CA1328319C - Process for the production of filler-containing, polymer-bound compositions the compositions obtained by this process and their use - Google Patents

Abstract

A PROCESS FOR THE PRODUCTION OF FILLER-CONTAINING, POLYMER-BOUND COMPOSITIONS, THE COMPOSITIONS OBTAINED
BY THIS PROCESS, AND THEIR USE
ABSTRACT OF THE DISCLOSURE
The present invention relates to a process for the production of filler-containing, polymer-bound compositions useful as carriers for the biological treatment of waste-containing liquid comprising (A) mixing (i) from 5 to 97% by weight based on the solid content weight of components (i) and (ii) of a filler selected from the group consisting of (a) cellular plastics, (b) fossil lignocelluloses or natural materials containing finely-divided fossil lignocelluloses, (c) carbon powders, (d) finely divided distillation residues, (e) finely divided inorganic fillers, and (f) mixtures thereof, wherein the particle size of filler (a) is from 0.1 µm to about 1 cm and the average particle size of fillers (b) to (e) is from 0.1 to 1000 µm, with (ii) an aqueous polymer dispersion having a solids content of from 3 to 60% by weight selected from the group consisting of (a) polymer dispersions based on olefinically unsaturated monomers, (b) natural latex, and (c) mixtures thereof which are mutually compatible dispersions, said dispersion being stabilized by external and/or internal nonionic-hydrophilic, anionic, and cationic emulsifiers or hydrophilic groups, and (iii) optionally water, so that the water content, based on all the components, is between 20 to 90% by weight, and (B) coagulating said polymer dispersion.

Description

Mo-2820 LeA 23 91 A PROCESS FOR THE PRODUCTION OF FILLER-CONTAINING, POLYMER-BOUND COMPOSITIONS
THE COMPOSITIONS OBTAINED BY THIS PROCESS AND
THEIR USE
BACKGROUND OF THE INYENTION
The present invention relates to a new process for the production of filler-containing, polymer-bound compositions by mixing the fillers with an aqueous polymer-based binder and then coagulating the polymer dispersed in water and to the compositions obtained by this proce~s. The compositions can be used in the bio-logical treatment of sewage, as carriers in the bio-logical fermentation stage of bioconversion processes, as carriers for plant growth or as adsorbents for finely dispersed materials, particularly crude oil.
There are already several known processes for impregnating foams and foam particles in which the foams are impregnated with a reactive component, for example with polvisocyanates, and then reacted with the other reaction components, for example polyols, polyamines or vapors of diamines (see, e.g. German Offenlegungs-schriften 3,039,146 and 2,131,206, Japanese Patent 50-103 571, French Patents 1,587,855 and 1,574,789, or U.S. Patent 2,955,056).
The foams may also be exposed to the action of a liquid having a swelling effect and then to the action of the polyurethane reaction components, resulting in hardening ant stiffening of the foam and, in some cases, in incorporation in the swollen foam matrix (see, e.g., French ~atents 1,341,717, 1,587,855 and 1,574,789 or German Auslegeschrift 1,911,645). Matrix foams of this type show typical foam properties, although different hardness, elasticities or chemical and mechanical ~h~
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Many other patents describe the bonding or compression molding of foam particles (preferably flexible polyurethane foam waste particles) using polyisocyanates, NCO prepolymers and polyols, - ;~
polyamines, water or other reactant~ (optionally with addition of cork, fibers, cellulose powder, flame-proofing agents, pigments, metal powders or carbon black), to form new composite materials. Composite materials of this type are used, for example, as insulating panels, linings, mattresse6 or moldings.
Corresponding processes are described, for example in German Offenlegungsschriften 2,940,260, 3,213,610, 2,908,161, ant 3,120,121, British Patents 1,337,413 and 1,540,076, U.S. Patent 4,254,177, and Japanese Patent 57-028 180.
Technical significance haslbeen attained in the production of composite block foam from size-reduced polyurethane foam, 10 to 20% by weight of iæocyanate compounds, up to about 10Z by weight of fillers and small quantities of water. In this case, the filler consists primarily of colored pigments to provite the composite foam (which may consist of differently colored foam batches) with a uniform color. The water used in the production of the composite foam is instrumental as a reactive component in converting the polyisocyanate groups into polyurea groups with evolution of carbon dioxide. The quantity of water used i~ selected to correspond substantially to the stoichiometric demand of the isocyanates, but at most is present in only a relatively small excess. Otherwise, difficulties would be involved in removing the moisture from the 40 to 60 cm thick composite blocks.

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_3_ 1328319 In the biological sewage treatment field, numerous processes have already been proposed with a view to increasing the degradation effect and to obtaining purified water, free from contaminants. Thus, attempts have been made to oxidize the contaminants by increasing the supply of oxygen to the activated sludge.
In addition, special oxidation processes (including for example treatment with ozone or hydrogen peroxide) have been proposed.
Catalytic oxidation of the æewage in~redients with air in the presence of active carbon, followed by precipitation, has also been recoFmended (see, e.g., German Patent 2,239,406; German Offenlegungsschrift 3,025,353; A. Bauer et al., Chemie-Technik, No. 6, pages 3-9 (1982); K. Fischer et al., GWT-WSSER/Abwasser, No. 2, pages 58-64 (1981); R. E. Perrotti et al., Chemical Engineering Progress (CEP), Vol. 69 (11), 63-64 (1973); G. Wysocki et al., ZC-Chemie-Technik, 3 (6), 205-208 (1974); and 3rd Report "Adsorptive Abwasser-reinigung (Adsorptive Sewage Treatment)" (October 1975)of the Ausschuss Wasser und Abwasser beim VCIeV.).
The processes mentioned above have either proved to be technically too elaborflte or too expensive or the degrading effect i8 inadequate. The many attempts which have been made to use active carbon in the treatment of water have failed despite an improvement in tegradation because, even in its bound (granulated) form, the active carbon disintegrates even under the effect of very weak flows (which are at least periodically necessary in the settling tanks) and is discharged. To date, there have been no known successful attempts to use strongly bound active carbon in sufficiently active large quantities while, at the same time, maintaining bioactivity in the settling tank.

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German Offenlegungsschriften 3,032,882 (EP-A
46,900) and 3,032,869 (EP-A 46,901) describe the use of a macroporous material of low density (10-200 kg/m3) as carrier for nitrifying bacteria in the clarification of 5 activated sludge. The macroporous material is, for example, a typical polyurethane foam. Foam particles of this type are described in reference to a process and an apparatus for the anaerobic biological treatment of sewage. The improved results are reported, for example, 10 in GWF-Wasser/Abwasser, 124, (1983), No. 5, 233-239.
However, foams of this type tend to float in activated-sludge tanks and disrupt the process in various ways. Particulate foams based on polyurethanes ~ -have also been recommended in various special processes 15 as a loose filling (German Patent 2,839,872 and German Patent 2,550,818) or as a trickling filter material -~
(Australian Patent 248,354) for the biological treatment of sewage. The use of relatively abrasion-resistant, -open-cell polyurethane ureas with a urea to urethane 20 ratio of less than 5 as a carrier medium for `
microbiologically active cells in the treatment of sewage is described in U.S. Patent 4,503,150 which cites as prior art a number of other publications describing the use of foams in the biological treatment of sewage.
Canadian Patent 1,184,857 describes the use of particulate polyurethane foam as a filtration medium -from which accumulated soil is periodically washed out by certain methods to regenerate the foam.
The combination of surface-active solids with 30 microorganisms to increase their activity in bio-conversion processes is also known. Thus, the adsorption of cells on, for example, aluminium oxide, bentonites aDd SiO2 and the subsequent embedding thereof ;

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in polyacrylates is described, for example, in German Offenlegungsschriften 2,633,259 and 2,703,834. In addition, German Offenlegungsschrift 2,629,692 describes the incorporation of cells in photohardening poly-urethanes containing photohardening acrylate doublebonds.
It is also known that cells capable of growth can be embedded in polyurethane hydrogels (see, e.g., Tanaka et al., European Journal of Applied Microbiology and Biotechnology, 7, (1979), pages 371 et seq). German Offenlegungsschrift 2,929,872 also describes a process for the production of hydrophilic, gel-like or foamed biocatalysts heavily charged with enzymatically active material by polymer inclusion of whole cells from cell fragments or enzymes, by mixing an aqueous suspension of the enzymatically active material with hydrophilic poly-isocyanates to form an enzymatically highly active, hydrophilic polyurethane network in block form or bead form. On page 7 of that Offenlegungsschrift other prior art publications are cited. In addition, the immobilization of microbial cells in polyurethane matrices, such as polyurethane foams or gels, i8 described by J. Klein and M. Klug in Biotechnology Letters, Vol. 3, No. 2, pages 65 to 90 (1981).
The production of polyurethanes containing enzymatically active materials is difficult and is attended by the disadvantage that, in view of the high reactivity of the isocyanate groups, bacteria and cells are at least partly destroyed or enzymatically active material is inactivated. Thus, residual activities of from 7 to 48% for example are typically measured.
Accordingly, it is also not favorable to incorporate live bacteria in hydrophilic polyurethanes during the production process in order to use them, for example, Mo-2820 1~283~3 for the treatment of sewage. The quantities in which bacteria of the type in question can be incorporated is limited. In addition, many of the bacteria are deactivated by isocyanate reactions. The continuous production of active, bacteria-containing polyurethane compositions and their "live storage" involves production and storage problems in order to supply the settling tanks, which generally have a capacity of several thousand cubic meters, with the necessary quantity and concentration of bacteria incorporated in polymers. A drastic reduction in the ability of the bacteria to proliferate occurs during their immobilization in the reaction medium, even if they are directly introduced locally in the treatment plant, because of their short survival time.
Accordingly, a solution still has to be found to the problem of developing suitable processes for producing new carrier materials for new, economic and effective processes for the improvet treatment of sewage.
The present invention seeks to solve the problem of providing highly water-absorbing, highly filled polymer carrier materials which do not float in water and which may be used as carriers for biomasses in the biological treatment of ~ewage.
DESCRIPTION OF TNE INVENTION
The present invention relates to a process for the production of filler-containing, polymer-bound compositiohs comprising (A) mixing ti) from 5 to 97% by weight, based on the solid content ~i~t of components (i) and (ii) of a filler selected from the group consisting of (a) cellular plastics, Mo-2820 13283~9 (b) fossil lignocelluloses or natural materials containing fin~ly divided fossil lignocelluloses, (c) carbon powders, (d) finely divided distillation residues, (e) finely divided inorganic fillers, and (f) mixtures thereof, with (il) an aqueous polymer dispersion having a solids content of from 3 to 60% by weight, and optionally with addition of (iii) water, 80 that the total water content, based on all the components, is between 20 and 90%
by weight, and (B) coagulating said polymer dispersion.
The invention also relates to the filler-containing polymer-bound carrier materials obtained by this process.
T~ invention also rela~es to a prooess of biological ~eabrent of was~ce .
20 containing liquids by ~e ~val of org~nic nat~er by m~croor~ani~ns or to a fernentation process, ~ inprw~t, which c~prises adding ~e carrier calposiffcns acoDrding tothe invention to said liquid.
The fillers (i) are an essential constituent of the polymer carrier materials according to the 25 invention. The unexpectedly high water absorbency and the strong degradation effect are obta~ned through an interaction between the fillers and the polvmer carrier material. Such a high degree of hydrophilicity, i.e.
water absorbency, is introduced into the carriers either 30 by the polymers and/or (preferably) by hydrophilic or cellular fillers (for example, lig~ite or black peat and/or polyurethane foams).
Suitable fillers (i) include, cellular plastics, such as, for example, polymers or copolymer~ -of ethylene, styrene, acrylonitrile, (methyl) butadiene and other vinyl compounds. Suitable fillers are, for example, expandet polystyrene granulates, expanded poly-, ~, .

