Mechanochemical process for producing valuable products free from persistent organic pollutants and other organohalogen compounds from waste comprising plastics and plastic laminates

Abstract

A mechanochemical process for preparation of valuable products free from persistent organic contaminants and other organic halogen compounds, from waste of non-mixed and mixed, plastics and plastic laminates which is contaminated with persistent organic contaminants and/or contain the organic halogen compounds. Shredded waste is filled into a mill containing milling balls and is further shredded by milling. At least one dehalogenating agent is added. The mixture is milled further, and milling is stopped after a set time period. Before or after this step a further additive is added. The resulting products are separated from the milling balls, and the resulting halogen containing water-soluble products are jettisoned by washing with aqueous solvents and/or the resulting halogen containing, water-insoluble products are not washed out, but remain in the valuable products as fillers. Valuable products prepared in accordance with the process, and methods for their use are also provided.

Claims

1. A mechanochemical process for preparation of products free from organic halogen compounds, from disposable waste of mixed and unmixed plastics and plastic laminates, said plastics and plastic laminates being contaminated with organic halogen compounds, the process comprising the process steps of: (i) shredding the disposable waste containing the organic halogen compounds, (ii) milling the shredded waste into a mill containing milling balls, (iii) adding at least one reductive dehalogenating agent, selected from the group consisting of solutions of alkali metals and alkaline earth metals in liquid ammonia, liquid amines or aqueous solvents, Zintl phases, graphite intercalation compounds of alkali metals, saline hydrides, complex hydrides, complex transition metal hydrides or metal hydrides, aluminum, iron, zinc, lanthanum, the lanthanides and the actinides, into the milled shredded waste to form an admixture, (iv) further milling the admixture containing milled shredded waste and the at least one reductive dehalogenating agent, the further milling providing mechanical energy for a reaction of the at least one reductive dehalogenating agent with the organic halogen compounds to change structure of the admixture, (v) (a) separating the milling balls, and (b) separating formed halogen containing water-soluble products by washing with aqueous solvents, and (vi) checking washed water-insoluble products after drying as to whether they still contain the organic halogen compounds, and (vii) before and/or after the process step (iv) adding at least one additive, selected from the group consisting of charcoals, bio charcoals, pyrogenic char, polyoxometalates and sands.

2. The mechanochemical process of claim 1, wherein the products free from organic halogen compounds are selected from the group consisting of: plastics, wherein the organic halogen compounds are at least reduced or completely eliminated, polymers which form copolymers, blockcopolymers, graftcopolymers, combcopolymers and polymer blends from otherwise incompatible polymers, polymers having a modified surface cross-linked by radical reactions at the ends of the polymers, polymers with a diamondoidal reinforcement, polymers with a graphene insertion providing high stabilization, polymer composite materials activated by the mechanochemical process, microcrystalline and nanocrystalline co-crystals of the polymers built up during the mechanochemical process by self organization, polymer composite materials, polymer alloys and microcrystalline and nanocrystalline co-crystals, doped with impurity atoms, selected from the group consisting of scandium, yttrium, lanthanum, the lanthanides, uranium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury, boron, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulfur, selenium and/or tellurium, copolymers with superabsorbers, superabsorbers by addition of oxygen radicals, peroxides and/or ozone, reacting with the radicals at end groups of the polymers, MOFs, rotoxanes, cage-like compounds, metalorganic lattice works and selforganizing systems, mesoporous materials with different pore sizes, pore size distributions, degrees of cross-linking, mesh-values, hydrophobic, superhydrophobic, hydrophilic, superhydrophilic and hydrophilic-hydrophobic polarities and/or thermal and electric conductivities and/or magnetic properties, polymer additives homogeneously distributed in the polymeric products and have applicational properties, including a reinforcement against pressure, shear forces and/or tensile forces, resilience towards weathering, radiation and/or chemicals, a higher cross-linking, a lower solubility, a lower swelling because of a higher cross-linking, a lower solubility, a lower swelling because of cross-linking and/or a better capability to bind water or lipids, sand-filled composites for building materials, and topological materials.

3. The mechanochemical process of claim 2, wherein the composites for building materials are filled with desert sand.

4. The mechanochemical process of claim 2, further comprising manufacturing materials comprising the products free from organic halogen compounds, the materials being selected from the group consisting of high-grade polymeric engineering materials, polymer additives, reversible and irreversible absorbents for water or oils, materials for desalination of seawater and of oversalted soils, catalysts, electrode materials for batteries, building materials and shieldings of electrical and magnetic fields.

5. The mechanochemical process of claim 1, wherein the at least one additive comprises tungstensilicic acid H.sub.4[Si(W.sub.3O.sub.10).sub.4].

6. The mechanochemical process of claim 1, wherein the disposable waste comprises polyether ketone (PEK) and polyether sulfone (PES) moldings contaminated with polychlorobiphenyl (PCB).

7. The mechanochemical process of claim 1, wherein the disposable waste comprises aluminum-EPDM (ethylene propylene diene monomer) polymer bilayer foil contaminated with polychlorobiphenyl (PCB).

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) The plastic wastes can derive from thermoplastic polymers, polycondensation resins and/or (co-)polymers as well as their mixtures.

(2) As the thermoplastic polymers, all customary and known linear and/or branched resins and/or blocklike, comblike and/or statistically structured polyaddition resins, polycondensation resins and/or (co-)polymers of ethylenically unsaturated monomers come into question.

(3) Examples of suitable (co-)polymers are (meth)acrylate(co-)polymers and/or polystyrene, polyvinyl ester, polyvinyl ether, polyvinyl halides, polyvinyl amides, polyacrylonitrile, polyethylene, polypropylene, polybutylene, polyisoprene and/or their copolymers.

(4) Examples of suitable polyaddition resins or polycondensation resins are polyesters, alkyds, polylactones, polycarbonates, polyethers, proteins, epoxy resin-amine adducts, polyurethanes, alkyd resins, polysiloxanes, phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, cellulose, polysulfides, polyacetals, polyethyleneoxides, polycaprolactams, polylactides, polyimides and/or polyureas.

