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WO2002046294A1 - Procede de fabrication de particules d'hydrate de carbone spheriques et a stabilite de forme, et utilisation desdites particules - Google Patents

Procede de fabrication de particules d'hydrate de carbone spheriques et a stabilite de forme, et utilisation desdites particules Download PDF

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Publication number
WO2002046294A1
WO2002046294A1 PCT/EP2001/014375 EP0114375W WO0246294A1 WO 2002046294 A1 WO2002046294 A1 WO 2002046294A1 EP 0114375 W EP0114375 W EP 0114375W WO 0246294 A1 WO0246294 A1 WO 0246294A1
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WIPO (PCT)
Prior art keywords
particles
cellulose
carbohydrate
spherical particles
spherical
Prior art date
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Ceased
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PCT/EP2001/014375
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German (de)
English (en)
Inventor
Manfred Kühn
Jochen Saunus
Günther Mann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ATC Dr Mann eK
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Original Assignee
ATC Dr Mann eK
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
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Priority claimed from DE10150998A external-priority patent/DE10150998A1/de
Application filed by ATC Dr Mann eK, Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV filed Critical ATC Dr Mann eK
Priority to AU2002233229A priority Critical patent/AU2002233229A1/en
Publication of WO2002046294A1 publication Critical patent/WO2002046294A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/19—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/018—Granulation; Incorporation of ion-exchangers in a matrix; Mixing with inert materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • 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
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose