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13283~9 ethylene or polymer-based waste foam. These fillers are less preferred and are generally used in combination with the preferred fillers. Preferred fillers include, for example, preformed polyurethane foam particles or rigid or semi-rigid polyurethane foam granulates or powders.
Of particular economic interest, are the cellular plastics, particularly the flexible polyurethane foam waste commercially accumulating in vast quantities. This polyurethane foam waste (preferably where it i6 based on polyethers), may be used in the form of an inexpensively obtainable, irregular particulate granulate with edge lengths of from a few mm to several cm, and even as a mixture of different foam densities. Foam particles having densities of from about 10 to 100 kg/m3 are preferably used. In particular, the flexible polyurethane foams are used in particulate form, while rigid, brittle polyurethane foam particles are preferably used in powdered form. Surprisingly, however, even waste flexible foam flakes having average densities of less than 50 kg/m3 bound in accordance with the inventiDn are eminently suitable carriers for growing biomasses. The voids in the foams are almost completely or at least partly filled during binding with the polymer matrix 80 that densi y and mechanical strength increase to a sufficient extent, ensuring that the foam flakes no longer float and are permanently resistant to mechanical influences in water.
Other fillers, which may be used either on their own or optionally together with the foam fillers, include for example, fossil lignocelluloses or naturally occurring products contain~ng fossil lignocellulose derivatives, such as in particular lignite. By virtue Mo-2820 , . . . . . .

_9_ 1328319 of their high water-absorbing power, they also produce highly water-absorbing carriers. Lignite is a parti-cularly advantageous hydrophilic filler and is particularly preferred (preferably being used as sole filler or in combination with polyurethane foam particles). Lignite is capable of hydrophilically binding large quantities of water without feeling wet.
For example, more than 150% of water can be bound, based on lignite dry matter. In addition, lignite creates 1~ favorable topological conditions for the production of porous carrier materials of the type which are parti-cularly suitable as carriers in the biological treatment of sewage.
Lignite from fossil deposits, for example from the Aachen area, generally ha~ a water content of around 60% by weight. This water-containing lignite may be used as such where cationic polymer dispersions are used as component (ii). It is only where anionic polymer disper~ions are used that the water content of the lignite is best reduced before it is used as a filler because this drying process is often accompanied by a desirable reduction in the content in the lignite of water-soluble constituents which can have a troublesome effect where anionic polymer dispersion6 are used. The ~implest way of doing this i8 to sub~ect the water-containing lignite to a drying process which greatly reduces its water content, at least to ~elow 20Z by weight and better still to below lOX by weight. As the natural moisture content continues to decresse and the drying temperature and time continue to increase, conversion or condensation reactions take place in a tempering process with enlargement of the molecule, greatly reducing the solubility in water of the huminic acids and reducing the brown coloration of the water in which a sample of lignite for example is suspended.
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After this drying process, the lignite is much more suitable and hence particularly preferred for the preferred use according to the invention as a poly-urethane urea carrier in aqueous medium.
Another method of reducing the proportion of soluble compounds in the lignite is a chemical treatment, for example using excess amounts of isocyanate compounds. The reactive groups in the optionally still more or less moist lignite react with di- and polyisocyanates, (which may be monomeric or polymeric) again with enlargement of the molecule. At the same time, a polyurea coating is formet in the presence of residual moisture with elimination of carbon dioxide. Both methods, namely tempering with reduction and/or removal of moisture and the treatment of the lignite with polyisocyanate, are most easily combined with one another in the actual production of the polymer carrier materials.
It has also been found that carriers containing lignite bound to anionic polymers are also suitable for use as carriers for bacteria in the treatment of sewage even when water-soluble residual constituents, for example huminic acid impurities or yellowing compounds, initially bleed out. The carrier materials according to the invention improve the biological purification of ~ewage to such a considerable extent, particularly in cases of high pollutant concentrations, that the soluble components emanating from the lignite do not appear in the efflueht of the biological treatment stages, even in the initial phase after installation of the carrier materials.
According to the invention, peat is also suitable as the filler (i). However, peat is known to contain significantly larger quantities of water-soluble Mo-2820 constituents than lignite (which even turn water dark brown in color). Accordingly, the measures described above for reducing solubility are particularly recommended, especially where the carriers are used in accordance with the invention as carriers for microbial conversion processes.
81ack peat is generally more suitable than white peat. In a preliminary tempering treatment, most of the water present in the black peat (water content 80% by weight, based on the natural material) is removed to a residual moisture content of below 20% by weight and preferably below 10% by weight, based on the total quantity. A polyurethane modification of the largely water-free black peat with low molecular weight or relatively high molecular weight diisocyanates or poly-isocyanates at temperatures of, for example, from 70 to 110C additionally provides for a greater reduction in the water-soluble components. It is preferred to use aromatic di- and polyisocyanates in such a quantity that from 0.5 to 2.5 kg of black peat, based on dry matter, are reacted per isocyanate equivalent (i.e. 42 g of isocyanate groups).
In the presence of anionic groups, the black peat is preferably used in this modified form. However, an exception is possible if, for example, the compositions are to be used as carriers for seets for the propagation of seedlings in horticulture. In this case, the bleeding out of water-soluble compounds from the peat is of no significance. The otherwise less suitable white pèat may even be used for this purpose, despite its higher content of water-soluble compounds compared with black peat.

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Other filler components (i) include, for example, -carbon powders, such as coal, charcoal, active carbon or lignite coke which are used in powder-form and which are preferably used in combination with the above-mentioned foam and/or fossil 5 lignocellulose fillers. It is also possible to use carbon powder as sole component A), although this is less preferred and does not lead to the maximum effect obtainable in accordance with the invention.
Other suitable fillers (i) include for example, residues from the distillation of tolylene diisocyanate, of the type obtained by introduction of the distillation residues into water with denaturing and subsequent granulation. These TDI
residues may optionally be subsequently modified by treatment with compounds containing reactive hydrogens, such as ammonia, 15 polyols or polyamino compounds. In many cases, they also contain small quantities of NCO groups or reactive modification products of isocyanates which are capable of reacting with the biomasses or with the compounds to be degraded. Distillation residues of the type in question are described, for example, in German Offenlegungsschriften 2,846,814, 2,846,809 and 2,846,815.
Other distillation residues, for example high-melting distillation residues of the type accumulating in the working up of amines, phenols or caprolactam by distillation, are also suitable as fillers (i) and are preferably used in combination with the preferred fillers.
Inorganic fillers (such as quartz, sea sand, pyrogenic silica (Aerosil*), silicates, aluminosilicates, bentonites, aluminium oxide, pumice stone, silica sols, 30 waterglass and also calcium oxide, calcium carbonate, heavy spar, gypsum, iron(II) and/or iron(III) oxides, *Trade-mark Mo-2820 but especially finely divided, optionally magnetic oxides, such as magnetite, chromium(IV) oxides, barium ferrites, iron powder or ~-Fe2-03 in pigment form) can also be used in certain quantities. ~hese can help regulate the specific gravity of the 5 carrier materials, so that they sink or remain suspended in, but never float on, the liquid to be clarified. Particularly finely divided inorganic fillers (for example containing primary particles less than 10 ~m in size and having a large surface, for example Aerosil* or iron oxides, especially in the magnetite accumulating in the manufacture of iron oxide), promote the transfer of oxygen to the clarified sludge bacteria and hence, provide for better degradation. Metal oxides apparently preform particularly favorable, specific oxygen transfer functions and, hence, develop favorable degradation effects in accordance with 15 the invention. Other suitable modifying filler additives include fibers (for example inorganic fibers), such as glass fibers or natural and synthetic fibers ~for example cotton dust).
The average particle size of the fillers is generally from 0.1 to 1000 ~m, preferably below 300 ~m and more preferably below 100 ~m. The smaller particle sizes are more preferred in particular for actlve carbon and inorganic constituents and also in the case of coal powder or charcoal powder than for example, in the case of peat or lignite dust. Peat and l;gnite 25 optionally contain fibrous constituents up to several millimeters in length.
The particle size limitation does not apply to foam particles used as fillers. Foam particles as large as a few mm in size (for example from 1 to 40 mm and preferably from 2 to 20 30 mm) may be used. Even 2 to 10 mm thick polyurethane foam sheets can be used.

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The total filler content should be above 5X by weight, preferably at least 30Z bg weight and more preferably m~re than 50% by weight (and, in many cases, more than 75~) by weight, with an upper limit of 97% by weight and preferably 95~ by weight. These percentages are based on the total weight of components (i) and (ii) (solid content). The lo,Jer limits are a~ly reached in exceptional cases where extremely light and voluminous fillers are used. The upper limit is generally determined by the cohesion and abrasion resistance of the carriers according to the invention. In extreme cases, it is even possible to increase the filler content to~97% by weight if a fixed-bed arrangement is used for the 6ubsequent use of the carriers in the biological treatment of sewage.
Particularly preferred carriers are materials containing filler combinations of fossil ligno-celluloses (particularly lignite dust) and/or carbon powder and/or polyurethane foam particles (preferably flexible polyurethane foam waste particles). Favorable properties are obtained with a combination of polyurethane foam particles with lignite. With the exception of the ferromagne~ic fillers, the fillers namely inorganic fillers or distillation residues, and other fillers of the type already mentioned used in addition to the preferred filler6 are preferably used in quantities of less than 35% by weight aLld more preferfibly in quantities of less than 20X by weight.
klthough the foam particles and the preferred lignite may be mixed in any ratios, they are preferably mixed in weight ratios of from 1:10 to 10:1 and more preferably in ratios of from 1:5 to 5:1.

