WO2008136741A1 - Abaissement de la teneur de certaines substances dans une boisson - Google Patents

Abaissement de la teneur de certaines substances dans une boisson Download PDF

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Publication number
WO2008136741A1
WO2008136741A1 PCT/SE2008/050487 SE2008050487W WO2008136741A1 WO 2008136741 A1 WO2008136741 A1 WO 2008136741A1 SE 2008050487 W SE2008050487 W SE 2008050487W WO 2008136741 A1 WO2008136741 A1 WO 2008136741A1
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adsorbent
adsorptive
ligands
liquid
groups
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PCT/SE2008/050487
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English (en)
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Jan Håkan BERGLÖF
Göran Emanuel Samuel LINDGREN
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Bio-Works Company Limited
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Publication of WO2008136741A1 publication Critical patent/WO2008136741A1/fr

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    • 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
    • C12H1/0416—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 organic added material
    • C12H1/0424—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 organic added material with the aid of a polymer
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/70—Clarifying or fining of non-alcoholic beverages; Removing unwanted matter
    • A23L2/80—Clarifying or fining of non-alcoholic beverages; Removing unwanted matter by adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • 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
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
    • 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
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/3212—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • 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
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
    • B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
    • B01J20/3219—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond involving a particular spacer or linking group, e.g. for attaching an active group
    • 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
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • 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
    • B01J20/34—Regenerating or reactivating
    • B01J20/3425—Regenerating or reactivating of sorbents or filter aids comprising organic materials
    • 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
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
    • 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
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/04—Processes using organic exchangers
    • 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
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • 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
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/54—Sorbents specially adapted for analytical or investigative chromatography
    • 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
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/58—Use in a single column
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents

Definitions

  • the present invention relates to an adsorption method for removal of polyphenolic substances from a liquid containing such substances.
  • the method is primarily useful for treating process liquids in which there are polyphenolic substances that will have negative effects on the end product of the process, e.g. beverages. See further below.
  • the adsorption encompasses complete removal of the polyphenolic substances as well as only partial removal and includes optional collection of fractions enriched in polyphenolic substances by desorption.
  • flavour instability depends on polyphenolic substances there are advantages with lowering of the content of these substances in beverages.
  • the problem is that the lowering must be balanced against the positive effects polyphenols have on the flavour.
  • Sufficient physicochemical stability or colloidal stability of beverages means an acceptable low tendency to form haze upon storage. The lower the tendency the better it is. Haze is formed because of the fact that certain proteins (haze-forming proteins) and polyphenolic substances aggregate. Again it is apparent that there should be advantages with lowering of the amount of polyphenolic substances and/or haze-forming proteins on the physico-chemical stability of beverages which contain thee kind of substances. However, the problem is to properly balance the removal against the positive effects proteins and polyphenols have on the beverage, such as beer. The balancing must for instance be against desired foaming characteristics which require presence of foam proteins.
  • the adsorbent in CSS comprises an anion exchanger based on cross-linked agarose to which quaternary ammonium ligand are covalently attached via a conventional spacer to an oxygen atom of the agarose backbone (Taylor et al, "Use of the Combined Stabilisation System and its impact on beer composition” (2006) Proceedings of the Institute of Brewing & Distillation Asia Pacific Section, Hobart, Australia). See also the manufacturer's report: Initial Assessment Report - Application A600 - Food Standards - Australia New Zeeland 1-07; March 21, 2007) for the structure of their commercialized variant.
  • Protein adsorption in CSS has been considered to be based on ion exchange (charge-charge interaction).
  • the underlying mechanism for the adsorption of polyphenolic substances has so far not been understood. This means that it has been difficult to optimize selective adsorption of polyphenolic substances with respect to physico-chemical stabilization and flavour stabilization, in particular if the two goals are to be achieved in the parallel in the same process while maintaining desired characteristics such as flavour, foam stability, colour etc.
  • a first objective is to provide a simple method for removing or lowering of the content of polyphenolic substances in liquids of the kinds referred to in this specification. This may be for decolourization purposes, flavour purposes, stability purposes where flavour and stability mainly relate to beverages.
  • Another objective is to provide a method comprising selective adsorption of polyphenolic substances from a liquid of the kinds discussed in this specification with a subsequent release (desorption) from the adsorbent and collection of one or more fractions of the eluate which are enriched with respect to polyphenolic substances.
