EP1841526A2 - Procede pour fabriquer des substances adsorbantes cationisees, agents de sorption ainsi obtenus et utilisation privilegiee - Google Patents

Procede pour fabriquer des substances adsorbantes cationisees, agents de sorption ainsi obtenus et utilisation privilegiee

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Publication number
EP1841526A2
EP1841526A2 EP06706266A EP06706266A EP1841526A2 EP 1841526 A2 EP1841526 A2 EP 1841526A2 EP 06706266 A EP06706266 A EP 06706266A EP 06706266 A EP06706266 A EP 06706266A EP 1841526 A2 EP1841526 A2 EP 1841526A2
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EP
European Patent Office
Prior art keywords
layered silicate
cationized
sorbent
use according
biomolecule
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
EP06706266A
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German (de)
English (en)
Inventor
Ulrich Sohling
Hubertus Besting
Genovefa Wendrich
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Sued Chemie AG
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Sued Chemie AG
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Filing date
Publication date
Application filed by Sued Chemie AG filed Critical Sued Chemie AG
Publication of EP1841526A2 publication Critical patent/EP1841526A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/08—Mechanical or thermomechanical pulp
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/10—Mixtures of chemical and mechanical pulp

Definitions

  • the present invention relates to a process for producing a cationized layered silicate in a "dry" process. Also described is an advantageous cationized layered silicate (adsorbent having a positive surface charge) obtainable and its preferred use.
  • Adsorbents with a positive surface charge are of interest for a variety of applications. This concerns for example a removal of impurities from paper cycles. For many colloidal contaminants (eg tree rosin colloids) negative surface charges are generally discussed. Another application of such adsorbents is their use in separation processes in biotechnology for the purification of proteins and nucleic acids.
  • US 4,964,955 describes a method for pitch control in papermaking. First, a water-soluble polymer is dissolved in water and contacted with a particulate substantially water-insoluble substrate, thereby obtaining a slurry of the composite impurity eliminating component. This method corresponds to the known from the prior art method for the cationization of kaolin clays.
  • the invention thus relates to a process for producing a cationized sorbent, wherein a dry particulate substrate is dry-ground with a polyelectrolyte. More specifically, one aspect of the present invention relates to a method according to claim 1. Advantageous embodiments are given in the subclaims.
  • the invention relates to a process for producing a cationized layered silicate, comprising the steps of: (a) providing a dry particulate layered silicate, (b) contacting the dry particulate layered silicate with at least one cationic polyelectrolyte, wherein contacting according to step b) by a dry grinding and wherein no suspension or slurry of the layered silicate is formed, but directly a dry cationized layered silicate is obtained.
  • the dry particulate phyllosilicate is brought into contact with the at least one cationic polyelectrolyte by grinding. It has thus been found, surprisingly, that a particularly advantageous cationization of the particulate phyllosilicate can take place by the grinding during the incipient introduction. It is believed, without the invention being limited to the correctness of this assumption, that the grinding when contacting the dry particulate layered silicate with the at least one cationic polyelectrolyte produces new (fresh) surfaces of the layered silicate which can be directly occupied by the polyelectrolyte , This creates both a very stable and on the Surface concentrated loading , of the sheet silicate with the polyelectrolyte.
  • Dry milling also minimizes the incorporation of the polyelectrolyte.
  • Such incorporated polyelectrolytes are only conditionally available when using the cationic layered silicates. It "is assumed, without the invention being limited to the accuracy of this assumption that or by avoiding a slurry or suspension during milling. Contact of the two components, a particularly advantageous surface coverage of the particulate phyllosilicate with the can be done a cationic polyelectrolyte at least.
  • the products of the invention are characterized in that that the positive charges are located on the outside of the adsorbent particle and are readily accessible to adsorbates, which is particularly advantageous for separation processes when it comes to the separation of large colloids, such as impurities in papermaking, or the separation of large molecules such as biomolecules, e.g. B. DNA.
  • Milling is preferably understood to mean a treatment in which the average particle size (D50) of the Layer silicate by at least 5%, preferably at least 10%, in particular at least 20%, more preferably at least 40% reduced.
  • the D90 value of the layered silica particles decreases by at least 5%, preferably at least 10%, in particular at least 20%, more preferably at least 40%.
  • both components are preferred, i. H. the particulate substrate, in particular the smectic layered silicate and the at least one cationic polyelectrolyte dry, d. H. as solids, used and mixed / ground.
  • the high surface coverage of the layered silicate favors.
  • the method according to the invention also ensures that the polyelectrolytes attach themselves to the surface of a particle of the layer silicate particularly tightly and over at least a large part of the molecule length of the polyelectrolyte and thus can produce a higher surface charge density than in the case of one Mixing in a suspension where there is a risk of "storage" of the polyelectrolyte.
  • the cationized phyllosilicates (in dry form) produced by the process according to the invention are substantially more storage-stable than the slurries or suspensions produced according to the prior art.
  • the surface charge density and the zeta potential hardly decreases even with prolonged storage over days, weeks or even months.
  • At least one dry particulate phyllosilicate is used.
  • dry is intended to clarify the contrast to a use or mixture in the form of a slurry or suspension.
  • the particulate smectic sheet silicate used is free-flowing.
  • the layered silicate has a water content (moisture content) of 25% by weight or less, in particular 20% by weight or less, more preferably between 3 and 20% by weight. -%, in particular between 6 and 15 wt. -%, determined by drying to constant weight at 130 0 C, on. This favors the above-described surface coverage with high charge density.
  • the particle size of the layered silicate used can vary within wide limits, depending on the intended application. It can be both a powder and a granulate. Even larger moldings are conceivable.
  • the particulate layered silicate used is relatively finely divided. According to a preferred embodiment of the invention, it has an average particle size Sizes (D50, based on the sample volume) between 0, 1 and 30 .mu.m, in particular between 0, 1 and 25 .mu.m, preferably between 0, 5 and 15 .mu.m, more preferably between 0, 5 to 10 .mu.m. It has been shown that the advantages of the "dry" cationization according to the invention are particularly evident in such fine-particle phyllosilicates. For many applications in solution z. B.
