / l iOis mg / 1 potassium 2800 mg / 1 1800 mg / 1 1120 mg / 1 2100 mg / l Tartaric acid 3800 mg / 1 3700 mg / 1 2100 mg / 1 2550 mg / l Malic acid 700 mg / 1 480 mg / 1 1520 mg / 1 1620 mg / l Lactic acid 450 mg / 1 390 mg / l 520 mg / 1 590 mg / 1 fl. acid 243 mg / l 172 mg / 1 178 mg / 1 250 mg / l total sulphurous acid 45 mg / 1 35 mg / 1 35 mg / 1 44 m ° /! free sulphurous acid 690 mg / 1 390 mg / l 570 mg / l 850 mg / 1 Potassium sulfate 198 mg / 1 147 mg / l 170 mg / 1 212 mg / l phosphate 6900 mg / l 6800 mg / 1 3800 mg / 1 3650 mg / 1 Total acid 1800 mg / 1 1300 mg / 1 2200 mg / 1 2650 mg / 1 ash 18 ml η NaOH 13 ml η NaOH 21 ml η NaOH ISmInNaOH Ash alkalinity 85.9 g / l 85.3 g / l 92.3 g / l 91.7 g / l alcohol 21.4 g / 1 19.9 g /! ! 9.8 g / l 21.2 g /! Total extract 1.7 g / l 1.7 g / l 2.4 g / l 2.3 g / l sugar

10

Il A (Fig. 2)

Come on To be stabilized
before the
treatment Grape must
after
treatment As a rinsing liquid in the anode compartment
used grape must
before entering after leaving
the rinsing circuit the rinsing circuit 965 mg / 1 1300 mg / 1 potassium 1420 mg / 1 1008 mg / 1 980 mg / 1 2880 mg / 1 3900 mg / 1 Tartaric acid 3500 mg / 1 2450 mg / 1 1920 mg / 1 4010 mg / 1 4900 mg / 1 Malic acid 4200 mg / 1 3750 mg / 1 3520 mg / 1 165 mg / 1 210 mg / 1 Lactic acid 200 mg / 1 180 mg / 1 160 mg / 1 220 mg / 1 180 mg / 1 fl. acid 210 mg / 1 205 mg / 1 200 mg / 1 - - total sulphurous acid - - - - free sulphurous acid - - - 260 mg / 1 170 mg /! Potassium sulfate 280 mg / 1 260 mg / 1 250 mg / 1 160 mg / 1 172 mg / 1 phosphate 147 mg / 1 140 mg / 1 158 mg / 1 5200 mg / 1 8900 mg / 1 Total acid 7200 mg / 1 7300 mg / 1 4020 mg / 1 2140 mg / 1 2540 mg / 1 ash 2680 mg / 1 2210 mg / 1 2020 mg / 1 24 ml η NaOH 24 mg η NaOH Ash alkalinity 27 ml n NaOH 18 ml η NaOH 21 ml η NaOH > 5g / l 5 g / l alcohol > 5g / l > 5 g / l > 5g / l 179 g / l 143 g / l Total extract 156 g / l 152 g / l 180 g / l 158 g / l 123 g / l sugar 132 g / l 131 g / l 158 g / l HB (Fig. 3) As a rinsing liquid in the cathode compartment
used grape must
before entering after leaving
the rinsing cycle the rinsing cycle Content of To be stabilized
before the
treatment Grape must
according to your
treatment 940 mg / 1 potassium 1380 mg / 1 1030 mg / 1 4200 mg / i Tartaric acid 2700 mg / i i 760 mg / i 5200 mg / 1 Malic acid 3400 mg / 1 2980 mg / 1 210 mg / 1 Lactic acid 180 mg / 1 170 mg / 1 170mg / l fl. acid 150 mg / 1 150 mg / l - total sulphurous acid - - - free sulphurous acid - - 180 mg / 1 Potassium sulfate 240 mg /! 210 mg / 1 175 mg / l phosphate 190 mg / 1 175 mg / 1 9800 mg / 1 Total acid 5400 mg / 1 5500 mg / 1 2100 mg / 1 ash 2620 mg / 1 2090 mg / 1 21 ml η NaOH Ash alkalinity 28 ml η NaOH 18 ml η NaOH 5 g / l alcohol 5 g / l 5 g / l 142 g / l Total extract 175 g / l 173 g / l 120 g / l sugar 1Sl σ / 1
οι- 152 g / 1

For this purpose 3 sheets of drawings

Claims (1)

