WO1999015023A2 - Procede de recuperation - Google Patents

Procede de recuperation Download PDF

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Publication number
WO1999015023A2
WO1999015023A2 PCT/NZ1998/000140 NZ9800140W WO9915023A2 WO 1999015023 A2 WO1999015023 A2 WO 1999015023A2 NZ 9800140 W NZ9800140 W NZ 9800140W WO 9915023 A2 WO9915023 A2 WO 9915023A2
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WO
WIPO (PCT)
Prior art keywords
substance
resin
solution
recovered
particles
Prior art date
Application number
PCT/NZ1998/000140
Other languages
English (en)
Other versions
WO1999015023A3 (fr
Inventor
Lynton Alexander Bridger
Original Assignee
Kiwi Co-Operative Dairies Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kiwi Co-Operative Dairies Limited filed Critical Kiwi Co-Operative Dairies Limited
Priority to AU93685/98A priority Critical patent/AU9368598A/en
Publication of WO1999015023A2 publication Critical patent/WO1999015023A2/fr
Publication of WO1999015023A3 publication Critical patent/WO1999015023A3/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C7/00—Other dairy technology
    • A23C7/04—Removing unwanted substances other than lactose or milk proteins from milk
    • A23C7/043—Removing unwanted substances other than lactose or milk proteins from milk using chemicals in liquid or solid state, e.g. flocculating, adsorbing or extracting agents
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C9/00—Milk preparations; Milk powder or milk powder preparations
    • A23C9/14—Milk preparations; Milk powder or milk powder preparations in which the chemical composition of the milk is modified by non-chemical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/005—Pretreatment specially adapted for magnetic separation
    • B03C1/01—Pretreatment specially adapted for magnetic separation by addition of magnetic adjuvants

