Process for treating biomasses; modified biomasses and their application.

The present application relates to a new process for working up biomass with the aid of carbonyl and / or thiocarbonyl compounds and compounds capable of aminoplast or phenoplast formation. The application also relates to the modified biomass itself and its use which are obtained in the process according to the invention.

When carrying out numerous technical and semi-technical fermentation processes with the help of enzymes or With biomasses and microbial systems of various types in cell division, large quantities are produced worldwide in the production of feed, food, pharmaceuticals, in the isolation of enzymes and antibiotics etc., in the production of alcoholic beverages, feed and nutritional yeasts of the most varied types biomass containing protein, descxy and ribonucleic acid, which so far could only be used for a fraction of their useful use. In addition, the numerous expansions of fully biological plants or the construction of new plants for the purification of industrial and municipal wastewater lead to a rapidly increasing increase in the production of biomass, whereby such biomasses are isolated in the form of costly processes, costly dewatered and usually despite their high protein content as a result of possibly existing ones Pollutants, such as high levels of metal ions, pesticide residues, pathogenic germs etc. must be destroyed, for example, by combustion.

The simple isolation and chemical modification of a wide variety of biomasses, which has so far not been technically feasible to a satisfactory extent, their assembly under standardized conditions with simultaneous complete destruction of pathogenic germs, the storage-stable preservation of all cell contents with total enzyme deactivation, the deactivation of contained pesticide residues or antibiotic residues and the beneficial use of such deactivated biomass in the sense of economic recycling processes is of worldwide importance. This can also be seen from the information below.

Without taking into account the large amounts of biomass generated in the most diverse technical fermentation processes, modern individual plants in the large chemical industry process up to 100,000 m in the fully biological purification of industrial and municipal wastewater³ Wastewater per day, with biomass from microorganisms, the dry weight of which. between 1200 and 1500 tonnes per month per individual plant. In the Federal Republic of Germany alone, amounts of around 2 million tons per year of such proteinaceous biomass are produced. This amount is constantly increasing as a result of the construction of further necessary fully biological cleaning systems. The biomass generated in the whole of Europe, the USA and Canada therefore already represents huge monthly tonnages of cell components, such as interesting proteins or phosphorus-containing cell substances. They are not only isolated and dehydrated by expensive processes, but also generally because of the possible presence of pathogenic bacteria, protozones, fungi, pesticides, herbicides or due to excessive metal ion contents etc. after dewatering, burned using expensive processes or stored in landfills.

The destruction of such huge amounts of proteins and other valuable cell contents is equivalent to the destruction of valuable plant nutrients and thus indirectly also valuable animal nutrients.

There has been no shortage of attempts to process the resulting biomass and use it profitably. However, the results achieved so far are not entirely satisfactory.

A process for the treatment of sewage sludge has already become known, which consists in the fact that<ul id="ul0001" list-style="none"><li>- the sewage sludge resulting from the biological clarification is first filtered,</li><li>- crushing the filter cake to particle sizes of about 3 mm and below,</li><li>- Reduces the moisture content of the particles to about 30 to 50% and</li><li>- then brings an aqueous solution of a separately alkaline precondensed N-methylolurea with the partially dried sewage sludge to react, a temperature between about 30⁰C and 80 ° C and a pH value of 3 to 5 is maintained in order to produce a granular reaction product that can be used as fertilizer or feed additive for animals (cf. DT-OS 25 23,483).</li></ul>

However, this method has several disadvantages. For example, the process can only be carried out using partially dried sewage sludge. Living mycelium-like biomass with a content of 75 - 80% of bound cell water and a content of 100 - 300% of extracellular water cannot be used as starting materials. The method is also unsuitable for processing any and living biomass, i.e. in the state of maximum turgescence and cell division, since the cell walls of many bacteria, bacilli, fungi and a wide variety of microbial systems, especially living microbial systems such as pseudomonas, etc ., from biological or fully biological sewage treatment plants under the implementation conditions are not destroyed or hydrolyzed and blown up and broken down. - It is also disadvantageous that the production of the partially dried sewage sludge requires complex filtration and mechanical comminution, as well as drying which is associated with high costs. Furthermore, the process products are still rich in resistant spore-forming microorganisms, which causes bacteria or fungi to form again. Another disadvantage is that only odorless, partially dried sewage sludge can be converted into odorless process products. If malodorous substances are contained in the sewage sludge particles used, these are not largely destroyed by the process condensations.

Finally, it should be mentioned that the products accessible by the process described in DT-OS 25 23 483 contain relatively high amounts of uncomplexed or insufficiently complexed metal ions, which are present in water-soluble form, are therefore released in relatively high concentrations and are of practical use of the process products.

Furthermore, it has already been known that biomass waste with a solids content of up to 60% by weight can be processed by mixing the biomass sludge with formaldehyde (to kill bacteria), then adding concentrated nitric acid, giving a homogeneous mixture forms and the available nitrogen dioxide has an oxidizing effect on the waste sludge, and then urea is added to the homogeneous mixture, after which polymerization and then agglomeration occurs within a certain time (cf._PS 3 655 395). However, this method has the same disadvantages as the previously known method mentioned above. It should be emphasized that the waste sludge that can be used must have the highest possible solids content. Therefore, a complex pre-drying of the sludge is essential. In addition, a relatively large amount of nitric acid is used as an oxidizing agent.

It is also known that sewage sludge can be converted into nitrogen fertilizer by first mixing the sludge with peat and solid urea, then adding an aqueous urea-formaldehyde solution and an aqueous solution of a strong mineral acid and then adding aqueous ammonia. Solution neutralized (see U.S. Patent 3,073,693). Here, too, it is necessary to bring the sewage sludge into solid form, that is, to largely drain and pre-dry it. Since these operations, as already described in connection with the method known from DT-OS 2 523 483, are very complex, the method is unprofitable for practical use.

Finally, it is already known to solidify waste sludge and to make it usable for various purposes by mixing the waste sludge with polymerizable or condensable monomers, such as acrylic acid or low molecular weight aldehydes and benzene derivatives, e.g. phenols, and carrying out the polymerization or condensation under customary conditions ( see U.S. Patent 3,226,318). This method also has the disadvantages which have already been mentioned in the course of the discussion of the method disclosed in DT-OS 2 523 483. For example, it is expressly pointed out that the water content of the waste sludge must be as low as possible. For this reason, too, labor-intensive and costly pre-drying of the waste sludge is absolutely necessary.

The present invention relates to a new method for processing biomass, which is characterized in that biomass of all kinds<ul id="ul0002" list-style="none"><li>- In a first reaction phase, optionally with hydrolytic degradation or with denaturation of the cell walls present in the biomass in an aqueous medium with carbonyl compounds, thiocarbonyl compounds and / or carbonyl compounds which are in dissociation equilibrium with low molecular weight, uncondensed N-alkylol compounds, optionally in the presence of a catalyst and optionally condensed in the presence of additives,</li><li>- Then in a second reaction phase, the unreacted carbonyl compounds, thiocarbonyl compounds and / or carbonyl compounds, which are in equilibrium with low molecular weight, non-condensed N-alkylol compounds, in an aqueous medium with aminoplast formers, which may contain N-alkylol groups, or with phenoplast formers, if appropriate in the presence of a catalyst and if appropriate in the presence of chain terminators and if appropriate in the presence of additives, and</li><li>- The resulting modified biomass, if necessary, subsequently freed of any undesirable substances still present and / or subjected to post-treatment.</li></ul>

The invention furthermore relates to modified biomasses which are produced by the process according to the invention. They are characterized by a content of<ul id="ul0003" list-style="none"><li>with carbonyl compounds, thiocarbonyl compounds and / or carbonyl compounds which are in dissociation equilibrium with low molecular weight, uncondensed N-alkylol compounds,</li><li>- And with aminoplast formers, which may contain N-alkylol groups or with phenoplast formers</li></ul>

condensed biomass cell constituents or other reactive substances occurring in biomass, and optionally by a content of additives.

The modified biomasses according to the invention are characterized in that they are obtained by using a wide variety of biomasses<ul id="ul0004" list-style="none"><li>- In a first reaction phase, where appropriate with hydrolytic degradation or by blowing up the cell walls present in the biomass in an aqueous medium with carbonyl compounds, thiocarbonyl compounds and / or carbonyl compounds which are in dissociation equilibrium with low molecular weight, uncondensed N-alkylol compounds, if appropriate in the presence of a catalyst and optionally condensed in the presence of additives,</li><li>- Then in a second reaction phase, the unreacted carbonyl compounds, thiocarbonyl compounds and / or carbonyl compounds, which are in equilibrium with low molecular weight, uncondensed N-alkylol compounds, in an aqueous medium with aminoplast formers, which may contain N-alkylol groups or with phenoplast formers, if appropriate in the presence of a catalyst and if appropriate in the presence of chain terminators and if appropriate in the presence of additives, and</li><li>- The resulting modified biomass, if necessary subsequently freed of any undesirable substances still present, and / or subjected to a post-treatment.</li></ul>

The invention also relates to the use of the modified biomasses according to the invention for various purposes. For example, substances according to the invention are suitable for fixing metal ions or organic or inorganic acids. Furthermore, substances according to the invention can be used as reactive fillers and combination fillers, flame retardants and anti-aging agents in plastics, such as natural or synthetic rubbers, polyamides and epoxy resins. In addition, substances according to the invention can act as catalysts or as carriers for catalysts or other substances. For example, certain substances according to the invention are suitable as catalysts for the synthesis of formose and sugar mixtures based on high-percentage formalin solutions. Finally, substances according to the invention can be used to deactivate crop protection agents, as nutrient media for bacteria and as agricultural chemicals or as feed additives.

The smooth and reproducible feasibility of the process according to the invention can be described as surprising, because, as extensive tests have shown, 'there has so far been no generally applicable, rational processing of biomasses of various origins<ul id="ul0005" list-style="none"><li>by treating biomass with a wide variety of highly reactive reagents which are usually used for the precipitation and denaturation of proteins,</li><li>- still by thermal denaturation and flocculation of the biomass,</li><li>- or by condensation of biomass with carbonyl or thiocarbonyl compounds,</li><li>- or by other flocculation and modification reactions</li></ul>

succeeded in a satisfactory manner.

_So Many denaturations, flocculations and salting out with reagents that can be carried out on protein substances, such as well-hydrating ammonium sulfate, trichloroacetic acid, copper sulfate, zinc hydroxide, ethanol or acetone, or thermal denaturing and flocculation with many biomasses, e.g. pseudomonas or yeasts, do not easily lead to powdery filterable products. In addition, the added substances get into the wastewater in a relatively high concentration, creating new wastewater problems. Likewise, in the case of condensation before biomasses with carbonyl compounds, such as formaldehyde, glyoxal, glyoxal sulfate, trichloroacetaldehyde, furfural or isobutyraldehyde or thiocarbonyl compounds, such as thioformaldehyde or polymeric thioacetaldehyde, which, although causing strong enzyme deactivations and sterilization of biomasses, in many biomasses, for example, pseudomonas, for example P Microorganisms are usually present in fully biological sewage treatment plants, only difficult to filter, get sticky, slimy masses. Furthermore, modification reactions and flocculation of biomass with acylating agents, alkylating agents, sulfur chlorides, phosphorus chlorides, phosgene and precipitants containing sulfonic acid groups are not generally applicable. It was therefore not to be expected that a wide variety of biomasses could be processed in a simple manner with the aid of the reactions according to the invention.

The method according to the invention has a number of advantages. It enables biomass to be processed easily and on a technical scale. In addition, the process is not limited to special biomasses, but is generally applicable. A preliminary drainage of the Bianassen to be used is not necessary. The resulting products do not stick together in the aqueous phase, can be filtered without complications and can be dried in an energy-saving manner. They are completely stable in storage and free of pathogenic pathogens. Due to total enzyme deactivation and complete cell death of the biomass in the process products according to the invention, decomposition, putrefaction, fermentation and unpleasant odors of enzymatically or microbiologically degradable cell contents are completely prevented. The process products are therefore completely stabilized in the long term in the dry state and in filled containers with regard to unpleasant odor formation and further enzymatic degradation. In addition, the process products are useful for a variety of purposes. In addition, the versatility of the method according to the invention makes any significant contribution to solving important environmental problems. While previously high-quality, protein-containing substances, nucleic acids and valuable cell contents contained products because of admixtures of pollutants, storage instability or because of the presence of excessive metal contents, pathogenic pathogens etc. generally isolated and dried and then burned or deposited in landfills for later burns, using expensive processes, it is possible with the aid of the process according to the invention to use such substances in a meaningful way. The method according to the invention and the products according to the invention therefore represent a valuable addition to the technology.

As already mentioned, this is the invention _Vexperienced suitable for processing any biomass. This is possible, although most cell components of any cell type, for example the cytoplasm X, the deoxyribonucleic acid Y and ribonucleic acid Z (X + Y + Z) of a plant or animal single cell with the cytoplasm X_m, the deoxyribonucleic acid Y_m and ribonucleic acid Z_m (= X_m + Y_m+ Z_m) of a differentiated multi-cell strong characteristic variations in the molecular structure of (X + Y + Z) compared to (X_m+ Y + Z_m) exhibit.

In the present case, biomasses include all biosystems from microorganisms, such as prokaryotes, Eukar, which are in the state of division, dormancy, partial or complete cell death, or already in the enzymatic decomposition or in the decomposition by foreign cultures^yonts, bacteria, fungi, yeasts, algae, protozoa and unicellular organisms etc., as well as biosystems of highly differentiated cells of plant or animal origin, for example cell components of the blood, such as erythrocytes, granulocytes, lymphocytes and platelets.

The following products are considered as preferably usable biomasses when carrying out the method according to the invention:<ul id="ul0006" list-style="none"><li>- biomass, the<ul id="ul0007" list-style="none"><li>a) arise in processes for the production of products of primary metabolism, for example in the biotechnical production of ethanol, butanol, acetone, citric acid, lactic acid, tartaric acid, simple aliphatic carboxylic acids, amino acids etc.,</li><li>b) occur in technical fermentation processes for the production of products of secondary metabolism, for example in the production of antibiotics, vitamins, growth substances, steroid hormones, alkaloids etc.,</li><li>c) in processes for the production of cell components, such as enzymes, nucleic acids or polysaccharides, and</li><li>d) in processes for the production of cells as biomass, for example yeasts for baking or for alcoholic fermentation, or yeasts for the production of proteins from methane, petroleum and methanol.</li></ul></li><li>- Biomasses from microorganisms from biological wastewater treatment plants.</li><li>- Biomasses that occur in processes of biotransformation, i.e. in processes in which microorganisms are used as catalysts for organic chemical reactions, such as oxidations, reductions, decarboxylations, phosphorylations, aminations, deaminations, acetylations, deacetylations, etc.</li><li>- Biomass of various vegetable origin.</li><li>- Biomasses of a microbial or bacterial nature.</li><li>- Biomass from animal waste products.</li></ul>

Particularly preferred biomasses are:<ul id="ul0008" list-style="none"><li>- The most varied types of yeast (types of mushrooms) from technical processes, for example from fermentation processes of alcoholic fermentation or alcohol-beer production, as well as bottom-fermenting and top-fermenting yeasts.</li><li>- Biomasses from the production of acetic, lactic acid, citric acid, tartaric acid or white cabbage, as well as odorlessly unobjectionable biomasses of these processes and bacterial cultures that ferment as a result of enzymatic processes.</li><li>- Missing lots of yeast cultures.</li><li>- Biomasses of protein production based on various hydrocarbon sources, such as paraffin blends, methane or methanol. Biomasses from special yeast cells of the large-scale plants for the production of protein from petroleum fractions, which contain about 60% crude protein, divide within one hour and contain about 40% digestible protein, and defective batches of such biomass are particularly suitable. Such yeast biomasses contain, for example, about 30 g of lysine, 7.5 g of methionine, 9 g of cystine, 12.5 g of tryptophan and about 9 g of vitamin B and vitamin D per 220 g of crude product. Interestingly, biomasses can also be used from unicellular microorganisms, which are used in the production of protein from natural gas (methane), which consist of mixed bacterial cultures, have protein contents of about 7C% and correspond to approximately high-quality fish meal. Also particularly suitable are biomasses from Pseudomonas bacteria, which are grown in the fermenter at about 37 ° C. and produce protein-rich biomasses from methanol as a carbon source.</li><li>- Biomasses of penicillin production, e.g. Penicillium notatum and Penicillium chrysogenum.</li><li>- Biomasses from the final stage of the tetracycline He.r position (Streptomycetes).</li><li>- Biomass from filamentous bacteria of the sisomicin production (Micromonospora), as well as other Streptomyces species.</li><li>- Biomasses from biological cleaning plants of industrial and municipal wastewater. Such biomasses largely consist of Pseudomonas species and other types of bacteria, algae and fungi, which work optimally at a P: N: C ratio of 1: 5: 100 and can be described as omnivores . The biomass originating from sewage treatment plants, which are also referred to as activated sludge, can also be used in the process according to the invention if they contain traces of ions of mercury, cadmium, zinc, iron, chromium and / or lead.</li><li>- Algae species, such as blue-green algae (Nostoc, Spirulina), green algae (e.g. Chlorella, Scenedesmus and Coleastrum), diatoms, yoke algae (e.g. Spirogyra), scourge algae (e.g. Chlamydomonas), brown algae (bladder wrack) and red algae as well as protozoa.</li><li>- Blood plasma biomass, extracellular and cellular components of the blood, e.g. erythrocytes, granulocytes, lymphocytes and thrombocytes.</li><li>- Biomass from the fish industry.</li><li>- Biomass from animal waste, such as liver cells, nerve cells, bone marrow cells etc.</li><li>- Biomass from the realm of bacteria, in particular those of the order Eubacteriales such as the Pseudomonadaceae families (e.g. Pseudomonas, Rhizobium, Acetobacter), the Enterobacteriaceae (e.g. Escherichia coli, Flavobacterium, Proteus, Serratia, Salmonella), the Bacillaceae (e.g. B. subtilis, B. megaterium, Clostridium), the Lactobacteriaceae (e.g. Lactobacillus), the Micrococcaceae (e.g. Leuconostoc), the Bacterioidaceae (e.g. Desulfovibrio), the Methanobacteriaceae (e.g. Methanobacter), but also sliding bacteria (such as Beggiatoa), vaginal bacteria (e.g. Sphaerotilus), phototropic bacteria (such as Chromatium) as well as bacteria of the order Actinomycetales (such as Streptomyces, e.g. S. rimosus, Micromonospora, Actinoplvnes, Streptosporangium) the realm of mushrooms both higher and lower fungi, Basidiomycetes (e.g. Agaricus), Ascomycetes (e.g. Penicillium, Aspergillus, Saccharomyces), Phycomycetes (e.g. Mucor) as well as Fungi imperfecti (e.g. Fusarium), and numerous other microbial biomasses as described in the literature (cf. Synthesis 4, 120-134 and 147-157 (1969)). Of course, these biomasses can also be obtained from pure cultures from mixed cultures, ie consist of cultures that are infected during fermentation processes and are therefore unusable and, of course, also contain, in a mixture, dead cells of a plant type or cell contents such as hemicelluloses, cell wall components of a plant type such as cellulose and other additives such as homogenized cellulose waste and lignin waste.</li><li>- Mixed cultures of the most diverse bacteria, fungi, algae etc., as well as infected cultures of biomass, which are characterized by infection with fungi, different types of bacteria etc. and have a complex composition. Mixed cultures which form on spent grains in decomposition, nutrient media such as gelatin, molasses, starches, polysaccharides in the open air and in the moist state, and on protein-containing algae still living or already in decomposition may be mentioned as examples. Also worth mentioning are biomass that is used in plant species and cell constituents (eg Sugar cane residue homogenisates, sugar beet residue homogenisates, molasses, homogenisates of broad-leaf plants or grass homogenates) during storage in water or in the moist state aerobically and anaerobically arise from protein degradation and enzymatic degradation and often contain malodorous substances.</li><li>- Earthy materials, such as biologically active garden soil, earthy materials with normal bacteria, algae and / or fungus content,</li><li>- Biomasses that form on spoiled nutrients and also on castor oil residues (e.g. on warm and moist castor meal), yeast masses, cottonseed meal, soybean meal, fish meal, animal meal, bone meal, algae meal, castor bean meal, cornstarch, dextrins, peptones, lignin, moist cellulose powders, moist homogenized coniferous wood and homogenized agar-bearing material, wet-toned agglomerated leaf material, wet-toned agglomerated leaf material, Meat extract powders, improperly stored malt sprouts, tobacco ribs, residues of non-crystallizing sugars and sugar beet pulp, as well as on moist lignin sulfonates from sulfite waste liquors from the paper industry and on improperly stored seaweed.</li><li>- Biomasses in which cell death is already well advanced, for example those biomasses that contain a lot of cell contents (polysaccharides, plant pectin substances, gelatin-like products) outside the cell membrane in aqueous solution.</li><li>- Products from the potato starch industry containing biomass, for example soluble protein components in mother liquors of starch processing infested with various bacterial and yeast-like microorganisms. Products from the cellulose industry can also be used, for example neutralized sulfite liquors from the pulp industry infested with bacteria, fungi, algae or yeast.</li><li>- Various types of digested and organic sludges as well as biomass with high proportions of Escherichia coli and / or various plant suspended matter.</li><li>- Biomasses of anaerobic digestion (= intensive digestion), waste sewage sludge composting products, for example from thermophilic digestion processes (= aerobic-thermophilic process), as well as products of aerobic sewage sludge composting according to the system of rapid rot: tet furthermore microbial infested fiber sludge , Sludges from the food and beverages industry, sludges from dairies and slaughterhouses as well as bio-sludge which has already been dried and is in landfills.</li></ul>

Mixtures of various biomasses can also be used in the method according to the invention. Furthermore, the method according to the invention can also be used if the biomass contains a wide variety of impurities. Biomass in which heavy metal salts, pesticides, antibiotics or other organic or inorganic chemicals are present may be mentioned in this context.

The following can act as reactive components of the biomass:<ul id="ul0009" list-style="none"><li>- All proteins of any cell type, from unicellular to highly differentiated _Mhonor.</li><li>- All lipoproteins from a wide variety of cell types in living nature.</li><li>- Various deoxyribonucleic acids and a wide variety of ribonucleic acids.</li><li>- Glycoproteins as components of a wide variety of enzymes.</li><li>- nucleoproteins.</li><li>- phosphorus proteins.</li><li>- Phosphatides, especially inositol phosphatide, colamine cephalin and serine cephalin.</li><li>- Lipoids or plasmalogens, insofar as they contain bound as base colamine in the form of a phosphoric acid ester.</li><li>- All sugars and polysaccharide-like cell reserves and cell contents, hemicelluloses, starches, pectins and lignins.</li><li>- Components of the cell walls of various types of bacteria. Such substances are, for example, polymers of amino sugars (acetylglycosamine + N-acetylmuramic acid) which are crosslinked in the N-acetylmuramic acid portion via polypeptides.</li><li>- Cell wall components of a wide variety of fungi and algae. Examples include celluloses, hemicelluloses and other polysaccharides and chitin components with acetyl-glucosamine or acetyl-galactosamine components.</li><li>- Enzymes such as glucose oxidase, catalase, glucose isomerase, invertase, lactase, naringinase, lipases, asparaginases, α-amylases and glycoamylases, cellulases, lysozymes, proteases, etc.</li></ul>

Biomasses of penicillin production (Penicillium chrysogenum) can be used as living mushroom masses, as dead cell aggregates or as systems which have already passed through fermentation and decomposition or partial rotting in the process according to the invention. The biosystems of penicillin production, which are filtered off, for example, by filter presses, can be condensed according to the invention even with a certain adsorbed penicillin content, penicillin still adsorbed on the biomass being completely deactivated in its antibiotic activity by condensation.

Biomasses from sisomizine production, which consist of micromonospora (= filamentous bacteria), and in which the active substance is first formed intracellularly and then converted into the aqueous phase by cell disruption in the acidification process, are obtained as insoluble, sticky products and, as such, can occur in the implementation according to the invention are used; Biomasses from Streptomyces species and coli bacteria are also suitable.

