EP0946636A1 - Production and use of formulations consisting of cellulose, kalium caseinate and cross-linked vinyl pyrrolidone homopolymers and/or vinylimidazol/vinylpyrrolidone copolymers - Google Patents

Production and use of formulations consisting of cellulose, kalium caseinate and cross-linked vinyl pyrrolidone homopolymers and/or vinylimidazol/vinylpyrrolidone copolymers

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Publication number
EP0946636A1
EP0946636A1 EP97954353A EP97954353A EP0946636A1 EP 0946636 A1 EP0946636 A1 EP 0946636A1 EP 97954353 A EP97954353 A EP 97954353A EP 97954353 A EP97954353 A EP 97954353A EP 0946636 A1 EP0946636 A1 EP 0946636A1
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EP
European Patent Office
Prior art keywords
weight
cellulose
caseinate
polymer
vinyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP97954353A
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German (de)
French (fr)
Inventor
Michael Lappas
Bernhard Fussnegger
Gabriele MÜLLER
Knuth Horst Jung
Georg Tasser
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BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0946636A1 publication Critical patent/EP0946636A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
    • C08L89/005—Casein

Definitions

  • the invention relates to formulations consisting of cellulose, alkali caseinate and crosslinked homopolymers or copolymers of Isf-vinyl lactams and / or polymers based on a basic N-vinyl heterocycle with a pK a value of at least 3.8, the production and use thereof for the treatment of biological liquids of vegetable origin in a non-fermented, partially fermented or fully fermented state.
  • the disadvantage with the native and modified proteins and the crosslinked polymers is that they require a certain pretreatment by swelling. This means a very large amount of time. Since the vast majority of products medium is extracted together with the suspended turbidity by sedimentation, this step is also very time-consuming and can take up to 6 weeks. In addition, these products have the disadvantage that they do not remove all phenolic substances or classes of substances to the same extent, but that there is in each case a preferred interaction with a certain group of phenolic substances.
  • the anfal ⁇ lumbar sediments are mostly schleimigpast Surprise masses, which is removed by a downstream treatment liquid in order to bring them into a results processed further or landfillable state.
  • the invention was therefore based on the object of finding a product which does not have the disadvantages mentioned above and is able to reduce the content of different groups of phenolic compounds and at the same time also the concentration of dissolved heavy metals. At the same time, manageability should be improved by eliminating the complex preparation phase of the feed material.
  • the invention relates to solid preparations consisting of
  • alkali casemate (b) is understood in the following to mean above all potassium casemate, which is obtained by treating casem with potassium hydroxide solution or solutions of alkaline potassium salts of organic or inorganic acids such as e.g. Phosphoric acid or citric acid is obtained.
  • Casem comes from short-term skimmed milk with a maximum fat content of 0.05%. Thickening to separate the whey is done with acids by adjusting the pH to the isoelectric point of the casein 4.5 + 0.2. After heat treatment, separation of the whey and hot water washing, the raw casa is obtained. This is further processed as a wet break or after drying to Casemat by bringing it to the solution by adding potassium hydroxide or other alkali hydroxides. The drying takes place by means of spray drying or extrusion processes.
  • the products obtained which are particularly suitable for the preparation of the formulations according to the invention, have a water content of 5 to 10% and a protein content of 87% to 92% and an ash content of 3% to 8%.
  • N-Vmyllactams here mean 3-methyl-N-vmylpyrrolidone, in particular N-Vmylcaprolactam and N-Vmylpyrrolidone (VP), which are used all or in a mixture with one another.
  • the monomers (c) are used in an amount of 90% to 99.5%, preferably 98% to 99% by weight, based on the total polymer.
  • Suitable crosslinkers are those which contain two or more radically copolymerizable Vmyl phenomenon in the molecule.
  • Particularly suitable are alkylenebisacrylamides such as methylenebisacrylamide and N, N'-bisacryloylethylene diamine, also N, N '-divmylethylene urea, N, N'-divmylpropylene urea, ethylidene dis-3 - (N- inyl-pyrrolidone) and N, N' - Divmyldiimidazolyl - (2, 2 ') -1, 4-butane and 1, 1' -Bis (3, 3 '- mylbenz ⁇ m ⁇ dazol ⁇ d-2-one) 1, 4-butane.
  • crosslinking agents are, for example, alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and tetramethylene glycol di (meth) acrylate, aromatic divmyl compounds such as divmylbenzene and divmyltoluene as well as alkyl acrylate, divmyldioxane, pentaerythritol and their triallyl ether. In the presence of water they are of course only polymerized suitable insofar as they are soluble in the aqueous monomer mixture.
  • alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and tetramethylene glycol di (meth) acrylate
  • aromatic divmyl compounds such as divmylbenzene and divmyltoluene as well as alkyl acrylate, divmyldioxane, pentaerythritol and
  • the crosslinkers are used in an amount of 0.5-10, preferably 1-2% by weight, based on all the monomers of the polymer.
  • Basic Vmylheterocycles are to be understood here as saturated and aromatically unsaturated heterocycles with a Vmyl distr and at least one basic tertiary Rmg atom with a pK a of at least 3.8.
  • the ring can also carry alkyl groups with 1 to 4 carbon atoms, phenyl or benzyl groups or also a fused second ring. Examples include: N-Vmylimidazole (VI) and derivatives thereof we 2-methyl-l-vmyl ⁇ m ⁇ dazol, 4-methyl-l-vmyl ⁇ m ⁇ dazol, 5-methyl-l-vmyl ⁇ m ⁇ dazol,
  • 2-ethyl-1-methylimidazole 2-propyl-1-vinylimidazole, 2-isopropyl-1-methylimidazole, 2-phenyl-1-methylimidazole, 1-methyl-4,5-benzimidazole.
  • the following can also be used, for example: 2-methylpym, 4-methylpmdm and 2-methyl-5-methylpyrm. Mixtures of basic methyl heterocycles with one another can of course also be used.
  • Preferred monomers for this are N-methylimidazole and 2-methyl-N-ylimidazole.
  • These monomers are used in an amount of 50-99.5, preferably 60-96% by weight, based on the total polymer.
  • the comonomers are polymerized in amounts of up to 49.5, preferably up to 30% by weight, particularly preferably up to 20% by weight, based on the total monomer mixture.
  • suitable comonomers are styrene, acrylic ester, methyl ester, acrylic ide and N-methyl dihydropyridme.
  • N-Vmyllactams such as 3-methyl-N-mylpyrrolidone, ms-particular N-Vmylcaprolactam and N-Vmylpyrrolidone (VP) are preferably used as comonomers.
  • Suitable crosslinkers for the polymers (d) are also those which contain two or more free-radically copolymerizable methyl groups in the molecule.
  • Particularly suitable are alkylenebisacrylamides such as methylenebisacrylamide and N, N'-bisacryloylethylene diamine, also N, N'-divmylethylene urea, N, N'-divmylpropylene urea, ethylidene-b ⁇ s-3 - (N-vmylpyrrolidone) and N, N'-divi- nyldumidazolyl- (2,2 ') -1,4-butane and 1,1'-bis (3,3' -vmylbenzimi-dazolid-2-one) -1,4-butane.
  • crosslinking agents are, for example, alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and tetramethylene glycol di (meth) acrylate, aromatic divinyl compounds such as divinylbenzene and divinyltoluene as well as allyl acrylate, divinyldioxane, pentaerythritol triallyl ether and mixtures thereof.
  • alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and tetramethylene glycol di (meth) acrylate
  • aromatic divinyl compounds such as divinylbenzene and divinyltoluene as well as allyl acrylate, divinyldioxane, pentaerythritol triallyl ether and mixtures thereof.
  • polymerization in the presence of water they are of course only suitable if they are soluble in the aqueous monomer
  • crosslinkers are nevertheless used for the polymers (d) in an amount of 0.5-10, preferably 1-4% by weight, based on all the monomers of the polymer.