  • finely divided materials in particular having an average particle size (D50, based on the sample volume) of between 0.1 and 30 ⁇ m, in particular between 0.1 and 25 ⁇ m, preferably between 0.5 and 15 ⁇ m, more preferably between 0.5 to 10 ⁇ m are used.
  • D50 average particle size
  • the particle size (D90) after grinding it will often be advantageous for the particle size (D90) after grinding to be at least about 20 ⁇ m, preferably at least 40 ⁇ m, in particular at least 60 ⁇ m. In one embodiment, the D90 value is about 150 ⁇ m or less.
  • any phyllosilicates including natural or synthetic phyllosilicates and mixtures thereof can be used according to the invention. These are known to those skilled in the art.
  • Two- or three-layer silicates, in particular smectic layered silicates, are preferably used, since their structure is particularly suitable for use with polyelectrolyte with grinding.
  • Preferred smectite layered silicates include, for example, those containing montmorillonite, hectorite, nontronite or saponite.
  • the smectitic layered silicate is a montmorillonite, in particular a bentonite, more preferably a calcium bentonite.
  • smectic layered silicates which, as an alternative or in addition to calcium, have one or more other cations in the intermediate layers, such as, for example, B. Sodium, magnesium, potassium or the like. It can be both untreated bentonite as well acid-activated phyllosilicates can be used. In this case, the acid activation can be carried out by any method familiar to the person skilled in the art. Preferably it is not organophilic clay materials or. layered silicates coated with organic cations (eg onium ions). The phyllosilicates used should also preferably not have been previously brought into contact with a polyelectrolyte before being brought into contact with the polyelectrolyte according to the invention by dry grinding.
  • any substrates can be used as long as they have a surface which can be modified or coated with at least one polyelectrolyte.
  • Both inorganic and organic substrates are included.
  • the substrate is substantially insoluble in the medium containing the at least one molecule to be sorbed. Preference is given to inorganic substrates.
  • the substrate is selected from the group of natural and synthetic phyllosilicates, silicic acids, in particular precipitated silicas, silica gels, magnesium silicates, zeolites, aluminas, in particular porous aluminas, Titanium dioxide, zirconium oxide, or mixtures thereof.
  • these substrates are essentially insoluble in the preferred media and have good sorption properties.
  • the statements on layered silicates as substrates for the coating with polyelectrolyte therefore also apply correspondingly to other substrates.
  • the particulate layer silicate is wholly or partly replaced by another particulate substrate, in particular selected from the above group of inorganic substrates.
  • the inorganic substrates may be of both synthetic and natural origin. Suitable substrates of natural origin are, for example, bentonites in sodium form, calcium form or sodium / calcium bentonites. Also suitable are substrates such. B. Attapulgite, hectorite, mica and others a. However, preferred materials here are those with particularly high specific surface areas such as phyllosilicates, bleaching earths, silica gels, filled silicas, porous aluminas, etc.
  • a non-limiting preferred range is therefore a BET surface area of at least 50 m 2 / g, in particular at least 100 m 2 / g, particularly preferably at least 130 m 2 / g, or a BET surface area between 10 and 300 m 2 / g, in particular between 40 and 200 m 2 / g (determined according to DIN 66131).
  • the smectic layered silicate used has a swelling capacity of about 5 to 50 ml / 2g, in particular from about 8 to 40 ml / 2g.
  • At least one cationic polyelectrolyte is used for cationizing the smectic layered silicate.
  • Polyelectrolytes as such are familiar to the person skilled in the art, wherein, for example, Römpp Lexikon Chemie, 10th edition (1998), Georg Thieme Verlag, p. 3438/3439 can be referenced.
  • the polyelectrolyte is preferably a cationic polymer, in particular a water-soluble cationic polymer.
  • the polyelectrolytes are preferably used in solid form. Preferred are polyelectrolytes with permanent positive charge.
  • polyelectrolytes which, owing to their pH, are positively or protonated in solutions or with reactions of acid groups on the surface of the smectic layered silicate.
  • Suitable for the surface modification are, without limitation, for example, the following polyelectrolytes: poly (diallyl-dimethylammonium chloride), abbreviated Polydadmac, cationic polyacrylamides, polyethyleneimines, cationized starches, cationized celluloses.
  • the polymers can be used both linearly or in branched form.
  • Useful cationic polymers also include those listed, for example, in US 4,964,955, e.g. Salts, such as quaternary ammonium salts and acid addition salts of aminoacrylates and salts, such as quaternary ammonium salts and acid addition salts of diallylamines containing substituents such as carboxylate, cyano, ether, amino (primary, secondary or tertiary ), Amide, hydrazide and hydroxyl groups and the like whose zeta potential is sufficiently positive to produce particulate smectic phyllosilicates having zeta potentials of at least about +30 mV, preferably between about +60 and about +80 mV (about + 0, 06 to about +0, 08 V) or higher.