Biomasses, which consist of microorganism masses from fermentation processes of the pharmaceutical, enzyme, food and luxury food industry, have a special position compared to the microorganism masses from biological sewage treatment plants - the so-called waste water or excess sludge ("activated sludge") - in that they (the first-mentioned biomasses) have a very uniform composition and are completely free of heavy metal salts. They are therefore also preferred as reaction components in the process according to the invention, provided the process products are used in the agricultural or animal feed sector. Particularly preferred within this complex are industrially used microorganisms whose metabolism can be controlled to obtain high-quality organic and pharmaceutical products from natural raw materials.

Suitable carbonyl compounds which can be used as reaction components when carrying out the process according to the invention are all customary carbonyl compounds with sufficiently reactive carbonyl groups. These preferably include aldehydes and ketones.

Particularly preferred aldehydes are saturated, aliphatic, optionally halogen-substituted or hydroxy-substituted mono-aldehydes, such as formaldehyde, acetaldehyde, butyraldehyde, isobutyraldehyde, pivalinaldehyde, chloral, hydroxyacetaldehyde, hydroxypivalinaldehyde, glyceraldehyde, hydroxyaldehydes, which are contained in formose-sugar mixtures, and hydroxyaldehyde mixtures that arise from other aldehydes through aldol condensation. Particularly preferred aldehydes are furthermore unsaturated aliphatic aldehydes, such as acrolein and crotonaldehyde, furthermore cycloaliphatic aldehydes, such as cyclohexanaldehyde, furthermore aliphatic dialdehydes such as glyoxal, methylglyoxal, glyoxal sulfate and glutardialdehyde, furthermore aromatic aldehydes such as benzaldehyde and 4-methylaldehyde, t-methylaldehyde, 4-methylaldehyde as well as aldehydes derived from heterocycles, such as furfural and hydroxymethylfurfural. "Masked aldehydes", that is to say those compounds which release aldehydes under the reaction conditions or react like aldehydes, can also be used with preference. Paraformaldehyde, triaxane, chloral hydrate, hexamethylenetetramine and hemiacetals of aldehydes, in particular of formaldehyde, with mono-, di- or polyfunctional alcohols such as methanol, ethanol, butanol, ethylene glycol and diethylene glycol may be mentioned specifically in this context.

Particularly preferred ketones are hydroxyacetone, dihydroxyacetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone and quinones such as benzoquinone.

Mixtures of aldehydes and / or ketones can also be used, mixtures of formaldehyde and other aldehydes or ketones being particularly preferred. Mixtures of formaldehyde with numerous aldehydes or ketones which have α-hydrogen atoms can, in situ, cause hydroxy aldehydes by aldol condensation or hydroxyketones are formed, as is illustrated for formaldehyde and isobutyraldehyde by the formula scheme below.<chemistry id="chem0001" num="0001"><img file="EP0010243A1_D0001.tif" /></chemistry> Particular mention should also be made of those hydroxy aldehydes whose formation is represented by the reaction equations below.<chemistry id="chem0002" num="0002"><img file="EP0010243A1_D0002.tif" /></chemistry><chemistry id="chem0003" num="0003"><img file="EP0010243A1_D0003.tif" /></chemistry><chemistry id="chem0004" num="0004"><img file="EP0010243A1_D0004.tif" /></chemistry><chemistry id="chem0005" num="0005"><img file="EP0010243A1_D0005.tif" /></chemistry>

The implementation according to equation (d) corresponds to the Butlerow-Löw formose reaction.

The reaction according to equation (e) is an acyloin condensation which can take place if cyanide ions are contained in the reaction mixture in a catalytic amount.

Analogously, ketones with dv-containing hydrogen atoms can react with formaldehyde. The resulting hydroxy aldehydes and polyhydroxy ketones easily undergo addition reactions to N-alkylol compounds , in particular in the weak to strongly alkaline range, for example with urea and many aminoplast formers, which in turn represent condensation partners for the abovementioned biomasses.

Suitable thiocarbonyl compounds which can be used as reaction components when carrying out the process according to the invention are all customary thiocarbonyl compounds with sufficiently reactive thiocarbonyl groups. These preferably include thioaldehydes and thioketones. Particularly preferred thioaldehydes and thioketones are those which are derived from those aldehydes and ketones which have already been mentioned as being particularly preferred.

"Capped thioaldehydes", that is to say those compounds which release thioaldehydes under the reaction conditions, can also be used with preference. The trimeric thioformaldehyde, the trithiane, which decomposes at elevated temperature in the presence of acids into thioformaldehyde may be mentioned specifically.

Suitable carbonyl compounds which are in dissociation equilibrium with low molecular weight, non-condensed N-alkylol compounds are preferably simple aldehydes, in particular formaldehyde, which is in equilibrium with the corresponding N-methylol compounds. Such N-methylol compounds include in particular N-methylol-urea, N, N'-dimethylol-urea, methylolated dicyandiamide, methylolated oxamide, N-methylol-thiourea, N, N'-dimethylol-thiourea and methylolated melamines, such as hexamethylolmelamine and trishydroxymethyl -melamine of the constitution<chemistry id="chem0006" num="0006"><img file="EP0010243A1_D0006.tif" /></chemistry>

Monomethylol ethylene urea of ​​the constitution should also be mentioned<chemistry id="chem0007" num="0007"><img file="EP0010243A1_D0007.tif" /></chemistry>

Monomethylol-ethylenethiourea of ​​the constitution<chemistry id="chem0008" num="0008"><img file="EP0010243A1_D0008.tif" /></chemistry>

and tetramethylolacetylene diurea of ​​the constitution<chemistry id="chem0009" num="0009"><img file="EP0010243A1_D0009.tif" /></chemistry>

Alkylol compounds which are derived from simple aldehydes, preferably those with up to 5 carbon atoms, are also suitable. In particular, when carrying out the process according to the invention, the following substances are suitable as carbonyl compounds: formaldehyde, acetaldehyde, isobutyraldehyde, crotonaldehyde, glyoxal, furfurol, hydroxymethylfurfurol, salicylaldehyde and their hemiacetals, and also polymers of formaldehyde, such as parafonnaldehyde and trioxane, and also hexamethylene tetranehyde and also hexamethylene tetranehyde such as thioformaldehyde. The following are particularly suitable as uncondensed - (low molecular weight) N-A1-alkylol compounds when carrying out the process according to the invention: N-methylolurea, dimethylolurea, trimethylolmelamine, hexamethylolmelamine, monomethylol-ethylene urea, monomethylol-ethylene-thiourea and tetramethylolacetylene-diurea.

Aminoplast formers are also used as starting materials in the process according to the invention. Aminoplast formers are understood here to mean all those nitrogen compounds which are capable of forming N-oligo- and N-polycondensation products with reactive carbonyl compounds.

These include nitrogen compounds, such as ureas, for example the urea itself, acetylene urea, dimethylacetylene urea and N-methylene urea, furthermore thioureas, such as the unsubstituted thiourea, further diureas, such as hexamethylene diurea, tetramethylene diurea and ethylene diaryl urea, such as by means of polyhydric alcohols, also by means of reaction with polyhydric alcohols, also by means of polyhydric alcohols, by means of reaction with polyhydric alcohols, also by means of reaction with polyhydric alcohol araliphatic di- or triisocyanates or also biuret polyisocyanates with ammonia or primary amines can be obtained, moreover polycarboxylic acid amides, such as oxalic acid diamide, succinic acid diamide and adipic acid diamide, furthermore mono-, di- and polyurethanes, such as the reaction products of aliphatic, cycloaliphatic and aromatic, araliphatic Mono- or bischloroaraic acid esters with ammonia or primary amines, also biurets, melamines, such as the melamine itself, amidines such as dicyandiamidine, guanidines such as aminoguanidine, further guanazole, guanamine, cyanamide, dicyandiamide, primary monoamines, secondary monoamines, arylamines, ammonia, diamines, triamines, hydrazines and carboxylic acid hydrazides, such as hydrazodicarbonamide, carbacinic acid ester and hydrazodic acid esters also similar nitrogen compounds capable of aminoplast formation, preferably the N-alkylol groups corresponding to the aforementioned nitrogen compounds, preferably derivatives containing N-methylol groups and the corresponding C₁-C₄ Alkyl ether of these N-alkylol derivatives.

Also suitable as amine plasticizers are also higher molecular weight α, W-di-ureas, their N-methylol derivatives and N-methylolalkyl ethers, and also α, W-bis-alkoxymethyl urethanes which are polyethers between the α, ω-functional groups, Polythicäther-, polyacetal, polyester, polyesteramide or polycarbonate residues with an average molecular weight of 400 to 10,000 and optionally additional urethane or substituted urea groups. Particularly preferred as higher molecular weight nitrogen compounds capable of aminoplast formation are water-soluble or water-dispersible compounds, for example compounds which contain, between the α, ω-functional urethane or urea groups, polyethylene oxide residues or residues of niche polymers of ethylene oxide with propylene oxide or tetrahydrofuran or of water-soluble polyacetals, made from di-, tri- or tetraethylene glycol and formaldehyde.

These aminoplast formers required as starting compounds are known or can be prepared by methods known in principle (cf. Houben-Weyl "Methods of Organic Chemistry", Volume XIV, Part 2 (1963), pages 319-402, Georg Thieme-Verlag, Stuttgart) .

When carrying out the process according to the invention, “modified aminoplast formers” are preferably also considered as aminoplast formers. These are to be understood as aminoplast formers, which contain additional easily installable substances. Examples include compounds that can be installed quickly and easily by mixed condensation. These preferably include polyurethanes and polyureas with NH₂-End groups, polyamides from poly- (ß-alanine) with molecular weights up to 2000, N-methylolmethyl ether from polycaprolactam, polythiolactams, polypeptides from N-carboxy-α-aminocarboxylic acids, low molecular weight polyamides from aliphatic dicarboxylic acids and diamines, polyamides from cycloaliphatic components and aromatic components , Polyamides with 0 or S- or N- as heteroatoms, polyesteramides, mixed condensates which, in addition to amide groups, also contain ester, urethane or urea groups, ethoxylated and propoxylated _Mono- and polyamides, polyhydrazides and polyaminotriazoles, polysulfonanides, formaldehyde mixed condensates with urea, melamine and dicyandiamide, low molecular weight aniline-forraldehyde condensates, sulfonic acid amides, mono- and dinitriles, acrylonitrile, urotropin, hexahydrotriazines from primary amines and formal amines and Schiff's and ketimines or polyketimines, such as those from one mole of hexamethylenediamine and 2 moles of cyclohexanone, addition products and polycondensation products of melamine and other amino heterocycles with aldehydes and alcohols, polyaddition and polycondensation products of nitriles with aldehydes, reaction products of phosphorous acid and dialkylphosphites with carbonyl compounds and amines or polyamines. Also come as capable of aminoplast formation_VIn this context, connections also include those connections which are listed on pages 7 to 12 of DE-OS 2 324 134.

The modified aminoplast formers which can be used in the process according to the invention also include N-alkylol compounds and in particular N-methylol compounds, some of which are etherified with compounds such as<ul id="ul0010" list-style="none"><li>polyfunctional hydroxyl compounds, for example polyalcohols, ethylene glycol, glycerin, formose-sugar mixtures, glucose, oligo- and polysaccharides and starch being mentioned as examples;</li><li>- Polyethers of more or less high OH functionality, as used in polyurethane chemistry, for example Polyethers made from propylene oxide, which partially contain ethylene oxide segments, be it in mixing blocks, in random distribution or preferably as terminal segments and which have primary hydroxyl groups as end groups, these polyethers being able to contain up to 70% by weight and more of polyethylene oxide segments and are preferred 13-30% by weight, based on built-in propylene oxide segments, of polyethylene oxide segments;</li><li>- High-melting, pure polyethylene oxides with an average molecular weight of 500-60,000, in particular addition products of propylene oxide to trimethylolpropane or glycerol, which are reacted in a second stage with ethylene oxide in such a way that about 83-87 parts by weight of bound propylene oxide are approximately 17-13 parts by weight of ethylene oxide are eliminated;</li><li>Polyhydroxyl compounds with an average molecular weight of 250-14,000, preferably 400-6,000, which are optionally present in a mixture with low molecular weight polyhydroxyl compounds of the molecular weight range 62-250;</li><li>- High molecular weight polyhydroxyl compounds, such as polyethers having at least two terminal hydroxyl groups, in which preferably at least 10% of the hydroxyl groups represent primary hydroxyl groups;</li><li>- Polyhydroxyl polyesters, as are used in a wide range of variations in the diisocyanate polyaddition process.</li></ul>

Depending on the component, the proportion of alcohols or polyalcohols in these products can be up to 60% by weight, based on the sum of the percentages of nitrogen compounds and alcohols.

When carrying out the process according to the invention, the following substances are particularly suitable as aminoplast formers: urea, thiourea, diureas, such as, for example Hexamethylene diurea, tetramethylene diurea, ethylene urea, acetylene urea, dimethylacetylene urea, oxalic acid diamide, succinic acid diamide, adipic acid diamide, mono- or bishydrazides such as hydrazodicarbonamide, carbazinic acid and aliphatic diesters, di-aliphatic diesters, di-aliphatic diesters, di-aliphatic diesters, hydrazodic acid, di-aliphatic diesters, hydrazodic acid, di-aliphatic diesters, hydrazodic acid, di-aliphatic diesters, hydrazodic acid, di-aliphatic diesters, hydrazodic acid, di-aliphatic diesters, hydrazodic acid, di-aliphatic diesters, hydrazodic acid, di-aliphatic, di-aliphatic products, araliphatic and aromatic mono- or bis-chloroformic acid esters with ammonia and primary amines, also aniline, melamine, dicyandiamide, cyanamide, aminoguanidine, dicyandiamidine, guanamines, guanazoles, also polyureas and polybiurets, as obtained by reacting aliphatic, cycloaliphatic, or araliphatic Triisocyanates, as well as biuret polyisocyanates with an excess of ammonia or primary amines are obtained.

Incidentally, when carrying out the process according to the invention come as amino^pAzulmic acids with almost no defects, so-called modified azulmic acids containing defects, azulmic acids stabilized by condensation with carbonyl compounds, further stabilized azulmic acids by condensation with carbonyl compounds and aminoplast formers or their low molecular weight condensation products, as well as metal salt complexes of the aforementioned azulmic acids. In the process according to the invention, these substances are preferably used together with other aminoplast formers, in particular urea.

Almost flawless azulmic acids are brown-black to black hydrocyanic acid polymers which are insoluble in all inert solvents and which, according to a suggestion by Th. Völker, essentially have the following formula (cf. Angew. Chem 72, (1960) pages 379-384) :<chemistry id="chem0010" num="0010"><img file="EP0010243A1_D0010.tif" /></chemistry>

A degree of polymerization (HCN) of X = 15-24 was calculated from the oxygen contents of these azulmic acids, so that values ​​of 1 to 4 result for m (formula I). The maximum molecular weights achieved for the polymers are slightly above 700.

Such azulmic acids which are almost free of defects are known (cf. Houben-Weyl, Volume 8 (1952), page 261), DT-PS 662 338 and DT-PS 949 600).

Azulmic acids (modified azulmic acids) containing defects are to be understood as those azulmic acids which contain from 0.5 to 55 percent by weight of ionic groups of the formula<chemistry id="chem0011" num="0011"><img file="EP0010243A1_D0011.tif" /></chemistry>in which<ul id="ul0011" list-style="none"><li>R represents hydrogen, ammonium, an equivalent of a protonized or quaternized organic nitrogen base, a sulfonium cation or an equivalent of a metal cation,</li><li>and a content of 0.5 to 15 percent by weight of groups of the formula which have undergone decarboxylation reactions<chemistry id="chem0012" num="0012"><img file="EP0010243A1_D0012.tif" /></chemistry></li><li>exhibit.</li></ul>

preferably usable in the process according to the invention are those modified azulmic acids in which R is hydrogen, ammonium or an equivalent of a cation of a metal from the I. to V. main group or from I. to VIII. Subgroup stands, where as cations lithium, sodium, potassium, beryllium, magnesium, calcium, strontium, barium, aluminum, thallium, tin, lead, bismuth, copper, silver, gold, zinc, cadmium, mercury, titanium, zirconium, chromium, Manganese, iron, cobalt, nickel, platinum and palladium, rhodium and ruthenium may be mentioned as examples. those modified azulmic acids in which R is equivalent to one are also preferably usable

protonized alkylamines having 1 to 6 carbon atoms, a protonized dialkylamine having 1 to 6 carbon atoms per alkyl group, a protonized trialkylamine having 1 to 6 carbon atoms per alkyl group, a protonized hydroxyalkylamine having 1 to 6 carbon atoms, a protonized di (hydroxyalkyl) amine with 1 to 6 carbon atoms per hydroxyalkyl group, a protonized tri- (hydroxyalkyl) amine with 1 to 6 carbon atoms per hydroxyalkyl group, a protonized cycloalkylamine with 3 to 8 carbon atoms, a protonized alkylene diamine with 2 to 6 carbon atoms, a protonized guanidine, melamine or dicyandiamide or a protonized, saturated or unsaturated heterocyclic nitrogen base with 5 to 7 ring members and 1 to 3 nitrogen atoms in the heterocyclic ring, and for stands for those cations which are quaternized, such as Permethylation, the aforementioned basic nitrogen compounds arise. 3escnders preferred nitrogen bases in this context are methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, tert-butylamine, ethanolamine, diethanolamine, triethanolamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, ethylenediamine, pyrrolidine, piperidene, morpholine, morpholine, morpholine, morpholine, morpholine, morpholine, morpholine, morpholine, 2,4-triazole, 1,2,3-triazole, 2-ethylimidazole and aminotriazole.

Those modified are further preferred _AZulminic acids in which R stands for trialkylsulfonium cations, especially for the triethylsulfonium cation.

Existing in the modified azulmic acids (F₁) - and (F₂) Groups have their origin in nitrile groups which are present in the azulmic acid and can be regarded as breakpoints of the cyclizing nitrile polymerization.

In an idealized representation, the transition from a nitrile group of azulmic acid to a corresponding carboxyl group can be illustrated as follows:<chemistry id="chem0013" num="0013"><img file="EP0010243A1_D0013.tif" /></chemistry> Of course, the formation of amide or imide groups from nitrile groups is also given. For example, the formation of amide groups can be represented by the formula scheme below.<chemistry id="chem0014" num="0014"><img file="EP0010243A1_D0014.tif" /></chemistry> The generation of (F₁) - and (F₂) Groups occur not only on nitrile groups which are already present in the polymer used, but also on those nitrile groups which are formed by catalytic decyclization. In addition, various other hydrolysis reactives are responsible for the formation of defects. For example, one<chemistry id="chem0015" num="0015"><img file="EP0010243A1_D0015.tif" /></chemistry>

which is to be regarded as α-aminonitrile in the molecular association of azulmic acid, is converted into a carbonyl group by hydrogen cyanide elimination and subsequent topochemical hydrolysis reaction according to the following formula scheme<chemistry id="chem0016" num="0016"><img file="EP0010243A1_D0016.tif" /></chemistry>

The following are the ionic groups of the formula<chemistry id="chem0017" num="0017"><img file="EP0010243A1_D0017.tif" /></chemistry> as F₁-Fault locations and the groups of the formula<chemistry id="chem0018" num="0018"><img file="EP0010243A1_D0018.tif" /></chemistry>as F₂-Defects identified.

The F₂Flaws arise from the F₁- Defects where R represents hydrogen or another suitable ion, according to the following formula:<chemistry id="chem0019" num="0019"><img file="EP0010243A1_D0019.tif" /></chemistry>or in the molecular association of azulmic acid:

Defects due to decarboxylation reaction<chemistry id="chem0020" num="0020"><img file="EP0010243A1_D0020.tif" /></chemistry><chemistry id="chem0021" num="0021"><img file="EP0010243A1_D0021.tif" /></chemistry>

Since the formation of the F-fault locations with the release of ammonia and the formation of the F₂-Fault sites coupled with the release of carbon dioxide, the released amount of ammonia and carbon dioxide represents a quantitative measure of the amount of the generated error sites. The quotient of the released molar amount of ammonia and the released molar amount of carbon dioxide provides information about the ratio of F ↑ - to F₂- defects.

The defect site content in modified azulmic acids expressed in percent by weight can be determined in each case by the equivalent weight of the defect site in question (= ionic or nonionic grouping F₁ or F₂) in relation to the corresponding weight size (100g) not converted into an ionic or non-ionic grouping. For example, the flaw concentration is calculated for an F₁-Fault location, in which R stands for hydrogen, from the molar amount of ammonia formed in each case and the fact that the associated ionic grouping of the formula<chemistry id="chem0022" num="0022"><img file="EP0010243A1_D0022.tif" /></chemistry>has an equivalent weight of 73.

The F is calculated in an analogous manner₂-Fault location content from the respectively released molar amount of carbon dioxide and the fact that the relevant grouping of the formula<chemistry id="chem0023" num="0023"><img file="EP0010243A1_D0023.tif" /></chemistry>has an equivalent weight of 29.

The aforementioned azulmic acids containing defects are not yet known. However, they can be produced in a simple manner by several processes. Such modified azulmic acids are obtained by<ul id="ul0012" list-style="none"><li>- Almost free of defects known azulmic acids in aqueous medium at temperatures between 0 ° C and 200 ° C, preferably between 20 ° C and 120 ° C.<ul id="ul0013" list-style="none"><li>a) treated with organic or inorganic acids, or</li><li>b) treated with bases or basic salts, or</li><li>c) treated with water in the neutral range, or</li><li>d) treated with vegetable ashes, catalytically active natural substances and / or fertilizers, or</li><li>e) optionally treated with metal salts in the presence of oxidizing agents and optionally in the presence of organic acids, or</li><li>f) treated with metal salt complexes stabilized azulmic acids, or</li><li>g) treated with oxidizing agents, or that one</li></ul></li><li>Hydrocyanic acid with the aid of basic catalysts, such as sodium cyanate, polymerized under hydrolyzing conditions in an aqueous medium at temperatures between 0 ° C. and 100 ° C., preferably between 20 ° C. and 95 ° C., optionally in the presence of additives, or that one</li><li>- Modified azulmic acids in aqueous medium at temperatures between 50 ° C and 120 ° C, preferably between 60 ° C and 110 ° C, with strong bases, such as sodium hydroxide or potassium hydroxide, and if necessary then exchanges the cation by treatment with metal salts, or that one</li><li>- Modified azulmic acids in an aqueous medium at temperatures between 0 ° C and 200 ° C, preferably between 20 ° C and 120 ° C, treated with organic or inorganic acids.</li></ul>

The reaction products are isolated in all of these processes by customary methods. In general, the procedure is such that after the reaction has ended, the solid reaction product is filtered off, washed and dried.

“Azulmic acids stabilized by condensation with carbonyl compounds” are to be understood as those azulmic acids which contain from 0.5 to 55 percent by weight of ionic groups of the formula<chemistry id="chem0024" num="0024"><img file="EP0010243A1_D0024.tif" /></chemistry>in which<ul id="ul0014" list-style="none"><li>R has the meaning given above,</li><li>and a content of 0.5 to 15 percent by weight of groups of the formula formed by decarboxylation reactions<chemistry id="chem0025" num="0025"><img file="EP0010243A1_D0025.tif" /></chemistry></li></ul>

have and are stabilized by reaction with carbonyl compounds against hydrocyanic acid elimination.