  • Celluloses (a) which are particularly suitable for the use according to the invention are those which contain less than 1% water-soluble substances and have a fiber length of 20 ⁇ m to 200 ⁇ m, preferably 25 to 50 ⁇ m, and a fiber diameter of 5 ⁇ m to 50 ⁇ m, preferably have 10 to 20 ⁇ m.
  • Alkalic caseinates (b) which are particularly suitable for the use according to the invention are potassium caseinates with good solubility, preferably greater than 99% and high bacteriological requirements, preferably with a total bacterial count of less than 5000 kBE / g, yeast less than 10 / g and mold less than 10 / g.
  • Polymers (c) which are particularly suitable for the use according to the invention are those composed of N-vinylpyrrolidone (VP) and N, N '-divmylethyleneurea (DVEH), in particular those composed of 98-99.5% by weight of VP and 0.5 -2.0% by weight DVEH.
  • VP N-vinylpyrrolidone
  • DVEH N, N '-divmylethyleneurea
  • Polymers (d) which are particularly suitable for the use according to the invention are those of N-vinylimidazole (VI), N-vinylpyrrolidone (VP) and N, N '-divinylethyleneurea (DVEH), in particular those of 80-90% by weight of VI, 5-15 wt% VP and 2-5 wt% DVEH.
  • VI N-vinylimidazole
  • VP N-vinylpyrrolidone
  • DVEH N '-divinylethyleneurea
  • the particle size distribution of the polymer particles (c) and (d) is usually in the range from 0.01 to 100 ⁇ m, preferably in the range from 5 to 50 ⁇ m.
  • the preparation is prepared in a process variant 1 in such a way that in a solution of alkali caseinate (b), preferably in a concentration of 2% by weight to 20% by weight dry matter, the cellulose (a) and the polymers (c) and / or (d) suspended become.
  • concentrations of components (c) and / or (d) are between 2% and 20% of the dry matter of the suspension.
  • the suspension is spray-dried, preferably using a single-component nozzle at pressures from 50 bar to 150 bar, preferably less than 100 bar.
  • process variant 2 components (a) and (b) are introduced as shown in process variant 1 by suspending the cellulose (b) in an aqueous solution of the alkali caseinate. This suspension is then atomized, the resulting primary aerosol being brought directly into contact with the powdery polymer components in the moist state and the resulting polymer-containing suspension droplets being dried. Components (c) and / or (d) are blown into the atomization zone of the tower in a correspondingly dry manner.
  • powders are produced according to process variants 1 or 2, first dried in the tower to a residual moisture content of 10 to 15% by weight and to achieve an additional agglomeration effect at a powder temperature of 70 ° C up to 40 ° C, preferably from 60 ° C to 50 ° C, carried out on tape for post-drying and adjusted to a residual moisture content of 6-10% by weight at a supply air temperature of 60 ° C to 110 ° C. Post-drying at an elevated temperature results in an additional agglomeration effect.
  • Partially fermented or completely fermented biological liquids of plant origin are treated with 25 to 250 g / hl, in a preferred form with 40 to 150 g / hl and in a particularly preferred application form with dosage amounts of 50 to 100 g / hl.
  • Particularly suitable liquids are wine, grape must or wine-like drinks and their non-fermented musts (berry and fruit juices). All forms of solid / liquid separation, such as centrifuges, decanters, layer and diatomaceous earth filtration and membrane technologies, are suitable for separating the formulations from the application medium.
  • V f filtrate volume in m 3 V f filtrate volume in m 3 , t filtration time in s, A filter area in m 2 ,
  • the preparations according to the invention can be used to stabilize liquids of vegetable origin in a particularly advantageous manner against changes in color and taste.
  • alkali caseinate and cross-linked! By precipitating the caseinate at the IEP in close connection with the crosslinked polymer, the polymer is increased in surface area, which has a particularly effective stabilizing effect against oxidative changes.
  • a formulation consisting of 70 kg of cellulose, 20 kg of potassium casemate and 10 kg of polymer (d) with a proportion of N-vinylimidazole (VI) of 90% by weight and a proportion of N-vinylpyrrolidone (VP) of 7% by weight .-% and a proportion of N, N '-divinylethylene urea (DVEH) of 3 wt .-% was prepared by dissolving the potassium casemate in 400 l of water at 60 ° C and suspending the cellulose therein. The suspension was atomized at 185 ° C. at 70 bar through a 10-component nozzle and the polymer was blown into the atomization zone.
  • a formulation consisting of 50 kg cellulose, 30 kg potassium casemate, 10 kg polymer (c) and 10 kg polymer (d) was prepared as follows:
  • the potassium caseinate (b) was dissolved in 320 l of water at 60 ° C. and the cellulose (c) was suspended in it.
  • the suspension was atomized at 180 ° C. at 50 bar through a single-component nozzle and a mixture of the two polymers (c) and (d) was blown into the atomization zone with a mixing ratio of 1: 1.
  • Table 1 summarizes the findings immediately after treatment and bottle filling and after a storage period of 28 days at 35 50 ° C.
  • 25 E absorbance at 320, 420, 520 nm; Layer thickness in cm
  • the treatment reduces the browning, expressed as an absorbance value at 420 nm.
  • the difference values of the extinctions at 420 nm and 520 nm show that the wine treated has a lower tendency to change color than the untreated comparison.
  • Table 2 shows the results immediately after treatment and bottle filling and after a storage period of 28 days at 50 ° C. 45 The bottle was filled with a head space of 150 ml of air. Table 2
  • the difference in absorbance at 420 nm confirms that the treated person has less tendency to undergo oxidative color changes than the untreated comparison.
  • Table 3 shows the calculated filter medium resistance ß and the mean specific filter cake resistance ⁇ of the three batches.
  • the filter properties of the must trub suspensions are significantly improved depending on the dosage of the added formulation.

Abstract

The present invention relates to the production and use of formulations consisting of (a) 10 to 90 wt.% cellulose; (b) 5 to 60 wt.% alkalicaseinate containing as polymer consitutents (c) 5 to 85 wt.% polymer obtained from N-vinyl lactames or (d) 5 to 85 wt.% polymer obtained form 50 to 99.5 wt.% of at least one basic vinyl heterocycle with a pka value of at least 3.8 or a mixture thereof. The present invention also relates to the use of these formulations in the treatment of biological liquids of vegetable origin in an unfermented, partially or completely fermented state for sensory stabilization of products with a view to preserving taste and color.

Description

PULVERFÖRMIGE ZUBEREITUNGEN UND IHRE VERWENDUNG ZUR BEHANDLUNG VON FLÜSSIGKEITEN PFLANZLICHEN URSPRUNGS. POWDERED PREPARATIONS AND THEIR USE FOR TREATING LIQUIDS OF VEGETABLE ORIGIN.
Beschreibungdescription
Die Erfindung betrifft Formulierungen, bestehend aus Cellulose, Alkalicaseinat und vernetzten Homopolymeren oder Copolymeren aus Isf—Vinyllactamen und/oder Polymerisaten auf Basis eines basischen N—Vinylheterocyclus mit einem pKa-Wert von mindestens 3,8 deren Herstellung und Verwendung zur Behandlung von biologischen Flüssigkeiten pflanzlichen Ursprungs in nichtvergorenem, teilweise vergorenem oder vollständig vergorenem Zustand.The invention relates to formulations consisting of cellulose, alkali caseinate and crosslinked homopolymers or copolymers of Isf-vinyl lactams and / or polymers based on a basic N-vinyl heterocycle with a pK a value of at least 3.8, the production and use thereof for the treatment of biological liquids of vegetable origin in a non-fermented, partially fermented or fully fermented state.