Definitions

  • the present invention relates to a method for producing dimensionally stable, spherical carbohydrate particles, and corresponding spherical particles from carbohydrates, and their use as sorption, separating and carrier material.
  • Spherical particles especially pearl-shaped materials made of carbohydrates with adjustable and therefore variable porosities, are of particular importance in various branches of the life sciences as a separating material and as a matrix for the immobilization of catalysts, especially biocatalysts.
  • carrier materials such as the cross-linked dextrans and agaroses and the pearl-shaped chitosan are worth mentioning.
  • pearl-shaped, porous cellulose products with advantageous properties have also appeared on the market.
  • Cellulose and many of its derivatives are frequently used as carrier materials in chemistry, biotechnology, medicine and pharmacy.
  • Cellulose is preferably also used as fiber or powder.
  • their use in these forms is associated with considerable disadvantages.
  • cellulose can only be used in small columns.
  • Pearl celluloses do not have such adverse properties, which is why spherical particles of carbohydrates have a wide range are of technical interest, especially because they are finishing products of renewable raw materials.
  • Dextrans and agarose are expensive carbohydrates. They are cross-linked with the highly toxic epichlorohydrin to form porous pearl materials. This means that considerable safety measures are required for their manufacture and complicated and expensive methods of disposing of the pollutants and residual substances have to be used.
  • the cross-linked dextrans and agaroses are therefore used almost exclusively in technical processes for the chromatographic isolation and extraction of high-quality products such as proteins and enzymes.
  • An application, for example in the environmental sector and in water desalination, is out of the question for such high-quality and expensive cross-linked dextrans and agaroses for cost reasons.
  • pearl cellulose A cheaper alternative to the cross-linked dextrans and agaroses is pearl cellulose, which has been commercially available for some years. It is known that it is produced by spraying or suspension processes. These processes are characterized by three reaction steps:
  • the cellulose solution is divided into droplets by means of nozzles, which are added dropwise to a solvent that is immiscible with the cellulose solution.
  • nozzles which are added dropwise to a solvent that is immiscible with the cellulose solution.
  • the cellulose esters which are soluble in organic solvents, are sprayed into aqueous solutions, to which, if appropriate, emulsifiers have been added.
  • the resulting spherical particles of the cellulose esters are then filtered off and then have to be washed carefully and lengthily in order to remove the organic solvents from the pores of the particles. Finally, to obtain the pure, unmodified cellulose particles, the ester groups are split by hydrolysis.
  • the object of the invention was therefore to develop a suitable, cost-effective and environmentally friendly method for producing spherical particles from naturally present, insoluble carbohydrates or chemically modified and insoluble derivatives of the carbohydrates or composite materials from the carbohydrates mentioned. It is said to be spherical carbohydrate particles are provided that are easily chemically modifiable and thus enable a wide range of applications.
  • spherical carbohydrate particles are obtained by first suspending at least one high molecular weight carbohydrate in powder or fiber form in an aqueous urea solution.
  • derivatives of the high molecular weight carbohydrates can also function as starting products, if appropriate also mixtures of several carbohydrates and / or corresponding derivatives, it also being possible to use combinations of carbohydrates or their derivatives with solid fillers as starting products according to the invention.
  • the reaction is preferably carried out in a heatable mixing vessel with the possibility of mixing or stirring.
  • low or high molecular weight chemical compounds which are soluble or insoluble in aqueous and / or organic solvents are optionally added to the suspension.
  • the water is first evaporated. This process is preferably carried out with stirring and with an increase in temperature to 80 ° C. to 120 ° C. A vacuum may be applied to protect the reactor contents or to save time.
  • the temperature is increased further to 200.degree. C., preferably to temperatures of 120.degree. C. to 160.degree. C., to complete the reaction.
  • the reactor contents are deformed into spherical particles in ellipsoidal or round form, which after their workup and cleaning in aqueous solutions or organic solvents remain dimensionally stable and can be used for a wide range of uses, such as for applications as sorption, separating and carrier materials in numerous scientific and technical fields.
  • a variety of high molecular weight and insoluble carbohydrates can be used as starting materials for the preparation of the spherical particles of the carbohydrates, e.g. the celluloses, starches of different origins, pectins, galactomannans, xylans and chitosan obtained from chitin.
  • cellulose, lignocellulose and hemicellulose are preferably used as high molecular weight carbohydrates.
  • These carbohydrates are available in large quantities and have not yet been chemically modified.
  • derivatives of the insoluble carbohydrates can also be used to form spherical particles, e.g. Cellulose derivatives such as e.g. Hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, cellulose sulfate, sulfoethyl cellulose and cellulose phosphate.
  • the weight ratios of urea to carbohydrate are 0.5 part by weight to 5 parts by weight of urea per part by weight of carbohydrate, preferably 2-3 parts by weight of urea to one part by weight of carbohydrate.
  • This amount of urea is dissolved in water or an aqueous solution, which may also contain inert foreign salts or buffer substances.
  • the water is first removed from the suspension of carbohydrate and aqueous urea solution by evaporation. This happens at temperatures in the boiling range of the water, and also below when a vacuum is applied.
  • the particles With further heating with simultaneous stirring to temperatures of up to approximately 200 ° C., preferably to temperatures of 120 ° C. to 160 ° C., the particles then form.
  • the spherical particles formed are removed by known methods to remove excess urea and soluble reaction by-products, for example by washing with cold and / or hot water, dilute alkalis and acids and distilled water until the wash water has a neutral reaction. After the washing steps described, the spherical particles can be sieved as an aqueous suspension by particle size.
