Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
  • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12H—PASTEURISATION, STERILISATION, PRESERVATION, PURIFICATION, CLARIFICATION OR AGEING OF ALCOHOLIC BEVERAGES; METHODS FOR ALTERING THE ALCOHOL CONTENT OF FERMENTED SOLUTIONS OR ALCOHOLIC BEVERAGES
  • C12H1/00—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages
  • C12H1/02—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material
  • C12H1/04—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material
  • C12H1/0408—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material with the aid of inorganic added material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2220/00—Aspects relating to sorbent materials
  • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
  • B01J2220/46—Materials comprising a mixture of inorganic and organic materials

Definitions

• the present invention pertains to adsorbents having low beverage soluble iron content in beverages, such as beer.
• U.S. Patent 4,134,857 to Bradley discloses reducing the BSI by washing a filter aid such as diatomite with an aqueous solution of tannic or gallic acid or mixtures thereof, with the aid of citric acid for color control.
• the present invention provides an adsorbent having a low beverage soluble iron (BSI) content for use in the removal of certain components from a bevera'ge to reduce chill haze.
• the adsorbent is made by introducing a polyphosphate sequestering agent during the production of the adsorbent.
• the process involves contacting a polyphosphate sequestering agent, such as sodium tripolyphosphate, with a reactant of a silica gel or a wash solution containing a precursor of the silica gel, or both.
• the reactant may be a sodium or potassium silicate solution used in conjunction with a mineral acid to make a silica hydrogel.
• FIG. 1 is a schematic view of a first embodiment of a process for making an adsorbent according to the present invention.
• FIG. 2 is a schematic view of a second embodiment of a process for making an adsorbent according to the present invention.
• the present invention relates to a process and composition for removing contaminants and preventing chill haze formation in beverages, while minimizing the leaching of iron from the adsorbent to the beverage.
• the term "beverage” is intended to encompass all beverages which include certain proteins which, if left in the beverage, tend to form haze upon chilling but can be adsorbed by the present invention.
• Such beverages include a number of vegetable based or malt based beverages, such as beer, ale, and wine, and fruit juices.
• the present invention is particularly applicable to beer, including lager, Pilsner, Kunststoff beers and ale, porter, and stout.
• removing as in "removing components from a beverage” implies removing at least some percentage of selected components, such as the proteins which cause chill haze, but does not necessarily contemplate removing one hundred percent of any of these components. In some cases, however, a component may be removed to such an extent that it cannot be detected by known quantitative analysis procedures.
• a polyphosphate sequestering agent is a compound which includes the anion P n 0 3n+1 and is capable of sequestering cations, most notably in this case the ferric or ferrous cation.
• the polyphosphate sequestering agent may include an alkali or alkaline earth metal in its formulation. It has been found that sodium tripolyphosphate, Na 5 P 3 O ⁇ o, is suitable for purposes of the present invention. Methods of making the adsorbent of the present invention are discussed in connection with Figs. 1 and 2.
• these methods involve first contacting a polyphosphate sequestering agent with a reactant of the silica gel or a wash solution containing a precursor of the silica gel (or a combination of both), then forming the silica gel adsorbent from the precursor.
• a reactant of the silica gel may include a starting material which undergoes a chemical reaction with another starting material to form a precursor of the silica gel.
• Reactants include sodium or potassium silicate solutions which, when combined with an acid and forced through a jet nozzle under certain conditions, form a hydrogel.
• a precursor is a material which has substantially the same chemical composition as the final silica gel, but may undergo some physical changes, such as changes in porosimetry properties, changes in moisture content, or a physical retention of another compound within its pores.
• Forming is done by conventional means and includes any hydrothermal treatment (although not done in the examples discussed below), washing, milling, and drying, as discussed below.
• a polyphosphate sequestering agent such as sodium tripolyphosphate (STPP)
• STPP sodium tripolyphosphate
• the sequestering agent source 104 may provide a solution of STPP dissolved in water. This solution combines with either the potassium or sodium silicate provided from the silicate source 102 to form STPP-doped silicate mixture in a mixer 106.
• the STPP-doped silicate mixture is mixed for a sufficient period of time to achieve adequate mixing, such as between 2-6 hours, although this may vary dependent upon other factors.
• the amount of polyphosphate sequestering agent to be added depends on the iron content of the silicate, which can be determined by conventional quantitative analysis techniques.
• the sodium tripolyphosphate may be added to the sodium or potassium silicate solution in an amount to achieve a sodium tripolyphosphate ⁇ ron molar ratio of between about 0.5:1 and 50:1, preferably between about 5:1 and 10:1.