(5) As is known in the art, thermosets are prepared from multifunctional, low molecular and/or oligomeric compounds by thermally initiated (co-)polymerization and/or by (co-)polymerization initiated by actinic radiation. As multifunctional, low molecular and/or oligomeric compounds, the reactive diluents, catalysts and initiators mentioned below come into question.

(6) Moreover, wastes of polymer blends such as styrene/phenylene ether, poly amide/polycarbonate, ethylene-propylene-diene elastomers (EPDM), acrylonitrile-butadiene-styrene copolymers (ABS) or polyvinyl chloride/polyethylene can be reacted mechanochemically.

(7) Furthermore, the plastic wastes can derive from functionalized polymers which contain the functional groups and/or the functional additives as hereinafter described.

(8) Customary and Known Functional Groups

(9) Fluorine, chlorine, bromine and iodine atoms; hydroxyl, thiol, ether, thioether, amino, peroxy, aldehyde, acetal, carboxyl, peroxycarboxyl, ester, amide, hydrazide and urethane groups; imide, hydrazone, hydroxime and hydroxamic acid groups; groups which derive from formamidine, formamidoxime, formamidrazone, formhydrazidine, formhydrazidoxime, formamidrazone, formoxamidine, formhydroxamoxime and formoxamidrazone; nitrile, isocyanate, thioisocyanate, isonitril, lactide, lactone, lactame, oxime, nitroso, nitro, azo, azoxy, hydrazine, hydrazone, azine, carbodiimide, azide, azane, sulfene, sulfene amide, sulfonamide, thioaldehyde, thioketone, thioacetal, thiocarboxylic acid, sulfonium, sulfur halide, sulfoxide, sulfone, sulfimine, sulfoximine, sultone, sultame, silane, siloxane, phosphane, phosphinic oxide, phosphonium, phosphoric acid, phosphorous acid, phosphonic acid, phosphate, phosphinate and phosphonate groups.

(10) Customary and Known Functional Additives for Plastics

(11) Examples of suitable additives are reactive thinners which can be cured thermally or by actinic radiation, low boiling organic solvents and high boiling organic solvents (“long solvents”), water, UV-absorbers, light protecting agents, radical scavengers, thermolabile radical initiators, photoinitiators and co-initiators, cross-linking agents as they are used in one-component systems, catalysts for the thermal cross-linking, defoamers, deaerating agents, siccatives, slip additives, polymerization inhibitors, emulsifiers, wetting agents, dispersing agents, and tensides, adhesion promoters, spreading agents, film forming agents, sag control agents (SCA), rheology agents (thickeners), flame retardants, drying agents, anti-skinning agents, corrosion inhibitors, waxes, matting agents, reinforcing fibers, sands, in particular desert sands, and precursors of organically modified ceramic materials.

(12) Examples of suitable thermally curable reactive thinners are the isomeric diethyloctane diols or hydroxyl group containing hyperbranched compounds or dendrimers as they are disclosed, for example, in the German patent applications DE 198 05 421 A1, DE 198 09 643 A1 and DE 198 40 405 A1.

(13) Examples of suitable reactive thinners which are curable by actinic radiation are described in Römpp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 491 under the heading »Reaktivverdünner«. In the context of the present invention, actinic radiation means corpuscular radiation, like electron radiation, alpha radiation, beta radiation and proton radiation as well as electromagnetic radiation like IR-radiation, visible light, UV-radiation, x-rays and gamma rays. In particular, UV-radiation is used.

(14) Examples of suitable low boiling organic solvents and high boiling organic solvents (“long solvents”) are ketones like methyl ethyl ketone, methyl isoamyl ketone or methyl isobutyl ketone, esters like ethyl acetate, butyl acetate, ethylethoxy propionate, methoxypropyl acetate or butyl glycol acetate, ethers like dibutyl ether or ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol or dibutylene glycol dimethyl, diethyl or dibutyl ether, N-methylpyrrolidone or xylenes, and mixtures of aromatic and/or aliphatic hydrocarbons like Solventnaphtha™, benzene 135/180, dipentene or Solvesso™.

(15) Examples of suitable thermolabile radical initiators are peroxides, organic azo compounds or C—C-splitting initiators like dialkyl peroxides, peroxocarboxylic acids, peroxodicarbonates, peroxoesters, ketone peroxides, azodinitriles or benzpinakolylsilylether.

(16) Examples of suitable catalysts for the cross-linking are dibutyltin dilaurate, dibutyltin dioleate, lithium decanoate, zinc octoate or bismuth salts like bismuth lactate, or dimethylolpropionate.

(17) Examples of suitable photoinitiators or co-initiators are described in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag Stuttgart, 1998, pages 444 bis 446.

(18) Examples of additional cross-linking agents, as they are used in so-called one-component systems, are aminoplast resins, as they are described in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, page 29, »Aminoharze«, in the textbook “Lackadditive”, of Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 242 and following, the textbook “Paints, Coatings and Solvents”, second completely revised edition, Edit. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pages 80 and following, in the patent documents U.S. Pat. No. 4,710,542 A 1 or EP-B-0 245 700 A 1 and in the paper of B. Singh et al., “Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry”, in Advanced Organic Coatings Science and Technology Series, 1991, volume 13, Seiten 193-207, carboxyl group containing compounds or resins, as they are described, for example, in the patent document DE 196 52 813 A 1, hypoxy group containing compounds or resins, as they are described for example in, the patent documents EP 0 299 420 A 1, DE 22 14 650 B 1, DE 27 49 576 B 1, U.S. Pat. No. 4,091,048 A or U.S. Pat. No. 3,781,379 A, blocked polyisocyanates, as they are described, for example, in the patent documents U.S. Pat. No. 4,444,954 A, DE 196 17 086 A 1, DE 196 31 269 A 1, EP 0 004 571 A 1 or EP 0 582 051 A 1 and/or tris(alkoxycarbonylamino)-triazine, as they are described in the patent documents U.S. Pat. Nos. 4,939,213 A, 5,084,541 A, 5,288,865 A oder EP 0 604 922 A 1.

