Use of silicate particles in beverage production
10182586 · 2019-01-22
Assignee
Inventors
Cpc classification
International classification
Abstract
The use of a material in the production of a beverage, wherein the material particles are added in the course of the production process to a starting material or an intermediate product of the beverage and are then separated off again prior to finishing of the beverage, wherein the particles of the material are characterized in that they at least partially comprise a silicate, wherein the silicate particles with respect to the total weight of the particles have a proportion of at least one metal ion in the range of between 1.5 and 30% by weight, wherein the at least one metal ion is selected from a metal ion of the elements La, Ce, Cu, Ag, Zn, Sn, Ca, Mg, Fe and Mn.
Claims
1. A method for brewing beer, wherein material particles are added in the course of the method to a mash comprising a fruit acid and are then separated off again prior to finishing of the beer, wherein the material particles comprise silicate particles and wherein the material particles comprise at least about 90 wt. % silicate, wherein the silicate comprises Ca.sup.2+ in the range of between 5% by weight and 30% by weight, and wherein the silicate particles are enriched at their surface with Ca.sup.2+ such that at least about 50 wt. % of the Ca.sup.2+ is located on the surface, and wherein the material particles are added to the mash in a range of about 80 g/hl to 120 g/hl.
2. The method for brewing beer as set forth in claim 1, wherein the silicate particles are comprised of at least 90 wt. % of a sheet silicate.
3. The method for brewing beer as set forth in claim 1, wherein the silicate particles are comprised of at least 90 wt. % of a montmorillonite clay.
4. The method for brewing beer as set forth in claim 1, wherein the silicate particles are comprised of at least 90 wt. % of bentonite.
5. The method for brewing beer as set forth in claim 1, wherein the silicate particles have a BET surface area in the range of between 5 and 850 m.sup.2/g.
6. The method for brewing beer as set forth in claim 1, wherein the silicate particles have a cation exchange capacity (CEC) of between 5 and 100 meq/100 g.
7. The method for brewing beer as set forth in claim 1, wherein the silicate particles with respect to the total weight of the particles have a proportion of Fe (II)<10% by weight.
8. The method for brewing beer as set forth in claim 1, wherein the silicate particles are added to the mash by way of a brewing water.
9. The method for brewing beer as set forth in claim 1, wherein the silicate particles are also added to a fermentation process.
10. The method for brewing beer as set forth in claim 1, wherein the silicate particles are at least partially separated off in a purifying step with spent malt.
11. The method for brewing beer as set forth in claim 1, wherein the silicate particles are also separated off in a filtering operation after a fermentation process.
12. The method for brewing beer as set forth in claim 2, wherein the silicate particles have a BET surface area in the range of between 5 and 850 m.sup.2/g.
13. The method for brewing beer as set forth in claim 2, wherein the silicate particles have a cation exchange capacity (CEC) of between 5 and 100 meq/100 g.
14. The method for brewing beer as set forth in claim 2, wherein the silicate particles with respect to the total weight of the particles have a proportion of Fe (II)<10% by weight.
15. The method for brewing beer as set forth in claim 3, wherein the silicate particles have a BET surface area in the range of between 5 and 850 m.sup.2/g.
16. The method for brewing beer as set forth in claim 3, wherein the silicate particles have a cation exchange capacity (CEC) of between 5 and 100 meq/100 g.
17. The method for brewing beer as set forth in claim 3, wherein the silicate particles with respect to the total weight of the particles have a proportion of Fe (II)<10% by weight.
18. The method for brewing beer as set forth in claim 1, wherein the fruit acid comprises oxalic acid.
Description
DESCRIPTION OF THE DRAWINGS
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DESCRIPTION OF THE INVENTION
(4) According to the invention that object is attained by the use of a particulate material in the production of a beverage, wherein the material particles are added in the course of the production process to a starting material or an intermediate product of the beverage and are then separated off again prior to finishing of the beverage, wherein the particles of the material are characterised in that they at least partially comprise a silicate, wherein the silicate particles with respect to the total weight of the particles have a proportion of at least one metal ion in the range of between 1.5 and 30% by weight, wherein the at least one metal ion is selected from a metal ion of the elements La, Ce, Cu, Ag, Zn, Sn, Ca, Mg, Fe and Mn.