  • the spherical carbohydrate particles obtained can be stored at 0 ° C. to 4 ° C. or at room temperature, preferably in the presence of an antibacterial agent.
  • the spherical particles can also be stored in a dry state.
  • the moist particles are either dried at elevated temperatures in a circulating air stream or treated by solvent exchange with methanol, acetone and drying at ambient temperature or only slightly elevated temperatures or by using a vacuum at ambient temperature.
  • derivatized spherical particles of high molecular weight carbohydrates preferably with bound phosphate groups
  • Carbohydrates are used, especially cellulose without ion exchange groups.
  • this modification takes place during the particle formation process in which primary ammonium phosphate and / or secondary ammonium phosphate or phosphoric acid are added to the suspensions from the carbohydrates and the urea solutions.
  • the weight ratios of the ammonium phosphates or phosphoric acid to urea are set at 0.1: 2 to 0.1: 20, preferably 1: 2 to 1: 6.
  • the spherical particles with phosphate groups produced in this way have good ones
  • Ion exchange properties Depending on the heavy metal, their binding capacities to heavy metals are 1.2 to 2.0 mmol heavy metal per gram of spherical particle.
  • spherical particles can also be produced in a simple manner as so-called composite particles, that is to say the spherical particles are composed of a plurality of high-molecular carbohydrates and / or their corresponding derivatives, or they consist of at least one high-molecular carbohydrate or derivatives thereof and other solids as
  • Synthetic soluble or insoluble macromolecules or inorganic compounds can be used as solid fillers.
  • Composite particles of the carbohydrates are carried out in analogy to the process already carried out. So either mixtures of high molecular carbohydrates or individual the above-mentioned carbohydrates or mixtures of the carbohydrates with synthetic macromolecules, which are preferably in powder form with particle sizes smaller than 200 ⁇ m, or with inorganic compounds, which are also available in particle sizes smaller than 200 ⁇ m, are introduced into the urea solutions. As described above, these mixtures are converted into spherical composite particles with high-molecular carbohydrates as a constituent under the same reaction conditions.
  • the weight ratios of urea to the above-mentioned composites are also 0.5 to 5 parts by weight of urea in water or in water mixed with inert foreign salts or buffer substances to a part by weight of composite, preferably in a weight ratio of 2 to 3 parts of urea to 1 part of mixture.
  • the weight content of the individual constituents of carbohydrates or carbohydrate and the additional solids in a composite for the production of spherical composite particles can be selected in a wide range.
  • the second carbohydrate or one of the other solids is introduced into the composite composition in an amount of 5 to 200% by mass, preferably 40% to 100%, based on a selected carbohydrate.
  • Particularly preferred exemplary embodiments of such composite particles in spherical form made of pure, high molecular weight carbohydrates are the particles made of cellulose and the other cellulose derivatives mentioned with ion exchange groups or cellulose and chitosan.
  • the process has the great advantage that spherical carbohydrate particles with ion exchange properties are already formed during the reaction in the reactor and do not have to be produced by subsequent chemical modifications, as is customary for cellulose-based ion exchangers.
  • the binding capacities of these ion exchangers to heavy metals are in the range from 0.2 to 0.8 mmol of heavy metal per gram of ion exchanger.
  • the soluble polymers are dissolved out of the spherical particles, the water-soluble polymers with aqueous solutions and uncrosslinked polystyrene, for example with acetone or nitromethane.
  • porous to highly porous pearl materials preferably pearl celluloses. Since the soluble polymers are available in different molecular weights, the pearl materials, in particular the pearl celluloses, can also be used different pore sizes and pore volumes can be obtained in this way.
  • spherical particles with interesting properties are obtained.
  • These spherical composite particles can e.g. be used as ion exchangers or as selectively specific
  • Adsorbents can be used for protein binding or can be chemically modified in a simple manner to form further derivatives of the carbohydrates.
  • Adsorbents such as powdered activated carbon, powdered bentonite or powdered zeolites, which are prepared in the same way as those previously described. This gives composite particles whose adsorption properties are comparable to those of the series adsorbents. In addition, these spherical composite particles have the advantage that they are much more hydrophilic and better wettable with water. 4.
  • composite particles containing alkali or alkaline earth carbonates can be treated with acids in order to detach the carbonates from the spherical particles. This creates cavities and channels in the spherical particles and thus spherical particles with small pores and small pore volumes.
  • the methods according to the invention for pore and pore volume formation, for magnetization and for the formation of ion exchangers can be applied to all spherical particles according to the invention, including the composite particles, by additionally adding either carbonates and / or magnetic materials and / or primary ammonium phosphate and / or secondary ammonium phosphate to the reaction mixtures for particle formation or phosphoric acid can be added.
  • the insoluble carbohydrates can be used as starting products for particle formation and do not first have to be converted into soluble derivatives.
  • composition (composite particles) are provided.
  • the spherical carbohydrate particles produced in this way can also be chemically modified very easily after their formation. All of the processes described for celluloses, pearl celluloses and other carbohydrates for their derivatization can also be applied to the spherical particles according to the invention. To improve the mechanical stability they can e.g. easily crosslinked with bifunctional compounds such as formaldehyde under acidic conditions, epichlorohydrin under alkaline conditions or diisocyanates under anhydrous conditions in organic solvents. By introducing functional groups through polymer-analogous reactions, cation or anion exchangers can subsequently be produced. This is also possible with functional groups for immobilizing biologically active compounds or selectively specific adsorbents.