(19) Examples for suitable deaerating agents are diazadicycloundecane oder benzoin.

(20) Examples of suitable emulsifiers, wetting agents and dispersing agents, or tensides are the customary and known anionic, cationic, non-onionic and zwitterionic wetting agent, as they are described in detail, for example, in Römpp Online, April 2014, Georg Thieme Verlag, “Netzmittel”.

(21) An example of a suitable adhesion promoter is tricyclodecane dimethanol.

(22) Examples of suitable film-forming agents are cellulose derivatives such as cellulose acetobyrate (CAB).

(23) Examples of suitable transparent fillers are those on the basis of silicon dioxide, aluminum oxide or zirconium oxide; additionally, reference is made to Römpp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, 1998, pages 250-252.

(24) Examples of suitable sag control agents are ureas, modified ureas and/or silicic acids, as they are described, for example, in the documents EP 0 192 304 A 1, DE 23 59 923 A 1, DE 18 05 693 A 1, WO 94/22968, DE 27 51 761 C 1, WO 97/12945 or “farbe+lack”, 11/1992, pages 829 and following.

(25) Examples of suitable rheology additives are known from the patent documents WO 94/22968, EP 0 276 501 A 1, EP 0 249 201 A 1 or WO 97/12945; cross-linked polymer microparticles, as they are disclosed, for example, by EP 0 008 127 A 1; inorganic layered silicates, such as aluminium-magnesium-silicate, sodium-magnesium- and sodium-magnesium-fluorine-lithium layered silicates of the montmorillonite type; silicic acids, such as Aerosil; or synthetic polymers with ionic and/or associating groups, such as wie polyvinylalkohol, poly(meth)acrylamide, poly(meth)acrylic acid, polyvinylpyrrolidone, styrene-maleicacid anhydride or ethylene-maleicacid ahydride copolymere and their derivatives or hydrophobically modified ethoxylated polyurethanes and polyacrylates.

(26) An example of a suitable matting agent is magnesium stearate.

(27) Examples of suitable reinforcing fibers are carbon fibers, basalt fibers, boron fibers, glass fibers, ceramic fibers, silicic acid fibers, metallic reinforcing fibers such as steel fibers, Aramide fibers, Kevlar fibers, polyester fibers, nylon fibers, Teflon fibers, polyethylene fibers, polypropylene fibers, PMMA fibers, lignin fibers, cellulose fibers and other natural fibers, such as

(28) Seed Fibers:

(29) Cotton, kapok, pappelflaum, akon, bamboo, nettle, hemp, jute, kenaf, linen, hops or china grass fibers;

(30) Hard Fibers:

(31) Pineapple, caroa, curaua, henequen, Newseeland flax, sisal or coconut fibers; Wool and fine animal hairs:

(32) Wools from sheep, alpaka, lama, vikunja, guanaco or angora, rabbit fur, camel hair, caschmir and mohair;

(33) Coarse Animal Hairs:

(34) Cattle, horse or goat hair;

(35) Silk:

(36) Mulberry silk, tussah silk or mussel silk;

(37) Mineral Fibers:

(38) Erionite, attapulgite, sepiolithe or wollastonite fibers;

(39) Cellulose Fibers:

(40) Viskose, Modal, Lyocell, Cupro, Acetate or Triacetate fibers;

(41) Rubber Fibers

(42) Plant Protein Fibers:

(43) Soja protein or zein and other prolamine fibers;

(44) Protein Fibers:

(45) Fibers on the basis of casein, albumines, collagen, glykoproteines, globulines, elastine, nucloproteines, histones, keratine, chromoproteines, protamines, fibrinogene, phosphoproteines, myosine, lipoproteines or hydrophobines; Fibers on the basis of starches and glucose:

(46) Alginate or Chitosan Fibers;

(47) Fibers on the Basis of Synthetic Biologically Polymers:

(48) Polylactide fibers (PLA) and polyesters (cf. Biologisch abbaubare Polyester—Neue Wege mit Bismutkatalysatoren, DISSERTATION zur Erlangung des Grades eines Doktors der Naturwissenschaften des Fachbereichs Chemie der Universität Hamburg, vorgelegt von Gesa Behnken, aus Hamburg, Hamburg 2008).

(49) The fabric can consist of multiple different fibers; therefore, they can be mixed fabrics.

(50) Suitable precursors for organically modified ceramic materials are hydrolyzable metal organic compounds, in particular of silicon and aluminum.

(51) Additional examples of the additives mentioned above as well as examples of suitable UV-absorbers, radical scavengers, spreading agents, flame retardants, siccatives, drying agents, skin-preventing agents, corrosion inhibitors and waxes are described in detail in the textbook “Lackadditive” of Johan Bielemann, Wiley-VCH, Weinheim, New York, 1998.

(52) Further examples of additives are dyes, colored pigments, white pigments, fluorescent pigments and phosphorescent pigments (phosphors) as well as the materials hereinafter described.

(53) Carbohydrates:

(54) Glyceric aldehyde, erythrose, threose, ribose, arabinose, xylose, lyxose, fructose, allose, altrose, glucose, mannose, idose, galactose talose, rhamnose, amino sugars like neuramic acid, muraminic acid, glucosamine and mannosamine, aldonic acids, ketoaldonic acids, aldaric acids, pyranose, saccharose, lactose, raffinose, panose as well as homopolysaccharides and heteropolysaccharides und proteoglycanes, wherein polysaccharide proportion outweighs the protein proportion like starch, dextran, cyclodextrine, arabinogalactane, celluloses, modified celluloses, lignocelluloses, chitin, chitosan, carageene and glycosaminoglycane.

(55) Monoalcohols:

(56) Methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert.-butanol, amylalcohol isoamylalcohol, cyclopentanol, hexanol, cyclohexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol their stereoisomers.

