FI89072B - FREQUENCY REQUIREMENTS FOR THE USE OF FYLLMATERIAL INNEHAOLLANDE POLYMERBUNDNA BAERARMASSOR, MED DETTA FOERFARANDE FRAMSTAELLDA BAERARMASSOR OCH DERAS ANVAENDNING - Google Patents

Abstract

1. Process for the preparation of polymer-bound carrier masses containing fillers, characterised in that A) fillers based on prefinished, lumpy or pulverulent voams and/or fossil ligno cellulose powders and/or carbon powders and optionally other inorganic or organic fillers and/or optionally living and/or dead biological cell material in a quantity of from 5 to 97% by weight, based on A) and B), are mixed with B) nonionic-hydrophilic, anionic or cationic, aqueous, coagulable and film forming polymer dispersions having a solids content of from 3 to 60% by weight, optionally with the addition of C) water so that the total water content, based on all components, amounts to 20 to 90% by weight, and optionally with the addition of D) other auxiliary agents and additives and the polymer dispersion is then brought to coagulation.

Description

1 89072

The present invention relates to a process for the preparation of polymer-bonded carrier compositions containing excipients by mixing the excipients with a polymer-based binder mixed with water, resulting in a water-dispersed polymer-based binder. the carrier masses obtained by the process and their use in biological wastewater treatment, as a carrier in the context of biological fermentation in biological transformation processes, as a plant growth medium or as adsorbents for finely divided substances, in particular crude oil.

A number of methods have been proposed for impregnating foams and foam particles, in which the reactive component, for example polyisocyanates, is absorbed into the foam and the mixture is then reacted with other reactants, for example polyols, polyamines 20 or diamine vapors. , JP Patent Publication 50-103,571, FR Patent Publication 1,587,855 or 1,574,789, DE Application Publication 2,131,206 or U.S. Patent No. 2,955,056.

It is also possible to treat the foams with a swellable liquid and then to allow the polyurethane reaction components to act, whereby hardening and stiffening of the foam is possible and consequently r is stored in the expanded foam matrix (see, e.g., FR 1 341 717, 1 587). and 1,574,789 and DE 1 911 645). Such matrix foams still have typical foam properties, although other types of hardness, elasticity, chemical or mechanical properties are also present.

A number of other patents describe the gluing or compression of foam plastic particles (preferably soft polyurethane foam waste particles) by means of polyisocyanates, NCO prepolymers, polyols, polyamines, water or other reactants, cellulose fiber, possibly with the addition of a cap, substances, pigments, metal powders or soot, into novel composite materials which may be provided with or welded to coatings or films or metal sheets. Such composite materials are used, for example, as insulation boards, linings, mattresses 10 or moldings. Similar methods are described, for example, in DE-A-2 940 260, GB-A-1 337 413, DE-A-3 213 610, GB-A-1 540 076, US-A-4 254 177, DE-A-2 908 161, DE-A-2 908 161, -15 in 3,120,121 and JP Patent Publication 57/028,180.

However, to date, only the production of composite block foam from comminuted polyurethane foam, from 10 to 20% by weight of isocyanate compounds, up to about 10% by weight of fillers and small amounts of water has gained technical significance. The filler then consists mainly of color pigments to impart a uniform color to the composite foam, which may consist of foam plastic cartridges of different colors. The water used in the manufacture of the composite cellular felt as a reactant causes the polyisocyanate groups to be converted to polyurea groups to form carbon dioxide. The amount of water is then chosen to correspond approximately to the stoichiometric amount required for the isocyanate; however, at most only a relatively small excess of water is present, as otherwise there will be difficulties in removing moisture from the 40-60 cm thick composite ingots.

However, according to the invention, highly water-absorbent, preformed particulate cell plastics and / or fossil lignocellulosic substances and / or 35 carbon powders and possibly other fillers, high filler, possibly 3,89072 ionically converted polymeric masses, which swell relatively strongly in water and / or bind large amounts of water to and / or between the foam and / or filler particles so that the water absorption capacity (WAF) is at least 30% by weight, preferably t 50% by weight and at most 97% by weight (see measurement methods ) and which can be used in particular as carrier masses in biological waste water treatment.

In the context of biological wastewater treatment, many methods have been proposed to improve the decomposition efficiency and to obtain purified water that is as free of harmful substances as possible.

Thus, attempts have been made to oxidize harmful substances by supplying more oxygen to the activated sludge, as well as special oxidation methods, such as, for example, ozone or hydrogen peroxide treatment.

Catalytic oxidation of substances in wastewater with air and addition of activated carbon combined with subsequent settling has been proposed / see. for example, DE DE 2,239,406; A. Bauer et al., Chemie-Technik No. 6 (1982) 3-9; K. Fischer et al., GWF-Wasser / Abwasser, No. 2 (1981) 58-64; RE. Perrotti et al.,

Chemical Engineering Progress (CEP) 69 (No. 11) (1973) 61-64; G. Wysocki et al., ZC-Chemie-Technik, 3 (No. 6)

25 (1974) 205-208 and the 3rd report of the VCIeVrn Water and Wastewater Committee "Adsorptive Abwasserreinigung" (October 1975) .J

However, the above-mentioned methods have proved to be technically far too laborious or too expensive, or their disintegration efficiency is still unsatisfactory. Numerous attempts to use activated carbon in water treatment technology have so far failed despite improved decomposition efficiency, as activated carbon, even in its bound form (granulated), is unbearably broken and dissipated in small flows that inevitably occur in clarification tanks at least occasionally. To date, no successful attempts have been reported in which 4,89072 have used sufficiently large amounts of activated carbon and achieved sufficient binding while retaining biological activity in the clarification tanks.

DE-A-3 032 882 (EP-A-5 46 900) and DE-A-3 032 869 (EP-A-46 901) describe the use of a high porosity material with a low specific gravity (10-200 kg / m 3) for nitrification. as a carrier for thiobacteria in activated sludge treatment. These are, for example, typical poly-10 urethane foams. The use of such cellular plastic particles in a method and apparatus for biologically anaerobically treating wastewater is also described. Better results already obtained in this field are described, for example, in GWF-Wasser / Abwasser 124 (No. 5) 15 (1983) 233-239. However, such foams float in open activated sludge tanks and lead to various process disturbances. Particulate foams, which are (among others) polyurethane-based, are also recommended for use in various special processes as poured fillers (DE patent 2 839 872 and DE publication 2 550 354) or as biological filtration masses (AT patent publication 248 354) in biological waste . The use of relatively durable open-cell polyurethane urea foams with a urea-urethane ratio of <5 as a carrier for microbiologically active cells in wastewater treatment is described in U.S. Patent 4,503,150. That publication discloses a number of other related publications describing the use of foams. in biological wastewater treatment.

EP-A-77 441 describes the use of PUR cellular plastic bodies as a filtration medium from which the dirt load is occasionally removed by a special rinsing method.

The incorporation of surfactant solids into 35 microorganisms to improve their activity in biological mutation processes is also known, for example 5,89072 DE-A-2 633 259 and DE-A-2 703 834 describe the adsorption of cells to, for example, alumina, bentonite and Siedin and then Siedakla. DE-A-2 2 629 692 further describes the encapsulation of cells in photocurable polyurethanes containing photocurable acrylate double bonds.

It is also known to enclose growth cells in polyurethane hydrogels, cf. for example, Tanaka et al., et al., European Journal of Applied Microbiology and Biotechnology 7 (1979), page 371. DE-A-2 929 872 also describes a process for the treatment of hydrophilic, gel-like or foamed biocatalysts which are heavily loaded with an enzymatically active substance. by encapsulating whole cells, cell parts or enzymes in polymers by mixing an aqueous suspension of the enzymatically active substance with hydrophilic polyisocyanates to form an enzymatically highly active, hydrophilic polyurethane network in ingot or bead form. Other publications in the field are also mentioned on page 7 of said application publication. Likewise are J. Klein and M.

Klug / 'Biotechnology Letters, 3 (No. 2) (1981) 61-90, / ku encapsulated "microbial cells" in PUR matrices, such as PUR foams or PUR gels. However, the preparation of polyurethanes containing enzymatically active substances is difficult and has the disadvantage that the high reactivity of the isocyanate groups causes the death of bacteria or cells or at least partial inactivation of the enzymatically active substance. For example, residual activities of 7-48% have been determined in the examples. Thus, it is also not advantageous to include live bacteria in hydrophilic polyurethanes in their preparation if the products are to be used, for example, for wastewater treatment. The number of bacteria to be incorporated into the pulps is limited, in addition the majority of bacteria 6 89072 are deactivated due to isocyanate reactions and the continuous production and "survival" of active bacterial polyurethane pulps clarification tanks. A dramatic decrease in bacterial growth ability was observed even with local direct incorporation in the treatment plant, as the bacteria survive for only 10 short periods of time upon immobilization.

Thus, the problem to be solved was to further develop methods for producing new types of carrier materials that are better suited to new, economical and efficient methods for wastewater treatment.

It is therefore also an object of the invention to provide water-absorbent, water-non-floating, high-filler polymeric carrier masses which can be used in biological wastewater treatment as biomass carriers.

This object was achieved by developing the method according to the invention, which will be described in more detail below.

The invention relates to a process for the preparation of polymer-bonded carrier compositions containing fillers, which process is characterized by mixing A) fillers based on preformed particulate or powdered foams and / or fossil lignocellulose powders and / or optionally carbon-free powders. - 30 or organic fillers and / or possibly living and / or dead biological cell material in an amount of 30-97% by weight of the sum of A) and B), B) non-ionic hydrophilic, anionic or cationic aqueous substances, coagulable and film-forming polymer dispersions with a solids content of 3 to 60% by weight, optionally with 7,89072 C) of water, so that the total water content is 20 to 90% by weight of all ingredients, and optionally with the addition of D) other additives. and excipients 5 and then subjecting the polymer dispersion coagulate.

The invention also relates to polymer-bonded carrier masses containing fillers obtained by this method.

The invention also relates to the use of filler-containing, polymer-bound carrier masses obtained by this process as carriers for the biomass incorporated or growing therein in biological wastewater treatment, as carriers in biological fermentation processes in biological fermentation processes, as plant growth media 15 or for finely divided oilseeds and / or .