  • the purpose of collecting the polyphenols may be for isolation and further purification and/or for investigation of structure of polyphenolic substances and their relation to flavour stability, physico-chemical stability, characteristics such as flavour, etc and for use as flavour enhancing additives foods, e.g. in beverages, sweets, sauces, premanufactured meals etc.
  • a main objective for beverages is to provide a method that opens up an opportunity to better control the content of polyphenolic substances in a stabilized or an unstabilized beverage of the kinds discussed in this specification, i.e. to efficiently remove polyphenolic substances by adsorption while retaining the desired characteristics of the beverage.
  • Characteristics of interest are bitterness, astringency, foam stability and/or an acceptable shelf-life with respect to the tendency for haze- formation and/or flavour stability to the extent it depends on polyphenolic substances.
  • a first subobjective is to provide an adsorption method for lowering of the content of polyphenolic substances with > 10 %, such as > 15 % or > 25 %. Measurement of polyphenolic substances is according to methods 2.1 and/or 2.2 of the experimental part.
  • a second subobjective is to provide an adsorption method for lowering of the content of proteins simultaneously with lowering of the content of polyphenolic substances, e.g. the latter is in accordance with the first subobjective.
  • the typical reduction in content of protein is > 10 %, such as > 15 % or > 25 % of the measured value for protein content according to method 1.1 of the experimental part..
  • Typical goals with stabilization in this context means that a value for a test measuring stabilization has been changed at least 10 % towards stabilization.
  • the test is selected among Alcohol Chill Test and Accelerated Aging Test Method (3.1 and 3.2, respectively, of the experimental part).
  • a fourth subobjective is to provide an adsorption method in which the ratio between the reduction in the percentage content of total polyphenolic substances and/or anthocyanogens (measured according to methods 2.1 and 2.2, respectively of the experimental part) and the reduction in the percentage content of protein (measured according to method 1.1 of the experimental part) is > 0.25, such as > 0.5 or > 0.75 or > 1 or > 1.1 or > 1.5 or > 2 or > 3 (controlled or selective removal/lowering of polyphenolic substances and/or of proteins).
  • a fifth subobjective is to provide an adsorption method for increasing flavour stability that will render it easier to secure acceptable shelf-lives with respect to undesired bitterness and/or undesired astringency that can be created during storage and depends on polyphenolic substances, for instance.
  • Subobjectives are combinations of two or more of the subobjectives given above.
  • Subobjectives are in particular applicable to beer, wine etc and other alcoholic beverages, but also apply to other beverages such as tea, fruit juices, vegetable juices etc.
  • the present invention is based on our recognition that polyphenolic substances in beverages selectively will adsorb to adsorbents that exhibit ligands exposing ether structures and/or double and/or triple bonds.
  • ether structures the adsorption is caused by interaction between their free electron pairs (n-electrons) and the aromatic ⁇ -electrons of polyphenolic substances (adsorption via n- ⁇ electron interaction).
  • Ether structures that are close to each other will cooperate and result in a stronger adsorption than ether structures that are remote from each other.
  • polyphenolic substances will adsorb to ⁇ -electron rich groups that are exposed on the adsorbent (adsorption via ⁇ - ⁇ electron interaction).
  • the invention is also based on our recognition that it is sufficient to focus on removal of polyphenolic substances instead of on removal of both proteins and polyphenols to accomplish sufficient physicochemical stabilization of a beverage. It would thus be possible to accomplish simultaneous stabilization with regard to both haze formation and flavour of the unpleasant kind discussed above by focusing on n- ⁇ and/or ⁇ - ⁇ electron interactions for the adsorption.
  • the demand on ion exchange adsorptive ligands for protein adsorption becomes lower, i.e.
  • the invention is a method meeting one or more of the objectives/subobjectives discussed above and comprises selective adsorption of polyphenolic substances such as polyphenols and antocyanins, from a liquid of the kinds discussed in this specification.
  • the characteristic feature is that the method comprises the steps of: a) contacting the beverage with a water-insoluble porous adsorbent, preferably hydrophilic, which on its surfaces exhibits adsorptive ligands which are capable of associating with aromatic compounds via n- ⁇ and/or ⁇ - ⁇ electron interaction, and b) optionally recovering the liquid from the adsorbent,
  • the term "content” refers primarily to concentration.
