WO2003011453A1 - Produits absorbants obtenus a partir de matieres premieres renouvelables, procede de production et utilisation desdits produits - Google Patents
Produits absorbants obtenus a partir de matieres premieres renouvelables, procede de production et utilisation desdits produits Download PDFInfo
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- WO2003011453A1 WO2003011453A1 PCT/EP2002/008141 EP0208141W WO03011453A1 WO 2003011453 A1 WO2003011453 A1 WO 2003011453A1 EP 0208141 W EP0208141 W EP 0208141W WO 03011453 A1 WO03011453 A1 WO 03011453A1
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- adducts
- adducts according
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- renewable raw
- adsorber
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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
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/16—Cellulose or wood; Derivatives thereof
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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
- B01J20/24—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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3206—Organic carriers, supports or substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3206—Organic carriers, supports or substrates
- B01J20/3208—Polymeric carriers, supports or substrates
- B01J20/3212—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3268—Macromolecular compounds
- B01J20/3272—Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3268—Macromolecular compounds
- B01J20/328—Polymers on the carrier being further modified
- B01J20/3282—Crosslinked polymers
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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
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/13—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
Definitions
- the invention relates to adducts obtainable from renewable raw materials, a process for their preparation and their use.
- renewable raw materials the products made from them and the residues resulting from their processing and direct use - hereinafter referred to collectively as renewable raw materials - have great and largely unused economic potential as raw materials for the production of valuable materials.
- adsorber materials One way of producing valuable materials from these renewable raw materials is to convert them into adsorber materials.
- a large number of adsorber materials are known and are technically used on a large scale in various areas. chen used. Most of these adsorbers, if they are not made of inorganic material, which is less common, are made from fossil raw materials such as oil and coal, which are only available in limited quantities.
- renewable raw materials also offer the possibility of developing adsorber materials.
- Adsorption properties of renewable raw materials e.g. against heavy metals are known, but in most cases these binding properties of unmodified renewable raw materials are not sufficient for industrial use.
- cation exchange materials with good binding properties for heavy metals were produced from agricultural and forestry renewable raw materials and residues such as straw or sawdust through the subsequent incorporation of cation-binding, functional groups (e.g. in DE 42 39 749, DE 1 97 18 452, DE 1 97 53 196 ).
- binders for mineral oils have already been developed from popcorn-like shaped bodies of cereal grains (DE 42 03 928). With the production of cation exchangers and hydrophobic adsorbers, the potential of extracting adsorber materials from renewable raw materials is far from being exhausted.
- oxo complexes oxo complexes of chromium, molybdenum, antimony, arsenic or selenium
- toxic gases and soluble organic oxo complexes of chromium, molybdenum, antimony, arsenic or selenium
- Compounds or medically relevant 'endotoxins are not yet available in suitable adsorbers based on renewable raw materials and residues.
- compounds with the required diverse binding properties are polyamines such as the polyalkyleneimines or polyalkylene polyamines. They undergo compounds with cations, e.g. with heavy metals, various organic compounds, preferably those with acidic and with groups which are easily exchangeable according to nucleophilic reaction mechanisms, acidic gases, various aldehydes and with remarkable selectivity with medically relevant endotoxins, for example lipopolysaccharides from Pseudomonas aeruginosa or phosphorylated lipids from Escherichia coli on.
- polyamines are usually in a liquid form that is not very suitable for industrial adsorption processes.
- the object of the invention is therefore to provide improved adsorbers which, among other things, solve the problems mentioned above, in particular with regard to practicability, taking into account environmental and cost considerations.
- this object is achieved in that adducts obtainable by means of a process comprising the step of introducing carboxylic acid, sulfonic acid, phosphate and / or Renewable raw material modified with phosphonic acid groups, which is reacted with a polyamine selected from the group consisting of polyalkylene polyamines and polyalkylene imines.
- adduct is understood below to mean the products of a reaction in which the substances which initially react with one another are bound to one another by adsorption or TECH, that is to say by predominantly weaker, non-covalent bonds.
