DE1160812C2 - Process to increase the protein stability of beer - Google Patents

Description

The invention relates to a method for increasing the protein stability of beer.

Because of the German purity law Bentonif (aluminum silicate) is generally used here to improve the protein stability of beer of the Moatmorillonite type). 'For this purpose, the bentonite is in the to be stabilized Beer introduced, resulting in a very fine suspension with strong swelling. This The suspension cannot be filtered or is extremely difficult to filter. The removal of the bentonite " For this reason, the beer becomes through sedimentation achieved. To do this, the Bentonite® beer must go through its own process, the dam sees that in itself finished g & reifts beer an additional storage of Is subjected to 5 to 12 days, during which the Bentoaii then largely settles as a sediment. The overhanging clear beer is filtered and bottled. The bentonite sludge with the contained therein Beer mostly has to be discarded, especially because the beer cannot be recovered from it with safe means; came to be won. The resulting beer loss depends on the amount of bentonite and can be up to 6% and above.

The bentonite turns the beer into high molecular weight Removed protein substances, but not very selectively. The Beatonite doesn’t only bind that specifically responsible for the formation of cloudiness Protein. Rather, it also removes other protein substances from the beer, their presence in the beer from Reasons for foaming and also for full-bodiedness is quite desirable. So it happens that Bfere, because of special demands on the stability treated with higher amounts of bentonite. must (100 g / hl and more) in their foam retention They may also be essential in taste Exhibit changes to their disadvantage.

The treatment of beer with freshly precipitated silicic acid hydrate or with ■ preservation of the hydration character dried silica hydrate to increase the protein stability is also already known. The silica gels used in this procedure but proved to be compared to bentonite in terms of their protein-stabilizing effect inferior. Also taking into account the complexity of the procedure and the lack of purity of the law of rhyming led to the fact that the procedure was not used in practice. Attempts by the inventor with the silica gels prepared according to the known regulations led to unsatisfactory Results.

ίο It ist.bekannt that the adsorptive properties of silica depend on their physical and chemical <fine structure. This' fine structure depends on the production method of the silica gels and can vary within extremely wide limits.

The adsorptive properties thus naturally also vary, so that by no means any arbitrary Silica gel is suitable for protein adsorption from beer or has advantages over bentonite.

During the systematic investigation of silica gels of various types of production, showed that only very specific products are used for the adsorption of haze-forming proteins from beer These are so-called wide-pored silica gels in a very specific way Nature. Wide-pored silica gels per se have already been made using the aforementioned known method already used to increase the protein stability of beer.

The invention is therefore based on a method for increasing the protein stability of beer using wide-pored silica gel as adsorbent, which is characterized in that the beer is treated with a fine powdery, largely dehydrated and thus storable silica xerogel, which has a surface area of 200 to 400 m ² / g, a pore volume of more than 0.6 ml / g and a pore diameter of more than 60 Å.

Storable silica gels (xerogels) are those that do not change their volume when water is absorbed, so do not swell, do not shrink when water is released and where the absorption and release of the Capillary water is reversible.

Bs ha ^ i agreed that it should be done very carefully Washing 'such wide-pored silica succeeds in reducing its proportion of water-soluble substances to below 1%, so that from the point of view of the purity law there are no concerns about the Use of such silica gels for protein stabilization consist of beer. Careful washing of the white-pored silica gels is therefore a necessary prerequisite for carrying out the invention.

The production of such flexible silica gels is known. Wide-pore products can be obtained in the familiar way via the manufacture of Silicic acid products come from alkali silicate and acids. Likewise, one can also use silica precipitates that arise e.g. from the precipitation of silica with mineral acids, if while certain Kautelen are adhered to or if you use the silicic acid from alkali silicate Carbon dioxide falls. You can also use 'crystallized sodium metal! silicate with 40% sulfuric acid convert or digest other silicates with acids. But there are also many more Ways known (see Gmelins Handbook of Inorganic Chemistry, Vol. 15 B, Verlag Chemie, 1959),.