  • the liquids referred to are typically process liquids containing an end product or an intermediate and include liquids in the main process stream when processing of biological material such as supernatants in cell culture, process liquid in sugar manufacture, beverages, waste water in general including for instance sewages, etc.
  • Typical beverages of interest in the invention are alcoholic beverages such as beer, wines, cider etc and non-alcoholic beverages such as fruit juices, vegetable juices etc.
  • the method of the invention may contain additional steps subsequent to step (b) above, such as a step (c) comprising regenerating the adsorbent, possibly combined with a step (d) comprising reusing the regenerated adsorbent obtained in step (c) in one or more cycles each of which comprises steps (a)-(c) for additional batches of the same or of a different kind of liquid, for instance of the same or a different kind of beer, wine, juice etc. If cycling is used, the regenerating step (c) is typically excluded in the final cycle.
  • An n- ⁇ and/or ⁇ - ⁇ electron interacting adsorptive ligand is typically organic and hydrophilic.
  • the ligand comprises a cluster of one, two, three, four or more functional groups each of which is capable of participating in n- ⁇ and/or ⁇ - ⁇ electron interactions.
  • these functional groups are selected amongst a) ether groups, and b) multiple bonds, i.e. double and triple bonds.
  • At least one, two or more of these functional groups when present in a cluster has another one of the functional groups (a) or (b) within a distance of none, one, two, three, or four atoms, with preference for all of these atoms being sp 3 -hybridised carbons when the functional group is an ether group.
  • this other functional group is typically an ether group and for a multiple bond this other functional group is typically a multiple bond.
  • Mixed clusters may also be at hand, i.e clusters containing functional groups of both types.
  • the adsorbent typically comprises a base matrix to which the adsorptive ligands are attached. This attachment may be via a single point (single point attachment) or at two or more points (multi point attachment).
  • the base matrix consists of polymer chains, typically of a hydrophilic polymer, and an adsorptive ligand is attached via several points the adsorptive ligand defines a cross-link that is either intra-chain or inter-chain.
  • a hydrophilic adsorptive ligand is typically defined as a ligand in which the ratio between the the number of carbon atoms and the sum of the number of the heteroatoms (oxygen, nitrogen and sulphur) is ⁇ 4, such as ⁇ 3 or ⁇ 2.
  • Adsorptive ligands containing ether groups Adsorptive ligands containing ether groups.
  • An ether group of an adsorptive ligand has the formula -X- where X is oxygen (oxygen ethers) or sulphur (thioethers).
  • X oxygen (oxygen ethers) or sulphur (thioethers).
  • Each free valence (-) binds directly to a carbon that is present within the ligand and to which one, two, or three other carbons and/or one, two or three hydrogens are directly attached, with preference for only these two kinds of atoms being directly attached to a carbon at this position (attached directly to X).
  • Either one or both of the two carbons directly attached to a free valence in -X- may be sp 3 -, sp 2 - or sp-hybridised, and typically are selected amongst alkyl carbons, and carbons in carbon-carbon doubles, carbon-carbon triple bonds and in aromatic rings.
  • the ether group may thus primarily be selected amongst: dialkyl ethers, alkyl aryl ethers (i.e. monoaryl ethers and monoalkyl ethers), diaryl ethers, divinyl ethers, vinyl alkyl ethers (monovinyl or mono alkyl ethers), vinyl aryl ethers (mono vinyl ethers and mono aryl ethers).
  • a cluster of ether groups (-X-) of an adsorptive ligand there are typically at least two ether groups that are at a distance of one, two, three, four, five, or six sp 3 -hybridised carbons from another ether group of the cluster, with preference for a distance of 2-6 or 3-6 sp 3 -carbons.
  • An adsorptive ligand containing ether groups may also have a hydroxy group directly attached to a carbon only binding carbon and/or hydrogen in addition to such a hydroxy group, for instance at the second carbon from X in an ether group. This includes that a hydroxy group may be placed on a carbon between two ether groups and/or between an ether group and a multiple bond, always with the proviso that a hydroxy and an ether group is not allowed on the same sp 3 -carbon.
  • all carbons are sp 3 -hybridised and directly bound to one, two, three or four carbons and/or to one, two or three hydrogens and/or to one heteroatom selected amongst oxygen, nitrogen and sulphur.
  • At least a fraction of the adsorptive ligands that contains a cluster of ether groups comprises in each ligand one or more structures selected amongst -O(CH 2 ) m CH(O-)(CH 2 ) m O- (structure I) and/or
  • the linker structure according to (b) in turn is typically attached to the base matrix via a heteroatom, such as an oxygen atom, that is part of the base matrix.