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As already mentioned, the "~n situ" incor-poration of m"croorgani~ adapted for biological treabrent in sewage plants in polyurethanes or other plastics is not possible, even under ve~ mild and technically elaborate conditions,without significant losses of bacteria and a serious reduction in bio-activity. The production conditions must be adapted accordingly, particularly in regard to temperature (around +10C). Nevertheless, this process i8 not preferred and, in most cases, is not necessary because biomasses grow onto the foam, lignite or peat-containing polymer carriers in excellent fashion.
In principle, the polymer dispersions (ii) are any plastics dispersions which can be coagulated by addition of a coagulant and/or by the effect of heat, (i.e. aqueous dispersions of polymers produced by polymerization, polycondensation or polyaddition). The dispersibility of the polymers in water is guaranteed either by nonionic or by anionic or even by cationic emulsifiers which, in turn, may be present both in the form of external emulsifiers which are not incorporated in the polymer structure and in the form of internal emulsifiers chemically incorporated in the polymer structure. Tbe aqueous dispersions generally have a solids content of from 3 to 60Z by weight and preferably from 25 to 55Z by weight.
Aqueous dispersions of polymers of olefinically unsaturated monomers or aqueous polyurethane dispers~ons are particularly fiuitable. Natural lati~es, for example ~ -natural rubber latices, may also be used. The polymer 30 dispersions or latices generally contain primary particles having an average particle diameter of from -0.01 to 10 ~m, preferably below 3 ~m and more preferably below l~m. This means that the very finely divided latices prepared by emulsion polymerization have the Mo-2820 13283~ 9 advantage over the polymer dispersions prepared by suspension or bead polymerization. However, agglo-merates of primary particles may have a several times larger particle diameter.
The polymer dispersions suitable for use in accordance with the invention may be prepared by any of the known methods described, for example, in Houben-Weyl, Makromolekulare Stoffe, Vol. XIV/1. Suitable starting materials for the preparation of polymer d~spersions according to the invention are the usual olefinically unsaturated monomers, for example vinyl compounds, such as styrene, acrylonitrile, meth-acrylonitrile, acrylic acit, methacrylic acit, (meth) acrylates, allyl methacrylate, hydroxyalkyl acrylate, acrylic acit amite, ethylene, propylene, vinyl chloride, vinyl acetate, vinyl pyridine or semiesters of maleic acid. Preferred divinyl compounds are 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene and 2-chlorobutadiene (chloroprene), and p-divinyl-benzene.
The preferred polymer dispersions are polymer dispersions which form elastic films, whereas the dispersions which dry to form hard and brittle films are generally used solely as a co-component. Particularly interesting are, for example, the styrene-butadiene latices prepared by emulsion polymerization; latices of butadiene and acrylonitrile and methacrylic acid (these dispersions are optionally modified by copolymerized alkyl (meth)acrylates containing from 1 to 6 carbon atoms in the alkyl group); the known polyvinyl acetate dispersions which may contain alcoholic groups through partial hydrolysis; synthetic polyisoprene latices or natural rubber latex. Other suitable polymer dispersions include, for example, the known polychloro-Mo-2820 " .
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132~3~9 prene latices. Particularly preferred are the corresponding cationically modified latices because they have a fixing effect on the soluble constituents present in lignite dust or peat. Cationically modified latices are obtained, for example, when the monomers used are compounds containing tertiary nitrogen atoms which may be converted before, during or after the polymerization reaction into cationic ~roups, (for example by neutrali-zation with a suitable acid, such as for example hydro-10 chloric acid, sulfuric acid or phosphoric acid, or byquater.nization with a quaternizing agent, such as dimethyl sulfate for example). Polymer dispersions containing incorporated anionic centers may be obtained, for example, by using monomers containing carboxyl or 15 carboxylate groups. The neutralization of the carboxyl groups present, if any, is carried out with bases, such as for example sodium or potassium hydroxide or tri-ethylamine, during or after the polymerization reaction.
External emulsifiers present may be, for example, fatty 20 soaps, resin soaps, sulfates or sulfonates containing relatively long hydrophobic hydrocarbon radicals, ammonium salts based on paraffin amines, chlorides, sulfates or nitrates of esters based on paraffin fatty -~
acits and aminoalcohols, such as dimiethylaminoethanol, 25 or polyethylene glycolethers of fatty acids or fatty acid amides.
Aqueous polyurethane dispersions may also be used. Both nonionic-hydrophilically and also cationically and anionically modified polyuerethane 30 dispersions may be used. Preferred are those poly-urethane dispersions which contain the particular "emulsifiers" in chemically incorporated form. The preparation of suitable aqueous polvurethane dispersions is known and is described, for example, in "Die .
Mo-2820 Angewandte Makromolek~llare Chemie" 98 (1981), pages 133 to 165, and in "Progress in Organic Coatings" 9 (1981), pages 281 to 340. Cationically modified polyether-poly-urethane dispersions are particularly preferred, particularly where fossil lignocelluloses are used as fillers. Polyurethane dispersions containing ester groups are less preferred due to their susceptibility to hydrolysis. It is often preferred to use aqueous dispersions of branched polyurethanes in the form of sedimenting and redispersible aqueous suspensions.
The aqueous polyurethane dispersions may also be prepared by mixing an optionally ionically modified isocyanate prepolymer with water. A chain extending agent, for example a diamine, such as ethylene diamine, hexamethylene diamine or 4,4'-diaminodicyclohexylmethane or the sodium salt of N-(2-aminoethyl)-2-amino-ethane sulfonic acid (anionically modified diamine) may be incorporated in the system, so that formation of the polyurethane dispersion takes place with chain extension (which could also take place with pure water with urea formation).
The NCO-free dispersions thus prepared may be used in the process according to the invention immediately after its preparation or after storage for an indefinite period.
The preferred crosslinked polyurethane dispersions used as component (ii) in the process according to the invention contain dispersed particles having an average particle diameter of from 0.5 to 3 ~m, settle on storage for several day~, are readily dispersible and, when applied, for example to a glass plate, form water-resistant films.

Mo-2820 As far as the choice of the polymer dispersion is concerned, preferred are those type~i which form soft and elastic films. The particularly preferred polymer dispersions form films havin~ a Shore A hardness below 98, preferably below 95 and more preferably below 90.
Another component (iii~, which may optionally be used, is water which should be added to the systems to adjust a water content in the mixtures of (i) and (ii) to a value of from 20 to 90% by weight, preferably from 30 to 80% by weight and more preferably fro~ 35 to 65% by weight. The water i8 of particular 6ignificance to the process according to the invention. Not only does it provide for finely disperse distribution of the polymers, it is also an e~isential suspension ant/or emulsion aid for the fillers (i) and for any other additives. Since the optimal water content for any mixture depends on a number of parameters, including the nature of and quantitative ratio between the constituents, it is of advantage to determine those 20 parameters in preliminary tests. If too much water is used, coagulation is complicated and bleeding out of the polymer dispersions is often unavoidable. If too little water is uset, the fillers are not uniformly incorporated in abrasion-resistant form during the 25 subsequent gelation ant coagulation process.
Other auxiliaries and additives which may optionally be used include, in particular, substances havin~ a stabilizing ant/or crosslinking effect (including for example the known rubber auxiliaries 30 which may be used for crosslinking, such as for example zinc oxide and/or sulfur) and antiagers for avoiding --sensitivity to heat and light by autoxidation in the presence of oxygen. Suitable antiagers are, for example, phenolic compounds or aromatic amines or Mo-2820 13283~

iminothiazoles, such as o-tert.-butylphenol, metal salts or phenol thioethers, N-phenyl-2-aminonaphthalene, phenothioazine and tert.-butylpyrocatechol or 5-benzyl-lidene-3-hexadecyl-o-phenylimino-4-thiazolidone.
The auxiliaries which may optionally be used include, organic polyisocyanates which include both the usual low molecular weight polyisocyanates, such as for ex&mple 2,4- and/or 2,6-diisocyanatotoluene, 4,4'-diiso-cyanato-diphenylmethane, liquid derivatives of this diisocyanate or polyisocyanate mixtures of the diphenyl-methane series (phosgenation products of aniline/formal-dehyde condensates), including sump residues thereof, and NC0 prepolymers based on simple diisocyanates of the type ~ust mentioned and polyhydroxyl compound~ haYing a molecular weight in the range from 62 to 10,000 and preferably in the range from 400 to 6000. The polyester polyols and, in particular, polyether polyols known from polyurethane chemistry with molecular weights in the last-mentioned range are preferably used for the preparation of the NCO prepolymers, the corresponding tiols preferably be~ng used with higher polyols.
Trifunctional and higher polyols are used either on their own or in admixture with difunctional polyols for controlling the overall functionality of the NCO
25 prepolymers, so that the NCO functionality is from 2.1 to 3.5 and preferably from 2.2 to 2.8. Particularly preferred are the corresponding polyether polyols in the preparation of which ethylene oxide and/or propylene oxide are used. In many cases, it is also of advantage to use hydrophilically modified NCO prepolymers. These 30 hydrophilically modified NCO prepolymers may be both nonionic-hydrophilically modified prepolymers ~where the hydrophilicity is attributable to a high content of ethylene oxide units incorporated into polyether chains) Mo-2820 ; . , . , :
- ~ -.. ~. , . , . . ~ .. :

~, . ,: , 1328~19 and anionically or cationically modified NC0 prepolymers (which are obtained in cases where the NC0 prepolymers are prepared using polyhydroxyl compounds containing ionic centers or centers convertible into ionic centers). Polyhydroxyl compounds such as these include, aminopolyethers of the type obtained by alkoxylation of nitrogen-containing starter molecules, for example the alkoxylation products of N-methyldiethanolamine, ethanolamine, aniline or ethylene diamine; polyether diols containing sulfonate groups, for example of the type mentioned in U.S. Patent 4,108,814; or poly-hydric alcohols containing carboxyl or carboxylate groups, such as for example tartaric acid or dimethylol propionic acid and alkali salts thereof. Where poly-hydroxyl compounds containing tertiary nitrogen are usedin the preparation of the NC0 prepolymers, the conversion of the tertiary nitrogen atoms into ammonium groups may be carried out, for example, by subsequent quaternization, whereas the conversion of the carboxyl groups initially present, if any, into carboxylate groups may be carried out by reaction of bases, for example triethylamine, after formation of the prepolymer.
The polyisocyanates optionally used generally have an average functionality of at least 2, preferably of at least 2.1 and more preferably of at least 2.5.
Where NC0 prepolymers are used, as is preferably the case, they have an NC0 content of from 2 to 12% by weight and preferably of from 2.5 to 8Z by weight.
Under certain conditions, all the starting components required for preparation of the NC0 prepolymer may also be directly used in the fully continuous production of the filled carrier materials according to the invention, i.e. separate preparation of Mo-2820 ~ ,.. . , ... . .... , .. ... . ~ : , . .,, :

; .; - . , . - . . .: - -: - .-: . : .

.. , . , . . -, . . . . . .
`. . ' : .. , ' ~ :, . : ,: . :
. :. . , . , , ~ :.

-22- 132 83 lg the NCO prepolymer and intermediate storage are not absolutely essential. In this "in situ" preparation of the prepolymer, it has proved to be sufficient to react the low molecular weight or relatively high molecular weight polyols with aromatic di- and polyisocyanates in a flow mixer for brief periods, for example for periods of only about 10 to 60 seconds, at elevated temperatures of from 50 to 120C and preferably in the range from 80 to 100C.
If, after this short period, the isocyanate content is less than 50% and preferably less than 25%
above the calculated value for formation of the NCO
prepolymer, the incomplete NCO prepolymer formation does not adversely affect the properties of the carriers 15 produced therewith. On the other hand, this procedure is of considerable advantage for fully continuous production, particularly in cases where it is intended to use NCO prepolymers which have a limited storage life or which undergo a considerable increase in viscosity 20 during storage. NCO prepolymers of the type in question are, for example, those which contain certain quantities of compounds containing tertiary amino groups, for example diols or triols containing tertiary amines, in incorporated form.
The polyisocyanates mentioned by way of example are used, if at all, in quantities of up to 25% by weight and preferably in quantities of up to 15% by weight, based on the weight of components (i) and (iiXsclidc~t).
In this connection, however, it must be emphasized that, where fossil lignocellulose powders, particularly peat 30 and/or lignite powders, are used as component (i) in combination with ionically modified polymer dispersions as component (ii), it is preferred not to use nonionic or 2ni~ic NCO prepolymers or to use only low molecular Mo-2820 , . ; . - , -, ~ . . . . -;. , -, ~ . . , . - . ~.