- renewable raw materials is preferably understood to mean insoluble but also insolubilized materials of biological origin or modification products containing cation exchange groups thereof in aqueous systems and / or organic solvents and / or mixtures of the two.
- Such preferably used materials of biological origin are, for example, the biomass of mosses, algae, fungi and / or bacteria.
- materials of biological origin that are preferably used in the context of the invention are selected from the group consisting of carbohydrates, in particular raw materials and residues from agriculture, forestry, fishing, paper, and food industry containing cellulose and / or lignocellulose ,
- Such materials of biological origin preferably used in the context of the invention future will be selected from the group consisting of wood residues, bark residues, sawdust, sawdust, straw of all cereals, straw of all fiber plants, corn spindles, beet pulp, cereal bran, paper pulp and crab shells.
- renewable raw materials in the sense of the invention may also only be obtained by implementation or modification.
- Modified renewable raw materials according to the invention are modified by introducing carboxylic acid, sulfonic acid, phosphate and / or phosphonic acid groups.
- renewable raw materials mentioned above are used in relation to their
- the polyalkylene polyamine with which the renewable raw materials can be reacted is selected from the group consisting of H 2 N- (CH 2 ) n -NH 2 (2 ⁇ n ⁇ 12), diethylenetriamine, triethylene tetramine, tetraethylene pentamine , Pentaethylene hexamine, N, N-diethyldiethylenetriamine, bis- (dimethylamino) methane to bis- (dimethylamino) exane [this means that the series of alkyl residues is ascending from methyl residue to hexyl residue, including the isomers] ,
- the adducts according to the invention can be obtained by allowing polyalkyleneimines, including preferably polyethyleneimine with molecular weights between 1000 and 100000, to react with the renewable raw materials as the polyamine.
- the reaction of the polyamine with the renewable raw materials is carried out in such a way that the reaction with the polyamines takes 5 minutes to 10 hours, preferably 2 to 5 hours.
- the reaction takes place in aqueous solutions or is carried out in organic solvents, for example in alcohols, ketones or cyclic ethers or mixtures thereof which are immiscible with water, including mixtures of aqueous and organic solvents. Because of the good solubility of the polyamines in water, aqueous solutions are preferred.
- the reaction temperature during the reaction is in the range from 0 ° C. to the decomposition point of the raw materials, preferably between 20 ° C. and 100 ° C., most advantageously at ambient temperature.
- new adsorber materials are obtained from renewable raw materials for many applications under the conditions mentioned.
- Such stable but not crosslinked adsorber materials are formed in particular by treating modification products of the renewable raw materials and polyamines functionalized with ion exchange groups for cation binding.
- the so-called cation exchangers based on renewable raw materials contain carboxylic acid groups, but sulfonic acid, phosphate and / or phosphonic acid groups are additionally and subsequently introduced into renewable raw materials.
- These adsorber materials are suitable for all applications in which no significant changes in the ionic strength or the pH values in the application solutions occur during the application or are required in the application processes.
- a more stable connection between the renewable raw material and polyamine is preferred.
- a more stable connection between the renewable raw material and polyamine is preferred.
- To improve the chemical and mechanical stability of the Adducts made from renewable raw materials and polyamines are subsequently chemically covalently cross-linked to the surface-bound polyamines.
- crosslinking agents are crosslinking agents selected from the group consisting of formaldehyde, glutaraldehyde, 1,4-butanediol-bis-epoxypropyl ether, ethylene glycol bis-epoxypropyl ether, bis-epoxypropyl ether, epichlorohydrin, cyanuric chloride, dihaloalkane, in particular Ci - to C 2 o-dihaloalkanes, about 1, 2-dibromoethane, dihaloalkanols - particularly preferably C ⁇ _ to C 2 o-dihaloalkanols -, about 1, 3-dibromo-2-propanol, diisocyanates, especially hexamethylene diisocyanate, toluene-2, 4-diisocyanate, quinones, especially benzoquinone, naphthoquinone, dicarboxylic acid dihalides, especially oxalyl chloride,
- the chemical crosslinking reactions can be carried out both in aqueous solutions and in organic solvents.
