JP2001506860A - Aggregated silica - Google Patents

Abstract

  (57) [Summary] Non-flyable silica agglomerates for use in stabilizing beer

Description

FIELD The present invention DETAILED DESCRIPTION OF THE INVENTION aggregated silica invention relates to a novel granular composition. In particular, the invention relates to agglomerated synthetic amorphous silica and its use in stabilizing fermented beverages against the development of haze during storage. BACKGROUND OF THE INVENTION Alcoholic fermented beverages, such as beer, tend to produce haze, which may be of biological or physical-chemical origin, and a number of products and methods have been used to remove haze-forming components. I have. The effects of gross haze are resolved by filtration, flocculation, or centrifugation, but due to the interaction of certain aggregated and precipitated polypeptides with polyphenols, secondary effects on storage can occur. Clouding occurs. Thus, this haze is only noticeable at those stages where the beverage cannot be manufactured for consumption and removal can be performed. Numerous organic and inorganic substances, such as tannic acid, polyvinylpyrrolidone, bentonite, activated carbon and silica, can be used to remove the polypeptide and polyphenol precursors prior to packaging and thus stabilize the beverage. Amorphous silica hydrogels and xerogels and mixtures thereof selectively remove polypeptide haze precursors without compromising properties such as body, scent, color, and head formation For example, Hough, JS, “Silica Hydrogels for Chill Proofing Beer”, MBAA Technical Quarterly, vol. 13, No 1, pp 34-39 (1976); Halcrow, RM, “Silica Hydrogels”, The Brewers Digest, pp 44 (1976, August) and Hough, JS and Lovell, AL, "Recent Developments in Silica Hydrogels, for the Treatment and Processing of Beers", MBAA Technical Quarterly vol. 16, No 2, pp 90-100 (1979 )reference. Amorphous silica hydrogel is a non-dispersible, easily handled powder. Amorphous silica xerogels, on the other hand, are effective beer stabilizers, but offer the problem of being extremely scattering and difficult to handle. An object of the present invention is to provide a silica gel having a low scattering property and a large stabilizing effect, which is used for stabilizing a beverage. The present invention relates to the treatment of beer including lager, Pilsner, Dortmund and Minato beers and top fermented beers such as ale, porter and stout. However, it may also be applied to other fermented liquids that tend to cloud on storage, as well as non-fermented beverages that can cloud on storage, such as fruit juices and iced tea. The known literature includes silicas in the form of hydrogels, xerogels and precipitated silicas and mixtures thereof, having a surface area of 200-1100 m ² / g, a pore volume of 0.35-2.5 cc / g and a pore volume of 3-30 microns. It has been shown that silica having a particle size of 10 removes protein from beer and can therefore be used to stabilize the beverage during storage against the formation of haze. In particular, GB (UK Patent) 1,215,928 discloses the use of silica hydrogels having a surface area of more than 700 m ² / g for treating beer. EP-A (European Patent Publication) 0683322, US-A (US Patent Publication) 4,515,821, EP-A 0287232, US-A 5,149,553 disclose the fine particle xylogel and precipitated silica have one significant disadvantage, That is, it has remarkable scattering properties when introduced into a supply device usually used in a brewery. Mixtures of silica hydrogel or hydrogel and xerogel containing 30-60 wt% of SiO ₂ is effectively is a non-friable, these materials are extremely cohesive property (cohesive), as a result, these Large volumes require specially designed equipment. The use of agglomeration to reduce the dispersibility of precipitated silica or siliceous materials is disclosed in US-A 3,646,183, US-A 4,336,219, GB-A (UK Patent Publication) 2,013,165, JP (Japan) No. 56314/1982, DE-A (German Patent Publication) 2,150,346 and DE-A 1,807,714, US-A 4,052,334, GB-A 1,543,576 and GB-A 1,365,516 . These materials have been used as rubber fillers or catalyst supports and as such do not have a suitable pore structure for use in beer stabilization applications. Use of the agglomerated silica for beer stabilization applications is not disclosed in the known literature. Standard Procedure The agglomerates of the invention and their constituent particles are defined by their physico-chemical properties. The test methods for determining these properties are as follows: i) Surface area and pore volume Surface area and pore volume were measured using an automatic BET specific surface area measurement device: Micromorphics ASAP 1400 using nitrogen. It was measured according to the BET method based on the adsorption of. The measurement was performed with reference to the following documents S. Brunauer, PH, Emmett and E. Teller, J. Am. Chem. Soc., 60, 309 (1938). The sample was degassed under vacuum at 270 ° C. for 1 hour and then measured at about −196 ° C. ii) Average pore diameter (MPD) The average pore diameter was calculated according to a cylindrical model using MPD = 4,000 × PV / SA nm. Here, PV is the pore volume (cc / g), and SA is the specific surface area (m ² / g) with respect to nitrogen as measured in (i) above. iii) Total moisture content The total moisture content was determined from the weight loss of the silica when ignited at 1000 ° C in a heating furnace to constant weight. iv) a weight average particle size (Weight Mean Particle Size) The weight average particle size of the silica prior to agglomeration Worcestershire, provided Malvern Instruments of Malvern location (Malvern Instrument) manufactured by, MS 15 samples exhibited device (sample presentation unit) It was measured using a Malvern mastersizer type X. This device uses the principle of Fraunhoffer diffraction utilizing a low power He / Ne laser. The particles are ultrasonically dispersed in water for 7 minutes to form an aqueous suspension, stirred mechanically, and then measured using the appropriate lens in the device described in the manual for the device. Was done. Malvern