Such stabilized azulmic acids can preferably be used in the process according to the invention<ul id="ul0015" list-style="none"><li>- in which R has the meanings which have already been given for R in connection with the description of the modified azulmic acids, and</li><li>- In which simple aldehydes, especially formaldehyde, were used as carbonyl components for stabilization.</li></ul>

The azulmic acids stabilized by condensation with carbonyl compounds are not yet known. However, they can be produced in a simple manner by several processes. Such azulmic acids stabilized by condensation with carbonyl compounds are obtained by<ul id="ul0016" list-style="none"><li>- Modified azulmic acids containing 0.5 to 55 percent by weight of ionic groups of the formula<chemistry id="chem0026" num="0026"><img file="EP0010243A1_D0026.tif" /></chemistry>in which<ul id="ul0017" list-style="none"><li>R has the meaning given above,</li></ul>and containing 0.5 to 15 percent by weight of groups of the formula<chemistry id="chem0027" num="0027"><img file="EP0010243A1_D0027.tif" /></chemistry>in an aqueous medium at temperatures between 10 ° C and 250 ° C, preferably between 50 ° C and 150^OC, condensed with carbonyl compounds, or that one</li><li>- Acid addition salts or complex compounds of modified azulmic saunas with a content of 0.5 to 55 percent by weight of ionic groups of the formula<chemistry id="chem0028" num="0028"><img file="EP0010243A1_D0028.tif" /></chemistry> in which<ul id="ul0018" list-style="none"><li>R has the meaning given above,</li></ul>and containing 0.5 to 15 percent by weight of groups of the formula<chemistry id="chem0029" num="0029"><img file="EP0010243A1_D0029.tif" /></chemistry>condensed in an aqueous medium at temperatures between 10 ° C. and 250 ° C., preferably between 50 ° C. and 150 ° C., with carbonyl compounds, or that one</li><li>azulmic acids almost free of defects in an aqueous medium at temperatures between 10 ° C. and 250 ° C., preferably between 50 ° C. and 150 ° C., condensed with carbonyl compounds, or that one</li><li>Hydrocyanic acid with the aid of basic catalysts, such as sodium cyanate, under hydrolyzing conditions in an aqueous medium at temperatures between 0 ° C. and 100 ° C., preferably between 20 ° C. and 95 ° C., optionally polymerized in the presence of additives and then condensed in an aqueous medium with carbonyl compounds without prior isolation of the reaction products, if appropriate in the presence of additives, at temperatures up to 250 ° C., or that one</li><li>- Modified azulmic acids containing 0.5 to 55 percent by weight of ionic groups of the formula<chemistry id="chem0030" num="0030"><img file="EP0010243A1_D0030.tif" /></chemistry>in softer<ul id="ul0019" list-style="none"><li>R has the meaning given above,</li></ul>and containing 0.5 to 15 percent by weight of groups of the formula<chemistry id="chem0031" num="0031"><img file="EP0010243A1_D0031.tif" /></chemistry>reacted in an aqueous medium with strong bases such as sodium hydroxide or potassium hydroxide, optionally exchanging the cation by treatment with metal salts and then condensed with carbonyl compounds in an aqueous medium at temperatures between 10 ° C. and 250 ° C., preferably between 50 ° C. and 150 ° C. or that one<ul id="ul0020" list-style="none"><li>modified azulmic acids treated in an aqueous medium with organic or inorganic acids and then optionally condensed with carbonyl compounds in the presence of additives in an aqueous medium at temperatures between 10.degree. C. and 250.degree. C., preferably between 50.degree. C. and 150.degree.</li></ul>or that one<ul id="ul0021" list-style="none"><li>- Almost flawless azulmic acids in the presence of hydrolytically degradable natural substances and in the presence of acid in an aqueous medium at temperatures between 10 ° C and 250 ° C, preferably between 50 ° C and 150 C, condensed with carbonyl compounds.</li></ul></li></ul>

Aldehydes and ketones with reactive carbonyl groups can be used as carbonyl compounds in these processes. All those carbonyl compounds which can also be used when carrying out the process according to the invention can preferably be used. Formaldehyde is particularly preferred as the carbonyl component.

The reaction products are isolated in all of these processes by customary methods. In general, the procedure is such that after the reaction has ended, the solid reaction product is filtered off, washed and dried.

Of the azulmic acids stabilized by condensation with carbonyl compounds, azulmic acids stabilized partially with carbonyl compounds, in particular formaldehyde, can preferably be used in the process according to the invention, by which are meant those azulmic acids containing defects in which only a part of the available reactive groups with carbonyl compounds, in particular Formaldehyde was implemented.

“Azulmic acids stabilized by condensation with carbonyl compounds and aminoplast formers or their low molecular weight condensation products” are to be understood as those azulmic acids which contain from 0.5 to 55 percent by weight of ionic groups of the formula<chemistry id="chem0032" num="0032"><img file="EP0010243A1_D0032.tif" /></chemistry>in which<ul id="ul0022" list-style="none"><li>R has the meaning given above,</li><li>and a content of 0.5 to 15 percent by weight of groups of the formula formed by decarboxylation reactions<chemistry id="chem0033" num="0033"><img file="EP0010243A1_D0033.tif" /></chemistry></li></ul>have and are stabilized against reaction with hydrocyanic acid by reaction with carbonyl compounds and aminoplast formers or their low molecular weight condensation products.

Stabilized azulmic acids which can preferably be used in the process according to the invention are<ul id="ul0023" list-style="none"><li>- In which R has those meanings which have already been given for R in connection with the description of the modified azulmic acids and</li><li>- In which simple aldehydes, such as formaldehyde, and simple aminoplast formers, in particular urea, or low-molecular addition products from such carbonyl compounds and aminoplast formers, for example monomethylol urea or dimethylol urea, or their oligonucleus condensation products, were used as carbonyl components for stabilization.</li></ul>

The azulmic acids stabilized by condensation with carbonyl compounds and aminoplast formers or their low molecular weight addition or condensation products have hitherto not been disclosed. However, they can be produced in a simple manner by several processes. Such azulmic acids stabilized by condensation with carbonyl compounds and aminoplast formers or their low molecular weight addition or condensation products are obtained by<ul id="ul0024" list-style="none"><li>- Modified azulmic acids containing 0.5 to 55 percent by weight of ionic groups of the formula<chemistry id="chem0034" num="0034"><img file="EP0010243A1_D0034.tif" /></chemistry>in which<ul id="ul0025" list-style="none"><li>R has the meaning given above,</li></ul>and containing 0.5 to 15 percent by weight of groups of the formula<chemistry id="chem0035" num="0035"><img file="EP0010243A1_D0035.tif" /></chemistry>in aqueous medium at temperatures between 0 ° C and 200 ° C, or preferably between 10 ° C and 150 ° C, optionally in the presence of catalysts and optionally in the presence of chain terminators with aminoplast formers and carbonyl compounds or their freshly prepared addition or condensation products , or that one</li><li>Acid addition salts or complex compounds of modified azulmic acids with a content of 0.5 to 55 percent by weight of ionic groups of the formula<chemistry id="chem0036" num="0036"><img file="EP0010243A1_D0036.tif" /></chemistry>in which<ul id="ul0026" list-style="none"><li>R has the meaning given above,</li></ul>and containing 0.5 to 15 percent by weight of groups of the formula<chemistry id="chem0037" num="0037"><img file="EP0010243A1_D0037.tif" /></chemistry>in aqueous medium at temperatures between 0 ° C. and 200 ° C., preferably between 10 ° C. and 150 ° C., if appropriate in the presence of chain terminators and if appropriate in the presence of catalysts, with aminoplast formers and carbonyl compounds or their freshly prepared addition or condensation products, or that one</li><li>- azulmic acids almost free of defects in an aqueous medium at temperatures between 0 ° C. and 200 ° C., preferably between 10 ° C. and 150 ° C., optionally in the presence of catalysts with aminoplast formers and carbonyl compounds or their freshly prepared addition or condensation products, or that one</li><li>Hydrocyanic acid with the aid of basic catalysts, such as sodium cyanate, under hydrolyzing conditions in an aqueous medium, if appropriate in the presence of additives, at temperatures between 0 ° C. and 100 ° C., preferably between 20 ° C. and 95 ° C., polymerized and then without prior isolation of the reaction products, if appropriate in the presence of additives and if appropriate in the presence of catalysts and if appropriate in the presence of chain terminators with aminoplast formers and carbonyl compounds or their freshly prepared addition or condensation products at temperatures up to 200 ° C., preferably up to 150 ° C, condensed in aqueous medium, or that one</li><li>Hydrocyanic acid with the aid of basic catalysts, such as sodium cyanate, in the presence of aminoplast formers under hydrolyzing conditions in an aqueous medium, if appropriate in the presence of additives, at temperatures between 0 ° C. and 100 ° C., preferably between 20 ° C. and 95 ° C., polymerized and then without prior isolation of the reaction products, if appropriate in the presence of additives and if appropriate in the presence of catalysts and if appropriate in the presence of chain terminators with carbonyl compounds and aminoplast formers or their freshly prepared addition or condensation products in an aqueous medium at temperatures up to 200 ° C., preferably up to 150 ° C, condensed, or that one</li><li>- Modified azulmic acids containing 0.5 to 55 percent by weight of ionic groups of the formula<chemistry id="chem0038" num="0038"><img file="EP0010243A1_D0038.tif" /></chemistry>in which<ul id="ul0027" list-style="none"><li>R has the meaning given above,</li></ul>and containing 0.5 to 15 percent by weight of groups of the formula<chemistry id="chem0039" num="0039"><img file="EP0010243A1_D0039.tif" /></chemistry>in aqueous medium with strong bases, such as sodium hydroxide or potassium hydroxide, at temperatures between 50 ° C and 120 ° C, preferably between 60 ° C and 110 ° C, if necessary, exchanging the cation by treatment with metal salts and then in aqueous medium at temperatures between 0 ° C and 200 ° C, preferably between 10 ° C and 150 ° C, if appropriate in the presence of catalysts and if appropriate in the presence of chain terminators, with aminoplast formers and carbonyl compounds or their freshly prepared addition or condensation products, or that one</li><li>- Modified azulmic acids in an aqueous medium at temperatures between 0 ° C and 200 ° C, preferably between 20 ° C and 120 ° C, treated with organic or inorganic acids and then in an aqueous medium at temperatures between 0 ° C and 200 ° C, preferably between 10 ° C and 150 ° C, optionally in the presence of catalysts and optionally in the presence of chain terminators with aminoplast formers and carbonyl compounds or their freshly prepared addition or Converts condensation products, or that one</li><li>- Almost flawless azulmic acids in the presence of hydrolytically degradable natural substances in the presence of acid in an aqueous medium, if necessary in the presence of catalysts and optionally in the presence of chain terminators with kminoalastformanten and carbonyl compounds or their freshly prepared addition or condensation products at temperatures between 0 ° C and 200 ° C, preferably between 10 ° C and 150 ° C, or that one</li><li>- Azulmic acids partially or completely stabilized with carbonyl compounds in an aqueous medium at temperatures between 0 ° C and 200 ° C, preferably between 10 ° C and 150 ° C, optionally in the presence of catalysts and optionally in the presence of chain terminators with aminoplast formers and carbonyl compounds or . implements their freshly prepared addition or condensation products, or that one</li><li>- Hydrocyanic acid polymers pretreated thermally at temperatures up to 550 ° C. in an aqueous medium, if appropriate in the presence of additives and if appropriate in the presence of catalysts and if appropriate in the presence of chain terminators with aminoplast formers and carbonyl compounds or their freshly prepared addition or condensation products Converts temperatures between 0 ° C and 200 ° C, preferably between 10 ° C and 150 ° C, or that one</li><li>- On the surface chemically modified azulmic acids in an aqueous medium at temperatures between 0 ° C and 200 ° C, preferably between 10 ° C and 150 ° C, optionally in the presence of catalysts and optionally in the presence of chain terminators with aminoplast formers and carbonyl compounds or their fresh prepared additive or condensation products.</li></ul>

Aldehydes and ketones with reactive carbonyl groups can be used as carbonyl compounds in these processes. All those carbonyl compounds which can also be used when carrying out the process according to the invention can preferably be used. Formaldehyde is particularly preferred as the carbonyl component.

All customary aminoplast formers can be used as aminoplast formers in these processes. All those aminoplast formers which can also be used when carrying out the process according to the invention can preferably be used. Urea is particularly preferred as an aminoplast former.

N-alkylol compounds, in particular N-methylol compounds, can preferably be used as low-molecular addition or condensation products from aminoplast formers and carbonyl compounds, with monomethylol urea and dimethylol urea being mentioned as examples.

All conventional condensation catalysts can be used as catalysts in these processes. These preferably include all those acids, bases and salts which are also preferred as condensation catalysts in the process according to the invention (see page 6₀).

As a warp^pAll conventional monofunctional compounds suitable for chain termination reactions can be used in these processes. In this case, preference is given to all those chain terminators which are also preferred as chain terminators in the process according to the invention (cf. page 61).

The reaction products are isolated in all of these processes by customary methods. In general, the procedure is such that, after the reaction has ended, the solid reaction product is filtered off, washed and dried.

From the condensation with aminoplast formers and carbonyl compounds or their low molecular weight freshly prepared additic or Condensation products stabilized azulmic acids can preferably be used in the process according to the invention, partially stabilized azulmic acids, which are to be understood as meaning azulmic acids containing defects in which only a part of the available reactive groups with aminoplast formers, in particular urea, and carbonyl compounds, in particular formaldehyde, or with their low molecular weight Addition or condensation products was implemented.

The metal salt complexes of the aforementioned modified and stabilized azulmic acids are not yet known. However, they can be prepared by stirring the aforementioned modified or stabilized azulmic acids in an aqueous medium at temperatures between 20 ° C. and 120 ° C., preferably at 50 ° C. to 110 ° C., with the substances to be complexed. The processing takes place according to usual methods. In general, the reaction products are isolated by filtration.

In the process according to the invention, all customary compounds capable of phenoplast formation can be used as phenoplast formers. These preferably include phenols and compounds derived therefrom. Examples include phenols, cresols, bisphenol A, nitrophenol, pyrocatechol, hydroquinone and naphtholsulfonic acid.

All customary condensation catalysts can be used as catalysts in the process according to the invention. These include acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, other acids derived from phosphorus, formic acid, acetic acid, thioacetic acid, maleic acid and oxalic acid, as well as bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, lead hydroxide, zinc oxide, magnesium oxide and others Metal oxides and their hydrates, furthermore salts, such as phosphates, for example primary or secondary potassium hydrogen phosphate, ammonium sulfate, copper, zinc, tin (II), cadmium and magnesium salts of various organic acids, as well as numerous organic acid anhydrides and acid-releasing compounds such as ammonium chloride, trimethylammonium formate, chloral hydrate, and also amine salts of formic acid and other organic carboxylic acids, maleic acid semiesters, tertiary amine salts and tertiary amines, dibenzoyl peroxide, carbonic acid, N-carbamic acids, Glycol chlorohydrin, glycerol chlorohydrin and epichlorohydrins.

Preferred catalysts are acids such as phosphoric acid, phosphorous acid, nitric acid, hydrochloric acid, sulfuric acid, formic acid, oxalic acid and maleic acid, and also bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, lead hydroxide, benzyldimethylamine and triethylamine.

If phosphoric acid or sulfuric acid is used as condensation catalysts, the acids mentioned can often advantageously be precipitated quantitatively on the process products by precipitation with calcium or, in the case of phosphoric acid, with iron or aluminum ions, so that washing-out operations of the process products and waste water pollution are eliminated.

All customary monofunctional compounds suitable for chain termination reactions can be used as chain terminators in the process according to the invention. Preferred monofunctional chain terminators are lactams, such as ε-caprolactam, valerolactam, butyrolactam and the corresponding thiolactams, furthermore formamide and acetamide, furthermore alcohols, such as methanol, ethanol, propanol, butanol, allyl alcohol, isopropanol, oleyl alcohol and benzyl alcohol, which grow Stop aminoplast segments by etherification reactions. - Chain breakers that can preferably be used are also those connections as are described on pages 13 and 14 of German Offenlegungsschrift 2,324,134. In a particular embodiment of the process according to the invention, N-methylolcaprolactam, N-methylolvalerolactam, N-methylolbutyrolactam and N-methylolazalactams, such as, for example, basic methylol compounds of azalactams of the constitution, can also be used as chain terminators<chemistry id="chem0040" num="0040"><img file="EP0010243A1_D0040.tif" /></chemistry>

act. The latter substances are not yet known. However, they can be prepared from the corresponding azalactams by methylolation with formaldehyde by customary methods. The azalactams required are known (cf. DE-OS 2 035 800).

Organic natural substances and products obtained therefrom, inorganic natural substances and products obtained therefrom, synthetic organic products, synthetic inorganic products and / or mixed products of organic and inorganic products can be used as additives when carrying out the process according to the invention.

Preferred organic natural substances and products derived therefrom are wood powder, lignin powder, ligninsulfonic acids, ammonified ligninsulfonic acids, humus, humic acids, ammonified humic acids, peat, proteins and their degradation products, for example Hydrolysis products of yeasts, algae material (alginates), polypeptides such as wool and gelatin, fish meal and bone meal, furthermore amino acids, oligopolypepides, pectins, monosaccharides such as glucose and fructose, disaccharides such as sucrose, oligosaccharides, polysaccharides such as starch and cellulose, furthermore hemicellulose , homogenized materials of vegetable and animal origin, activated carbons as well as ashes, which by partial oxidation, complete oxidation or combustion of organic, substances formed by photosynthesis or conventional fuels are available, fir ash, gorse ash, Serbian spruce ash, oak ash, birch ash, beech ash, willow ash and tobacco leaf ash being specifically mentioned.

Silicates, such as aluminum silicates, calcium silicates, magnesium silicates and alkali silicates, also sea sand and other naturally occurring silicon dioxides, silicas, in particular disperse silicas, silica gels, furthermore clay minerals, mica, carbonates and phosphates like calcium carbonate, phosphorite are considered as inorganic substances and products derived therefrom such as calcium phosphate and ammonium magnesium phosphate, sulfates such as calcium sulfate and barium sulfate, in addition oxides such as zirconium dioxide, nickel oxide, palladium oxide, barium oxide, disperse antimony oxides and aluminum oxides such as bauxite, aluminum oxide hydrate, in addition fly ash and various types of soot.

Suitable synthetic organic products are preferably aminoplast condensates, in particular those made from urea, dicyandiamide, melamine or oxamide and aldehydes, such as formaldehyde, acetaldehyde, isobutyraldehyde, hydroxypivalinaldehyde, crotonaldehyde, hydroxyacetaldehyde, furfurol, hydroxymethylfurfurol, glyoxal and glucose products, specifically mentioning glyoxal and glucose from urea and formaldehyde, urea and glyoxal, urea and acetaldehyde, urea and isobutyraldehyde, Urea and crotonaldehyde, urea and hydroxypivalinaldehyde and 2-0xo-4-methyl-6-ureido-hexahydropyrimidine, which is a known condensation product of 1 mol of crotonaldehyde and 2 mol of urea, which is formed from intermediate crotonylidene diurea and saturates the double bond and which the constitution<chemistry id="chem0041" num="0041"><img file="EP0010243A1_D0041.tif" /></chemistry>

comes to. Polyalkylidene ureas, such as polymethylene ureas, also polymethylene thioureas, highly crosslinked aminoplast condensates, urea hydrazodicarbonamide-formaldehyde condensates, dicyandiamide condensates, oxamide condensates and high molecular weight polyammonium polyphosphates of the constitution may also be mentioned<chemistry id="chem0042" num="0042"><img file="EP0010243A1_D0042.tif" /></chemistry> Also suitable as synthetic organic products are preferably plastics, such as polyamide powder, polyurethane powder and polycarbodiimides, furthermore polymeric quinones, addition or condensation products from quinones, in particular benzoquinone, with amines or ammonia, furthermore with aldehydes, in particular formaldehyde, crosslinked gelatin, synthetic soil conditioners , such as the product known as Hygromull (= urea-formaldehyde resin flakes), in addition synthetic sugars, such as, for example, formose-sugar mixtures prepared from formaldehyde, and also poorly soluble cane sugar complexes, such as the sucrose-calcium oxide complex of the composition 1 mol of sucrose. 3 moles of calcium oxide, and finally organic ammonium salts such as ammonium carbaminate and other organic nitrogen compounds such as hexamethylenetetramine and hexahydrotriazines.

Synthetic inorganic products which are preferably considered are fertilizers such as superphosphate, Thomas slag, rhenania phosphate, phosphorite, calcium cyanamide, calcium ammonium nitrate, leunasal nitrate, potassium phosphate, potassium nitrate and ammonium nitrate, furthermore pigments such as iron oxides and titanium dioxide, as well as metal oxides and metal hydroxides, such as metal oxides and metal hydroxides Calcium oxide, calcium hydroxide, lead hydroxide, bismuth hydroxide, manganese hydroxide and magnesium hydroxide, hydroxides produced in situ are particularly preferred, also sulfur, poorly soluble metal sulfates, carbonates, phosphates and silicates, heteropolyacids of tungsten, vanadium and molydane, further synthetic silicas, in particular silica prepared in situ and their salts, and also water glass, salts such as cobalt methylbate, ammonium carbonate and calcium carbonate, and also catalysts, in particular heavy metal catalysts, of all kinds.

Neutral, basic or acidic soils, natural soil improvers and biologically active garden soil are preferred as mixed products from inorganic and organic products.

Otherwise, phenoplast formers can also be added in the process according to the invention before the condensation of the biomass with carbonyl compounds and aminoplast formers is carried out. In this context, phenolic formers are to be understood as meaning phenols and compounds derived therefrom. Examples include phenols, cresols, bisphenol A, nitrophenol,_Benzkatechin, hydroquinone and naphtholsulfonic acid. In this way of carrying out the method according to the invention, aminoplast-phenoplast segments are introduced into the condensation products. Such mixed condensates often increase the speed of the flocculation reaction and can offer advantages in improving the filterability and reducing the stickiness of the process products.

In addition, when carrying out the method according to the invention, it may be advantageous to convert the biomasses to hydroxyalkanephosphonic acid esters before carrying out the condensations. Hydroxyalkanephosphonic acids, in particular hydroxymethylphosphonic acid esters or hydroxymethylphosphonic acid, are added, since these substances enter into mixed condensations with aminoplast formers via their hydroxymethyl group and at the same time are catalytically active.

The addition of 10-20% by weight of mono- and polynitriles to the biomasses, for example acrylonitrile and in particular hydroxyacetonitrile, can be advantageous before carrying out the condensations, since e.g. B. hydroxyacetonitrile in the presence of formaldehyde and aminoplast formers, such as urea, mixed condensation.

When carrying out the process according to the invention, an aftertreatment of the process products can also be carried out by optionally using them in the presence of diluents, such as, for example, anhydrous organic solvents, at temperatures between 0 ° C. and 150 ° C., preferably between 10 ° C. and 120 ° C. treated with a wide variety of reagents or subjected to a wide variety of reactions. Chemical reactions occur to a small extent on the surface of the process products, so that chemically modified products are obtained on the surface.

