WO2003011453A1

WO2003011453A1 - Adsorber materials made of renewable raw materials, method for the production thereof and their use

Info

Publication number: WO2003011453A1
Application number: PCT/EP2002/008141
Authority: WO
Inventors: Manfred Kühn
Original assignee: Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
Priority date: 2001-07-26
Filing date: 2002-07-22
Publication date: 2003-02-13
Also published as: DE10136527A1

Abstract

The invention relates to adducts, which can be obtained by means of a method involving the step of reacting a renewable raw material (particularly raw materials and recyclings, which contain carbohydrates and which are from the areas of agriculture, forestry, fish farming, paper industry and foodstuffs industry) with a polyamine selected from the group consisting of polyalkylene polyamines and polyalkylene imines. The adducts can be chemically or thermally cross-linked by means of additional method steps. These adducts are suited for use as adsorber materials, particularly as ion exchangers for the exchange of heavy metals, for decontaminating gasses, soils and waste waters.

Description

Adsorber materials from renewable raw materials, processes for their production and their use

description

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.

In recent years, however, and still have been, attempts have been made, raw materials and residues from agriculture, forestry and fishing, as well as paper and food industries, as well as the huge amounts of biomass from moss, algae, fungi or bacteria to transform into valuable 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.

In principle, 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.

A subsequent chemical modification should, however, be able to improve the binding capacity of renewable raw materials to a wide variety of substances. In the past, attempts have been made to solve this problem using different technical approaches.

For example, effective 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 ). On the other hand, 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. For a large number of pollutants, such as for heavy metals present anionically as oxo complexes (oxo complexes of chromium, molybdenum, antimony, arsenic or selenium) or for toxic gases and soluble organic. Compounds or medically relevant 'endotoxins are not yet available in suitable adsorbers based on renewable raw materials and residues.

However, 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.

The main disadvantage of polyamines, however, is that they are usually in a liquid form that is not very suitable for industrial adsorption processes.

Therefore, according to US Pat. No. 5,194,279, purely physically fixed polyethyleneimine was immobilized in the pores of silica gel for the immobilization of enzymes. set. Organic carrier materials modified with polyethyleneimine have been used for various purposes, such as for immobilizing enzymes, other biological materials (US Pat. No. 4,525,456), separating gases and binding heavy metals and organic substances such as sugar molecules etc. (US Patents 5,807,636, 5,245,024, 4,659,590, 4,892,719, 3,659,400, JP 02251251, JP 63305904, DE 36 09 021, EP 186 528, CS 252229.

However, the above-mentioned application variants in the form of polyalkyleneimines and polyalkylene polyamines covalently or adsorptively bonded to inorganic, organic or bioorganic carrier materials are not used in practice, since the carrier materials used for this purpose are too expensive to immobilize the polyamines or the bonds of the polyamines technical requirements with regard to stability are not sufficient for these properties and / or chemicals which are too expensive and toxic have to be used for the covalent binding of the polyamines.

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.

According to the invention, 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.

The term 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 ionism, that is to say by predominantly weaker, non-covalent bonds.

In the context of the present invention, the term 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.

Further such 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 ,

Still further 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.

The 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.

All previously mentioned renewable raw materials modified within the meaning of the invention, but also from these raw materials and other materials of biological origin isolated and purified and - as described above - chemically functionalized with carboxylic acid, sulfonic acid, phosphate and / or phosphonic acid groups, modification products of about microcrystalline or fibrous cellulose, starch, xylans, agarose, dextrans, lignins, humic acids, chitin, chitosan and co-macromolecules of these biomacromolecules with one another (so-called composite materials of these biomacromolecules) are subsumed under the term of renewable raw materials in the context of the present invention and can be used to produce the adducts according to the invention are preferably used.

According to the invention, the renewable raw materials mentioned above are used in relation to their

Properties of particularly favorable adducts lent if 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] ,

According to another embodiment of the invention, 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.

In all of the above-mentioned embodiments of the invention, 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.

As a rule, sufficiently stable, modified with polyamines, 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.

According to the invention, 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.

For a number of other applications for the adducts according to the invention, but especially for those obtained from unmodified renewable raw materials, 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. Particularly suitable 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 Cι_ 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, terephthaloyl 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.