Fillers A are an essential component of the water-absorbent polymeric carrier masses according to the invention and the interaction between the fillers and the polymeric carrier mass 20 provides an unexpectedly high water absorption capacity and also a strong disintegrating effect when using the carrier masses according to the invention. Either polymers and / or (preferably) hydrophilic or cellular fillers (e.g. lignite or black peat and / or PUR foams) provide a hydrophilicity, i.e. a water absorption capacity of the carrier corresponding to said water absorption values.

Suitable fillers A) are, for example, cellular plastics.

Examples are polymers or copolymers of ethylene, styrene, acrylonitrile, (methyl) butadiene and other vinyl compounds. Thus, for example, blown polystyrene granules, expanded polyethylene or polymer-based cellular waste are suitable.

However, these excipients are less preferred and are in any case used as blend components alongside the preferred β 89072 excipients A). Preferred fillers A) include, for example, preformed polyurethane foam particles or (semi-) hard polyurethane foam granules or powders.

5 From an economic point of view, the use of cellular plastics, in particular PUR soft cellular plastic waste, which inevitably generates huge quantities, is of particular interest. These PUR foams, which are preferably polyether-based, can be used as inexpensive, irregular, lumpy granules ranging in size from a few millimeters to several centimeters and also as mixtures of foams of different densities as a filler which is bonded to anionic polyurethane. The PU matrix preferably includes PUR foam particles having densities of about 10-110 kg / m 2. Soft PUR foams are used in particular in unit form, while hard, brittle polyurethane particles are preferably used ground. Surprisingly, however, even soft waste cell plastic-20 flakes with an average density of less than 50 kg / m 2 in the bound form according to the invention are excellently suitable carriers for growing biomasses. Upon bonding, the on-cavity spaces of the foam are filled substantially or at least partially with the polymer matrix and thus the density and mechanical strength increase sufficiently so that the foam flakes are no longer Floating and are also permanently resistant to mechanical stresses in water.

Other fillers A) which can be used alone or possibly in combination with foam fillers are, for example, natural substances containing fossil lignocellulosic substances or their derivatives, such as in particular lignite. Due to their high water absorption capacity, they also provide carriers that absorb water well. Rus-35 carbon is a very particularly preferred hydrophilically active filler and is particularly preferred for use, with lignite preferably being used as the sole filler or in combination with polyurethane foam particles and possibly other fillers.

Lignite has the ability to hydrophilically bind large amounts of water without these materials feeling wet and thus can bind, for example, more than 150% water based on lignite dry matter. In addition, lignite provides favorable topological conditions for the production of porous carrier masses which are particularly suitable for use as carriers in biological wastewater treatment.

Lignite obtained from fossil deposits, for example from the Aachener lignite region, generally contains about 60% by weight of water. This aqueous lignite can be used as it is when cationic polymer dispersions are used as component B); only when using anionic polymer dispersions is it often advisable to reduce the water content of lignite before using it as a filler, as this drying provides the often desired reduction in the concentration of water-soluble constituents which are detrimental to the use of anionic polymer dispersions.

The simplest way to achieve this is to dry the aqueous lignite and vigorously reduce its water content to at least less than 20% by weight, preferably less than 10% by weight. As the natural moisture content decreases and the drying temperature and drying time increase, molecular size-enhancing transformation or condensation reactions occur during heat treatment, greatly reducing the water solubility of humic acids and reducing the browning of water in which the lignite sample is suspended.

After this drying, lignite is substantially more suitable and therefore particularly advantageous as a filler for the preferred use according to the invention for polyurethane urea carrier masses used in an aqueous environment.

ίο 89072

Another method for reducing the proportion of lignite-soluble compounds is chemical treatment, for example with excess isocyanate compounds. Possibly even more or less moist brown carbon-containing hydrogen atom reactive groups react with di- and polyisocyanates, which may be monomeric or polymeric, in the same way as increasing the molecular size and at the same time coating with polyurea in the presence of residual moisture upon release of carbon dioxide. Both of these methods, the dehumidifying or dehumidifying heat treatment and the lignite polyisocyanate treatment, can be combined in their simplest form directly in the production of polymeric carrier masses.

However, it has been found that carriers containing lignite bound with anionic polymers are suitable as bacterial carriers for wastewater treatment, even when they are initially briefly extracted with water-soluble residues, for example humic acid impurities strongly, especially with increasing impurity content, that the soluble constituents, if they come from lignite, are not detectable in the water leaving the biological treatment step, even in the initial stage after the addition of the carrier masses.

Peat is also in principle suitable as filler A) in connection with the invention. However, peat is known to contain significantly higher amounts of water-soluble constituents than lignite, which may stain water even dark brown. Therefore, the use of the above measures is particularly necessary to greatly reduce solubility, especially if the product is to be used advantageously as a carrier. in microbial change processes.

11 89072

Black peat is in principle better suited than white peat. In the pre-heat treatment, most of the water is removed from the black peat containing up to 80% by weight (of natural starting material) / so that the residual moisture is as clearly as possible less than 20% by weight, preferably less than 10% by weight of the total. The conversion of polyurea with a large proportion of dehydrated peat with low or high molecular weight di- or polyisocyanates at temperatures of, for example, 70-110 ° C further reduces the proportion of water-soluble constituents. Preferably, aromatic di- and polyisocyanates are used in amounts such that 0.5 to 2.5 kg of black peat, based on dry weight, is reacted per equivalent of isocyanate (i.e. 42 g of isocyanate groups).

In the case of interfering anionic groups, black peat is used in the process according to the invention for the preparation of anionic polymeric carrier masses, preferably in this modified form. However, it is possible to deviate from this if polyurethane ureas are to be used, for example, as a seed substrate for growing seedlings for horticulture. In this context, the extraction of water-soluble compounds from peat is irrelevant. Even less suitable white peat can be used for this purpose, despite the higher concentration of water-soluble compounds compared to black peat.

Other filler components A) are, for example, other carbons, such as coal, charcoal, activated carbon or lignite coke, which are used as powdered and preferably blended components together with the above-mentioned cellular plastic fillers and / or fossil lignocellulosic fillers. In principle, however, it is possible to use the latter excipients alone as component A), although this is less advantageous and does not lead to the best possible effect obtainable according to the invention.

12 89072

Other suitable excipients A) or excipient components are, for example, distillation residues from the distillation of tolylene diisocyanate, which are obtained, for example, by passing the distillation residues into water, whereby denaturation takes place and then the product is granulated. These TDI residues can possibly still be subsequently converted by treatment with compounds containing reactive hydrogen atoms, such as ammonia, polyols or polyamino compounds. They often still contain small amounts of NCO groups or reactive conversion products of isocyanates remaining in the structure, which can react with biomass or degradable compounds. Such distillation residues are described, for example, in DE-A-2 846 814, 2 846 809 and 2 846 815.

Other distillation residues, for example high-melting distillation residues obtained in the distillation processes of amines, phenols or caprolactam, are in principle suitable as fillers A) for use according to the invention, in particular as components to be mixed with the preferred fillers A).

Also inorganic fillers such as quartz, sea sand, burnt silica (Aerosil), silicates, aluminosilicates, bentonite, alumina, pumice and water glass, but also calcium oxide, calcium carbonate, barite and iron, gypsum, iron or iron (III) oxide, barium ferrite, iron powder or 7-Fe 2 O 2 in pigment form are used in special embodiments in addition to possibly fossil lignocellulosic substances and / or cellular plastic fillers and / or carbonaceous fillers in order to adjust the specific gravity of the carriers to such an extent that sink to the bottom or swim below the surface (in the fluidized state) in the liquid to be clarified, but in no case do Float. Particularly finely divided inorganic fillers (e.g., those with a primary particle size of less than 10 microns and a large surface area, e.g., Aerosil and iron 89072 oxide, especially magnetite inevitably obtained in the production of iron oxide) promote oxygen transfer to activated sludge bacteria when present in the carriers of the invention. and thus improve the disintegration efficiency or disintegration-5 effect; the metal oxides apparently have a particularly favorable, specific oxygen transfer effect and thus produce favorable decomposition phenomena according to the invention. Fibers (e.g. inorganic fibers), such as glass fibers 10 or natural or synthetic fibers (e.g. cotton wool) can also be used as additional modifying fillers.

The average particle size of the fillers is generally from 0.1 to 1000 [mu] m, preferably less than 300 [mu] m, particularly preferably less than 100 [mu] m, the activated carbon and inorganic constituents as well as coal powder or charcoal powder in particular having a smaller particle size than, for example, peat or lignite. , which may optionally include fibrous portions of several mm in length.

The size limit does not apply to so-20 foam pieces used as filler. For this purpose, cellular plastic pieces of a few mm (for example 1-40, preferably 2-20 mm) or even PUR cell plastic sheets with a thickness of about 2-10 mm can be enclosed in the polyurethane (urea) matrix.

The total proportion of fillers in the compositions used according to the invention should be at least 30% by weight: and preferably more than 50% by weight and often more than 75% by weight; the upper limit is 97% by weight, preferably 95% by weight. These: percentages are calculated from the dry matter of components A) and B). Values close to the lower limit of the concentration range are only achieved in exceptional cases, in particular when using extremely light and high-volume fillers. The upper limit is generally determined by the cohesion and abrasion resistance of the carrier masses according to the invention. In extreme cases, it is possible; The list 35 increases the proportion of filler to as much as 97% by weight if a solid bed arrangement is used in connection with the biological wastewater treatment of 14,89072 carrier masses in accordance with the invention.

Particularly preferred are polymeric carrier compositions containing filler combinations of fossil lignocellulosic materials, in particular lignite pulp and / or carbon powder and / or PUR foams (preferably soft PUR foams). Preferred properties are provided by a combination of polyurethane cellular-10 green particles and lignite. In addition to the preferred types of fillers mentioned, fillers to be used, such as inorganic fillers or distillation residues and other fillers already mentioned, are used, with the exception of ferromagnetic fillers, preferably 15 <35% by weight, in particular <20% by weight.

The mixing ratio of the foam particles and the preferred lignite may be desired, however, the mixing ratio is preferably 1; 10 to 10; 1, particularly preferably 1: 5 to 5: 1.

The fillers are mixed into the polymer matrix according to various embodiments, described in more detail below.