: .~ .. :

.
~: - :. ' .:: ',, : ' ~
" , , ': . ':~ ' 13283~9 weight difunctional and/or trifunctional polyisocyanates in small quantities. Unless they are dispersible in water, the organic polyisocyanates are emulsified in the polymer dispersion. If they contain hydrophilic centers an~ are therefore, dispersible in water, they are preferably used in the form of aqueous emulsions.
Where ionically modified polymer dispersions (ii) and ionicallv modified polyisocyanates, particularly NC0 prepolymers, are used, it is not absolutely essential for these starting materials to be charged in the same way. Thus, it is possible for example to combine anionic polymer dispersions with cationic NC0 prepolymers or vice versa, so that an ampholyte is formed or the cationic NC0 prepolymer acts as a coagulant for the dispersion.
To carry out the process according to the invention, components (i) and (ii) and, optionally, (iii) and other additives are mixed at 10 to 70C and preferably at 20 to 40C. Polyisocyanates containing tertiary nitrogen atoms are preferably used where the fillers contain ac~dic groups (for example lignite containing huminic acids or peat containing huminic acid), so that the solubility in water of the huminic acids is reduced or suppressed by humate formation.
Where this procedure is adopted, anionically modified polymer dispersions are preferably used as component (ii). Where foams are used, the carriers formed when these starting components are mixed together preferably have a dry matter content of fr~m 35 to 120 kg Fer m3 of carrier-suspension 30 (in water without supernatant water)jin the absence of fo~, the carriers nave dry matter content of from 150 to 350 kg/m~ of suspension. Where fillers of high specific gravity, such as magnetite for example, are used, these values are comparably low in the presence of preformed foams, but amount to as high Mo-2820 .: , .

as 400 kg/m3 of suspension in the absence of foams.
However, in many applications, for example in the bio-logical treatment of sewage, the carriers have to be put at least periodically into and kept in a state of motion. Accordingly, high specific gravity fillers of the type in question with dry matter contents in excess of 150 kg/m3 of/suspension have to relatively finely divided, preferably with a particle diameter below 5 mm and preferably below 2 mm.
lO After mixing, the polymer dispersion (ii) is coagulated. Coagulation is based on a complicated colloid-chemical process which is influenced by a nu~ber of parameters and which takes place more or less quickly in several stages. Coagulation may be carried out both at room temperature by addition of a suitable coagulation aid and also, where thermally labile dispersions (ii) are used, by a heat treatment at 40 to 100C and preferably at 60 to 100C. Where ionically modified disperaions are used, suitable coagulation aids (flocculants or coagulants) are electrolytes which are preferably incorporated in the mixtures in the form of dilute, i.e. 0.5 to 5% by weight and preferably 1 to 2Z
aqueous solutions. Suitable electrolytes are, for example, sodium chloride, magnesium chloride, magnesium sulfate, calcium chloride or trisodium phosphate.
Highly dilute mineral acids, such as sulfuric, nitric or hydrochloric acid, or even carboxylic acids, such as acetic or formic acid, are also suitable flocculants.
It is also possible to add relatively highly concentrated, for example 10 to 30X by weight, oppositely charged polymer dispersions after preparation of the mixtures, resulting in ampholytic carrier ma~erials according to the invention. In many cases, coagulation is even best obtained both by addition of a flocculant and by a heat treatment.
Mo-2820 . .
.' . , ' :. ` ~ ,- ' .
- ... ... .
, . . ~- : :, .
.
,- . ~ . , ' , . . . . .

_~5_ 1328319 Surprisingly, nonionic, low molecular weight or relatively high molecular weight polyisocyanates also have a favorable effect in regard to coagulation on anionic polymer dispersions in particular, so that in many cases readily controllable, gradual gelation and coagulation takes place even in the absence of conventional coagulants at temperatures as lows as room temperature or slightly elevated temperature.
In cases where heat treatment is used for coagulating heat-sensitive dispersions, it may be carried out, for example, in a heating cabinet, optionally under reduced pressure, at temperatures of from 80 to 100C or in a hot air tun~el at 60 to 100C
and preferably at 85 to 97C. The water is optionally partly removed or, in some cases, almost completely removed. A particular form of thermal coagulation is the action of infrared radiation or microwaves. Where coagulation i6 induced by microwaves, the polvmer dispersions finely dispersed in the fillers are often converted in 20 to 60 seconds into a water-insoluble film which binds the fillers in abrasion resistant form.
Polymer carriers of relatively low specific gravity, of the type obtained for example where preformed poly-urethane foam granulates are used, may be carried by a stream of hot air into a cyclone in order to complete coagulation and, optionally, for simultaneous air separation for separating off certain particle sizes.
Products having a low residual moisture ~ontent are obtained in a short time.
During the coagulation process, the mixture may only be moderately moved unless porous foam particles are used as the filler (i). Preferably, the mixture should not be moved at all during the coagulation process to ensure that no primary filler particles which Mo-2820 : , . . :
- , ~ . . . ;
- - ~

4 . ~',",;'' ;.',' '" '' ' "'' . ' . .7; ''""'"'~ ' . ' ~ ' ',. .
~ ' . . . . .

1328~19 are not coated bv the coagulating dispersions remain behind. It is only where open-cell foams are used that this point is less critical to the extent that, surprisingly, coagulation may even be carried out with vigorous movement of the mixture so that the foam particles do not stick to one another.
However, coagulation of the dispersion should preferably take place only when the mixture as a whole is stationary, measures having been taken to ensure that the aqueous binder is uniformly dispersed beforehand.
To carry out coagulation, therefore, the flocculant is incorporated by mixing in the mixture of components (i) and (ii) and, optionally (iii), and other additives in the case of ionic coagulation, after which - apart from the exception mentioned above - the reaction mixture is left standing without any further movement. Depending on the nature of the polymer dispersion and upon the type of filler and flocculant used, coagulation begins in 30 seconds to 10 minutes and preferably in less than 3 minutes after addition of the flocculant. As men~ioned above, it may if desired be accelerated by simultaneous heat treatment. In cases where ionic NC0 prepolymers having a different charge from the pclymer dispersion (ii) are used, these ionic prepolymers are preferably added after preparation of the mixtures of (i) and (ii) 80 that the crosslinking produced by the prepolymer with water (~ith formation of polyureas~ accompanies the coagulation of the polymer dispersion which takes place particularly rapidly through the ionic charge of the prepolymers. If the polymers contain isocyanate reactive groups, the prepolymer may even be combined with the polymer through chemical bonds (not only being ionically connected).

.o-2820 ~,.: : . .

.. . .

13283~

The preparation of the mixtures and the incorporation of the flocculant by mixing may be carried out in mixing units of any type, for example in a screw trough or using a kneader or mixers equipped with plowshare-like tools. After coagulation, the carrier materials according to the invention accumulate in particulate form or as a granulate. If desired, they may be mechanically further size-reduced. It is often advisable to remove any ionic coagulation aids which may have been used by washing out the carriers accumulating with water if the coagulation aids in question could affect stability in storage or interfere with the subsequent application.
The process according to the invention may be carried out both continuously and also non-continuously.
Where flexible foams are used as component (i) in one preferred method, im~ediately after the starting components have been mixed and before coagulation begins, the material- iE compressed (optionally together with the coagulation aid,) to a fragment of its bulk in a suitable apparatus, for example a box-shaped metal container, and coagulated under pressure and optionally under heat in order to obtain a carrier material of predetermined size and dens~ty. This method is of particular interest where particularly light block polyurethane foams are used as component (i). Starting out from foam waste having a density of 25 kg/m3, it is thus possible, for example using only 15~ by weight of polymer dispersion (based on solids), to produce composites having a density increased by 6 to 10 times.
The compression-molded products may be cut into layers of any thickness or into sheets or size-reduced to any size in chopping machines.

Mo-2820 , . . . :
-: ;,, - .

. , :
, :

13283~9 As already mentioned, the production of carriers according to the invention, which are produced without foams as component (i) or as part of component (i), leads to carrier materials having a considerably s higher specific gravity.
In aqueous suspension, the polymer carriers filled to 100~ volume (without supernatant water) have a ~y ~t~r(~)c~toff~ ~x~t ~ ~ 3~ kg ~rm3 ~ ~sca~iersus~nsi~.
The types produced with foams have a preferred DM
content in aqueous suspension of from 40 to 95 kg/m3 while comparable types produced without foams, except for those produced with peat, have a DM content of from 150 to 350 kg/m3. By virtue of the saving of starting components (for the same volumes of suspension), the considerably larger proliferation surface for microorganisms and the fact that they may readily be used as required in a fixed bed, moving bed or fluidized bed, the highly filled carriers according to the invention are particularly superior. As mentioned above, the density of the carriers according to the invention varies within wide limits in dependence upon the nature of and quantitative ratio between the startin~ component~, their water content during production, the described degree of compression, if any, and particularly upon the specific gravity of the fillers (i). For an average water o~t ~ ~by weight, the density is generally in the ange from 300 to 700 kg~m and preferably in the range from 400 to 550 kg/m3. T~e water absorbency of the carriers (WA, explained hereinafter in the Examples) amounts to between 30 and 97Z by weight of water and preferably to more than 85% by weight of water, based on the total dry weight. The average particle size of the end products which generally accumulate in particulate form or as --Mo-2820 ., ~ . : .: , , . , ., ...... .;:. ~ ,... .. .

- :

13283~ 9 granulates is in the range from 1 to 10 mm and preferably below 5 mm, depending on the particle size of the fillers (i) used and on the formation of aggolomerates during mixing in the absence of foams.
Further aggolomeration may largely be avoided by rapidlv coating the fillers with the polymer dispersion. The polymer carriers which are correspondingly lighter with preformed foams may even accumulate and be used in much larger particle sizes. The fillers, more especially the foams preferably used, are present in the carriers according to the invention in completely changed form so far as their original structure and physical properties are concerned. As photographs taken with an electron microscope clearly show, the cell structure of the preferred flexible polyurethane foams is considerably strengthened by the coagulation of polymers from aqueous phase in accordance with the invention. The coagulated polymers coat the cell bridges of the foams and thus become an integral part of the foams with matrix-like, abrasion resistant incorporatlon of the fillers preferably used, such as lignite dust, so that, although the cells are reduced in size or in some cases are completely filled, they remain highly elastic with a specific gravity increased by 2 to 5 times, based on the foam used. Carriers of incre~sed specific gravity which sink slowly in water and which have very high water absorbency, penetratable proliferation surfaces and protective voids for microorganisms are thus obtained from worthle~s waste foams.
Inorganic fillers in very finely divided form may also be used for regulating specific gravity during production of these highly filled compositions. In this way, it is possible to adjust the necessary specific gravity for the clarified liquid and optionally to promote the transfer of oxygen to the bacteria.
Mo-2820 . ;: . ; ,. :

' ;' ' . ~ `,- "' ':, , `, , ' ' ;: .
' - !-. - ~ ' _30_ 1328319 In preferred formulations, the water-swollen hydrophilic carriers according to the invention are flexible, elastic, abrasion-resistant particles ~hich generally feel dry and which may be suspended in water and remain suspended therein or preferably sink 810wly.
It was not foreseeable that the optionally foam-containing polymers highly filled with such fillers as lignite would be able to be produced as highly hydrophilic, homogeneous or cellular carriers in sufficiently abrasion-resistant form, or would have such a favorable effect upon the biological treatment process, even though the active fillers, such as lignite for example, are embedded in the polymer material. It was also not foreseeable that the biomass of the bacteria would initially be present in the outer, coherent aqueous phase, only growing inwards from that phase.
The carriers used in accordance with the invention are suitable for most of the usual processes for the biological, aerobic or anaerobic treatment of sewage both in industrial and also in communal sewage treatment plants.
The biological conversion of organic impurities by means of bacteria with consumption of oxygen in bacterial masses consi~ting predominantly of carbo-hydrates and proteins and formed through proliferation, into C02 and water and, optionally, nitrates is known as aerobic sewage treatment.
The conversion of organic impurities, preferably carbohydrates, protein and fats without supply of oxygen using acid-forming bacteria, sulfate-reducing bacteria and methane-producing bacteria to form hydrogen sulfide, carbon dioxide and, in particular, methane, is known as anaerobic sewage treatment.