The same problems arise as with wine and sparkling wine ο ι. also with grape juice. The grape juice contains ment claims: usually enough tartaric acid and potassium that Tartar is excreted, even if the grape process to stabilize wine tartar, 5 juice mostly over a longer period of time.
Applying grape must and grape juice As consumers use wines, sparkling wines and grape juices of electrodialysis, characterized by this, without requiring crystalline precipitates, are used in net, that as rinsing liquids in the anode and cellar economy, wine is unstable Cathode compartment Wine, grape must or grape-cooled in order to juice the excretion of the tartar different tartaric acid and potassium io speed. In general, the wine is used in Gehaites are used. an insulated cooling tank close to its freezer point cooled and stirred for several days at this temperature. If the cost of installing refrigeration 15 systems are avoided, the wine can also go through Carbonated snow by means of the so-called tartar Cold protection can be cooled. The cooling remains but an expensive measure. Besides the content of potassium, calcium and wine 20 acid are the alcohol content and the pH value for the Crystallization of wcinsicin is decisive. In scientific papers are curves for that Solution equilibrium has been established from which The subject of this invention is a method for determining whether the wine is tartar-stable Tartar stabilization of wine, grape must and »5 is when it is and when it is not. When on Grape juice using electrodialysis. Reason for the factors mentioned is determined that If the wine falls during or after fermentation, if the wine is unstable, it must be refrigerated. Frequently Traubii.most potassium bitartrate, also tartar gc- but when cooling it is found that it is long despite in crystalline form. The vulgar term of constant cooling is no longer tartar "Weinstein" was already known in ancient times. 30 is eliminated. This leads to the conclusion that besides the Potassium and tartaric acid ions are already mentioned in the juice as well as other factors that excretors contain ripe grapes. Influence the deposition of tartar,
The advice of potassium in wine is above all by the Formation of ethanol during fermentation causes, because tartar is formed by cooling the wine through In ethanol, tartar is much less soluble 35 stirring or pumping or moving it through than in water. Also the lowering of the temperature to inoculate the addition of tartar crystals. Despite the storage of the wine in the cellar and the biological measures of this kind, it happens that the wine's acidity decrease contributes to the deposition of tartar after bottling, nor tartar from. The latter causes an increase in pH, which separates in, i.e. is not tartar-stable.
Range below pH 3 is (at this pH value 40. Investigations have shown that this is the minimum of the solubility wedge of tartar). Delays the excretion of tartar and leads to a reduction in the solubility of the tartar, mainly due to polymeric and colioid substances leads. Conversely, the pH value is lowered and the condensed polyphenols in the wine occur during the precipitation of tartar, provided that it was previously below pH 3.5, which inhibits the crystallization. A change in pH 45 ken. can also be the reason for the fact that the cooling of the wine for the purpose of tartar mixing Stabilization of two wines that are individually stable to tartar does not always lead to the desired result Deposition of tartar occurs. Success; it is unsafe and costly. Potassium bitartrate and calcium tartrate easily form From the knowledge that polymeric substances the oversaturated solutions. The elimination of these salts 50 Delay or completely delay the elimination of tartaric acid from the wine therefore takes several months in preventing attempts have been made to add wines to wines Claim. The excretion of tartar from the polymeric substances against the oversaturated crystallization Solutions is particularly useful to stabilize tartaric acid. Since the year unpleasantly noticeable when the wine, like the 1956 it is known, polyuseefschaft the wine for this purpose In the case of consumer wines, the esters of tartaric acid are definitely lower, obtainable by heating waits and wishes to be filled with bottles of tartaric acid to 170 ° C in small quantities early on. Consumers reject wines with such exposure. After addition to wines, sects and grape divorces in the wine, although they are juicy in terms of health, the tartar excretion is mostly about are harmless, generally prevented for 9 months due to ignorance. Operations. ⁶ ° Other substances that may delay the In sparkling wine, in which the increase in the separation of tartar is known, the gum ethanol content in the second fermentation are the unstable and polymeric phosphates,
tat (tendency to separate out) of the dissolved tartar Another possibility, the excretion of can increase again, this has the unpleasant consequence of digesting tartar from tartar-unstable beverages the carbon dioxide, which prevents the separated 65, consists in the tartaric acid, the potassium Crystals of the tartar can easily give birth to and or remove both from it. One way that then suddenly changing the concentration of tartaric acid undesirably when opening the bottle consists in becomes free. the tartaric acid z. B. by adding calcium compounds