DE2323487A1 - Beer stabilization by filtration - using silica-contg. hydrogel and silicic acid filler combination - Google Patents

Abstract

Beer is stabilized by treating simultaneously with a mixt. of 50-95 (70-90) wt. pts. hydrogel having a surface >300 m2/g and contg. 30-66 wt.% SiO2 and 5-50 (10-30) wt. pts. silicic acid filler having a surface of 50-300 (100-250) m2/g and contg. 85-95 wt.% SiO2. Hydrogel and filler may be ground together or separately and mixed homogeneously in a measuring device with kieselguhr, the other filter auxiliaries, water or beer. Filter life is prolonged by 35-40%. Beers are more brilliant and have higher cold- and long-term stability. Filter cake vol. is reduced by 30%.

Description

Method for stabilizing beer It is known that in beer the presence of polyphenols and proteins, the cold cloudiness and permanent cloudiness of the beer cause. The tendency to cloudiness in beers can already be reduced by reducing the protein content alone can be significantly reduced.

For removing protein - especially high-molecular protein - Silica is mainly made from beer in the form of hydrogels or in the more strongly dried form State used as so-called xerogels. After the numerous publications By stabilizing beer with silicic acids, their surfaces can reach 200 up to 1000 m2 / g, the pore volumes from o.35 to 1.8 ml / g and the most common pore diameters vary from 30 to 120 2. Judging from the literature, almost all are silica in the form of hydrogels or xerogels with an SiO2 content of 20 to almost 100 % in finely divided state usable for protein adsorption. In recent years Besides bentonites, mainly synthetic xerogels were used to stabilize beers the silica used. The use of finely ground xerogels had some major disadvantages. The entry into the dosing device caused a lot of dust nuisance and at higher dosages / hl, the filter performance decreased (hl / h), which was caused by a change in the cucumber combination and amount of gurgles / hl not balanced could be. These disadvantages would result from a coarser grinding of the xerogels can be reduced, but a better filter performance was with coarser xerogel only possible at the expense of the adsorption activity and capacity of the silica.

Silica hydrogels with about 30 to 60 wt.% SiO2 have the Advantage that these products practically do not generate dust and filter faster than finely ground xerogels with the same adsorption activity and capacity.

But also the silica hydrogels could not be used in terms of filtration fully satisfied because they made the filter too permeable for beer filtration. Absolutely shiny and stable beer could only be obtained if - in particular at dosages of more than 50 g hydrogel / hl beer - the amount of gurgles was greatly increased. This means, that - in contrast to the xerogels - when using silica hydrogels the more filter belt had to be pressed into the beer stream, the more silica hydrogel was used when a long storage stability of the beers was desired. this led to a much higher filter filter consumption with all of its economic Disadvantages. It was particularly disadvantageous that the trub volume of the filter was already was exhausted after a short downtime and the emptying and cleaning operations had to be carried out after half or 2/3 filter performance.

The precipitation of silicas from water glass or from aqueous Alkali silicate solutions and acids lead depending on the manufacturing conditions to so-called coherent or incoherent silica gels. The prototype for coherent Products is the silica gel and for incoherent silica the "filler" made of practical pure silica. Both types differ fundamentally in their physical properties Properties. The silicas produced as coherent products dry out very hard and abrasion-resistant xerogels. The surfaces - measured by N2 adsorption according to the BET method - are mostly over 350 m2 / g. The products are very porous and the pore volume is greater than 0.4 ml / g. The surface must be with these products primarily referred to as the "inner surface". The incoherent silicas dry to relatively soft agglomerates that are easy to crush very finely. The surface areas are rarely more than 250 m2 / g. The fine powders are practical non-porous, and the entire surface can be thought of as the outer surface. The differences shown are not complete, but are sufficient for understanding the terms "coherent" and "incoherent" silicas.

According to their different physical properties are the areas of application. The coherent silicas are popular because of their porosity and large surface areas are used as adsorbents, while the incoherent silicas among other things because of their good spreadability as fillers for e.g. rubber compounds, plastic products, Varnishes and paints, etc. find use.

The incoherent silicas with filler character are not yet been used for beer stabilization.

This is because the adsorption effect of the fillers - related on the SiO2 content - is relatively weak and because of their fineness they are too large Filtration technical difficulties would lead. Surprisingly, it was now found that combinations of silica hydrogels and silica fillers are ideally suited for the cold stabilization of the beers.