- Crosslinking agents such as the water-soluble aldehydes, the epichlorohydrin and the dihaloalkanols are advantageously used in aqueous solutions at temperatures from 0 ° C. to 100 ° C., preferably at ambient temperature.
- the crosslinking agents which are insoluble or chemically unstable in aqueous solutions are used in organic solvents, preferably in water-miscible solvents such as the alcohols methanol, ethanol, isopropanol, the ketone acetone or the cyclic ones
- Ethers of tetrahydrofuran or dioxane For the reactions of the crosslinking agents in water miscible organic solvents, the adducts and the adsorbers that can be prepared from them must be conditioned before crosslinking by washing with water-soluble organic solvents and then with water-insoluble organic solvents (for example toluene). For the reaction conditions of the reactions in organic solvents, the same conditions apply to the preferred embodiments as those which have already been described above for the crosslinking reactions in aqueous solutions (ie duration, temperature).
- the polyamines cross-linked by chemical methods on the surfaces of the renewable raw materials are solid and stable and cannot be removed by acidic or basic solutions or by organic solvents.
- the renewable raw materials loaded with the polyalkyleneimines are exposed to temperatures of 30 ° C. to 150 ° C., in particular 50 ° C. to 100 ° C., for 15 minutes to 12 hours, preferably 2 to 5 hours.
- the polyalkyleneimines crosslinked by thermal treatment on the surface of the renewable raw materials cannot be removed under any conditions.
- the adducts provided according to the invention and the adsorber materials made available on the basis thereof have a wide range of applications.
- ion exchangers they can bind heavy metals in both their cationic and anionic form with great application possibilities, especially in the environmental field.
- the heavy metals are preferably bound in the pH range> 3 and the heavy metals are eluted with dilute acids.
- Aldehydes used in technology are removed from both the gas phase and the liquid phase.
- the aldehydes can be eliminated from aqueous phases and from organic solvents. These elimination reactions are possible in all temperature ranges up to the decomposition temperature of the adsorber materials, especially at ambient temperature.
- Acids and particularly acidic gases such as HF, HCl, HBr, HJ, C0 2 , H 2 S, the sulfur oxides S0 2 and S0 3 as well as the nitrogen oxides NO, N0 2 , N 2 0 3 and N 2 0 5 , are by the invention
- organic substances can also be extracted from waste water, e.g. Landfill leachate, are removed, which is indicated by the lowering of the chemical oxygen demand (a measure of the pollution of waste water with organic substances) and by increasing the pH value of the waste water.
- the adsorber materials according to the invention need only be brought into contact with the waste water at pH values between 1 and 7, either in a batch or column process.
- Acidic pollutants mainly humic acids, are bound to the adsorber materials.
- the adducts provided according to the invention or the adsorber materials formed therefrom, which can be produced by the processes described, have many advantages over the adsorber materials according to the prior art. They are made from renewable raw materials that are available in huge quantities worldwide. This conserves only limited natural resources, i.e. oil and coal.
- the adsorber materials are easy to manufacture and can be disposed of easily after use by composting or burning at low temperatures without soot formation. Since they are made from renewable raw materials, the carbon dioxide balance is almost neutral with these disposal processes, too does not apply to petroleum or coal-based adsorbers.
- the surfaces loaded with the polyamines can easily be crosslinked in order to further improve the stability of the polyamines applied, the thermal crosslinking described above being particularly advantageous since it can be carried out easily and does not require any additional chemicals and solvents.
- the surfaces of the renewable raw materials loaded with the polyamines have primary, secondary, tertiary and, after appropriate treatment, quaternary amino groups, which on the one hand explains their special and diverse binding properties, but on the other hand also further modifications for the production of products with new binding properties and possible uses allows.
- the adsorber materials according to the invention which conventional and commercially available ones generally do not have, are therefore particularly advantageous.