(5) Preferably the proportion of the at least one metal ion with respect to the total weight of the particles is at least 2% by weight. Still more preferably the proportion of the at least one metal ion with respect to the total weight of the particles is at least 5% by weight. In particularly preferred embodiments the proportion of the at least one metal ion with respect to the total weight of the particles is at least 8% by weight. In particularly preferred embodiments the proportion of the at least one metal ion with respect to the total weight of the particles is at least 10% by weight. In certain embodiments the proportion of the at least one metal ion with respect to the total weight of the particles is even at least 15% by weight or indeed at least 20% by weight.
(6) In many embodiments it may be advantageous if the proportion of the at least one metal ion with respect to the total weight of the particles is less than 30% by weight. In certain embodiments the proportion of the at least one metal ion with respect to the total weight of the particles is limited to a maximum of 25% by weight or indeed only 20% by weight.
(7) Detection of the metal ion content of the particles according to the invention can be effected for example by atomic absorption spectrometry (AAS) or by mass spectrometry with inductively coupled plasma (ICP-MS).
(8) The present invention also embraces combinations which have two or more of the above-specified metal ions, with the proviso that at least one of the metal ions is contained with a minimum proportion in the above-specified ranges in the silicate particles and the sum of the two or more of the above-specified metal ions does not exceed the upper limits specified hereinbefore for the at least one metal ion contained in the particles.
(9) In preferred embodiments the at least one metal ion or at least one of the at least one metal ion is a divalent metal ion. In a special embodiment of the invention the at least one metal ion or at least one of the metal ions is Ca.sup.2+.
(10) Due to the silicate particles used according to the invention, unwanted surface-active constituents can be removed from the starting materials or intermediate products of beverages at a relatively low level of effort and inexpensively as those unwanted constituents are bound to the surfaces of the silicate particles so that by subsequent separation of the silicate particles in the course of the production process, the substances bound to the surfaces thereof are also removed without in that case markedly impairing the aroma profile of the product.
(11) In that way for example the hydrophobins which emerge in beer brewing, proteases and polar lipids can be removed, whereby one of the major causes of gushing can be eliminated.
(12) The advantage of using silicate particles with a proportion of at least one of the above-specified metal ions in the specified ranges is that in that way fruit acids which are unwanted in the end product or in the production process of beverages can be reduced or indeed completely removed with a relatively slight effort and inexpensively without in that respect noticeably impairing the aroma profile of the product as the fruit acids such as for example oxalic acid bind to the metal ions present in the silicate particles so that the fruit acids bound to the surfaces of the silicate particles can be removed in the course of the production process by subsequently separating off the silicate particles.
(13) Therefore for example when brewing beer the essential identified causes of gushing can be eliminated with the silicate particles according to the invention, namely a high oxalate content as well as surface-active hydrophobins and proteases.
(14) In contrast to the oxalate precipitation known from the state of the art with calcium chloride or calcium sulfate the silicate particles of the present invention also have the decisive advantage that the added particles can be removed completely again for example by filtration.
(15) Moreover, using the silicate particles according to the invention increases the pH value, thereby greatly reducing the solubility of the salts from the above-specified metals with fruit acids. Accordingly this promotes precipitation of the corresponding salts. Moreover the increase in the pH value is also advantageous in terms of protein aggregation.
(16) The term silicates is used in accordance with the present invention to denote polycondensates of ortho-silicic acid such as for example kieselsol and kieselguhr but also all silicate minerals such as for example nesosilicates, sorosilicates, cyclosilicates, chain and band silicates, sheet silicates, framework silicates and amorphous silicates.
(17) Preferably the silicate particles at least partially comprise a sheet silicate. Sheet silicates (also known as leaf or phyllo silicates) in accordance with the present invention are silicates whose silicate anions comprise layers of corner-linked SiO.sub.4 tetrahedra, wherein the layers are not linked together by way of further SiO bonds. According to the invention these embrace the silicate minerals of the mica, chlorite and serpentine group as well as kaolin and the sheet silicate clay minerals.
(18) In certain embodiments of the invention the silicate particles at least partially comprise a sheet silicate clay material. The sheet silicate clay materials include the minerals of the talc-pyrophyllite, the smectite, the vermicullite and the mica group. In still more specific embodiments of the invention the sheet silicate clay material is a mineral of the smectite group such as for example a montmorillonite, beidellite, nontronite, saponite or hectorite.
(19) In a preferred embodiment of the invention the silicate particles at least partially comprise a montmorillonite clay.
(20) In a particularly preferred embodiment the silicate particles at least partially comprise montmorillonite clay-bearing bentonite.
(21) The silicate particles used according to the invention are preferably in the form of a powder or granular material.