Mo-2820 .. . , ~ , ., , . . .... ,, . / . ~: .

: . : - . :
. . . .
. , - . .. . . . ~ .

. ~ . , .
... . :
, 13283~

Both in their stationary form and also in their preferred, moving form, the highly filled, highly water-absorbing carrier materials according to the invention provide or the improved biological treatment of sewage, including very surprisingly sewage having very low concentrations of contaminants, for example below 500 mg/l, which is very important for the final treatment stage in sewage treatment plants for the satisfactory removal of clarified water.
Accordingly, the treatment according to the invention may be carried out in the first activated sludge stage and/or in following activated sludge stages by delivering the carriers at any point to one or more combined activated sludge tanks. Since the carriers according to the invention are highly abrasion-resistant in water despite their relatively low polymer content, they may be used both in high-turbulence settling tanks and in tanks where the clarified sludge is moved only slightly, if at all. Thus, the highly filled carriers may be used in corresponding fluidized bed, movin~ bed or fixed bed arrangements.
Considerable turbulence is generated in the widely used aerobic treatment processes by introduction of air andtor (pure) oxygen. In this way, the highly filled carrlers and the activated sludge are kept in a state of vigorous movement in a so-called fluid bed.
Nevertheless, a covering of bacteria is formed on the surface and, to some extent, also ins~de the highly filled carrier. The filler incorporated in the carrier has a favorable effect in many respects on the improved disposal process. Depending on the nature of the fillers and of the polymer matrix, the mechanical strength and hydrophilicity of the carrier material are improved and, in particular, the biological Mo-2820 - -, . ~ -~ .
"

assimilability of the organic materials dissolved in the effluent is surprisingly increased. In addition, the filler or filler mixture incorporated in the polymer carrier is also a regulator for maintaining optimal specific gravities of the water-permeable carriers used in accordance with thP invention, so that the carriers are uniformly dispersed with a slight tendency to sink or a state of suspension is obtained in the usual, highly filled activated sludge tanks (which sre from about 4 to 12 meters deep). This is of particular importance or even an essential requirement in terms of process technology for most of the modern community or industrial biological sewage treatment plants.
In a special embodiment of the invention, the polymer carriers with their fillers and additives, if any, are formulated in such a way that they ~ink immediately or in a matter of seconds in the activated-sludge tank of the sewage treatment plant.
Despite adequate flooding with air and oxygen, they form with the adhering biomass, which grows considerably in volume after a certain time, a fluidized, moving or fixed bed permeated by an oxygen-containing gas with a supernatant carrier-free layer of water which may be changed by correspondingly vigorous gassing as required, for example for the occaslonal or continuous removal of surplus sludge. The highly filled, hydrophilic carriers used in accordance with the invention are not discharged in this case either.
In addition to the widely used aerobic biological treatment of sewage, the anaerobic treatment of effluents has also acquired considerable commercial significance, particularly for effluents of high carbo-hydrate content, for example in the food and cellulose industries. The polymer carriers produced and used in Mo-2820 ~, .~ . . . . I . . . . . .................... .

''' ' ' ' ' ' . " ' , ' ~. . ' ,~ ' . :

' '' ' - . ~ ' ' ' ' ' ' ' ' ' " ' . ' ' ' ' ~

accordance with the invention are eminently suitable for biologically controlling even very high pollutant concentrations in excess of 25,000 mg/l in a single effluent treatment stage or even for eliminating hitherto non-readily degradable organic chlorine compounds. In some cases, combined anaerobic and aerobic biological effluent treatment is particularly effective.
The degree of hydrophilicity in the highly filled polymer carrier materials according to the invention is preferably adjusted in such a way that a high uptake of water occurs over a period of a few hours or a few days with strong swelling or a relatively large quantity of water is present as disperse phase during the actual production of the polyurethane compositions, so that the carriers are already fully swollen. In anaerobic and also aerobic sewage treatment, the products according to the invention are capable of effectively eliminating relatively large quantities of gaseous products, such as carbon dioxide, methane or hydrogen sulfide.
As already mentioned, the "in situ"
incorporation of microorganisms in polyurethanes or other plastics in the case of the biomasses used for sewage treatment i8 not possible in practice, even under very mild and technically elaborate conditions, without losses of proliferatable bacteria and a considerable reduction in bioactivity. Such is not necessary for the use according to the invention because a large percentage of the bacterial cultures take a firm hold in the fully reacted, highly filled polymer carriers, suprisingly even in fluidized beds, and are even able to penetrate into the highly filled, highly swellable suspended carriers and are thus protected against Mo-2820 ,- . . ............ : , . . .

, :, .;

_34_ 1328319 mechanical damage. The bacteria are located at the same place at which the highly filled polymer carriers produced an increased concentration of dissolved contaminants through adsorption.
The efficiency of degradation and treatment, i.e. the improvement in effluent quality, obtained by the carriers of the invention is not confined solely to a distinct reduction in the chemical oxygen demand, but also promotes a drastic reduction in toxicity to daphniae and fish through elimination of otherwise non-readily degradable or non-degradable toxic compounds. In addition, the foul odor occurring in and around many sewage treatment plants is largely eliminated and the clarified sewage undergoes an additional distinct lightening in color. In addition, the capacity of existing biological treatment plants may be significantly increased.
As carriers, the highly filled polymer carrier materials according to the invention improve the treatment efficiency of biological treatment plants quite considerably in two respects. Not only can effluent ingredients generally be concentrated at the surface of the carriers, but it is also possible to enrich materials (for example chlorinated hydrocarbons, such as ethylene chloride), from effluents which otherwise could not be utilized by the microorganisms of the acti~ated sludge in their dissolved form tue to their low concentration among other readily degradable compounds. The substrate concentration of compounds of this type is thus raised to the level required for biological degradation. At the same time, microorganisms colonize the highly filled carriers and proliferate because of the highly enriched substrate.
Adsorption surfaces for substrates, (i.e. for the organic compounds present in relatively low con-Mo-2820 . ., , - ~ , ,, ,: - . . - . ~ . . : , ; . . . : : , - . . ' ~ , -~ -., . . , ` : : , .
~ ' centrations in the effluent) are released again after the conversion by bacteria. The processes of adsorption and utilization of dissolved effluent ingredients on the carriers on which the microorganisms have grown take place continuously. An equilibrium state is established between adsorption and enrichment of the materials dissolved in the water and the biological degradation by the micoorganisms which havè also populated the surface of the carrier. In this way, the surface is continuously regenerated. Similarly, an equilibrium is established between biomass growth on the highly filled polymer carriers and elimination of the materials depending upon the substrate available, 80 that increased biomass activity iB permanently maintained on the carriers.
It is possible to increase and, in general, to at least double the concentration of activated sludge in biological sewage treatment plants by using the carriers of the invention and hence to increase the volume-time load several times, so that the capacity of existing sewage treatment plants i8 considerably increased. New plants may also be built with smaller tank volumes.
One 6imple application of the carriers iB in their addition to a conventional biological activated-sludge tank. The carrier particles are kept in ~uspension and uniformly distributed in the activated sludge tank by gas/liquid flow. By vircue of their extremely high abrasion resistance, the highly filled carriers may also be used without difficulty in activated sludge tanks equipped with surface aerators.

Mo-2820 k~
? - ;
,: , : . . ~ . ;

13283~ ~

The carriers may be used in the nitrification and denitrification of sewage, because the microorgan-isms required for this purpose grow slowly and preferentially on growing surfaces.
For aerobic sewage treatment, plants may be operated as fluidized-bed reactors. In the case of fixed-bed reactors, the direction of flow may be both upwards and also downwards. They may also be operated as trickling filters. By virtue of their particularly large surface, the highly filled, preferably cellular polymer carriers may also be advantageously used as a covered surface (immersion trickling filter).
For use in the field of sewage treatment, several possibilities are open. As already mentioned, the plants may be operated both as moving or fluidized beds and as fixed beds. In the case of fixed-bed operation, the highly filled polymer carriers may be used in granular form or in the form of fixtures, for example in the form of rolled-out mats or preformed inserts. In this case, too, the direction of flow through the fixed bed may be both upwards and also downwards. In general, the mote of operation is generally determined by the particular condition and special characteristics of the sewage.
In addition, it is even possible effectively to free conventionally biolcgically pretreated effluents from contaminants of the type which con ain a relatively very large percentage of non-readily degradable organic residues.
It is also possible with the carriers according to the invention to free offgases from organic consti-tuents (for example offgases from sewage treatment plants or the offgases from production processes for organic compounds,) by single or repeated suction Mo-2820 . . - ~ . , , .. .. .. ~ .. . -.

' . ~ .

_37_ 1 3 2 8 3 1 9 through or in contact with moist or wet or water-suspended highly filled polymer carriers.
For e~ample, waste air can be introduced (for example from above) and, at the same time, water trickled downwards through one or more columns arranged in series which are filled with the carriers of the invention in the form of a packing compressed to between 50 and 80% by volume and to which suitable microorganism suspensions may optionally have been added for biological degradation. After residence times of only about 5 to 60 seconds, there is a marked biological elimination of organic contaminants which, after a relatively short starting phase, leads to a vigorous proliferation of degrading microorganisms. Even in this economically favorable process, as in aqueous suspensions, the adsorption of the contaminants and their degradation are completed at the same time and at the same place in a physical-biological equilibrium in the presence of a film of moisture on and in the carrier material. The surplus of growing microorgani6ms may be removed by occasionally filling the bioreactor columns one or more times with water and passing a vigorous air stream through them.
The disposal of the carrier materials used in accordance with the invention is relatively simple by virtue of their inert character. For example, in sewage treatment plants in which the surplus activated sludge is burned in a fluidized bed furnace, the carriers may be discharged (optionally together with the surplus activated sludge) after long-term use and burned as an energy source. In general, however, it is not necessary to replace the carrier as a whole.