Surprisingly, however, it has now additionally been found that the products made from renewable raw materials and the polyalkyleneimines used according to the invention can be crosslinked and stabilized by thermal treatment.

For this purpose, 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.

For particularly preferred embodiments of these

Process management (choice of renewable raw materials, choice of polyamines etc.) also applies that already mentioned in connection with the embodiment described above on a purely adsorptive basis.

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. As 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, especially formaldehyde, 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 Adsorber materials bound and can be extracted from the ambient air and waste water.

However, 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. For the purpose of removing organic pollutants from 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 wide-ranging uses of the adsorber materials according to the invention, which conventional and commercially available ones generally do not have, are therefore particularly advantageous. For example, they can be used as cation exchangers and the same adsorber materials under changed pH conditions - which is particularly surprising - as an anion exchanger. This means that new adsorber materials for the elimination of heavy metals from the environment are available, which bind both the cationic and the anionic heavy metals from the environment which are present as oxo complexes. This, and also because of the possibilities for easy disposal of used adsorbers, simplify and reduce the cost drive the heavy metal elimination from the environment significantly.

Special uses for the adsorbers according to the invention also result from their ion exchange properties in biotechnology for the isolation of biological active substances and in medicine for the elimination of endotoxins from the blood.

Because 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.

Further inexpensive and inexpensive applications of the adsorber materials according to the invention in environmental protection result from the fact that the chemical oxygen requirement can be reduced in a simple manner as a measure of the pollution of waste water by binding organic pollutants in waste water (for example the humic acids) to the adsorber materials according to the invention and at the same time the pH values of the waste water are increased without the salt load of the waste water, as is the case with neutralization ons reactions with bases is unfortunately inevitable, it would increase.

The disposal of 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. Such 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.

According to the invention, it is therefore possible to convert renewable raw materials which have hitherto not been used as adsorber materials into new valuable materials with a broad adsorption potential and thus to open up new application possibilities for these cheap and natural resources which are available in large quantities.

Because of the unusually diverse binding properties of the adsorber materials according to the invention, there are also many areas of application in

Life sciences and medicine as well as in the offer like chemistry, biotechnology and above all in environmental protection and nuclear technology.

The invention is illustrated below by examples, which, however, are not to be interpreted restrictively.

example 1

100 g of phosphorylated corn grits were washed with distilled water until the eluate was colorless. 200 ml of a 15% strength solution of polyethyleneimine with a molecular weight of 20,000 in distilled water were added to the brown corn grits and the suspension was stirred for 2 hours at room temperature. The modified maize spindle meal was then filtered off and washed with distilled water until the eluate was free from polyethyleneimine (test with trinitrobenzenesulfonic acid). The adsorber obtained was then washed with ethanol, dried at room temperature and kept at 90 ° C. for 5 hours. Thereafter, 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. For example, 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.

Example 2

100 g of phosphorylated wheat bran 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.

Example 3

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. At the end of the washing process, 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.

To bind formaldehyde, 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. At the end of the chromatography column, 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.

Example 4

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. In addition, 3 ml of 40% sodium hydroxide solution are added dropwise to the suspension and, with stirring and ice cooling, 5 ml of oxalyl chloride dissolved in 50 ml of dry acetone. The suspension was stirred at 0 ° C for 30 minutes and at ambient temperature for 30 minutes. The adsorber was filtered off and washed with acetone, ethanol and distilled water. The moist adsorber was filled into a column which was provided with hose connections at the top and bottom. A suspension with distilled water was prepared from 0.25 mol of ammonium chloride in a three-necked flask, and semi-concentrated sulfuric acid was slowly added dropwise to the stirred suspension with gentle heating to 40 ° C. 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. Example 5

100 g of sulfoethyl cellulose 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.

20 g of the dry adsorber material described in this example were introduced into 2 liters of an acetate buffer with a pH of 4.0 (0.1 mol / 1) while stirring. Within 5 minutes the pH of the acetate buffer rose to 7.2 due to the acid trapping in the buffer. As a result, the solution lost all buffer capacity.

Example 6

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.