  • Salts such as quaternary ammonium salts and acid addition salts of aminoacrylates and salts, such as quaternary ammonium salts and acid addition salts of diallylamines containing substituents such as
  • Such cationic polymers are poly (alkyltrimethylammonium chlorides), poly (alkyltrimethylammonium bromides), poly (dialkyldiallylammonium halides) such as poly (diallyldimethylammonium chloride) and poly (diallyldimethylammonium bromide), poly (methacryloyloxyethyltrimethylammonium methylsulfate), poly (methacryloyloxyethyltrimethylammonium chloride), poly (methoxy) acryloyloxyethyldimethylammonium chloride), poly (methacryloyl-oxyethyldimethylammonium acetate), poly (methyldiallylammonium acetate), poly (diallylammonium chloride), poly (N-methyldiallyl-artunonium bromide), poly (2,2'-dimethyl-N-methyldiallylammonium chloride), poly (N ethyldiallylammonium bro
  • N-acetamido diallyl ammonium chloride poly (N-cyanomethyldiallyl ammonium chloride), poly (N-propionamido diallyl ammonium bromide), poly (N-acetyl ethyl ester substituted diallyl ammonium chloride), poly (N-ethyl methyl ester substituted diallyl auronyl chloride), poly (N-ethylamine diallyl ammonium chloride), poly (N- hydroxyethyldiallylammonium bromide), poly (N-acetohydrazide substituted dialkylammonium chloride), poly (vinylbenzyltrimethylammonium chloride) , Poly (vinylbenzyltrimethylammoniumbromid), poly (2-vinyl pyridinium chloride), poly (2-vinylpyridinium bromide) r poly (meth acrylamidopropyldimethylaininoniumchlorid), poly (3-meth
  • Another class of cationic polymers useful in the practice of the present invention include naturally occurring polymers such as casein, chitosan and their derivatives.
  • a particularly preferred cationic polymer is poly (diallyl dimethyl ammonium chloride) having the repeating unit:
  • n is preferably about 600 to about 3500, d. H .
  • Poly (di-allyldimethylammonium) chloride polymers having an average molecular weight between about 100,000 and about 500,000. It is also possible to use mixtures of two or more of the above polyelectrolytes.
  • Multilayer polyelectrolyte coatings of the smectic layered silicate are conceivable and covered by the present invention.
  • oppositely charged polyelectrolytes are applied alternately "dry” (as described herein) to the layered silicate.
  • the zeta potential of the inventively prepared cationized phyllosilicates at more than 35 mV, in particular at more than 50 mV.
  • the surface charge density of the cationized layer silicates prepared according to the invention is more than 10 ⁇ eq / g, in particular more than 20 ⁇ eq / g.
  • the mixture produced by the contacting can contain so much solvent that the particles in the mixture become moist and, if appropriate, form agglomerates, but no slurry or suspension is produced.
  • a dry cationized phyllosilicate according to step (b) above it may be advantageous, after contacting to produce a dry cationized phyllosilicate according to step (b) above, to carry out a conventional drying on the desired degree of drying after application and, if appropriate, grinding to the desired degree of grinding.
  • the production of any shaped bodies, eg. B. using binders is possible.
  • the present invention relates to a cationized smectic layered silicate obtainable by a process as described herein.
  • the "dry" process according to the invention causes a special type of surface coating of the layered silicate, resulting in particularly advantageous product properties such as a higher surface charge density (at the same weight fraction of the polyelectrolyte) and, for example, an improved storage stability than products of the prior art expresses.
  • the products prepared by the process according to the invention z. B. in the removal of contaminants in papermaking or in the sorption of biomolecules such as DNA better results.
  • another aspect of the present invention relates to a process for impurity binding in papermaking, comprising the following steps:
  • the groundwood content in the paper pulp or the fiber suspension is at least 10% by weight, in particular 30% by weight. %, based on the total pulp or pulp suspension.
  • Another aspect of the present invention relates to the use of a cationized layered silicate obtainable by a process as described herein for contaminant binder. fertil in papermaking, especially in a process as set forth above.
  • anionic impurities which are introduced into the paper machine by recycling paper broke. This paper break is typically redispersed and introduced into the paper machine. As a result, the ingredients and aids contained in it are completely recycled. Entered thereby be additionally z.
  • Other anionic charged impurities are the latexes used in the paper coating which, while typically hydrophobic, still carry anionic charges. These are highly prone to agglomeration, whereby the agglomerates are deposited as sticky, white residues on the paper machine (so-called white pitch).
  • the adsorbents of the invention are typically suitable for binding these impurities, as shown by the examples given below.
  • the adsorbents according to the invention reduce the need for cationic charges in the paper headbox. This demonstrates the binding of the negatively charged impurities by charge exchange bonds.
  • the cationic charge requirement is typically determined by a titration with short-chain polyelectrolytes.
  • the removal of the impurities can also be detected by further experimental methods, such.
  • B. Turbidity measurements which prove in particular that large colloids, such.
  • B. Tree resin (so-called pitch) can be removed using the adsorbents of the invention.
  • a further use according to the invention therefore relates to the use of a cationized layered silicate obtainable by a process as defined above for the sorption of biomolecules such as proteins, nucleic acids, polysaccharides or lipids, in particular of nucleic acids such as DNA.
  • the invention relates to a method for sorption, in particular for enrichment or depletion, removal or recovery or separation of at least one biomolecule from a liquid or fluid medium with the aid of a sorbent, wherein the sorbent comprises at least one adsorbent (cationized layered silicate) prepared according to the method described herein.
  • the sorbent according to the invention for example, for separation or. Purification of DNA and the separation or purification of proteins are used, even in a supported form.
  • the adsorbents according to the invention can be used instead of conventional adsorbents in appropriate form (for example as powder, granules, shaped bodies, supported, as column packing, etc.) and metering, if appropriate.
  • the adsorbents or sorbents used according to the invention have a surprisingly high binding capacity for biomolecules, such as nucleic acids, which are even better than those of commercial adsorption systems of the prior art. Furthermore, they show a particularly rapid binding kinetics. It is also advantageous that the bound biomolecules can be practically quantitatively removed again from the sorbent.
  • adsorbents which are suitable for selectively binding or separating biomolecules.
  • ion exchangers represent the most frequently used adsorbents for the separation of proteins with other biomolecules.
  • the adsorbents according to the invention provide interesting new alternatives for the binding of Proteins, DNA and other biomolecules via a charge interaction.
  • the cationic adsorbents according to the invention for a separation of proteins to bind those proteins in which one has adjusted in the adsorption solution pH values which are above the isoelectric points of the proteins.
  • a particular aspect of the present invention relates to a method for sorption, in particular for attachment or depletion, removal, recovery or separation of at least one nucleic acid molecule, preferably from a liquid or fluid medium, in particular a polar as well as an aqueous or alcoholic medium Help of a sorptive onsstoffs, wherein the sorbent comprises at least one cationized adsorbent as defined in more detail herein.
