DE1642767B - Adsorbents for fermented beverages - Google Patents

Description

that acid-treated minerals of the polyphosphoric acids-treated montmorin mines

Montmorin Group, e.g. B. bleaching earth, which comes from CaI-

Cium bentonite were produced, although free from tact.

Substances soluble in water, but that they are surprisingly under the attack the weakly acidic pH - as it is wine and s made that acidic digested, according to the invention Beer possess - considerable amounts of iron and treated with polyphosphates or polyphosphoric-aluminum give to the drink in question Possibly one of the reasons for the fact that there is over comparison products without this treatment acid activated bleaching earth for protein stabilization - also an improved protein stabilizing effect tion of wine and beer have not introduced io own. This effect is so good that it falls in In the case of beer, for example, in the beer z. B. compete with silica gel preparations all textbooks find information about which can and also do not harm sodium bentonite Influence the iron on the quality of the stand, but at the same time the initially geschil beer exercises. It promotes oxidation processes, the other advantages, namely those with the lack of swelling better technical handling associated with both the colloidal stability and the more palatable Have a negative impact on durability. Level.

It is so well known of the salts of aluminum that bleaching earth produced in the manner indicated has a precipitating effect on protein substances, and that more products can after the usual washing with them than is the case with other salts, due to the water either only strongly squeezed out or partially denied trivalent character of aluminum. ao or completely dried and then ground up For example, go from a good fuller's earth to be. The powdery product is in solution when used for no more than 0.1 to 0.2% if the beverage clarification is suspended in a small amount of water, a sample of which is suspended in distilled water. or drink and then this suspension. It is also found that practically no iron and added to the drink to be treated,
also no aluminum goes into solution. If you stir the 25 You can also add bleaching earth, which does not require grinding, in a buffer solution and bring the partially or completely dried material, which has the pH value of the beer, i.e. about 4.5, on the market in granular form. It then turns out that iron (Fe) alone has the advantage that under certain circumstances 0.2 ⁿ / o can go into solution during weighing. of the adsorbent in the brewery or wine-On the practical beer treatment with a wine press no strong dust formation occurs. If you transfer such fuller's earth, this means that you can then find the granular material with a little flux that ζ. B ,. when using 100 g of bleaching paste, and with the help of rapidly moving earth, the iron content of the beer per hectolitre of beer is finely reduced in the dispersing device. This may be increased by up to 2 mg per liter. Type of comminution leads to particularly fine Sus-AIs permissible limit for the iron content of beer 35 pensions, the adsorptive effectiveness of which is higher, but around 0.4 to 0.5 mg per liter are considered. than that of a comparative product, which is dried and analogous, the situation in the treatment of was dry-milled with the usual mills. Wine. Here, too, it is not desirable that additional The possibility of granular, dry pale iron comes into the drink. In the case of aluminum, the situation is similar. 40 Grinding with the help of a dispersing device. While high-quality bleaching earth products are used, the gentler the product, the better the fact that practically no aluminum has been dried in water beforehand - When the temperature is low (up to 150 ° C), such as wine or beer, notably much aluminum lends softer granules than if the minium amounts of the bleaching earth can be extracted very quickly and at very high temperatures. For example, you can find doors in the model test.

with buffer solutions or 0.5% malic acid, the adsorbent according to the invention can with

which, with their pH value in the range of wine, have other adsorbents or stabilization agents

and beer lie that up to 0.3 per cent of aluminum is combined in Löfahr. Its application can

sung can go. 50 at the end of the production process before filtration

According to the invention, the use of and filling will take place or, as required, with

acid activated montmorin minerals. after intermediate stages of the manufacturing process,
an acid digestion with aqueous or acidic

Solutions of polymeric phosphates or Polyphos- Example 1

is- 55

ssssr ^ isz sw »s ^ _T ^ _T

Recommended This treatment achieves only a small amount of iron and aluminum

that - depending on the concentration used - ^{weakly acidic flux fluids from} S ^lbs

the amount of 280 g Ca bentonite in the weakly acidic liquids from the camps near Moosburg

Soluble iron and aluminum on less than 60 in Bavaria are crushed and mixed with 11 water over

a fifth of the usual amount reduced overnight. Then 280 ml of concentrated

can be. Those with polyphosphate or poly- trated hydrochloric acid are added. It will take 6 hours

Phosphoric acid treated bleaching earths then have boils. After that, the approach is divided into two equal parts

no longer have the disadvantages outlined above when sharing.