The chemical modification of the surface of the mixed condensates which can be produced by the process according to the invention is preferably used<ul id="ul0028" list-style="none"><li>- treatment with urea melts (= isocyanic acid supplier);</li><li>treatment with acylating agents such as formic acid, acetic anhydride, butyric anhydride, mixed acid anhydrides from acetic acid and oleic acid, preferably in the presence of sodium or potassium acetate;</li><li>- Treatment with cyclic acid anhydrides, such as maleic anhydride, phthalic anhydride or hexahydrophthalic anhydride;</li><li>- Treatment with melts of dicarboxylic acids, such as adipic acid, phthalic acid, hexahydrophthalic acid or trimelitic acid;</li><li>- Treatment with inorganic acid chlorides, such as cyanogen chloride, phosgene, thionyl chloride, sulfur chlorides, phosphorus oxychloride, phosphorus pentachloride, silicon tetrachloride, antimony trichloride or titanium tetrachloride;</li><li>- Treatment with organic acid chlorides, such as acetyl chloride, benzoyl chloride, chloroformate of the formula<chemistry id="chem0043" num="0043"><img file="EP0010243A1_D0043.tif" /></chemistry>in which<ul id="ul0029" list-style="none"><li>R 'represents alkyl having 1 to 8 carbon atoms, bifunctional chloroformates of the formula<chemistry id="chem0044" num="0044"><img file="EP0010243A1_D0044.tif" /></chemistry>in which</li><li>R "represents alkylene with 2 to 8 carbon atoms, _Benzenesulfonic acid chlorides, phosphoric acid ester chlorides, chloromethanesulfochloride or cyanuric acid chloride;</li></ul></li><li>treatment with alkylating agents, such as dimethyl sulfate, methyl iodide or methyl bromide,</li><li>- by treatment with dichloroethane, glycol chlorohydrin, ethyl chloroacetate, ethyl dichloroacetate. Chloroacetaldehyde di-ethylacetal, allyl chloride, benzyl chloride, trichloromethyl isocyanide dichloride or other isocyanide dichlorides or alkylating reagents;</li><li>- Treatment with ε-caprolactam, ε-caprolactone, hydroxypivalic acid lactone, cyclic 6-membered or 8-membered siloxanes, azalactams as known from DT-OS 2 035 800, glycol carbonate, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, Butyrolactone, valerolactone, oxazolidines, oxazolines, imidazolidines, isatoic anhydride or Leuchsian anhydrides from amino acids and phosgene;</li><li>- Treatment with acrylonitrile or other vinyl monomers, such as acrylic acid, methacrylic acid or their methyl, ethyl, B-hydroxyethyl or propyl esters;</li><li>treatment with alcohols or bifunctional alcohols, such as ethylene glycol, hexanediol or octanediol, under the conditions of the Pinner reaction (preferably in anhydrous HCl and alcohols);</li><li>- Treatment with mono- or bis-cyanates or mono- or bis-cyanamides;</li><li>- Treatment with hydroxyalkanephosphoric esters or the underlying acids, in particular with hydroxymethylphosphonic esters or the free hydroxymethylphosphonic acid;</li><li>- Treatment with chloromethylalkoxysilanes, for example those of the formulas<chemistry id="chem0045" num="0045"><img file="EP0010243A1_D0045.tif" /></chemistry><chemistry id="chem0046" num="0046"><img file="EP0010243A1_D0046.tif" /></chemistry><chemistry id="chem0047" num="0047"><img file="EP0010243A1_D0047.tif" /></chemistry></li><li>- Treatment with a wide variety of mono- or polynitriles, preferably hydroxymethyl nitrile, under the conditions of the Thorpe reaction catalyzed by hydroxyl groups.</li></ul>

The following may also be mentioned as aftertreatment reagents: sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium sulfide, rongalite, ammonium polysulfides, diethyl phosphite and dimethyl phosphite.

A wide variety of mixed polymerizations or polymerizations of vinyl monomers can also be carried out in these aftertreatment reactions, the biomass mixed condensates being encased or microencapsulated by the resulting polymers. Of course, the "envelope materials" can also be used in a large excess.

The process according to the invention is preferably carried out in an aqueous medium or in an aqueous-alcoholic medium. Additional inert organic solvents can also be used; the latter are used for azeotropic removal of the water after the reaction has ended. However, water without additional organic solvents is preferred as the reaction medium.

In the case of the process according to the invention, the reaction temperatures can be varied within a substantial range. In general, temperatures between 0 ° C and 200 ° C, preferably between 10 ° C and 150 ° C. However, it is also possible to complete the mixed condensation according to the invention in the course of the drying process, for example during spray drying, at temperatures up to 250 ° C. In many cases, the process according to the invention can also preferably be carried out at room temperature. Any remaining pathogenic germs can be killed by sterilization in the drying phase.

The reaction according to the process of the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure. For example, the process according to the invention can be carried out under elevated pressure, for example at temperatures between 120 ° C. and 160 ° C., and besides sterilization of the products, a targeted breakdown of proteins, ribonucleic acids, deoxyribonucleic acids, nucleoproteins and / or other cell contents can also take place. 3rd

When carrying out the process according to the invention, 1 kg of biomass with a solids content of 1 to 16 percent by weight, about 0.1 to 6 mol, preferably 0.2 to 5 mol, of carbonyl compounds, thiocarbonyl compounds and / or low-molecular weight, uncondensed N are used Alkylol compounds which are in dissociation equilibrium with carbonyl compounds, and 0.1 to 6 mol, preferably 0.2 to 5 mol, of aminoplast formers or Phenolic formers are used, furthermore chain terminators, optionally catalysts and, if necessary, an amount of additives such that their proportion in the end product is between 1 and 95 percent by weight, preferably between 5 and 90 percent by weight.

Catalysts are generally used in amounts of 0.05 to 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of all reaction components involved in the polycondensation. In some cases, however, significantly higher catalyst concentrations can also be used. For example, especially if the condensation is carried out with the use of azulmic acids, 0.4 to 0.6 mol of acidic catalyst, preferably phosphoric acid or nitric acid, can be used per 100 g of biomass and azulmic acids. This creates products in which the catalyst acids are fixed to basic groups of the mixed condensates.

Chain terminators can be used in amounts of 0.5 to 60% by weight, based on the total amount of the starting compounds capable of aminoplast formation. If N-methylollactams or N-methylolazalactams serve as chain terminators, their concentrations are generally between 0.5 and 20% by weight, preferably between 2 and 14% by weight, based on the total amount of aminoplast formers and carbonyl compounds or Thiocarbonyl compounds.

Phenoplast formers can be used in amounts of 0.5 to 100% by weight, based on the biomass.

The process according to the invention is generally carried out in practice by adding carbonyl compounds, thiocarbonyl compounds and / or carbonyl compounds, which are in a dissociation equilibrium with low molecular weight, uncondensed N-alkylol compounds, to an aqueous biomass dispersion, if appropriate in the presence of additives, optionally adding a catalyst and initiating the condensation, then added in the second reaction phase with an aqueous solution of aminoplast formers (also partially alkylated or partially methylolated products) or phenoxy formers or with an aqueous solution of still soluble aminoplast formers (e.g. polyalkylol or polymethylol compounds), optionally adding additives, catalysts and chain terminators and carries out the condensation and, if appropriate, subsequently carries out post-treatment reactions. However, it is also possible to provide aqueous dispersions or solutions of carbonyl compounds, thiocarbonyl compounds and / or carbazyl compounds which are in dissociation equilibrium with low molecular weight, uncondensed N-alkylol compounds, these then with the aqueous biomass dispersion and, if appropriate, with additives and / or or to add catalysts and to initiate the condensation and then to proceed in the second reaction phase, as previously described.

The reaction according to the invention is preferably carried out in such a way that an aqueous solution or dispersion of the aminoplast-forming or phenoplast-forming compounds is acidified - brought to pH values ​​between 1 and 4, for example - and this mixture is allowed to act on the biomass. The reactions are very quick. It can be based on an NH₂- or NH equivalent of all reactants 0.2 to 1,₄ Equivalents of carbonyl compounds come into play.

Also preferred is the procedure in which the aminoplast former and carbonyl compound are dissolved in water or lower alcohols and these reactive solutions, in which equilibria are established between the starting compounds and N-alkylolation products or N-methylolation products, at temperatures between 20 ° C. and 100⁰C drips into the aqueous biomass dispersions provided with vigorous stirring. One can also proceed in such a way that solutions of partially alkylated, in particular partially methylolated compounds or already partially precondensed, still soluble polyalkylol, in particular polymethylol compounds are added in one pour to the dispersed biomass and the condensation by heat, in the basic or acidic range, with removal of the water at normal pressure or under reduced pressure.

It is often also advantageous to add the compounds capable of aminoplast formation to an aqueous biomass dispersion in a first phase, to alkylate or methylolate the latter in the pH range between 7.5 and 10 by adding the corresponding carbonyl compounds, and to do so pre-formed N-alkylol compounds or Bring N-methylol compounds, possibly also their ether, to the biomass in the presence of insoluble aminoplast formers (additives).

In the process according to the invention, the reaction products are isolated by customary methods. In general, the procedure is such that, after the reaction has ended, the solid reaction product is filtered off, washed and dried.

It is often advantageous to treat the mixed condensates according to the invention with ammonia, primary or secondary amines or to fumigate them, or to wash them with aqueous ammonia-hydrazine solutions, hydrazine hydrate, methylhydrazine or aqueous cyanide solutions in order to trace traces of formaldehyde or remove other aldehydes or ketones quantitatively. When exposed to ammonia or Primary amines, for example, in the small amounts of formaldehyde still present in the products condensed with formaldehyde are converted into hexamethylenetetramine or hexahydrotriazines. It is often advisable to carry out a post-treatment with a 25% aqueous ammonia solution. - All of these cleaning operations can be carried out technically, for example by gassing in a fluidized bed or coupled with the spray drying of the products.

If catalyst residues are still present in the products according to the invention after their production, it is often advisable to wash them out or to deactivate them chemically by reaction with suitable reagents. If acids or bases were used as catalysts, it is advisable to neutralize them by adding bases or acids.

If organic products still contain soluble substances in the products according to the invention, they can be removed by washing the products with organic solvents, such as acetone.

If biomass is used in the process according to the invention, the chlorophyll. a and b, these chlorophyll types are used when carrying out the process, for example in the condensation to produce polymethylene ureas (at pH = 2 and temperatures between 60 and 70⁰C) mostly fixed in condensed form in the resulting powders. These chlorophyll types can be partially isolated by extraction with acetone.

The process according to the invention can also be carried out on an industrial scale in conventional kettles, screws and reaction vessels. For biomasses containing pathogenic pathogens, it is expedient to work in closed reactors in order to prevent the spread of bacteria through aerosol formation.

In the preparation of the products according to the invention, it is also possible to proceed in such a way that, after the mixed condensation on the process products according to the invention, in the form of their water-insoluble dispersions, virtually any amounts of polymethylene ureas, polyalkylidene ureas and poorly or insoluble compounds, ie highly crosslinked aminoplast condensates, are produced. which, due to their insolubility, do not covalently link to the biocompound due to the process products. Mixtures of this type in which the non-covalently bound portion of aminoplast condensates or Phenoplast condensates can be practically arbitrary, in particular for the case of loading with polymethylene thioureas, crosslinked polymethylene melamine powders, urea hydrazodicarbonamide formaldehyde condensates and dicyandiamide, oxamide condensates, are extremely interesting flame retardants for a wide variety of polyurethane foams, preferably for polyurethane foams.

Poorly or insoluble polymethylene or polyalkylidene ureas which can be precipitated on the products according to the invention are, for example, those which can be illustrated by the idealized constitutional formulas given below:<chemistry id="chem0048" num="0048"><img file="EP0010243A1_D0048.tif" /></chemistry><chemistry id="chem0049" num="0049"><img file="EP0010243A1_D0049.tif" /></chemistry><chemistry id="chem0050" num="0050"><img file="EP0010243A1_D0050.tif" /></chemistry><chemistry id="chem0051" num="0051"><img file="EP0010243A1_D0051.tif" /></chemistry><chemistry id="chem0052" num="0052"><img file="EP0010243A1_D0052.tif" /></chemistry>

In these formulas, X can represent numbers from O to 20.

Otherwise, other poorly or insoluble fillers, flame retardants, pigments, dyes, etc. can also be deposited on the products according to the invention. For example, metal salts present in excess or added later can be converted into poorly soluble metal hydroxides or metal oxides by adding bases. In addition, metal salts in the form of poorly soluble metal phosphates, metal sulfates, metal carbonates or metal silicates can be precipitated in many cases by adding appropriate acids. Salts of tungsten, vanadium and molybdenum can be precipitated in the form of heteropolyacids. Polysilicic acids can be produced on the products according to the invention by adding sodium or potassium water glass solutions and gassing with carbon dioxide. Sulfur can also be deposited on the insoluble mixed condensates by adding sodium or ammonium polysulfides and strongly acidifying them.

Also of interest is the subsequent loading of the mixed condensates according to the invention with the sparingly soluble melamine phosphate, the sparingly soluble urea oxalate, or urea nitrate, the sparingly soluble ammonium magnesium phosphate. Also the addition of alumina hydrates, aluminum oxides, titanium dioxide and calcium carbonate, quartz powder and the addition of linear or cross-linked polymethylene ureas, powdery melamine-formaldehyde condensates, urea hydrazodicarbonamide condensates and high-molecular polyammonium polyphosphates of the constitution<chemistry id="chem0053" num="0053"><img file="EP0010243A1_D0053.tif" /></chemistry>is important. The resulting products are ideal as flame retardants for plastics, especially for polyurethane plastics.

Furthermore, in the process according to the invention, especially when azulmic acids are also used, preferred additives are also sugars, such as cane sugar and other sugars which have no free aldehyde groups, or formose sugar mixtures prepared from formaldehyde. These various types of sugar can be fixed in the channels and pores of the rigid azulmic acid bodies they contain. In addition, the various sugars are also known to build up on the mixed condensates in the form of their mostly poorly soluble calcium complexes.

Furthermore, if the products according to the invention contain azulmic acids, it is always possible to gase the products with ammonia and carbon dioxide simultaneously after their production. Ammonia and carbon dioxide penetrate the contained azulmic acid framework as small molecules to a considerable extent. You get eg when gassing with ammonia and carbon dioxide in the fluidized bed, the unstable ammonium carbaminates, ammonium bicarbonates and, insofar as ammonia and carbon dioxide are introduced in the presence of water, ammonium carbamate of the formula<chemistry id="chem0054" num="0054"><img file="EP0010243A1_D0054.tif" /></chemistry>fixed in the channels of the azulmic acid mixed condensates. In this form, the carbamic acid ammonium exhibits reduced decomposability at room temperature.

Products of this type are suitable as fertilizers for the long-term supply of plants with nitrogen and, depending on the load, with other macro and / or micronutrients.

In the azulmic acids which can be used in the process according to the invention, the number of defects can be increased, if desired, before or during the reaction. Furthermore, the number of defects in the azulmic acids can also be increased in the products containing azulmic acid prepared by the process according to the invention after the mixed condensation has ended. For this purpose, all those methods are suitable which are already in connection with the description of the manufacture of the modified, that is to say containing errors _. Azulmic acids have been listed. If the fault location is to be carried out after the mixed condensation has been carried out, the reaction products are stirred in an aqueous medium, if appropriate at elevated temperatures, with the reagents used to generate the fault location. The products are isolated by filtration.

When carrying out the process according to the invention, especially when using highly reactive carbonyl compounds such as formaldehyde or crotonaldehyde, even those biomasses which tend to form resistant spores can be completely deactivated. If necessary, the known methods of pasteurization can be used in the case of particularly highly resistant spores, for example by completely deactivating traces of aldehyde contained in the process products by ammonia, then adding peptones and dextrins, and stimulating the spores again at 37 ° C. to revitalize and cell division and then, for example, with small amounts _Monomethylol urea and formaldehyde, the mixed condensation according to the invention is repeated, if appropriate, several times at 70-80 ° C.

Evidence that the biomass used can be rapidly and quantitatively sterilized in the method according to the invention can be provided in a known manner in petri dishes containing sterile agar and peptones, these primarily for sterilization in a conventional manner at 120 ° C. for about 40 minutes in a steam atmosphere get abandoned. Measurements on culture media sterilized in this way and inoculated with the process products show no nucleation under standardized test conditions in saturated sterile water atmosphere both after 24 hours and after 48 hours in the case of bacterial biomasses sterilized according to the invention, likewise not after 72 or more hours. The same applies to mushrooms and yeasts which are condensed and sterilized or pasteurized according to the invention. The germ test is negative in all cases. Corresponding tests on anaerobic or aerobic microorganism condensates under optimal cultivation and temperature conditions indicate the complete sterilization of the biomass when the method according to the invention is carried out.

In the process according to the invention, sterilization of the biomass used can also be achieved particularly advantageously by carrying out the condensation in the temperature range from 10 ° C. to 140 ° C. under greatly reduced pressure. As a result, sterilization, plasmolysis, cell wall blasting of microorganisms such as bacteria, algae, yeast, etc. can be accelerated extraordinarily.

In order to achieve maximum cell killing, enzyme deactivation and odor improvement in any biomass when carrying out the method according to the invention, but at the same time not hydrolytically splitting valuable cell contents into water-soluble products (= protein degradation, polysaccharide degradation), it has proven particularly advantageous to use the biomass primarily with a 1 to 2 molar excess of aldehydes, such as formaldehyde, isobutyraldehyde, crotonaldehyde or glyoxal, at temperatures between 20 ° C and 100 ° C, preferably between 40 ° C and 70 ° C, in the pH range between 6 and 7.5, alo practically neutral, to condense in 30 minutes up to 2 hours and then after adding a Aminoplast formers, such as urea, melamine or preferably urea-azulmic acid or melamine-azulmic acid, to complete the mixed condensation in the presence of phosphoric acid or sulfuric acid at pH values ​​between 1 and 4 and at temperatures between 20 ° C and 70 ° C within 1 to 4 hours. Completely tack-free, easily filterable, powdery mixed condensates with the highest storage stability are obtained with complete enzyme deactivation. Such mixed condensates are completely germ-free.

Moreover, with the method according to the invention, complete sterilization can also be achieved with the aid of earthy materials of normal bacterial content, algae and fungus content. For example, in the process according to the invention, young cell nutrient yeast suspensions containing about 2% by weight of solid are additionally used as an additive for 1 liter<ul id="ul0030" list-style="none"><li>a) 100 cm³ River water (= 1 cm contains 10,000 to a trillion bacteria)</li><li>b) 100 cm³ normal tap water (= 1 cm³ contains approx. 1000 bacterial germs)</li><li>c) 20 g of moist garden soil mixed with peat (= 1 g contains millions of microorganisms such as bacteria, small algae and fungi),</li></ul>Thus, after carrying out the condensation according to the invention and after determining the degree of sterility after mixed condensation with 60 g urea and 30 g formaldehyde, complete sterility is found in biological tests. Here, phosphoric acid or sulfuric acid is the preferred condensation catalyst, since the catalyst can be precipitated practically quantitatively by adding calcium oxide, calcium carbonate or lime milk or, if desired, phosphoric acid can also be precipitated as aluminum phosphate with freshly precipitated aluminum hydroxide, so that no filtrate-containing filtrate contaminates the wastewater.

If a particularly rapid enzyme deactivation is to be achieved in the process according to the invention, the procedure is expediently that in the first reaction phase 0.5-2% by weight of water-insoluble aldehydes, such as isobutyraldehyde and in particular crotonaldehyde, are added before the addition of urea and add formaldehyde.

When carrying out the process according to the invention, a wide variety of biomasses can, if desired, be pretreated with small amounts of oxidizing agents, such as nitric acid, chlorine solution, calcium hypochlorite, hydrogen peroxide, chromic acid or potassium permanganate, before the condensation. As a result, odor carriers are partially destroyed and the color of the filtrates is improved.

In addition, it is often advantageous to produce poorly soluble urea nitrate on the biomass and then to carry out the condensation according to the invention with formaldehyde and azulmic acids. Likewise, primarily poorly soluble ammonium magnesium phosphate can be generated on the biomass as a carrier and then the condensation according to the invention can be carried out.

Mixtures of several aminoplast formers, phenoplast formers and / or mixtures of several carbonyl compounds can of course also be used for the condensation in the process according to the invention. For example, such aldehyde mixtures can be used which may arise in situ from formaldehyde and numerous other aldehydes or ketones under the conditions of aldol condensation, formose synthesis or acyloin condensation (cf. Reaction equations on pages 26 and 27). Hydroxy aldehydes of this type react easily with addition to N-alkylolverbin to the extent of their formation, in particular in the weak to strongly alkaline range with aminoplast formers, such as, for example, urea_dwhich are then mixed cords.

In a special variant of the process according to the invention, the process is carried out by allowing special aldehydes, preferably formaldehyde, to act on other aldehydes in an alkaline medium, in the presence of the substances used for aminoplast formation. Although N-alkylol compounds or N-methylol compounds are formed, these are not the most thermostable derivatives and the more thermostable hydroxyaldehydes are formed. In the course of the reaction according to the invention, the latter lead to aminoplast condensates containing hydroxyl groups, which give the spray-dried products a desired crumbly structure. This variant of the method according to the invention can above all also influence the swelling work of the products according to the invention. In addition, this reaction can be used in the presence of calcium hydroxide or lead hydroxide deposited on azulmic acid to synthesize caramelized sugars (Butlerow-Löw formose reaction), which take part in the aminoplast condensations and ensure a crumb structure of the products according to the invention.

When carrying out the mixed condensation according to the invention, potassium ions and cyanide ions can exercise their known catalytic activity and _e.g.._B. Cause acyloin condensations (see reaction equation (e) on page 27). The resulting products can participate in the condensation in the course of the aminoplast condensations, in particular in the case of base-catalyzed reactions, and furthermore, when formaldehyde is offered, can be converted into methylolated ketones by aldol condensations, which are also condensation partners.

A further variant of the process according to the invention is that the aminoplast formers used are those azulmic acids which, prior to the actual reaction, have partially condensed with carbonyl compounds, such as formaldehyde, glyoxal or glyoxal sulfate, and have thus been stabilized against hydrocyanic acid elimination. The products according to the invention thus obtained are distinguished with a particularly high thermal resistance.

Furthermore, an advantageous variant of the process according to the invention is that urea, melamine or dicyandiamide are initially introduced in aqueous solution, then azulmic acid and biomass _n dispersed, then condensed with formaldehyde and produced by adding phosphoric acid or oxalic acid from unreacted melamine or urea poorly soluble melamine phosphate or urea oxalate. In this case, generation of defects in the azulmic acid and mixed condensation take place simultaneously. The resulting products are high-quality reactive fillers and flame retardants for plastics, especially polyurethane plastics.

The condensation of the biomasses according to the invention in the presence of azulmic acids can also be carried out under oxidative conditions with small amounts of oxidizing agents, such as hydrogen peroxide, chlorine solution, chlorine lime or potassium permanganate.

In a further variant, the process according to the invention can also be carried out in the form of a one-pot reaction. The procedure is to mix biomass with large amounts of aminoplate formers, such as urea, and optionally in the presence of other soluble aminoplast formers, and optionally in the presence of mono- and polyalcohols and small amounts of phenoplast formers, such as phenol or o-Krescl, for example Pretreated at 70 ° C., then adding aldehydes, such as crotonaldehyde, and then preferably condensed in the pH range 1 to 2.5 with formaldehyde.

Another variant of the process according to the invention is that 10 to 500 parts by weight of about 30% aqueous sodium or potassium silicate solutions are added in the mixed condensation to 100 parts by weight of biomass, it usually being expedient at about 40 ° C. to condense up to 100 ° C with carbonyl compound and aminoplast former, or to subsequently react the mixed condensates with the abovementioned amounts of alkali silicates.

After the reaction has ended, excess dissolved sodium or potassium silicate can be precipitated by simply gassing the respective dispersions with carbon dioxide, or can be precipitated in a particularly advantageous manner by adding phosphoric acid or calcium chloride mixed with potassium or sodium phosphates or calcium silicates. The resulting products are interesting combination fillers with reactive groups.

Another interesting variant of the process according to the invention consists in the use of such aminoplast formers, which are particularly good complexing agents for heavy metals. B. thiourea and N-methylol groups containing polymethylene thioureas of the constitution<chemistry id="chem0055" num="0055"><img file="EP0010243A1_D0055.tif" /></chemistry><ul id="ul0031" list-style="none"><li>n = Il, CH₂ OH</li><li>x = 0 to 14,</li></ul>

also ring-shaped ethylene thiourea condensates such as<chemistry id="chem0056" num="0056"><img file="EP0010243A1_D0056.tif" /></chemistry><ul id="ul0032" list-style="none"><li>R = H, GH₂OH</li><li>X = O to 14</li></ul>

Furthermore aminoplast formers with ionic groups, for example the connection of the constitution<chemistry id="chem0057" num="0057"><img file="EP0010243A1_D0057.tif" /></chemistry>and also phosphonic acids, for example that of the constitution<chemistry id="chem0058" num="0058"><img file="EP0010243A1_D0058.tif" /></chemistry>

When using such complexing agents, harmful heavy metal ions contained in biomass from sewage treatment plants for industrial and municipal wastewater can be bound so tightly that when using the biomass condensation products according to the invention as long-term fertilizers, no plant damage by heavy metals such as mercury, lead, chromium, cadmium and zinc , occur.