  • Sorbents are thus both suitable to separate biomolecules such as nucleic acids or proteins, as well as from appropriate solutions / media to accumulate or deplete to win or remove:
  • the almost quantitative recovery rate on elution with suitable, usually high-salt buffers shows that it it is also possible to recover the bound biomolecules again.
  • the fields of application for such sorbents are diverse. Without limiting this invention to the following examples, a few possible applications are to be cited.
  • B. a separation of nucleic acids from a multi-substance mixture or the depletion of DNA from wastewater from biotechnological production residues with genetically modified organisms.
  • the sorbent according to the invention can also be used for all molecular biological, microbiological or biotechnological methods in connection with biomolecules, in particular their enrichment or depletion, separation, transient or permanent immobilization or other utilization. Exemplary methods and methods can be found in relevant textbooks, such as Sambrook et al. , "Molecular Cloning: A Laboratory Manual", CoId Spring Harbor Press 2001 and are familiar to those skilled in the art. Also in the context of the chromatographic separation of nucleic acids or proteins, the present sorbent can be used.
  • Nucleic acids are to be understood primarily DNA and RNA species, including genomic DNA and cDNA and their fragments, mRNA, tRNA, rRNA and other nucleic acid derivatives of natural or synthetic origin of any length.
  • sorption is intended to include both adsorption and absorption.
  • adsorbent is used synonymously with “absorbent”. The adsorbent is obtained by treating the substrate with the at least one cationic polyelectrolyte.
  • sorbent is intended to clarify that in addition to the adsorbent (also referred to as “ cationized adsorbent” or “ cationized layered silicate ⁇ ) may be included in other adsorbents (for biomolecules).
  • the sorbent used in the invention is based on an adsorbent to which at least one cationic polyelectrolyte has been adsorbed (referred to herein as a cationized adsorbent), d. H. at least 50%, preferably at least 75%, in particular at least 90 or even 95% of the sorbent according to the invention consisting of the cationized adsorbent, as defined herein.
  • the sorbent according to the invention consists essentially or completely of at least one cationized adsorbent as described herein.
  • the sorbent used according to the invention can also be used together with other sorbents or further components which appear suitable to a person skilled in the art.
  • biomolecule mixtures such as nucleic acid mixtures
  • a matrix (carrier) containing the sorption agent according to the invention containing the sorption agent according to the invention.
  • the adsorbents according to the invention are, however, in principle also suitable for the separation or purification of proteins and other biomolecules.
  • a biomolecule is understood as meaning a molecule which has nucleotides or blocks as building blocks. Nucleosides (nucleobases), amino acids, monosaccharides and / or fatty acids in particular proteins, nucleic acids, polysaccharides and / or lipids, preferably nucleic acids such as DNA and proteins.
  • the use for the sorption of nucleic acids is particularly preferred.
  • any desired substrates can be used as long as they have a surface which can be modified or coated with at least one polyelectrolyte.
  • Both inorganic and organic substrates are included.
  • the substrate is substantially insoluble in the medium containing the at least one biomolecule.
  • inorganic substrates Preference is given to inorganic substrates. It has also been found that particularly advantageous results are obtained when the substrate is selected from the group of natural and synthetic phyllosilicates, silicic acids, in particular precipitated silicas, silica gels, magnesium silicates, zeolites, aluminas, in particular porous aluminas, Titanium dioxide, zirconium oxide, or mixtures thereof.
  • these substrates are essentially insoluble in the preferred media and have good sorption properties.
  • the adsorbent is selected from the group of natural or synthetic layered silicates or mixtures thereof.
  • layered silicates are familiar to the person skilled in the art and include, in particular, the smectitic or montmorillonite-containing layered silicates, such as bentonite.
  • both so-called naturally active and non-naturally active layered silicates can be used, in particular di- and tri-octahedral sheet silicates of the serpentine, kaolin and TaIk- pyrophylitzy, snaektites, vermiculites, hats and chlorites and those of the sepiolite Palygorskit group, such as for example B. Montmorillonite, soda lime, saponite and vermiculite or hectorite, - -
  • Weathering products of clays with a specific surface area of more than 200 m 2 / g, a pore volume of more than 0.5 ml / g and an ion exchange capacity (CEC) of more than 40 meq / 100 g in acid-activated form have also proven particularly useful proved.
  • the BET specific surface area is particularly preferably in the range from 200 to 280 m 2 / g, in particular between 200 and 260 m 2 / g.
  • the pore volume is preferably in the range of 0, 7 to 1, 0 ml / 100 g, in particular in the range of 0, 80 to 1, 0 ml / 100 g.
  • Acid activation of such crude clays may be performed as specified further herein. Such clays are described for example in DE 103 56 894.8 of the same Applicant, which is hereby expressly incorporated by reference into the present specification.
  • the two-layered and the three-layered layered silicates after the modification with at least one cationic polyelectrolyte can be advantageously used for the sorption of nucleic acids and other biomolecules.
  • the smectitic layered silicates see above
  • a bentonite more preferably a sodium, calcium or sodium / calcium bentonite. It can both untreated phyllosilicates and phyllosilicates activated with acid or alkali (eg soda) can be used.
  • the (acid) activated phyllosilicates are particularly preferred since, after cationization (occupancy with the polyelectrolyte), the best results were obtained in the sorption of biomolecules.
  • the bentonites as such ie without cationization with polyelectrolyte, already have surprisingly good sorption properties for biomolecules.
  • One aspect of the present invention therefore relates to a process for the sorption of biomolecules as described herein using at least one bentonite as adsorbent or sorbent. More preferably, the bentonite is an alkaline (e.g., soda) or bentonite activated acid.
  • the above unactivated or activated bentonites are coated with at least one polyelectrolyte as defined herein, as these materials are particularly well suited as. Substrates are suitable and after the occupation with the polyelectrolyte particularly good sorption properties for biomolecules can be obtained.