The incorporation of microorganisms "in situ" into polyurethane or other plastics is not possible, as already mentioned, even under quite economical and technically difficult conditions, without the substantial disappearance of reproductive bacteria and a sharp reduction in biological activity. The manufacturing conditions must then be adjusted to suit the temperature (approx. + 10 ° C). Nevertheless, this method, which is possible in special cases, is not advantageous and in most cases not necessary, since biomasses grow excellently in polymeric carrier masses containing cellular plastic and lignite or peat.

Suitable polymer dispersions B) are, in principle, the desired plastic dispersions which can be coagulated by adding and / or heating a coagulant, i.e.

89072 Aqueous dispersions of polymers prepared by polymerisation, polycondensation or polyaddition, whereby the dispersibility of the polymers in water can be effected by means of either non-ionic, anionic or cationic emulsifiers, which in turn may be in the form of internal emulsifiers or internal emulsifiers not incorporated into the polymer. in the form of emulsifiers. The solids content of the aqueous dispersions is generally from 3 to 60% by weight, preferably from 25 to 55% by weight.

Particularly suitable are dispersions of polymers of olefinically unsaturated monomers or aqueous dispersions of polyurethanes. Natural non-latexes, for example natural rubber latexes, can also be used. Suitable polymer dispersions or latexes generally have an average diameter of 0.01 to 10 [mu] m, preferably less than 3 [mu] m and in particular less than 1 [mu] m. This means that rather fine latexes prepared by emulsion polymerization are more advantageous than polymer dispersions prepared by suspension or bead polymerization. In any case, the particle diameter of the primary particle agglomerates is a multiple.

With regard to the preparation of polymer dispersions suitable according to the invention, reference should be made to the known methods described, for example, in Houben-Weyl, Macromolecular Stoffe, Part XIV / 1. Suitable starting materials for the preparation of the polymer dispersions according to the invention are the customary olefinically unsaturated monomers, for example vinyl compounds, such as styrene, acrylonitrile, methacrylonitrile, acrylic acid, acrylic acid, methacrylic acid, (meth) acrylic acid, (meth) acrylic acid, esters, , vinyl acetate, vinylpyridine or maleic acid half esters. Preferred divinyl compounds are buta-1,3-diene, 2-methyl-butyl-1,3-diene (isoprene), 2,3-dimethylbuta-1,3-1,89072 diene, 2-chlorobutadiene (chloroprene) and p- divinyl-benzene.

Preferred polymer dispersions include polymer dispersions that form flexible films, while dispersions that dry into hard and brittle films are generally only suitable as blend components. Of particular interest are, for example, styrene-butadiene latexes prepared by emulsion polymerization, latexes prepared from butadiene, acrylonitrile and methacrylic acid, which dispersions can be optionally modified with polymerized acrylic or methacrylic acid esters, which may contain alcohol moieties formed by partial saponification, synthetic polyisoprene-15 latexes and natural rubber latex. Other suitable polymer dispersions include, for example, known polychloroprene latexes. Particularly preferred are the corresponding cationic-converted latexes, since they have the effect of fixing the soluble constituents present in lignite or peat. Such cationic latexes are obtained, for example, by using among the monomers compounds containing tertiary nitrogen atoms which can be converted into cationic groups before, during or after the polymerization reaction, for example by neutralization with a suitable acid such as hydrochloric acid, sulfuric acid or phosphoric acid or quaternizing. dimetyylisulfaatil-la. Polymer dispersions with anionic centers incorporated in the structure can be obtained, for example, by using a number of carboxyl group or carboxylate group-containing monomers, whereby any carboxyl groups present are neutralized with bases such as sodium or potassium hydroxide or triethylamine during polymerization. Possible external emulsifiers present are, for example, fatty acids, rosin soaps, sulphates or sulphonates with a long hydrophobic hydrocarbon chain, paraffin amine-based ammonium salts, fatty acids of paraffin fatty acids and esters of paraffin fatty acids or amino alcohols such as dimethylaminoethanol, such as dimethylaminoethanol. poly-glycol ethers.

Aqueous dispersions of polyurethanes can also be used instead of or in combination with the polymer dispersions mentioned as examples. Equally non-ionic hydrophilic as well as cationic or anionic converted polyurethane dispersions can be used, preferably using polyurethane dispersions which in each case contain the respective "mulchers" in chemically incorporated form.

The preparation of suitable aqueous polyurethane dispersions is known and is described, for example, in Die Angewandte Makromolekulare Chemie 98 (1981) 133-165 and Progress in Organic Coatings 9 (1981) 281-340. Particularly preferred are cationically converted polyethylene-20-polyurethane dispersions, especially when fossil lignocellulosic materials are used as fillers. Polyurethane dispersions containing ester groups are less preferred due to their sensitivity to hydrolysis. Aqueous dispersions of branched polyurethanes in the form of sedimentable and redispersible aqueous suspensions are often preferred.

Aqueous dispersions of polyurethanes can also be prepared by mixing an optionally ionized NCO prepolymer with water, optionally incorporating an optionally ionized chain extender, for example a diamine such as ethylenediamine, hexamethylenediamine (hexamethylenediamine) or 4,4'-diamino or the sodium salt of N- (2-aminoethyl) -2-aminoethanesulfonic acid 35 (anionized diamine), so that the formation of the polyurethane dispersion results in chain elongation ie 89072 (which could also occur when water alone is used to form urea).

The NCO-free dispersion thus prepared can be used directly after its preparation or after intermediate storage of the desired length in the process according to the invention.

Preferred dispersions of crosslinked polyurethanes used as component B) in the process according to the invention contain dispersed particles with an average particle diameter of 0.5 to 3 [mu] m, the dispersions sedimenting on standing for several days, but are easily redispersible and form, for example, when applied to a glass plate. films.

In principle, it can be said that in the selection of a polymer dispersion, those dispersions which form flexible films are preferred, while those which form brittle or rather hard films can be used only as blend components in addition to the preferred types mentioned. Particularly preferred polymer dispersions form films with a Shore A hardness of less than 98, preferably less than 95 and particularly preferably less than 90.

Other possible components C) include water which is optionally added to the system to adjust the water content of the mixtures of A) and B) to 20-90% by weight, preferably 30-80% by weight and in particular 35% by weight. -65% by weight. Water is of particular importance for the method according to the invention. Not only does it allow fine distribution of the polymers, but it is also a necessary suspending and / or emulsifying agent for fillers A and possibly other additives D. Since the optimal water content of each mixture depends on many factors, the quality of the ingredients and their proportions, it is very useful to determine ve-35 content by preliminary tests. When too much water is used, coagulation becomes difficult and leaching out of the polymer dispersions 19,89072 is often inevitable. When the amount of water is too small, the fillers do not bind evenly and wear-resistant during subsequent gelation and coagulation.

Other excipients and additives D) which may be used are, in particular, stabilizers and / or crosslinking agents. These include, for example, known rubber auxiliaries which can be used for crosslinking, such as zinc oxide and / or sulfur, as well as anti-aging agents to avoid self-oxidation by heat and light in the presence of oxygen. Suitable anti-aging agents are, for example, phenolic compounds, aromatic amines or iminothiazoles, such as o-tert-butylphenol, metal salts of phenolthioethers, N-phenyl-2-aminonaphthalene, phenothiazine and tert-butylpyrocatechol or 5-benzylidene o-phenyl-iminotiatsolidoni- (4).

Among the possible excipients D) are, in particular, organic polyisocyanates, which in the context of the invention include the customary small-molecular polyisocyanates, such as, for example, 2,4- and / or 2,6-diisocyanate toluene, 4,4'-diisocyanate-diphenylmethane, liquid derivatives of this diisocyanate, polyisocyanate mixtures of the diphenylmethane series 25 (phosgenation products of aniline / formaldehyde condensates) including their bottoms, as well as simple diisocyanates and polyhydroxyl compounds of the type exemplified above, 6,000f NCO prepolymers. Polyester polyols known in polyurethane chemistry and in particular polyether polyols in said molecular weight range are preferably used for the preparation of NCO prepolymers, the corresponding diols being preferably used as blend components in addition to polyvalent polyols. Tri- and polyfunctional polyols are used alone or in admixture with difunctional polyols to adjust the overall functionality of NCo prepolymers so that the NCO functionality is 2.1 to 3.5, preferably 2.2 to 2.8. as polyether-5 polyols, compounds known per se in the field of polyurethane chemistry are used. Particularly preferred are the corresponding polyether polyols which have been prepared using ethylene oxide and / or propylene oxide as a mixture or in the desired order. It is also often preferred to use hydrophilically converted NCO prepolymers. These can be either non-ionic hydrophilized prepolymers with a high concentration of ethylene oxide units placed in the polyether chain or centers that can be converted into centers. Such polyhydroxyl compounds include, for example, amino polyethers obtained by alkoxylation of nitrogen-containing starting molecules, for example alkoxylation products of N-methyldiethanolamine, ethanolamine, aniline or ethylenediamine, or carboxylic acid carbons or sulfones of the species mentioned in U.S. Pat. No. 4,108,814. polyhydric alcohols containing silyl groups, such as tartaric acid or dimethylolpropionic acid or their alkali metal salts. When using tertiary nitrogen atom-containing polyhydroxyl compounds for the preparation of NCO prepolymers 30, the conversion of tertiary nitrogen atoms to ammonium groups can be done, for example, by subsequent quaternization, while the conversion of any carboxyl groups present to the carboxylate groups can be done after bases, e.g.

21 89072

The (average) functionality of the polyisocyanates which may be used is at least 2, preferably at least 2.1 and in particular at least 2.5. In the preferred use of NCO polymers, these have an NCO content of 2 to 12% by weight, preferably 2.5 to 8% by weight.

Under certain conditions, all the starting material components required for the preparation of NCO prepolymers can also be used directly in connection with the completely continuous production of the filler-containing carrier masses according to the invention, i.e. separate preparation and intermediate storage of NCO prepolymers are not necessary. In the context of this "in situ" preparation of prepolymers, it has proved sufficient that, in particular, small or high molecular weight polyols, in particular the preferred polyether polyols and, if appropriate, the addition of acidic hydrogen-containing chain extenders, are reacted extensively in a flow-through mixer. - and polyisocyanates for a short time, for example for only about 10-60 seconds, at an elevated temperature of 50-120 ° C, preferably 80-100 ° C.