  • a heteroatom such as an oxygen atom
  • this heteroatom is for instance part of an amino, amido, a hydroxy, a carboxy etc.
  • Base matrixes exhibiting hydroxy groups, such as in polysaccharide based matrixes, are preferred since they among others enable attachment of adsorptive ligands via ether linkages. .
  • a particular useful method to introduce clusters of ether groups on a base matrix that exposes hydroxy groups on its surface is to use an at least bifunctional reagent in which two or more of the reactive groups are alkylating with at least one of them being hydroxy alkylating.
  • a typical such reagent contains an epoxy group or a precursor to an epoxy group (carbon-carbon double bond, halohydrin, vicinal dihalid etc) as hydroxyalkylating reactive group possibly combined with an alkylating reactive group such as -CH 2 -X' where X' is a suitable leaving group such as halo, sulphate, tosylate etc.
  • a carbon chain containing 1-15 such as 1-10
  • sp 3 -hybridised carbons possibly broken at one or more positions by a heteroatom selected amongst oxygen, nitrogen and sulphur and possibly substituted at a carbon at one or more positions by a lower alkyl (Ci -5 ), lower alkoxy (Ci -5 ).
  • this kind of carbon chain there is at most one heteroatom attached to one and the same carbon atom.
  • the preference for this kind of reagents depends on the fact that each time a reagent molecule reacts with a hydroxy group to form an ether group there will also be formed a hydroxy group.
  • the hydroxy group formed may subsequently react in a second reaction with a new molecule of the reagent thereby forming a new ether group and a new hydroxy group etc.
  • This kind of serial reaction is very easy to refine by step-wise reaction of the appropriate bifunctional reagent.
  • a bifunctional reagent such as allyl halide that contains at one end an alkyl halide function and at the other end a epoxide/halohydrin precursor function (C-C double bond)
  • stepwise addition of portions of the reagent to the base matrix with intermediate steps involving addition of HOBr to the C-C double bond followed by formation of vicinal diols during alkaline conditions will lead to stepwise building up of the appropriate adsorptive ligand containing clusters of ether functional groups.
  • WO 94004192 G Lindgren.
  • the number of cross-linking adsorptive ligands will be high leading to rigid adsorbent materials that is of advantage in the invention. See below.
  • Systems of double or triple bonds in clusters typically define conjugated systems of double and triple bonds.
  • Typical double and triple bonds are between carbon-carbon, carbon-nitrogen, carbon-oxygen, carbon-sulphur, nitrogen-nitrogen, nitrogen-oxygen.
  • the conjugated system may be part of an aromatic ring system or of an unsaturated system.
  • a multiple bond may be at a distance of one, two, three or four sp 3 -hybridised carbons from another multiple bond or from X of an ether group -X-.
  • Adsorptive ligands containing other functional groups Adsorptive ligands containing other functional groups.
  • the inner and outer surface of the adsorbent may also exhibit ligands that are capable of adsorbing via other principles, for instance principles in which n- ⁇ and/or ⁇ - ⁇ electron interaction is not significant.
  • ligands contain other kinds of functional groups, for instance selected amongst charged groups (typically adsorbing via electrostatic attraction) and/or hydrophobic groups (typically adsorbing via hydrophobic interaction).
  • adsorptive ligands may be separate from or coincide with the adsorptive ligands that contain n- ⁇ or ⁇ - ⁇ interacting groups.
  • Charged groups are typically used in ion exchange chromatography for isolating and/or removing proteins from various kinds of mixtures. They are of two main kinds: anionic groups (that are cation exchanging) and cationic (that are anion exchanging). Ion exchanging groups are most active in adsorbing substances that carry charges that are opposite to the charge of the group. In the context of the invention this means that ion exchange groups are effective in adsorbing proteins which in the liquid to be treated according to the invention have the opposite charge in the beverage. Their adsorption capacity for polyphenols should be low, in particular for liquids, such as beverages that like beer have a relatively low pH (about 4.5 i.e. ⁇ pH 7).
  • Typical cation exchanging groups are carboxy groups (-COO " ), sulphonic acid groups (-SO 2 O " ), phosphonic acid groups etc.
  • Typical anionic exchanging groups are primary, secondary, tertiary and quaternary ammonium groups (-N + Ri 5 R 25 R 35 R 4 ).