  • bifunctional compounds such as formaldehyde under acidic conditions, epichlorohydrin under alkaline conditions or diisocyanates under anhydrous conditions in organic solvents.
  • the spherical particles are preferably used to create sorption, separating and carrier materials with a wide range of applications in chemistry, biochemistry, biotechnology, medicine, pharmacy and environmental protection. Due to their outstanding hydrophilic properties of the carbohydrates used, which are transferred to the particles, these spherical particles are readily wettable with water. This property makes working in aqueous solutions much easier. They are also very inexpensive because of the cheap starting materials for their preparation, the simple reaction procedure and work-up techniques. Because of their low price compared to the previously known Carrier materials based on carbohydrates can be used, for example
  • the spherical particles are washed with deionized water, in sodium hydroxide solution, deionized water, in hydrochloric acid and deionized water and stored at 4 ° C after the washing process. After drying by solvent exchange with methanol and acetone at 30 ° C in a vacuum, the pearl cellulose has an average pore volume of 15%.
  • Example 2
  • a pearl cellulose containing amino groups 10 ml of the pearl cellulose prepared according to Example 1 are washed on a frit with 100 ml of methanol and 200 ml of dry acetone.
  • the acetone-moist pearl cellulose is suspended in 50 ml of dry acetone.
  • 1 ml of triethylamine and then 3 ml of hexamethylene diisocyanate in 10 ml of dry acetone are added at 0 ° C.
  • the suspension is stirred for 1 hour and then added to distilled water at room temperature.
  • the aqueous suspension is stirred for 60 minutes at 50 ° C., then filtered, washed with deionized water and acetone and dried at room temperature.
  • the test for primary amino groups with trinitrobenzenesulfonic acid is positive.
  • the pearl cellulose is colored red-orange. After activation with glutaraldehyde, 0.2 mg of methemoglobin per milliliter of carrier are bound to the amino-containing pearl cellulose.
  • the immobilized methaemoglobin has pseudoperoxidative activity.
  • the pearl cellulose modified with carboxymethyl groups is filtered off and washed neutral with deionized water, 0.1N hydrochloric acid and deionized water.
  • the CM pearl cellulose obtained has a binding capacity of 0.2 to 0.4 mmol of copper per gram of carrier.
  • Trivalent valence levels of metals such as iron or chromium are bound in smaller quantities. The binding capacities for these metals are in the range from 0.5 to 0.8 mmol of metal per gram of carrier.
  • a mixture of 2 kg of fibrous cellulose, 2 kg of chitosan and 8 kg of urea is converted into spherical composite particles as described in Example 1.
  • 500 g of the reactor contents are filled into a chromatography column half-filled with deionized water and successively with 1 liter of deionized water, 250 ml of 0.5 N sodium hydroxide solution, 500 ml of 0.5 N sodium hydroxide solution heated to 60 ° C., 250 ml of deionized water, 250 ml 1N hydrochloric acid washed.
  • the moist co-compound of cellulose and chitosan in spherical form is transferred to a beaker, 200 ml of 5N hydrochloric acid are added and the suspension is cooled to 0 ° C to 4 ° C.
  • a solution of 2 g of sodium nitrite in 75 ml of deionized water is added to the suspension with stirring. After the sodium nitrite has been added, the temperature of the suspension is brought to room temperature, and stirring is continued at this temperature for a further 20 minutes.
  • the spherical composite compound is then filtered off and washed with 0.1N hydrochloric acid, deionized water, 0.1N sodium hydroxide solution and deionized water.
  • the reaction to the primary amino groups of chitosan in the composite particles with trinitrobenzenesulfonic acid is positive (Rotor-colored).
  • the composite particles bind heavy metals, a property of the chitosan in the particles. For example, copper is bound to the particles that were produced according to this specification in an amount of 0.45 mmol per gram of particles.
  • Composite particles are produced from 2 kg of fibrous cellulose and 500 g of powdered (ball mill) and sieved (the fraction with a particle size smaller than 200 ⁇ m is used), strongly acidic cation exchanger of the polystyrene type and 5 kg of urea, with the exception that the reaction temperature in the Reactor of 125 ° C is not exceeded.
  • the reactor contents are washed with deionized water and 0.1N hydrochloric acid. Compared to heavy metals, this absorber has a binding capacity of 0.8 to 1.2 mmol per gram of composite particles.
  • spherical composite particles made of fibrous cellulose and activated carbon or magnetic iron powder (magnetite) (magnetic particles are not washed with 0.1N hydrochloric acid, but only with deionized water).
  • Spherical composite particles are produced from 2 kg of fibrous cellulose and 400 g of polyvinylpyrrolidone (MW: 40,000) and 5 kg of urea, as described in Example 1, but deviating from the manufacturing instructions given there, at a short-term, maximum reaction temperature of 140 ° C. for ten minutes.
  • the reactor contents are washed with cold and 70 ° C hot, deionized water in order to completely remove the polyvinylpyrrolidone Particles.
  • the sulfur content of the tosylate of pearl cellulose is 1.23%.
  • an adsorber for heavy metals can be produced from the tosylate of pearl cellulose and the dihydrochloride of 5-amino-8-hydroxyquinoline, which is able to bind up to 0.4 mmol heavy metal per gram of carrier.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Procédé de fabrication de particules d'hydrate de carbone sphériques et à stabilité de forme, qui consiste à mettre en suspension au moins un hydrate de carbone non soluble, à poids moléculaire élevé, fibreux ou pulvérulent et / ou au moins un dérivé chimiquement modifié dudit hydrate de carbone, éventuellement en combinaison avec au moins une matière de charge solide et / ou un réactif de modification solide ou liquide dans une solution d'urée aqueuse, à faire évaporer l'eau par agitation et élévation de la température à 80-120 DEG C, à élever encore la température pour la formation des particules sphériques jusqu'à 200 DEG C et à nettoyer les particules sphériques ainsi obtenues selon des procédés connus.
PCT/EP2001/014375 2000-12-08 2001-12-07 Procede de fabrication de particules d'hydrate de carbone spheriques et a stabilite de forme, et utilisation desdites particules Ceased WO2002046294A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002233229A AU2002233229A1 (en) 2000-12-08 2001-12-07 Method for producing dimensionally stable, spherical carbohydrate particles and the use thereof