When the isocyanate content after this short time is less than 50%, preferably less than 25% higher than the concentration calculated for the NCO prepolymer reaction, incomplete formation of NCO prepolymers does not adversely affect the properties of the carrier masses made therefrom and is of great advantage, especially when , when NCO prepolymers with limited shelf life or with a strong increase in viscosity during storage must be used. Such NCO-30 prepolymers are, for example, those which contain in their structure a number of compounds containing tertiary amino groups, for example di- or triols containing a tertiary amine.

Exemplary polyisocyanates, when present, are used in an amount of up to 25%, preferably up to 15% by weight of the total dry matter of components A) and B). In this connection, however, it must be emphasized that the use of fossil lignocellulose powders, in particular peat and / or lignite powders together with the ion-5 modified polymer dispersions used as component B) as component B) completely eliminate the use of nonionic or cationic NCO prepolymers or use only small amounts of low molecular weight di- and / or trifunctional polyisocyanates. Organic polyisocyanates, unless they are water-dispersible, are emulsified in a polymer dispersion or, if they contain hydrophilic centers, are preferably used as an aqueous emulsion.

When ionized polymer dispersions B) and ionized polyisocyanates, in particular NCO prepolymers, are used, it is not absolutely necessary for these feedstocks to be charged in the same ionic form. Thus, for example, it is possible to combine anionic polymer dispersions with cationic NCO prepolymers or vice versa so that an ampholytic 20 is formed or the cationic NCO prepolymer acts as a dispersion coagulation agent.

To carry out the process according to the invention, components A) and B) and optionally C) and D) are mixed together at a temperature of 10-70 ° C, preferably 20-40 ° C, using fillers containing acidic groups, for example lignite containing humic acids or humic acid peat is preferably used among tertiary nitrogen-containing polyisocyanates to remove or reduce the water solubility of humic acids through the formation of humates. In connection with this procedure, anionically converted polymer dispersions are preferably used as component B). The dry matter content of the mixtures resulting from the thorough mixing of the starting materials is preferably between 35 and 120 kg / m 2 in the case of cellular plastics and 150-350 kg / m 3 of suspension without foams. If particularly heavy fillers such as magnetite are used, these values are relatively small in mixtures containing preformed foam particles, but without cellular plastic they are up to about 400 kg / m of suspension. However, in many applications, for example in the context of biological wastewater treatment, the carrier masses must be moved or maintained, at least from time to time. Therefore, such particularly heavy fillers with a dry matter content of more than 150 kg / m of suspension must be used in the form of relatively fine particles, preferably with a particle diameter of less than 5 mm or preferably less than 2 mm.

After mixing, coagulation of the polymer dispersion B) follows. This is a complex colloid-chemical event involving many factors and which takes place more or less rapidly in several stages. Coagulation can be carried out either at room temperature by the addition of a suitable coagulation aid or by the use of thermolabile dispersions B) by heat treatment at 40-100 ° C , preferably at 60-100 ° C.

Suitable coagulation aids (flocculants or coagulants) in the case of the use of ionically modified dispersions are electrolytes which are introduced into the mixtures preferably in dilute, i.e. aqueous solutions containing 0.5 to 5, preferably 1-2% by weight of electrolyte. Suitable electrolytes are, for example, sodium chloride, magnesium chloride, magnesium sulphate, calcium chloride or trisodium phosphate. Highly diluted mineral acids, such as sulfuric, nitric or hydrochloric acid, or also carboxylic acids, such as acetic or formic acid, are also suitable as flocculants. It is also suitable to add possibly more concentrated, about 10-30% by weight, oppositely charged polymers at the end of the preparation of the mixtures, resulting in carrier compositions of the ampholytic nature according to the invention. Often it is also expedient to carry out the coagulation both by adding a flocculant and also by using a heat treatment.

24 89072

Surprisingly, nonionic, low or high molecular weight polyisocyanates also have a beneficial effect on coagulation, especially in the case of anionic polymer dispersions, so that often already at room temperature or at slightly elevated temperature results in well-controlled gradual gelation and coagulation with conventional coagulation. in the absence of.

When heat treatment is used to coagulate heat-sensitive dispersions, this can be done, for example, in a heat cabinet, possibly under reduced pressure, at a temperature of 80-100 ° C or in a hot air duct at 60-100 ° C, preferably 85-97 ° C, with some or almost perfectly. A special type of heat-15 coagulation is treatment with IR or microwave radiation. When microwaves are used, finely divided polymer dispersions in the fillers often change into water-insoluble films in 20-60 seconds, which bind the fillers in a wear-resistant manner. Polymeric carriers with a relatively low specific gravity, such as those obtained using preformed PUR foam granules, can be cycloneed by hot air to complete products with low residual moisture to complete coagulation and possibly separate certain particle sizes by wind separation.

During coagulation, the mixture only needs to be mixed moderately unless porous foam particles are used as filler A). Preferably, the agitation of the mixture should be stopped completely during coagulation so as not to leave any primary filler particles that are not coated with the coagulable dispersion. Only in the case of the use of open-cell foams is this fact less decisive, and coagulation can then surprisingly be carried out even with vigorous stirring of the mixture, so that the cellular particles do not stick to each other.

25 89072

However, the sudden coagulation of the dispersion should particularly preferably be carried out with the whole mixture in place, in which case care must be taken to ensure that the aqueous filler is pre-distributed evenly.

In order to effect coagulation, the flocculant is thoroughly mixed with the mixture of components A) and B) and possibly C) and D) in the case of ionic coagulation, after which, with the exception mentioned above, the reaction mixture is left to stand unmixed. Depending on the type of polymer dispersion, filler and flocculant, the coagulation takes place within 30 seconds to 10 minutes of the addition of the flocculant and can, if desired, be accelerated by simultaneous heat treatment, if already mentioned. In the case of the use of the above-mentioned ionic NCO prepolymers, which prepolymers have a different brand charge than the polymer dispersion B), such ionic prepolymers are preferably added to A) and B) and possibly C) and After preparation of the mixture of D) (with the exception of said prepolymers), the crosslinking of the polymer dispersion due to the ionic charge results in a particularly rapid coagulation of the polymer dispersion due to the crosslinking of the prepolymers and water (resulting in the formation of polyureas). If the polymers contain groups containing acidic hydrogen atoms, the polyurethane urea can be attached to the polymer even through homeopolar bonds.

The preparation of the mixtures of components A), B) and possibly C) and D) and also the mixing of the flocculant is carried out in mixing devices of the desired type, for example in a screw conveyor device or using a mixer or mixers equipped with au-30 blades. After coagulation, the carrier masses according to the invention. . precipitate in lumps or granules and can be further mechanically comminuted if desired. It is often appropriate to remove any io-35 coagulation aid used in the group by washing the resulting carrier 26,89072 with water if this excipient could affect the storage stability or interfere with subsequent use.

The method according to the invention can be carried out either continuously or discontinuously.

A very specific process for the preparation of the carrier masses according to the invention, which can be used using soft foams as component A), is a process in which the mixture, optionally together with a coagulation aid, is pressed into a suitable device, e.g. a box-shaped metal container. to a fraction of its pour volume and coagulation is carried out under pressure and possibly by heating a carrier mass according to the invention of predetermined dimensions and density in such a way.

This method is of particular interest when particularly light polyurethane ingots are used as component A). Using foaming waste with a density of 25 kg / m 3 as a starting material, composite foams with a 6 to 10-fold increased density can be prepared in this way, using for example only 15% by weight of polymer dispersion (based on solids). The extruded molded plastics can be cut into layers or films of the desired thickness or comminuted in a cut to the desired size.

The preparation of the carrier masses according to the invention without the use of foams as component A) or as part of component A) results, as already mentioned, in significantly higher specific gravity carriers.

The dry matter content (TS) of the aqueous suspensions of polymeric carrier masses at a degree of filling of 100% by volume (without additional water) is about 40-350 kg / m 2. * The aqueous suspensions of the pulp types 3 prepared using cellular plastics preferably have a dry matter content of 40-95 kg / m - 35-350 kg / m of 35 types of non-plastic cells, excluding those containing peat. Savings of starting materials 27 89072 (with the same suspension volume), multiple growth surface of microorganisms and easily controlled and desired use in solid, fluid or vortex layer As mentioned above, the density of the carrier masses according to the invention varies over a wide range depending on the type and proportions of the starting materials, their water content, the possible compression ratio described above and the above-mentioned 10% excipient-containing carrier masses with a well-formed open-cell structure. and in particular according to the specific weight of the fillers A) used and corresponding to an average water content of 50% by weight 3, generally a pour weight of 300-700, preferably 400-550 kg / m 3. The water absorption capacity of the carrier masses (WAF, described below in connection with the examples) is 30-97% by weight of water based on the total dry weight, preferably more than 85% by weight. In general, the average particle size of the product obtained in unit or granular form depends on the particle size of the fillers A) used and the formation of agglomerates during the mixing 20 and is 1-10 mm, preferably less than 5 mm, unless foams are used as filler. The formation of agglomerates can be largely avoided by rapidly coating the fillers with a polymer dispersion. Correspondingly lighter polymeric strains containing preformed foams can also be prepared and used as substantially larger particles. The fillers, in particular the preferred foams, are in a completely altered form in the carrier masses according to the invention with respect to their original structure and physical properties. The coagulation of the polymers according to the invention from the aqueous phase substantially strengthens the cellular structure of the PUR foams used, preferably soft-flexible, as is clearly shown in the electroscopic images. The coagulated polymers cover the cell walls of the foam and thus become an integral part of the foam, binding in the same matrix-like, wear-resistant manner 28 B9072 preferably used fillers, such as lignite, so that the cell cavities are reduced or partially filled but remain very flexible. times the foam used in ver-5. The unusable, floating waste cell plastics thus become slowly settling carrier masses in water, with improved specific strength and relatively high water absorption capacity, and with accessible growth surfaces and protective cavities for microorganisms.

In order to control the specific gravity, inorganic fillers in very fine form can also be used in the production of these high-fill polyurethane (urea) pulps, which can be used to adjust the specific gravity to the level required by the clarification solution and possibly promote oxygen transfer to bacteria.

The water-swollen, hydrophilic carriers according to the invention are, in their preferred forms, soft-elastic, predominantly dry-feeling, abrasion-resistant particles which are suspended in water and float therein (floating) or preferably settle slowly to the bottom.