Such extensive pebbles show for the fi

white stabilization of beer has considerable advantages compared to the known bentonites. You own a particularly good and selective adsorption effect against the high molecular weight proteins of the beer, but there is also the advantage that the silica gel is always filtered, possibly with the per se known joint use of a filter aid »means, z. B. Kieselguhr or cellulose, can be removed from the beers can. The adsorption effect of a wide-pored silica gel is so good that, for example, when using 100 g / hl solion a few minutes exposure time is sufficient for extensive adsorption of the opacifying proteins to arrive. Naturally, the effect increases with a longer one A little more exposure time. But even then, there is no problem whatsoever to make filterability difficult Swelling of the silica gel, so that even if a silica gel sediment forms after a very long exposure time should have formed, this silica gel sediment can be filtered out completely without any loss of beer can. ■

A very substantial improvement in the adsorption effect or the increase in protein stability results if the silica gel of the inventive nature - regardless of how it was produced - is subjected to an additional acid treatment known per se after its wide-pored structure has been fixed. In principle, any strong acid is suitable for acid aftertreatment, but preference should be given to hydrochloric acid or nitric acid, because the last traces of these will evaporate after washing when the silica gel is finally dried. The effect of the acid increases with increasing concentration. The acid aftertreatment can be carried out either in the cold or in the warm. It is (bensmittelgesete Biersteuer- and L ©) with regard to the regulations in Germany of importance that the final products are so far free of excess acid, to have p-in a 5 ° / cent suspension in distilled water _H value of 5 to 7 have.

The advantage of the acid aftertreatment is that in addition to the well-known better washout effect with regard to water-soluble substances, a considerable improvement in the adsorptive properties, especially in terms of selectivity is achieved. The adsorption effect is also improved in quantitative terms, but this increase does not decrease as important as the selective improvement vity. The wide-pored character therefore apparently determines the amount of per weight unit Silica gel made from nitrogen bound by beer. The 'acid aftertreatment' causes the adsorbent in its effect bssondera is made selective, so that it specifically the protein substances binds, which is responsible for the protein cloudiness. and other proteins that are desirable in beer Beer leaves. ,

Comparative attempts with the erfindurtgsungsgem proposed Weitpodgen silica gels and with the known processes already mentioned above Already used to increase the protein stability of beer, while maintaining the hydration tract dried, granular silicic acid hydrates gave clear results. The cold cloudiness after the same storage times the beer was in consumption beer after treatment according to the procedure over four times as strong as after equivalent treatment with the same amount of the wide-pored silica gel. This was demonstrated in comparison with a wide-pored silica gel treated with acid aftertreatment beer even treated the same as the old process almost six times the cold cloudiness.

The following examples 1 to 3 provide more detailed information about these experiments:

Example!

It was bottled 12.5 ⁰ ZoIgCs consumption of beer in 1-1-Bierflascheii and cooled in ice water to 0 ° C. Graduated amounts of various silica gels described below were added to this beer. The samples were shaken vigorously and then remain in ice water for about 4 hours to allow the silica gel to sediment. All samples were then filtered in the same way at a room temperature of 2 ° C. through folded filters into other sample bags with a content of 0.351. This sample bottle, which all had the same empty space in the bottle neck of 10 ml, was then first placed for 4 days at 40 ° C. and then placed in melting ice for 24 hours. After 6 hours and after 24 hours, the increase in the relative turbidity was measured, which is to be regarded as a measure of the stabilization effect that had occurred. In addition, the ammonium sulfate precipitation limit was determined in the samples, which is also a measure of the stability of a beer. The results of this experiment are shown in Table 1 below.

Table 1

Ammonium suifate

Settlement Limit

Cold cloudiness

after

6 hours'

Ice .

24 hours

ice cream

Untreated, comparison beer ......

Pebble hedgehog B

0.25 g / l

"0.5 g / i .:

1.0 g / i

Silica gel ST

0.25 g / l

O ₅ S g / l

1.0 g / l

Pattern 1

1.0 g / l .- ;.