• the silica gel is formed by neutralizing the STPP-doped silicate mixture with an acid, such as a mineral acid. Sulfuric acid is used in the examples below.
• an acid such as a mineral acid. Sulfuric acid is used in the examples below.
• the production of the silica gel adsorbent containing the STPP component can be effected in any known manner for making conventional silica gel adsorbents.
• an acid source 100 may be used to supply an acid which is combined with the STPP-doped silicate mixture to form a hydrosol.
• silica hydrosols are formed by rapidly mixing aqueous solutions of an acid and sodium or potassium silicate. It has been found advantageous in this invention to adjust the concentrations and flow rates or proportions of the reactants so that the hydrosol contains between about 5-30% Si0 2 by weight, preferably between 10 to 20% Si0 2 by weight.
• the hydrogel is allowed to age on the belt, for a sufficient period of time for the hydrogel to become firm for further processing.
• the hydrosol contains about 18% Si0 2 , has a pH below about 1, and gels in a matter of a few minutes. Such a hydrosol forms beads on the belt 109.
• a reactant such as sodium or potassium silicate from silicate source 200 is mixed with an acid from acid source 202.
• This mixture is forced through a nozzle 203 to form a hydrosol which sets into a hydrogel 204, all in a known way, typically on a belt or container 205.
• the hydrogel is then aged, as described above, and directed to a washer 208. All of the relative concentrations are the same as in the embodiment shown in Fig. 1, except that the flow rates of the reactants are adjusted such that about 15-20% Si0 2 is present in the hydrosol.
• washer 208 contains an acidified mixture of water and the polyphosphate sequestering agent from unit 206.
• the polyphosphate compound may be STPP.
• the sodium tripolyphosphate may be added to the acidified mixture in an amount to achieve a concentration sufficient to reduce the amount of BSI to an acceptable level.
• concentration of the polyphosphate sequestering agent will depend on the amount of iron in wash water 208 (including both on the silica gel and in the acidified water), among other factors. In an embodiment of the invention, the concentration is between 0.01 and 1 weight percent sodium tripolyphosphate based on sodium silicate, preferably between 0.05 and 0.5 weight percent.
• the amount of STPP to be added may be accomplished by determining the moles of iron in the initial hydrogel.
• the moles of STPP i.e., the total amount of STPP used during the washing step
• the moles of iron is adjusted to the moles of iron to range from 5 : 1 to 20 : 1.
• the acidified mixture may be prepared by first dissolving STPP in water, with an STPP level of anywhere between 10 - 800 ppm, preferably between about 100-400 ppm (although this concentration may vary as mentioned above on the basis of either the silicate or the iron in the hydrogel), and then adjusting the pH of the solution to between 2.5 and 4.0, preferably 3.3 and 3.5, by using sulfuric acid.
• the silica gel is formed by washing the hydrogel 204 with the sequestering agent mixture.
• the washed hydrogel then enters the milling unit 210 and finally the packaging unit 214.
• the embodiment shown in Fig. 2 appears to achieve the best results with respect to the reduction of both the total iron content and the beverage soluble iron content of the adsorbent.
• An adsorbent combining the features of the embodiments shown in Figs 1 and 2 may also be made.
• an STPP-doped silicate solution may be used to form the hydrogel which may be washed with STPP-doped was water. It is believed that a silica gel having a wide range of porosimetry properties can be used with the present invention.
• a silica hydrogel having a pore volume of between about 1.5 to 2.5 cc/g; an average pore diameter of between about 75 and 125 Angstroms; a surface area of between about 750-850 m /g; and a moisture content of about 60-70% H 2 0 has been found to be suitable.
• the invention is also applicable to xerogels that have undergone hydrothermal treatment (described below) to reduce the surface area, after being washed with STPP-doped water. Such xerogels may have a pore volume of between about 1.0 to 1.4 cc/g; an average pore diameter of between about 75 and 125 Angstroms; and a surface area of between about 250-450 m 2 /g.
• silica gels are well-known in the art. For example, exposing the silica gel to elevated temperatures at alkaline pH leads to a rearrangement of the gel structure; surface area is reduced and the mean pore diameter of the final product is increased. This process is known in the art as "hydrothermal treatment.” An acid-set gel needs to be adjusted to alkaline or neutral pH for this to occur. Drying conditions will also affect porosimetry properties; rapid drying tends to result in higher pore volumes. The silica content of the hydrosol also affects porosimetry. All of these effects are well-known to those skilled in the art and are described in many publications and patents.
• the adsorbent is used in a process for removing components from a beverage to reduce chill haze, while having a relatively low BSI.
• the term "low BSI" is relative to the BSI of an adsorbent made by an identical process except for no exposure to a polyphosphate sequestering agent.