Beverage treatment on. 65 A. Part A is placed on a suction filter, the

Preferably, the drinks are suctioned off with the sour final acid and then with a total of

activated, according to the invention with aqueous or 2 liters of tap water on the suction filter

acidic solutions of polymeric phosphates. or wash.

B, The other half is placed on the suction filter and the digestion acid is sucked off, now a solution of 2 g of sodium metaphosphate + 10 ml of concentrated hydrochloric acid in 200 ml of water are sucked through the filter cake. Then with 1800 ml of tap water washed,

Both filter cakes are dried then milled at 15O ⁰ C overnight and yield per xo about 100 g, based on this yield was therefore the use of sodium metaphosphate in batch B is about 2% of the dry substance of the treated clay,

Determination of soluble iron * 5

and soluble aluminum

1.5 g of the dried and ground products are dissolved in 15 ml of citric acid phosphate buffer, pH 4.5, according to Mc. Ilvaine, suspended and under ao Occasional shaking and left to stand for 1 day. It is then centrifuged off and that which has dissolved Iron determined colorimetrically.

Result: as

A. Blank sample without phosphate treatment:

2.0 mg Fe per gram dry matter = 0.2%.

B. Sample with phosphate treatment:

0.8 mg Fe per gram dry matter = 0.08%.

In an analogous manner, 15 g of the two test products are dissolved in 150 ml of 0.5% malic acid solution suspended for 1 day. Thereafter, the iron and aluminum dissolved in this substrate become definitely.

Result:

A. Blank sample without phosphate treatment:

Fe - 0.56 mg per gram of dry matter,
Al = 2.3 mg per gram of dry matter,

B, sample with phosphate treatment:

Fe = 0.17 mg per gram of dry matter,
Al => 1.2 mg per gram of dry matter.

Example 2

Beer stabilization with inventive,
acid activated bleaching earth

In a small trial, acid activated fuller's earth without phosphate treatment, acid activated fuller's earth with phosphate treatment (both test materials from Example 1) and, for comparison, finely ground silica gel are added to untreated bottled beer. Amounts are used that correspond to a dosage of 100 g per hectolitre. These amounts of adsorbent are put into the sample beer, which is kept ^{at 0 ° C. for 2 days after vigorous shaking.} The beer is then clarified by centrifugation and transferred to colorless sample bottles. This sample bottles are to accelerate the aging process for 3 days in an oven at 4O ⁰ C and then for 1 day in melting ice. The resulting cold cloudiness is measured with a measuring device and expressed in EBC units. The lower the measured turbidity, the better the stabilizing effect of the adsorbent. This experiment is carried out with four different, untreated, light full beers from Munich breweries. The result is shown in the table.

Bierl

Beer 2

Beer 3

Beer 4

100 g / hl acid activated fuller's earth without phosphate treatment

100 g / hl acid activated fuller's earth with phosphate treatment

100 g / hl finely ground, wide-pored silica gel

Comparative beer without additives, for example

11.8
6.5
8.4

30th

6.6
4.3

5.7
20th

11.5
8.5
6.9

30th

12th
9.2
7.4

30th

The above example shows that in all beers the acid activated bleaching earth, those with phosphate post-treated and thus considerably reduced in their iron and aluminum release to the beer was, had a much better stabilizing effect than the acid activated fuller's earth without Phosphate treatment. With beer 1 and 2, the stabilizing effect was even better than that of the comparative used silica gel. With beer 3 and 4, the stabilizing effect reached that of the silica gel not quite. If one looks at the arithmetic mean of the measured turbidity values, one finds that the acid activated and phosphate treated bleaching earth is about as effective as the silica gel.

Example 2a

Filtration behavior of inventive,
acid activated bleaching earth

A small-scale test is carried out in which the precoat filtration of beer on a small scale is carried out. A

60

65 glass apparatus is used, which has a filter area of 5 cm ² . On the sintered glass surface of this filter apparatus, a base coat of 0.5 g of "Standard Supercel" kieselguhr is first applied. 1 liter of beer, in which 0.7 g of the same kieselguhr and 0.5 g of bleaching earth or calcium bentonite had been suspended, is filtered under an overpressure of 0.5 atm. The beer was unfiltered light full beer from a Munich brewery. The test temperature was Ü ° C. The test conditions are therefore comparable with those in practice, both in terms of temperature and the amount and type of filter aids.