Example 7

100 g of 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 dark yellow adsorber material was introduced into 1 liter of black landfill leachate with a pH of 6.4 and a COD value (COD = chemical oxygen demand) of 6800. 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. Finally, 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.

Claims

Expectations

1. Adducts obtainable by means of a process comprising the step that a renewable raw material modified by introducing carboxylic acid, sulfonic acid, phosphate and / or phosphonic acid groups with a polyamine selected from the group consisting of polyalkylene polyamines and polyalkylene imines, is implemented.

2. Adducts according to claim 1, wherein the polyalkylene polyamine is selected from the group consisting of H ₂ N- (CH 2) n -NH ₂ (2 <n <12), diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, N , N-diethyldiethylenetriamine, bis (dimethylamino) methane to bis (dimethylamino) hexane.

3. Adducts according to one of the preceding claims, wherein the renewable raw material is a material of biological origin which is insoluble in aqueous or organic solvents or in their mixtures or a modification product containing the same as ion exchange groups.

4. Adducts according to one of the preceding claims, wherein the material of biological origin is selected from the group consisting of the biomass of mosses, algae, fungi, bacteria.

5. Adducts according to one of the preceding claims, wherein the material of biological origin is selected from the group consisting of carbohydrates-containing raw materials and residues from agriculture, forestry, fishing, paper, and food industry.

6. Adducts according to one of the preceding claims, the material of biological origin being selected from the group consisting of wood residues, bark residues, sawdust, sawdust, straw of all types of grain, straw of all fiber plants, corn spindles, beet pulp, cereal bran, paper pulp and crab shells.

7. Adducts according to one of the preceding claims, wherein the renewable raw material is a biomacromolecule, preferably selected from the group consisting of cellulose, starch, xylans, agarose,

Dextrans, lignins, humic acids, chitin, chitosan and composite materials of these biomacromolecules.

8. Adducts according to one of the preceding claims, the reaction with the polyamines taking 5 minutes to 10 hours, preferably 2 to 5 hours.

9. Adducts according to one of the preceding claims, the reaction temperature during the reaction being in the range from 0 ° C. to the decomposition point of the raw materials, preferably between 20 ° C. and 100 ° C.

10. Adducts according to one of the preceding claims, wherein the method by which the adducts are obtainable comprises the further step that a chemical crosslinking step is carried out, preferably using a crosslinking agent selected from the group consisting of formaldehyde and glutaraldehyde. hyd, 1,4-butanediol-bis-epoxypropyl ether, ethylene-glycol-bis-epoxypropyl ether, bis-epoxypropyl ether, epichlorohydrin, cyanuric chloride, dihaloalkanes, in particular C _x - to C ₂ o-dihaloalkanes, dihaloalkanols, preferably Ci to C ₂ o -Dihaloalkanols, diisocyanates, quinones, dicarboxylic acid dihalides.

11. Adducts according to claim 10, wherein the step of crosslinking is carried out in an aqueous solvent or an organic solvent or a mixture of both.

12. Adducts according to claim 10 or 11, wherein the step of crosslinking takes place at a temperature in the range of 0 ° C and 100 ° C.

13. Adducts according to one of the preceding claims, wherein the polyamine is polyalkyleneimine and the method with which the adducts can be obtained comprises the further step that a step of thermal crosslinking takes place.

14. Adducts according to claim 13, wherein the thermal crosslinking at a temperature of 30 ° C to

150 ° C, preferably at 50 ° C to 100 ° C.

15. Adducts according to claim 13 or 14, wherein the thermal crosslinking lasts 15 minutes to 12 hours, preferably 2 hours to 5 hours.

16. Adducts according to one of the preceding claims, wherein the polyalkyleneimine is polyethyleneimine, preferably with a molecular weight in the range from 1,000 to 100,000.

17. A method for producing the adducts according to any one of claims 1 to 16, wherein the method comprises the step that a renewable raw material is reacted with a polyamine selected from the group consisting of polyalkylene polyamines and polyalkylene imines.

18. The method according to claim 17, wherein the method is modified such that the adducts according to at least one of claims 2 to 16 are obtained.

19. Use of the adducts according to one of claims 1 to 16 as adsorber materials, in particular as an ion exchanger for the exchange of heavy metals, for the decontamination of gases, soils and waste water.