  • acid or alkali e.g., soda
  • activated phyllosilicates selected from the above group of natural and synthetic phyllosilicates or the above clay weathering products, in particular from the bentonites, which are reacted with at least one cationic polyelectrolyte such as - -
  • the present invention also generally relates to the use of ⁇ ron acid-activated or alkali-activated layered silicates coated with at least one cationic polyelectrolyte for the sorption of biomolecules and a composition containing such acidified or alkali-activated cationized layered silicates and at least one Biomolecule.
  • the acid activation can be carried out by any method familiar to the person skilled in the art.
  • the temperature and the duration of the acid treatment, and the porosimetry of the acid-activated phyllosilicates can be selectively influenced.
  • the conditions in the acid activation of the layered silicates ie in particular the amount or concentration of the acid used, the temperature and the duration of the acid treatment, and the porosimetry of the acid-activated phyllosilicates can be selectively influenced.
  • the conditions in the acid activation of the layered silicates ie in particular the amount or concentration of the acid used
  • the temperature and the duration of the acid treatment, and the porosimetry of the acid-activated phyllosilicates can be selectively influenced.
  • a greater porosity of the layered silicates are effected, especially in the region of smaller pores having a diameter of less than 50 nm, in particular less than 10 nm, determined according to CC14 method according to method section.
  • the sorption capacity of the acid-activated phyllosilicate or its rate of ab- and desorption can be optimized by acid activation on a case-by-case basis by routine examination of a series of different acid-activated phyllosilicates.
  • the pores / cavities in the sorption agents according to the invention can be modified in the manner provided for in EP 0 104 210 or US Pat. No. 4,029,583 (see above).
  • phyllosilicates are brought into contact with at least one acid.
  • any organic or inorganic acids or mixtures thereof can be used.
  • acid can be sprayed using a so-called SMBE process (Surface Modified Bleaching Earth).
  • SMBE process Surface Modified Bleaching Earth
  • the substrates are preferably not organophilic clay materials or phyllosilicates coated with organic cations (eg onium ions).
  • the substrate used in particular in the case of a bentonite, has an ion exchange capacity (cation exchange capacity, CEC) of at least 50 meq / 100 g, preferably of at least 75 meq / 100 g.
  • CEC ion exchange capacity
  • the adsorbent used has an average po- - -
  • ren ren nm and 25 nm, in particular between about 4 and about 10 nm.
  • adsorbents can be advantageously coated with cationic polyelectrolyte, and allow a particularly good. Sorption of biomolecules such as nucleic acid molecules.
  • the pore volume, determined by the CC14 method according to the method part of pores to 80 nm diameter between about 0, 15 and 0, 80 ml / g, in particular between about 0, 2 and 0, 7 ml / g
  • the corresponding values for pores up to 25 nm in diameter are in the range between about 0, 15 and 0, 45 ml / g, in particular 0, 18 to 0, 40 ml / g.
  • the corresponding values for pores up to 14 nm are in the range between about 0, 10 and 0, 40 ml / g, in particular about 0, 12 to 0, 37 ml / g.
  • the pore volumes for pores between 14 and 25 nm in diameter may for example be between 0, 02 and 0, 3 ml / g.
  • the pore volume of pores of 25 to 80 nm may, for example, be in the same range.
  • used sorbent can be used in the form of a powder, granules or an arbitrarily shaped molding.
  • powders the use in the form of suspensions of the sorbent in the at least one nucleic acid molecule containing media offers.
  • coarser milling can also be used to adjust particles which exhibit the usual particle size distribution in chromatography, so that the materials can also be packed into gravity columns or chromatography columns.
  • the use of the sorbents may be in any form, including supported or immobilized forms. For example, it is also used in the separation of different nucleic acid components - -
  • the particle size of the adsorbent or sorbent used according to the invention will depend on the particular application. All particle sizes or agglomerate sizes are possible here.
  • the sorbent can be used in powder form, in particular with a D 50 value of from 1 to 1000 ⁇ m, in particular from 5 to 500 ⁇ m.
  • Typical useful granules are in the range (D 50 ) between 100 ⁇ m to 5,000 ⁇ m, in particular 200 to 2,000 ⁇ m particle size.
  • it is advantageous to use moldings from or with the sorption agents for example in chromatography columns, including gravity or centrifugation columns, solid-phase chromatographies, filter cartridges, membranes, etc.
  • the adsorbent or sorbent used according to the invention can be present in immobilized form.
  • the sorbent may in a FII terpatrone ', an HPLC cartridge or a comparable dosage form to be embedded.
  • An embedding in gels, such. B. Agarose gels or other gel-like or matrix-like structures is preferably possible.
  • Such applications are often sold as part of so-called kits for the purification of nucleic acid molecules, such as. B. the products of the company Quiagen, such as Quiagen genomic tip or the like.
  • the medium containing the nucleic acid molecules of interest is passed through a sorbent-containing column or filter cartridge or the like. Then it can be washed with suitable buffers to remove adhering impurities. It follows - -
  • the adsorbent or sorbent has a BET surface area (determined to DIN 66131) of at least 50 to 800 m 2 / g, in particular at least 100 to 600 m 2 / g, particularly preferably at least 130 to 500 m 2 / g, up. Due to the high surface area, both the advantageous workability with the cationic polyelectrolyte and the interaction with. facilitates the nucleic acid, the desorption possibility is surprisingly preserved.
  • the nucleic acids are DNA or RNA molecules in double-stranded or single-stranded form with one or more nucleotide units.
  • the method according to the invention is particularly advantageous in the case of media containing oligonucleotides or nucleic acids having at least 10 bases (pairs), preferably at least 100 bases (pairs), in particular at least 1000 bases (pairs).
  • the method according to the invention can also be used for nucleic acids between 1 and 10 bases (pairs) or for quite large nucleic acid molecules, such as plasmids or vectors with, for example, 1 to 50 kB or longer genomic or c-DNA fragments. Equally included are restriction digested DNA and R-NA fragments, synthetic or natural oligo- and polymers of nucleic acids, cosmids, etc.