particle size measuring devices measure the weight particle size of particles. The weight average particle size (d50), the 50th percentile, the 10th percentile (d10) and the 90th percentile (d90) are readily obtained from the data generated. v) Stabilization of beer Protein in beer which precipitates in the presence of tannic acid, a so-called sensitive protein-see Chapon, L., J. Inst. Brew., vol. 99, 49 (1993)- Is considered to be the major polypeptide haze precursor. The desensitized protein content of the degassed beer was measured using a Tannometer supplied by the Bearwell International System at 125 St. Mary Road, Market Harborough, Leicestershire, UK. Measured. Measurements were taken from a 0.01% by weight tannic acid solution (Brewtan C, Omnichem n, v, Coppallaan 91, B9230, Betteren, Belgium, according to the haze generated in the EBC unit, Brewtan C, Belgium. Supplied at 25 ° C. The haze formed at an added tannin concentration of 10 mg / l was recorded. The results were expressed in percentage reduction in the haze value after beer was treated with 30 g / h1 silica and contacted overnight or for 10 minutes. vi) Cohesive strength Cohesive strength is manufactured by Misonics, Inc., Farmingdale, New York, and supplied in the UK by Labacaire System, Inc., Avon. Measurements were made using a Microson XL2020 Sonicator, a programmable ultrasonic liquid processor. The Microson XL2020 sonicator ultrasonic liquid processor has a maximum output of 550 watts with a 20kHz converter and has a 3/4 inch threaded horn. The processor has a variable amplitude controller and a microprocessor controlled digital timer integrated with a pulsar cycle timer with output and elapsed time display. Piezoelectric converters convert electrical energy to mechanical energy at a frequency of 20kHz. The vibration of the piezoelectric crystal is transmitted and concentrated by a titanium distortor horn, which releases energy to the liquid under test. The phenomenon known as cavitation, the formation and destruction of microscopic vapor bubbles generated by strong sound waves, produces shearing and tearing effects. Almost all activity occurs just before the probetip. The generator provides the energy of the high voltage pulse at 20 kHz and adjusts for varying loading conditions such as viscosity and temperature. The generator detects the change in impedance and automatically increases or decreases the power to the probe tip. The 3/4 inch probe is a medium strength horn for adjusting the volume from 25 to 500 ml. The maximum amplitude at the tip of this probe is 60 microns. Thus, a sonicator processor operating at an output control setting of 10 has an amplitude of 60 microns at the probe tip (peak-to-peak amplitude of the radiation surface of the tip). Thus, there is a linear relationship between the output control knob (or amplitude adjustment knob) and the amplitude at the tip of the probe, ie, 6 microns per control knob setting. Thus, the generator draws energy and maintains a constant amplitude at the tip for a given output control setting. This is the power displayed on the power% meter and expressed in watts (ie, power-% / 100 ^* 550 watts effective = X watts supplied). 9th Choonpakogyo Association Annual Technology Symposium in ^{(9 th Annual Technical Symposium of the} Ultrasonic Industy Association), "Applica-ion of Ultras onic Processors (Power vs intensity of in Sonification" S.Beline r Mr. entitled (Technical Services Heat Systems by ultrasonic published reports of Inc directors), 3/4 for more detailed information of the principles associated with this experimental technique is provided. adiabatically Pyrex beaker procedure 250 ml, adapt to the ultrasonic probe A lid with an inch hole in the center and a 1/8 inch hole on the side to fit the temperature probe was installed.To obtain a final weight of 200 g in the insulated beaker, the desired amount of water and The desired amount of inorganic particles was introduced, a magnetic stir bar was inserted into the beaker and the beaker was placed on a magnetic stirrer hot plate equipped with a temperature sensor [Ormo Scientific, Manchester; Obtained, placed on a Heidorph MR 3003 magnetic stirrer hot plate equipped with a stainless steel PT-100 temperature sensor and a rpm stirrer.The contents of the beaker were stirred at a set value of 3 (-300 rpm). The ultrasonic probe was immersed in the liquid to a depth of 5/8 inch and the temperature sensor was inserted into the liquid to constantly monitor the temperature.The sonicator ultrasonic processor was switched on and the process time and pulse mode were checked. The information was programmed as prescribed, cavitation was introduced into the system by changing the output control knob to the desired amplitude settig, while the temperature distribution was monitored closely, maintaining the amplitude at the tip. When the cavitation process was complete, the stirrer was switched off and the magnetic stirrer rod was removed. To retain the dispersed, and stirring was continued by hand using a spatula. +45 micron wet sieve test methods inorganic particle dispersion was poured through a 45 micron sieve. The residue in the beaker, half of the initial water The sieve was then dried to constant weight in an oven at 150 ° C. The residue remaining on the top of the 45 micron sieve was weighed and the original weight of the inorganic particles was determined. Expressed as% based on The greater the amount that remains on the sieve, the greater the cohesive strength of the particles and the more difficult it is to break the particles. The optimal product will have no residue on the sieve. For particles to be broken to a satisfactory degree in beverage applications, set at 10 (amplitude 60 microns), after sonication for 7 minutes, less than 5% weight residue on a +45 micron sieve, preferably Will remain in an amount of up to 2% by weight, most preferably up to 1% by weight. vii) Particle size distribution by sieve analysis An accurate measurement of the particle size distribution of the granular composition is performed using a sieve analysis. A 100 g sample was placed on top of a series of BS sieves with sieve