The invention relates to a method of production and use of beer stabilizers that increase the cold and long-term stability of the beers, on the basis of hydrogels over 300 m2 / g, (measured according to the BET method) thereby characterized that hydrogels with a surface area of over 300 m² / g and a SiO2 content of 30-66% by weight with active silicas - so-called fillers - which are at least have a surface area of 50 m2 / g and a maximum of about 300 m2 / g, in a ratio of 95 parts by weight of hydrogel and 5 parts by weight of fillers, up to 50 parts by weight Hydrogel and 50 parts by weight of fillers mixed homogeneously and for protein adsorption be added to the beer. Although the active silicas are only one on their own have relatively low protein adsorption, show the claimed combinations sometimes a higher or only a slightly smaller adsorption effect for protein products, determined according to the ammonium sulfate test, than that used for the combination pure silica hydrogel.

The fact that the silica mixtures with the same gurgeon amount and combination in the filter an ideal one Set up a room filter that is particularly shiny with the same filter performance (hl / m2 time) and provides stable beer and that the filter cake that builds up is about 30% less Owns volume. This is the very special advantage of the invention. The following Descriptions and tables illustrate these findings.

The adsorption activity and the technical filtration properties the starting materials and the mixtures were tested using the following methods: A) Determination of the adsorption activity with the help of the ammonium sulfate beer is decarbonised by filtration before treatment. Be from this beer 20 ml each pipetted into large test tubes. The beer samples are saturated with (NH4) 2S04 solution with a difference of 0.5 ml.

The amount of (NH4) 2SO4 solution that is added must be dosed in this way be that with the smallest amount the beer stays clear and that with the largest amount Amount of (NH4) 2S04 becomes cloudy. 20 minutes after the addition, the opacity becomes visible to the eye judged.

For measurements on the photometer, blank samples are required, the 20 ml of beer and the amount of least. Contain water, like the corresponding samples (NH4) 2SO4 solution contain. 50 minutes after adding the (NH4) 2S04 solution, when the final value the The extinction (E) is measured in the photometer with a 405 m filter. For this purpose, the samples are transferred to 2 cm cuvettes and the blank samples are first opened E = 0 set. Then the sample, which contains as much (NH4) 2SO solution as the blank sample contains water, placed in the beam path and the extinction directly read. For the next measurement, E = 0 is set again with the blank sample and then measured the sample again. This method that the increase in absorbance by measuring the (NH4) 2SO4 dosage, has shown that up to an extinction of o, llo the beer appears clear or opal to the eye. If the absorbance is greater than o, llo, the beer is called cloudy. The consumption of saturated (NH4) 2S04 solution can be determined graphically with an accuracy of 0.1 ml. The consumption in ml Saline solution plotted against absorbance. The intersection of the curve with the o, llo line indicates the consumption of saturated (NH4) 2S04 solution, which is necessary until the first cloudiness appears.

B) Carrying out the test filtration to determine the technical filtration Properties The test filtration is carried out with an overpressure of 0.5 atmospheres. A laboratory device from Seitz-Werke GmbH, Bad Kreuznach, is used for this.

40 g of beer clarifying agent are added to the ready-to-use filter is suspended in 2 1 water, via the filling opening, closes the filling opening and represents by means of Nitrogen or compressed air from a steel cylinder (with reducing valve and manometer) a constant overpressure of 0.5 atm.

The test filtration time is determined by looking at the onset of positive pressure starts a stopwatch. The filter is observed; just before the end of the filtration the filter drain is irregular. Shortly afterwards, the gas is clearly audible through the Blown drain. Now press the stopwatch. The time read is the Filtration time.

Investigation of the technical filtration properties and adsorption activity of silica hydrogel / filler mixtures without kieselguhr. Homogeneous mixtures were obtained from a silica hydrogel and an active silica after grinding of the individual products. Table 1 contains the results of the ammonium sulfate test and the technical filtration information, such as test filtration time, cake volume and cake starch.

Hydrogel 1: 450 m² / g, 46.0% by weight SiO2 filler I: 135 "94.1% by weight SiO2 Table 1 Samples (NH4) 2SO4 Diffe Test Filtra Cake Cake renz tion volume strength ml ml min./sec. cm³ mm O-beer, export 1.66 - - - -hydrogel 1: Filler I proportions 100 - 2.90 1.24 1! 58 "56.03 4.5 95: 5 2.79 1.13 5'40" 74.7 6 90: 10 2.72 1.06 8'13 "49.8 4 80: 20 2.80 1.14 26'51" 49.8 4 70: 30 2.69 1.03 37'43 "56.03 4.5 60:40 2.69 1.03 45'09" 68.48 5.5 50:50 2.57 0.97 58'02 "80.93 6.5 -: 100 2.81 1.15 157'0 "136.95 11 The numerical values make it clear that even without the use of a belt, the volumes of the mixtures pass through a minimum and illustrate through the test filtration times and the cake volume, that the pure filler I is unsuitable as a beer clarifier, although the filler I - based on the same weight - practically the same adsorption effect as owns the hydrogel.