It was not foreseeable that many excipients, such as lignite and possibly cellular plastics, as carrier polymers with highly hydrophilic properties, homogeneous or cellular structure and sufficient abrasion resistance, and such a beneficial effect on biological purification could be prepared, although active excipients , such as lignite, are enclosed in a polymer matrix acting as a closed matrix, and the bacterial biomass first appears in the outer, coherent aqueous phase and only then grows from the outside inwards.

The carriers used according to the invention are suitable for most biological, aerobic or 29,89072 anaerobic, wastewater treatment methods and for both industrial and municipal treatment plants.

The literature describes the use of polyurethane-based soft foams as a carrier in biological waste-5 water treatment processes. However, it has been found that lightweight foams 3, usually with a density of 15-35 kg / m 3, which are commercially available as foam waste, cannot in any case be successfully used alone as carriers in activated sludge tanks. Such foams are always permitted, leading to blockages and other operational difficulties in treatment plants. Soft polyurethane foams 3, which have a relatively high density of about 90 kg / m 3, are somewhat more advantageous, but still float to a large extent on the surface of the clarification pool after months (see comparative example). Depending on the respective layer thickness of the foam, they also lead to blockages in the outlet or even exit with the water leaving the pool. Such surface-floating foams are very inefficient for biomass and cause insurmountable technical difficulties. There is also no advantage in adding activated carbon to the foams even when they are pre-pressed into the foam mechanically.

The biological conversion of organic contaminants in reproductive bacterial masses consisting mainly of carbohydrates and proteins in an oxygen-consuming manner (X 1 and water and, in addition, possibly nitrate) is called aerobic wastewater treatment.

The conversion of organic impurities, preferably carbohydrates, proteins and fats, without oxygen supply by acid-forming bacteria, sulphate-reducing bacteria and methane-producing bacteria to hydrogen sulphide, carbon dioxide and in particular methane is called anaerobic wastewater treatment.

30 89072

The high-filler, water-absorbent polymeric carrier masses according to the invention provide improved biological wastewater treatment, both in situ and preferably when moved, especially surprisingly also in the case of wastewater with a relatively low concentration of harmful substances, for example less than 500 mg / l, which is very important for the final cleaning stage of the treatment plants in order to achieve a perfectly clean removable water.

The purification according to the invention can therefore be carried out in the first and / or subsequent other activated sludge steps by feeding the carrier to the desired locations in one or more combined activated sludge tanks. Since the polymeric masses 15 according to the invention used as carriers are quite wear-resistant in water, despite the relatively small proportion of polymers, they can be used both in tanks with high mixing and in tanks using stationary or sparsely movable active slurries, i.

20 filler-rich polymeric carrier masses, can be used in fluidized bed, vortex and fixed bed arrangements.

The supply of air and / or (pure) oxygen results in considerable mixing in a widely used aerobic purification process. Thus, the high-filler polymeric carrier masses and the activated sludge are kept in a vigorous motion in the so-called liquid fluidized bed. Nevertheless, a bacterial growth is formed on the surface and in part also on the interior of the high-filler polymer, which provides the surprisingly improved cleaning efficiency described in the experimental section. The filler incorporated into the polymer has a beneficial effect in many respects on the improved purification process. Depending on the type of filler and polymer matrix, the mechanical strength and hydrophilicity of the carrier 35 material are improved and, surprisingly, the biological assimilation capacity of the organic substances 31 89072 dissolved in the wastewater is substantially increased. In addition, the filler or filler mixture bound to the polymeric carrier also acts as a regulator to provide the optimum specific gravity of the water-permeable carrier of the invention, so that in conventional heavily loaded activated sludge tanks at depths of about 4-12 m it is possible to provide a carrier with a mild tendency to sink to the bottom, even distribution i.e. maintenance of the fluidized space. This is a particularly relevant or even operational technical requirement for most existing municipal or industrial 10 biological treatment plants.

On the other hand, as already mentioned, conventional, cellular, high-porosity plastics which have not been modified according to the invention, including polyurethane foams, cannot be used as efficiently or as required in many years of use in current treatment technology, as these foams, even relatively large ones, in the case of densities of 3 about 90 kg / m, they still float considerably on the surface of the clarification tanks even after months-20 and cause technical difficulties (eg blockages). The use of low-density foams 3 with a density of 20-35 kg / m (so-called waste cell plastic mixtures) has proved to be completely impractical. These foams float on the surface of the water 25 even when vigorously agitated.

As already mentioned, in a particular form, the polymeric carrier masses with fillers and possibly additives are adjusted so that they settle to the bottom immediately or in a few hours in the activated sludge tanks of the treatment plant and, despite sufficient air and oxygen permeation, form carriers with a significant amount of adhering biomass, a vortex, fluidized bed or solid bed, through which oxygen-containing gas flows, supported by a layer of water free of carrier and which can be treated with 32 89072 gases with sufficient intensity if necessary, for example to remove excess sludge intermittently or continuously. The high filler hydrophilic polymeric carrier masses used according to the invention do not migrate here either.

5 In addition to the widely used aerobic biological waste water treatment, anaerobic waste water treatment is also of great technical importance, especially in the case of high-carbohydrate waste water, for example in the food or pulp industry.

The polyurethane carrier masses prepared and used according to the invention are excellently suitable for the removal of even very high impurity concentrations, more than 25,000 mg / l, in a single wastewater treatment step or also for the removal of hitherto hardly decomposable organochlorine compounds. In some cases, combined anaerobic and erobic wastewater treatment is particularly effective. The high-filler hydrophilic carriers according to the invention can also be used advantageously for this purpose.

The degree of hydrophilicity in the high-filler polymer masses according to the invention is preferably adjusted so that strong water absorption takes place in hours or a few days, and the strong swelling or polymer masses already contain a large amount of water as a mass-distributed phase during preparation and are thus fully expanded. In the context of anaerobic clarification technology as well as aerobic waste-water treatment, the products according to the invention are able to allow the removal of larger amounts of gaseous products, such as carbonic acid, methane or hydrogen sulfide.

The incorporation of microorganisms "in situ" into polyurethane or other plastics is not, as already mentioned, practically possible in the context of biomass used for waste water treatment, even under rather economical and technically difficult conditions, without the disappearance of 33 89072 bacteria and thus a strong loss of biological activity. preferred. In the case of the use according to the invention, it is also unnecessary, since a large part of the bacterial cultures surprisingly adhere to the fully reacted, high-filler polymeric carriers surprisingly even in the fluidized bed and the bacteria can even penetrate the high-filler, highly swellable, suspended and suspended carriers. bridge from damage. The bacteria are located in the same area where the dissolved impurities are enriched through the adsorption effect of the filler-rich polymeric carriers.

The decomposition and cleaning effect of the process of the invention, i.e. the improvement of wastewater quality, is not only limited to a clear reduction in chemical oxygen demand (EQS), but also dramatically reduces toxicity to daphnia and fish through otherwise difficult to decompose or decompose towers. is at least as important. In addition, a sharp reduction in the unpleasant odor present in several treatment plants and, in addition, a clear lightening of the color of the treated water is achieved. In addition to the above, the capacity of the biological treatment plant in question can be clearly increased.

The high-filler polymeric carrier masses according to the invention, when used as carriers, improve the cleaning efficiency of the biological treatment plant in two decisive ways. The carriers 30 according to the invention not only make it possible to generally concentrate the substances contained in the effluent on the surface of the carrier, but also to enrich the effluents in a directed manner, for example chlorinated hydrocarbons, such as ethylene chloride, which cannot otherwise be used by activated sludge microorganisms. due to their dissolved form and low concentration 34,89072. The substrate concentration of such compounds thus rises to the level required for biodegradation. At the same time, the microorganisms settle on high-filler carriers and proliferate optimally due to the well-enriched substrate supply.

The adsorption surfaces of the substrates, i.e. organic compounds containing lower concentrations of wastewater, are re-released after degradation by the bacteria. Adsorption of substances dissolved in wastewater on carriers 10 with which microorganisms grow and their utilization alternates continuously. A state of equilibrium is established between the adsorption and enrichment of substances dissolved in water and the biodegradation by microorganisms settled on the surface of the support. Thus, continuous surface regeneration is achieved. Similarly, a substrate supply-dependent balance is formed between biomass growth and substance elimination in high-filler polymeric carrier masses, so that biomass activity remains consistently high on the carriers.

The carriers according to the invention make it possible to clearly increase, in most cases at least double, the activated sludge content of the biological treatment plant and thus to multiply the volume-time load, so that the capacity of the finished treatment plants increases considerably or the new plants have sufficiently smaller pool volumes.

The simple technical use of the carrier consists in addition to a conventional, biological activated sludge pool. The gas / liquid flow keeps the particles in the Lei space and evenly distributed in the activated sludge space.

30 Due to their extremely good wear resistance, high-content polyurethane carriers can also be used in activated sludge tanks with surface aerators.

The use is particularly advantageous in connection with the nitrification and denitrification of the effluent, since the microorganisms required for these purposes are slowly and advantageously growing on growing surfaces.

In the aerobic zone of wastewater treatment, these plants can operate in a fluidized bed or solid bed reactor. Flow-through in the fixed bed can take place either from the bottom up or from the top down. It is also possible to use it as a biological filter. Due to their particularly large surface area, high filler-containing, preferably cellular, polymeric carrier masses are preferably also used as growing surfaces (subsurface biological filters).

The high-filler carrier masses which can be used according to the invention have many uses in connection with wastewater treatment. As already mentioned, the plants can operate as well as the fluidized bed or vortex bed principle as well as as fixed bed plants. In the case of the solid bed process, high-filler anionic polymeric carrier masses can be used as granules or solid structures, such as in the form of rolled-up mats or preformed filling bases. Also in this connection, the flow through the solid layer can take place either from the bottom upwards or in the opposite direction. The mode of operation is usually chosen according to the quality and specific characteristics of the effluent in question.

Technical progress of the use according to the invention In addition, and in particular, Leena considers that the use of high-filler polymeric carriers and carriers can even effectively remove harmful substances from the biologically pre-treated effluent which contain a relatively large proportion of persistent organic residues, which can no longer be degraded by microorganisms in a conventional biological plant due to the degree of dilution, slow growth and the risk of leaching.