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10062502 2000-12-08
DE10062502.9 2000-12-08
DE10150998A DE10150998A1 (de) 2000-12-08 2001-10-04 Verfahren zur Herstellung von formstabilen, sphärischen Kohlenhydratpartikeln sowie ihre Verwendung
DE10150998.7 2001-10-04

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WO2002046294A1 true WO2002046294A1 (fr) 2002-06-13

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CN104979091A (zh) * 2015-06-25 2015-10-14 西南大学 一种碳包裹磁性纳米粒子及其制备方法和应用
CN105377411A (zh) * 2013-07-31 2016-03-02 巴斯夫欧洲公司 具有长储存期限的在有机相中的纤维的可泵送悬浮液
CN105817205A (zh) * 2015-12-15 2016-08-03 浙江海洋学院 一种吸附重金属离子的纳晶纤维素磁性粒子的制备方法
CN106732425A (zh) * 2016-12-28 2017-05-31 西北师范大学 季铵盐壳聚糖改性的膨润土吸附材料及其制备和在吸附废水中铅离子的应用
CN109293952A (zh) * 2018-10-25 2019-02-01 南京工业大学 一种利用季铵碱制备磁性纤维素微球的方法
WO2021116006A1 (fr) 2019-12-10 2021-06-17 Akzo Nobel Coatings International B.V. Composition de revêtement à base de solvant à deux constituants
CN113415798A (zh) * 2021-05-12 2021-09-21 江西农业大学 一种磷掺杂微孔、中孔和大孔共存等级孔孔隙结构纳米碳球的制备方法
CN113880262A (zh) * 2021-11-22 2022-01-04 南京环保产业创新中心有限公司 一种用于处理微污染水源的木材纤维素-碳纳米管复合丝状生物填料及其制备方法

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CN105377411A (zh) * 2013-07-31 2016-03-02 巴斯夫欧洲公司 具有长储存期限的在有机相中的纤维的可泵送悬浮液
CN105377411B (zh) * 2013-07-31 2017-07-07 巴斯夫欧洲公司 具有长储存期限的在有机相中的纤维的可泵送悬浮液
CN104979091A (zh) * 2015-06-25 2015-10-14 西南大学 一种碳包裹磁性纳米粒子及其制备方法和应用
CN105817205A (zh) * 2015-12-15 2016-08-03 浙江海洋学院 一种吸附重金属离子的纳晶纤维素磁性粒子的制备方法
CN105817205B (zh) * 2015-12-15 2021-01-15 浙江海洋学院 一种吸附重金属离子的纳晶纤维素磁性粒子的制备方法
CN106732425A (zh) * 2016-12-28 2017-05-31 西北师范大学 季铵盐壳聚糖改性的膨润土吸附材料及其制备和在吸附废水中铅离子的应用
CN106732425B (zh) * 2016-12-28 2019-10-01 西北师范大学 季铵盐壳聚糖改性的膨润土吸附材料及其制备和在吸附废水中铅离子的应用
CN109293952A (zh) * 2018-10-25 2019-02-01 南京工业大学 一种利用季铵碱制备磁性纤维素微球的方法
WO2021116006A1 (fr) 2019-12-10 2021-06-17 Akzo Nobel Coatings International B.V. Composition de revêtement à base de solvant à deux constituants
CN113415798A (zh) * 2021-05-12 2021-09-21 江西农业大学 一种磷掺杂微孔、中孔和大孔共存等级孔孔隙结构纳米碳球的制备方法
CN113880262A (zh) * 2021-11-22 2022-01-04 南京环保产业创新中心有限公司 一种用于处理微污染水源的木材纤维素-碳纳米管复合丝状生物填料及其制备方法
CN113880262B (zh) * 2021-11-22 2023-10-10 南京环保产业创新中心有限公司 一种用于处理微污染水源的木材纤维素-碳纳米管复合丝状生物填料及其制备方法

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