Bei der Herstellung von flüssigen Produkten aus nichtvergorenen, teilweise vergorenen oder vollständig vergorenen Vorprodukten ist deren Stabilität hinsichtlich Farbe, Geruch und Geschmack ein herausragendes Merkmal. Diese drei Merkmale sind in biologischen Flüssigkeiten pflanzlichen Ursprungs von der Konzentration an phenolischen Inhaltsstoffen und vom Gehalt an Schwermetallionen abhängig. Die kontrollierte Einstellung der Konzentration dieser Inhaltsstoffe ist somit eine entscheidende Voraussetzung für die Produktion sensorisch stabiler Endprodukte.When producing liquid products from non-fermented, partially fermented or completely fermented intermediate products, their stability with regard to color, smell and taste is an outstanding characteristic. In organic liquids of plant origin, these three characteristics depend on the concentration of phenolic ingredients and the content of heavy metal ions. Controlling the concentration of these ingredients in a controlled manner is a crucial prerequisite for the production of sensory stable end products.
Zur Beeinflussung phenolischer Substanzen finden bisher Produkte Verwendung, die durch Komplexbildung, Adsorption oder Fällung reagieren. Als Produkte kommen native Proteine wie z.B Gelatine, Caseinat, Eiklar, Ovalbumin, Hausenblase oder Blutpulver sowie modifizierte Proteine wie z.B. Kaliumcaseinat in Frage. Desweiteren werden vernetzte Polymere auf Basis von Vinylpyrrolidon (Crospovidone, PVPP) eingesetzt. So wird in der EP-A-088 964 ein Verfahren zur Herstellung von unlöslichen, in Wasser nur wenig quellbaren Polymerisaten eines basischen N-Vinylheterocyclus und dessen Copolymerisaten mit bis zu 30 Gew. -% copolymerisierbarer Monomerer beschrieben. Die Komplexierung von Übergangsmetallkationen zur Herstellung von Katalysatoren auf Basis der beschriebenen Polymerisate wird vorgeschlagen. Diese Polymerisate besitzen vor allem als Adsorberharze ein breites AnwendungsSpektrum. Sie adsorbieren sehr gut Proteine, speziell Enzyme und eignen sich ebenfalls zur adsorptiven Entfernung von störenden Poly- phenolen und Farbstoffen aus wäßrigen Lösungen.Products which react by complex formation, adsorption or precipitation have hitherto been used to influence phenolic substances. Native proteins such as gelatin, caseinate, egg white, ovalbumin, house bladder or blood powder as well as modified proteins such as e.g. Potassium caseinate in question. Crosslinked polymers based on vinylpyrrolidone (Crospovidone, PVPP) are also used. For example, EP-A-088 964 describes a process for the preparation of insoluble polymers of a basic N-vinyl heterocycle which are only slightly swellable in water and their copolymers with up to 30% by weight of copolymerizable monomers. The complexation of transition metal cations for the production of catalysts based on the polymers described is proposed. These polymers have a wide range of applications, especially as adsorber resins. They adsorb proteins, especially enzymes, very well and are also suitable for the adsorptive removal of disruptive polyphenols and dyes from aqueous solutions.
Bei den nativen und modifizierten Proteinen sowie den vernetzten Polymeren besteht der Nachteil, daß sie einer bestimmten Vorbehandlung durch Quellung bedürfen. Dies bedeutet einen sehr großen Zeitaufwand. Da der überwiegende Anteil der Produkte dem Anwen- dungsmedium gemeinsam mit den suspendierten Trübstoffen durch Sedimentation entzogen wird, ist auch dieser Schritt sehr zeitaufwendig und kann bis zu 6 Wochen dauern. Darüber hinaus besteht bei diesen Produkten der Nachteil, daß sie nicht alle phenoli- sehen Substanzen oder Substanzklassen in gleichem Maße enfernen, sondern daß jeweils eine bevorzugte Wechselwirkungen mit einer bestimmten Gruppe von phenolischen Substanzen besteht. Die anfal¬ lenden Sedimente sind meist schleimigpastöse Massen, denen durch eine nachgeschaltete Behandlung Flüssigkeit entzogen wird, um sie in einen weiterverwert- oder deponierbaren Zustand zu bringen.The disadvantage with the native and modified proteins and the crosslinked polymers is that they require a certain pretreatment by swelling. This means a very large amount of time. Since the vast majority of products medium is extracted together with the suspended turbidity by sedimentation, this step is also very time-consuming and can take up to 6 weeks. In addition, these products have the disadvantage that they do not remove all phenolic substances or classes of substances to the same extent, but that there is in each case a preferred interaction with a certain group of phenolic substances. The anfal ¬ lumbar sediments are mostly schleimigpastöse masses, which is removed by a downstream treatment liquid in order to bring them into a results processed further or landfillable state.
Der Erfindung lag daher die Aufgabe zugrunde ein Produkt zu finden, das die oben genannten Nachteile nicht aufweist und in der Lage ist, den Gehalt verschiedener Gruppen von phenolischen Verbindungen und gleichzeitig auch die Konzentration von gelösten Schwermetallen zu vermindern. Gleichzeitig sollte die Handhabbarkeit durch Wegfall der aufwendigen Vorbereitungsphase des Ein- satzstoffes verbessert werden.The invention was therefore based on the object of finding a product which does not have the disadvantages mentioned above and is able to reduce the content of different groups of phenolic compounds and at the same time also the concentration of dissolved heavy metals. At the same time, manageability should be improved by eliminating the complex preparation phase of the feed material.
Gegenstand der Erfindung sind feste Zubereitungen, bestehend ausThe invention relates to solid preparations consisting of
(a) 10 bis 90 Gew. -% Cellulose,(a) 10 to 90% by weight of cellulose,
(b) 5 bis 60 Gew. -% eines Alkalicaseinats(b) 5 to 60% by weight of an alkali caseinate
undand
(c) 5 bis 85 Gew. -% eines Polymerisats aus 90 bis 99,5 Gew. -% eines oder mehrerer N-Vinyllactame und 0,5 bis 10 Gew. -% eines Vernetzers(c) 5 to 85% by weight of a polymer of 90 to 99.5% by weight of one or more N-vinyl lactams and 0.5 to 10% by weight of a crosslinking agent
oderor
(d) 5 bis 85 Gew. -% eines Polymerisats aus 50 bis 99,5 Gew. -% mindestens eines basischen Vinylheterocyclus mit einem pKa-Werc von mindestens 3,8 und 0 bis 49,5 Gew. -% eines anderen copolymerisierbaren Monomeren sowie 0,5 bis 10 Gew. eines Vernetzers,(d) 5 to 85% by weight of a polymer of 50 to 99.5% by weight of at least one basic vinyl heterocycle with a pK a value of at least 3.8 and 0 to 49.5% by weight of another copolymerizable Monomers and 0.5 to 10% by weight of a crosslinking agent,
oder Gemischen der Polymerisate (c) und (d) ,or mixtures of the polymers (c) and (d),
sowie deren Herstellung und Verwendung.as well as their manufacture and use.
Unter Cellulose (a) sind im folgenden die verschiedenen Formen der Cellulose wie z.B. Zellstoffasern, mikronisierter Zellstoff, fibrillierter Zellstoff oder auch mikrokristalline Cellulose zu verstehen, die Schüttdichten zwischen 0,15 und 0,45 g/cm3, mitt- lere Faserlangen zwischen 15 μm und 900 μm und einem durcnschnitt- lichen Faserdurchmesser von 5 um bis 50 μm aufweisen.Cellulose (a) in the following means the various forms of cellulose such as cellulose fibers, micronized cellulose, fibrillated cellulose or also microcrystalline cellulose, the bulk densities between 0.15 and 0.45 g / cm 3 , average have longer fiber lengths between 15 μm and 900 μm and an average fiber diameter of 5 μm to 50 μm.
Unter einem Alkalicasemat (b) wird im folgenden vor allem Kali- umcasemat verstanden, das durch die Behandlung von Casem mit Kal umhydroxidlosung oder Losungen von alkalisch reagierenden Kaliumsalzen organischer oder anorganischer Sauren wie z.B. Phosphorsaure oder Zitronensaure erhalten w rd.An alkali casemate (b) is understood in the following to mean above all potassium casemate, which is obtained by treating casem with potassium hydroxide solution or solutions of alkaline potassium salts of organic or inorganic acids such as e.g. Phosphoric acid or citric acid is obtained.