spacing of about 50 microns to cover the entire size range of the granules. The finest sieves are arranged at the bottom of the superimposed sieve and the coarsest sieves are arranged at the top. The sieve was placed on a mechanical vibrator, for example, an Inclyno Mechanical Sieve Shaker manufactured by Pascall Engineering, covered with a lid, and vibrated for 10 minutes. The fraction of each sieve was accurately weighed and the result was calculated:% Residue = Weight of Residue / Weight of Sample × 100 Brief Description of the Invention According to the present invention, the fermented alcoholic beverage was prepared on a dry basis. A method for treating a fermented alcoholic beverage which is contacted with a granular composition containing 45-98% by weight of water-insoluble particles, wherein the water-insoluble particles are at least 75% by weight on a dry basis, preferably 90% by weight on a dry basis. % Or more are formed from amorphous silica having a weight average particle size of 5-30 microns, preferably 10-30 microns, a pore volume of 1 cc / g or more, and a pore diameter of 60 Å or more, and The composition is characterized by having a particle size such that at least 75%, preferably at least 95%, by weight of the granular composition has a particle size of 45 microns or more, as determined by dry sieving analysis. Beverage processing A method is provided. Preferably, the granular composition is sieved at 125-600 microns, such that at least 90% by weight of the granular composition has a particle size of 125-600 microns. The granular composition is less than 5% by weight, more preferably Less than 2% by weight, most preferably less than 1% by weight of the residue has a particle strength such that it remains on a 45 micron wet sieve after sonication at a set value of 10 (amplitude 60 microns) for 7 minutes. preferable. Also, it preferably has a total water content of 40% or less, preferably 30% or less, more preferably 20% or less. Amorphous silica that can be used in the present invention can be prepared via an acid gel route or an alkaline precipitation route. Specific Description of the Invention Examples of the preparation of agglomerated synthetic amorphous silica are illustrated below, but the invention is not limited by these examples. Preparation of agglomerates Silica gels having the properties shown in Table 1 were individually prepared in a 200 g powder batch size (laboratory scale) Silmon from Metcalfe Catering Equipment, Blaneau Ffestiniog, Wales. ) Agglomerated with deionized water using a CV6 mixer. The resulting wet agglomerates were then dried in an oven at 150 ° C. for 4 hours, gently passed through a 600 micron screen and sieved at 125 microns to collect a fraction greater than 125 microns. Agglomerates A to E were prepared by aggregating each of the silicas 1 to 5 by this method. Another method of preparing the agglomerates is to feed about 1 kg of silica powder from Alexanderwerk AG-D-42857, Remscheid-Kippdorfstasse 6-24, feed rate no. Dry compaction was performed using an Alexander Berg roller compactor WP50 / N75 set to. The strength of the agglomerates prepared in this way depends on the pressure applied to the rollers. The silica described in Table 1 as silica number 1 was agglomerated in this way at 15 bar (symbol F) and 50 bar (symbol G). Example H was also prepared in this way using silica number 1 silica, but was stiffer after multiple passes at 50 bar. The prepared agglomerates were classified and sieved as described for the wet process product. Cohesive strength The strength of the prepared aggregate was measured by the method described above. Table 2 shows these strengths as the energy required to reduce 50% of the structure to a size below 45 microns. The results in Table 2 show that a wide range of strength is obtained, and that this strength is a function of the physical properties of the silica particles forming the structure and the pressure applied to the agglomerator and the number of passes through the agglomerator. ing. Beer Stabilization Only flocculated silica having a flocculated particle size greater than 45 microns is effective in stabilizing beer if these are broken down to particles of 20 microns or less. The results shown in Table 3 for adjunct lager illustrate this effect. The effect on removing sensitive proteins from beer was measured before aggregation (ie, as large particle aggregates) of samples G and H and after de-agglomeration by dispersing in beer samples. Samples were prepared from common materials (ie, silica sample 1 in Table 1) under conditions set to induce various cohesive strengths. The results in Table 3 show that when aggregated to a large particle size, the stabilizing effect of silica is lost. Aggregate G has better performance than H because it has a weak structure (see Table 2) and is partially destroyed when added to beer. By applying a shear force to the system (ie, the magnetic stirrer bar), sample G is deagglomerated, so that the sample can again effectively remove proteins. The strength of Sample H is such that, when a gentle shear is applied, the shear is not sufficient to return to primary particles, and thus the protein before aggregation cannot be removed. Table 4 shows that for beers different from those tested in Table 3, applying sufficient energy (see Table 2) to reduce the agglomerates to small particle size induces the beer stabilizing performance of the particles before agglomeration. It is effective for Aggregate D (prepared from silica sample 4 in Table 1) does not have a suitable pore structure to stabilize the beer, ie, an average pore diameter of less than 60 Å and a pore size of less than 1 cm ³ / g. Due to their volume, they are poor stabilizers in both the pre-agglomerated form and the deagglomerated form. The remaining samples are all good stabilizers and recover their performance after deagglomeration. Table 1: Physical properties of silica before aggregation Table 2: aggregate intensity - energy for reducing 50% of the structure below 45 microns Table 3: Effect of particle size on removal of sensitive proteins Table 4: Beer stabilization-sensitive protein reduction%