If you want to avoid protein hydrolysis of glycoproteids, nucleic acids and other cell contents as much as possible when carrying out the method according to the invention, it proves to be advantageous to first of all use the biomass in the strict neutral range at PH 7 with urea and formaldehyde or Condensate dimethylol urea or monomethylol urea in a dilution of about 60 g urea per liter of 8-10% solids aqueous biomass at 60-80 ° C in the presence of 80-100 g azulmic acids, then cool down to 35-20 ° C and then spontaneously Acids (pH = 1.5 - 2.5) carry out the further condensation of the methylolation products formed. As a result, the hydrolyzed and water-soluble content of cell contents can be reduced to a minimum, especially when a wide variety of azulmic acids are used. In individual cases it may be advantageous to use 2-10% by weight of melamine or dicyandiamide, based on the urea used.

Since N-alkylol compounds and in particular N-methylol compounds easily undergo etherification reactions in the acidic pH range, the process products according to the invention can be prepared by using z. B. 10 - 60 wt .-% of polyfunctional hydroxyl compounds, such as polyalcohols such as ethylene glycol, glycerin, formose-sugar mixtures, glucose, poly- and oligosaccharides,. Starch, etc., modify etherification reactions.

The products according to the invention cannot be clearly defined in terms of formula. However, they are precisely characterized by the starting components and the process for their production. - A common feature of the substances according to the invention is that they contain molecular segments "A" which are formed by the condensation of carbonyl compounds or thiocarbonyl compounds and aminoplast formers or phenoplast formers with reactive groups of the biomass.

The segment "A" can stand for the following residues:<ul id="ul0033" list-style="none"><li>- Aralkylidene - polythiourea residues, polyalkylidene-polythiourea residues and in particular polymethylene-polythiourea residues, which can be illustrated by the following idealized formula<chemistry id="chem0059" num="0059"><img file="EP0010243A1_D0059.tif" /></chemistry>in which<ul id="ul0034" list-style="none"><li>X stands for integers from 0 to 18 and</li><li>R preferably for hydrogen, methyl, ethyl, propyl, isopropyl and for residues of the formulas<chemistry id="chem0060" num="0060"><img file="EP0010243A1_D0060.tif" /></chemistry><chemistry id="chem0061" num="0061"><img file="EP0010243A1_D0061.tif" /></chemistry><chemistry id="chem0062" num="0062"><img file="EP0010243A1_D0062.tif" /></chemistry><chemistry id="chem0063" num="0063"><img file="EP0010243A1_D0063.tif" /></chemistry>stands for isomeric hydroxyaldehyde residues, as they are present in the formose sugar mixtures, also for oligosaccharides and also for the residues of the formulas<chemistry id="chem0064" num="0064"><img file="EP0010243A1_D0064.tif" /></chemistry>stands;</li></ul></li><li>- Biuretsulfones of the constitution<chemistry id="chem0065" num="0065"><img file="EP0010243A1_D0065.tif" /></chemistry> or.<chemistry id="chem0066" num="0066"><img file="EP0010243A1_D0066.tif" /></chemistry>wherein R has the meaning given in the formula (A-1),</li><li>Hydrouracil residues that arise from 1 mole of unsaturated carboxylic acid, eg crotonic acid, 1 mole of urea and formaldehyde, the rest of the constitution<chemistry id="chem0067" num="0067"><img file="EP0010243A1_D0067.tif" /></chemistry>be mentioned as an example;</li><li>Residues of reaction products of maleic acid with aldehydes, preferably formaldehyde, the rest of the constitution<chemistry id="chem0068" num="0068"><img file="EP0010243A1_D0068.tif" /></chemistry>be mentioned as an example;</li><li>. Lactam and azalactam residues containing methylene groups, for example residues of the constitution<chemistry id="chem0069" num="0069"><img file="EP0010243A1_D0069.tif" /></chemistry></li><li>- Residues of cyclic compounds of the constitution containing methylene groups<chemistry id="chem0070" num="0070"><img file="EP0010243A1_D0070.tif" /></chemistry>wherein<ul id="ul0035" list-style="none"><li>X represents oxygen or sulfur and</li><li>R¹, R² and R³ are identical or different and represent hydrogen, methyl, ethyl or methylene groups;</li></ul></li><li>- Residues of ethylene diurea containing methylene groups, such as the constitution<chemistry id="chem0071" num="0071"><img file="EP0010243A1_D0071.tif" /></chemistry></li><li>Residues of ethylene urea, vinylidene urea and dihydroxyethylene urea containing methylene groups, such as residues of the formulas<chemistry id="chem0072" num="0072"><img file="EP0010243A1_D0072.tif" /></chemistry><chemistry id="chem0073" num="0073"><img file="EP0010243A1_D0073.tif" /></chemistry></li><li>Residues of urea containing methylene groups, such as residues of the constitution<chemistry id="chem0074" num="0074"><img file="EP0010243A1_D0074.tif" /></chemistry></li><li>- Methylene or alkylidene residues of 2-oxo-4-methyl-6-ureido-hexahydropyrimidine of the constitution<chemistry id="chem0075" num="0075"><img file="EP0010243A1_D0075.tif" /></chemistry>where R has the meaning given above;</li><li>- Methylene or alkylidene residues with melamine structures such as<chemistry id="chem0076" num="0076"><img file="EP0010243A1_D0076.tif" /></chemistry> where R has the same meaning;</li><li>- Remains of the formula<chemistry id="chem0077" num="0077"><img file="EP0010243A1_D0077.tif" /></chemistry>wherein<ul id="ul0036" list-style="none"><li>R has the meaning given above;</li></ul></li><li>- Methylene or alkylidene residues with sulfonamide structures such as<chemistry id="chem0078" num="0078"><img file="EP0010243A1_D0078.tif" /></chemistry>or.<chemistry id="chem0079" num="0079"><img file="EP0010243A1_D0079.tif" /></chemistry><ul id="ul0037" list-style="none"><li>wherein R has the meaning given above;</li></ul></li><li>- Methylene or alkylidene residues with dicyandiamide, guanidine, formaldehyde or isobutyraldehyde structures;</li><li>- Aromatic and aliphatic amines, polyamines, hydrazines, hydrazides, hydrazodicarbonamides, dicarboxylic acid dihydrazides, ethyl hydrazinecarboxylates and phosphoramide residues substituted by methylene or alkylidene radicals.</li></ul>

The substances according to the invention are germ-free, stable in storage and in most cases odorless. They can be used for a variety of purposes.

Products according to the invention can thus be used as multicomponent fillers with reactive groups in all kinds of plastics.

In the production of optionally cellular plastics using mixed condensates according to the invention as fillers, other common fillers, flame retardants and additives of various types can of course also be used. Water-soluble or water-dispersible inorganic salts, double salts or complex compounds, for example ammonium sulfate, ammonium sulfate-containing end liquors from caprolactam production, calcium sulfate, (NH₄)₂SO₄.H₂O.Ca (H₂PO₄) 2, ammonium phosphate, CaNaPO₄.Ca₂SiO₄, 5 CaO.P₂O₅.SiO₂, Approx₄P₂O₉, (CaMg) O.Al₂O₃. 4 SiO₂, Al₂O₃.2 SiO₂. 2 H₂0, KCl.MgSO.3 H20, K₂S0₄.MgS0₄.6 H₂0, Si₂O₆AlK, sodium nitrate, ammonium nitrate, secondary sodium ammonium phosphate and similar substances.

Numerous substances according to the invention can be used as flame retardants or anti-aging agents to prevent oxidative degradation in a wide variety of vinyl polymers, polyamide plastics, rubbers and epoxy resins. Particularly suitable for this purpose are those substances according to the invention which are condensed azulmic acids and at the same time phosphoric acid, phosphorous acid, polymethylene ureas, polymethylene melamines, calcium phosphates, calcium carbonate, titanium dioxide, alumina hydrates, aluminum phosphates, aluminum silicates, aluminum oxide hydrate, water glass, melamine phosphate, barium phosphates, ammonium magnesium phosphates and / or Contain urea oxalate.

In addition, substances according to the invention can be used as support materials for numerous catalysts, resulting in mixed catalysts which can be used in a variety of ways.

In addition, substances according to the invention can be used as feed additives, as a nutrient medium for bacteria as soil improvers and as fertilizers. They are particularly suitable for long-term supply of plants with nitrogen and, depending on the components they contain, also for supplying plants with other macro and / or micronutrients. The most suitable fertilizers here are those products that consist of heavy metal-free biomass from the drug, luxury food and food industries. Also also those products that are made from biomass from biological or fully biological sewage treatment plants for industrial and municipal wastewater, provided that the wastewater in question before the biological or fully biological purification of a sulfide precipitation, for example by means of ammonium sulfide, sodium sulfide, hydrogen sulfide, etc., and the resulting biomass mixed condensates thus contain only tiny amounts of heavy metals.

The process according to the invention is particularly suitable for the problem-free processing of various types of biomass when using highly reactive carbonyl compounds, such as formaldehyde. The resulting products are germ-free, easy to filter, storable and mostly free from odors.

When carrying out the process according to the invention, all enzymes occurring in the biomass, such as oxidations, reductions, hydrolytic reactions, acylations and condensations, aminations, decarboxylations, introductions of hydroxyl groups into steroids, hydroxyl amounts and further oxidations, oxidative ring openings, dehydrogenation reactions, hydrogenation reactions become more olefinic Double bonds, hydrolysis of amide groups, of urea groups and hydantoin groups, hydrolytic elimination of substituents such as NH₂- Can be completely deactivated by OH groups, fermentative water additions to double bonds, hydrolytic ring opening reactions, phosphorylation reactions, regrouping and degradation reactions on nucleotides, acyloline condensations, deamination reactions, transamination reactions, amidation reactions or decarboxylation reactions with subsequent coupled ß-oxidation.

Furthermore, with the aid of the method according to the invention, those biomasses which occur in a large number of technical fermentation processes or in the fully biological purification of waste water and which are very difficult or impossible to filter can be readily converted into easily filterable products even at low temperatures transfer, which are completely tack-free powder after drying and do not form colloidal solutions.

The process according to the invention can also be used with particular advantage in order to completely deactivate biomass contaminated with pesticide residues, such as, for example, activated sludge from biological sewage treatment plants or biomass containing antibiotics, in the manufacture of penicillin and convert it into usable products. -The deactivation of pesticide residues still present in biomass from the biological purification of industrial and municipal wastewater is possible, for example, by condensing or hydrolyzing these active ingredients and often by way of functional groups that occur in condensation reactions with carbonyl compounds or N-methylol compounds. For example, carbamates condense on their NH groups, for example with formaldehyde and / or N-methylol compounds; likewise 3-amino-1,2,4-triazole on NH₂- and NH groups; Dithiocarbamates hydrolyze and are deactivated; A wide variety of phosphoric acid esters are generally hydrolyzed and deactivated, for example, by formaldehyde condensation in the phenol part. Active substances containing mercury and other metals are deactivated by using azulmic acids as aminoplast formers by channeling, active substances containing urea groups are, for example, condensed by their NH groups deactivated with formaldehyde or N-methylol compounds. Active ingredients of the thiophosphoric acid series are hydrolyzed, active ingredients containing phosphoric acid groups are hydrolyzed, active ingredients containing sulfamide groups are condensed hydrolyzing. Phenol and nitrophenol derivatives as active ingredients are condensed in the unsubstituted ortho and para positions, for example with formaldehyde or N-methylol compounds, as are benzothiazolylureas on their NH groups.

2,4-dichlorophenoxyacetic acid and similar active ingredients are fixed and deactivated in a salt-like manner when azulmic acids are also used. Active ingredients containing imidazolidine and uracil groups are condensed and deactivated on free NH groups. N-Trichloromethylthiophthalimid is condensed hydrolyzing. The active ingredient 4-amino-6-tert-butyl-31methylthio) -1,2,4-triazine-5 (4th_H ) -on is deactivated by condensation of the highly reactive NH2 group, for example with formaldehyde or N-methylol compounds. 3-Dimethyl-3- (2-benzothiazolyl) urea is deactivated by condensation on the reactive NH group, as are thiadiazole derivatives and benzimidazole derivatives containing NH groups.

The process according to the invention is particularly suitable when thiourea or other highly complexing compounds are used as aminoplast formers to bind heavy metal ions contained in the biomass, such as ions of lead, copper, mercury, cadmium or zinc, so firmly that When using such products as fertilizers, no plant damage occurs.

If the process according to the invention is carried out with the use of azulmic acids (crude azulminic acids, modified azulmic acids and / or stabilized azulmic acids), water-soluble cell constituents of the biomass such as polysaccharides, water-dispersible or soluble glycolipids, lipoproteids, degraded proteins, nucleic bases, degraded but not condensed acids can normally be very easily are completely adsorbed on azulmic acids, so that the wastewater is not contaminated with the nutrients valuable for humification and plant nutrition.

Furthermore, the method according to the invention can be special _` be used advantageously for processing such biomasses in which the formation of unpleasant odor carriers through decomposition reactions has already progressed and in which enzymes of microorganisms in particular contribute to the formation of the odor carriers.

Such biomasses can form on spoiled nutrients, also on castor oil residues, yeast masses, cottonseed meal, soybean meal, fish meal, animal meal, bone meal, algae meal, ricinus seed meal, starch meal, dextrins, peptones, lignin, moist cellulose powders, moist, homogenized gelatinous material, and moist, homogenized gelatinized gelatinous material, and homogenized gelatinous material , Peptone-agar combinations, Meat extract powder etc ... According to the invention, such mixtures of natural substances with biomass can be completely sterilized or pasteurized and their odorants largely eliminated by condensation reactions. The resulting products have an increased nitrogen content compared to the starting materials and can therefore be used particularly well as nitrogen fertilizers with long-term effects.

The method according to the invention is also particularly suitable for workup<ul id="ul0038" list-style="none"><li>- of biomass in the presence of larger proportions of extracellular colloids,</li><li>- also of biomasses in which cell death is already well advanced, ie biomasses which contain a large amount of cell contents outside the cell membranes in aqueous solution,</li><li>- also of biomasses of cellular and extracellular blood components,</li><li>- as well as slimy, completely unfilterable biomass.</li></ul>

These biomasses, difficult to filter suspended solids, digested and bio-sludges of the most varied _Art and biomasses with high proportions of Escherichia coli precipitated as powder under sterilizing conditions.

With the aid of the method according to the invention, extremely large quantities of bacterial cells can also be killed and their most important cell contents condensed. Bacteria with 1_/u Size with the densest ball packing in a cube of 1 cm³ approx. ₁₀¹² Bacteria and per liter 10¹⁵ Contain bacteria. When using 10 liters of an aqueous, approximately 10% biomass (= dry weight approx. 1 kg.) It is therefore possible, for example, with 6-10 moles of urea and 6-10 moles of formaldehyde 1₀¹⁵ Bacteria and her _Eto kill the enzyme spectrum. By destroying the bacterial cell walls and by hydrolysis of the poly-ß-hydroxybutyric acid contained, the smell of ß-hydroxybutyric acid occurs. By briefly washing with a 2% ammonia solution and by neutralizing with calcium salts, their smell can be largely eliminated.

Furthermore, the method according to the invention can be used with particular advantage for working up industrially used microorganisms. Such biomasses, such as those obtained in large quantities during penicillin production, cannot be effectively dewatered mechanically because of their high cell-bound water content. Even when laboriously drying to crumbly filter cakes, it is difficult to accommodate these biomasses in landfills, since they liquefy again through so-called autolysis - and also easily decompose with the development of odors. Using the method according to the invention, however, such biomasses can be denatured in a simple manner. In addition, the resulting products, which are free of heavy metals and have a high nitrogen content, can not only be disposed of in an environmentally friendly manner, but can even be used in a variety of ways.

Wherever there is primarily no continuity in the analytical composition of biomass from industrial and municipal wastewater treatment plants, the method according to the invention can be used particularly advantageously because the lack of uniformity in the composition is compensated for by the fact that, for example, pollutants such as heavy metals or Plant protection products, especially when using azulmic acids as additional aminoplast components, are so firmly bound that there are no longer any harmful effects. Incidentally, non-condensed or non-deactivated organic substances such as chlorinated hydrocarbons or nitrobenzene, which are difficult to degrade and possibly adhere to the activated sludge, can easily be extracted from the products according to the invention by organic solvents.

With the aid of the method according to the invention, products of the potato starch industry containing biomass, for example soluble protein portions in mother liquors of the starch preparation infested with various bacterial and yeast-like microorganisms, can preferably be worked up without costly evaporation of the mother liquors. The same applies to corresponding products of the cellulose industry, such as for neutralized sulfite waste liquors from the pulp industry, infested with bacteria, fungi, algae or yeast.

The inventive method enables the o^r- ganic portion of growing cells, which often consists of 40 to 60% protein and of the order of about 20% cell wall polymers (carbohydrate fractions), nucleic acids and and lipids, largely to convert into powdery, nitrogen-rich substances. Cells that are at rest, in which the protein contents are lower (= often 30% protein components and nucleic acid components of 5 to 8%), behave identically when used and used for the mixed condensation according to the invention. Variations in the lipoid content, ie in neutral fat, in the waxes, phospholipids, steroids and in the individual building blocks of the cell wall polymers in resting and unilaterally nourished cells do not have a disruptive effect on the process according to the invention. Reserve bodies, such as ß-hydroxybutyric acid and neutral fats, which occur more strongly in cells fed on one side, yeasts and fungi are easily fixed on the mixed condensates by adsorption, as are starch-like products, such as algae, which can be formed to a greater extent. Also extracellular mucilages such as dextrans to coal h fed in fermentations^ythirds can be adsorbed in powder form on the process products.

All of the microorganisms in the biological sludge from sewage treatment plants that are in the state of post-fermentation are condensed into completely odorless process products.

The process according to the invention also offers the interesting possibility of obtaining hydrolysates of cell sludges and biomasses, for example when carrying out the condensation according to the invention under hydrolyzing conditions, with simultaneous removal of heavy metals via commercially available ion exchangers, practically colorless hydrolysates, enriching them in water and concentrating them in isolate colorless form. Such hydrolyzates can, for example can be used as a breeding ground for a large number of microorganisms in technical fermentation processes. The resulting hydrolysates contain sugar-like components, ammonium salts of phosphoric acid and condensed, water-soluble amino acids.

The method according to the invention also converts biomasses from the brewery yeast group, which are in enzymatic decomposition, into storage-stable, odorless products and thus standardizes decomposition biosystems, furthermore those infested with microorganisms _Tresidues of boar, excess sludge from the rendering of animal carcasses, microbially infected animal meal and supplementary products from waste from factory farms. This shows a way to solve previously difficult or impossible to solve removal problems in a simple manner. The same advantages are offered in the case of activated sludge which is rotting, with bacteria and fungi etc. infested soy proteins, for wet and digested sludge to achieve hygienic safety and to remove odorants.

In addition, the method according to the invention enables problem-free processing of biomasses of anaerobic digestion (= intensive digestion), of biomasses from aerobic stabilization processes, waste sewage sludge - composting products, for example from methods of thermophilic digestion (= aerobic-thermophilic methods), in which the released heat of reaction of the microbial metabolism is used to heat the sludge (= process temperatures approx. 70 ° C), also of products of aerobic sewage sludge composting according to the system of rapid rotting (= process duration 10 - 15 days), whereby post-rotting of about 6 weeks is avoided. Also microbial infested fiber sludges from the pulp and paper industry, sludges from the food and beverage industry, for example Sludges from dairies, slaughterhouses, decomposition residues from fermentation processes, odorless yeasts that have already been dried and biosludges that have already been dried and are in landfills, for example biosystems dried according to the Porteous process, can be stabilized in accordance with the invention with an odor.

According to the process according to the invention, the condensation reactions described can substantially improve dewatering processes under process conditions which are easy to implement on an industrial scale or, for example, are already practiced in sewage treatment plants; ie sewage sludge or other biomass with a significantly increased solids content is obtained.

The process according to the invention is illustrated in detail by the following examples.

Comparative examples

example 1

Condensation of bacterial biomass with certain aldehydes or ketones using conventional methods

In the reactions described below under (a) to (d), a black-brown bacterial activated sludge from a fully biological plant for wastewater treatment of industrial and municipal wastewater is condensed with formaldehyde. The biomass used consists of Pseudomonas species, flagellates, algae and other microorganisms as well as extracellular components. The biomass used contains approx. 85 g of dry weight, protein content in the dry matter about 42% by weight.<ul id="ul0039" list-style="none"><li>a) 1000 g of the above-mentioned bacterial biomass are reacted with 100 g of a 30% strength aqueous formaldehyde solution (1 mol) in the course of 6 hours in the presence of 0.5 g of potassium carbonate as a methylolation catalyst at 60 ° C. under condensing conditions.</li><li>b) 1000 g of the above-mentioned bacterial biomass are condensed at pH = 7.5 with 100 g of a 30% strength aqueous formaldehyde solution (1 mol) over a period of 6 hours at 100 ° C. There are conditions under which N-methylolation products of proteins or N-methylolation products of nucleic acids and deoxyribonucleic acids form in their adenine, guanine, thymine, cytosine content and, in addition to N-methylolation products, the formation of -N-CH , -N-and<chemistry id="chem0080" num="0080"><img file="EP0010243A1_D0080.tif" /></chemistry>^- Segments cannot be excluded.</li><li>c) 1000 g of the above-mentioned bacterial biomass are condensed with 100 g of a 30% strength aqueous formaldehyde solution (1 mol) in the presence of 25 g of 85% strength phosphoric acid at 80 ° C. in the course of 8 hours. Here, conditions exist under which proteins such as DNA, RNA and bacterial cell walls, with simultaneous hydrolytic degradation reactions, preferentially form branched and crosslinked ones<chemistry id="chem0081" num="0081"><img file="EP0010243A1_D0081.tif" /></chemistry>Segments and<chemistry id="chem0082" num="0082"><img file="EP0010243A1_D0082.tif" /></chemistry>Segments.</li><li>d) 1000 g of the above-mentioned bacterial biomass are condensed with 25 g of a 30% aqueous formaldehyde solution (0.25 mol) in the presence of 18.4 g of concentrated sulfuric acid at 100 ° C. in the course of 6 hours. Conditions exist under which, due to the relatively low formaldehyde concentration, predominantly crosslinking reactions between proteins and oligopeptides and similar substances with the formation of N, N-methylene bonds between types of peptides<chemistry id="chem0083" num="0083"><img file="EP0010243A1_D0083.tif" /></chemistry>Amide groups, NH₂- Use groups of the purine bases or nucleotides and nucleosides.</li></ul>

The biomass condensates, which are produced according to the methods described in (a) to (d), prove to be unfilterable. The biomass condensates can be isolated by centrifugation, but glue-like, very sticky condensates are obtained which are sticky even after gentle drying at 80 ° C and cannot be converted into powdery form.

If formaldehyde is used in accordance with the methods described under (a) to (d)<ul id="ul0040" list-style="none"><li>- biomass from the series of vinegar bacteria (Acetobacter),</li><li>Biomass from the series of the bacteria of the order of the Eubacteriales (Escherichia coli),</li><li>- biomass with protein-decomposing hay bacilli (bacterium subtilis),</li><li>- biomass with bacteria from the series of Chlamydobacteriales (thread bacteria),</li><li>- Biomasses with microorganisms from the Actinomycetales range</li></ul>um, so also mucilaginous condensation products arise, which are not filterable.

One does not use formaldehyde in the reactions described above, but instead<ul id="ul0041" list-style="none"><li>- acetaldehyde,</li><li>- glyoxal,</li><li>- glutardialdehyde,</li><li>- isobutyraldehyde,</li><li>- chloral hydrate,</li><li>- crotonaldehyde,</li><li>- acrolein,</li><li>- furfural,</li><li>- salicylaldehyde,</li><li>- methyl ethyl ketone,</li><li>- cyclohexanone,</li></ul>

in turn, only unfilterable biomass condensates are obtained.