Table 2 shows the values for the combination of hydrogel 2 with Filler II indicated.

Hydrogel 2: 550 m² / g, 34.1% by weight SiO2 filler II: 240 m² / g, 93.0 Wt.% SiO2.

Table 2 Samples (NH4) 2SO4 Diffe- Testfiltra- Cake- Cake restriction volume strength ml ml min./sec. cm³ mm O-beer, export 1.80 - - - -Hydrogel 2: filler II proportions 100: - 3.23 1.43 1'47 "56.0 4.5 95: 5 3.97 2.17 3'52" 68.5 5.5 90: 10 3.39 1.59 5'38 "49.8 4.0 80: 20 2.88 1.08 9'0" 56.0 4.5 70: 30 3.32 1.52 14'27 " 62.3 5.0 60:40 3.15 1.35 18'21 "80.9 6.5 50:50 3.11 1.31 19'45" 87.2 7.0 -: 100 2.90 1.10 78'11 "137.0 11.0 The mixture with a filler with a relatively large surface is particularly suitable for beer stabilization, because not only good filtration times and small cake volumes, but also better ones Adsorption values can be achieved than with pure hydrogel. This is all the more astonishing because the adsorption values for the pure filler are even lower than for the pure hydrogel.

In Table 3, the hydrogel 2 with a filler is of particular small surface combined.

With these mixtures, good filtration times are achieved in all areas and achieves small cake volumes in special mixing ratios. Since the adsorption values of the pure filler and also the mixtures with the hydrogel at ratios below 9o: 1o show significantly lower adsorption values than the pure hydrogel, Fillers with 50 m2 / g are not preferred products and also represent the lower limit for usability.

Hydrogel 2: 550 m² / g, 34.1% by weight SiO2 2 filler III: So m / g, 94.9 wt% SiO2. Table 3 Samples (NH4) 2SO4 Diffe- Testfiltra- Cake cake limit volume starch ml ml min./sec. cm³ mm O-beer, export 1.69 - - - -Hydrogel 2: Filler III proportions 100: - 3.52 1.83 1'50 "56.3 4.5 95: 5 3.52 1.83 3'10 "62.3 5.0 90:10 3.23 1.54 3'50" 49.8 4.0 80: 20 3.00 1.31 5'00 " 49.8 4.0 70: 30 3.01 1.32 5'40 "74.7 6.0 60: 40 2.79 1.10 4'36" 87.2 7.0 50: 50 3.08 1.39 6'24 "87.2 7.0 -: 100 2.22 0.53 8'15" 124.5 10.0 Of the The standard filtration test described above was carried out on 40 g of substance mixture fixed because with this amount in the experimental device with the usual fine-coarse-coarse beer stabilization mixtures a filter layer of lo - 13 mm is produced and this is also the average The filter cake layer is in a technical precoat filter during the Tool life between 2 cleaning operations builds up. Furthermore, through the comparison confirmed with practice that the filtration behavior of filter belts as well as their Mixtures can be accurately predicted by the test filtration time. the Test filtration method is so accurate and sensitive that even small differences in large-scale filtration behavior between e.g. 2 fine grains on the one hand or 2 coarse grains on the other hand and between their possible combinations with certainty can be foreseen.

In the following it is explained how with the help of the invention filtration technology Problems are solved.

With a current dosage of 70 g fine grains / hl, loo g coarse grains / hl and With 120 g of hydrogel, the beer was sufficiently cold-stable, but the gloss finish was not secured. It was registered as particularly disadvantageous that through the high dosages of Guren and beer stabilizers the filter service life greatly shortened. When the amount of Guru was reduced, the fineness of the beer when reducing the amount of hydrogel the stability was not enough off and when replacing the hydrogel with a xerogel, the output (hl / hour) of the filter considerably. The hydrogels in the range of 430 - 850 m2 / g and with SiO2 contents of 30-60% by weight behaved the same in terms of filtration. the The most varied of gher combinations led neither in terms of gloss fineness nor on the filter service life for better results.

The test filtration time of the operating mixture of gurs and hydrogel was 5'52 ", the cake thickness was lo mm and the cake volume was 124.5 ml. It had to be outside the known ways to find a way to reduce the cake volume, without affecting the filtration time, i.e. the filter performance and the fineness of gloss Surprisingly, the solution, which was satisfactory in all respects, was achieved the problems in that part of the hydrogel is covered by an active silica filler was replaced, as the test filtration times with 40 g mixture each show.