36 89072

The carriers according to the invention can also be used to purify exhaust air of organic constituents, for example exhaust air from refineries or organic compound production processes by sucking or otherwise contacting the air through a moist or wet or high-filler polymer carrier suspended in water.

For example, exhaust air (e.g. from above) and simultaneously water can be passed through one or more columns connected in series, filled with a carrier mass available according to the invention, concentrated to 50-80% by volume and optionally added for biodegradation. suitable micro-organism suspensions. Even after a delay of about 5-60 seconds 15, a strong elimination of organic impurities takes place, which after a relatively short start-up period leads to a vigorous increase of degrading microorganisms. Also in the case of this economically advantageous method, as in the case of an aqueous suspension, the adsorption and decomposition of the impurities take place simultaneously and in the same area in the presence of the liquid film on and within the carrier in the presence of a physical-biological equilibrium. Excess microorganism growth can be removed from time to time by filling the bioreactor columns 25 one or more times with water and vigorously blowing air through them.

Disposal of the carrier masses used according to the invention is unproblematic due to their inert nature. Thus, for example, in treatment plants where the excess sludge is incinerated in a fluidized bed furnace, it can be removed during years of long-term use, possibly in combination with additional activated sludge, and used in incineration as an additional energy source. In general, however, it is not necessary to change the entire carrier material.

35 Another important use is the use of these products as carriers of bacteria or enzymes in biological 37 89072 transformation processes that produce complex organic compounds. The particulate polymeric carrier masses are easily removed from the reaction or fermentation solutions by filtration, for example in the preparation of citric acid from starch, in the hydrolysis of penicillin G by acylases to 6-aminopenicillanic acid, in the preparation of stereospecific, biologically active compounds or in sugar-containing aqueous sugar.

The use of the polymeric carrier masses according to the invention, preferably containing cellular plastic and brown coal or peat, is based on their high hydrophilicity and possibly a slightly porous structure. Therefore, they can also be used as soil improvers or as a hydrophilic, special growth medium for plants with good rooting properties, as they can contain the desired nutrients, water and possibly fertilizers remain in them for a long time and can be easily expanded again.

In connection with the preparation, seeds can also be mixed into the carrier masses, which are then germinated and can be used, for example, as parsley growing plates or as polymer carrier pieces containing trout.

In addition, particulate carriers can be used in water as a filtration medium for finely divided, emulsified or suspended impurities, which can be regenerated, for example, by countercurrent rinsing. The carriers according to the invention can be used particularly effectively as adsorbents for (crude) oil or other water-insoluble organic liquids.

Examples 1. Preliminary remarks Characterization of filler-containing polymeric carrier masses: 35 To the obtained, optionally granulated carrier material, add excess water, allow to swell 38 89072 completely for 24 hours (at room temperature), mix and decant the excess water. The value obtained from this experiment, which indicates the percentage by weight of water in the expanded carrier and its intermediate spaces (filler silicon-5 in the second carrier), is referred to herein as the water absorption capacity (WAF) (see further description below).

The solids content of the aqueous suspension of granules thus prepared, which is in the form of a strongly expanded carrier material, is (for Example 1) 59.5 g of solids-10 ta / l suspension (without excess water).

The solids content per liter of such a suspension (without excess water) is called the dry matter of the suspension / abbreviated TS (S) _7 · The liter weight of a suspension (without excess water) of such a strongly expanded carrier 15 is called the weight of the suspension (abbreviated SG).

The liter weight (SG) of the suspension and the carrier dry mass (TS-S) it contains give the so-called suspension factor (F4). The value of the suspension factor (F4) minus 1 (F4-1) indicates the multiple amount of water (calculated on the basis of dry matter) the suspension contains in total (as swelling water and / or as water inside or between the carrier particles).

The suspension factor is determined in practice by determining the carrier dry mass per liter of aqueous carrier suspension (without excess water) and dividing the weight of the suspension (SG) by the weight of the carrier dry mass contained therein (TS (S) 7:30 F4 = TS1S). Characteristic water absorption (WAF) of the carrier masses according to the following formula: 39 89072 WAF = F4-Fj- -1- X 100 (%) This water absorption value (WAF) (% by weight) gives an illustrative picture of the strongly expanded carrier mass, possibly with water-absorbing intermediate spaces. from the space when using the mass expanded in the treatment plant. Example 1 has a dry matter content per liter of suspension, which does not contain excess water, 59.5 g solids. With a suspension weight of 1,001 g / l, the suspension is obtained from the suspension factor F4 = 1,001 / 59.5 = 16.8. One part by weight of the dry matter of the carrier mass thus gives the expanded suspension described with 15.8 times the amount of water.

In other words, the water absorption capacity is 15.8 / 16.8 x 100 = 94%.

51. Dump weight, drained: 15 The carrier mass is kept suspended in a large excess of water for 24 hours, then this expanded mass is placed on a sieve with holes 2 mm in a layer 10 cm thick and allowed to drain for one hour; the remaining mass is then weighed in a measuring container and the tipping weight per liter is calculated.

52. Landfill weight, compressed:

The carrier mass drained according to S1 is pressed with a 1 mm sieve for five minutes at a pressure of three bar and then the mass is weighed in a measuring vessel. Calculate the tipping weight S2 per liter.

53. Landfill weight, dried:

The moist, compressed carrier mass is dried (approximately) for one day at 100 ° C under reduced pressure to constant weight and weighed in a measuring vessel as above.

30 In the above example, the values S1 to S3 thus determined are: 51 (drained) 492 g / 1 52 (compressed) 214 g / 1 53 (dried) 73.5 g / 1 35 In order to improve the comparability of the values, the following factors are further defined: F1 : Volume factor is the liter weight of the swollen sample in water divided by the quantity of dry matter per liter of aqueous suspension föS (S) J.

40 S9072 5 F1 = flk) F2: The compression factor is the weight of the compressed sample per liter (pour weight S2) divided by the amount of dry matter per liter of suspension.

10 "S2 F2" TS1S) F3: the expansion factor is the weight of the drained sample (S1) divided by the dry weight / TS (S1) / obtained by removing 15 completely of water from the drained sample.

- S1 F3 'TS (S1)

The examples determined the chemical oxygen demand 20 according to DIN 38409, Part 41 (December 1980), the toxicity to fish according to DIN 38412, Part 15 (June 1982) and the toxicity to daphnia according to DIN 38412, Part 11 (October 1982) and the odor threshold according to the German standard water test method ( Loseblatt-Sammlung, 25 1982, Verlag Chemie-Weinheim).

2. Composition and manufacture of special polyurethane feedstock components_ 2.1. Preparation of NCO prepolymers, a discontinuous process for patent examples_NCO prepolymers are prepared in a manner known per se in a mixing device by heating the starting materials (high molecular weight polyhydroxyl compound, optionally low molecular weight polyols, optionally polyols, calculated NCO concentration. The composition is given in Table 1.

41 89072 tn *: rd tr *

S N M X

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Co +> «• H>,> J>> J« „> o · η q α a n m o m -h tn S H o o o o o ό +>> • h .S '' J * x x x x x o - x m mj b, o. a. a. a. 3¾¾

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5- i>, irä <m w n <m m O Cn E

m h im ..... -h, ¾

A! OS «O 00« O O CO 4 -> \ CN

° <o · n Tr n m m o m -h -¾ -o cm • n 4) (1) C * E: <0 en -h m o im 3 o -n 4-> 4->

E DDD tn 0) <d VJ

P -H H H H -H E -H: m 4-) 4-> M O 04 m M 4-1 Ή a) 4-1 CU Ή o 2 4J m> 1 tn

O JS 2 X -H 4J

-¾ S <1 n »on m Cu · * ·

> -: fd V4 Oi 4-1 "H

- »<n p m O in rt> i 54 54 CU S‘ 2 ^ (M -H x 4-1 (1) (1)

Cu "'3 i -o g

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cu om> 1 C Oi a) -H r4 0) o - 4-1 -PO - <4 tJ 4-> Oi m 54 ZO-NfM c: mc-p ea) »- JL m: mo) tn -h 0) to LO (M -H -Pr4d) tn E 54 H m I o> 4 n): m> oi 1-4 a) tn -huo

0 E C -H> 2 C

CU-h u S 0) tn X -H

Ή ti · r4 C <1) C m tn tt ift O Ή C -H 0) Oi

0) $ esi Οι Λ (1) --4 C

1 4J -s- -HOCiH-Hm-P

O -P tn o O tn U4 -H -h e -P: m

U tn »o O O) O tn E O ·· O

2 S n · »o i> 4 x -Hm: m tn Du O Ό: m vo 4) CU: m

-HEPO m U> 1 E ^ m O S

T-> - 8 B B N K X -

O II II II II

X

X -H -H

p a CU X Oi ^ ξ * X Cu a, Oi

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m G o to se> »E4 | ^ E4 o m «42 B9072 Isocyanates used: TDI = toluene diisocyanate, 80:20 mixture of 2,4- and 2,6-isomers

Polyether polyols: 5 PHILV = hydrophilic, branched polyether, starting from trimethylolpropane reacted with 40 parts of propylene oxide and 60 parts of ethylene oxide, OH number 26.

PHOBV = hydrophobic, branched polyether, starting with trimethylolpropane, reacted first with 80 parts of propylene oxide and then with 20 parts of ethylene oxide, OH number 28.

PHOBL = hydrophobic linear polyether, starting materials 1,4-butanediol and propylene oxide, OH number 56. 15 Compound containing a tertiary nitrogen atom: NM = N-methyldiethanolamine Stabilizer (partial salt formation).

SS = concentrated sulfuric acid Quaternizing agent: 20 DMS = dimethyl sulfate.