  • z .B the chromatographic separation of biological macromolecules such as long-chain oligonucleotides, high molecular weight nucleic acids, tRNA, 5S rRNA, other rRNA species single-stranded DNA, double-stranded DNA (eg plasmids or fragments of genomic DNA), etc.
  • biological macromolecules such as long-chain oligonucleotides, high molecular weight nucleic acids, tRNA, 5S rRNA, other rRNA species single-stranded DNA, double-stranded DNA (eg plasmids or fragments of genomic DNA), etc.
  • adsorbents used can be used in a wide temperature range, show high loadability, high pressure resistance and a long service life.
  • nucleic acids such as. B. high-purity plasmid DNA
  • the protocols known in the art for the high-purity purification of nucleic acids are often costly and / or time-consuming, unsuitable for use on a large scale or for therapeutic purposes not safe enough, since toxic solvents or enzymes of animal origin, such as. RNAse can be used.
  • the adsorbent or sorbent according to the invention can be used in j e Love media. Preference is given to polar media in which the biomolecules or nucleic acid of interest are generally contained.
  • aqueous or alcoholic media all water or alcohol-containing media, including aqueous-alcoholic media understood.
  • all media are also included in which water is completely miscible or completely mixed with other solvents.
  • Cited are in particular alcohols, such as methanol, ethanol and C 3 - to C 10 alcohols having one or more OH groups or acids.
  • Also conceivable are 'completely water-miscible solvents and their mixtures with water and alcohol.
  • these are in practice aqueous, aqueous-alcoholic see or alcoholic media in connection with a solution, suspension, dispersion, colloidal solution or emulsion.
  • Typical examples are aqueous or alcoholic buffer systems as used in science and industry, industrial or non-industrial effluents, process effluents, fermentation residues, media from medical or biological research, liquid or fluid contaminated sites, and the like.
  • the adsorbent or sorbent according to the invention may contain other components, as long as it does not unacceptably affect the adsorption of the nucleic acids and, if provided, their desorption.
  • additional components may include, but are not limited to, organic or inorganic binders (see below), other sorbents for biomolecules or other inorganic or organic substances of interest from the medium, or also excipients such as glass, plastic or ceramic materials or the like.
  • the adsorbent or sorbent particles can be bonded to larger agglomerates, granules or shaped bodies via a suitable binder or applied to a support.
  • the shape and size of such parent structures containing the primary sorbent or layered silicate particles will depend on the particular application desired. It 'can thus all- known to the expert and are used in individual cases suitable shapes and sizes. For example, rate with a diameter of more than 10 .mu.m, in particular, be more preferably microns' as 50 in many cases agglomerates.
  • rate with a diameter of more than 10 .mu.m in particular, be more preferably microns' as 50 in many cases agglomerates.
  • In a 'bed of chromatography columns and the like can be a Kugelf ⁇ rm - -
  • a possible carrier is, for example, calcium carbonate, plastics or ceramic materials.
  • any binder known to the person skilled in the art as long as the attachment or incorporation of the biomolecules into or onto the adsorbent or sorbent is not impaired too much or the stability of the particle agglomerates or shaped bodies required for the particular application is ensured ,
  • binders agar-agar, alginates, chitosans, pectins, gelatins, lupine protein isolates or gluten.
  • the invention relates to a method comprising the following steps:
  • d) optionally, separation or ⁇ desorption of at least one biomolecule from the adsorbent or sorbent.
  • the inventive method for accumulation or incorporation of biomolecules on or in the adsorbent or sorbent can be used both for enrichment (ie increasing the concentration of the desired biomolecule) as well as depletion (ie reducing the concentration of the desired biomolecule) or separation of several different biomolecules.
  • the sorbent containing the biomolecules can be disposed of in a further step.
  • the disposal can take place, for example, by thermal treatment to remove the layered silicate containing the biomolecules, wherein after the thermal disintegration of the biomolecules, the sorbent can be disposed of.
  • biomolecules such as nucleic acids
  • the depletion or removal of biomolecules from culture media can also be carried out.
  • bioreactors owing to the high concentration of nucleic acid molecules present in the medium, in particular high molecular weight nucleic acids, an undesirable increase in viscosity may occur.
  • an efficient and biocompatible removal of the interfering nucleic acid molecules from the culture medium can take place via the method according to the invention.
  • the viscosity can also be adjusted to a desired level.
  • the nucleic acid molecule can be desorbed or recovered from the sorptive agent in a further step, as a result of which the sorbent can also be used again, if appropriate after renewed acid activation of the layered silicate.
  • compositions comprising an adsorbent or sorbent as defined herein and at least one biomolecule as defined herein in a fluid or liquid medium, preferably an aqueous or alcoholic medium containing at least one biomolecule.
  • a further aspect of the present invention relates to the use of the sorption agents according to the invention as inorganic vectors for introducing biomolecules into cells or as a pharmaceutical composition, in particular as a reservoir for the storage and controlled release of biomolecules, preferably of nucleic acids.
  • the sorbents according to the invention are also suitable for an efficient introduction of these biomolecules into prokaryotic or eukaryotic cells.
  • biomolecules, in particular nucleic acids can be "packaged” in a particularly advantageous manner for introduction into cells by the process according to the invention.
  • the principle mechanism of such an introduction using the example of DNA-LDH nanohybrids is described, for example, in US Pat Reference Choy et al. , Angew.
  • an adsorbent or sorbent for biomolecules obtainable by a process as described hereinbelow.
  • Such an adsorbent or sorbent is known to be u. a. through a better sorption capacity for biomolecules like DNA than conventional adsorbents.
  • the adsorbents were mixed with 1% by weight in water for 10 min. stirred with a magnetic stirrer. 10 ml of this stock solution are pipetted into the measuring cell, sheared for 5 minutes in the measuring cell and then titrated with PES-Na O 7 OlN or Polydadmac 0, 0IN. The results are given in meq / .g adsorbent.