(22) The wording the silicate particles at least partially comprise includes in accordance with the present invention both those embodiments in which only a part of the particles of the particulate material are silicate particles which comprise the specified material, and also those embodiments in which all particles of the particulate material are silicate particles which consist of the specified material. In addition that expression in accordance with the present invention also embraces those embodiments in which all or only a part of the particles of the particulate material only in part or completely comprise the specified material. For example the present invention also embraces those embodiments in which the particles in relation to the total weight of the particles comprise the specified silicate material in respect of 70% by weight, 80% by weight, 85% by weight, 90% by weight, 92% by weight, 95% by weight, 98% by weight, 98.5% by weight, 99% by weight or 100% by weight.
(23) To achieve the above-described advantages of the silicate particles according to the invention with the specified proportions of at least one of the specified metal ions, in the case of the silicate particles which do not inherently involve those proportions the silicate particles are preferably enriched with at least one metal ion selected from a metal ion of the elements La, Ce, Cu, Ag, Zn, Sn, Ca, Mg, Fe, Mn and combinations thereof.
(24) In that respect the term enriched is used to denote increasing the proportion of the respective metal ion in relation to the proportion of the metal ion in the original silicate particle. If for example silicate particles which are formed by a bentonite inherently have a Ca content of 1% by weight with respect to the total weight of the particles, then an enriched silicate particle in accordance with the present invention occurs if with respect to the total weight of the particles there is an increase in the original Ca content of the silicate particles to over 1% by weight of Ca, like for example to 1.5% by weight of Ca.
(25) Preferably the silicate particles of the present invention are enriched in particular at their surface with at least one of the above-specified metal ions, wherein that enrichment results in silicate particles in which, with respect to the total proportion of the at least one metal ion, at least 50% by weight of that metal ion are on the surface. Preferably, with respect to the total proportion of the at least metal ion, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight or indeed at least 99% by weight are on the surface, wherein the proportion of the metal ion on the surface is particularly great preferably in the embodiments which have a relatively high total content of the respective metal ion.
(26) The silicate particles of the present invention, in particular due to the proportion thereof in respect of at least one of the specified metal ions in the specified ranges, in the form of crystallization seeds, induce the production of metal-fruit acid crystals like for example oxalate crystals. Those crystals grow very well and quickly on the silicate particles as the silicate particles of the present invention have a large surface area.
(27) To achieve a contact surface area which is as large as possible with the intermediate products or the starting materials to be processed certain embodiments of the silicate particles according to the invention have a BET surface area in the region of 5-850 m.sup.2/g. Preferably the BET surface area is >100 m.sup.2/g, still more preferably >250 m.sup.2/g and particularly preferably >500 m.sup.2/g, wherein determination of the BET surface area is effected by means of nitrogen adsorption at a temperature of 77 K in accordance with DIN ISO 9277:2003-05.
(28) In certain embodiments of the invention the silicate particles are characterised in that they have a cation exchange capacity (CEC) of between 5 and 100 meq/100 g, wherein the cation exchange capacity is effected in accordance with the method described by Dohrmann and Kaufhold in Determination of exchangeable calcium of calcareous and gypsiferous bentonites in the year 2010 in Clays and Clay Minerals Vol. 58, pages 513-522. Preferably the cation exchange capacity is <75 meq/100 g, still more preferably <60 meq/100 g.
(29) In certain embodiments of the invention the silicate particles are characterised in that the silicate particles with respect to the total weight of the particles have a proportion of Fe (II)<10% by weight. In preferred embodiments the silicate particles with respect to the total weight of the particles have a proportion of Fe (II)<1% by weight. Still more preferably the proportion of Fe (II) in the silicate particles with respect to the total weight of the particles is <1% by weight.
(30) The present invention also concerns a method of producing a beverage in which the silicate particles in accordance with the invention are added in the course of the production process to a starting material or an intermediate product of the beverage and are then separated off again prior to finishing the beverage.
(31) Examples of beverage production processes in which the silicate particles in accordance with the present invention are used are wine production, the production of fruit juices and brewing beer. In that respect the silicate particles according to the invention can be added in various phases of the production process to a starting material or an intermediate product of the beverage and then separated off again prior to finishing of the beverage, in which respect the time of the addition operation and the time of the subsequent separation operation depends on the respective beverage and the individual production process. The necessary dosages depend on the brewing water used and are in the region of between 80 and 120 g/hl of mash, preferably at 100 g/hl of mash.
(32) In a preferred beer brewing process in which silicate particles having the above-specified features are used the silicate particles of the invention are added to the mash. In a preferred embodiment the particles are added to the mash by way of the brewing water. In a specific embodiment the silicate particles are additionally also added to the fermentation process. In brewing beer the operation of separating off the silicate particles is preferably effected in the purifying operation together with the spent malt and/or in the filtering operation after the fermentation process.