Definitions

  • This invention relates to a recovery process More particularly, it relates to a process for recovering minor components from solutions for use in the food and health/pharmaceutical industries It particularly but not solely relates to a process for recovering minor components from whole milk, skim milk, cream, whey or whey permeate
  • Chromatography media used in the dairy industry comprise particles of highly porous material (including cellulose derivatives such as cross linked dextran, or styrene or acrylate polymers)
  • the functional groups are attached generally to glucose units m and around the matrix by stable ether linkages
  • the affinity of the functional groups to find and bind with the component(s) of interest with such resins is therefore limited by the ability of the influent to be passed around and into the porous spheres
  • viscous solutions are difficult to treat, as are solutions in which the minor components it is desired to separate are present in low concentrations and/ or bind weakly with the affinity group
  • solutions containing suspended solids cannot be treated by passage through beds of porous spheres, the usual method of choice
  • solutions of economic interest to the food and pharmaceutical industries include uncla ⁇ fied fruit juices, whole fermentation broths, slurries of tea, coffee or hops, and whole blood
  • the present invention therefore has as its object the provision of alternative processes for recovering such minor components
  • the processes of the invention are believed by the applicants to represent improvements over processes currently employed and as a minimum offer the public a useful choice.
  • the invention provides a process for the separation of a useful substance from a solution containing said substance, which process includes the steps of:
  • the process includes the further steps of:
  • the sites which bind the substance to be recovered have affinity for and are selective for the substance.
  • the solution is whole milk, skim milk, cream, whey, whey permeate or colostrum.
  • the substance recovered is a mineral ionic species such as calcium or magnesium.
  • the substance recovered is or includes a protein such as an enzyme.
  • the conditions of dissociation are selected to ensure that the protein component is not denatured.
  • the substance recovered is a vitamin, a flavouring compound, a pigment, a lipid, a fatty acid or a biologically active compound such as a growth factor.
  • the solution may be a fermentation broth or other reaction product mixture and the useful substance recovered is a product of fermentation or other reaction product.
  • the composite magnetic resin particles be regenerated for reuse following dissociation of the recovered substance.
  • the magnetic particles of the composite magnetic resin comprise a core of a magnetic material surrounded by a mixture of a fibrous material and a solid binding agent.
  • the solution from which the substance has been removed is collected for further processing.
  • further processing may include recovery of a further substance or substances therefrom by a process as defined above but with sites on the composite magnetic resin particles having affinity for and being selective for the further substance(s).
  • the invention provides a substance recovered by a process as defined above.
  • the invention provides a composite magnetic resin suitable for use in a process as defined above, said resin comprising magnetic particles embedded in a polymeric matrix which either contains or has attached thereto sites which bind to a substance naturally present in whole milk, skim milk, cream, whey, whey permeate or colostrum.
  • the sites have affinity for and are selective for the substance.
  • the sites have affinity for a substance selected from mineral ions (such as calcium), lipids (such as phosphatidylcholine or sphingolipids) , fatty acids (such as linoleic acid), enzymes (such as sialyltransferase), other proteins (such as immunoglobulins or lactoferrins), growth factors (such as sialyllactose and IGF), and vitamins (such as riboflavin).
  • the sites comprise magnesium silicate and are selective for riboflavin.
  • the magnetic particles of the composite magnetic resin comprise a core of a magnetic material surrounded by a mixture of a fibrous material and a solid binding agent.
  • this invention is broadly directed to a process for the recovery of valuable substances from solutions which contain them.
  • the process has particular application to recovery of substances useful in the food, health and pharmaceutical industries.
  • Solutions from which such useful substances can be recovered include natural dairy products or solutions obtained during dairy processing, including whole milk, skim milk, cream, whey, whey permeate and colostrum.
  • Other solutions to which the process of the present invention is applicable include fruit juices, grape juices, wine and other alcoholic beverages, and extracts of tea, coffee, hops, soy and cocoa beans.
  • the applicants further contemplate that the process may be used to extract useful reaction or fermentation products from reaction mixtures or fermentation broths which contain them in solution.
  • the process may also be used to extract useful substances from hydrolysates, homogenates, blood, blood serum, or urine.
  • solution includes mixtures containing suspended solids, but in which the useful substance to be recovered will itself be in solution.
  • process of this invention employs a combination of selective ion exchange /affinity binding and magnetic separation. This combination provides particular advantages.
  • the process of the present invention can be generally characterised as a modification or adaptation of the processes of United States Patent 5,397,476 and EP 0,666,577.
  • the methods of US 5,397,476 and EP 0,666,577 are directed to the removal of pollutant ions from an aqueous solution by a combination of ion exchange and magnetic filtration.
  • the specific focus of those methods is on the removal of pollutants such as heavy metals and radio-nuclides from contaminated solutions to render the solutions safe.