  • adsorbents to be investigated in each case an aqueous suspension with dist. Water produced.
  • the suspension to be measured was adjusted to pH 7 in each case.
  • the zeta potential of the particles was determined by means of the Zetaphoremeter II from Particle Metrix according to the manufacturer's instructions according to the zip of the microelectrophoresis.
  • the migration speed of the particles was measured in a known electric field.
  • the particle movements that take place in a measuring cell are monitored by means of a microscope.
  • the direction of migration gives information about the type of charge (positive or negative) and the particle velocity is directly proportional to the electrical interface charge of the particles or to the zeta potential.
  • the particle movements in the measuring cell are recorded by means of image analysis and, after the measurement has been completed, the trajectories traveled are calculated and the resulting. Particle velocity determined.
  • the zeta potential (stated in mV) was calculated from this according to the manufacturer's instructions.
  • Nessler's reagent (Merck, Art. 9028); Boric acid solution, 2%; Caustic soda, 32%; 0, 1 N hydrochloric acid; NaCl solution, 0.1%; KCl solution, 0, 1% -ig
  • the washed NH 4 + bentonite is removed from the filter, 2H dried at 110 0 C, ground, sieved (63 micron sieve), and again at 110 0 C for 2 hours dried. Thereafter, the NH 4 + content of the bentonite is determined according to Kjeldahl.
  • the CEC of the clay is the Kjeldahl NH 4 + content of the NH 4 + bentonite (CEC of some clay minerals). The data are given in mval / 100 g clay (meg / 100 g).
  • the selected stock (eg 45% pulp and 55% peroxide bleached wood pulp) can either be obtained directly from the paper mill or stored in the refrigerator before use.
  • the stock was then shaken well at 20g dry to 2% with warm deionized water in a 2000ml beaker. While stirring at 400 rpm, the paper stock batch heated using a hot plate at 40 0 C. If the temperature is reached, the amount of adsorption to be tested sorbent with the aid of a Pasteur pipette to the stock approach - o -
  • the adsorption time in the material approach 30 is fixed min at 40 0 C and the mixture is stirred at 400 rpm. Thereafter, the paper stock batch with the ad is sorbent diluted to 1% solids using deionized water (4O 0 C).
  • a calibrated 100 ml graduated cylinder is distilled with 100 ml. Filled with water. 2, 0 g of the substance to be measured are added slowly in portions of 0, 1 to 0, 2 g to the water surface. After lowering the material, the next quantum is abandoned. After the addition is complete, wait for 1 hour and then read the volume of the swollen substance in ml / 2g. - -
  • the indicated (mean) pore diameters, volumes and areas were determined using a fully automatic nitrogen adsorption meter (ASAP 2000, Micro- metrics) according to the manufacturer's standard program (BET, BJH, trplot and DFT).
  • the percentage figures for the proportion of certain pore sizes refer to the • total pore volume of pores between 1.7 and 300 nm in diameter (BJH Adsorption Pore Distribution Report).
  • the desiccator connected to the graduated cold trap, pressure gauge and vacuum pump is then evacuated to boiling the contents. 10 ml of carbon tetrachloride are evaporated and collected in the cold trap.
  • the desiccator content is allowed to equilibrate for 16 to 20 hours at room temperature, then slowly let air into the desiccator. After removing the desiccator lid, the jar is immediately closed and weighed back on the analytical balance.
  • Pore volume in ml / g substance Pore volume in ml / g substance.
  • Fig. Figure 1 is a graph of the colloidal "pitch" particles in white water using cationized adsorbents of the invention for non-impurity binding in papermaking, and not according to the present invention; the concentration of the colloidal particles of impurities (in 10 ⁇ / ml of the batch) is plotted as a function of the concentration of the adsorbent used per ton of stock;
  • Fig. Figure 2 is a graph of the colloidal "pitch" particles in white water using another cationized adsorbent of the present invention and a comparative material for impurity binding in papermaking; the concentration of the colloidal particles of impurities (in 10 6 / ml of the batch) is plotted as a function of the concentration of the adsorbent used per ton of stock;
  • Fig. 3 is a graph showing the DNA binding capacities of cationized adsorbents of the present invention and a comparison material as a function of the DNA concentration in the test solution;
  • the dry particulate smectic phyllosilicate and the polyelectrolyte polymer powder are mixed dry and ground with a Rotschotormühle Fa. Retsch (sieves: 0, 12mm or 0, 08mm).
  • Example 1 of US Pat. No. 4,954,955 was worked up, with the proviso that, instead of kaolin, a calcium bentonite (see below) at a solids content of 15 wt. % was mixed with the polyelectrolyte in an aqueous suspension.
  • the amount of polyelectrolyte was such that the same weight fraction resulted in the cationized product produced as in the products produced according to the invention.
  • Example 1 Coating of bentonite with the cationic polyelectrolyte Polydadmac (production method according to the invention)
  • a powdered calcium bentonite (bentonite 1) according to Table 1 was ground together with the Polydadmac powder (Certrex, CIBA) in a Rotary Rotor Mill from Retsch and finally to particle sizes ⁇ 0.12 mm or ⁇ 0.08 mm sieved.
  • the amount of Polydadmac powder, based on the weight of the layered silicate, is given in - -
  • polyelectrolyte wt .-% Polydadmac
  • pure bleaching earth was ground accordingly.
  • Polyelectrolyte contents of 2, 5 and 5% based on the end product for the occupied (cationized) samples were set.
  • Example 2 Characterization of the powder samples prepared in Example 1
  • Example 1 The powders prepared in Example 1 were characterized in terms of their BET surface area or particle size distribution. Finally, the surface charge density was determined by titration with PES sodium (0, 01 normal) (Mütek-PCD-0, 3 device, see Methods). Furthermore, the powders were characterized in terms of their zeta potential. The characteristic data of the samples are shown in the following Tables 2 and 3: - -
  • the production process according to the invention is outstandingly suitable for producing smectic layer silicates with negative surface charge or negative zeta potential adsorbents which have a high positive surface charge density on the surface and also have a high positive zeta potential. It is also possible to control the surface charge density or the zeta potential in a targeted manner by the amount of polyelectrolyte added. This allows a production ⁇ TO ⁇ .