- they can be used as cation exchangers and the same adsorber materials under changed pH conditions - which is particularly surprising - as an anion exchanger.
- the surfaces of the renewable raw materials are loaded with basic groups, all types of compounds with acidic properties such as acids and acidic gases can be bound and then easily removed from the adsorbers. Since some of the basic groups of the adsorber materials according to the invention are also primary amino groups, the adsorbers are also suitable for binding aldehydes. This is of considerable importance in the area of environmental protection as an inexpensive alternative, for example for the disposal of formaldehyde or other technically used toxic aldehydes.
- adsorber materials based on inorganic or organic carrier materials poses a difficult problem according to their consumption.
- Adsorbers made of inorganic material can only be disposed of in repositories and cannot be removed from the distance.
- organic material adsorbent materials e.g.
- the predominantly used aromatic-based adsorber materials can be burned, but a great deal of effort is required because of the soot formation that occurs.
- Combustion is not a problem for the adsorber materials according to the invention based on the renewable raw materials. It can be carried out at low temperatures without soot formation, and in most cases even composting can take place. This means that disposal can take place without energy consumption.
- the polyethyleneimine cannot be washed off the adsorber by changing the ionic strength or by acids, and the adsorber is suitable for the elimination of heavy metals from aqueous solutions.
- 0.95 mmol of copper, 1.12 mmol of lead, 1.05 mmol of cadmium, 0.80 mmol of chromate and 0.90 mmol of molybdate are bound per gram of adsorber.
- phosphorylated wheat bran 100 g were, as described in Example 1, first with polyethylene imine with a molecular weight of 50,000 to Load 100,000. 100 ml of a 2% glutaraldehyde solution were added to this modified wheat bran and the suspension was stirred for 2 hours at room temperature. The adsorber was filtered off, washed with distilled water and ethanol and dried at 50 ° C. The adsorber was also suitable for the heavy metal elimination from aqueous solutions. In 10 attempts to eliminate copper from a 1 mmol / 1 solution of copper sulfate with 1 g adsorber, the same adsorber, after regeneration with dilute acids, eliminated amounts of copper in the range from 0.75 to 0.80 mmol.
- a thick slurry was made from 100 g of long fiber, phosphorylated cellulose and 100 ml of a 10% solution of polyethyleneimine with a molecular weight of about 2000. 50 g of coarse table salt were stirred into this slurry. This slurry was filled into a column of 50 cm high and 3 cm in diameter, which was closed at the lower end with a porous glass frit and a hose connection, at a height of 3 cm. A round, porous glass frit with a column diameter was placed on the slurry, and 3 cm of the mixture of long-fiber, phosphorylated cellulose, polyethyleneimine and common salt were placed in water again. This stratification was repeated ten more times and the glass frit was finished with glass wool layered on top.
- the column was placed in a drying cabinet and the adsorber mixture was dried first at 40 ° C. and then Maintained at 90 ° C for 3 hours.
- the column was then filled with distilled water, closed at the top and connected to a container with distilled water at the top.
- the column outlet was opened and distilled water was run through the column.
- the round adsorber disks became damp, swelled and the sodium chloride was released from the disks.
- the water was allowed to drain completely from the column, but left it in the moist state.
- the column was stored in the refrigerator before further use.
- the column with adsorber material was connected via a hose connection and a glass capillary to a three-necked flask which was filled with 100 g paraformaldehyde. Air was pressed into the three-necked flask via a second opening in the three-necked flask, and formaldehyde was released from the paraformaldehyde by heating to 80 ° C. and pressed through the chromatography column with the adsorber material.
- the gas stream was introduced into 200 ml of distilled water, which was divided into 2 wash bottles. In this aqueous solution, the formaldehyde was determined after 24 and 48 hours using an enzyme electrode for formaldehyde. No formaldehyde was detected in the solutions of both wash bottles.
- 250 g of phosphorylated wood chips become 200 ml of a 2% solution of N, N-diethyldiethylenetriamine added in distilled water and the suspension was stirred at room temperature for 3 hours.