Example 2

Condensation of fungal biomass with certain aldehydes or ketones using conventional methods

1000 g each<ul id="ul0042" list-style="none"><li>a) aqueous white-yellowish, decomposed bakery yeast culture containing about 70 parts by weight of dry matter,</li><li>b) white-yellowish biomass dispersion of a colloidal commercial young cell nutrient yeast culture with 20 parts by weight of dry substance on yeast cells,</li><li>c) a brownish, top-fermented brewer's yeast dispersion with a dry weight of 50 parts by weight</li></ul>

are reacted with aqueous formaldehyde solution in the proportions given in Example 1 under (a) to (d).

In the same way, the above-mentioned fungal biomasses are mixed in according to the methods given in example 1 under (a) to (d) in the quantitative ratio specified there<ul id="ul0043" list-style="none"><li>- glyoxal,</li><li>- isobutyraldehyde,</li><li>- crotonaldehyde,</li><li>- acrolein,</li><li>- cyclohexanone</li></ul>implemented.

In all cases, unfilterable biomass condensates are obtained.

Example 3

Condensation of plant and microbial biomass with formaldehyde using conventional methods

<ul id="ul0044" list-style="none"><li>a) 1000 g each of an aqueous grass homogenate which is in microbiological decomposition, - (dry substance of the plant cells approx. 14% by weight, protein content of the homogenate approx. 12th % By weight, based on dry matter) -, the microbiological decomposition of which was initiated aerobically by fermentation with the addition of 1 g of garden soil by heating to 35 ° C. for 48 hours are given according to those in Example 1 under (a) to (d) Methods implemented in the quantitative ratio specified there with aqueous formaldehyde solution. An extremely difficult to filter condensate dispersion is obtained.</li><li>b If the condensation described in this example under (a) is carried out on the same plant cell homogenate but after fermentation with microbially active garden soil under anaerobic conditions (fermentation duration as stated under (a)), one reaction to formaldehyde becomes extremely difficult after each reaction filtering, sticky drying condensate dispersion obtained.</li></ul>

Example 4

Condensation of biomasses from the group of cyanophyceae, blue-green algae, green algae, flagellates, brown algae, dinatoms, mycomycetes and amoebas with formaldehyde by conventional methods

10,000 g of an activated sludge with a solids content of 2 to 3 percent by weight of a mixture of biomasses from the series of blue-green algae, green algae, which additionally contain lunch flagellates, the most diverse types of algae and slimy extracellular constituents, are at pH = 7.5 with 100 g of a 30% aqueous formaldehyde solution (1 mol) condensed at 100 ° C over 6 hours. A biomass condensate is obtained which is even more difficult to filter than the underlying untreated biomass.

Example 5

Condensation of cellular blood components with formaldehyde

<ul id="ul0045" list-style="none"><li>a) 500 g fresh bovine blood, the biomass part of which mainly consists of erythrocytes (approx. 44% of the cell volume) and granulocytes, lymphocytes, thrombocytes (= approx. 1% of the total cell volume) and whose extracellular components consist of blood plasma (6 - 8% proteins ) and blood serum are diluted with 500 g of distilled water and then with 100 g of a 30% aqueous solution of formaldehyde (1 mol) in the presence of 25 g of 85% phosphoric acid in the course of 4 hours at 40⁰C condenses.</li><li>b) In an analogous manner, 500 g of fresh bovine blood of the above composition after the _Vdilute with 500 g of distilled water with 25 g of a 30% aqueous formaldehyde solution (0.25 mol) condensed in the presence of 18.4 g of concentrated sulfuric acid at 40 ° C. in the course of 4 hours.</li></ul>

In both cases, simultaneous formation of mucilaginous oligopeptides and degraded blood components gives sticky condensates that are difficult to filter.

Example 6

1000 g of a bacterial activated sludge (biomass mycelium) that cannot be filtered at normal pressure from a fully biological plant for the purification of industrial and municipal wastewater (composition of the biomass as stated in example 1; dry weight of the biomass about 85 g) are pressed onto a pressure filter at 5 atm for 10 hours. This gives a biomass with a dry weight of about 11.6 percent by weight. The filters used clog after a short time.<ul id="ul0046" list-style="none"><li>a) 1000 g of the above-mentioned unfilterable aqueous biomass mycelium are in accordance with the procedure described in DT-OS 25 23 483 with 1 mol of an alkaline methylol urea solution, previously in an alkaline medium in 20 minutes at a temperature of 30 ° C. was converted into a higher molecular weight oligocondensate, condensed in 200 g of water for half an hour at a pH of 3, the pH being adjusted by adding hydrochloric acid. A slime-like, practically non-filterable reaction mixture is obtained.</li><li>b) 1000 g of the above-mentioned unfilterable aqueous biomass mycelium are, according to the procedure described in DT-OS 25 23 483, with 1 mol of an alkaline methylol urea solution, previously in an alkaline medium in 20 minutes at a temperature of 80 ° C. was converted into a higher molecular weight oligocondensate, condensed in 200 g of water for half an hour at a pH of 5, the pH being adjusted by adding sulfuric acid. A slime-like, practically non-filterable reaction mixture is obtained.</li></ul>

Extending the reaction time to 4 hours in the condensations given under (a) and (b) also gives non-filterable biomass dispersions with a slimy character. Extremely unpleasant odors are also not bound.

Examples according to the invention

Example 7

a) 1000 g of an unfilterable or unfilterable under normal pressure Bacterial activated sludge with a solids content of about 8.5% by weight, which is extremely difficult to filter, from a fully biological sewage treatment plant for municipal and industrial wastewater, is first mixed with reflux condenser, thermometer and stirrer with 0.2 mol of formaldehyde for 20 minutes condensed at 60 ° C and then with 90 g (1 mol) on a freshly prepared monomethylol urea solution (prepared by dissolving ₉₀ g of monomethylol urea in 200 g of water) and heated to 80 ° C. for 20 minutes. The mixture is then allowed to cool to 50 ° C. and the biomass mixed condensation is catalyzed by adding 18.4 g of concentrated sulfuric acid at a pH of approximately 1.9. After 1 to 2 hours, the mixed condensation and polymethylene urea formation have ended. Filtration samples show that excellent filterable, non-sticky biomass mixed condensate powder forms after only 10 minutes of condensation. For working up, the batch is neutralized with 14 g calcium hydroxide, with poorly soluble calcium sulfate being deposited on the biomass mixed condensate. An excellently filterable biomass mixed condensate is obtained which, after drying at 80 ° C. under reduced pressure, is obtained in the form of a gray powder. The yield is 160 g of biomass mixed condensate. It contains 14.2% by weight of nitrogen and, due to the condensed or crosslinked nucleic acids and phosphorus-containing cell contents, about 1.5% by weight of phosphorus. This conversion thus increases the nitrogen content of the biomass used by about 8% by weight. By treating the moist or dried, powdery biomass mixed condensate with a 2% aqueous ammonia solution, traces of formaldehyde in_'Hexamethylenetetramine converted and traces of hydroxybutyric acids removed. A practically odorless powder is obtained.

Biological tests for sterility of the powders obtained in this way, as well as of the filtrates, show that the process products and the mother liquors are completely free from bacteria, spore-forming microorganisms and pathogenic pathogens.

By concentrating the mother liquors under reduced pressure, approximately 18 g of water-soluble cell constituents, which consist of polysaccharides, urea-formaldehyde condensates and soluble cell reserve substances, are isolated in a form which is highly lightened compared to the starting color of the biomass. In the embodiment of this example, about 93% by weight of urea and 93% by weight of formaldehyde, based on the urea used, react to form powdery biomass mixed condensates.

Parallel experiments and analytical investigations on biomass mixed condensates, which are obtained according to the procedure described in this example, show due to the phosphoric acid content of the procedure^pProducts that 132 g of the powdery biomass-polymethylene urea mixed condensate contain about 27.6 g of condensed ribonucleic acids, deoxyribonucleic acids and phosphorus-containing cell contents (= approx. 21% by weight).

b) The procedure is as described under (a), but instead of _Monomethylol urea now 1 mole monomethylol thiourea.

A gray, powdery, easily filterable biomass mixed condensate is obtained in a yield of 145 g.<ul id="ul0047" list-style="none"><li>N content: 12.8%</li><li>S content: 17.2%</li></ul>

Example 8

The procedure is as described in Example 7, variant (a), the same type and amount of biomass are used and the biomass is first precondensed with 100 g of a 30% strength aqueous formaldehyde solution (1 mol) in the presence of 100 g of 85% by weight phosphoric acid under hydrolyzing conditions in a period of 4 hours at 100 ° C. Then after cooling to 80^0C add a solution of 60 g urea (1 mole) and 20 g aqueous formaldehyde solution. The condensing grafting of polymethylene ureas to biomass starts immediately with slight heating. After a 1-hour condensation period, a powdery biomass mixed condensate which can be easily isolated by filtration is obtained. The condensate is freed from unbound phosphoric acid by repeated stirring with 2% aqueous ammonia solution and at 80⁰C dried in vacuo. Yield: 136 g of N content = 18.5. The process product consists of approximately 52% by weight of condensed and sterilized biomass, approximately 2.9% by weight of phosphorus and approximately 45% by weight of urea-formaldehyde condensates (polymethylene polyureas). In a particularly advantageous variant of this process, the washing out of the phosphoric acid still contained in the biomass is spared by converting the free phosphoric acid into poorly soluble calcium phosphate or aluminum phosphate by adding calcium hydroxide or freshly prepared aluminum hydroxide after the condensation has been carried out. By using excessive amounts of calcium hydroxide, water-soluble oligosaccharides are precipitated as poorly soluble calcium oxide-oligosaccharide complexes.

Example 9

The procedure is exactly as described in Example 7, variant (a), but the condensation is carried out at a pressure of 18 Torr at a temperature between 55 and 6₀^O_C. through, distilling off small amounts of water. This procedure destroys and attacks bacterial cell walls and cytoplastic material much faster than with the previously described method. After a reaction time of 45 minutes, the biomass-polymethylene urea mixed condensate is isolated in powder form by simple filtration.

Example 10

The procedure is exactly as described in Example 7, variant (a), but instead of 1 mol of monomethylol urea, a mixture of 0.7 mol of momomethylol urea and 0.3 mol of monomethylol thiourea is now used. - After working up, 144 g of a polymethylene urea-polymethylene thiourea-biomass mixed condensate are obtained, which can be filtered very well.

This mixed condensate binds harmful heavy metal ions such as those of mercury and lead, and metal ions, eg ions of cadmium, nickel, chromium and zinc, very firmly and can therefore be used as an ion exchanger and as a heavy metal ion scavenger for waste water containing mercury and lead . For example, in a wastewater that has a mercury content of 50 ppm and a lead content of 2100 ppm, after treatment with the above-mentioned mixed condensate, the concentration of mercury is only 0.5 ppm and that of lead is only 0.8 ppm.

Example 11

The procedure is exactly as described in Example 7, variant (a), but the same type and amount of biomass from a fully biological sewage treatment plant are used and only the aqueous monomethylolurea solution is replaced by:<ul id="ul0048" list-style="none"><li>a) 1 mol of dimethylol urea, dissolved in 4₀₀ g water,</li><li>b) 1 mole of dimethylolthiourea, dissolved in ₄₀₀ g water,</li><li>c) 1 mole of trimethylolmelamine, dissolved in 4₀₀ g hot water,</li><li>d) 1 mol of hexamethylolmelamine, dissolved in 6₀₀ g boiling hot water,</li><li>e) 1 mol of a methylolated dicyandiamide from 1 mol of dicyandiamide and 2 mol of formaldehyde,</li><li>f) 1 mol of monomethyloloxamide in 200 g of water,</li><li>g) 1 mol of monomethylol ethylene urea of ​​the constitution<chemistry id="chem0084" num="0084"><img file="EP0010243A1_D0084.tif" /></chemistry></li><li>h) 1 mole of monomethylorethylene thiourea of ​​the constitution<chemistry id="chem0085" num="0085"><img file="EP0010243A1_D0085.tif" /></chemistry></li><li>i) 1 mole of tetramethylolacetylene diurea of ​​the constitution<chemistry id="chem0086" num="0086"><img file="EP0010243A1_D0086.tif" /></chemistry></li><li>j) 0.5 mol<chemistry id="chem0087" num="0087"><img file="EP0010243A1_D0087.tif" /></chemistry>and 0.5 mole of urea.</li></ul>

In the case of the reactions (a) to (j), a biomass mixed condensate is obtained in which about 82 88% by weight of 85 g of biomass used (solid fraction) by mixed condensation with the aminoplast formers mentioned and by self-condensation of the aminoplast formers mentioned filterable, powdery condensates result. The remaining 18-12% by weight of the biomass used (solids content) can be isolated as water-soluble cell constituents by evaporating the mother liquors. Due to the neutralization of the sulfuric acid with calcium hydroxide, all process products contain about 22-27 g of calcium sulfate. The yields of mixed biomass condensates for reactions (a) to (j) are:<tables id="tabl0001" num="0001"><img file="EP0010243A1_D0088.tif" /></tables>

The condensate mixtures which are obtained in reactions (a) to (j) are gray, storage-stable powders in which all enzymes in the biomass are completely deactivated by condensation. No annoying odors can be observed even after storage periods of any length.

When the above itic condensations are carried out, the reactions (a) to (j) can be carried out in each case _Acidification also replace the sulfuric acid used with 25 g of 85% aqueous phosphoric acid. After neutralization of the batches with calcium oxide or calcium hydroxide, a precipitation of poorly soluble calcium phosphate in an amount of 22 to 28 g is uniformly distributed over the biomass mixed condensates.

Example 12

The procedure is exactly as described in Example 7, variant (a), but only in each case 100 g of the biomass described therein, 1.9 g of sulfuric acid and one of the following mixtures capable of aminoplast formation are used:<ul id="ul0049" list-style="none"><li>a) 0.01 mol of a hexamethylene diurea of ​​the constitution methylolated with 4 mol of formaldehyde<chemistry id="chem0088" num="0088"><img file="EP0010243A1_D0089.tif" /></chemistry>and 0.09 mole of monomethylol urea.</li><li>b) 0.1 mole of the methylolated diurethane of the constitution<chemistry id="chem0089" num="0089"><img file="EP0010243A1_D0090.tif" /></chemistry>and 0.01 mole of monomethylol urea.</li><li>d) 0.01 mol of tetramethylolhydrazodicarbonamide of the constitution<chemistry id="chem0090" num="0090"><img file="EP0010243A1_D0091.tif" /></chemistry>and 0.09 mole of dimethylol urea</li><li>d) 0.01 mol of an adipic acid diamide permethyloliorten with 4 mol of formaldehyde and 0.09 mol of monomethylolurea.</li><li>e) 0.01 mol of a sulfonic acid diamide of the constitution permethylolated with 4 mol of formaldehyde<chemistry id="chem0091" num="0091"><img file="EP0010243A1_D0092.tif" /></chemistry>and 0.09 mole of monomethylol hara.</li><li>f) 0.01 mol of a phosphoric acid triamide of the constitution methylolated with 4 mol of formaldehyde<chemistry id="chem0092" num="0092"><img file="EP0010243A1_D0093.tif" /></chemistry>and 0.09 mole of monomethylol urea.</li><li>g) 0.01 mol of calcium cyanamide, 0.03 mol of formaldehyde and 0.09 mol of monomethylol urea.</li><li>h) 0.01 mol of a permethylolated, higher molecular weight, urethane group-containing d, ω-diurea and 0.09 mol of monomethylol urea in 100 g of water. - The required α, ω-diurea is prepared by reacting 1 mole of an α, ω-dihydroxypolyethylene oxide with an average molecular weight of 1500 with 2 moles of hexamethylene diisocyanate, then reacting the NCO prepolymer with excess., Aqueous ammonia and methylolation with 4 moles of formaldehyde Use of 0.5 g of potassium carbonate as a methylolation catalyst.</li><li>i) 0.025 mol of trimethylol melamine and 0.05 mol of monomethylol urea.</li></ul>

_Min the case of reactions (a) to (i), easily filterable biomass mixed condensates with the aminoplast formers mentioned. The products are gray, almost odorless powders.

The yields of mixed biomass condensates for reactions (a) to (i) are:<tables id="tabl0002" num="0002"><img file="EP0010243A1_D0094.tif" /></tables>

Example 13

The inventive implementation of the biomass described in Example 7 can be achieved in a simplified manner by carrying out the formation of the monomethylolurea in the biomass in situ from 1 mol of urea and 1 mol of formaldehyde (30% strength formalin solution)<ul id="ul0050" list-style="none"><li>a) by basic catalysis of the methylolation with 0.3 g of potassium carbonate,</li><li>b) by basic catalysis of the methylolation with 0.4 g of calcium hydroxide,</li><li>c) by basic catalysis of the methylolation with 0.5 g of triethylene amine,</li><li>d) by thermal condensation without additional catalyst.</li></ul>

The reactions (a) to (d) are carried out exactly according to the method described in Example 7, variant (a), but all the reaction components are mixed without prior N-methylolation of the _Aminoplast former. The temperature control and acid-catalyzed condensation then take place exactly as disclosed in Example 7, variant (a).

The yields of biomass mixed condensate in reactions (a) to (d) are:<tables id="tabl0003" num="0003"><img file="EP0010243A1_D0095.tif" /></tables>

Example 14

The procedure is exactly as described in Example 7, variant (a), using a bacterial activated sludge from fully biological wastewater treatment - that is to say with a biomass which contains different, type-like microbial compositions - but the condensation is carried out at only 35 ° C. and precedes to carry out the mixed condensation in each case 100 g of one of the following pigment-like, sparingly soluble, powdery carriers:<ul id="ul0051" list-style="none"><li>a) 100 g of a polymethylene urea and 400 g of water,</li><li>b) 100 g of an ethylidene polyurea and 400 g of water,</li><li>c) 100 g of a polyisobutylidene polybarea and 400 g of water,</li><li>d) 100 g of a sparingly soluble condensate composed of 2 moles of urea and 1 mole of crotonaldehyde and 400 g of water,</li><li>e) 20 g of quartz sand and 80 g of a polymethylene polyurea and 400 g of water,</li><li>f) 20 g of alumina hydrate (= aluminum hydrate) 80 g of an isobutylidene polyurea and 400 g of water,</li><li>g) 30 g of calcium phosphate and 70 g of a polyisobutylidene polyurea and 400 g of water,</li><li>h) 30 g of aluminum silicate and 70 g of a polyisobutylidene urea and 400 g of water.</li></ul>

The acidic condensation is carried out exactly as in Example 7 using sulfuric acid as a catalyst at room temperature.

In the case of the reactions (a) to (h), excellently filterable biemass mixing condensates are obtained, which are intimately mixed with the added glass fibers.

The yields for reactions (a) to (h) are:<tables id="tabl0004" num="0004"><img file="EP0010243A1_D0096.tif" /></tables>

Example 15

In terms of quantity, the procedure is exactly as described in Example 7, variant (a), but the condensation is carried out at room temperature over a period of 8 hours. The biomass mixed condensate isolated by filtration is then dried at 110 ° C. This results in complete sterilization of the process product. There is only a very small amount of cell contents in the mother liquor.

A biomass mixed condensate is obtained in a yield of 175 g; Nitrogen content: 18.4

Example 16

The procedure is exactly as described in Example 7, variant (a), but the mixed condensation is carried out at 75 ° C. After condensation and neutralization of the reaction mixture with ammonia and cooling to 35 ° C., 2 g of dextrin powder and 3 g of a meat extract nutrient solution are added. The mixture is then stirred at 35 ° C. for 48 hours in order to stimulate spore-forming microorganisms for nucleation and cell division. The mixture is then heated to 80 ° C. for 2 hours with the addition of 20 g of a 30% strength formalin solution. - After filtration and drying, 165 g of mixed condensate with a nitrogen content of 18.5% are obtained.

The coupled pasteurization and sterilization by the reagents used leads to a completely germ-free mixed condensate.

Example 17

a) 1000 g of a bacterial activated sludge which comes from a fully biological sewage treatment plant for industrial and municipal waste water and contains about 8.5% solids, which consists of a wide variety of microorganisms and contains traces of plant protection agents (herbicides)<ul id="ul0052" list-style="none"><li>N-methyl-isopropyl-carbamate (0.5 g)</li><li>4-amino-6-tert-butyl-3-methylthio-4,5-dihydro-1,2,4-triazin-5-one (0.5 g),</li><li>N- (3-benzothiazolyl) -N, N'-dimethylurea (0.5 g)</li><li>is contaminated, are first heated to 80 ° C. in a cut glass beaker while stirring vigorously with 100 g of a 30% formalin solution (1 mol) and 25 g 85% phosphoric acid. Bacterial cell walls are blown up and the pesticides contained by the reaction of their NH₂- or NH functions with formaldehyde with N-methylolation<chemistry id="chem0093" num="0093"><img file="EP0010243A1_D0097.tif" /></chemistry>or methylene linkage<chemistry id="chem0094" num="0094"><img file="EP0010243A1_D0098.tif" /></chemistry>deactivated and hydrolyzed. - After this primary reaction, samples are taken and centrifuged. By titrating the formaldehyde in the filtrates, it is determined analytically that 0.05 mol of formaldehyde has been consumed. - A solution of 60 g 'urea (1 mol) in 100 g water and 10 g of a 30% formalin solution (0.1 mol) are then added to the reaction mixture. The mixture is allowed to condense at 70 ° C. for 15 minutes, then cooled to 45 ° C. within 30 minutes and an easily filterable, powdery biomass mixed condensate is obtained. This biomass mixed condensate is neutralized with calcium hydroxide, with poorly soluble calcium phosphate being reflected in the finely divided form in the biomass condensate dispersion. The powdery product is filtered off, washed with a 2% aqueous ammonia solution, the product is then dried at 70 ° C. under reduced pressure and an almost odorless powder is thus obtained in a yield of 176 g; the nitrogen content is 13.4%.</li></ul>

The process product contains, based on the mixture of condensed proteins, enzymes, nucleic acids and other cell contents, about 39% by weight of polymethyleneureas of the idealized constitution<chemistry id="chem0095" num="0095"><img file="EP0010243A1_D0099.tif" /></chemistry>where x is unknown and the proportion of (K) fused to functional groups of the biomass cannot be determined analytically at the moment due to the insolubility of the mixed biomass condensate.

Biological tests for sterility of the powdery biocondensates as well as the filtrates show that the powdery process products and the filtrates are free from bacteria and pathogenic pathogens.

b) The procedure is exactly as described under (a), but the phosphoric acid used as catalyst is replaced by 18.4 g of concentrated sulfuric acid. After the condensation has been carried out, the mixture is neutralized with calcium hydroxide. A biomass mixed condensate containing calcium sulfate is isolated. Yield: 171 g.

Example 18

a) As described in Example 17, an amount of 865 g of the bacterial activated sludge mentioned there, which contains about 73.8 g of dry substance, is heated to 70 ° C. for 30 minutes in the presence of 0.1 mol of formaldehyde with vigorous stirring, then adds 63 g of melamine and, after a further 5 minutes, 150 g of a 30% strength aqueous formalin solution (1.5 mol) and 0.2 g of potassium carbonate as the methylolation catalyst are added. Essentially the trimethylolmelamine of the constitution is produced in the biomass within half an hour<chemistry id="chem0096" num="0096"><img file="EP0010243A1_D0100.tif" /></chemistry>

Then it is cooled to 45 ° C. After the internal temperature of the still unfilterable biomass dispersion is 45 °_C. reached, add 18 g of concentrated sulfuric acid. The biomass trimethylol melamine condensation starts immediately at a pH of approx. 2.5. The mixture is stirred for 2 hours and neutralized with 24 g of calcium hydroxide. The biomass mixed condensate is filtered off and drops to 70 after drying⁰_C. in vacuo in a yield of 184 g. Nitrogen content of the biomass mixed condensate: 28.1%. The nitrogen content of the biomass mixed condensate has thus been increased from approx. 7.4% by weight, based on the dry weight of the starting product, to 28.1%, ie increased by a value of Δ = + 20.7%. The phosphorus content of the mixed condensate is 2%, the calcium sulfate content is approximately 12.8% by weight.