  • US 5,397,476 employs composite magnetic resin particles generally having a relatively small overall diameter (less th.an 20 micrometers) to maximise the surface to volume ratio.
  • These particles comprise a composite in which magnetic particles are embedded in a polymeric matrix which either contains, or has attached thereto, sites which are selected for the pollutant ions which are to be removed from the contaminated solution.
  • the composite magnetic resin particles described in EP 0,666,577 include a core of magnetic particles comprising a magnetic material surrounded by a mixture of a fibrous material and a solid binding agent.
  • iron oxide is used as the magnetic material
  • cellulose fibres as the fibrous material
  • agar as the binding agent, preferably cross-linked using a suitable agent such as formaldehyde or epichlorohydrin.
  • the magnetic particles are embedded in a polymeric matrix which contains active sites.
  • the polymeric matrix can be a silicate based polymer or an organic polymer (such as polyacrylamide) or a mixture of polymers.
  • the composite magnetic resin particles disclosed in US 5,397,476 and EP 0,666,577 are similar to those employed in the present process.
  • the essential difference between the composite magnetic resin particles employed by the applicants and those disclosed in US 5,397,476 and EP 0,666,577 is in terms of the affinity or ion selecting component.
  • this component is selected for pollutant ions, whereas in the present process the selective component has affinity for the valuable substance to be recovered.
  • the composite magnetic resin particles employed in the present process are similar to those described in EP 0,666,577. These particles have the advantage of having very good durability.
  • the restrictions on particle size are not so important because the particles have a porous surface dedicated to the affinity binding/ion exchange function.
  • composite magnetic resin particles suitable for use in the present invention may be prepared, using the preparative methods described in EP 0,666,577.
  • polymeric resins can be engineered to contain specific function ⁇ groups, which will adsorb selectively a particular substance which it is desired to recover from a solution containing it. It will also be understood how selective adsorbers may be bound to a polymeric matrix.
  • the sites selective for the desired substance will be affinity binding groups where the desired substance is present in the solution in a non-ionic state, and can be either selective ion exchange groups or affinity binding groups where the desired substance is present in the solution in an ionic state.
  • Caseinomorphins linoleic acid and other fatty acids sialyltransferase IGF immunoglobulins lactoferrin lactoperoxidase lactose micellar casein phosphatidylcholine riboflavin sphingolipids sodium, milk antiinflammatory factor milk oligosaccharides sialyl lactose lactose phosphates creatine.
  • riboflavin is a vitamin
  • carotene is a food colouring agent
  • lactoferrin is a natural antibiotic
  • lactoperoxidase is a natural food preservative
  • phosphatidylcholine is a natural emulsifier
  • sphingolipids are anti- carcinogens.
  • solutions processed in the dairy industry include other useful substances such as ketones, aldehydes, phenolic compounds, sulphur compounds, fatty acids, alcohols, esters and lactones which may be useful as flavouring compounds.
  • the process of the invention is not limited to solutions processed in the dairy industry but has application to other solutions containing useful substances.
  • fruit juices contain anthocyanins which are colouring compounds.
  • affinity binding/ selective ion exchange groups which may be used to recover the useful substances.
  • the affinity group may conveniently be magnesium silicate.
  • a carboxylic acid ion exchange group is desirable, but for selectivity of Ca + or Mg 2+ over competing proteins, an iminodiacetic acid (IDA) group is preferable.
  • IDA iminodiacetic acid
  • affinity binding/ ion exchange functional groups which may be useful in the processes of the present invention, depending on the substance it is desired to recover, include the standard carboxylates, sulphonates, diethylaminoethyl and quaternary ammonium ion exchange groups, dye-ligands for recovering immunoglobulins and other proteins, and bound metal ions for metal ion affinity chromatography.
  • the process can be performed.
  • the process has two essential steps.
  • the first essential step is that of contacting the solution being processed (usually whole milk or whey) with the composite magnetic resin particles. This can be achieved for example by contacting the particles with a flowing stream of the solution being processed.
  • the contacting step may be carried out in a reactor operated batchwise or continuously and may take the form of a stirred tank or a fluidised bed or preferably a magnetically stabilised fluidised bed.
  • Agitation of a stirred tank may be by low-shear impeller or by a moving electromagnetic field preferably developed by stationary coils energised by poly-phase electricity.
  • sterilised magnetic resin particles may be injected periodically into a fermenter then captured by electromagnets in the fermenter wall.
  • the composite magnetic resin particles mix with the solution and selectively bind the substance to be recovered.
  • the pH of the solution should be less than 7 (preferably less than 6) and the temperature less than 80°C (preferably less than 60°C), to avoid competition with phosphates, hydroxides, sulphates and citrates precipitating.
  • the pH should preferably be less than 7 to avoid alkaline breakdown of the riboflavin. Exposure to light should also be avoided.
  • the second essential step of the process is separation of the magnetic resin particle /bound substance complex from the solution being processed. This is achieved by magnetic separation (such as magnetic filtration) using techniques and equipment which are known in the art.
  • magnetic separation such as magnetic filtration
  • Such known equipment includes rotating magnetic drum separators, stationary electromagnetic filters with an internal ferritic stainless steel matrix, and electromagnetic filters with continuous discharge achieved by a moving magnetic field.