────────────────────────────────────────────────── ─── Continuation of front page    (81) Designated countries EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, L U, MC, NL, PT, SE), OA (BF, BJ, CF) , CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (GH, KE, LS, MW, S D, SZ, UG, ZW), EA (AM, AZ, BY, KG) , KZ, MD, RU, TJ, TM), AL, AM, AT , AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, F I, GB, GE, GH, HU, ID, IL, IS, JP , KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, M W, MX, NO, NZ, PL, PT, RO, RU, SD , SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW

Claims (1)

[Claims]   1. Fermented alcoholic beverages contain 45-98% by weight water-insoluble particles on a dry basis A method for treating a fermented alcoholic beverage that is brought into contact with the granular composition More than 75% of insoluble particles on a dry basis have a weight average particle size of 5 to 30 microns and 1 cc / g or less. From amorphous silica with a pore volume above and a pore diameter greater than 60 angstroms Formed and the granular composition is determined by dry sieving analysis to determine the granular composition. Particle size should be such that at least 75% by weight of the powdery composition has a particle size of at least 45 microns. A method for treating a fermented alcoholic beverage, comprising:   2. 90% or more of the water-insoluble particles on a dry basis are formed from the amorphous silica. The method of claim 1, wherein   3. The amorphous silica has a weight average particle size of 10 to 30 microns. Is the method described in 2.   4. The particulate composition has a minimum of 95% by weight, measured by dry sieving analysis, of 45 microns or less. A particle according to any of claims 1, 2 or 3 having a particle size such that it has a particle size above. Method.   5. The particulate composition was sonicated for 7 minutes at a set point of 10 (amplitude 60 microns). Later, the particle strength is such that no more than 5% by weight of the residue remains on the 45 micron wet sieve. The method according to claim 1, wherein the method comprises:   6. The particulate composition was sonicated for 7 minutes at a set point of 10 (amplitude 60 microns). Later, the particle strength is such that no more than 2% by weight of the residue remains on the 45 micron wet sieve. The method according to claim 1, wherein the method comprises:   7. The particulate composition was sonicated for 7 minutes at a set point of 10 (amplitude 60 microns). Later, the particle strength is such that no more than 1% by weight of the residue remains on the 45 micron wet sieve. The method according to claim 1, wherein the method comprises:   8. 8. The method according to claim 1, wherein the particulate composition has a total water content of 40% or less. The method described in any of them.   9. 8. The method according to claim 1, wherein the particulate composition has a total water content of 30% or less. The method described in any of them.   Ten. 8. The method according to claim 1, wherein the particulate composition has a total water content of 20% or less. The method described in any of them.