Mo-2820 ;. ..
,. , ., ~:

132831~

Another important use for the carrier materials is as a carrier for bacteria or enzymes in bioconversion processes for the production of complicated organic compounds. The particulate polymer carrier materials may readily be separated off from the reaction vapors or fermentation vapors by filtration (for example for the production of citric acid from starch, for the hydrolysis of penicillin G by acylases to form 6-aminopenicillanic acid, for the production of stereo-specific biologically active compounds or for thefermentation of sugar containing waters in the sugar beet industry).
The value of the polymer carrier materials according to the invention lies in their highly hydrophilic character and, in some cases, in their light porous structure. Accordingly, they may also be used for improving soil or as special growth substrates for hydrophilic, quick-rooting plants because they may contain plant nutrients, may carry a long lasting supply of water and fertilizer and will reswell without difficulty.
In addition, seeds may be mixed with the carrier materials during their production, subsequently germinated and used.
The part~culate carriers may also be used as a filtering medium for finely divided, emulsified or suspended impurities in water and may b regenerated, for example by back-washing. The carriers according to the invention may be used as adsorbents for (crude) oil or other, water-insoluble organic liquids.
The invention is further illustrated but is not intended to be limited by the following examples in which all p~rts and percentages are by weight unless otherwise specified.

Mo-2~20 . . - ` -. ~

_39_ 1328319 EXAMPLES
1. Preliminary Observations:
Characterization of the filler-containing polymer characters:
Excess water is added to the carrier material obtained (which may be granulated) which is then completely swollen for 24 hours (at room temperature).
After stirring, the supernatant water is decanted off.
The value derived therefrom, which is the percentage by weight of water in and between the swollen carrier (filler-containing polymer carrier), i8 referred to as the water absorbency (WA) value.
The solid~ content of the aqueous su6pension of the granulate thus prepared in the form of a now highly swollen carrier material amounts (for Example 1) to 5g.5 g of solids per liter of "suspension" (without supernatant water).
The solids content in 1 liter of this suspension (without supernatant water) i8 referred to as the dry matter content of the su~pension (DM(S) for short).
The weight of 1 liter of this suspension of the highly swollen carrier material (without supernatant water) is referred a8 the suspension weight (SW for 8hort).
The value of the so-called suEpension factor (F4) i8 derived from the weight of 1 liter of the suspension (SW) and the value of the dry latter of the carrier (DM-S) contained therein. The value of the 30 suspension factor F4 minus 1 (F4-1) indicates how much water (based on carrier dry matter) i9 present in the suspension as a whole (as swelling water and as water in the interstices in or between the carrier particles).

Mo-2820 - , , ~ , In practice, the value of the suspen.sion factor F4 is determined by dividing the weight o~ the suspension (SW) by the weight of the carrier dry matter (DM(S) contained therein:

F4 = SW
DM ( S ) .
The water absorbency (WA) value, as a charac-teristic of the carriers to be used in accordance with the invention, may be determined from the value of the suspension factor F4 in accordance with the following equatiOn WA = F4 minus l . 100; (in %) This water absorbency (WA) value expressed in % by weight gives a picture of the state of the highly swollen csrrier materials. In Example 1, for example, the dry matter content of 1 liter of the suspension without supernatant water amounts to 59.5 g solids. For a suspension weight of 1001 g per liter of suspension, the suspension factor F4 is thus 1595 or 16.8.
Accordingly, l part bg weight of carrier dry matter is converted into the described swollen suspension form with 15.8 times the quantity of water. In other words, the water absorbency value amounts to 15.8 divided by 16.8 times 100 ~ 94%.
Sl: densitv, dr~ined:
The carrier i8 suspended for 24 hours in a large excess of water. A 2 mm mesh sieve is then filled to a height of lO cm with the swollen carrier and left to drain for 1 hour. The residual filling is then weighed in a measuring vessel and converted to the density (g~l).

Mo-2820 ,, . - . .- . .. . . . .

~; . - : . - . .. ..
- , : .
., ~ ~ , ' . . - . . . .

S2: density, squeese-dried:
The carrier drained as in Sl is exposed for 5 minutes to a pressure of 3 bars on a 1 mm sieve and then weighed in a measuring vessel. The density S2 is determined after conversion to 1 liter.
S3: densltY dried:
The moist, squeeze-dried carrier as in S2 is dried in vacuo for about l day at 100C to constant weight and weighed as above in a measuring vessel.
In the Example mentioned above, the values thus determined for Sl to S3 are as follows:
Sl (drained) 492 g/l S2 (squeeze-dried) 214 g/l S3 (dried) 73.5 g/l.
For better comparability of the values, the following factors are also defined:
Fl: The volume factor i8 the quotient of the weight of the drained samples swollen in water per liter and the quantity by weight of dry matter from 1 liter of aqueous 20 suspension (DM(S).
Fl = Fl DM ( S ) F2: The 6queezing factor is the quotient of ~he quantity of the squeeze-dried sample per liter (tensity S2) and the quantity of dry matter per liter of suspen6ion.
F2 = S2 DM(S) .

F3: The swelling factor is the quotient of the quantity by weight of the drained sample (Sl) and the quantity by Mo-2820 ,.. ~ . . . , . - : -- , . . . . . . . , . -, . - - .
.: , - . . . . - . -: . . . . ..

-42- 132831~
weight of dry matter determined after complete removal of the water from the drained sample (DM(Sl)).

F3 = Sl DM(Sl) In the Examples, the chemical oxygen demand was determined in accordance with DIN 38 409, Part 41 (December 1980), the fish toxicity in accordance with DIN 38 412, Part 15 (June 1982), the daphniae toxicity in accordance with DIN 38 412, Part 11 (October 1982) and the odor threshold value by the Deutsche Einheits-verfahren zur Wasseruntersuchung, Loseblatt-S c lung (German Standard Methods for Testing Water, Loose-leaf Collection) 1982 Edition, Verlag Chemie-Weinheim.
2. Composition and Production of Special Pol~urethane Startin~ Components 2.1 Production of the NCO prepolymers, non-continuous process for the Examples The NCO prepolymers are prepared in known manner in a stirrer-equipped apparatus by heating the starting components (relatively high molecular weight polyhydroxyl compound, optionally low molecular weight polyols, optionally polyols containing tertisry nitrogen snd polyisocyanates) at temperatures of from about 70 to 90C until the calculated NCO content is substantially reached. For compositions, see Table 1.

Mo-2820 ~ , ~ . . . . .

s ,- , .
- - .

V7 ,~
C~ N
N
~:
V) O
~, I _l _ ~ J
~ o Om 8 m u_ ~ I I S I 0-LO ~ C~ C~ t~C~ ~) L _ C-Oc ~ ._ O
~, c c~l u~ ~ ~ ~ cn 0._ 0 U:~ 0 U~~D N
O ~ ~ ~ r~e~
g c~ cr c Co Z . . _ _ .
_~ ~ ,Co, C~ l O
.~ ~ ~ ~ C~ U
C O
O ~ _ _ ~ c~ E
.~ ~, ~ O
C ~') ~ ~ 4-V~ ~ U~o L~ _ C
C~J ~ CL o --~ . ~ _ C . L E
. ,> o o ~ o O ~ Vl C ~ O~ C
O Z In 1~i L C~
G IIS
._ 8 ., CL Z
~C L m ~, c ~ ~ _~
m .~ N o c~ o O ~n O . ~ o7 L
L~ O O ~ ~) L V~
V~ tO ~ ~ ~ ~ O

U~ _ _ C C Z ~
~ C ~ ~ .~ C
L ._ ~ ._ ~,1 ~I ~ O) ~o 3 ~
" " 1, "
C ~ C~
C~ o o ~ ~
~ o m ~ ~ o m o --Mo-2820 ,- . : , . . , : :

- , : ,, ' ~' ' . . . ' ' ~: ' ' : ' . ' .:

_44_ 1328319 Isocyanates used:
TDI Tolylene diisocyanate (80:20 2,4-: 2,6-isomer mixture) Polyether polyols:
PHILV = Hydrophilic, branched trimethylol-propane-started polyether reacted with 40 psrtæ of propylene oxide and 60 parts of ethylene oxide, OH number 26.
0 PHOBV e Hydrophobic, branched trimethylol-propane-started polyether reacted with 80 parts of propylene oxide and then with 20 parts of ethylene oxide, OH number 28.

5 PHOBL - Hydrophobic, linear polyether of 1,4-butane diol and propylene oxide, OH number 56.
Compound containing tertiary nitrogen:
NM e N-methyl diethanolamine.
Stabilizer (partial ialt formation~:
SA - Concentrated sulfuric acid Quaternizing agent:
DMS - dimethyl sulfate.
2.2 Preparation of aqueous polYurethane ures dispersions (PUR)(HS)) from NCO prepolYmers 5 2.2.1 Cationic PUR tisPersion 1 - CPURl The dehydrated mixture of the li~ear and branched hydrophobic polyether polyols (for composition, see Table 1) is comb~ned at around 100 to 130C with the tolylene diisocyanate isomer mixture left at room temperature in a flow mixer i.e. a high-speed barbed stirrer mixer equipped with barbs in the stator and rotor. An NCO prepolymer is formed after an average residence time of about 20 to 60 seconds and is combined Mo-2820 .. , . . ~ . . , _45_ 13283~9 in a following flow mixer with 2.1 times the quantity of water (based on NC0 prepolymer) heated to 20 - 30C.
The chain-extending reaction which takes place rapidly in the water under heat, even in the absence of catalysts (with polyurea formation and elimination of C02), is completed under high turbulence in a large-volume stirrer vessel. In the preparation of the 35% cationic polyurethane (HS) dispersion CPURl from the branched cationic polyether-NC0 prepolymer COPP, the extending reaction in the water takes 5 minutes at 50 to 70C and 15 minutes at room ~emperature for complete reaction of the isocyanate groups.
2.2.2 Anionic PUR dispersion - APUR2 In the preparation of the anionlc PUR
dispersion APUR2 from the nonionic branched poly-ether-NC0 prepolymer OPP, a dilute aqueous solution heated to 30C of the sodium salt of N-~2-aminoe~hyl)-ethane sulfonic acid is used instead of pure water as in 2.1.1. The extending reaction with the diamine is immediate and, with the water, takes about 30 minutes at 50 to 60C.
The aqueous ionic polyurethane-urea dispersions prepared in accordance with 2~2.1 and 2.2.2 have a solids content of 35~ by weight and a particle size of from 0.5 to 3 ~m, show a tendency towards partial sedi-mentation on standing for several days, but are redispersible after indefinite storage and are eminently suitable for use as binders and coating agents for producing the highly filled polymer carriers according to the invention where the carriers are required to show lon~-term resistance to water.
3. Characteristics of the Ionic PUR
Dispersions Mo-2820 " , . . .

.. - - : : .
.. ..
. .

.,. : .