2.0 g / i

Pattern 2

1.0 g / l

2.0 g / l

Pattern 3

Oo 1.0 g / l

0.90 350 0.97
1.08
. 1.34 190
120 ■
90 1.15 ■
1.35
1.73 95
'70 - ·
65 0.95
1.07 230
200 0.96
■ 0.98 230
200 0.95
1.00 ' 370
180

560

320 240 170

130

370 310

380 310

480 360

The following different types of silica gels were used:.
6g - '
Silica gel B

Wide-pored ■ silica gel (hand ice product) with the following properties:

160 812

Inner surface (m ² / g) .. 300 to 350

Pore volume (cm ³ / g) 0.75 to 0.80

Mean pore diameter (Ä) 80 to 90

Bulk weight (kg / 1) ...... 0.38 to 0.42

Silica gel ST.

Wide-pored silica gel (commercial product) with the aforementioned properties treated with acid.

Pattern 1

From water glass 40 Be diluted with water 1: 1 by stirring and cooling Entry in 1: 1 concentrated hydrochloric acid diluted with water (in the ratio 2.8 parts of dilute waterglass solution to 1 part of dilute acid) obtained and with 25% Ammonia solution precipitated, granulated and dried at 100 ° C silica gel with the following Characteristics:

Inner surface (nWg) 136.3

Pore volume (cm ³ / g) 0.605

Mean pore diameter (A) ... 177.6

Bulk weight (kg / 1) 0.222

Pattern 2

From water glass diluted 1: 1 with water by adding it, with stirring, to 3η hydrochloric acid cooled in ice water (in the ratio 4.5 parts of dilute waterglass solution to 1 part of acid) obtained by adding 25% ammonia solution precipitated, granulated and dried in a warm air stream silica gel.

Pattern 3. "'

As in sample 2, but with 1.5N hydrochloric acid (in a ratio of 2.25 parts of dilute waterglass solution to 1 part acid) obtained, as in sample 2 precipitated with ammonia and dried Silica gel with the following properties:

inner surface (nWg) 125.7

Pore volume (cm ³ / g) 0.76

Mean pore diameter (Ä) .... 239.8

Bulk weight (kg / 1) 0.452

Example 2

The procedure indicated in Example 1 was followed, but a different beer was used. In contrast to In Example 1, the cold stability test was carried out after the samples had been stored at 40 ° C. for days. In addition, after this cold test, the samples were again kept at 40 ° C. for 4 days and then checked again for cold drag. The results can be found in Table 2 below.

Table 2

Ammonium sulphate precipitation limit First cold test
Turbidity after

hours
ice cream

24 hours

ice cream

Second cold test turbidity after

6 hours

ice cream

24 hours of ice

Untreated beer for comparison

Silica gel ST

0.25 g / l

0.5 g / l

1.0 g / l

Pattern 2

1.0 g / 1

2, OgA .....

Pattern 3

, 1.0 g / l

2.0 g / l

Pattern 5

1.0 g / l

2, OgA

Pattern 6

1, OgA

2.0 g / l

0.95

1.14 1.29 1.45

1.05 1.14

1.05

1.12

0.96 1.02

1.08 1.12 400

100
60
40

160
90

200
140

200
150

240
200

960

230

140

60

290
210

350
190

300
250

420
290

960

420
280
150

740
440

950
800

900
850

900
600

1950

950 840 350

1100 950

1800 1000

1700 1100

1800 1000

The following different types of silica gel were used:

Silica gel ST

As indicated in example 1.

Pattern 2

As indicated in example 1.

Pattern 3

As indicated in example 1.

Pattern 5. . .

One from sample 1 after suspending in distilled water (40 g of silica gel in 11) for 1 hour Shaking, suctioning off, shaking again for an hour in distilled water, suctioning off,

repeated shaking in distilled water and drying of the product then sucked off Silica gel obtained at 150 ° C. for 4 hours.

Pattern 6

One from sample 1 by stirring with nitric acid (40 g silica gel, 400 ml distilled water and 100 ml of concentrated nitric acid), left to stand overnight, followed by 3 hours Boiling, adding the batch to 5 liters of distilled water, after 3 hours of decanting, Silica gel obtained with suction, washing and drying for 4 hours at 150 ° C.