(57) Polyols:

(58) Glycerol, trimethylolpropane, pentaerythritol, alditols, cyclitols, dimers and oligomers of glycerol, trimethylolpropane, pentaerythritol, alditols and cyclitols; in particular, tetritols, pentitols, hexitols, heptitols and octitols; in particular arabinitol, ribitol, xylitol, erythritol, threitol, galactitol, mannitol, glucitol, allitol, altritol, iditol, maltitol, isomaltitol, lactitol, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, deca-, undeca- und dodecaglycerol, -trimethylolpropan, -erythritol, -threitol and -pentaerythritol, 1,2,3,4-tetrahydroxycyclohexane, 1,2,3,4,5-pentahydroxycyclohexane, myo-, scyllo-, muco-, chiro-, neo-, allo-, epi- und cis-Inositol.

(59) Polyhydroxycarboxylic Acids:

(60) Glyceric-, citric, tartaric, threonic, erythronic, xylonic-, ascorbinic, gluconic, galacturonic, iduronic, mannuronic, glucuronic, guluronic, glycuronic, glucaric, ulusonic, diketogulonic and lactobionic acid.

(61) Polyhydroxyrthenols and Polyhydroxycarbonic:

(62) Pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-trishydroxybenzene, phloroglucine, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dihydroxybenzoic- and 2,4,6-, 2,4,5-, 2,3,4- and 3,4,5-trihydroxybenzenic acid (bile acid).

(63) Amines:

(64) Ammonia, ammonium, mono-, di- und trialkyl-, -aryl-, cycloalkyl-, -alkylaryl-, -alkylcycloakyl-, -cycloalkylaryl- and -alkylcycloalkylarylamine, such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, tert.-butylamine, benzylamine, cyclohexylamine, dodecylamine, cocoa amine, talc amine, adamantylamine, aniline, ethylendiamine, propylendiamine, butylendiamine, piperidine, piperazine, pyrazolidine, pyrazine, quinuclidine und morpholine.

(65) Thiols:

(66) Mercaptopropionic acid, dimercaptosuccinic acid (DMSA), dithiothreitol (DTT) and octadecanethiol.

(67) Click-Chemistry:

(68) Compounds for click-reactions, such as the copper catalyzed cycloaddition of azides and alkines, Diels-Alder reactions, reactions, for example, of folic acid with alkine groups and dipolar cycloadditions, for example, with poly(tert.-butylacrylate).

(69) Fatty Acids:

(70) Laurinic-, myristinic, oleic-, palmitinic, linolic, stearinic, arachinic and behenic acid.

(71) Polymers and Oligomers with Functional Groups:

(72) Poly(trimethylammonium-ethylacrlylate), polyacrylamide, poly(D,L-lactide-co-ethyleneglykol), Pluronic®, Tetronic®, polyvinylalcohol (PVA), polyvinylpyrrolidone (PVP), poly(alkylcyano acrylate), poly(lactic acid), poly(epsilon-caprolacton), polyethylenglykol (PEG), poly(oxyethylene-co-propene)bisphosphonate, poly(acrylic acid), poly(methacrylic acid), hyaluronic acid, algininic acid, pectinic acid, poly(ethyleneimine), poly(vinylpyridine), polyisobutene, poly(styrenesulfonic acid), poly(glycidylmethacrylate), poly(methacryloyloxyethyl-trimethylammoniumchloride) (MATAC), poly(L-lysine) und poly(3-(trimethoxysilyl)propylmethacrylate-r-PEG-methylethermethacrylat), proteins, such as treptavidin, trypsin, albumin, immunoglobulins, oligo- and polynucleotides, such as DNA and RNA, peptides like arginylglycylaspargic acid (RGD), AGKGTPSLETTP-peptide (A54), HSYHSHSLLRMF-peptide (C10) and gluthathione, enzymes like glucoseoxidase, dendrimers like polypropylenimine-tetrahexacontaamine-dendrimer generation 5 (PPI G5), poly(amidoamine) (PAMAM) and guanidine-dendrimers, phosphonic acid und dithiopyridine functionalized polystyrenes, functionalized polyethylenglykols (PEG: degree of polymerization 4-10, in particular, 5) like PEG(5)-nitro DOPA, nitrodopamine, mimosine, hydroxydopamine, hydroxypyridine, hydroxypyrone and carboxyl.

(73) Chelating Agents:

(74) Complexones like nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid (EDTA), phosphonic acids like [(2-aminoethyl)hydroxymethylene]- and [(5-aminopentyl) hyroxymethylenediphosphonic acid, and crown ethers.

(75) Metal Complexes:

(76) Customary and known coordination, sandwich und chelate complexes of metals and their cations with organic and inorganic anions, in particular, fluoride, chloride, bromide, iodide, cyanide, cyanate, isocyanate, sulfide, thiocyanate and/or isothiocyanate, and/or molecules like ammonia, amines, phosphines, thiols, boranes, carbon monoxide, aromatic oder heteroaromatic compounds.

(77) Sands:

(78) River sand, sea sand, desert sand, beach and fossilized minable sand.