13283~9 CPURl: A 35% cationic crosslinked polyether polyurethane (HS) dispersion of the NC0 prepolymer COPP (see Table 1) and water.
APIJR2: A 35% anionic crosslinked polyether polyurethane (HS) dispersion of the NC0 prepolymer OPP (Table 1), a diol sulfonate and water (see preparatiOn).
APUR3: An anionic,crosslinked polyether poly~rethane (HS) dispersion based on an NCO-prepolymer prepared by rezction of a branched (P~BV) and linear polyether (~H~') polyol (ratio by weight 88:12), dimethylolpropionic acid (in such a quantity, to introduce 200 milli-equivalents of carboxylate groups/ kg polyurethane), with isophorone diisocyanate to form a NCO-prepolymer with 3,7 % NCOj, chain extended and dispersed with water under addition of triethylamine to form the carboxylate salt.
CPmR4: A cationic, slightly crosslinked polyureth~ne (HS) dis-persion, based on a prepolymer t3,2% NCO), prepared by reaction of the linear polyether (PHOBL) and hexandiol-1,6-polycarbonate (OH-number 56) in a ratio by weight of 35:65, under addition of 1 ~ by weight of the NCO-pre-polymer of trimethylolpropane and N-methyl-diethanolamine (to introduce 300 milliequivalents of tertiary nitrogen per kg polyurethane) with excess hexamethylene diisocyanate arld chain extension and dispersion with water and quaternization with dimethylsulfate.
4. Characteristics of Polymer Dispersions The di6persions are referred to as latex, LAT
for short; A -i anionic, C - cationic, NLAT ~i natural rubber lateY..
CLATl: A cationic polymer, 40~ dispersion of butadiene, acrylonitrile and trimethylol ammonium ethyl-methacrylic acid ethylester chloride in a ratio by weight of 68:28:4.
ALAT2: An anionic polymer, 40Z dispersion of butadiene, acrylonitrile and sodium methacrylate in a ratio by weight of 52:41:7; Shore A hardness of the film: 50.

, . - i ; .~

. ~? ,:, `; : , :

', _47_ 1328319 ALAT3: An anionic, 40% dispersion as ALAT2, but distinctly softer formulation (Shore A 20), of butadiene, acrylonitrile and sodium methacryle.te in a ratio by weight of 62:34:4.
ALAT4: An anionic polymer, 50% dispersion of styrene, acrylonitrile and sodium methacrylate in a ratio by weight of 55:42:3.
ALAT5: An anionic polymer, 40% dispersion of styrene, butadiene and sodium acrylate in a ratio by weight of 78:20:2.
ALAT6: An anionic polymer, 40% dispersion of equal parts by weight of butylacrylate and vinyl-acetate with 2% by weight of sodium acrylate, based on solids.
5 CLAT7: A cationic polymer having a small anionic content, i.e. a partially ampholytic 40X aqueous heat-sensitive dispersion of 2-chlorobutadiene (chloroprene).
NLAT8: A natural rubber latex stabilized with natural protein.
5. Characteristics of the Foam Used As Filler (Examples 1 to 15) Mixtures of irregularly size-reduced waste of various densities (from about 15 to about 110 kg/m3) from the intustrial production of polyether-polyurethane block and molded foams were used for the flexible foam.
The dry powder dens~ty of the flexible foams, consisting predominantly of block foam waste, is approximately 14 g/l. Particle size 1 mm to 12 mm.
Powder densities after suspension in water Sl: 263 g/l;
S2: 101 g/l; S3: 14 g/l; DM-S (dry matter content in aqueous suspension): 12.5 g/l suspension.
Mo-2820 ; : . : :: , ... :: :: - , 6.1 General procedure for the non-continuous production of filled polYmer carriers in accordance with the invention.
6.1.1 Production method Dl usin~ preformed PUR foams The production of the highly fllled polymer carriers used in the Examples is carried out at around room temperature or at moderately elevated temperature (up to 60C) on the batch principle either in an intensive mixer consisting of a heatable cylindrlcal container mounted obliquely on a rotatable plate and equipped with a stirrer designed to be introduced eccentrically and to rotate in the opposite direction to the plate, or (for ~he production of relatively large quantities) in horizontally mounted mixers equipped with plowshare-like tools.
The fillers are initially introduced, water is ~-optionally added in a quantity exceeding the water content of the polymer dispersion and the aqueous polymer dispersion is intensively stirred in. A dilute aqueous solution, emulsion or suspension of the preselected coagulant (electrolyte or polyelectrolyte) is optionally added to the mixture over a per~od of about 2 to 3 minutes, optionally followed by heating.
The rotational speed of the mixer must be slowed down considerably to avoid the formation of undesirable fines.
6.1.2 Production method D2 without preformed foams In the absence of preformed pol~arethane foam granulates, intensive mixing is carried out for only 30 to 60 seconds at room temperature or for about 30 seconds at 45 to 60~C, after which the coagulant is optionally stirred in over a period of about 10 seconds.
The mixture is then left standing until coagulation is over. The granular product is then applied to enamelled Mo-2820 f' ~ , ` : ' , , "" : ; . ' . : :
~ ' . : ' . "' ~ ', ' ' , ' ' ' , .
': ' ,, ' ' 'i ' `' ' ' ' ' 'f, . . ' , , , ~ ' :
` ' ` ' ' ' ~ ' ~ ~, ' _49_ 1328319 steel sheets and dried. DependinR on the mixer, the quantity of water used and the coagulation rate and also the temperature, a more or less granular to bead-like coagulate which has the particle size subsequently S required is actually formed during the final phase of stirring. Coarser fractions may be size-reduced to the necessary particle size in a chopping machine on completion of coagulation. Where preformed foams are used, the reaction mixture may be at least moderately stirred in the mixer during the actual coagulation process, resulting in the formation of highly filled polymer carrier particles corresponding in their particle size to the foam used.
6.1.3 Production method D3 (composite foam) The mixtures containing preformed foam granulates (after all the components have been mixed in over a total period of about 40 to 120 seconds) are introduced into molds and, depending on the required density, are compressed to the corresponding volume and coagulated. A composite foam i8 formed and may be cut into any shapes or granulated. This method gives polymer-bound products which ave a comparatively higher density than the products coagulated in the absence of pressure. A density of 280 kg/m3 was obtained for Example 13 and a density of 160 kg/m3 ior Example 14.
The formulations and physical propertie~ of the composite foams granulated to> 6 mm are shown in Tables 2 and 3.
6.2 General procedure for the continuous Production of polymer carrier materials in accordance with the invention (continuous process ~ CP) The apparatus used is a twin-paddle screw trough having a capacity of approx. 180 liter and a length of approx. 300 cm in which the paddle shafts Mo-2820 . . ..... . . .
, . . . , . . - , ~ , ., . ~ ~ .

_50_ 1328~19 rotate in opposite directions. The product is forced along from the iniet opening towards the outlet opening, the reaction mixture being kneaded or compressed to a certain extent between the paddle shafts. The size-reduced polyurethane foam waste and other fillers are separately introduced into the screw trough through metering screws. The water, if any, additionally necessary and the aqueous polymer latex and optionally low molecular weight polyisocyanates and the NCO
prepolymer used, if any, are introduced at the same place by means of piston pumps and gear pumps~
respectively. It is advisable, although not absolutely necessary, to intensively mix the polyisocyanate compounds with the polymer dispersion or with approximately twice the quantity of water at 10 to 25C
for 1 to 3 seconds in a flow mixer or in a static mixer and thus to convert them into an emulsion because, in this way, the dried add~tional fillers used, if any, are wetted extremely quickly and uniformly with the rest of the water heated to 30 - 60C, which may be separately introduced. The aqueous polymers uniformly coat the solids in very finely divided form.
After a residence time in the screw trough of about 3 minutes, a dilute aqueous solution of the coagulant is sprayed through a 1 mm diameter nozzle into the last third of the mixing unit. Through an opening in the underneath of the trough at its end, the pregelled and, partly, already coagulated polymer carrier is carried by means of a conveyor belt into a hot air drying tunnel where coagulation is completed over a period of 3 to 10 minutes at a product temperature of 40 to 90C. In a following, inclined rotary tube washer with forced downward circulation, in the interior of which a perforated metal tube with Mo-2820 .- . . . . .
~c - . , s.~ , , ¢ . ., : :

.

installed washing jets is coaxially mounted, the product is washed with such a quantity of water that any troublesome fines or soluble salts are eliminated during the discharge of the reaction product. For an average residence time of 2 minutes, approximately 3 times the quantity of water, based on the dry matter content of the polymer carrier, is required for washing. A
th~oughput of about 1 to 2 tons per hour, based on the formulation as a whole, is reached.
6. EXAMPLES 1 to 24 (Production and use of the polymer carriers according to the invention) EXAMPLE 1 (Production) A porous, flexible polymer carrier containing foam and lignite and bound with CLATl.
40 parts by weight of the flexible foam granulate described in 5 above, and 53.8 parts by weight of a native, thermally highly dehydrated lignite from the Aachen lignite field having a residual moisture content of 7% by weight, which had been size reduced into particles less than 100 ~m in size and which are therefore present as lignite dust, are introduced into an Eirich mixer at room temperature by method Dl and combined by intensive stirring with 25 parts by weight of the latex CLATl. After 2 minutes, 10 parts by weight of a 2X sulfuric acid solution are added. The stirrer is then switched to a much lower speed and the reaction mixture is heated to 90C. In 10 minutes, a carrier material is formed in the form of a water-swollen, slightly elastic solid which largely remains in the form of particles less than 12 mm in size and, in general, does not have to be size-reduced any further.
The carrier material obtained, which does not bleed in water, is then suspended in excess water, Mo-2820 . , : - -,;. - - . - . . :. . .
; , . .
.
: . . . . ., ~ , , . , : : .
. : , . . ~ , completely swollen for 24 hours (at room temperature) and the supernatant water is decanted off. The value derived therefrom, which represents the percentage by weight of water in and between the swollen carrier (filler-containing polyurethane urea), is referred to here as the water absorbency (WA) value.
In Example 1, the dry matter content of 1 liter of the suspension without supernatant water amounts to 59.5 g of solids. For a suspension weight of 1010 g per liter of suspension, the suspension factor F4 works out at ~ 5 = 16.8. Accordingly, 1 part by weight of carrier dry matter is converted with 15.8 times the quantity of water into the swollen suspension form described above. In other words, the water absorbency value amounts to 15.8 divided by 16.8 times 100 ~ 94%.
For further characterizing the carriers, the densities S1 to S3 (in g/l) are determined after different forms of treatment.
In the Example mentioned above, the values thus determined for Sl to S3 are as follows:
Sl (drained) 492 g/l S2 ~squeeze-driet) 214 g/l S3 (dried) 73.5 g/l.
The compositions and the values of the volume, squeezing and swelling factors Fl to F3 of Example 1 are shown in Tables 2 and 3 below together with the corresponding data of other Examples.

Mo-2820 , : . -- - ~ , . . . , - : , : -. , . ~ ~ :. , . -_53_ 13283~9 E r~ ,~ 0 ~r-- ~ ~ co r~
~ ~ o Ll ) V~ ~D C~J ~ ~ ~ N
-O .Q ~ t~ O 1~ 1~ ~
X V) 11~0'1 ~ N '~ C~l ~ U'~ 00 ~O
_, ~ ~ ~tel~ In ~ el ~~t U) U~ O 0 0 ~ O O O~0 ~
E o :E _ X ~ .
o o ~ o o U~ ~ o U~
L :~: . -- e~ ~C~l el C~.l ~ el1` ) O O C~ ~ O O O O O O O O O
~ O ~ . Il~
~ C~ O O O U~ O U~ O, O U~
_ S :--~ cn X 0~ ~ ~O 0 O~ 0 0 Ul .
_l ~
E ~ Z Z z Z z _) z z z ~ ~ .
_ L~J J C Vl I--II N Cl C
l~ _~ S
-J E _.
a~ _C~J z. O~ I l_ I I I I I I O
--' ~ ~ ~ ~D 0 ~) .-- ~ _ J J~ ~ ~ I I
~ OD
._ ._, . O ~ 0 ~ o o c U~ . ~ ~ ~
~ ~ ~y. .
._ ~ . I~ ~ C
O L . O O O
C ~ . .
~4 o O
(~ ~ . .