  • the free valence indicates a covalent link to a base matrix of the adsorbent and is typically through an organic spacer structure for instance alkylene or hydroxy alkylene.
  • Ri -3 is typically hydrogen or lower alkyl (Ci -5 ) that may be substituted with one or more hydroxy groups.
  • CM carboxymethyl
  • SP -(CH 3 ) 3 SO 3 "
  • quaternary ammonium groups may in particular be mentioned.
  • -N + (CH 3 ) 3 that when linked to the matrix via the spacer -CH 2 CHOHCH 2 - or - CH 2 CHOHCH 2 -O-CH 2 CH 2 - is called a Q-group (the right free valence then binds to the free valence of-N + (CH 3 ) 3 .
  • an ion exchanging group is typically matched to the pH of the liquid to treated, for instance a beverage, and to the charge of the substance to be adsorbed from the beverage.
  • an adsorbent capable of exhibiting both kinds of principles should be selected, i.e. exhibits ether groups/multiple bonds and ion-exchanging groups, in particular anion exchanging groups that are charged at this pH, i.e. ammonium groups as discussed in the preceding paragraph.
  • Adsorptive ligands that exhibit pronounced hydrophobic interaction typically have abroad specificity for adsorbing proteins.
  • the ligands as well as their hydrophobic groups are typically characterized in containing a low number of heteroatoms (oxygen, nitrogen and sulphur) relative to their number of sp 3 -hybridised carbons.
  • the ratio between the sum of the number of oxygen, nitrogen and sulphur and the number of carbons, which do not bind to oxygen, nitrogen or sulphur is typically ⁇ 0.5, such as ⁇ 0.25 or ⁇ 0.1.
  • Preferred hydrophobic groups are typically introduced on base matrices exhibiting hydroxy groups by so called alkylation that may include hydroxyalkylation.
  • Pure alkylation may be accomplished by a reagent R-X" where R is an pure alkyl group containing at least one, two or three carbons and typically at most 12 carbons, and X" is a suitable leaving group as discussed above.
  • Hydroxyalkylation may be accomplished by a reagent R'-Y where R' has the same meaning as R above and Y is an epoxide or an epoxide precursor as discussed above.
  • Carbons are typically sp 3 -hybridised but also sp- and sp 2 -carbons may be present.
  • the adsorbent may alternatively be in the form of a fluidised bed that may be in expanded form (also called unmixed, stabilised or classified) or completely mixed or stirred. Fixed beds and expanded beds are preferred since chromatographic principles then can be applied to the method of the invention meaning a more efficient use of the adsorbent. Mixed or stirred variants of fluidised beds are better suited for batch- wise adsorption processes.
  • Adsorbents in the form of expanded beds are in particular useful for unclarified beverages which are to be delivered to the market in unclarified forms or which are to be clarified subsequent to being subjected to the present innovative method.
  • Other kinds of beds are preferably useful for beverages that have been clarified prior to being subjected to the method of the invention.
  • the adsorbent is typically hydrophilic in the sense that it is capable of being saturated with water by self-suction, provided it is in bed form and placed in liquid contact with an excess of water.
  • the particles may be monosized/monodispersed or polysized/polydisper-sed.
  • Monosized/monodispersed particles contemplate that the particles of the adsorbent has a size distribution within 70%, such as within 85% or within 95% of the particles falling within a range which width is 0.1 to 10 times the mean particle diameter, preferably 0.3 to 3 times the mean particle diameter. For an irregular particle, the size/diameter is the longest distance/diameter between two opposite sides of the particle. Particle populations that are not monosized are polysized.
  • the matrix may be built up of organic material but is normally built up of a polymeric network such that polymer chains and hydrophilic groups, such as hydroxy groups and/or amide groups, are exposed on the inner and outer surfaces of the matrix that are in liquid contact with the liquid, such as a beverage, during the process of the invention.
  • Suitable polymers are mostly organic and of biological origin (biopolymers), even if fully synthetic polymers are also contemplated. They typically exhibits a plurality of hydroxy groups and/or amide groups and are thus polyhydroxypolymers and/or poly amide polymers. In the poly amide polymers the amide groups are typically projecting from the polymer chain.