(79) Moreover, the polymers wastes can contain diamagnetic micro- and nanoparticles, such as oxides from the group consisting of scandium oxide, yttrium oxide, titanium dioxide, zirconium dioxide, yttrium-stabilized zirconium dioxide, hafnium dioxide, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, iron oxide, chromium oxide, molybdenum oxide, tungsten oxide, zinc oxide, oxides of the lanthanides, preferably, lanthanium oxide und cerium oxide, in particular cerium oxide, oxides of the actinides, magnesium oxide, calcium oxide, strontium oxide, barium oxide, aluminium oxide, zinc-doped aluminium oxide, gallium oxide, indium oxide, silicon dioxide, germanium oxide, tin oxide, antimony oxide, bismuth oxide, zeolites, spinels, mixed oxides of at least two of the mentioned oxides like antimony-tin oxide, indium-tin oxide, bariumtitanate, leadtitanate oder lead-zirkonate-titanate; phosphates wie hydroxylapatite or calciumphosphate; sulfides, selenides and tellurides of the group consisting of arsenic, antimony, bismuth, cadmium, zinc, iron, silver, lead and copper sulfide, cadmium selenide, tin selenide, zinc selenide, cadmium telluride and lead telluride; selenium and selenium dioxide (cf. Shakibaie et al, »Anti-Biofilm Activity of Biogenic Selenium Nanoparticles and Selenium Dioxide against Clinical Isolates of Staphylococcus Aureus, Pseudomonas Aeruguinosa, and Proteus Mirabilis«, Journal of Trace Elements in him Medicine and Biology, Vol. 29, January 2015, pages 235 to 241); nitrides like boron nitride, silicon nitride, aluminium nitride, gallium nitride und titanium nitride; phosphides, arsenides und antimonides of the group consisting of aluminium phosphide, gallium phosphide, indium phosphide, aluminium arsenide, gallium arsenide, indium arsenide, aluminum antimonide, gallium antimonide and indium antimonide; Carbons like fullerenes, graphene, graphene oxide, functionalized graphene, in particular, functionalized with hydroxyl groups, carbonyl groups, amino groups and epoxy groups, functionalized graphite, graphite oxide, graphite intercalation compounds, diamond and functionalized and non-functionalized carbon nanotubes; nanocellulose particles, like cellulose nanofibers (CNF), cellulose microfibrils (MFC), nanocrystalline celluloses (CNC), microcrystalline cellulose (MCC) and bacterial nanocellulose (BNC), ausgewählt; metal organic frameworks (MOFs); carbides like boron carbide, silicon carbide, tungsten carbide, titanium carbide or cadmium carbide; borides like zirkonium boride; and silicides like molybdenum silicide.

(80) Furthermore, the polymer wastes can contain magnetic and/or magnetizable nanoparticles and/or microparticles, such as iron, cobalt, nickel and alloys of iron with at least one metal selected from the group consisting of ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium scandium, yttrium, lanthanum, cerium, praseodym, neodym, samarium, europium, gadolinium terbiumoxid, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, titan, zirkonium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, aluminum, gallium, indium, thallium, germanium, tin, lead, antimony and bismuth; examples of suitable metal alloys are magnetically soft metal alloys like Permalloy® on the basis of nickel and iron, nickel-iron-zinc alloys oder Sendust on the basis of aluminum, silicon and iron; RE.sub.1−yFe.sub.100−v−w−x−zCo.sub.wM.sub.zB.sub.x, wherein RE designates a rare earth metal from the group of cerium, praseodym, neodym, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium and M designates a metal from the group of titanium, zirkonium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten and v=5-15, w≥5, x=9-30, y=0.05-0.5 and z=0.1-5; the aforementioned metals and metal alloys can contain at least one additional metal and/or non-metal, which is or are selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, carbon, silicon, nitrogen, phosphorus, arsenic, oxygen, sulfur, selenium, tellurium, fluorine, chlorine, bromine and iodine in non-stoichiometric amounts. A particularly useful material of this kind is NdFeB; and metal oxides, garnets, spinels and ferrites; examples of particularly useful materials of this kind are Fe.sub.3O.sub.4, CoFe.sub.2O.sub.4, NiFe.sub.2O.sub.4, MnFe.sub.2O.sub.4, SrFe.sub.2O.sub.4, BaFe.sub.2O.sub.4, CuFe.sub.2O.sub.4, Y.sub.3Fe.sub.5O.sub.12, CrO.sub.2, MnO, Mn.sub.3O.sub.4, Mn.sub.2O, FeO, Fe.sub.2O.sub.3, NiO, Cr.sub.2O.sub.3, CoO, Co.sub.3O.sub.4, BaFe.sub.12O.sub.19, (Bi, La,Tb)(Fe,Mn,DyPr)O.sub.3, Ba.sub.3Co.sub.2Fe.sub.24O.sub.41, Y.sub.3Fe.sub.5O.sub.12, NiZnFe.sub.2O.sub.4, Cu.sub.0.2Mg.sub.0.4Zn.sub.0.4Fe.sub.2O.sub.4, Fe.sub.3O.sub.4(Cu,Ni,Zn)Fe.sub.2O.sub.4, TbMn.sub.2O.sub.5, PbNi.sub.1/3Nb.sub.2/3TiO.sub.3—CuNiZn, BaTiO.sub.3—NiZnFe.sub.2O.sub.4, doped BaTiO.sub.3, doped SrTiO.sub.3, (Ba,Sr)TiO.sub.3, Pb(Zr,Ti)O.sub.3, SrBi.sub.2Ta.sub.2O.sub.9, PbN.sub.1/3Nb.sub.2/3TiO.sub.3—PbTio.sub.3, PbMg.sub.1/3Nb.sub.2/3TiO.sub.3—PbTiO.sub.3, lanthanum-modified and lanthanum-strontium modified Pb(Zr,Ti)O.sub.3, Pb(Zr.sub.xTi.sub.1−x)O.sub.3, wherein x is greater than or equal to 1, PbHfO.sub.3, PbZrO.sub.3, Pb(Zr,Ti)O.sub.3, PbLa(Zr,Sn,Ti)O.sub.3, PbNb(ZrSnTi)O.sub.3, Pb.sub.1−xLa.sub.x(Zr.sub.yTi.sub.1−y).sub.(1−x)/4O.sub.3, wherein x is greater than or equal to 1 and y is greater than or equal to 1, NaNbO.sub.3, (K,Na)(Nb,Ta)O.sub.3, KNbO.sub.3, BaZOr.sub.3, Na.sub.0.25K.sub.0.25Bi.sub.0.5TiO.sub.3, Ag(Ta,Nb)O.sub.3 or Na.sub.0.5Bi.sub.0.5TiO.sub.3—K.sub.0.5Bi.sub.0.5TiO.sub.3—BaTiO.sub.3.

(81) The wastes can also derive from plastic laminates, which are built up from at least two different plastics.