  • Example 1 As a comparison, the same calcium bentonite was used as indicated in Example 1, and according to US Pat. No. 4,964,955 (there Example 1) was coated with polydadmac (see comparative method b) before Example 1 above).
  • the resulting adsorbents were characterized in terms of surface charge and zeta potential.
  • the respective values for the inventive adsorbents and the comparative examples in the case of Ca are "• bentonite compared (Table 4).
  • the samples" modification 1 "and” modification 2 "correspond to those of Table 2 above.
  • the surface charge densities were each measured immediately after sample preparation and after the indicated storage time.
  • the adsorbents according to the invention are storage-stable. They can be produced inexpensively and freshly mixed in the form of slurries if necessary.
  • the well-shaken wood pulp (from the refrigerator) is diluted 20 atro to 2% with deionized water (45 0 C).
  • the stock While stirring at 400 rpm, the stock is heated to 40 ° C using a hot plate. When the temperature is reached, the amount of the respective adsorbent to be tested is added to the pulp batch by means of the Pasteur pipette. The reaction time in the batch is 30 minutes at 40 ° Celsius.
  • the stock batch is diluted with the adsorbent to 1% solids content using deionized water (40 0 C).
  • FIG. 1 clearly shows that the bentonite dry-coated with 5% polydadmac according to the invention has substantially better effects than the comparison material according to US Pat. No. 4,964,955. This demonstrates the positive properties of the process according to the invention. It should also be noted that the comparison materials were freshly prepared before the experiments. In practice -
  • the bentonite according to modification 2 was used as described in Example 4 in filtration experiments. The results are shown in FIG. As can be seen, the acid-activated bentonite is also suitable after the cationization according to the invention excellent for reducing impurities in white water.
  • Example 6 Use of the cationized bentonites according to the invention for attachment or depletion of biomolecules
  • the DNA concentration was determined photometrically. In this case, a wavelength of 260 nm was set for the measurement. To calibrate the method with the DNA salt used, a measurement was carried out with a concentration series. The obtained calibration line was used for the photometric determination of the DNA concentration in the adsorption experiments. - -
  • a herring sperm DNA solution with a concentration of 1 mg / ml, 2 mg / ml, 5, 63 mg / ml and 9, 9 mg / 1 was prepared and adjusted to pH 8 using 10 mM Tris / HCl and ImM EDTA , Subsequently, 0.1 g. each of the adsorbents is mixed with 5 ml of the DNA solution and shaken for 1 hour at room temperature. It was then 15 min. centrifuged at 2500 rpm and the supernatant was sterile filtered. Finally, the DNA concentration in the supernatant was measured and used to calculate the binding capacity for DNA. The results are summarized in the following Table 8 and in FIG.
  • BK binding capacity -> converted to mg of DNA based on 1 g of adsorbent
  • herring sperm DNA binds very well to both adsorbents according to the invention, but the binding capacity decreases with increasing surface coverage with positive _
  • Polyelectrolyte (Polydadmac) too.
  • the unoccupied adsorbent shows a lower binding capacity.
  • the weakly basic anion exchanger is functionalized on its surface with diethylaminoethanol.
  • the matrix consists of large-pored silicate particles with a particle size of 100 ⁇ m. and a hydrophilic surface.
  • the anion exchanger is optimized according to the manufacturer specifically for the purification of nucleic acids and allows the separation of RNA, proteins, sugars and other impurities.
  • the strongly basic anion exchanger consists of a polymer matrix with quaternary (trimethyl) ammonium groups on the surface and chloride as the counterion. The average. Particle diameter is 50 ⁇ m, the nominal pore size

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Abstract

L'invention concerne un procédé pour fabriquer un silicate stratifié cationisé, ce procédé consistant à préparer un silicate stratifié sous forme de particules sèches et à mettre en contact ce silicate stratifié avec au moins un polyélectrolyte cationique, la mise en contact étant réalisée par broyage à sec, qui permet d'obtenir non pas une suspension de silicate stratifié mais directement un silicate stratifié cationisé sec. L'invention concerne également un silicate stratifié cationisé obtenu par ce procédé et son utilisation privilégiée.
EP06706266A 2005-01-21 2006-01-17 Procede pour fabriquer des substances adsorbantes cationisees, agents de sorption ainsi obtenus et utilisation privilegiee Withdrawn EP1841526A2 (fr)

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CN112439390A (zh) * 2020-10-30 2021-03-05 广西大学 一种磁性氨基化淀粉膨润土废水处理剂及其制备方法

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CN104128164B (zh) * 2014-07-21 2016-08-31 黄淮学院 KH-550交联SiO2改性壳聚糖吸附剂
CN105727889B (zh) * 2016-02-25 2019-08-09 淮阴工学院 一种海藻酸钠复合微球的制备方法
DE102016212960A1 (de) * 2016-07-15 2018-01-18 BioLog Heppe GmbH Adsorbens für die Schadstoffabtrennung aus Flüssigkeiten und Verfahren zu seiner Herstellung
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CN106964312A (zh) * 2017-04-28 2017-07-21 明光市飞洲新材料有限公司 一种去除废水中bod的凹凸棒吸附剂的制备方法
CN107715853B (zh) * 2017-10-16 2020-06-12 华南农业大学 一种功能化纤维素嫁接沸石的方法及废水处理方法
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CN112439390A (zh) * 2020-10-30 2021-03-05 广西大学 一种磁性氨基化淀粉膨润土废水处理剂及其制备方法
CN112439390B (zh) * 2020-10-30 2022-07-05 广西大学 一种磁性氨基化淀粉膨润土废水处理剂及其制备方法

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