(33) The use of the method according to the invention in beer brewing can already remove from the wort during the mash process the assumed causes of uncontrolled foaming of beer, namely high oxalate content and surface-active hydrophobins and proteases. The residual post-precipitation can be eliminated in the final yeast separation operation or filtration step.
(34) According to the invention the silicate particles are preferably introduced prior to or during the mash process. In the mash the silicate particles react with the oxalic acid present and the oxalic acid almost completely precipitates out as Ca oxalate bound to the silicate particles. In addition the silicate particles increase the pH value of the brewing water and thus reduce the solubility of calcium oxalate, which promotes the precipitation thereof. The precipitated oxalate can thus already be removed in the purifying operation together with the spent malts.
(35) Normally a brewing water in the pH range of between 5.2 and 5.4 is used for the mash. With the method proposed here the pH-value of the brewing water is increased to up to pH>5.8. That pH-value shift not only reduces the solubility of calcium oxalate but at the same time also reduces the aggregation of the 17 kD hydrophobin and thus overall the gushing potential. In addition hydrophobins and proteases are already reduced in the mash and are removed from the wort in the purifying operation (see
(36) The precipitated products are thus already almost completely removed for the major part in the purifying operation with the spent grain so that no additional method step is required.
(37) In addition there is also an entire series of further advantages in using the silicate particles according to the invention in beer brewing in comparison with the state of the art.
(38) Thus due to the difficult solubility of the substances used there is almost no mineral change in the beer and thus also no sensory impairment. In professional tasting sessions (the DLG (German Agricultural Society) system) the beers treated with the new method, in comparison with the conventionally treated beers, were even assessed as having higher drinkability.
(39) In addition the hop yields of the beers treated with the silicate particles according to the invention were about 8-10% higher than those of the standard beers. In the comparative tests better levels of foam stability could also be found. At the same time no reduction at all in the chemical-physical durability of the beers was found, and it was also not possible to find any yield worsening (extract) by virtue of the somewhat higher pH-value of the mash.
(40) Moreover the silicate particles according to the invention are in conformity with the German Purity Law in accordance with the Bavarian State Order of 1516.
(41) For the purposes of the original disclosure it is pointed out that all features as can be seen by a man skilled in the art from the present description, the Figures and the claims, even if they are described in specific terms only in connection with certain other features, can be combined both individually and also in any combinations with others of the features or groups of features disclosed here insofar as that has not been expressly excluded or technical aspects make such combinations impossible or meaningless. A comprehensive explicit representation of all conceivable combinations of features is dispensed with here only for the sake of brevity and readability of the description.
(42) It is further pointed out that it is self-evident to the man skilled in the art that the embodiments by way of example hereinafter only serve to set out by way of example the possible embodiments of the present invention, which are set forth as specific embodiments. The man skilled in the art will therefore readily understand that in addition all other embodiments having the features or combinations of features according to the invention as recited in the claims are within the scope of protection of the invention. The comprehensive explicit representation of all conceivable embodiments is dispensed with here only for the sake of brevity and readability of the description.
EXAMPLES
(43) 1. Investigation of Precipitation by Scanning Electron Microscopy (SEM)
(44) The growth of Ca-oxalate crystals on the surface of the silicate particles was investigated using SEM (see
(45) In detail
(46) left: Ca silicate particles based on pure silicate (silicic acid) prior to use, and
(47) right: growth of Ca oxalate on the surface of the particles after use.
(48) In detail
(49) left: Ca bentonite particles prior to use, and
(50) right: growth of Ca oxalate on the surface of the particles after use (white cross=Ca oxalate).
(51) 2. Hydrophobin Binding Activity to Silicate Particles
(52) The hydrophobin binding activity to silicate particles was investigated by means of SDS-PAGE. In that case, with a dosage of 100 g/hl, it was possible to achieve a depletion by <30%. Analysis was implemented with a hydrophobin cell extract from Fusarium fungi (
(53) The hydrophobin exhibits a band at about 17 kDa (left in
(54) In detail
(55) left: 1) marker 10 l, 2) hydrophobin (1:50) 6 l, 3) hydrophobin (1:20) 6 l, 4) wort 18 l, 5) beer 18 l, 6) marker 6 l
(56) right: 1) marker 5 l, 2)+3) hydrophobin-bearing beer, 3)+4) hydrophobin-bearing beer after silicate particle treatment.