70 g fine grain / hl) the same for all examples.

loog Grobgur / hl Pass-through cake cake time volume strength min./sec. ml mm Example 1 120 g / hl hydrogel - 700 m² / g, 34% by weight SiO2 - 3'33 "115.3 9.5 105 g / hl hydrogel 15 g / hl filler 5'43" 87.2 7.0 700 m² / g, 34 % By weight SiO2, 135 m² / g, 93.5% SiO2 Example 2 120 g / hl hydrogel - 450 m² / g, 46% by weight SiO2 - 3'55 "130.7 10.5 105 g / hl hydrogel 15 g filler 6'00" 87.2 7.0 450 m² / g, 46% by weight SiO2 190 m² / g, 92.7% SiO2 Example 3 120 g / hl hydrogel - 450 m² / g, 32 % By weight SiO2 - 3'52 "115.3 9.5 105 g / hl hydrogel 15 g filler 5'46" 80.9 6.5 450 m² / g, 32% by weight SiO2, 130 m² / g, 93.8% SiO2 Example 4 120 g / hl hydrogel - 462 m² / g, 60% by weight SiO2 - 5'28 "115.3 9.5 96 g / hl hydrogel 24 g / hl filler 6'47" 87.2 7.0 462 m² / g, 60% by weight SiO2, 130 m² / g, 93.8% SiO2 Pass-through cake Cake difference time volume strength (NH4) 2SO4) min./sec. ml mm ml Example 5 With 120 g mixture / hl of hydrogel and filler 450 m² / g, 46% SiO2 130 m² / g, 93.8% SiO2 proportions 98: 2 4'37 "124.5 10 -96: 4 4'44" 124.5 10 -90: 10 503 "87.2 7 0.80 80:20 6'00 "87.2 7 1.12 70: 30 5'59" 80.9 6.5 1.00 60:40 7'26 "80.9 6.5 0.70 50: 50 8'00 "80.9 6.5 0.85 Example 6 120 g / hl hydrogel - 450 m² / g, 32% by weight SiO2 - 3'52 "115.3 9.5 108 g / hl hydrogel 22 g filler 5'38" 87.2 7.0 450 m² / g, 32 wt% SiO2, 55m² / g, 94.7% SiO2 Those determined in the laboratory test Data have not only been confirmed in practice, but the results are Better in terms of filter cake volume and beer stability. So could with a hydrogel / filler combination in a ratio of 85:15, the filter service life can be increased from 700 hl to 100 hl and the medium and long-term stability of this Beers were significantly higher than the beers stabilized with 120 g / hl hydrogel.

Even if in this filtration process with 70 g fine grain and loo g Grobgur / hl was dosed, filtergur was still saved because the Gur could be used for the pre-flooding for an additional 400 hl of beer. With the same filter performance (hl / hour), the mixture produced beers with a higher gloss fineness achieved. This is not only important for the subjective view of the Consumer, but still relieves the downstream layers to a considerable extent in the disinfection filter.

In principle, it is also possible to use the Saving hydrogel / filler mixture during the ongoing dosing of filter belt. Furthermore, the method according to the invention can be modified by including small Amounts of fillers are added to the filter belt during beer filtration, if the Filtration is carried out without stabilizing agents based on hydrogels.

This can be beneficial in cases where it is difficult to filter Beers require an exceptionally high gourdosage.

In summary, the use of the silica hydrogel / filler mixtures results the following advantages: Extension of the filter service life by 35 - 40%, reduction the consumption of gurgles during precoating and ongoing dosing, finer shine Beers and beers with high cold and long-term stability.

Claims (5)

Claims Process for stabilizing beer by treatment with hydrogels the silica, characterized in that the beer is simultaneously with one Mixture of 50 to 95 parts by weight of a hydrogel with a surface area over 300 m2 / g and an SiO2 content of 30 to 66 percent by weight, and 5 to 50 parts by weight a silica filler with a surface area of 50 to 300 m2 / g and an SiO2 content treated from 85 to 95 percent by weight. 2. The method according to claim 1, characterized in that the silica filler has a surface area of 100 to 250 m2 / g. 3. The method according to claim 1 or 2, characterized in that mixtures from 70 to 90 parts by weight of the hydrogel and lo to 30 parts by weight of the silica filler be used. 4. The method according to claim 1 to 3, characterized in that the The hydrogel and the filler are ground together. 5. The method according to claim 1 to 4, characterized in that the The hydrogel and the filler are ground separately and placed in the dosing device with the Gur and other filter aids can be mixed homogeneously together with water or beer.