- the suspension was filtered and the adsorber was washed with distilled water, ethanol and acetone until the eluate was free of amine (test with trinitrobenzenesulfonic acid).
- the adsorber was then dried at 40 ° C. For crosslinking, the adsorber was transferred to a three-necked flask and 250 ml of acetone were added.
- the resulting HCl gas was passed with nitrogen through the column filled with the adsorber material, and the resulting exhaust gas was introduced into two wash bottles, each of which was filled with a 5% solution of silver nitrate.
- the HCl gas formed from the ammonium chloride was completely bound to the adsorber, as was shown by the fact that there was no clouding due to poorly soluble silver chloride in the solution of the silver nitrate.
- sulfoethyl cellulose 100 g were introduced into 300 ml of a 1% solution of polyethyleneimine with a molecular weight of 50,000 to 100,000 in distilled water and the suspension was stirred for 30 minutes.
- the modified sulfoethyl cellulose was filtered off, washed with distilled water and ethanol and transferred to a three-necked flask with a stirrer and reflux condenser. After the addition of 250 ml of ethanol, 10 ml of 1,3-dibromopropane in 50 ml of ethanol were added through the dropping funnel to the stirred suspension.
- the suspension was then stirred at 80 ° C to 90 ° C for 5 hours.
- the flask contents were then cooled, filtered and washed with ethanol and dried at ambient temperature.
- Example 1 100 g of the dry adsorber material from corn spindle semolina described in Example 1 were introduced into 2 l of a heavy metal-free landfill leachate (pH 1.0). The suspension was stirred at room temperature for 30 minutes and then the pH was measured again. He was on one Value of 5.4 increased without the salt load being increased by adding a base.
- phosphorylated wheat straw particles with a size of 0.5 to 1 mm were, as described in Example 1 for corn spindle meal, loaded with polyethyleneimine with a molecular weight of 20,000, crosslinked and worked up.
- the suspension was stirred at room temperature for 60 minutes, then filtered and the eluate was analyzed.
- the landfill leachate now present as a brown solution had a COD of 5200 and a pH of 7.2 after the treatment. Repeating the binding process with new adsorber material led to a light brown solution with a COD of 4450 and a pH of 8.0.
- the dark brown adsorber can be regenerated with 1 mol / 1 sodium hydroxide solution, but this was not recommended in view of the amount of new waste water containing pollutants. Rather, the cheap adsorber should be burned.
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- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10136527.6 | 2001-07-26 | ||
DE10136527A DE10136527A1 (de) | 2001-07-26 | 2001-07-26 | Adsorbermaterialien aus nachwachsenden Rohstoffen, Verfahren zu ihrer Herstellung und ihre Verwendung |
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WO2003011453A1 true WO2003011453A1 (fr) | 2003-02-13 |
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PCT/EP2002/008141 WO2003011453A1 (fr) | 2001-07-26 | 2002-07-22 | Produits absorbants obtenus a partir de matieres premieres renouvelables, procede de production et utilisation desdits produits |
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DE (1) | DE10136527A1 (fr) |
WO (1) | WO2003011453A1 (fr) |
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WO2005049197A1 (fr) | 2003-11-19 | 2005-06-02 | Chelos Ab | Materiau d'adsorption et procede de production associe |