  • the immediate result of the process is therefore a depleted solution from which the selected substance has been recovered, and the composite magnetic resin particles carrying the recovered substance.
  • the magnetic resin particle/recovered substance complex prefferably be dissociated to release the recovered substance.
  • This dissociation will desirably be performed under conditions which are not detrimental to the recovered substance.
  • the recovered substance is, or contains, protein (such as a commercially valuable immunoglobulin or enzyme)
  • the dissociation will be effected under conditions which do not denature the protein.
  • One particular advantage of the process of the present invention is associated with the fact that the ease by which separation of the magnetic resin from solution can be achieved means that the process need not take place in a chromatography column.
  • the magnetic composite resin particles on which the desired substance is adsorbed can therefore be agitated into a suspension which allows the suspension to be titrated with acid or base en masse to release the bound substance.
  • no one portion of the resin is exposed to unduly high or low pH which could destroy or denature the substance.
  • a quaternary ammonium functionalised magnetic composite resin which has been used to adsorb whey proteins can be agitated in water then gradually acidified to facilitate fractional elution of the whey proteins.
  • salt solutions would generally be used to achieve the required elution. These are expensive on an industrial scale.
  • Dissociation of the magnetic resin particle /recovered substance complex has two effects. The first, and most obvious effect, is to release the recovered substance. However, the second effect is to regenerate the particles for reuse. The regenerated particles can then be separated from the recovered substance by a second magnetic filtration step. It will of course be appreciated that the depleted solution itself can be subjected to further processing. Such processing may involve recovery of a further valuable substance or substances. This can be achieved by essentially repeating the process steps above but using composite magnetic resin particles having an affinity to, and selective for, a further substance.
  • the process of the present invention may be used to recover more than one substance at the same time, to obtain a mixture of desired substances.
  • the composite magnetic resin may contain two or more types of site, namely sites selective for each of the substances it is desired to recover, for example a mixture of riboflavin and calcium may be desired.
  • the composite magnetic resin contains sites having affinity for and selective for one particular substance
  • the apphcants also contemplate that the sites on the composite magnetic resin may bind more than one substance at once.
  • a desired mixture of substances is bound to the resin.
  • the substances can be eluted sequentially from the resin under appropriate conditions, with a magnetic separation step between each elution, in cases where the individual substances are desired.
  • the substances can be eluted simultaneously where what is desired is a mixture of the substances.
  • the binding sites on the resin may simply be cation exchange groups which will bind all of the desired proteins under appropriate conditions of pH and ionic strength.
  • the desired proteins may be eluted sequentially under appropriate conditions of pH and ionic strength, as is known in the art in relation to conventional (non-magnetic) ion exchange technology.
  • individual purified protein fractions may be obtained.
  • all of the bound proteins may be eluted simultaneously under appropriate conditions, to obtain a mixture of proteins.
  • the process of the invention will have particular application in removing useful reaction products from reaction mixtures such as fermentation broths.
  • fermentation and enzyme reactions are often limited in their yield and productivity by product inhibition.
  • Product inhibition may be palhated by the selective removal of product during reaction, provided the agent of selective removal can be disengaged from the reaction mixture or fermentation broth for regeneration.
  • the process of the present invention may be used to remove caseinomorphin compounds generated by enzymatic hydrolysis of casein.
  • Example 1 Calcium removal from fresh whey
  • a magnetic resin was prepared essentially as described in EP 0,666,577 but with active sites (functional groups) of carboxylic acid groups of sufficient density to give a cation exchange capacity of 2.3 meq/g of dry magnetic resin.
  • the resin was washed with 2 bed volumes of 0. 1 M NaOH with stirring for 10 minutes.
  • the magnetic resin was held with a strong rare earth magnet (approximately 6 Gauss) while decanting the wash.
  • Bovine skimmed milk (0% fat, 200 ml) was added to a 500 ml beaker fitted with a thermometer probe, pH probe and magnetic follower on a stirrer hot plate. The pH was adjusted to pH 4.6 with 1 M HCl. The coagulum was heated to 40°C and this temperature maintained for 20 minutes with stirring. A metal coffee filter was used to coarsely separate whey from curds. The whey was refiltered with a fine filter (Whatman No 1 filter paper) giving a clear whey solution. This solution (pH 4.9-4.95) was diluted with 200 ml of deionised water and stirred to a uniform mixture.
  • the resin was held by a magnet and the treated whey decanted.
  • the resin was washed with deionised water to free non-bound material.
  • the decanted diluted and treated whey was sampled for further analysis.
  • the washed resin was placed in a 500 ml beaker and calcium eluted using two bed volumes of 1 M HNO3.
  • the elution was repeated three times.
  • the experiment was repeated using 1 M HCl for elution. In all cases the eluted resin was washed with three bed volumes of deionised water. This was repeated three times and the wash water added back to the acid eluant.