(82) The wastes can also derive from plastic laminates which contain at least one layer which is not formed from plastics. Examples for such materials from which such layers can be formed are wood, hardboard, glass, textile, and/or metals like chromium, iron, copper, silver, gold or aluminum and their alloys.

(83) The wastes of the plastic laminates can furthermore contain adhesives or adhesive layers, as for example, chemically hardening adhesives, polymerization adhesives, cyanoacrylate adhesives (instant adhesives), methyl methacrylate adhesives, anaerobic hardening adhesives, unsaturated polyesters (UP resins), radiation curable adhesives, polycondensation adhesives, phenol-formaldehyde adhesives, silicones, silane cross-linking adhesives, polymeric adhesives, polyimide adhesives, polyisocyanate adhesives, physically binding adhesives, solvent containing wet adhesives, contact adhesives, dispersion adhesives, plastisols, adhesives without a solidification mechanism and pressure-sensitive adhesives.

(84) The aforementioned wastes can also be wastes of products of less value which have been prepared from plastics and plastic laminates.

(85) Moreover, the wastes change their structure and the properties by weathering, hydrolysis, oxidation, reduction, thermal stress, stress by actinic radiation which means IR-radiation, visible light and UV-radiation.

(86) Last but not least, the plastics and the plastic laminates are unavoidably contaminated after prolonged outdoor use and storage with ubiquitous persistent organic pollutants or long-lasting organic pollutants or POP, such as chloroorganic insecticides of the first generation as for example chlordane, DDT, dieldrin or toxaphen, industrially produced chemicals like PCB or side products of syntheses and combustion products like chlorinated of brominated dioxins or dibenzofurans build up unavoidably during the long-lasting outdoor use of the plastics and laminates. Representatives of these classes of compounds are also designated as “The Dirty Dozen”. The POP are semivolatile and can occur in the gas phase as well as bound to dust particles and are distributed worldwide by long-range transport mechanisms. Due to their lipophilicity, bioaccumulation in the fatty tissue of animals and of humans occurs. Some of the POP are said to be endocrinal disruptors or carcinogenic and are also associated with infertility, behavioral disorders and immunodeficiency.

(87) As the plastic wastes and laminate wastes are polluted with the ubiquitous occurring persistent organic contaminants (POPs) during a long-term wild dumping in the environment, during a long retention time in the seawater or during their long-term storage in a controlled landfill, they must be taken necessarily into account in the process of recycling of the plastic wastes so that the resulting valuable products are free from POPs and other organic halogen containing compounds. Well-known examples for such organic halogen containing compounds are perfluorooctaneic acid, brominated flame retardants like diphenylethers, dichloroethanes, trichloroethanes and tetrachloroethanes, hexachlorobutadiene, hexachlorocyclohexane or chloroparaffins, which among others can function as sources for dioxins and dibenzofurans.

(88) It is a particular advantage of the process of the invention that these halogen compounds are eliminated during the preparation of the valuable products.

(89) Moreover, a lot of other substances can adhere to the wastes described hereinbefore, such as minerals, sands, soils, petroleum, oils, fats, waxes, pitch, animals like mussels, plants, algae, foodstuffs (spoiled or non-spoiled), faeces, diapers, hairs, paper residues, corroded metal residues, glass residues, color residues, coatings, residues, and the like. It is a most particular advantage of the mechanochemical process of the invention that these contaminants must not necessarily be separated from the plastic wastes and plastic laminate wastes. Thus, they can be processed with the mechanochemical process of the invention and can be co-milled in order to be converted to valuable products together with the plastic wastes and plastic laminate wastes. This has the advantage that, with regard to the particles, the same conditions exist everywhere during the milling process of the invention so that uniform valuable products result. Preferably, the average particle size determined by sieve analysis is between 2 mm to 1 μm, more preferably 1 mm to 1 μm and most preferably 900 μm to 1 μm. Preferably, this process step is carried out with cutting mills, shredders, impact mills, spiral jet mills, fluidized bed-counter jet mills, bexmills, primary crushers, hammer mills or micro-pulverizers.

(90) The milling step, which is crucial for the invention can be carried out preferably in a ball mill, a drum mill, a vibration mill, a planetary mill, a shearer, a squeezer, a mortar and/or rubbing system. The crucial milling step can be carried out in a cascade of mills connected in series so that the wastes are optimally shredded and can be converted to uniform valuable products. However, it is also possible to use only one mill which is optimized for the given particular case. The average particle size of the resulting valuable products can vary broadly and can be adjusted by the process conditions. Preferably, the average particle size is less than 1000 nm to 1 nm, more preferably, 650 nm±200 nm.

(91) Suitable spherical grinding or milling media consist of, for example, zirconium dioxide (yttrium-stabilized), zirconium dioxide (cerium-stabilized), mixed zirconium oxide, zirconium silicate, aluminum oxide, steatite, diamond pearls, glass, carbon steel, chromium steel, nirosta steel, zirconium silicate/zirconium oxide/silicon nitride, boron carbide, silicon carbide or tungsten carbide. The skilled artisan can select the suitable grinding media specifically for each particular case on the basis of its general knowledge.

(92) Moreover, the process can be controlled by the following parameters: the impact, the grinding time, the size of the balls, the temperature ranges (freezing range: less than 0° C.; room temperature=23° C., warmth: 20° C. to 100° C.; heat: more than 100° C.), pressure ranges like negative pressure, standard pressure, and overpressure, the presence of inert gases, such as rare gases, nitrogen or carbon dioxide, the presence of liquid gases like nitrogen or liquid carbon dioxide, the presence of frozen liquids like carbon dioxide or ice and/or the presence of liquids like water.

(93) Furthermore, process can be controlled by the use of external cooling or heating devices. Thus, also, the temperature can be specifically adjusted in the temperature range between nitrogen and ice, as for example, by solid or liquid methyl cyclohexane (melting point: −126° C.).

(94) By way of cooling under or far under the glass transition temperature of the plastics to be ground, the latter become brittle and, therefore, are particularly well milled without smearing. This way, the grinding process is accelerated.