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DE2021629A1 (de) * | 1970-05-02 | 1971-12-30 | Heraeus Gmbh W C | Ionenaustauschmaterial zum Abfangen von Metallen aus waessrigen Loesungen |
US3885069A (en) * | 1972-08-11 | 1975-05-20 | Us Agriculture | Preparation of crosslinked polyethylenimine and impregnation of cellulosic material with in situ crosslink-polymerized ethylenimine |
EP0054778A2 (fr) * | 1980-12-20 | 1982-06-30 | S.E. Prof. Jörgensen | Procédé de préparation d'un échangeur d'anions et son utilisation |
WO1991019675A1 (fr) * | 1990-06-20 | 1991-12-26 | Ricoh Kyosan, Inc. | Procede et dispositif de purification d'eau |
DE4113602A1 (de) * | 1991-04-23 | 1992-10-29 | Falkenhagen Dieter Dr Sc Med | Endotoxinadsorber und verfahren zu seiner herstellung |
WO1995002452A1 (fr) * | 1993-07-15 | 1995-01-26 | Boris Afanasjevitch Velitchko | Procede de preparation de sorbants a partir de matieres premieres contenant des polysaccharides, sorbants et leur utilisation |
DE19859746A1 (de) * | 1998-12-23 | 2000-06-29 | Georg Haertel | Kombinationsprodukt aus Naturstoffen zur Abwasserreinigung |
-
2001
- 2001-07-26 DE DE10136527A patent/DE10136527A1/de not_active Ceased
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2002
- 2002-07-22 WO PCT/EP2002/008141 patent/WO2003011453A1/fr not_active Application Discontinuation
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US3311608A (en) * | 1963-02-12 | 1967-03-28 | John P Murphy | Cellulose isocyanate-aliphatic polyamine ion-exchange composition and method for making same |
DE2021629A1 (de) * | 1970-05-02 | 1971-12-30 | Heraeus Gmbh W C | Ionenaustauschmaterial zum Abfangen von Metallen aus waessrigen Loesungen |
US3885069A (en) * | 1972-08-11 | 1975-05-20 | Us Agriculture | Preparation of crosslinked polyethylenimine and impregnation of cellulosic material with in situ crosslink-polymerized ethylenimine |
EP0054778A2 (fr) * | 1980-12-20 | 1982-06-30 | S.E. Prof. Jörgensen | Procédé de préparation d'un échangeur d'anions et son utilisation |
WO1991019675A1 (fr) * | 1990-06-20 | 1991-12-26 | Ricoh Kyosan, Inc. | Procede et dispositif de purification d'eau |
DE4113602A1 (de) * | 1991-04-23 | 1992-10-29 | Falkenhagen Dieter Dr Sc Med | Endotoxinadsorber und verfahren zu seiner herstellung |
WO1995002452A1 (fr) * | 1993-07-15 | 1995-01-26 | Boris Afanasjevitch Velitchko | Procede de preparation de sorbants a partir de matieres premieres contenant des polysaccharides, sorbants et leur utilisation |
DE19859746A1 (de) * | 1998-12-23 | 2000-06-29 | Georg Haertel | Kombinationsprodukt aus Naturstoffen zur Abwasserreinigung |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2005049197A1 (fr) | 2003-11-19 | 2005-06-02 | Chelos Ab | Materiau d'adsorption et procede de production associe |
CN101468305B (zh) * | 2007-12-29 | 2012-06-20 | 中国船舶重工集团公司第七一八研究所 | 一种甲醛吸附剂及其制备方法 |
EP2471750A4 (fr) * | 2009-04-14 | 2015-12-16 | Nat Univ Chonbuk Ind Coop Found | Biomasse modifiée en surface, son procédé de préparation et procédé de récupération de métaux précieux à l'aide de ladite biomasse |
CN102886243A (zh) * | 2011-07-21 | 2013-01-23 | 中国科学院兰州化学物理研究所 | 一种用于选择吸附六价铬的吸附剂 |
CN102886243B (zh) * | 2011-07-21 | 2014-09-17 | 中国科学院兰州化学物理研究所 | 一种用于选择吸附六价铬的吸附剂 |
CN105561941A (zh) * | 2016-02-17 | 2016-05-11 | 济南大学 | 一种椰油酰胺丙基甜菜碱改性棉秆皮吸附剂的制备 |
CN105854822A (zh) * | 2016-04-21 | 2016-08-17 | 华南理工大学 | 一种玉米秸秆酶解残渣制备Cu2+吸附剂的方法及其应用 |
CN107970903A (zh) * | 2017-11-29 | 2018-05-01 | 郑州大学 | 一种吸附重金属离子的螯合功能纤维的制备方法 |
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