  • biopolymers examples include polysaccharides with base matrixes/adsorbents based on e.g. dextran (Sephadex, GE Health Care, Uppsala Sweden), agarose (Novarose, Innovata, Bromma, Sweden; and Sepharose, GE Health Care, Uppsala Sweden), starch, cellulose (Sephacel, GE Health Care, Uppsala Sweden) etc.
  • Appropriate examples of synthetic polymers are poly hydroxyalkyl acrylates, poly hydroxy alkyl methacrylates, poly hydroxy alkyl vinyl ethers, poly acryl amides and poly methacryl amides.
  • Amides are many times N-substituted with hydroxy-containing groups, e.g. hydroxy alkyl.
  • Cross-linking structures in synthetic polymers is typically introduced when they are produced by including the appropriate cross-linking monomer during the polymerization process.
  • Suitable biopolymers and synthetic polymers typically exhibit a plurality of hydrophilic functional groups along the polymer chains. Each of these functional groups as a rule exhibits one or more heteroatoms (oxygen, nitrogen and sulphur) and is selected amongst hydroxy or amido, for instance.
  • the polymers therefore typically have a pronounced hydrophilic character.
  • purely hydrophobic polymers such as polystyrenes including styrene-divinyl benzene copolymers, may be used.
  • the inner and outer surfaces of base matrices built up of this latter kind of polymers are typically hydrophilized, for instance by introducing a coat of sufficient hydrophilicity on them as defined elsewhere in this specification.
  • This kind of coat may be introduced by a) physical adsorption or b) grafting of coat molecules that subsequently may be cross-linked.
  • Hydrophilicity may also be introduced during the polymerization process by using the appropriate conditions including for instance presence of monomers that have a polymerizable hydrophobic end and a hydrophilic end.
  • Suitable coating agents are the above mentioned hydroxy-group containing polymers or a low molecular weight hydroxy group containing compound See for instance polystyrene- divinyl benzene particles sold under the name Source (GE Health Care, Uppsala, Sweden).
  • adsorbents By replacing the hydrogen on a plurality of the hydroxy groups of this kind of base matrixes with adsorptive ligands as discussed above suitable adsorbents to be used in the invention may be achieved.
  • the attachment of the ligands at the base matrix is preferable at oxygens that originally are present as a hydroxy group in the base matrix and therefore are part of the base matrix also in the adsorbent as used. If the adsorptive ligand is attached at several points it may define cross-links as discussed elsewhere in this specification.
  • a hydrophilic polymer is typically defined as a polymer in which the ratio between the sum of the number of carbon atoms and the sum of the number of the heteroatoms (oxygen, nitrogen and sulphur) is ⁇ 4, such as ⁇ 3 or ⁇ 2.
  • the matrix in particular in the case it is in particle form, may contain inorganic material. This in particular applies when the adsorbent is to be used in the form of an expanded bed (requires densities of the particles that are significantly different from the density of the beverage, preferably with particle densities that are larger than the density of the beverage).
  • the porosity of the adsorbent bed should be sufficient for high flow rates through the adsorbent without applying too high pressures. This typically means that if the bed is build up of particles they should be large, typically > 150 ⁇ m, more preferably > 250 ⁇ m such as > 350 ⁇ m (mean particle diameter) with a narrow particle size distribution (see above for suitable size distribution intervals). It is also important that the porosity of the base matrix/adsorbent is sufficient to allow for the undesired proteins and polyphenolic substances in the beverage to penetrate the adsorbent including the pores of the base matrix.
  • the porosity of the base matrix should be sufficient for penetration of globular proteins of molecular weights up to 1OxIO 6 kDa (such as thyroglobulin), or up to IxIO 6 kDa or up to 0.5 x 10 6 kDa.
  • the adsorbent when used as a fixed bed should have a considerable rigidity. This in particular applies when working at temperatures around O 0 C when many of the beverages concerned are highly viscous.
  • the adsorbent should permit flow rates of at least 500 cm/h such as at least 1000 cm/h when the adsorbent material is placed in a model column of 8 x 300 mm (diameter x height) and water is used as the eluent.
  • step (a) is typically taking place by splitting the flow of the liquid to be treated, e.g. a beverage, into one part passing through the adsorbent and the remainder bypassing the adsorbent and blending the two flows after passage.
  • the ratio between the two flows is adapted to compensate for the lowering of the adsorption capacity of the adsorbent taking place to thereby achieve the desired product consistency. See further Taylor et al (cited above).
  • Step (b) simply means collecting the eluate from the adsorbent.