Casem entstammt dabei aus kurzzeiterhitzter Magermilch mit einem maximalen Fettgehalt von 0,05 %. Die Dicklegung zur Abtrennung der Molke erfolgt mit Sauren durch pH-Werte stellung auf den lsoelektrischen Punkt des Caseins 4,5 + 0,2. Nach Wärmebehandlung, Abtrennung der Molke und Warmwasserwasche wird das Rohca- sein erhalten. Dieses wird als Naßbruch oder nach Trocknung zu Casemat weiterverarbeitet, indem es durch Zugabe von Kaliumhy- droxid oder anderer Alkalihydroxide Losung gebracht wird, die Trocknung erfolgt mittels Sprühtrocknung oder Extrusions- verfahren. Die erhaltenen Produkte, die sich für die Herstellung der erf dungsgemäßen Formulierungen besonders eignen, weisen einen Wassergehalt von 5 bis 10 % und einen Protemgehalt von 87 % bis 92 % sowie einen Aschegehalt von 3 % bis 8 % auf.Casem comes from short-term skimmed milk with a maximum fat content of 0.05%. Thickening to separate the whey is done with acids by adjusting the pH to the isoelectric point of the casein 4.5 + 0.2. After heat treatment, separation of the whey and hot water washing, the raw casa is obtained. This is further processed as a wet break or after drying to Casemat by bringing it to the solution by adding potassium hydroxide or other alkali hydroxides. The drying takes place by means of spray drying or extrusion processes. The products obtained, which are particularly suitable for the preparation of the formulations according to the invention, have a water content of 5 to 10% and a protein content of 87% to 92% and an ash content of 3% to 8%.
Unter N-Vmyllactamen (c) sind hier 3-Methyl—N-vmylpyrrolidon, insbesondere N— Vmylcaprolactam und N—Vmylpyrrolidon (VP) zu verstehen, die alle oder m Mischung untereinander eingesetzt werden .N-Vmyllactams (c) here mean 3-methyl-N-vmylpyrrolidone, in particular N-Vmylcaprolactam and N-Vmylpyrrolidone (VP), which are used all or in a mixture with one another.
Die Monomere (c) werden in einer Menge von 90 % bis 99,5 %, bevorzugt von 98 % bis 99 Gew. -% bezogen auf das Gesamtpolymer eingesetzt.The monomers (c) are used in an amount of 90% to 99.5%, preferably 98% to 99% by weight, based on the total polymer.
Geeignete Vernetzer sind solche, die zwei oder mehr rad kalisch copolymerisierbare Vmylgruppen im Molekül enthalten. Besonders geeignet sind Alkylenbisacrylamide w e Methylenbisacrylamid und N,N'—Bisacryloylethylendiamm, außerdem N,N' -Divmylethylennarn- stoff, N,N'—Divmylpropylenharnstoff , Ethyliden-Dis—3 - (N— inyl - pyrrolidon) sowie N,N' -Divmyldiimidazolyl - (2 , 2' ) -1, 4-butan und 1, 1' -Bis (3 , 3 '— mylbenzιmιdazolιd-2-on) 1 , 4-butan. Andere brauch- bare Vernetzungsmittel sind beispielsweise Alkylen- glykoldi (meth) acrylate wie Ethylenglykoldi (meth) acrylat und Tetramethylenglykoldi (meth) acrylat, aromatische DivmylVerbindungen wie Divmylbenzol und Divmyltoluol sowie Alkylacrylat , Divmyldioxan, Pentaerythrit—triallylether und deren Gemische. Bei Polymerisation Gegenwart von Wasser sind sie natürlich nur geeignet, soweit sie der wäßrigen Monomermiscnung löslich sind.Suitable crosslinkers are those which contain two or more radically copolymerizable Vmylgruppen in the molecule. Particularly suitable are alkylenebisacrylamides such as methylenebisacrylamide and N, N'-bisacryloylethylene diamine, also N, N '-divmylethylene urea, N, N'-divmylpropylene urea, ethylidene dis-3 - (N- inyl-pyrrolidone) and N, N' - Divmyldiimidazolyl - (2, 2 ') -1, 4-butane and 1, 1' -Bis (3, 3 '- mylbenzιmιdazolιd-2-one) 1, 4-butane. Other usable crosslinking agents are, for example, alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and tetramethylene glycol di (meth) acrylate, aromatic divmyl compounds such as divmylbenzene and divmyltoluene as well as alkyl acrylate, divmyldioxane, pentaerythritol and their triallyl ether. In the presence of water they are of course only polymerized suitable insofar as they are soluble in the aqueous monomer mixture.
Die Vernetzer werden m einer Menge von 0,5-10, bevorzugt von 1-2 Gew. %, bezogen auf alle Monomere des Polymerisats, eingesetzt.The crosslinkers are used in an amount of 0.5-10, preferably 1-2% by weight, based on all the monomers of the polymer.
Unter basischen Vmylheterocyclen (d) sind hier gesattigte und aromatisch ungesättigte Heterocyclen mit einer Vmylgruppe und mindestens einem basischen tertiären Rmg-St ckstoffatom mit einem pKa von mindestens 3,8 zu verstehen. Außer der Vmylgruppe kann der Ring auch Alkylgruppen mit 1 bis 4 Kohlenstoffatomen, Phenyl— oder Benzyl-Gruppen oder auch einen anellierten zweiten Ring tragen. Als Beispiele seien genannt: N-Vmylimidazol (VI) sowie Derivate davon w e 2-Methyl-l-vmylιmιdazol , 4-Methyl-l-vmylιmιdazol, 5-Methyl-l-vmylιmιdazol,Basic Vmylheterocycles (d) are to be understood here as saturated and aromatically unsaturated heterocycles with a Vmylgruppe and at least one basic tertiary Rmg atom with a pK a of at least 3.8. In addition to the methyl group, the ring can also carry alkyl groups with 1 to 4 carbon atoms, phenyl or benzyl groups or also a fused second ring. Examples include: N-Vmylimidazole (VI) and derivatives thereof we 2-methyl-l-vmylιmιdazol, 4-methyl-l-vmylιmιdazol, 5-methyl-l-vmylιmιdazol,
2—Ethyl-1—vmylimidazol , 2-Propyl—1—v ylimidazol , 2—Iso- propyl—1— mylimidazol , 2-Phenyl—l—vmylimidazol , 1—Vmyl-4 , 5-benzιmιdazol . Weiterhin können beispielsweise eingesetzt werden: 2—Vmylpyπdm, 4-Vmylpyrιdm sowie 2—Methyl-5-vmylpyrιdm. Selbstverständlich können auch Gemische von basischen Vmylheterocyclen untereinander eingesetzt werden.2-ethyl-1-methylimidazole, 2-propyl-1-vinylimidazole, 2-isopropyl-1-methylimidazole, 2-phenyl-1-methylimidazole, 1-methyl-4,5-benzimidazole. The following can also be used, for example: 2-methylpym, 4-methylpmdm and 2-methyl-5-methylpyrm. Mixtures of basic methyl heterocycles with one another can of course also be used.
Hierfür bevorzugte Monomere sind N-Vmylimidazol und 2-Methyl-N- v ylimidazol .Preferred monomers for this are N-methylimidazole and 2-methyl-N-ylimidazole.
Diese Monomeren werden m einer Menge von 50-99,5, bevorzugt von 60-96 Gew.-% bezogen auf das Gesamtpolymer eingesetzt.These monomers are used in an amount of 50-99.5, preferably 60-96% by weight, based on the total polymer.