2.2. Preparation of aqueous dispersions of polyurethane urea / "PUR (HS) J7 from NCO prepolymers_ 2.2.1 Cationic PUR dispersion 1 = KPUR1 A mixture of linear and branched hydrophobic poly-25 polyols (composition in Table 1) with water removed and having a temperature of about 100- 130 ° C, combined with a mixture of tolylene diisocyanate isomers at room temperature in a flow-through mixer 1, i.e. a high-speed rotary spike mixer with 30 stator and rotor equipped with spikes and an average residence time of about 20-60 seconds in which the NCO prepolymer is formed, in a flow-through mixer 2, similar to mixer 1, to 2.1 times the amount (calculated from the NCO polymer) of hydrogen at a temperature of 20 to 30 ° C. A rapid chain elongation reaction of 43 89072 (including polyurea and cleaved CO 2 and is completed to high volume in a mixing vessel with vigorous stirring. In the case of preparing a 35% cationic PUR (HS) dispersion KPUR1 from 5 cationic branched polyether-NCO prepolymer KOPP, the water-induced elongation reaction takes place until complete reaction of the isocyanate groups at 50-70 ° C in five minutes and at room temperature. at 15 minutes.

2.2.2 Anionic PUR dispersion = APUR2 10 In preparing the anionic PUR dispersion APUR2 from the nonionic branched polyether NCO prepolymer OPP, N- (2- (2)) at 30 ° C is used instead of water alone (used in 2.1.1). aminoethyl) dilute aqueous solution of the sodium salt of ethanesulfonic acid. The chain extension reaction with diamine-15 takes place immediately, when water is used the same reaction is completed at 50-60 ° C in about 30 minutes.

Both ionic polyurethane urea aqueous dispersions prepared according to section 2.2 have a solids content of 20 to 35% by weight and a particle size of 0.5 to 3 microns, tend to partially sediment when standing for several days, but are redispersible after the desired storage time and are particularly suitable for binding. and as coatings for the preparation of the high filler polymeric carrier masses of the invention when long-term water resistance of the carrier is required.

3. Characteristics of ionic PUR dispersions Cationic crosslinked polyethylene-30 ri-PUR (HS) dispersion formed from KPUR1: NCO prepolymer KOPP (see Table 1) and water, 35%.

APUR2: Anionic crosslinked polyether-PUR (HS) dispersion formed from NCO prepolymer OPP (Table 1), di-sulfonate and water, 35%.

APUR3: Anionic branched polyethylene-PUR (HS) anion formed from branched and linear polyethers (weight ratio 88:12), N-methylpyrrolidone, dimethyl 44,89072 lipropionic acid, triethylamine and isophorone diisocyanate.

KPUR4: Cationic, slightly branched PUR (HS) formed from a mixture of linear polyether and polycarbonate-5 diols (weight ratio 35:65), trimethylolpropane, N-methyldiethanolamine and dimethyl sulphate and hexamethylene diisocyanate.

4. Characteristics of Polymer Dispersions 10 Dispersions are referred to as latexes, abbreviated LAT; A = anionic, K = cationic, NLAT = natural rubber latex.

KLAT1: Cationic polymer, a 40% dispersion of butadiene, acrylonitrile and trimethylolammonium methylmethacryl-15-acid ethyl ester chloride in a weight ratio of 68: 28: 4.

ALAT2: Anionic polymer, 40% by weight dispersion of butadiene, acrylonitrile and sodium methacrylate in a weight ratio of 52: 41: 7, Shore A 20 film hardness 50.

ALAT3; Anionic 40% dispersion analogous to ALAT2, but a clearly softer mixture; butadiene, acrylonitrile and sodium methacrylate in a weight ratio of 62: 34: 4 (Shore A: 20).

ALAT4: Anionic polymer, a 50% dispersion of styrene, acrylonitrile and sodium methacrylate in a weight ratio of 55: 42: 3.

ALAT5: Anionic polymer, 40% dispersion of styrene, butadiene and sodium acrylate in a weight ratio of 78: 20: 2.

ALAT6: Anionic polymer, 40% dispersion of equal parts by weight of acrylic acid butyl ester and vinyl acetate containing 2% by weight of sodium acrylate on a dry weight basis.

35 KLAT7: Cationic polymer containing a small amount of anions, i.e. a partially ampholytic 40%, water-sensitive aqueous dispersion of 2-chlorobutadiene (chloroprene).

NLAT8: Natural protein latex stabilized with natural protein.

5. Characteristics of the polyether-PUR cellular material used as filler (Examples 1-15 )_

Mixtures of irregularly comminuted wastes of varying densities (approximately 15-110 kg / m) from industrial polyether polyurethane ingot and shaped cellular plastics production were used as soft foams.

10 The poured weight of soft foam, which consists mainly of ingots, is about 14 g / l when dried. The particle size is 1-12 mm. Pour weight after suspension in water: S1, 263 g / l; S2, 101 g / l; S3, 14 g / l; TS-S (dry matter content of aqueous suspension), 12.5 g / l suspension.

15 6.1 General procedure for the preparation of filler-containing polymeric carrier masses according to the invention by a discontinuous process_ 6.1.1 Preparation method D1 using preformed PUR foams_ 20 The high filler-containing polymer masses used in the patent examples are prepared at room temperature or at a moderately elevated temperature (up to 60 ° C); in a manner in a power mixing device consisting of a heatable cylindrical container attached to a diagonally rotatable plate and provided with an eccentrically adjustable mixing means which rotates in the opposite direction to the plate; for the production of larger quantities, a horizontally mounted agitator 30 equipped with agitator-like agitators is used.

The fillers are charged, any amount of water in excess of the water content of the polymer dispersion is added, and the aqueous polymer dispersion is mixed vigorously. A dilute aqueous solution, emulsion or suspension of an optionally preselected coagulant (electrolyte or polyelectrolyte 46) is added to the mixture over a period of about 2-3 minutes and optionally heated, whereby the mixing power should be greatly reduced to avoid the formation of undesirable fines.

5 6.1.2 Manufacturing method D2 without the use of preformed PUR foams_

In the absence of preformed PUR foam granules, only mix vigorously for 30-60 seconds at room temperature or for about 30 seconds at 45-60 ° C and then optionally add a coagulant over about 10 seconds. The mixture is then allowed to stand until coagulation is complete. The granular product is then applied to an enamelled sheet and dried. Depending on the mixing device, the amount of water used, the coagulation rate and also the temperature, a more or less granular or beaded coagulation product with the desired particle size for later use is formed already at the end of the mixing. Larger particles can be comminuted to the desired particle size after coagulation is complete. When using preformed cellular plastics, the reaction mixture can be moved in the mixing vessel at least moderately also during coagulation to form high filler-containing polymeric carrier particles having a particle size corresponding to the particle size of the cellular plastic used.

6.1.3 Manufacturing Method D3 (Bonded Foam) In a particular embodiment, after mixing all the ingredients, the products containing preformed foam granules are placed in molds for about 40-120 seconds 30, compressed to the desired density volume (about 5-12% by volume of the original volume AD) and coagulated. . This forms a bonded cellular plastic that can be cut or granulated into the desired shape. This method yields polymer-bonded products 35 times the density of coagulated products without pressure. In Example 47 of Patent 8,89072 3, the density was 280 kg / m 2 and in Example 14 14,160 kg / m 2. The compositions and physical properties of bonded foams granulated to a particle size of less than 6 mm are given in Tables 2 and 3.

6.2 General instructions for the preparation of polymeric carrier masses according to the invention in a continuous manner (continuous process = KV) _

The device uses a twin-screw conveyor device with a volume of about 180 l and a length of about 300 cm and a mixing axis rotating in opposite directions. The product is forcibly fed from the feed opening towards the outlet, whereby a certain kneading or pressing takes place between the mixing shafts. The comminuted polyurethane foam waste and other fillers are fed separately through a batch chute to the mixer chute. Any additional water or aqueous polymer latex and possibly low molecular weight polyisocyanates and any NCO prepolymer that may be used with the gear pump are fed to the same location with the piston pump. It is expedient, but not absolutely necessary, to mix the polyisocyanate compounds with the polymer dispersion or about twice the amount of water (water temperature 10-25 ° C) in a flow-through mixer or static mixer effectively for 1-3 seconds and thus form an emulsion, so that any additional dried substances may be used. with the remainder of the water being fed rapidly and evenly, possibly separately, preferably heated to 30-60 ° C, and the water-mixed polymers 30 in very finely divided form cover the solids evenly.

After the mixture has remained on the screw conveyor for about three minutes, a dilute aqueous solution of the coagulant is injected into the last third of the mixing device by means of a nozzle (diameter 1 mm). Through the bottom opening 35 at the end of the mixer, the pre-coagulated and partially already coagulated polymer carrier mass is fed by means of a conveyor belt to 48 89072 hot air drying channels and the coagulation is completed in 3-10 minutes at a product temperature of 40-90 ° C. In an inclined rotary tube washer installed downstream of the dryer, fed constrained from top to bottom and coaxially mounted with a perforated plate in which the washing nozzles are placed, the product is washed with so much water that both potentially interfering very finely divided ingredients and soluble salts are exited the reaction product as it left the scrubber. With an average residence time of two minutes, about three times the amount of water required for the dry matter of the polymer carrier mass is required for washing. The production capacity is about 1-2 tons of total mixture per hour.

15 6, Patent Examples 1-24 (Preparation and use of polymeric carrier masses according to the invention)

Example 1 (manufacture)

Porous, soft-flexible, KLAT1-bonded polymer carrier mass containing PUR-20 foam and lignite.

40 parts by weight of the soft cellular plastic granules described in point 5 and 53.8 parts by weight of natural lignite extracted from the Aachener lignite zone, dried by vigorous heat treatment to a residual moisture content of 25 to 7% by weight and comminuted to a particle size of less than 100 and thus in the form of lignite according to method D1 at room temperature in an Eirich mixer and combined with vigorous stirring with 25 parts by weight of latex KLAT1. After two minutes, 10 parts by weight of 2% sulfuric acid solution are added, the stirring power is reduced considerably and the reaction mixture is heated to 90 ° C. Within 10 minutes, a carrier is formed which is in the form of a slightly swollen, slightly elastic solid in the water, which for the most part remains in pieces less than 12 mm in size 35 and generally does not require further comminution.

49 B 9 O 7 2

The resulting water-non-floating support is now suspended in excess water, swollen completely for 24 hours (at room temperature and decanted with any excess water. The value obtained from this test indicates 5% by weight of water remaining in the expanded support and its interstices (filler-containing polyurethane urea)). , is referred to herein as water absorption capacity (WAF).