~ ~ . .
~0 ~ ~ ' O
E ~:D In , , , ~ ~ , , ~CD
~0 ~ .
et al L ~ o o o o o O
U~

~ ~ 3 N O O O O 0 1~ 0 0 0 O C~ ~ etu~
._ ~ q~
._ _ C
O ~ 'CL
~. x E . .
O ~ X o 4-LLI Z _~ ~ ~ I~ 0 Mc)-2820 : , . . , . :. . . . ~
': , '' : ; , . .: :
, -54- 1328~1 U~
I~ cn ~ o~ o 1~ o _4 ~ ~~ ~ oo o~ ~ o~ ~t ~ ~
N~D O ~ CJ~ C~l~70~ ~ t-- ~D1-- CO
V~ ~ N
_~ O 1 U~ O ~D ~D ~-- ~OD ~ 1-- COr~ a~
_~ u~ et ~ ~ ~ ~ U~ e~ ~DU~
L0 N O U')U-~
. . . . . ~ o O
~ _ ~ O ~ ~O~ 0 U~
e_~
O U') U~ O OU'~ U) 0 0:~
d ~ ~ ~1 e~
_ ~ _ _ _ ~ ~UO~ U~
v7c~l O O O O C~~n o In u~ o u~
_I 01 ~D 00 O ~ O ~ O X 0 0 :~ _~
_~ ~ Z Z Z Z Z Z Z Z Z Z
~ J O
C L~
~ ~ I O
O O o- ~ O
Z _I C~l ~ t- 1~
C~J ~ e~ C ~ ~ J ~
OD ~ ~ ~ ~ ~ ~ O~
m J r_ u~ o co ~ ~ '~
~ ~ C~J
. r~
.. a~
~: ' . C~
V ~
.: ~ ~ ~ ~ ~o ~D

V U~ I I ~ ~ ~ ~
,:
~ e~ ~

U~ o o ~ o U-e~
~ C~ O ~D O 0 0~ 0 C- ~ ~ ~ U~
Q~
E
X O O _ ~ ~ ~ U'~ ~D 1~ 0~ O~ O
l~J Z ~ ~ N

;. ., . `

: ~ . . . .. , ~ :

:: . . : . ..
.:
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1328~19 Explanation of Table 2 Quantities in parts by weight, based on dry matter Columns 1 Example number 2-13 Composition and reaction conditions 5 2-6 Fillers (i) 2 PFW = polyether-polyurethane foam waste, for characteristics see under 5 3 Lignite dust, see Example 1 4 Active carbon, average size lO<~m, 50Z by weight 4<~m Carbonized lignite dust, average size 220<~m, 80% by weight lOO<~m 6 Magnetite, particle size 0.1-2 ~m 7+8 Polymer dispersions 15 7 Cationic (C) or anionic (A) PUR dispersion, see point 3 8 Cationic (C) or anionic (A) polymer dispersions see point 4 9 NCO compounds TDI - 2,4- and 2,6-diisocyanatotoluene in a ratio by weight of 80:20 Opp e hydrophobic NCO prepolymer, see Table 1 Electrolyte solutions Mg - 2Z magnesium sulfate solution (approx. 0.2% by weight magnesium sulfate, based on polymer solids) Sl - lN
sulfuric acid solution (approx. 0.2X by weight H2S04, based on polymer solids) S2 - 5X acetic acid solution (approx. 0.4% by weight acetic acid, based on polymer solids) L ~ lN sodium hydroxide solution (approx. 0.3% by weight sodium hydroxide, based on polymer solids) 11 For production methods, see description point 6 NC ~ non-continuous, CP = continuous Mo-2820 ~ . ', ' . ! . .

-56- 13283~9 12 Heat sensitization, temperature in C
(coagulation) 13 Water content (% by weight), based on total quantity ;M = water content of the mixture before coagulation;RM = residual moisture content after coagulstion 14-17 Physical properties 14 Dry matter content in kg per 1 m3 of suspension for lOOX
filling, i.e. without supernatant water) 15-17 Sl-S3, densities, ~ee Example 1 (drained, ~queeze-dried and dried) Mo-2820 ...

` ' ' ' . ~ ' , ,, ' ' ~ . ' .

, ', ', ; ~ ' .',, " ' . ~' ' - ' ' : .

_57_ 1 32 g3 Table 3:
Volume (Fl), squeezing (F2) and swelling (F3) factors of the highly filled polymer carriers for Examples 1 to 20, also suspension factors (F4), water absorbency (WA) and solids content of the suspensions (SCS).

Example No. Fl F2 F3 F4 ~WA %SCS
1 8.3 3.6 4.7 16.8 94.0 6.0 2 8.3 4.~ 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 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 8.1 3.3 5.2 16.3 93.g 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 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 ~2.8 17.2 2~ 19 3.1 3.1 3.3 5.4 81.5 18.5 2.0 2.0 2.0 4.0 75.0 25.0 EXAMPLES 21 to 24 -The use of carriers in biolo~ical sewa~e treatment:
Characterization of the biological fixed bed/fluidized bed bioreactor used The aerobic fixed-bed method is referred to as process Ia) and the fluidized-bed method correspondingly as process Ib).
Mo-2820 ~:

. .
- - ~ . . . - . : . ~

.
~ , :

13283~9 A sidestream of the ef~luent from the first activated sludge stage of an industrial plant having COD
values of 350 ilOO mg/l (are occasionally ~ 250 mg/l) and BOD5-values of 23 i 15 mg/l is pumped continuously into a 100 liter tower-like bioreactor. The bioreactor is two-thirds filled with the carrier material which the activated sludge mass is intended to colonize, i.e. the polymer carrier occupies a ~olume of 66.6%. The gas required for gassing and supplying oxygen to the reactor is delivered to the reactor from below through a frit or perforated plate. By supplying large quantities of oxygen-containing gas, the column may be operated as a fluidized bed or, where the gas is supplied in small quantities, as a fixed bed. The oxygen-containing gas emerges at the frit or perforated plate in the form of small bubbles and flows upwards through the reactor together with the water similarly feed in from below and exits thorugh the upper part of the reactor. In a few days, a biological covering is formed from the reactor filling (polymer carrier). After an average retention time of 4 hours, the treated sewage i8 introduced via the outlet into a settling tank. Particles of the biological covering flushed out from the bioreactor settle in the settling tank and may be removed through a shutoff cock. The biologically purified sewage leaves the settling tank with the improved data indicated in the Examples.
The acclimatization time is 4 wçeks. The analytical data shown in Table 4 represents the average 30 values of 5 analyses. The anaerobic biological treatment i8 essentially carried out by the fixed-bed method and it is only to avoid differences in concentration in the bioreactor that an inert gas is occasionally introduced at intervals into the bioreactor Mo-2820 ;v~ . . . .. . . -,; . . , - -,~ : ;. .:,: . . :

instead of air or the carrier is periodically subjected to a gentle mechanical movement.
EXAMPLES 21 to 24 Table 4 (COD elimination in aerobic biological treatment, COD =
chemical oxygen demand) Carrier COD-Example according elimination No. to Example Influent Effluent Process m~!l Z_ - none 379 357 - 22 6 none 240 211 - 29 12 none 682 660 - 20 3 21 1 379 170 Ia 209 55 22 6 379 141 Ib 238 63 23 15 240 129 Ia 111 45 24 1 682 218 Ib 462 68 EXAMPLES 25 and 26 Waste water from oxygen bleaching of a sulfite cellulose factory, which had a content of CSB 5500 mg/l were subjected in parallel and continuously operating arrangement to anaerobic microbial treatment.
The trials were performed in 1.6 liter capacity 25 anaerobic arrangements, as they are described by W. J.
Jewell in ';Journal of the Water Pollution Control Federation," Vol. 53, No. 4, p. 484, (Fig. lb). Average hydraulic residence time of the waste water in the --~
reactor was 38 hours (1.6 days). The decomposition 30 trials were performed in the following variations:
Arrangement 1 (blank test without carrier as comparison) (Example 25) -400 ml suspended cells Mo-2820 ~ -: ' ' - ' " ' : ' ' ' . ' . ' . . ' ' ' ' ' ' ~
.. . . .. . . ... . . . .

-60- 13283~
Arrangement 2 (according to the invention) 400 ml suspended cells plus 400 ml polyurethane polymer carrier mass of Example 1 (see Table 2).
Arrangement 3 (Example 26) 400 ml suspended cells and 400 ml polyurethane polymer carrier mass according to Example 6 (Table 2).
The suspended cells were taken from the anaerobic reactor of a sugar factory.

10 After the equilibrium conditions were reached (34 days), the following results were obtained:
Arrangement CSB in Polymer Carrier No. Discharge Mass,aCCo~i~ ~ ~scripti~ in:

Blank test 1 2190 --15 Example 25 2 1630 Example 1, Table 2 Example 26 3 1670 Example 6, Table 2 Although the invention has been described in detail in the foregoing for the purpose of illustration, it i~ to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claim~.

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Claims (8)

1. A process for the production of filler-containing, polymer-bound compositions comprising (A) mixing (i) from 5 to 97% by weight based on the solid content weight of components (i) and (ii) of a filler selected from the group consisting of (a) cellular plastics, (b) fossil lignocelluloses or natural materials containing finely-divided fossil lignocelluloses, (c) carbon powders, (d) finely divided distillation residues, (e) finely divided inorganic fillers, and (f) mixtures thereof, wherein the particle size of filler (a) is from 0.1 µm to about 1 cm and the average particle size of fillers (b) to (e) is from 0.1 to 1000 µm, with (ii) an aqueous polymer dispersion having a solids content of from 3 to 60% by weight selected from the group consisting of (a) polymer dispersions based on olefinically unsaturated monomers, (b) natural latex, and (c) mixtures thereof which are mutually compatible dispersions, said dispersion being stabilized by external and/or internal nonionic-hydrophilic, anionic, and cationic emulsifiers or hydrophilic groups, and (iii) optionally water, so that the water content, based on all the components, is between 20 to 90%
by weight, and (B) coagulating said polymer dispersion.

2. The process of Claim 1, characterized in that said filler is selected from the group consisting of (a) cellular plastic particles, (b) fossil lignocellulose powders, (c) carbon powders, and (d) mixtures thereof.

3. The process of Claim 1 wherein said filler is selected from the group consisting of (a) cellular plastic particles, (b) lignite powders, (c) peat, (d) active carbon, (e) coal powders, (f) carbonized lignite powder, (g) coke powders, and (h) mixtures thereof.

4. The process of Claim 3 wherein said filler further contains powder-form ferromagnetic inorganic material.

5. The process of Claim 1, characterized in that coagulation is obtained by the action of a coagulant and/or by the effect of heat.

6. A polymer-bound carrier material obtained by the process of Claim 1.

7. In the biological treatment of waste-containing liquid by the removal of organic matter by microorganisms, the improvement which comprises adding the carrier material of Claim 6 to said liquid.

8. In a fermentation process, the improvement wherein the carrier material of Claim 6 is added as a carrier for the bacteria or enzymes used in said process.