The stabilizing filter aids or acid activated bleaching earths according to the invention were used

dried, ground and sieved through a sieve of 0.1 mm mesh size calcium bentonite,

acid activated fuller's earth of Example 1, A, also dried, ground and thoroughly .0.1 mm sieved,

acid activated fuller's earth of Example 1, B, also dried, ground and thoroughly 0.1 mm sieved,

finely ground, wide-pored silica gel as in Example 2, also sieved through 0.1 mm.

In the present experiment, the time was stopped that was required for 600 ml of beer under the to filter specified conditions. The ammonium sulphate precipitation limit was used as a characteristic in the filtrate intended for the stability achieved.

Filtration time for 600 ml
(Seconds) Ammonium sulfate precipitation
limit (milliliters saturated
Ammonium sulfate solution
on 10 ml of beer) 1 liter of beer + 0.7 g of diatomaceous earth 2050 0.95 1 liter of beer + 0.7 g of diatomaceous earth
+ 05g calcium bentonite 2900 1.0 1 liter of beer + 0.7 g of diatomaceous earth
+ 0.5 g acid activated fuller's earth of example 1, A .. 1900 1.3 1 liter of beer + 0.7 g of diatomaceous earth
+ 0.5 g acid activated fuller's earth of example 1, B .. 1930 1.5 1 liter of beer + 0.7 g of diatomaceous earth
+ 0.5 g silica gel 2400 1.6

From the values in the table it can be seen that the calcium bentonite is essential for the filtration of the beer slowed down. In contrast, the filtration takes place in the presence of the two acid-activated bleaching earth products significantly faster than with the blind test. The acid activated fuller's earth can then So, as far as the filtration is concerned, can be used as a filter aid, at least for part of the filtration diatomaceous earth to replace. As far as the stabilizing effect is concerned, it can be seen that despite the short Contact time the two bleaching earth products resulted in a significant increase in the ammonium sulphate precipitation limit, wherein the inventive product 1, B due to the lower content of soluble iron has an improved stabilizing effect that almost reaches that of the wide-pored silica gel.

Example 3

Comminution of the acid activated fuller's earth produced according to the invention before use
for beer treatment

A batch according to Example 1, B is produced. After washing, the filter cake is divided into two parts

A. One half is dried at 200 ° C overnight, then ground and sieved. The part that goes through the 0.063 mm sieve is used for the beer stabilization test _go

B. It is also dried at 200 ° C. The resulting crumbs are for the Beer stabilization experiment crushed wet. To do this, 50 g with 100 ml of distilled water in minced in a blender for 10 minutes. After that, the whole thing is done with distilled water made up to 500 ml, so that there is a lOVoige suspension.

The sieved powder and the 10% suspension are used for beer treatment, with three Beers - according to Example 2 - are treated. 100 g of adsorbent are used (based on Dry matter) per hectolitre of beer. For comparison, the beer is also finely ground with 100 g per hectolitre Treated silica gel. In addition, it becomes a blank sample with no adsorbent treatment run along.

Result of the stabilization attempt

Beer 1 Beer 2 Beer 3 Acid activated fuller's earth as a powder 7.5 8.4 4.5 Acid activated fuller's earth Suspension, by wet grinding produced .. 6.2 6.4 3.0 Finely ground silica gel. 8.8 7.0 3.6 Blind sample, for example 30th 30th 20th

The above example again shows that the acidic activated fuller's earth produced according to the invention has a stabilizing effect in the powdery state that is of the order of magnitude of the finely ground silica gel. The suspension of the same prepared by wet milling The stabilizing effect of the material is significantly improved.