After carrying out the mixed condensation according to the invention, the aqueous supernatant above the biomass mixed condensate is isolated by centrifugation as an almost colorless or only slightly yellowish liquid. When this aqueous phase is evaporated at a pressure of 14 torr, about 7 g of a residue remain, which essentially consists of cell contents, such as polysaccharides and oligopeptides or Glycoproteins of unknown constitution exist and are suitable as a valuable nutrient for the most diverse microbial systems. In this variant of the method according to the invention, only a relatively small amount of cell constituents is thus transferred into the mother liquor.

b) The procedure is exactly as described under (a), with the difference that the amount of trimethylolmelamine used is reduced by using 31.5 g of melamine (0.25 mol) and 75 g of a 30% formalin solution (0.75 mol ). Otherwise, the condensation conditions are complied with, which are described under (a). An excellent filterable biomass mixed condensate is obtained.<ul id="ul0053" list-style="none"><li>Yield: 122 g; N content: 23.3%</li><li>P content: 2.8%</li></ul>

The product obtained binds ions from heavy metals such as lead, mercury and copper, as well as ions from metals such as zinc, cadmium and chromium.

c) The procedure is exactly as described under (b), but only 15.75 g (0.125 mol) of melamine and 37.5 g of an aqueous 30% formalin solution (0.375 mol corresponding to 11.2 g of formaldehyde) are used. - A powdery biomass mixed condensate is obtained in a yield of 100 g.

In this embodiment of the method according to the invention, about 21 g of three-dimensionally crosslinked polymethylene melamines are of the idealized constitution<chemistry id="chem0097" num="0097"><img file="EP0010243A1_D0101.tif" /></chemistry>

generated with unknown size of x. They convert about 74 g of the starting biomass used into mixed products through mixed condensers of their reactive centers. Due to the insolubility of the biomass mixed condensates, the proportion of (M) that is fixed on biomass cannot be determined. The filtrate of the mixture shows a remarkably light color. About 9% by weight, based on the biomass used, of bright polysaccharide and oligopeptide condensates, ie non-crosslinked cell contents, isolated by concentrating the mother liquors.

Nitrogen content of the biomass trimethylol melamine mixed condensate: 15.5

d) If, according to embodiment (c), only 0.03 mol of melamine (3.78 g) and 0.09 mol of formaldehyde (9 g of 30% strength formaldehyde solution) are used for the formation of trimethylolmelamine, and the procedure is as described under (a), a Obtain flocculable, filterable biomass mixed condensate. Yield: 79 g; Nitrogen content: 8.4%; P content: 3.9%.

e) The procedure is as described under (a), but a mixture of aminoplast formers of the following type is used: 6 g of urea (0.1 mol), 11.4 g of azulmic acid, - prepared according to DT-PS 662 338 -, 1.26 g Melamine (0.01 mol) and 18.4 g concentrated sulfuric acid as a catalyst. It is condensed, then neutralized with calcium oxide and worked up as described in Example 16. Yield: 121 g; Nitrogen content: approx. 11.7% by weight.

The presence of the co-condensing azulmic acid firmly binds ions of metals such as mercury, lead, cadmium, zinc, copper, nickel, iron, chromium and manganese in the biomass mixed condensate. Even a biomass mixed condensate, which contains 43 ppm mercury, 480 ppm zinc, 320 ppm copper, 2% iron, 216 ppm nickel, 230 ppm chromium, 0.21% lead and 440 ppm manganese, has no effect in the plant germ test negative.

f) The procedure is as described under (e), but a Bianasse which has already been dried at 110 ° C. and has been prepared by known technical processes is used, in which extensive cell death has occurred. Yield: 119 g of powdery substance.

g) The procedure is as described under (e), but the biomass used in (f), but stored in a landfill for 2 months, is infested with fungi and other microorganisms. A powdery biomass mixed condensate is obtained in a yield of 112 g. The product is able to bind metal ions very firmly.

h) When 6 g of thiourea are added to the reaction mixture given under (a), a biomass mixed condensate is also obtained which is able to bind ions of the metals mercury, lead, copper, chromium, zinc and cadmium.

Example 19

One-pot process in which N-methylol compounds of biomass and melamine are not used in isolated form, but are generated in situ after primary precondensation of the biomass with aldehyde and then acid-condensed.

1100 g of a bacterial activated sludge from a fully biological wastewater treatment plant for industrial and municipal wastewater, containing about 11.2% by weight of solids, which consists of various microorganisms, is first mixed with 200 g of water to improve stirrability. Then 100 g of a 30% aqueous formaldehyde solution (1 mol) are added. It is then condensed for 2 hours at pH = 7.5 in the absence of melamine at 96 ° C. Then 63 g (0.5 mol) of powdered melamine and an additional 50 g of 30% formalin solution (0.5 mol) are added and the mixture is condensed for one hour at 960C. The mixture is allowed to cool to 45 ° C., 1.84 g of concentrated sulfuric acid are added to the reaction mixture and the mixture is kept at this temperature for 4 hours with vigorous stirring. It is neutralized with calcium hydroxide and a very easily filterable biomass mixed condensate is obtained. Yield of the dried product: 195 g; Nitrogen content of the mixed condensate: 27.3%; Calcium sulfate content approx. 2.5% by weight.

In the biological test, the product proves to be completely germ-free. By evaporation of the aqueous mother liquor, about 10 g of polysaccharide and peptide-like cell contents are isolated, likewise about 0.9 g of hydroxybutyric acids as components of destroyed bacterial cell walls.

Example 20

<ul id="ul0054" list-style="none"><li>a) The procedure is as described in Example 17, variant (a), but the amount of biomass is increased to 2000 g and, in addition to 200 g of 30% formalin solution (2 mol), 200 g of 85% phosphoric acid are used. The mixture is heated to 80 ° C. for two hours, precondensation being carried out under hydrolyzing, protein-degrading conditions. Then 40 g of 30% formaldehyde solution and finally 120 g of urea (2 mol) are added, the mixed condensation commencing immediately. It is allowed to 45 over 2 hours⁰C cool down and then neutralized with calcium hydroxide. After filtration and drying, a biomass mixed condensate is obtained in a yield of 525 g. This condensate has a calcium phosphate content of about 46.6% by weight and a nitrogen content of 13.8% by weight due to the formation of insoluble calcium hydrogen phosphate when neutralizing the large amount of phosphoric acid used as a catalyst.</li><li>b) If an amount of only 20 g of 85% phosphoric acid is used as a catalyst and condensed exactly as described under (a), by carrying out the primary formaldehyde condensation at 98 ° C. for 8 hours at a pH of 3.4, that is works under conditions under which proteins, cell walls and cell constituents hydrolyze, so after filtering and drying a biomass mixed condensate is obtained in a yield of 341 g. The calcium hydrogen phosphate content is about 7.2% by weight; the nitrogen content is 17.8% by weight.</li></ul>

Example 21

Carrying out the method according to the invention at room temperature.

971 g of a bacterial activated sludge containing about 7.4% by weight of dry substance, the microbial components of which are still in full activity, are mixed with 100 g of water and 100 g of a 30% strength formalin solution (1 mol of formaldehyde) at room temperature without the addition of a basic methylolation catalyst for 90 minutes precondensed. Then 60 g of urea (1 mol) are dissolved in the dispersion, an additional 10 g of formalin solution (30% strength) are added, and after 10 minutes 18.4 g of sulfuric acid are added as an acidic condensation catalyst. It is condensed for 4 hours at room temperature under acidic conditions (pH = 2.3). The biomass mixed condensate is then filtered, freed from sulfuric acid by washing with water and dried at 80 ° C. under a pressure of 14 torr. 133 g of a powdery biomass mixed condensate are obtained, which has a nitrogen content of 24.7%.

Example 22

The biomass mixed condensation according to the invention can also be carried out by adding a relatively large amount of aldehyde in the first stage, predominantly methylolation products of proteins and N-methylolation products of nucleic bases within the macromolecules of the nucleic acids which are obtained in the second stage the respective aminoplast formers are condensed under acidic conditions.

1093 g of an activated biological sewage treatment plant for industrial and municipal wastewater, containing about 11.2% by weight of solid bacterial sludge, the microbial components of which still have a high activity, are mixed with 150 g of water and 200 g of a 30% aqueous formaldehyde Solution (2 mol) reacted at 98 C for 2 hours. It is then cooled to room temperature. At this point in time, the methylolated biomass is free of phatogenic pathogens, but it is not possible to isolate the N-methylolation products by filtration. A solution of 120 g of urea (2 mol) in 200 g of water is added and 18.4 g of concentrated sulfuric acid are added. It is condensed for 6 hours at room temperature at pH = 2.3 and then neutralized with calcium hydroxide. A powdery, easily filterable biomass mixed condensate is obtained. Yield after drying at 80 ° C: 257 g; Nitrogen content of the condensate: 22.7%; Calcium sulfate content: 9.4%.

Biological tests show that this biomass mixed condensate is sterile and free of phatogenic pathogens.

Example 23

1000 18.4 g of 85% phosphoric acid are added to 18 g of a biomass originating from a biological sewage treatment plant and containing approximately 8.4% by weight of dry substance and in the state of active cell division, and the mixture is heated to 96 ° C. for 2 hours. Here, an amount of 2.2 g of carbon dioxide is released by ongoing decomposition processes. The escaping carbon dioxide is collected in a template charged with sodium hydroxide solution and determined by titration using the barium carbonate method. After the carbon dioxide development has dropped to zero within 3 hours, proceed as follows:

100 g of black crude azulminic acid, prepared in accordance with DT-PS 662 338, and 100 g of a 30% strength aqueous formalin solution (1 mol) are added to 1000 g of the aforementioned biomass. It is condensed for 8 hours at 90 ° C., 1.36 g (0.03 mol) of carbon dioxide being released. This carbon dioxide evolution is due to the formation of F₂Defects due to decarboxylation of F_iDefects in azulmic acid. About 0.87% by weight of F₂-Flaws in the constitution<chemistry id="chem0098" num="0098"><img file="EP0010243A1_D0102.tif" /></chemistry>and about 9% by weight of F₁-Flaws in the constitution<chemistry id="chem0099" num="0099"><img file="EP0010243A1_D0103.tif" /></chemistry>

generated in the azulmic acid and free amino groups condensed with the formaldehyde used practically quantitatively with formation of aminal despite the insolubility of the azulmic acid.

The biomass-azulmic acid condensate mixture is then cooled to 80 ° C. and mixed with 60 g (1 mol) of urea. After 10 minutes, 100 g of a 30% formalin solution (1 mol) are added in one pour and then 18.4 g of 85% phosphoric acid are added. It is condensed for 2 hours at 80 ° C. and an excellent filterable biomass-azulmic acid-urea-formaldehyde condensate is obtained. Yield after washing with 2% aqueous ammonia solution and after drying at 80 ° C. under a pressure of 15 torr: 288 g; N content: 24.2%; Phosphorus content: 1.3%.

When the mother liquor is evaporated, only 8% by weight of polysaccharide and other cell contents are isolated.

In addition, the condensed azulmic acid was completely stabilized during the reaction against the release of hydrocyanic acid.

The metal quantities present in the starting biomass of 0.0043% mercury, 0.0005% cadmium, 0.042% zinc, 0.032% copper, 1.8% iron, 0.022% nickel, 0.03% chromium and 0.19% lead are in the obtained biomass mixed condensate. This is shown by the fact that the_Me-metal content in the mother liquor (= waste water) of the above biomass condensate mixture after the implementation according to the invention by a factor of 10² until 10³ has dropped. - The following metal concentrations were found in the wastewater:<ul id="ul0055" list-style="none"><li>0.25 mg zinc per liter</li><li>0.13 mg lead per liter</li><li>less than 0.1. 10th^-6 g chromium per liter</li><li>less than 0.1. 10th^-6 g copper per liter</li><li>less than 0.1. 10th^-6 g of mercury per liter</li></ul>

About 100 mg of the biomass used contained about 43 mg of mercury; of these, only 0.0001 mg reach the wastewater after the reaction according to the invention.

Example 24

1000 g of a biomass originating from a fully biological sewage treatment plant and containing about 8.4% by weight of dry substance and consisting of a wide variety of microorganisms are used. This 3-day storage at room temperature without further supply of nutrients already causes this biomass to decompose strongly, whereby malodorous odorants have formed. 100 g of an azulmic acid condensed with formaldehyde and stabilized against hydrocyanic acid cleavage are stirred into this aqueous biomass slurry. Then 100 g of 30% formalin solution are added, the mixture is heated at 80 ° C. for half an hour, then 60 g (1 mol) of urea are added, and after a further 10 minutes 25 g of 85% phosphoric acid are added. It is condensed at 80 ° C for 0.5 hours, then cooled to 50 ° C and filtered.

_Mreceives a powdery, black-gray biomass mixed condensate; Yield after drying at 80⁰C under a pressure of 16 torr: 291 g; Nitrogen content 23.9%; Phosphorus content: 1.35%.

The product proves to be completely germ-free in the biological test. It is almost odorless. Complete odorlessness is achieved by washing with a little acetone or methanol.

Example 25

1000 g of a bacterial activated sludge which comes from a biological treatment plant for industrial and municipal wastewater and contains about 8.4% by weight of solids and which is in cell division is used for an anionically catalyzed hydrocyanic acid polymerization.

For this purpose, 163 g of hydrocyanic acid, 440 ml of water, 25 ml of a 25% strength aqueous ammonia solution and 5 g of sodium cyanate are added to the stirred biomass. This mixture is kept at 7 for 7 hours₀- 90 C stirred, the hydrocyanic acid polymerized to azulmic acid. Thereafter, ammonia and hydrogen cyanide still present are drawn off in a water jet vacuum. The polymer-biomass dispersion foams very strongly.

After monomeric hydrocyanic acid has been removed, 120 g of 30% formaldehyde solution are added, and the mixture is stirred at 100 ° C. for one hour. It is then cooled to 400C. Now 120 g of urea (2 mol) are added. The mixture is left to stir at 40 ° C. for 30 minutes and 10 ml of 96% sulfuric acid are added (pH = 4). 200 g of 30% formalin solution (2 mol) are then added. Polymethylene urea formation and mixed condensation set in very quickly. The mixture is stirred at 40 ° C. for 6 hours and then neutralized with 13 g of calcium hydroxide. The biomass-azulmic acid-urea-formaldehyde mixed condensate obtained is powdery and is isolated by simple filtration. The_MIscondensation is washed with 1000 ml of water and then with 200 ml of a 2% aqueous ammonia solution. Yield after drying for 20 hours at 50 ° C. 315 g; Nitrogen content: 28.5% by weight. The mixed condensate binds about 10% by weight of water by adsorption.

The metal analysis of the process product according to the atomic adsorption method gives the following values:<tables id="tabl0005" num="0005"><img file="EP0010243A1_D0104.tif" /></tables>

The metal content in the mother liquor (= waste water) is per liter:<tables id="tabl0006" num="0006"><img file="EP0010243A1_D0105.tif" /></tables>

Example 26

The procedure is exactly as described in Example 25, the azulmic acid is produced by polymerizing the hydrocyanic acid in the presence of the same type and amount of biomass, but then the biomass-azulmic acid dispersion is condensed with trimethylolmelamine as an aminoplast former. To do this, proceed as follows:<ul id="ul0056" list-style="none"><li>1000 g of the approximately 8.4% solids-containing aqueous biomass described in Example 25 are mixed with 163 ml (= 110 g) of hydrocyanic acid, 440 ml of water, 25 ml of a 25% aqueous ammonia solution and 5 g of sodium cyanate. This mixture is stirred for 7 hours at 70-90 ° C., the hydrocyanic acid polymerizing to azulmic acids. At 20 - 30 ° C, residual hydrocyanic acid and ammonia are removed in a water jet vacuum and slow vacuum setting ensures that the azulmic acid-biomass dispersion, which cannot be filtered at this time, does not foam. 120 g of 30% formaldehyde solution are then added to the batch. It is condensed at 100 ° C for one hour. Then 126 g of melamine (1 mol) are added. The mixture is stirred at 100 ° C. for 30 minutes and 300 g of 30% formaldehyde solution are then added. After half an hour, let go to 45^OC cool down. 8 ml of 96% sulfuric acid (pH = 4) are then added. Han condenses for four hours at 45 ° C with intensive stirring. The pH is then adjusted to 7 with 10 g of calcium hydroxide. A readily filterable biohate azulmic acid trimethylol melamine condensate is obtained. It is rinsed with 1000 ml of water and 200 ml of 2% aqueous ammonia solution. Yield after drying for 20 hours at 50 ° C. in a vacuum drying cabinet: 430 g.</li><li>nitrogen content of the mixed condensate: 32.5%.</li></ul>

Metal content of the biomass-azulmic acid-trimethylolmelamine mixed condensate:

<tables id="tabl0007" num="0007"><img file="EP0010243A1_D0106.tif" /></tables>

Metal content per liter of wastewater:

<tables id="tabl0008" num="0008"><img file="EP0010243A1_D0107.tif" /></tables>The highly dried process product binds about 8-10% by weight of water adsorptively when stored open at normal atmospheric humidity, while maintaining its powdery form.

Example 27

1000 g of a biomass originating from a fully biological sewage treatment plant and containing about 8.4% by weight of dry substance and consisting of a wide variety of microorganisms are used. The biomass is stored at 25 for 5 days⁰C, without the supply of nutrients, was in microbial and enzymatic decomposition, and in addition to living Pseudomonas species, numerous _Mi-microorganisms are in the state of cell death. By enzymatic catalyzed decomposition reactions, decarboxylation^GHere, malodorous odorants are developed from amino acids and other cell contents. 100 g of 30% formalin solution (1 mol) are added to this biomass, stirred well and condensed at 95 for half an hour⁰_C.. 60 g of urea (1 mol) are then added at 74 ° C. and the polymethylene urea formation or condensing grafting of polymethylene ureas to reactive centers of the biomass is initiated by adding 18.4 g of 85% phosphoric acid. The mixture is kept at 75 ° C. for two hours, filtered and the easily filterable powder is washed with a 2% aqueous ammonia solution. After drying at 50 ° C. under a pressure of 18 torr, a biomass mixed condensate is obtained in a yield of 132 g in the form of an almost odorless powder.

N content of the biomass mixed condensate: 18.6% phosphorus content: 2.9

In parallel experiments it is found that sulfuric acid, oxalic acid, formic acid, hydrochloric acid, p-toluenesulfonic acid, phosphorous acid, trichloroacetic acid, dichloroacetic acid, hydrofluoric acid can also be used as condensation catalysts for the preparation of the biomass mixed condensates. Phosphoric acid, sulfuric acid and phosphorous acid are the preferred acids used.

Example 28

The procedure is exactly as described in Example 27, but before the addition of formaldehyde, 1.2 g of sodium sulfide, 0.5 g of sodium hydrogen sulfide and 0.4 g of ammonium polysulfides as methylolation catalyst and sulfur transfer agent are added to heavy metals such as mercury, lead, copper, cadmium etc. to convert into insoluble sulfides. The subsequent acidic condensation, which is carried out according to the information contained in Example 27, produces small amounts of hydrogen sulfide, which partially reacts with formaldehyde to form polythioformaldehyde. Under the acidic condensation conditions, the polythioformaldehyde undergoes condensation reactions, whereby hydrogen sulfide is split off. Yield of the hydrogen sulfide-free biomass mixed condensate: 133 g. N content of the biomass mixed condensate: 18.1% phosphorus content: 2.7%

Example 29

The procedure is exactly as described in Example 17, variant (a), but about 40 g of calcium hydroxide are used to neutralize the batch containing about 25 g of 85% phosphoric acid. By adding calcium hydroxide, sugar-like cell constituents, such as oligosaccharides and glycoproteides, dissolved in the mother liquor are also precipitated, in that complexes of approximately 3 CaO. 2 Form sucrose molecules. With this measure, the mother liquor is reduced by approx. 8th g poorer in hydrolyzed, water-soluble cell contents. Excess calcium hydroxide is then converted into calcium carbonate by gassing the reaction mixture with carbon dioxide.<ul id="ul0057" list-style="none"><li>Yield: 185 g</li><li>Nitrogen content: 11.9%</li><li>Calcium hydrogen phosphate content: approx. 13.8% by weight Calcium carbonate content: approx. 14% by weight</li></ul>

Less than 0.01 ppm of mercury is present in the mother liquor of the biomass condensate. According to A. Stock, this concentration of mercury occurs everywhere in living nature and presumably plays a positive, biologically important role in these trace concentrations.

Example 30

_MThe procedure is exactly the same as that described in Example 17, variant (a), but uses one of the following substances as a chain terminator for the polymethylene urea segments that occur before the urea is added:<ul id="ul0058" list-style="none"><li>a) 0.1 mol of N-methylolcaprolactam of the formula<chemistry id="chem0100" num="0100"><img file="EP0010243A1_D0108.tif" /></chemistry></li><li>b) 0.1 mole of an azalactam of the formula<chemistry id="chem0101" num="0101"><img file="EP0010243A1_D0109.tif" /></chemistry></li><li>c) 0.1 mol of benzenesulfonic acid amide,</li><li>d) 0.1 mol of acetamide,</li><li>5 e) 0.1 mol of thioacetamide,</li><li>f) 0.1 mol of glycerol,</li><li>g) 0.1 mole trimethylolpropane.</li></ul>

Otherwise, the condensation is carried out according to the information contained in Example 17, variant (a).

10th Yields of biomass mixed condensate:<tables id="tabl0009" num="0009"><img file="EP0010243A1_D0110.tif" /></tables>

15 By adding the chain terminators, finer-particle biomass mixed condensates are obtained than is the case without such additives. In the above reactions, biomass mixed condensates are obtained whose particle sizes are between 150 / um and 200 / um. If the reaction is carried out without a chain terminator, the particle sizes of the resulting products are between 350 μm and 550 μm.

Example 31

The procedure is exactly as described in Example 17, variant (b), but before the formaldehyde addition in the biomass, one of the following poorly or insoluble carriers or one of the following carrier mixtures is dispersed:<ul id="ul0059" list-style="none"><li>a) 20 g of a lignin-cellulose homogenate,</li><li>b) about 20 g of silica. This is produced by adding 126 g of an approx. 32% water glass solution, mixing it with the biomass at 70 ° C. and introducing carbon dioxide, as a result of which insoluble polysilicic acids are dispersed in situ in the biomass.</li><li>c) 20 g quartz powder,</li><li>d) 10 g of alumina hydrate and 10 g of antimony trioxide,</li><li>e) 20 g of soybean meal which is microbially infected and does not smell perfectly,</li><li>f) 20 g of microbial infected and decomposed fish meal.</li></ul>

Otherwise, the biomass mixed condensation is carried out according to the information contained in Example 17, variant (b).