  • the resin was activated twice using 3 bed volumes of 1 M NaOH. The residual NaOH is re-used after re-adjusting the molarity to 1 M. The resin was then washed with deionised water to neutral (pH 7.0-7.5). If the resin is to be used immediately, it was vacuum filtered to 50-75%. The resin could be bottle stored with added preservative (0.8% w/w) for further use at a later time.
  • Example 2 Calcium recovery from reconstituted whey
  • Reconstituted sweet whey 1000 g was prepared by dissolving the sweet whey powder known as Alaway 62 1 (obtained from New Zealand Milk Products Ltd, Wellington, New Zealand) (50.0 g) in de-ionised water (950 mL). Sodium azide (0.05%) was added as a preservative. The pH was adjusted down to pH 5.92 with
  • the combined eluates and washings were also analysed for total nitrogen by the Kjeldahl method. Although nitrogen levels were low in all cases they were below the limit of quantification in the case of the two IDA resins.
  • Powdered cellulose ( 100 g) and de-ionised water (100 mL) were manually mixed together into a dough.
  • the dough was transferred to a 1 L covered glass reaction vessel slowly agitated by a large diameter heavy stainless steel agitator and placed in an agitated water bath at room temperature.
  • the vessel had been part filled with deionised water (500 mL) and was further charged with finely powdered Fe 3 0 4 ( 100 g) and then adjusted to pH 12 with 50% NaOH.
  • the reactor was heated to 64°C by increasing the water-bath temperature set point. Once the desired temperature had been reached, epichlorohydrin (20 ml) was added and stirring continued for 90 minutes during which the temperature was permitted to drop.
  • reaction contents at about 58°C were transferred drop-wise to a 5 L plastic beaker containing 5% nitric acid (4 L) rapidly agitated by an overhead paddle stirrer. Rapid agitation was continued until the majority of particles were between 50 and 100 um diameter. The particles were permitted to settle and the solution, along with fine particles decanted off. The particles were washed five times with 4 L lots of de-ionised water at low agitator speed, settling and decanting after each wash. The magnetic core particles were then blotted on tissue paper and laid out to dry at room temperature.
  • the block produced was later broken apart, milled in a coffee mill, and sieved to an average particle size of about 150 ⁇ m then repeatedly washed in deionised water on a Buchner funnel.
  • the permeate employed was prepared by collecting the permeate from the ultrafiltration of cheddar cheese whey in a single stage UF plant operated in continuous mode at a volume concentration factor of 4 at 50°C using 4-inch spiral polysulphone membranes of nominal molecular weight cut off 10,000 Daltons. The permeate was collected fresh at pH 5.97 and placed in 500 mL plastic containers and stored in the dark at 4°C.
  • Permeate samples (500 mL), were contacted with magnesium silicate composite magnetic particles with gentle agitation by an overhead paddle stirrer for 0, 1, 5 and 10 minutes in glass 1 L beakers protected from light by aluminium foil. After the appointed time the magnetic beads were drawn to the side of the beaker with a hand-held rare earth permanent magnet and sufficient of the clear solution decanted to approximately fill 250 mL glass measuring cylinders.
  • the resin that had been contacted for 10 minutes was fully decanted and then washed twice with 200 mL of de-ionised water decanting between washes with the aid of the magnet.
  • the washed resin was divided in two approximately equal portions each placed in a 500 mL glass beaker. One portion was washed with 200 mL of 1 M NaOH then washed with twice 200 mL deionised water. The eluate and washings were combined to give a colourless, cloudy solution.
  • washed resin was washed with 200 mL ethanol then washed twice with 200 mL water and eluted.
  • the combined eluate and washings were yellow and very slightly cloudy, and fluoresced under UV light.
  • Example 4 Calcium recovery from reconstituted whey pre-treated for riboflavin removal
  • Sweet whey (Alaway 62 1 , 50. 13 g was reconstituted in deionised water (980 mL), preserved with sodium azide (57 mg) and adjusted to pH 6 with 1M HNO3. This reconstituted whey was stored in the dark at 4 C.
  • the pH of the untreated whey after contact with resin X2-Na was 7 81
  • the pH of the decolourised whey after contact with resin X2-Na was 7.93.
  • the process also offers advantages over conventional chromatographic separation processes as employed in the food industry.
  • the process of the present invention permits small sized particles of resin to be used, which could not easily be used in conventional processes.
  • the use of small size particles maximises the surface area to volume ratio and the availability of functional groups for recovery of the desired substance. This is turn allows high influent rates to be used and viscous solutions to be readily treated.
  • the process of the present invention is particularly suitable for separating substances present in low concentrations in a large volume of solution, especially in cases where it takes a relatively long time for the target substance to bind to the affinity group (ie the binding equilibrium is slow).
  • column processes a substantial proportion of the target material will not bind to the column in a first pass of the solution through the column.
  • the composite magnetic resin can be maintained in contact with the solution for a sufficient length of time to enable binding to occur, and then magnetic separation of the resin easily achieved.
  • a further advantage of the process of the invention is that it enables a fragile or friable substrate to be used in robust fashion, as is often required in food/health /pharmaceutical industry processes.
  • Substrates like silicates, zeolites, acitvated carbons and others are capable of forming strong affinity links but cannot withstand the physical stress of industrial scale applications. They become robust when potted in a polymeric matrix around a magnetic core, in accordance with the present invention.
  • the composite magnetic resins are also robust enough to enable sterilisation with agents such as sodium hydroxide or solvent.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dairy Products (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Peptides Or Proteins (AREA)