  • this step simply means filtering of the adsorbent or decanting the liquid, such as a beverage, after sedimentation.
  • Regeneration in step (c) is typically accomplished by treating the adsorbent with one or more regeneration solutions, for instance if the adsorbent is in bed form by flowing these kind of solutions through the adsorbent, preferably in the opposite direction to the direction used in step (a).
  • Regeneration solutions are designed to remove adsorbed substances with minimal destruction of the adsorbent permitting its use in subsequent cycles of steps (a)-(c).
  • Step (c) thus typically includes
  • a salt such as an alkali metal salt like sodium chloride
  • the regeneration solution may contain both alkali and the salt.
  • a regeneration solution may also contain other agents either alone or in combination with salt and/or alkali, for instance a detergent that is acceptable for this kind of process. Washing solutions may be included prior to, between, and/or subsequent to these two kinds of regeneration solutions.
  • the adsorption process may be performed under flow conditions or as a one step batch-wise procedure.
  • Flow conditions include variants in which the flow rate is altered during the process and may include that the flow is lowered to zero at certain time intervals.
  • the temperature at least during step (a) is typically above the freezing point for beverage and below +1O 0 C, such as below +5 0 C and preferably at about O 0 C (i.e. in the interval -2 0 C to +2 0 C.
  • the method of the invention is typically run so that the liquid obtained, such as a beverage treated according to the invention, complies with one or more of the objectives/subobjectives set forth in this specification.
  • the liquid referred to is collected from the adsorbent and includes a liquid that have been obtained by blending a liquid that has been in contact with the adsorbent with the same kind liquid not having been in contact with the adsorbent. There is no requirement that the two liquids derive from the same batch. However, it is preferred to start from a common liquid and split the process stream into two streams one of which is contacted with the adsorbent according to step (a) while the other stream is not, and blending the two streams downstream of the adsorbent. This kind of blending possibly with a split of the process stream upstream of the adsorbent is of particular benefits for beverages, such as beers, for which the goal is to only lower the content of polyphenolic substances in the liquid stream.
  • the regeneration step may comprise that the adsorbed polyphenolic substances are desorbed and collected during step (c).
  • the adsorbent has been selected to be highly selective for polyphenolic substances, e.g. by being devoid of efficient protein- adsorbing ligands such as ion-exchanging ligands and hydrophobic ligands.
  • the collected polyphenolic substances can be used for investigation of their structure and to study structure - flavour - stability relationships.
  • the desorbed substances could also be used as additives and flavour enhancers for other beverages, food, sweets etc.
  • the invention also can be defined as the use of the above-mentioned n- ⁇ and ⁇ - ⁇ interacting adsorptive ligands when being part of an adsorbent as discussed above for selective adsorption of polyphenols from the various liquids discussed above, in particular beverages.
  • the various features discussed above for the method, features of the various steps and the adsorbent, also apply to the use-aspect of the invention.
  • Anthocyanogens Mac Farlane et al (EBC Proceedings of the 8 th Congress (Vienna) 1961, 278-285). Anthocyano genes are phenolic substances which will be turned into red- couloured anthocyanidines by the treatment of hydrochloric acid.
  • Alcohol-chill-test When chilling beer, a reversible haze is formed, caused by precipitated polyphenol-protein complexes. The addition of alcohol decreases the solubility of these complexes and accelerates the precipitation.
  • EXAMPLE 1 Synthesis of an agarose separation gel from agar. Step-wise cross-linking in parallel with step-wise desulphating
  • Spherical agar beads were prepared using traditional method in a two phase system (water/toluene) with a suitable emulgator. The beads were classified in two different fractions by sieving in which the beads have diameters within the intervals of 200-300 ⁇ m and 40-60 ⁇ m, respectively.
  • the synthesis was essentially as generally outlined for polysaccharide gels in outlined in US 4973683 (Lindgren, G) and is particularly well adapted to result in rigid beads allowing high flow rates and high pressure differences across columns packed with the beads, e.g. in the large scale treatment of beverages. Compare example 2.
  • EXAMPLE 2 A. Introduction of adsorptive ligands that are capable of adsorbing polyphenolic substances via n- ⁇ and ⁇ - ⁇ interaction and B. Adsorption of polyphenols from a beverage.