Example 1 has a dry matter content of 59.5 g of 10 solids per liter of dehydrated suspension. When the weight of the suspension is 1,001 g / l of suspension, the suspension factor F4 = 1,001 / 59.5 = 16.8 is obtained. Thus, from one part by weight of the carrier powder, the described expanded suspension is obtained with 15.8 times the amount of water. In other words, the water absorption capacity is 15.8 / 16.8 x 15 100 = 94%.

To further characterize the carrier masses, the landfill weights S1 to S3 (g / l) are further determined after various treatments.

In the example above, the values S1 to S3 thus determined are 51 (drained) 492 g / 1 52 (compressed) 214 g / 1 53 (dried) 73.5 g / l.

The composition of the product of Example 1 and the values of the volume, compression and expansion factors F1 to F3 are given in Tables 2 and 3, as well as the corresponding data for the other examples.

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Clarifications for Table 2 Quantities are parts by weight based on dry matter Columns 1 Patent Example Serial No. 5 2-13 Composition and Reaction Conditions

2-6 Filler A

2 PSF = polyether-PUR foam waste, properties given in 5 3 Lignite, see Example 1 10 4 Activated carbon, <10 μm, 50% by weight <4 μm 5 Lignite, <20 μm, 80% by weight <100 μm 6 Magnetite, particle size 0.1 to 2 μm 7 + 8 Polymer dispersions 7 Cationic (K) or anionic (A) PUR dispersion, see

Item 15 3 8 Cationic (K) or anionic (A) polymer dispersion, see item 4 9 NCO compounds TDI = 2,4- and 2,6-diisocyanate toluene in a weight ratio of 80:20 OPP = hydrophobic NCO prepolymer, see Table 1 10 Electrolyte solutions

Mg = 2% magnesium sulphate solution (about 0,2% w / w magnesium sulphate on the polymer solid) 25 S1 = 1 N sulfuric acid solution (about 0,2% w / w H2SO4 on the polymer solid) S2 = 2% acetic acid solution (about 0,4% by weight -% glacial acetic acid on polymer solids) L = 1 N sodium hydroxide solution (about 0,3% by weight of 30% sodium hydroxide on polymer solids) 11 For preparation methods, see description in section 6 (D = discontinuous, KV = continuous) 12 Heat treatment, temperature ° C (coagulation) 13 Water content (% by weight) of the total 35 m = water content of the mixture before coagulation 53 89072 RF = residual moisture after coagulation and possibly partial drying 14- 17 Physical properties 3 14 Dry matter content (kg / m of suspension at 100% filling level, ie without extra water) 15-17 S1 to S3, tipping weights, see Example 1 (drained, pressed or dried).

Table 3:

The volume (F1), compression (F2) and expansion factors (F3), in addition to the suspension factors (F4), the water absorption capacity (WAF) and the solids content (FKS) of the suspensions containing the excipient-containing polymeric carrier masses according to Examples 1-20

Table 3

15 Example F1 F2 F3 F4 _ '/. WAF V.FKS

1 8.3 3.6 4.7 16.8 94.0 6.0 2 8.3 4.5 5.4 24.8 96.0 4.0 3 7.2 3.3 5.1 16 8 94.0 6.0 4 8.5 6.5 5.0 20.6 95.1 4.9 20 5 6.9 3.1 4.4 13.2 92.4 7.6 6 7.2 3.9 5.3 16.8 94.0 6.0 7 8.5 4.4 5.2 18.6 94.6 5.4 8 7.5 3.0 4.6 19.3 94.8 5.2 9 8.6 3.3 5.2 18.5 94.6 5.4 25 10 8.1 3.3 5.2 16.3 93.9 6.1 11 7.4 3.1 4 .7 15.9 93.7 6.3 12 6.1 3.3 4.1 16.7 94.0 6.0 13 7.8 3.7 4.9 16.5 93.9 6.1 14 9.0 3.6 5.7 23.1 95.7 4.3 30 15 4.9 2.9 3.3 10.1 90.0 10.0 16 2.2 2.2 2.8 3, 5 70.9 29.1 17 1.7 1.7 1.7 3.5 71.4 28.6 18 3.9 3.8 3.5 5.8 82.8 17.2 19 3.1 3 , 1 3.3 5.4 81.5 18.5 35 20 2.0 2.0 2.0 4.0 75.0 25.0 54 89072

Patent Example 21-24

Use of carrier masses in a biological purification process (according to the invention) - Characterization of the biological fixed bed / fluidized bed bio-5 reactor used In this connection, the aerobic process carried out by the solid bed process is referred to as process Ia) and the fluidized bed process as process Ib).

The effluent from the first activated sludge stage of a large industrial treatment plant with a KHK value of 350 ± 100 mg / l, an occasional t 250 mg / l and a PHK5 value of 23 1 15 mg / l is continuously pumped into a tower bioreactor with a volume of 100 l 2/3 of the bioreactor is filled with the support on which the activated sludge mass is to be placed, i.e. the polymer support mass fills 66.6% of the reactor volume. The gas required for the gas treatment and oxygen supply of the reactor is fed to the reactor from below by means of a sinter or an orifice plate. By feeding large amounts of oxygen-containing gas, the column can be used as a fluidized bed or, with a smaller gas feed, as a solid bed. The oxygen-containing gas comes from the sinter or perforated plate in small bubbles and flows through the reactor from the bottom up together with the water supplied from the bottom and exits through the upper end of the reactor. After a few days, the reactor charge (polymer support mass) forms a biological culture. After an average residence time of four hours, the treated wastewater is discharged through an outlet pipe to the clarifier. Small growth particles washed out of the bioreactor are separated in the clarifier and can be removed through the sul-30 slurry. The effluent from the clarifier has been biologically treated to achieve the improved results described in the examples.

The shelf life is four weeks. The analytical results given in Table 4 are the averages of 5 determinations in each case.

35 Anaerobic biological treatment mainly uses the solid bed method and only in order to avoid differences in concentration 55 89072 is introduced into the bioreactor from time to time without inert gas instead of air or from time to time the carrier is gently moved by mechanical means.

Patent Examples 21-24 5 Table 4 (Reduction of KHK in aerobic biological treatment, KHK = chemical oxygen demand)

Eg Carrier mass Income Expenditure Method GHG reduction resp. e.g.

___________mg / 1 _ '/% _ 10 - 379 357 - 22 6 "240 211 - 29 12" 682 660 - 20 3 21 1 379 170 Ia 209 55 22 6 379 141 Ib 238 63 15 23 15 240 129 Ia 111 45 24 1 682 218 Ib 462 68

Examples 25 and 26

The oxygen bleaching effluent of the sulphite pulp mill, with a KHK value of 5,500 mg / l, was treated anaerobically by microbes in parallel-connected continuous plants.

The experiments were performed in 1.6 L anaerobic equipment described, for example, by W.J. Jewell 25 ^ Journal of the Water Pollution Control Federation, 53 (No. 4), p. 484, Fig. 1b / · The average hydraulic residence time of the wastewater in the reactor was 38 hours (1.6 days). Degradation experiments were performed in the following alternative ways: Apparatus 1 (blank without vehicle - * 30 comparative test). 400 ml suspended cells

Apparatus 2 (according to the invention) (Example 25) 400 ml of suspended cells + 400 ml of PUR polymer carrier mass according to patent-35, mark 1 (see Table 2, p. 50) it 89072

Apparatus 3 (Example 26) 400 ml of suspended cells and 400 ml of the PUR polymer carrier mass according to Example 6 (Table 2, p. 50).

5 Suspended cells were obtained from a sugar factory anaerobic reactor.

Following equilibrium (34 days), the following results were obtained:

Equipment Polymer carrier mass of effluent 10 No. KHK (mg / 1)

Blank test 1 2 190

Example according to Example 1, 25 2 1 630 Table 2

Example according to Example 6, 15 26 3 1 670 Table 2

Claims (8)

57 89072 A process for the preparation of filler-containing polymer-bound carrier compositions, characterized in that A) fillers based on preformed particulate or powdered foams and / or fossil lignocellulose powders and / or carbon powders as well as possibly other inorganic powders are mixed. or organic fillers and / or possibly living and / or dead biological cellular material, in an amount of 30-97% by weight of the sum of A) and B), B) non-ionic hydrophilic, anionic or cationic aqueous, to coagulable and film-forming polymer dispersions with a solids content of 3 to 60% by weight, optionally adding C) water in such an amount that the total water content is 20 to 90% by weight, based on all the ingredients, and optionally adding D) other auxiliaries. and additives and the polymer dispersion is then coagulated of. Process according to Claim 1, characterized in that a filler which is a) a cellular plastic in the form of a piece or in powder form, b) a fossil lignocellulose powder, preferably lignite powder or peat, is used as component A). C) other carbon powder, preferably activated carbon, hard coal, lignite coke or charcoal powder, or d) a desired mixture of such fillers, optionally combined with e) powdered, ferromagnetic inorganic substances. se 89072 Process according to Claim 1 or 2, characterized in that component A) is a filler which is a) cellular or powdered cellular plastic 5 b) and / or fossil lignocellulose powder, preferably lignite powder or peat, c) optionally another carbon powder, preferably in the presence of activated carbon, coal, lignite coke or charcoal powder, or d) a mixture of such fillers, optionally combined with e) powdered, ferromagnetic inorganic substances. Process according to one of Claims 1 to 3, characterized in that the polymeric aqueous dispersion used is a) polymer dispersions based on olefinic unsaturated monomers, b) polyurethane dispersions, 20 c) natural latex or d) the desired compositions of such compatible dispersions. the stability of the dispersions is achieved by external emulsifiers which are not chemically incorporated into the structure and / or by internal nonionic hydrophilic, anionic and / or cationic emulsifiers or hydrophilic internal chemically incorporated into the structure of the solid macromolecule. Process according to one of Claims 1 to 4, characterized in that stabilizers and / or crosslinking additives are used as other auxiliaries and additives which may be used. Method according to one of Claims 1 to 5, characterized in that the coagulation is effected by means of a coagulant and / or heating. 59 89072 Polymer-bound carrier compositions, characterized in that they are prepared according to one of Claims 1 to 6. Use of polymer-bound carrier masses prepared according to one of Claims 1 to 6, characterized in that they are used as carriers for biomass incorporated or growing on the carrier in wastewater treatment, in particular in biological waste water treatment, as carriers in biological fermentation processes, as plant growth media or as adsorbents for finely dispersed substances and / or crude oil. 60 8 9 0 7 2