Die Comonomeren, werden m Mengen bis zu 49,5, vorzugsweise bis zu 30 Gew.— , besonders bevorzugt bis zu 20 Gew.-% bezogen auf die gesamte Monomermiscnung, empolymerisiert . Als Comonomere kommen beispielsweise Styrol, Acrylester, Vmylester, Acryla ide, N-Vmyl-dihydropyridme m Betracht. Bevorzugt werden als Comonomere (n) N-Vmyllactame wie 3-Methyl—N— mylpyrrolidon, ms- besondere N—Vmylcaprolactam und N—Vmylpyrrolidon (VP) verwendet .The comonomers are polymerized in amounts of up to 49.5, preferably up to 30% by weight, particularly preferably up to 20% by weight, based on the total monomer mixture. Examples of suitable comonomers are styrene, acrylic ester, methyl ester, acrylic ide and N-methyl dihydropyridme. N-Vmyllactams such as 3-methyl-N-mylpyrrolidone, ms-particular N-Vmylcaprolactam and N-Vmylpyrrolidone (VP) are preferably used as comonomers.
Geeignete Vernetzer für die Polymeren (d) sind eoenfalls solche, die zwei oder mehr radikalisch copolymerisierbare Vmylgruppen m Molekül enthalten. Besonders geeignet sind Alkylenbisacrylamide wie Methylenbisacrylamid und N, N'—Bisacryloylethylendiamm, außerdem N, N'—Divmylethylenharnstoff , N,N'—Divmylpropylen- harnstoff, Ethylιden-bιs-3 - (N—vmylpyrrolidon) sowie N,N'—Divi- nyldumidazolyl- (2,2' )—1, 4-butan und 1, 1'—Bis (3, 3 '—vmylbenzimi - dazolid—2-on) -1, 4-butan. Andere brauchbare Vernetzungsmittel sind beispielsweise Alkylenglykoldi (meth) acrylate wie Ethylen- glykoldi (meth) acrylat und Tetramethylenglykoldi (meth) acrylat, aromatische Divinylverbindungen wie Divinylbenzol und Divinyl- toluol sowie Allylacrylat , Divinyldioxan, Pentaerythrittriallyl- ether und deren Gemische. Bei Polymerisation in Gegenwart von Wasser sind sie natürlich nur geeignet, soweit sie in der wäßrigen Monomermischung löslich sind.Suitable crosslinkers for the polymers (d) are also those which contain two or more free-radically copolymerizable methyl groups in the molecule. Particularly suitable are alkylenebisacrylamides such as methylenebisacrylamide and N, N'-bisacryloylethylene diamine, also N, N'-divmylethylene urea, N, N'-divmylpropylene urea, ethylidene-bιs-3 - (N-vmylpyrrolidone) and N, N'-divi- nyldumidazolyl- (2,2 ') -1,4-butane and 1,1'-bis (3,3' -vmylbenzimi-dazolid-2-one) -1,4-butane. Other useful crosslinking agents are, for example, alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and tetramethylene glycol di (meth) acrylate, aromatic divinyl compounds such as divinylbenzene and divinyltoluene as well as allyl acrylate, divinyldioxane, pentaerythritol triallyl ether and mixtures thereof. In the case of polymerization in the presence of water, they are of course only suitable if they are soluble in the aqueous monomer mixture.
Die Vernetzer werden für die Polymere (d) gleichwohl in einer Menge von 0,5-10, bevorzugt von 1-4 Gew. -%, bezogen auf alle Monomere des Polymerisats, eingesetzt.The crosslinkers are nevertheless used for the polymers (d) in an amount of 0.5-10, preferably 1-4% by weight, based on all the monomers of the polymer.
Für die erfindungsgemäße Verwendung besonders gut geeignete Cel- lulosen (a) sind solche, die weniger als 1 % wasserlösliche Substanzen enthalten und eine Faserlänge von 20 μm bis 200 μm, bevorzugt 25 bis 50 μm, und einen Faserdurchmesser von 5 μm bis 50 μm, bevorzugt 10 bis 20 μm, aufweisen.Celluloses (a) which are particularly suitable for the use according to the invention are those which contain less than 1% water-soluble substances and have a fiber length of 20 μm to 200 μm, preferably 25 to 50 μm, and a fiber diameter of 5 μm to 50 μm, preferably have 10 to 20 μm.
Für die erfindungsgemäße Verwendung besonders gut geeignete Alkalicaseinate (b) sind Kaliumcaseinate mit einer guten Löslichkeit, bevorzugt größer 99 % und hohen bakteriologischen Ansprüchen, bevorzugt mit einer Gesamtkeimzahl von kleiner 5000 kBE/g, Hefen kleiner 10/g und Schimmel kleiner 10/g.Alkalic caseinates (b) which are particularly suitable for the use according to the invention are potassium caseinates with good solubility, preferably greater than 99% and high bacteriological requirements, preferably with a total bacterial count of less than 5000 kBE / g, yeast less than 10 / g and mold less than 10 / g.
Für die erfindungsgemäße Verwendung besonders gut geeignete Polymere (c) sind solche aus N-Vinylpyrrolidon (VP) und N,N' -Divmyl - ethylenharnstoff (DVEH), insbesondere solche aus 98-99,5 Gew.-% VP und 0,5-2,0 Gew.-% DVEH.Polymers (c) which are particularly suitable for the use according to the invention are those composed of N-vinylpyrrolidone (VP) and N, N '-divmylethyleneurea (DVEH), in particular those composed of 98-99.5% by weight of VP and 0.5 -2.0% by weight DVEH.
Für die erfindungsgemäße Verwendung besonders gut geeignete Polymere (d) sind solche aus N-Vinylimidazol (VI) , N-Vinylpyrrolidon (VP) und N, N' -Divinylethylenharnstoff (DVEH), insbesondere solche aus 80-90 Gew.-% VI, 5-15 Gew.-% VP und 2-5 Gew.-% DVEH.Polymers (d) which are particularly suitable for the use according to the invention are those of N-vinylimidazole (VI), N-vinylpyrrolidone (VP) and N, N '-divinylethyleneurea (DVEH), in particular those of 80-90% by weight of VI, 5-15 wt% VP and 2-5 wt% DVEH.
In EP—A-4 38713 werden solche Polymeren (d) zur Entfernung von Schwermetallen aus Wein und weinähnlichen Getränken eingesetzt. Auf diese Schrift wird hinsichtlich der Herstellung der Polymere ausdrücklich Bezug genommen.In EP-A-4 38713 such polymers (d) are used to remove heavy metals from wine and wine-like beverages. Reference is expressly made to this document with regard to the production of the polymers.
Die Korngrößenverteilung der Polymerisatpartikel (c) und (d) liegt üblicherweise im Bereich von 0,01 - 100 μm, bevorzugt im Bereich von 5 - 50 μm.The particle size distribution of the polymer particles (c) and (d) is usually in the range from 0.01 to 100 μm, preferably in the range from 5 to 50 μm.
Die Zubereitung wird in einer Verfahrensvariante 1 derart hergestellt, daß in einer Lösung aus Alkalicaseinat (b) , bevorzugt in einer Konzentration von 2 Gew. -% bis 20 Gew. -% Trockenmasse, die Cellulose (a) und die Polymerisate (c) und/oder (d) suspendiert werden. Die Konzentrationen der Komponenten (c) und/oder (d) betragen zwischen 2 % und 20 % der Trockensubstanz der Suspension.The preparation is prepared in a process variant 1 in such a way that in a solution of alkali caseinate (b), preferably in a concentration of 2% by weight to 20% by weight dry matter, the cellulose (a) and the polymers (c) and / or (d) suspended become. The concentrations of components (c) and / or (d) are between 2% and 20% of the dry matter of the suspension.
Die Suspension wird sprühgetrocknet, bevorzugt unter Einsatz einer Einstoffdüse bei Drücken von 50 bar bis 150 bar, bevorzugt kleiner 100 bar.The suspension is spray-dried, preferably using a single-component nozzle at pressures from 50 bar to 150 bar, preferably less than 100 bar.