In the above experiment, the material intended for wet milling was dried relatively sharply, so that hard particles were formed. If the drying, as already stated in the description, had been carried out under gentle conditions carried out this would have produced softer granules, which are easier and faster to wet-grind is possible

Claims (4)

1 2 patent claims: if these difficulties are mastered in a suitable way of working, this remains a disadvantage of the 1. The use of acid activated trium bentonite still includes the fact that it is im Montmorin minerals that swell after a drink to be treated with acid with aqueous or acidic solutions of 5 neatly finely divided and not by filtration polymeric phosphates or polyphosphoric acids can be removed again. Rather, you have to treated as adsorbents fermented for a sedimentation period of several days Scheduling drinks, e.g. wine or beer, during which the protein 2. The use of an adsorbent charged sodium bentonite by itself by Sedinach claim 1, characterized in that io mentation deposited from the drink. There remains the Montmorin minerals before another but then still a quite respectable Sedi wash with water with the aqueous or acidic ment volume, from which the drink can practically not be recovered solutions of polymeric phosphates or poly-
phosphoric acids have been treated. The disadvantages outlined are the calcium 3. The use of an adsorbent 15 bentonite not so pronounced. This material swells according to claim 1 or 2, characterized in that it is not as strong as sodium bentonite. It can net, that the Montmorin minerals after the therefore possibly even with the aid Washing with water pressed or partially or of filter aids, such as. B. Kieselguhr, by FiI-completely dried and ground. tration can be removed from the drink. 4. The use of an adsorbent 20 When the sedimentation process takes place the natural according to one of claims 1 to 3, characterized in that separation by sedimentation takes place more rapidly. the indicates that the calcium bentonite dough causing the partial or complete dry beverage loss Montmorin mineral in granular form with mud is more compact. For this, the material is available as a little bit of water made into a paste and, by means of it, quickly, but overall considerably less effective, The running dispersing device is extremely fine. A disadvantage is the sodium and calcium concentrate has been. Bentonite added that both materials are Fresh additions of other minerals may contain their effect on quality The invention relates to an adsorption of the beverage to be treated under certain circumstances agent for the treatment of fermented beverages, 3 ° can be quite negative. z. B. wine or beer, based on sour active- Best suited for beverage treatment fourth Montmorin Minerals. would the acid treatment from Montmorin It is known that fermented beverages, such as wine, have mineral-derived modification. Such pro- and beer, after they have been bottled and dukte are under the name fuller's earth or fuller- have been preserved for some time, precipitates of 35 earth have long been known. It produces fuller's earth or proteinaceous substances. To do this to Fuller's earth usually by using the raw clay avoid, it has been customary for a long time to pre-swell this water and then boil it Drinks from a treatment with adsorbents with mineral acid disintegrates. After that, the to undergo. This ensures that the elicitation acid is removed and the digested clay with it white substances that would later lead to precipitation, 40 carefully washed out with water. It close removed from the drink. Drying and grinding. It has also long been known that acidic bleaching earths are cheap. They don't swell treated clay minerals with a complexing - when suspended in water. So you can the substance, e.g. a solution of polymeric phosphorus from a drink through filtration again very much phaten to move. 45 can be easily removed. You can get such angry The clay minerals are even supposed to act as filter aids from the fourth bleaching earth themselves various impurities, especially dye use, similar to how this z. B. with kieselguhr or substance-containing impurities, exempted and happens for cellulose powder. the use as fillers or coatings in paper In the German patent 682 788 the one or other products are improved (USA. - 5 ° set of acid activated bentonites (bleaching earth) Patent 2,180,742). has already been described. Practically introduced As an adsorbent for the aforementioned, however, this is not because the effectiveness of the non-purpose are silicates with a swellable lattice structure, pre-swelling, acid activated bleaching earth for the egg whipping been. Greater practical importance white adsorption is too low. The German patent have the minerals of the Montmoring group reached, 55 script 874 742 indicates the relation between Advor especially montmorillonite, beidellite and nontronite sorption effect for beverage treatment and Clay (also known as bentonite) and the hectorite swelling capacity of bentonite and recommends desTone, because of little or no swelling bentonite In the case of bentonites, two treatments with alkali salts occur naturally to make them swelling. Modifications, the so-called sodium acid activated bleaching earth, can be used for the Bentonite and the calcium bentonite. Both modi drink and especially beer treatment, however, Cations are used to treat beverages when they are used, e. B. according to the Austrian turns. The stronger effectiveness developed by the patent specification 249 611, with finely ground silica gel two modifications of sodium bentonite. He mixed up. but the disadvantage that it is not at all initially necessary it is as simple as placing it in the beverage to be treated, a beverage clarifying agent based on to be entered because, due to its strong swelling, it contains acidic activated minerals of the Montmorin group immediately leads to lump formation. But also when to manufacture. It is found quite surprising