Abstract

Cette invention concerne un procédé permettant d'extraire d'une solution une substance utile. Le procédé consiste principalement d'abord (i) à mettre la solution en contact avec les particules d'une résine magnétique composite dont des particules magnétiques sont incluses dans une matrice polymère contenant ou à laquelle sont attachées des sites qui se lient à la substance à récupérer. Le procédé consiste principalement ensuite (ii) à extraire de la solution par séparation magnétique les particules de résine magnétique composite et la substance qui lui est liée. De préférence, le procédé consiste ensuite (iii) à dissocier la substance des particules de résine magnétique composite dans des conditions qui préservent sensiblement l'intégrité de la substance en vue de son utilisation ultérieure pour l'industrie alimentaire ou les industries de santé. De préférence, le procédé consiste enfin (iv) à récupérer la substance dissociée. Selon une réalisation préférée, la solution est un produit laitier ou une solution obtenue pendant le traitement en laiterie, et notamment du lait entier, du lait écrémé, de la crème, du lactosérum, de l'ultrafiltrat de lactosérum ou du lait colostral.
PCT/NZ1998/000140 1997-09-22 1998-09-22 Procede de recuperation WO1999015023A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU93685/98A AU9368598A (en) 1997-09-22 1998-09-22 Recovery process

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NZ32880797 1997-09-22
NZ328807 1997-09-22

Publications (2)

Publication Number Publication Date
WO1999015023A2 true WO1999015023A2 (fr) 1999-04-01
WO1999015023A3 WO1999015023A3 (fr) 1999-06-17

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2989897A1 (fr) * 2014-08-30 2016-03-02 DMK Deutsches Milchkontor GmbH Procedée pour la preparation du lait de fromage incolure et le fromage incolure qui en résultent
WO2019115770A1 (fr) * 2017-12-17 2019-06-20 Upfront Chromatography A/S Séparation d'oligosaccharides
WO2019162362A1 (fr) * 2018-02-22 2019-08-29 Universidade De Santiago De Compostela Procédé de détoxication d'aliments, d'aliments pour animaux et d'eau contaminés par des toxines naturelles

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4144373A (en) * 1975-12-24 1979-03-13 Commonwealth Scientific And Industrial Research Organization Materials for the separation of organic substances from solution
US4554088A (en) * 1983-05-12 1985-11-19 Advanced Magnetics Inc. Magnetic particles for use in separations
WO1994011103A1 (fr) * 1992-11-06 1994-05-26 Williams, John, Francis Supports magnetiques a phase solide
EP0666577A1 (fr) * 1994-02-07 1995-08-09 BRADTEC Limited Particules magnétiques, leurs procédés de fabrication et application à la purification de solutions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4144373A (en) * 1975-12-24 1979-03-13 Commonwealth Scientific And Industrial Research Organization Materials for the separation of organic substances from solution
US4554088A (en) * 1983-05-12 1985-11-19 Advanced Magnetics Inc. Magnetic particles for use in separations
WO1994011103A1 (fr) * 1992-11-06 1994-05-26 Williams, John, Francis Supports magnetiques a phase solide
EP0666577A1 (fr) * 1994-02-07 1995-08-09 BRADTEC Limited Particules magnétiques, leurs procédés de fabrication et application à la purification de solutions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2989897A1 (fr) * 2014-08-30 2016-03-02 DMK Deutsches Milchkontor GmbH Procedée pour la preparation du lait de fromage incolure et le fromage incolure qui en résultent
CN105519671A (zh) * 2014-08-30 2016-04-27 Dmk德意志牛奶股份有限公司 用于生产无色干酪用乳以及由其得到的无色干酪的方法
WO2019115770A1 (fr) * 2017-12-17 2019-06-20 Upfront Chromatography A/S Séparation d'oligosaccharides
WO2019162362A1 (fr) * 2018-02-22 2019-08-29 Universidade De Santiago De Compostela Procédé de détoxication d'aliments, d'aliments pour animaux et d'eau contaminés par des toxines naturelles

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AU9368598A (en) 1999-04-12
WO1999015023A3 (fr) 1999-06-17

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