In einer weiteren Verfahrensvariante (Verfahrensvariante 2) werden die Komponenten (a) und (b) wie in Verfahrensvariante 1 dar- gestellt vorgelegt, indem man die Cellulose (b) in einer wäßrigen Lösung des Alkalicaseinats suspendiert. Diese Suspension wird dann zerstäubt, wobei das dadurch entstehende Primäraerosol in feuchtem Zustand mit den pulverförmigen Polymerkomponenten unmittelbar in Kontakt gebracht und die entstehenden polymerhaltigen Suspensionstropfchen getrocknet werden. Die Komponenten (c) und/ oder (d) werden entsprechend trocken in die Zerstäubungszone des Turms eingeblasen.In a further process variant (process variant 2), components (a) and (b) are introduced as shown in process variant 1 by suspending the cellulose (b) in an aqueous solution of the alkali caseinate. This suspension is then atomized, the resulting primary aerosol being brought directly into contact with the powdery polymer components in the moist state and the resulting polymer-containing suspension droplets being dried. Components (c) and / or (d) are blown into the atomization zone of the tower in a correspondingly dry manner.
In einer weiteren Möglichkeit der Herstellung (Verfahrens - Variante 3) werden Pulver nach den Verfahrensvarianten 1 oder 2 hergestellt, zunächst auf einen Restfeuchtegehalt von 10 bis 15 Gew. -% im Turm getrocknet und zur Erzielung eines zusätzlichen Agglomerierungseffektes bei einer Pulvertemperatur von 70°C bis 40°C, bevorzugt von 60°C bis 50°C, zur Nachtrocknung auf Band aus - getragen und bei einer Zuluf ttemperatur von 60°C bis 110°C auf einen Restfeuchtegehalt von 6 - 10 Gew. -% eingestellt. Eine Nachtrocknung bei erhöhter Temperatur ergibt einen zusätzlichen Agglomeriereffekt .In a further possibility of production (process variant 3), powders are produced according to process variants 1 or 2, first dried in the tower to a residual moisture content of 10 to 15% by weight and to achieve an additional agglomeration effect at a powder temperature of 70 ° C up to 40 ° C, preferably from 60 ° C to 50 ° C, carried out on tape for post-drying and adjusted to a residual moisture content of 6-10% by weight at a supply air temperature of 60 ° C to 110 ° C. Post-drying at an elevated temperature results in an additional agglomeration effect.
Die Anwendung der Zubereitungen erfolgt in der Art, daß diese pulverförmig ohne Vorbehandlung dem Anwendungsmedium zugesetzt werden. Die Wirkung setzt unmittelbar nach Benetzung der Formulierung ein. Zur Behandlung von biologischen Flüssigkeiten pflanzlichen Ursprungs in nichtvergorenem Zustand wird eine Dosierung von 5 bis 150 g/hl , bevorzugt 10 bis 50 g/hl eingesetzt. Teilweise vergorene oder vollständig vergorene biologische Flüssigkeiten pflanzlichen Ursprungs werden mit 25 bis 250 g/hl, in einer bevorzugten Form mit 40 bis 150 g/hl und in einer besonders bevorzugten Anwendungsform mit Dosiermengen von 50 bis 100 g/hl behandelt. Als Flüssigkeiten kommen insbesondere Wein, Traubenmost oder weinähnliche Getränke sowie deren nicht vergorene Moste (Beeren- und Fruchtsäfte) in Betracht. Zur Abtrennung der Formulierungen aus dem Anwendungsmedium sind alle Formen der Fest-/Flüssigtrennung, wie zum Beispiel Zentrifugen, Dekanter, Schichten- und Kieselgurfiltration sowie Membrantechnologien geeignet.The preparations are used in such a way that they are added to the application medium in powder form without pretreatment. The effect starts immediately after wetting the formulation. A dosage of 5 to 150 g / hl, preferably 10 to 50 g / hl, is used for the treatment of biological liquids of plant origin in the non-fermented state. Partially fermented or completely fermented biological liquids of plant origin are treated with 25 to 250 g / hl, in a preferred form with 40 to 150 g / hl and in a particularly preferred application form with dosage amounts of 50 to 100 g / hl. Particularly suitable liquids are wine, grape must or wine-like drinks and their non-fermented musts (berry and fruit juices). All forms of solid / liquid separation, such as centrifuges, decanters, layer and diatomaceous earth filtration and membrane technologies, are suitable for separating the formulations from the application medium.
Bei diesen Prozessen hat sich überraschenderweise herausgestellt, daß sich die Filtrationseigenschaften mit der mit diesem Verfahren abgetrennten festen Bestandteilen, bestehend aus den zugesetzten Formulierungen und den im Anwendungsmedium suspendierten Trubpartikel, deutlich verbessern, da sich der Filtermittelwiderstand ß und der mittlere Filterkuchenwiderstand α deutlich erniedrigt. Diese Kennzahlen werden mit Hilfe der CarmangleichungIn these processes it has surprisingly been found that the filtration properties with the solid constituents separated off by this process, consisting of the added formulations and the suspended particles suspended in the application medium, markedly improve since the filter medium resistance β and the mean filter cake resistance α decrease significantly. These metrics are calculated using the carman equation
dVf / dt = Δp • A / ηf • (ß + α • ws • Vf / A)dV f / dt = Δp • A / η f • (ß + α • w s • V f / A)
ermittelt, wobeidetermined where
Vf Filtratvoiumen in m3 , t Filtrationsdauer in s, A Filterfläche in m2 ,V f filtrate volume in m 3 , t filtration time in s, A filter area in m 2 ,
Δp Druckdifferenz in Pa, ws Feststoffkonzentration in kg/m3 (Feststoff/Fluid) ηf dynamische Viskosität des Filtrates in Pas, α Filterkuchenwiderstand in m/kg, ß Filtermittelwiderstand in "1 Δp pressure difference in Pa, w s solids concentration in kg / m 3 (solid / fluid) η f dynamic viscosity of the filtrate in Pas, α filter cake resistance in m / kg, ß filter medium resistance in " 1
bedeuten.mean.
Mit Hilfe der erfindungegemäßen Zubereitungen lassen sich Flüs - sigkeiten pflanzlichen Ursprungs in besonders vorteilhafter Weise gegen farbliche und geschmackliche Veränderungen stabilisieren. Durch die kombinierte Anwendung von Alkalicaseinat und vernetzten! Polymerisat wird durch das Ausfallen des Caseinats am IEP in enger Verknüpfung mit dem vernetzten Polymerisat eine Oberflächen- Vergrößerung erzielt, die einen besonders effektiven Stabilisierungseffekt gegen oxidative Veränderungen zur Folge hat.The preparations according to the invention can be used to stabilize liquids of vegetable origin in a particularly advantageous manner against changes in color and taste. Through the combined use of alkali caseinate and cross-linked! By precipitating the caseinate at the IEP in close connection with the crosslinked polymer, the polymer is increased in surface area, which has a particularly effective stabilizing effect against oxidative changes.