Yield of easily filterable and odorless biomass mixed condensates:<tables id="tabl0010" num="0010"><img file="EP0010243A1_D0111.tif" /></tables>

Example 32

The procedure is exactly as described in Example 17, variant (b), the same type and amount (1000 g) of an 8.4% by weight dry substance originating from a biological sewage treatment plant (protein content approx. 45% by weight) based on dry matter) containing biomass, but uses one of the following compounds or one of the following compound mixtures as the carbonyl component:<ul id="ul0060" list-style="none"><li>a) 1 mole of acetaldehyde,</li><li>b) 1 mole of isobutyraldehyde,</li><li>c) 0.5 mol of crotonaldehyde, 0.2 mol of isobutyraldehyde and 0.2 mol of formaldehyde,</li><li>d) 0.5 _Mol glyoxal and 0.5 mol formaldehyde,</li><li>e) 0.5 mol of crotonaldehyde and 0.5 mol of formaldehyde,</li><li>f) 0.5 mol of acrolein and 0.5 mol of formaldehyde,</li><li>g) 1.5 mol of formaldehyde and 0.5 mol of cyclohexanone,</li><li>h) 2.5 mol of formaldehyde and 0.5 mol of methyl ethyl ketone,</li><li>i) 0.5 mol of glutardialdehyde and 0.5 mol of formaldehyde,</li><li>j) ₀,6 _Mol formaldehyde and 0.5 mol salicylaldehyde,</li><li>k) 0.5 mol of formaldehyde and 0.5 mol of furfural,</li><li>1) 0.5 mol formaldehyde and 0.5 mol chloral hydrate.</li></ul>

First, in the absence of urea and without acid, condense for 1 hour at 70 ° C. Then, in cases (a) to (1), the reaction mixture is mixed with one mole of urea and the temperature is reduced to 35 ° C. At this point, 25 g of 85% sulfuric acid are added to each batch at 35 ° C. The mixture is left to react for eight hours, then condensed for two hours at room temperature and, after neutralization with calcium oxide, biomass-aminoplast mixed condensates which are readily filterable are obtained, which after drying at 50⁰C under a pressure of 18 torr in fine powder form in the following yields:<tables id="tabl0011" num="0011"><img file="EP0010243A1_D0112.tif" /></tables>

Due to the neutralization of the sulfuric acid by calcium oxide, all biomass-aminoplast mixed condensates contain between 11 and 14% by weight of calcium sulfate intimately mixed with the bio-mixed condensates.

In the above reactions, acetaldehyde, crotonaldehyde, isobutyraldehyde, chloral hydrate react due to the relatively large dilution and due to the lower reactivity of the aforementioned carbonyl compounds towards formaldehyde between 60-70% of theory, based on the amounts of aldehyde used.

Example 33

The procedure is as described in Example 17, variant (b), and one of the following polymeric thioaldehydes is used as the carbonyl component:<ul id="ul0061" list-style="none"><li>a) polymeric thioformaldehyde (1.2 mol)</li><li>b) Trimers thioformaldehyde (Trithian) (1.5 mol)</li><li>c) polymer thioacetaldehyde (1.3 mol)</li></ul>

20 g of concentrated sulfuric acid are used to break down the thioaldehydes and 1 mol of urea is used as aminoplast former. The mixed condensation takes place at around 95 ° C with hydrogen sulfide release. It is condensed for 12 hours and worked up as described in Example 17, variant (b) by neutralizing the sulfuric acid used with calcium hydroxide. Exploit:<ul id="ul0062" list-style="none"><li>a) 158 g</li><li>b) 147 g</li><li>c) 142g</li></ul>

Example 34

The procedure is as described in Example 17, variant (b), but other biomasses are used, one of the following:<ul id="ul0063" list-style="none"><li>a) 1800 g of an aqueous biomass dispersion containing living cells of the bacterium Alcaligenes eutrophus (strain H₁₆, ATCC 176 999), which are used for the production of single-cell proteins (content of dry substance: approx. 2% by weight).</li><li>b) 1800 g of an aqueous biomass dispersion containing cells of the bacterial strain Serratia marcescens (dry matter content: approx. 2% by weight).</li><li>c) 900 g of an aqueous biomass dispersion containing bacterial cells from Streptomyces species (approx. 2% by weight dry substance), which are used to produce the antibiotic streptomycin.</li><li>d) 1000 g of an aqueous biomass dispersion consisting of thread-like bacteria, containing cells of the bacterium Mikromonospora, which are used to produce the broad-spectrum antibiotic sisomicin (approx. 5% by weight dry substance).</li><li>e) 1000 g of an aqueous biomass dispersion consisting of fungi from penicillin production, containing cells of the fungus Penicillium chrysogenum (Penicillium notatum) (containing about 5% by weight dry matter).</li><li>f) 1000 g of an aqueous biomass dispersion consisting of cells of the fungus Aspergillus niger (dry weight about 5% by weight).</li><li>g) 1000 g of an aqueous biomass dispersion consisting of fungal organisms from the series of highly active yeasts of alcoholic fermentation, additionally containing vegetable substances, furthermore Saccharomyces cerevisiae, Saccharomyces uvarum and other microorganisms, such as Botrytis cinerea, lactic acid and vinegar bacteria (dry weight: sum of vegetable and microbial material approx. 5% by weight).</li></ul>

The aforementioned aqueous biomass dispersions are each precondensed with 15 g of formaldehyde at 70 ° C. (methylolation and cell wall detonation), then 60 g (1 mol) of urea and 100 g of 30% formalin solution (1 mol) are added, and it is Condensed for 20 minutes at 70 ° C. 4 g of concentrated 96% sulfuric acid are used for the condensation with urea, so that a pH of about 2.2 is reached. The mixed condensation starts immediately in the case of reactions (a) to (g). The mixture is stirred at 70 ° C. for 0.5 hours, then cooled to room temperature and left to stir at room temperature for 4 hours. Excellent filterable, powdery biomass mixed condensates are obtained, which are freed from traces of sulfuric acid by washing with 2% aqueous ammonia solution.

Yields after drying at 50 C in a vacuum drying cabinet:<tables id="tabl0012" num="0012"><img file="EP0010243A1_D0113.tif" /></tables>

Concentrating the mother liquors in batches (a) to (f) isolates cell constituents such as polysaccharides, glycoproteids and oligopeptides of an unknown type, which have a white-yellowish color and are valuable nutrients for other bacterial cultures.

Yields of cell contents:<tables id="tabl0013" num="0013"><img file="EP0010243A1_D0114.tif" /></tables>

Example 35

The procedure is as described in Example 17, variant (b), but with 1000 g of an aqueous biomass containing about 4.8% dry matter, consisting of flagellates, Euglena, Escherichia coli, amoebas (change animals), slipper animals, thread algae (Spirogyra), and extracellular slimy masses and cells of dead plant parts. Otherwise, the procedure is exactly as described in Example 17, variant (b) and condensation is carried out at pH = 2.8.

Yield of biomass mixed condensate: 163 g nitrogen content: 16.4%.

In the biological test, the fine powdery product proves to be completely germ-free and free of pathogenic pathogens.

Example 36

1000 g of an aqueous, superficially growing and with the formation of odoriferous mushroom mycelium dispersion of various molds, growing on a mixture of cellulose powder, potato starch concentrates and peptones containing nutrient solutions, also containing cellulose-degrading asco- and deuteromycetes, also lignin-degrading fungi such as Phellinus igni Basidiomycetes, with a dry weight of approx. 8th % By weight, based on cellular and extracellular constituents<ul id="ul0064" list-style="none"><li>a) exactly as described in Example 17, variant (a), first condensed with formaldehyde and then with urea and formaldehyde,</li><li>b) exactly as described in Example 17, variant (a), first condensed with formaldehyde and then with the method described in Example 19 with trimethylolmelamine.</li></ul>

Exploit:<ul id="ul0065" list-style="none"><li>a) 161 g of polymethylene urea-biomass mixed condensate.</li><li>b) 153 g of polymethylene-melamine-biomass mixed condensate.</li></ul>

Example 37

Condensation is carried out primarily for 30 minutes with 0.1 mol of formaldehyde at pH = 8 and 80 ° C., then with 0.4 mol of monomethylolurea and 0.1 mol of trimethylolmelamine at 60 ° C. for one hour, each with one of the following aqueous biomass homogenates, which contain extracellular components:<ul id="ul0066" list-style="none"><li>a) 200 g of a fresh, aqueous, ground cell homogenate from legume roots which contain nitrogen-assimilating bacteria (= Rhizobium, Bacterium radiciola) by infection under natural growth conditions. Dry weight: approx. 15 g on plant cells and rhizobium.</li><li>b) 200 g of a fresh, aqueous cell homogenate from alder roots containing symbiotic actinomycetes.</li><li>c) 200 g of a fresh, aqueous grass homogenate which has a protein content of about 12% by weight, based on the dry weight used of about 10 g.</li><li>d) 200 g of an aqueous grass homogenate of mixed grass, which is found in anaerobic rot by adding one g of microbially active garden soil (= 7-day storage with exclusion of air at 37⁰C) on which numerous microorganisms and mucilaginous, extracellular components have formed; Dry weight: 12 g.</li><li>e) 200 g of an aqueous cell homogenate from mixed grasses and weeds in aerobic putrefaction at 35 ° C., in which numerous microorganisms have formed as biomasses after 7 days of storage in the presence of air, the formation of which was initiated mainly by the addition of ag microbially active garden soil , whereby these biomasses also contain sulfate-reducing, nitrite and nitrate bacteria; Dry weight approx. 16 g.</li></ul>

All of the aforementioned biomass cell homogenates are primarily unfilterable through the formation of extracellular mucilages. After carrying out the condensation under the conditions given in Example 17, variant (b) and after acidifying to pH 2.2 with sulfuric acid, the condensation is brought to an end. Easily filterable aminoplast-biomass mixed condensates are obtained, which are obtained in the following yields after removal of the catalyst by washing with water and after drying at 60 ° C. under reduced pressure:<ul id="ul0067" list-style="none"><li>a) 59 g</li><li>b) 57 g</li><li>c) 54 g</li><li>d) 53 g</li><li>e) 57 g</li></ul>

In the above reaction (c), plant cell constituents such as chlorophyll (a) and chlorophyll (b) have been largely mixed-condensed. Uncondensed smaller portions of such cell contents can be extracted with acetone.

Example 38

The condensation is carried out exactly as described in Example 37, but one of the following aqueous biomass systems is used in each case:<ul id="ul0068" list-style="none"><li>a) 1000 g of a microbially infected, about 87 _G% water and about 12% by weight dry matter (mainly consisting of casein, milk sugar and milk fat) containing milk which contains lactic acid bacteria and other types of bacteria.</li><li>b) 100 g of a bacterially infected whey, which after the excretion of milk fat and casein still contains milk sugar, salts and about 2% by weight of soluble protein.</li></ul>

The biomass systems mentioned under (a) and (b) are mixed-condensed exactly as described in Example 37.

Yields of aminoplast-biomass mixed condensates containing cross-linked extracellular substances:<ul id="ul0069" list-style="none"><li>a) 58 g</li><li>b) 51 g</li></ul>

The powdery aminoplast-biomass mixed condensates, which contain extracellular cross-linked components, have been shown to be completely germ-free in the biological test.

Example 39

The procedure is exactly as described in Example 37, but one of the following aqueous biomass homogenates is used in each case:<ul id="ul0070" list-style="none"><li>a) 60 g of an aqueous homogenate of plant plankton (= algae, mainly phaeophyceae and _Rhodophyceen (Desmarestia, Delesseria, _Bangia, porphyra and fucus). Dry weight approx. 3 g.</li><li>b) 180 g of plant plankton from the sea [= pyrrophyceae, chrysophyceae, diatomaceous earth, peridene, coccolithinee and silicoflagellate, which cannot be detected in meshes of the plankton network (nannoplankton)]; Dry weight: approx. 2% by weight.</li><li>c) 12 g of dispersed fish meal in decomposition in 200 ml of water.</li><li>d) 240 g of an aqueous Antarctic krill homogenate [= homogenized animal cells of the krill cancer type, which are a main food of the baleen whales = whale prawns, Euphausia superba, (= shrimp-like crabs of 2 - 4 cm length)], which is in the process of decomposition ; Dry weight about 18 g.</li></ul>

In the case of reactions (a) to (d), powdery, easily filterable polymethylene-polyurea-polymethylene-melamine-biomass mixed condensates are obtained which are completely odorless and are obtained in the following yields:<ul id="ul0071" list-style="none"><li>a) 56 g, nitrogen content: 40.8%</li><li>b) 51 ^G, Nitrogen content: 39.2%</li><li>c) 63 g, nitrogen content: 38.5%</li><li>d) 71 g, nitrogen content: 38.1%</li></ul>

Example 40

1000 g of a biomass originating from a fully biological sewage treatment plant for industrial and municipal wastewater and containing about 8.4% by weight of dry substance is first treated with 300 g of a 30% aqueous formaldehyde solution at 95 ° C. for 30 minutes. 15 g of calcium hydroxide slurried in water are then slowly added. Thereafter, about 2 moles of formaldehyde are converted into caramelized formose, a mixture of sugar-like hydroxyaldehydes, at 90 ° C. in the course of 4 hours. An additional 1 mol of urea is added, and finally the condensation of the urea with formaldehyde and the resulting hydroxyaldehydes is initiated with 34 g of sulfuric acid as a catalyst. It is then neutralized with calcium oxide. A filterable biomass mixed condensate is obtained. In order to avoid the removal of soluble cell contents, however, it is not filtered, but the water is removed under reduced pressure and the reaction mixture together with the caramelized sugars formed are evaporated on a sheet metal dish. A biomass mixed condensate containing calcium sulfate is obtained, which smells of caramelized sugars. The mixed condensate is obtained in a crumbly form with a peat brown color:<ul id="ul0072" list-style="none"><li>Yield: 332 g</li><li>Nitrogen content: 12.8%</li></ul>

Example 41

Use of amines, hydrazines and hydrazides for _Bio-mass mixed condensation.

100 g of a biomass originating from a fully biological sewage treatment plant for municipal wastewater and containing about 7.8% by weight of dry substance, in which, in addition to Pseudomonas species, numerous other microorganisms, for example _FLagellates, Escherichia coli bacteria, amoebas etc. and extracellular metabolic products, slimy components and suspended matter of plant-based cellulose and lignin-containing materials are first condensed with 10 g of a 30% aqueous formaldehyde solution (0.1 Mcl) at 95 ° C , whereby pathogenic pathogens and bacterial cell walls are already attacked and killed. The temperature is allowed to drop to 30 ° C. and one of the following, very rapidly condensing compounds (aminoplast or phenoplast) or compound mixtures are metered in over the course of one hour:<ul id="ul0073" list-style="none"><li>a) 0.05 mol of hexamethylenediamine</li><li>b) 0.1 mole of aniline</li><li>c) 0.01 mol of isophoronediamine of the formula<chemistry id="chem0102" num="0102"><img file="EP0010243A1_D0115.tif" /></chemistry></li><li>d) 0.05 mol aniline and 0.05 mol phenol</li><li>e) 0.05 mol aniline and 0.025 mol bisphenol A</li><li>f) 0.02 mol of hydrazine hydrate</li><li>g) 0.05 mol adipic dihydrazide and 0.02 mol thioacetamide</li><li>h) 0.05 mole of hydroxylamine and 0.005 mole of hexamethylene diamine</li></ul><ul id="ul0074" list-style="none"><li>i) 0.05 mol of p-phenylenediamine, 0.01 mol of salicylaldehyde and 0.01 mol of terephthalaldehyde.</li></ul>

It is then condensed for 4 hours at room temperature and powdery, filterable aminoplast-biomass mixed condensates are obtained in the form of brown-black powders. If hexamethylenediamine ('reaction a) or isophoronediamine (reaction b) is used as compounds capable of aminoplast formation, highly crosslinked polyhexahydrotriazine condensates are obtained in the mixture.

Yield after drying at 80 ° C at a pressure of 14 torr:<tables id="tabl0014" num="0014"><img file="EP0010243A1_D0116.tif" /></tables>

Example 42

Use of ammonia as a compound capable of aminoplast formation and benzoquinone as a carbonyl component for the mixed condensation of biomass.

100 g of the biomass mentioned in Example 41 are heated to 80 ° C., then 10.8 g of finely powdered benzoquinone are dispersed and gaseous ammonia is passed into the well-stirred dispersion at 85 ° C. Addition and polycondensation products are formed very quickly, which deepen the color of the dispersed biomass via brown-black to graphite-like black.

After filtration and drying, 19.4 g of biomass mixed condensate are obtained in the form of a powdery substance.

Example 43

Use of hexamethylenetetramine and other hexahydrotriazines as blocked carbonyl compounds and blocked aminoplast formers for the mixed condensation of biomass.

100 g of the aqueous biomass dispersion mentioned in Example 41 are first heated to 90 with 0.1 mol of formaldehyde for 20 minutes⁰C and then with one of the following compounds to 100 ° C:<ul id="ul0075" list-style="none"><li>a) 10 g of hexamethylenetetramine </li><li>b) 15 g of tri-n-butyl-hexahydrotriazine</li><li>c) 18 g 2,4,6-tris-dimethylaminomethylphenol</li></ul>

Ammonia (a) or n-butylamine (b) or dimethylamine (c) is continuously split off over the course of 2 hours, with condensation of residues of the abovementioned condensation partners containing N-methylene groups or C-methylene groups at active centers of the Biomass is done. After 6 hours of condensation, the following yields of mixed biomass condensates are obtained after filtration and drying:<ul id="ul0076" list-style="none"><li>a) 15.6 g</li><li>b) 11.8 g</li><li>c) 17.8 g</li></ul>

Example 44

Use of blood for mixed condensation with carbonyl compounds and compounds capable of aminoplast formation.<ul id="ul0077" list-style="none"><li>a) 450 g of fresh beef blood are first condensed at room temperature at pH = 8 with 0.1 mol of formaldehyde in the presence of potassium carbonate, the proteins contained in the blood being partially methylolated. A solution of 45 g (0.75 mol) of urea in 75 g (0.75 mol) of a 30% strength formalin solution and 325 g of water is then intimately mixed with the blood and, with vigorous stirring, about 98 with 18.4 g % sulfuric acid added. The reaction mixture has a pH value of 1.6, the condensation commencing immediately and the temperature rising to about 33 ° C. due to exothermic heat of reaction. After 15 minutes the control sample (5 ml) shows that the progressive mixed condensation of the biomass already gives excellent filterability. It is condensed for a further four hours at room temperature, then neutralized with calcium hydroxide and an excellent filterable, brownish blood-biomass mixed condensate is obtained. The filtrate is water-white and, after being concentrated under reduced pressure, contains practically no extracellular proteins, but only small amounts of polymethylene ureas and about 1.6 g of calcium sulfate. Yield after drying in a vacuum drying cabinet at 5₀° C: 170 parts by weight: 15.6% N calcium sulfate content: 11.2%.</li><li>b) The procedure is exactly as described under (a), but an increased amount of urea and formaldehyde is used, namely 90 g urea (1.5 mol) and 150 g 30% formalin solution. A biomass mixed condensate rich in polymethylene urea is obtained, which contains all the extracellular water-soluble proteins of the blood in a mixed condensed form. The completely colorless mother liquor contains only 10 g of urea-formaldehyde condensates as well as table salt and calcium sulfate. Yield after drying at 50 ° C in a vacuum drying cabinet: 232 g, 23.4% nitrogen content, calcium sulfate content approx. 10.3%.</li><li>c) If fresh pig blood is used according to (b), a biomass mixed condensate of peat-brown color is obtained in almost identical yield. Yield: 233 g, nitrogen content: 20%, calcium sulfate content: 10.5%.</li></ul>

Example 45

1000 g of an extremely difficult to filter bacterial activated sludge from a fully biological sewage treatment plant for industrial and municipal wastewater, containing about 8.5% dry matter, are reacted in the first stage with 0.6 mol formaldehyde and 0.4 mol isobutyraldehyde at 70 C for 30 minutes, where cell wall breakdown and plasmolysis of the microorganisms occur and N-alkylolation reactions and N, N-aminal formations of protein-containing and nucleic acid-containing cell contents take place. The mixture is then cooled to 30 ° C. and condensed for 4 hours with 60 g of urea using sulfuric acid as a catalyst. An easily filterable powdery biomass mixed condensate is obtained, which besides<chemistry id="chem0103" num="0103"><img file="EP0010243A1_D0117.tif" /></chemistry>also more easily degradable hydrolytically and biologically<chemistry id="chem0104" num="0104"><img file="EP0010243A1_D0118.tif" /></chemistry>Contains built-in segments. Yield: 118 g, N content: 19.5%.

Although the starting biomass contains extremely unpleasant odor carriers, the process product, after treatment with 2% aqueous ammonia solution and intensive washing with acetone, proves to be completely odorless.

Example 46

For each 100 g of the biomass mixed condensates prepared according to Example 17, variants (a) and (b), one of the hydroxides mentioned below is first precipitated in aqueous dispersion by adding excess aqueous sodium hydroxide solution:<ul id="ul0078" list-style="none"><li>Calcium hydroxide,</li><li>Barium hydroxide,</li><li>Magnesiumhydrc :: id,</li><li>Lead hydroxide,</li><li>Iron (II) hydroxide,</li><li>Aluminum hydroxide,</li></ul>

whereby these hydroxides arise from the previously added metal halides. The excess sodium hydroxide solution is then neutralized by adding an equivalent amount of phosphoric acid. Here, poorly soluble phosphates are generated on the biomass mixed condensate matrix. - Easily filterable, metal hydroxide and metal phosphate-containing biomass mixed condensates are obtained.

Example 47

Treatment of the surface of biomass mixed condensates by reacting these products with reagents which cause alkylation, acylation reactions, ring-opening addition reactions, Michael additions, polymerizations or mixed polymerizations and thus modify the surface of the biomass mixed condensates.

In each case 100 g of the process product produced according to Example 17 are mixed in the highly dried state (100 C, 12 Torr) with one of the substances or substance mixtures mentioned below:<ul id="ul0079" list-style="none"><li>a) with 30 g acetic anhydride and 50 g toluene using 0.4 g sodium acetate as a catalyst</li><li>b) with 80 g of styrene, 20 g of acrylonitrile (in 100 g of xylene) and 2 g of the radical generator azoisobutyronitrile</li><li>c) with 100 g of styrene, dissolved in 400 g of o-dichlorobenzene and 2 g of the radical generator azoisobutyronitrile</li><li>d) with 100 g of methyl methacrylate, dissolved in 400 g of o-dichlorobenzene and 2 g of azoisobutyronitrile</li><li>e) with 100 g of vinyl acetate, dissolved in 400 g of dichlorobenzene and 2 g of azoisobutyronitrile</li><li>f) 50 g of styrene and 50 g of methacrylic acid-β-hydroxypropyl ester. The mixture in question is heated to 150 ° C. and kept at this temperature for 6 hours. The products are worked up by precipitation of the products with methanol. In the case of reactions (a) to (f), modified biomass mixed condensates are obtained on their surfaces which are completely odorless.</li></ul>

Exploit:<ul id="ul0080" list-style="none"><li>a) 105 gc) 168 ge) 158 g</li><li>b) 175 gd) 162 gf) 172 g</li></ul>

Example 48

<ul id="ul0081" list-style="none"><li>a) 300 g of the biomass mixed condensate prepared according to Example 17, variant (a) are gassed in a fluidized bed additionally equipped with a stirrer, in a glass tube with a cross section of 2.5 cm in countercurrent from below with carbon dioxide and from above with ammonia, where the dosage is carried out in such a way that the molar NH₃/ CO₂ratio is 2: 1 and pressure equalization takes place through a side-mounted outlet pipe in the column. In this case, 100 g of carbamic acid ammonium of the formula are produced within the channels and pores of the biomass mixed condensate in the course of one hour<chemistry id="chem0105" num="0105"><img file="EP0010243A1_D0119.tif" /></chemistry> in addition to ammonium bicarbonate and ammonium carbonate. The resulting mixture contains the ammonium salts in a significantly improved storable form, in that ammonia is released more slowly into the air space of containers by a factor of 4 when stored at room temperature than is the case with the free salts. Yield: 400 g; N content: 18.8%.</li><li>b) If the production of carbamic acid ammonium is carried out for 4 hours, about 300 g of the fine powdery biomass mixed condensate are included or about 300 g of ammonium carbaminates are deposited or deposited on the biomass mixed condensate matrix.</li></ul>

Yield: 600 g, N content: 24.6%.

With increasing water content of the biomass mixed condensates used, ammonium forms in addition to the carbamic acid<chemistry id="chem0106" num="0106"><img file="EP0010243A1_D0120.tif" /></chemistry>to an increasing extent ammonium bicarbonate and ammonium carbonate.