  • a short column (25 x 50 mm) was packed with the beads and connected to a pump and equilibrated with water. Beer that had been degassed under vacuum for approximately 1 hour until no foam was created was allowed to run through the column at high flow rate (5 mL/min, 60 cm/min). After approximately 200 mL, samples of the processed beer were taken for analysis. The amount of polyphenols and proteins in the beer were measured before and after passing the column. Polyphenols were determined using method 2.1 above. Total protein was measured by method 1.1 above.
  • the uptake of polyphenols was 25 % and of proteins insignificant, i.e. the polyphenol content was lowered 25 % and the protein content was unchanged by passing the beer through the adsorbent.
  • EXAMPLE 3 Introduction of adsorptive ligands that are capable of increasing the adsorption of polyphenols and of proteins.
  • Adsorption from a beverage Beads synthesized according to example 2 were further derivatized with hydrophobic alkyl groups by treatment with excess of propylene oxide. The beads were packed in a column of the same kind as in example 2. The same kind of beer as used in example 2 was allowed to pass through the adsorbent. Polyphenols and total protein were measured in the beer before and after passing the adsorbent in the same manner as in example 2. The uptake of polyphenolic substances and of proteins was 35% and 25%, respectively.

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Abstract

L'invention concerne l'utilisation de ligands adsorbeurs interagissant avec n-π et π-π quand ils font partie d'un adsorbant pour l'adsorption sélective des substances polyphénoliques contenues dans un liquide, en particulier, une boisson.
PCT/SE2008/050487 2007-05-04 2008-04-29 Abaissement de la teneur de certaines substances dans une boisson WO2008136741A1 (fr)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
WO2010142364A1 (fr) * 2009-06-09 2010-12-16 Sartorius Stedim Biotech Gmbh Procédé d'extraction de substances végétales secondaires
WO2012047142A1 (fr) * 2010-10-05 2012-04-12 Bio-Works Company Limited Procédé pour l'élimination d'arsenic de l'eau utilisant des matrices à base de polymère comprenant des groupes chélateurs comprenant des ions métalliques
WO2012113494A1 (fr) 2011-02-26 2012-08-30 Sartorius Stedim Biotech Gmbh Procédé d'obtention de métabolites secondaires végétaux au moyen d'une membrane à groupes échangeurs de cations
EP2961510A4 (fr) * 2013-02-26 2016-11-16 Fundación Fraunhofer Chile Res Clarification et liaison sélective de composés phénoliques à partir d'un produit alimentaire liquide ou de boissons au moyen de polymères intelligents
US12011019B2 (en) 2014-12-22 2024-06-18 Red Bull Gmbh Method and device for treating food and/or containers for holding food

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WO1997043401A1 (fr) * 1996-05-10 1997-11-20 Intermag Gmbh Stabilisation de boissons
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WO1997043401A1 (fr) * 1996-05-10 1997-11-20 Intermag Gmbh Stabilisation de boissons
US5886155A (en) * 1997-06-18 1999-03-23 Bioresources International Inc. Purification of miraculin glycoprotein using tandem hydrophobic interaction chromatography

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010142364A1 (fr) * 2009-06-09 2010-12-16 Sartorius Stedim Biotech Gmbh Procédé d'extraction de substances végétales secondaires
US8557304B2 (en) 2009-06-09 2013-10-15 Sartorius Stedim Biotech Gmbh Method of obtaining secondary plant constituents
WO2012047142A1 (fr) * 2010-10-05 2012-04-12 Bio-Works Company Limited Procédé pour l'élimination d'arsenic de l'eau utilisant des matrices à base de polymère comprenant des groupes chélateurs comprenant des ions métalliques
WO2012113494A1 (fr) 2011-02-26 2012-08-30 Sartorius Stedim Biotech Gmbh Procédé d'obtention de métabolites secondaires végétaux au moyen d'une membrane à groupes échangeurs de cations
DE102011012569A1 (de) 2011-02-26 2012-08-30 Sartorius Stedim Biotech Gmbh Verfahren zur Gewinnung sekundärer Pflanzeninhaltsstoffe unter Verwendung einer Membran mit kationenaustauschenden Gruppen
EP2961510A4 (fr) * 2013-02-26 2016-11-16 Fundación Fraunhofer Chile Res Clarification et liaison sélective de composés phénoliques à partir d'un produit alimentaire liquide ou de boissons au moyen de polymères intelligents
US12011019B2 (en) 2014-12-22 2024-06-18 Red Bull Gmbh Method and device for treating food and/or containers for holding food

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