(95) In an advantageous embodiment of the mechanochemical process of the invention, the mills or the content can be irradiated with ultrasound, audible sound and/or actinic radiation, in particular microwave radiation, IR-radiation, visible light, UV-radiation, soft x-rays and electron radiation. This way, additional reactive radicals are produced on the particles to be ground which open up new reaction paths.

(96) Moreover, it is essential for the process of the invention, that the wastes are milled in the presence of a dehalogenation agent. The amount of the dehalogenation agent used conforms in first place with the amount of the halogens contained in the wastes. Anyway, at least so much of the dehalogenation agent has to be added that the persistent organic contaminants and the other organic halogen compounds are eliminated.

(97) Several possible methods are available for the dehalogenation.

(98) The Reductive Dehalogenation:

(99) As reductive dehalogenation agents, reducing agents, such as alkali metals like lithium, sodium, rubidium and cesium, earth alkali metals like magnesium, calcium and strontium, solutions of alkali metals and earth alkali metals in liquid ammonia and liquid amines, as well as in other water-like solvents, Zintl phases like Na.sub.4Sn.sub.9, Na.sub.4Pb.sub.9, Na.sub.2Pb.sub.10, Na.sub.3[Cu@Sn.sub.9], Na.sub.7[Ge.sub.9CuGe.sub.9] or Na.sub.12[Sn.sub.2@Cu.sub.12Sn.sub.20], graphite intercalation compounds of alkali metals like C.sub.8K, hydrides such as salt-like hydrides like calcium hydride, sodium hydride, complex hydrides like lithium aluminum hydride, sodium boronhydride or SUPER-HYDRID™ (Li[B(C.sub.2H.sub.5).sub.3H]), complex transition metal hydrides or metal hydrides like zirconium hydride or metals like aluminum, iron, zinc, lanthanum, the lanthanides and the actinides.

(100) Preferably, a hydrogen source with easily activatable hydrogen can be added to the reducing agents. Examples of suitable hydrogen sources are ethers, polyethers, the above-mentioned metal hydrides, liquid ammonia, trialkyl silanes and/or polyalkylhydrogen siloxanes.

(101) Examples of suitable ethers are simple symmetrical or asymmetrical aliphatic ethers or polyethers, as for example, diethyl ether, dipropyl ether, diisopropyl ether, di-n-butyl ether, dimeric or trimeric polyethers, crown ethers and cryptants or spherants for host-guest molecules.

(102) Examples of suitable amines are aliphatic amines like lower primary, secondary or tertiary aliphatic amines, as for example, primary, secondary or tertiary aliphatic or alicyclic monoamines or polyamines, in particular, methyl amine, ethyl amine, 1- and 2-propyl amine, 1- and 2-butyl amine, ethylenediamine, tri-, tetra-, penta- or hexamethylenediamine, diethyl amine, di-n-propyl amine, cyclopropyl and cyclohexyl amine, nitrogen heterocycles and perhydro nitrogen heterocycles, as for example, piperidine, 1-(2-aminoethyl)-piperazine, 1-(2-aminoethyl)-pyrrolidine, 1-(2-aminoethyl)-piperidine or 4-(2-aminoethyl)-morpholine.

(103) Examples of suitable amides as alternatives to the amines are 1,3-dimethyl-3,4,5,6-tetrahydroxy-2(H)-pyrimidinone (dimethyl propylene urea, DMPU), 1,3-dimethyl-2-imidazolidone (N,N-dimethyl ethylene, urea, DMEU), 1-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide, N,N-diethylpropioamide, and N,N-diethylisobutyramide.

(104) In the mechanochemical process of the invention, grinding aids can be used. Preferably, they are materials which can reduce the surface energy and/or the plastic deformation of solids upon the impact of mechanical energy. Examples of suitable materials of this kind are surface active substances in various conditions and preparations, as for example quaternary ammonium compounds, which cannot only be used as pure substances, but also immobilized on surface active carriers like layered silicates or clays (so-called organophilic bentonites), substituted alkyl imidazoles and sulfosuccine amide, fatty acids, fatty acid esters and amides, primary, secondary and tertiary alkylfatty amines, with one or more amino group(s), alicyclic amines, as for example, cyclohexyl amine, polyhydrogenated nitrogen heterocycles, as for example, piperidine, mono-, di- and triethanolamine, glycols, polyalkylene glycols as for example, polyethylene glycols and polypropylene glycols and their mono- or diethers, organosilicon compounds, in particular, silicones, as well as salts which are suitable for special purposes like aluminum chloride.

(105) It is a particular advantage of the reductive dehalogenation that, in the case of metal-plastic laminates and/or plastic wastes contaminated with metals, the metal part can function as the reducing agent.

(106) The metallic reducing agents can be present in the dispersed or suspended state in a preparation, as for example, in a non-oxidizing liquid or in the liquid hydrogen source. Dispersions of metals in white mineral oil, paraffins or polyethers are preferred. Moreover, the metallic reducing agents can be mixed with a solid inert carrier or there can be applied thereto.

(107) The Dehalogenation with Formation of Metal Oxyhalides:

(108) Oxides like antimony oxide, bismuth oxide, lanthanum oxide, yttrium oxide, cerium oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide and/or lutetium oxide can be used. With the organically bonded chlorine or bromine, these oxides form the corresponding oxychlorides and oxybromides, which themselves can be regarded as valuable products or they can be incorporated into the valuable products as fillers.

(109) The Dehalogenation with Formation of Metal Halides:

(110) Metal hydroxides like lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, lead, nickel, cobalt, copper and tin hydroxide as well as the iron hydroxides can be used as the dehalogenation agents. With the organically bonded chlorine or bromine, the hydroxides form the corresponding chlorides or bromides and which themselves can be regarded as valuable products or which can be incorporated into the valuable products as fillers.