• the adsorbent of the present invention may have a BSI less than 50% of the BSI of a comparative adsorbent, and preferably less than 25%, most preferably less than 10%, of a comparative adsorbent.
• the process for removing contaminants is accomplished by simply contacting the adsorbent of the present invention with the beverage, preferably in a manner which facilitates the adsorption, in a conventional manner.
• the adsorption step may be any convenient batch or continuous process. In any case, agitation or other mixing will enhance the adsorption efficiency of the adsorbent.
• the adsorbent of the present invention is an adsorbent comprising a silica component and a polyphosphate sequestering agent component. It is believed that the polyphosphate sequestering agent chemically bonds to the silica gel in the embodiment shown in Fig. 1, while it is merely physically retained in the pores of the silica gel in the embodiment shown in Fig. 2. Thus, in the former case, the silica gel and polyphosphate sequestering agent might alter one another somewhat; thus, in the final product they are referred to as a silica gel "component” and a polyphosphate sequestering agent "component.” In the latter embodiment, however, it is believed that the two constituents do not undergo any chemical interaction.
• the iron level in the gels represents the total iron (Fe). Both the total iron and the beverage soluble iron (BSI) were measured by atomic absorption (AA). Sample 1 had a total iron content of 83 ppm and BSI content of 2.4 ppm, while Control 1 had a total iron content of 27 ppm and a BSI content of 7 ppm.
• Sample 2 had a total iron content of 54 ppm and a BSI content of 3.6 ppm, while Control 2 had a total iron content of 38 ppm and a BSI content of 14.6 ppm.
• the same unwashed silica hydrogel of Example 3 was used.
• the STPP-doped acid water wash solution was prepared by first adjusting the pH of the solution to 3.5, and then dissolving STPP in the acid water, with an STPP level of 200 ppm on the basis of water The proportions of gel and wash water were adjusted so that the total amount of STPP used was equivalent to 0.5 wt.% on the basis of sodium silicate
• the silica gel produced under these conditions is designated as Sample 4 on Table 1.
• Sample 4 had a total iron content of 6.5 ppm and the BSI content was undetectable by atomic adsorption (AA).
• Control 4 had a total iron content of 20 ppm and a BSI content of 5 ppm
• an adsorbent's BSI was determined in accordance with procedure No. Q 2 01.004, revision April 26, 1994, from the American Society of Brewing Chemist Methods, Filter A ⁇ ds-4 and Beer-18B, incorporated herein by reference.
• this procedure involves suspending a sample of the adsorbent m decarbonated beer for a specified time and then separating by filtration. The beer filtrate is collected and analyzed by atomic adsorption spectroscopy by the method of standard additions. Then, the iron content of the untreated beer is subtracted from the iron content of the treated beer, with the difference being multiplied by a factor, and the product being reported as beer soluble iron expressed in ppm.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Analytical Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Food Science & Technology (AREA)
• Biochemistry (AREA)
• Bioinformatics & Cheminformatics (AREA)
• General Engineering & Computer Science (AREA)
• General Health & Medical Sciences (AREA)
• Genetics & Genomics (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Distillation Of Fermentation Liquor, Processing Of Alcohols, Vinegar And Beer (AREA)
• Silicon Compounds (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)

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• 2001
  • 2001-01-12 US US09/760,353 patent/US6555151B2/en not_active Expired - Lifetime
• 2002
  • 2002-01-14 EP EP02701048A patent/EP1385620A2/en not_active Withdrawn
  • 2002-01-14 AU AU2002234246A patent/AU2002234246A1/en not_active Abandoned
  • 2002-01-14 KR KR10-2003-7009304A patent/KR20030077574A/ko not_active Withdrawn
  • 2002-01-14 CA CA002433658A patent/CA2433658A1/en not_active Abandoned
  • 2002-01-14 JP JP2002555914A patent/JP2004530533A/ja active Pending
  • 2002-01-14 BR BR0206382-4A patent/BR0206382A/pt not_active IP Right Cessation
  • 2002-01-14 MX MXPA03006304A patent/MXPA03006304A/es active IP Right Grant
  • 2002-01-14 CN CNB02803659XA patent/CN1284620C/zh not_active Expired - Fee Related
  • 2002-01-14 WO PCT/US2002/001005 patent/WO2002055190A2/en not_active Ceased
• 2003
  • 2003-03-17 US US10/390,361 patent/US20030170361A1/en not_active Abandoned
  • 2003-07-08 ZA ZA200305278A patent/ZA200305278B/en unknown
• 2007
  • 2007-09-18 JP JP2007241602A patent/JP2008080332A/ja active Pending

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