Beispiel 1example 1
In einer Lösung von 10 kg Kaliumcasemat (b) in 400 1 Wasser bei 60°C, wurden 80 kg Cellulose (a) suspendiert. Die Suspension wird bei ca. 180°C mit 50 bar über eine Einstoffdüse zerstäubt und 10 kg Polymer (c) , bezogen auf 90 kg Kaliumcasemat- rockenprodukt, hergestellt aus 98 % N-Vinylpyrrolidon mit 2 % Vernetzer in Form von N,N' -Divinylimidazolidin-2-on, trocken in der Zerstäubungszone zudosiert. Beispiel 280 kg of cellulose (a) were suspended in a solution of 10 kg of potassium casemate (b) in 400 l of water at 60 ° C. The suspension is atomized at about 180 ° C. at 50 bar through a single-substance nozzle and 10 kg of polymer (c), based on 90 kg of potassium casemate rock product, made from 98% N-vinylpyrrolidone with 2% crosslinker in the form of N, N ' -Divinylimidazolidin-2-one, added dry in the atomization zone. Example 2
Eine Formulierung bestehend aus 70 kg Cellulose, 20 kg Kaliumcasemat sowie 10 kg Polymer (d) mit einem Anteil an N-Vinyli- 5 midazol (VI) von 90 Gew.-% , einem Anteil an N-Vinylpyrrolidon (VP) von 7 Gew.-% und einem Anteil an N,N' -Divinylethylenharn- stoff (DVEH) von 3 Gew.-% wurde hergestellt, in dem man das Kaliumcasemat in 400 1 Wasser von 60 °C löst und die Cellulose darin suspendiert. Die Suspension wurde bei 185°C mit 70 bar über eine 10 Einstoffdüse zerstäubt und das Polymer in die Zerstäubungszone eingeblasen.A formulation consisting of 70 kg of cellulose, 20 kg of potassium casemate and 10 kg of polymer (d) with a proportion of N-vinylimidazole (VI) of 90% by weight and a proportion of N-vinylpyrrolidone (VP) of 7% by weight .-% and a proportion of N, N '-divinylethylene urea (DVEH) of 3 wt .-% was prepared by dissolving the potassium casemate in 400 l of water at 60 ° C and suspending the cellulose therein. The suspension was atomized at 185 ° C. at 70 bar through a 10-component nozzle and the polymer was blown into the atomization zone.
Beispiel 3Example 3
15 Eine Formulierung bestehend aus 50 kg Cellulose, 30 kg Kaliumcasemat, 10 kg Polymer (c) und 10 kg Polymer (d) wurde wie folgt hergestellt:15 A formulation consisting of 50 kg cellulose, 30 kg potassium casemate, 10 kg polymer (c) and 10 kg polymer (d) was prepared as follows:
Das Kaliumcaseinat (b) wurde in 320 1 Wasser von 60 °C gelöst und 20 die Cellulose (c) darin suspendiert. Die Suspension wurde bei 180°C mit 50 bar über eine Einstoffdüse zerstäubt und eine Mischung der beiden Polymere (c) und (d) mit einem Mischungsverhältnis 1:1 in die Zerstäubungszone eingeblasen.The potassium caseinate (b) was dissolved in 320 l of water at 60 ° C. and the cellulose (c) was suspended in it. The suspension was atomized at 180 ° C. at 50 bar through a single-component nozzle and a mixture of the two polymers (c) and (d) was blown into the atomization zone with a mixing ratio of 1: 1.
25 Beispiel 425 Example 4
3 Liter Weißwein wurden mit 3 g der Formulierung 1 über einen Zeitraum von 30 Minuten behandelt. Die Formulierung wird dabei zweimal resuspendiert und anschließend mittels eines Einschich- 30 tenfilters unter Verwendung einer Celluloseschicht abgetrennt und in Flaschen mit 0,5 Litern Volumen gefüllt.3 liters of white wine were treated with 3 g of formulation 1 over a period of 30 minutes. The formulation is resuspended twice and then separated using a single-layer filter using a cellulose layer and filled into bottles with a volume of 0.5 liters.
In der Tabelle 1 sind die Befunde unmittelbar nach der Behandlung und Flaschenfüllung sowie nach einer Lagerdauer von 28 Tagen bei 35 50°C zusammengefaßt.Table 1 summarizes the findings immediately after treatment and bottle filling and after a storage period of 28 days at 35 50 ° C.
4040
45 Tabelle 145 Table 1
1010
1515
2020th
25 E: Extinktion bei 320, 420, 520 nm; Schichtdicke in cm25 E: absorbance at 320, 420, 520 nm; Layer thickness in cm
Durch die Behandlung wird die Bräunung, ausgedrückt als Extinktionswert bei 420 nm, gemindert. Nach der Streßlagerung zeigen die Differenzwertε der Extinktionen bei 420 nm und 520 nm, daß der 30 behandelte Wein eine geringere Neigung zur farblichen Veränderung aufweist als der unbehandelte Vergleich.The treatment reduces the browning, expressed as an absorbance value at 420 nm. After the stress storage, the difference values of the extinctions at 420 nm and 520 nm show that the wine treated has a lower tendency to change color than the untreated comparison.
Beispiel 5Example 5
35 10 Liter Most aus roten Trauben wurden mit 10 g der Formulierung 2 über einen Zeitraum von 30 Minuten behandelt. Die Formulierung wurde kontinuierlich resuspendiert und anschließend über einen Einschichtenfilter unter Verwendung einer Celluloseschicht abgetrennt. Der behandelte Ansatz wurde mit 0,2 g Reinzuchthefe bis35 10 liters of red grape must were treated with 10 g of formulation 2 over a period of 30 minutes. The formulation was continuously resuspended and then separated on a single layer filter using a cellulose layer. The treated batch was mixed with 0.2 g pure yeast
40 zum Aussetzen der C0 - Entwicklung vollständig vergoren, erneut filtriert und in Flaschen mit 0,5 Litern Volumen gefüllt.40 to suspend C0 development completely fermented, filtered again and filled into bottles with a volume of 0.5 liters.
Tabelle 2 zeigt die Befunde unmittelbar nach der Behandlung und Flaschenfüllung sowie nach einer Lagerdauer von 28 Tagen bei 50°C. 45 Die Flaschenfüllung erfolgte mit einem Kopfräum von 150 ml Luft. Tabelle 2Table 2 shows the results immediately after treatment and bottle filling and after a storage period of 28 days at 50 ° C. 45 The bottle was filled with a head space of 150 ml of air. Table 2
Die Differenzwerte der Extinktion bei 420 nm bestätigen, daß der behandelte Wem eine geringere Neigung zu oxidativ bedingten farblichen Veränderung aufweist als der unbehandelte Vergleich.The difference in absorbance at 420 nm confirms that the treated person has less tendency to undergo oxidative color changes than the untreated comparison.
Beispiel 6Example 6
Je 10 1 Most aus Weißburgundertrauben wurden mit 5,0 g bzw. 15,0 g der erfmdungsgemaßen Formulierung 2 versetzt. Ein weite - rer Ansatz von 10 1 verbleibt onne Zusatz. Nach einer Behandlungszeit von 22 h wurde die flüssige Phase vom erhaltenen Sediment abgezogen. Anschließend wurden die mit und ohne Zusatz der erfmdungsgemaßen Formulierung 2 erhaltenen Mosttrubsedimente über eine instrumentierte Filteranlage mit 130 cm2 Filterflache bei einer Druckdifferenz von 0,5 MPa filtriert.5.0 g and 15.0 g of formulation 2 according to the invention were added to each 10 1 must from Pinot Blanc grapes. Another approach of 10 1 remains without an addition. After a treatment time of 22 h, the liquid phase was drawn off from the sediment obtained. The must trub sediments obtained with and without addition of formulation 2 according to the invention were then filtered through an instrumented filter system with a filter area of 130 cm 2 at a pressure difference of 0.5 MPa.
Tabelle 3 zeigt die errechneten Filtermittelwiderstande ß sowie die mittleren spezifischen Filterkuchenwidersatnde α der drei Ansätze. Tabelle 3Table 3 shows the calculated filter medium resistance ß and the mean specific filter cake resistance α of the three batches. Table 3
Die Filtereigenschaften der Mosttrubsuspensionen, ausgedrückt durch sinkende Filtermittelwiderstände ß und sinkende Filterkuchenwiderstände α, werden in Abhängigkeit von der Dosierung der zugesetzten Formulierung deutlich verbessert. The filter properties of the must trub suspensions, expressed by decreasing filter medium resistances ß and falling filter cake resistances α, are significantly improved depending on the dosage of the added formulation.