Example 3

This example was carried out with a third, also 12.5% consumer beer. It became like Worked described in the previous examples, but the filtered samples were first Maintained at 60 ° C. for 4 days before the cold stability was checked. After this test came the samples again for 5 days at 40 ° C, in order to be examined a second time for cold stability. the The results can be found in the table below. The types of silica gel used corresponded to used in example 2.

table

Ammonium sulphate precipitation limit First cold test
Turbidity after

24 hours

ice cream

6 hours of ice Second cold test, turbidity after

6 hours of ice

24 hours of ice

Untreated beer for comparison

Silica gel ST

0.25 g / l

0.5 g / l

1.0g / l

Pattern 2

1.0g / l

2.0 g / l

Pattern 3

1.0 g / l-

2.0 g / l

Pattern 5

2.0 g / l,

Pattern 6

2.0 g / l

0.90

1.23

1.41

1.67

1.09
1.23

1.09
1.26

1.05
1.15

1.03

1.23

160

50 40

35

300

75
50
40

130
60

125
70

160
110

170
100

850

290 260 100

500 400

650 300

900 500

750 450

1700

950 550 240

900 750

950 500

1100 900

900 850

Example 4

is, the more stable the beer and the more selective the silica gel was.

Using a wide pore silica gel and treated with acid according to the invention, according to the invention having a _pH value of 8.0 after its preparation and thorough washing in 5 ° / cent aqueous suspension, is reacted with 5 N nitric acid for 1 hour at 100 ° C held. The acid is then washed out and the preparation is dried at 200 ° C. for 6 hours. From this preparation treated with acid and also from the starting material, 0.5 g of 60 and 1.0 g are placed in 500 ml of carbonated beer and shaken for ^{1 hour.} It is then filtered and the total nitrogen is determined in the filtrate. Its reduction provides information about the adsorption effect in quantitative terms. In addition, the ammonium sulfate precipitation limit is determined in the filtrate. This test provides information about changes in the colloidal stability. The higher the value

1. Analysis criteria Total N. Ammonium 6o 2. sulfate-
precipitation 55 68.6 mg / 100 ml border 0.9 Untreated beer _fi ³ Untreated 65.2 mg / 100 ml ⁶ 5 Silica gel 63.7 mg / 100 ml 1.24 0.5 g / 500 ml 1.47 1.0g / 500ml Acid treated 64.9 mg / 100 ml Silica gel 63.2 mg / 100 ml 2.40 0.5 g / 500 ml 2.90 1.0 g / 500 ml

309-19 / 433

9
Example 5

Deployment of wide-pored and acid-treated silica gel according to the invention compared to FIG Bentonite.

a) Beer is made with 150 g / hl bentonite (on the registration date available under the trademark "Deglutan" from Protex). It stays for Sedimentation of the bentonite stand for 7 days at 0 ° C. After that, the protruding, largely Clarified beer nitrated and bottled.

b) The same beer is with 150 g / hl of one according to the invention wide-pored, acid-treated silica gel and after an exposure time filtered off from 5 minutes and bottled.

c) The beer used under a) and b) is nitrated and bottled without treatment.

Results of the analyzes 5 total N. a) b) c) (mg / 100 ml) Ammonium sulfate 60.6 66.6 71.0 * maturity limit ... Foam value 1.3 2.4 0.9 ₁₀ Cold haze 119 127 128 Turbidity after 0 0 450 Forced test on Protein stability .. 350 410 > 2000

This example shows that beers a) ¹ S and b) have approximately the same protein stability. When the beer was treated with wide-pore silica gel, the total N was only reduced by 4.4 mg / 100 ml, while 10.4 mg N was bound by the bentonite. Among the nitrogen substances bound by bentonite there are therefore very many substances that are not at all important for protein stability. As a result of this little selective effect of the bentonite also foam-promoting substances with bound obviously been what a 5 trächtlichen drop in foam number expressed in the be ^a.

Claims (2)

Patent claims: 1. A process for increasing the protein stability of beer using wide-pore silica gel as adsorbent, characterized in that the beer is treated with a finely powdered, largely dehydrated and thus storable silica xerogel which has an inner surface area of 200 to 400 m ² / g Pore volume of more than 0.6 ml / g and a pore diameter of more than 60 Å. 2. The method according to claim 1, characterized in that that a silica gel is used which is subjected to a known acid aftertreatment and the usual subsequent washing with water was carried out to such an extent that the dry product shows a pH of 5 to 7.0 in 5% suspension in distilled water.