Claims

Patentansprüche claims
1. Pulverförmige Zubereitungen, bestehend aus1. Powdered preparations consisting of
(a) 10 bis 90 Gew. -% Cellulose,(a) 10 to 90% by weight of cellulose,
(b) 5 bis 60 Gew. -% eines Alkalicaseinats(b) 5 to 60% by weight of an alkali caseinate
undand
(c) 5 bis 85 Gew. -% eines Polymerisats aus 90 bis 99,5 Gew. -% eines oder mehrerer N-Vinyllactame und 0,5 bis 10 Gew. -% eins Vernetzers(c) 5 to 85% by weight of a polymer of 90 to 99.5% by weight of one or more N-vinyl lactams and 0.5 to 10% by weight of a crosslinking agent
oderor
(d) 5 bis 85 Gew.-% eines Polymerisats aus 50 bis 99,5 Gew. -% mindestens eines basischen Vinylheterocyclus mit einem pKa-Wert von mindestens 3,8 und 0 bis 49,5 Gew.-% eines anderen copolymerisierbaren Monomeren sowie 0,5 bis 10 Gew. -% eines Vernetzers,(d) 5 to 85% by weight of a polymer of 50 to 99.5% by weight of at least one basic vinyl heterocycle having a pK a of at least 3.8 and 0 to 49.5% by weight of another copolymerizable Monomers and 0.5 to 10% by weight of a crosslinking agent,
oder Gemischen der Polymerisate (c) und (d) .or mixtures of the polymers (c) and (d).
2. Zubereitungen nach Anspruch 1, enthaltend als Alkalicaseinat Kaliumcaseinat .2. Preparations according to claim 1, containing potassium caseinate as alkali caseinate.
3. Zubereitungen nach Anspruch 1 oder 2, enthaltend Polymerisate (c) , die als N-Vinyllactam, N-Vinylpyrrolidon oder N-Vinyl- caprolactam oder Mischungen davon enthalten.3. Preparations according to claim 1 or 2, containing polymers (c) which contain as N-vinyl lactam, N-vinyl pyrrolidone or N-vinyl caprolactam or mixtures thereof.
4. Zubereitungen nach einem der Ansprüche 1 bis 3, enthaltend Polymerisate (d) , die als basischen Vinylheterocyclus einen gegebenenfalls substituierten und/oder benzokondensierten, 5- oder 6-gliedrigen Vinylheterocyclus mit einem oder zwei Ringstickstoff tomen einpolymerisiert enthalten.4. Preparations according to one of claims 1 to 3, containing polymers (d) which, as a basic vinyl heterocycle, contain an optionally substituted and / or benzo-condensed, 5- or 6-membered vinyl heterocycle with one or two ring nitrogen atoms copolymerized.
5. Zubereitungen nach einem der Ansprüche 1 bis 4, in denen das Polymerisat N-Vmylimidazol, 2 -Methyl- 1 -vmylimidazol, 2-Vinylpyridin, 4 -Vinylpyridin oder 2 -Methyl -4 -vinylpyridin oder eine Mischung davon einpolymerisiert enthält.5. Preparations according to one of claims 1 to 4, in which the polymer contains N-vmylimidazole, 2-methyl-1 -vmylimidazole, 2-vinylpyridine, 4 -vinylpyridine or 2 -methyl-4-vinylpyridine or a mixture thereof in copolymerized form.
6. Verfahren zur Herstellung von Zubereitungen gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Cellulose (b) und die Polymerisate (c) und/oder (d) in einer wässrigen Lösung des Alkalicaseinats suspendiert werden und die Suspension der Sprühtrocknung unterworfen wird.6. A process for the preparation of preparations according to any one of claims 1 to 5, characterized in that the cellulose (b) and the polymers (c) and / or (d) in an aqueous Solution of the alkali caseinate are suspended and the suspension is subjected to spray drying.
7. Verfahren zur Herstellung von Zubereitungen gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Cellulose7. A process for the preparation of preparations according to any one of claims 1 to 5, characterized in that the cellulose
(b) in einer wäßrigen Lösung des Alkalicaseinats suspendiert und zerstäubt wird, wobei das dadurch entstehende Primärearo- sol in feuchtem Zustand mit den pulverförmigen Polymerkomponenten unmittelbar in Kontakt gebracht und die entstehenden polymerhaltigen Suspensionströpfchen getrocknet werden.(b) suspended and atomized in an aqueous solution of the alkali caseinate, the primary urosol thus formed being brought directly into contact with the powdery polymer components in the moist state and the resulting polymer-containing suspension droplets being dried.
8. Verwendung von Zubereitungen gemäß einem der Ansprüche 1 bis 5 zur stabilisierenden Behandlung von Flüssigkeiten pflanzlichen Ursprungs.8. Use of preparations according to one of claims 1 to 5 for the stabilizing treatment of liquids of plant origin.
9. Verwendung nach Anspruch 8 zur Behandlung von Wein oder wein- ähnlichen Getränken.9. Use according to claim 8 for the treatment of wine or wine-like beverages.
10. Verwendung nach Anspruch 8 oder 9, wobei pro Hektoliter der Flüssigkeit 5 bis 150 g der Zubereitungen eingesetzt werden. 10. Use according to claim 8 or 9, wherein 5 to 150 g of the preparations are used per hectoliter of the liquid.
EP97954353A 1996-12-18 1997-12-04 Production and use of formulations consisting of cellulose, kalium caseinate and cross-linked vinyl pyrrolidone homopolymers and/or vinylimidazol/vinylpyrrolidone copolymers Withdrawn EP0946636A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19652697A DE19652697A1 (en) 1996-12-18 1996-12-18 Production and use of formulations consisting of cellulose, potassium caseinate and crosslinked vinylpyrrolidone homopolymers and / or vinylimidazole / vinylpyrrolidone copolymers
DE19652697 1996-12-18
PCT/EP1997/006779 WO1998027150A1 (en) 1996-12-18 1997-12-04 Production and use of formulations consisting of cellulose, kalium caseinate and cross-linked vinyl pyrrolidone homopolymers and/or vinylimidazol/vinylpyrrolidone copolymers

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EP1115469B1 (en) * 1998-09-18 2003-10-15 Franz-Dietrich Oeste Fibrous products containing active substances, a method for the production thereof, and use of the same
WO2001068798A1 (en) * 2000-03-13 2001-09-20 Isp Investments Inc. Wine stabilizer and clarifier
US8018903B2 (en) * 2001-11-21 2011-09-13 Texas Instruments Incorporated Closed-loop transmit diversity scheme in frequency selective multipath channels
FR2832630B1 (en) * 2001-11-28 2005-01-14 Oreal COSMETIC AND / OR DERMATOLOGICAL COMPOSITION CONTAINING AT LEAST ONE OXIDATION-SENSITIVE HYDROPHILIC ACTIVE STABILIZED WITH AT LEAST ONE COPOLYMER OF N-VINYLIMIDAZOLE
ES2254885T3 (en) * 2002-06-20 2006-06-16 L'oreal COSMETIC AND / OR DERMATOLOGICAL USE OF A COMPOSITION THAT CONTAINS AT LEAST A HYDROPHYLE AGENT SENSITIVE TO OXIDATION FOR AT LEAST ONE MALEIC ANHYDRID COPOLYMER.
DE10261910A1 (en) * 2002-12-30 2004-07-15 Polymerics Gmbh Adsorber material for blood, blood plasma and albumin purification processes
US20060027321A1 (en) * 2004-08-09 2006-02-09 3M Innovative Properties Company Adhesive composition
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JPS5429599B2 (en) * 1974-12-28 1979-09-25
DE3209224A1 (en) 1982-03-13 1983-09-15 Basf Ag METHOD FOR THE PRODUCTION OF INSOLUBLE, LITTLE SWELLABLE POLYMERISATES OF BASIC VINYLHETEROCYCLES AND THE USE THEREOF
DD235887A1 (en) * 1985-03-29 1986-05-21 Univ Halle Wittenberg PROCESS FOR FILTRATION OF BEVERAGES
JPS6410976A (en) * 1987-07-03 1989-01-13 Toyo Roshi Kaisha Method for removing polyphenols in vegetable liquid beverage and filtering sheet used therefor
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CA2275254A1 (en) 1998-06-25
WO1998027150A1 (en) 1998-06-25
AU5854098A (en) 1998-07-15

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