(111) The Dehalogenation by Carbonates:

(112) Examples of suitable carbonates are carbonates of metals, the chlorides and bromides of which are easily water-soluble. Examples of particularly suitable carbonates are minerals like magnesite, strontianite, witherite, dolomite, aragonite, calcite, vaterite, zinc spar, gaylussite, nitrite soda, trona, mussel chalk and coral chalk as well as synthetic lithium carbonate, sodium hydrogen carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate and barium carbonate.

(113) The Oxidative Dehalogenation:

(114) Rhenium-catalyzed oxidative dehalogenation with hydrogen peroxide, enzymatic dehalogenation with oxidases/hydrogen peroxide, dehalogenases and peroxidases like homogenized radish, radish juice from raphanus sativus with hydrogen peroxide, advanced oxidation processes (AOP, activated oxidation processes) with the use of UV radiation, hydrogen peroxide and/or the catalytic wet oxidation by the formation of hydroxyl radicals can be used for the oxidative dehalogenation.

(115) Enzymatic Dehalogenation:

(116) Alkylhalidases, (S)-2-halogen carboxylic acid dehalogenases, haloacetate dehalogenases, haloalkane dehalogenases, 4-chlorobenzoate dehalogenases, atrazine chlorohydrolases, 4-chlorobenzoyl coenzyme, A-dehalogenases, (R)-2-halogen carboxylic acid dehalogenases, 2-halogen carboxylic acid dehalogenases (configuration inverting) and 2-halogen carboxylic acid dehalogenases (configuration retaining) can be used for the enzymatic dehalogenation.

(117) With the mechanochemical process of the invention, at least 99.5%, preferably, at least 99.6%, more preferably, at least 99.7% and, in particular, at least 99.8% of the initial quantity of the respective the POPs and, where applicable, of the organic halogen compounds present are eliminated. In particular, they are removed to the greatest possible extent so that their content in the valuable products is below the respective limits of detection of customary and known analytical procedures. In this sense, the valuable products are free from persistent organic contaminants and other organic halogen compounds.

(118) Before the milling, at least one functional additive can be added to the mixture of wastes and dehalogenation agents.

(119) Examples of suitable functional additives are activated carbons and charcoals, like biochar, pyrogenous carbon, plant char, wood char, active chars, mineral coals, animal charcoals, animal waste coals, pyrolyzed carbon with different degrees of pyrolysis, functionalized coals, pretreated coals, washed coals and extracted coals. In particular, biochar and/or pyrogenous carbon is used. These materials are customary and known and are disclosed, for example, by the German laid-open patent application DE 10 2015 010 041 A1, paragraphs [0055] to [0064].

(120) The active chars or the biochars can be prepared in situ during the milling from organic, municipal waste, organic industrial waste and waste from agriculture, forestry and horticulture as well as from lignin containing materials, as for example, green wastes, mulch material wastes of wood and wastes from biogas plants, which can be dried and/or filtered, and spelt.

(121) It is another particular advantage of the mechanochemical process of the invention that the wooden parts of wood- and cardboard-plastic laminates likewise undergo charring.

(122) The active chars and the coals can bind heavy metals, toxic and non-toxic gases, as well as halogens and hydrogen halides as charge-transfer complexes and they can function as catalysts, as crystal nuclei and for the formation of mesoporous or nanoporous materials.

(123) As another additive, acidic, basic on neutral water can be added as a reaction partner in order to accelerate the reactions during milling.

(124) Other suitable additives are materials which form co-crystals, which accelerate the reactions during the milling and/or improve the properties of the materials by generating radicals at the edges and the tips and other exposed locations of the additives, which radicals react with the plastic wastes and with the emerging mesoporous or nanoporous materials and enter into bonds by radical initiation.

(125) Examples of suitable additives of this kind are the aforementioned nanoparticles and nanofibers.

(126) Further suitable additives are the functional additives hereinbefore described as they are customarily used in plastics.

(127) Additional examples of suitable additives are in particular layered silicates which are present as nanoparticles and/or microparticles of an average particle size d.sub.50 of 1 nm to less than 1000 μm, preferably 10 nm to 900 μm, more preferably, 300 nm to 1000 nm, even more preferably 650 nm±200 nm, particularly preferably, 650 nm±150 nm and most preferably 650 nm±100 nm.

(128) The elemental composition and structure of the layered silicate microparticles and/or nanoparticles can vary very broadly. It is known to organize the silicates according to the following structures: island silicates, group silicates, ring silicates, belt and chain silicates, transitional structures between chain and layered silicates, layered silicates and framework silicates.

(129) The layered silicates are silicates, wherein the silicate ions consist of corner connected SiO.sub.4-tetrahedrons. These layers and/or double layers are not connected with each other. The clay minerals which are technically important and widespread in sedimentary rocks are likewise layered silicates. The layered structure of these minerals determines the form and the properties of the crystals. They are mostly tabular or flaky with good to perfect fissility parallel to the layers. The multiplicity of the rings the silicate layers are composed of often determines the symmetry and the form of the crystals. Water molecules, larger cations and/or lipids can intercalate between the layers.

(130) Examples of suitable layered silicates can be gleaned from the following TABLE 1. The listing is given only by way of example and is not final.

(131) TABLE-US-00001 TABLE 1 Moleculare Formulas of Phyllosilicates .sup.a) No. Type Molecular formular 1 Martinite (Na, Ca).sub.11Ca.sub.4(Si, S, B).sub.14B.sub.2O.sub.40F.sub.2•4(H.sub.2O) 2 Apophyllite-(NaF) NaCa.sub.4Si.sub.8O.sub.20F•8H.sub.2O 3 Apophyllite-(KF) (K, Na)Ca.sub.4Si.sub.8O.sub.20(F, OH)•8H.sub.2O 4 Apophyllite-(KOH) KCa.sub.4Si.sub.8O.sub.20(OH, F)•8H.sub.2O 5 Cuprorivaite CaCuSi.sub.4O.sub.10 6 Wesselsite (Sr, Ba)Cu[Si.sub.4O.sub.10] 7 Effenbergerite BaCu[Si.sub.4O.sub.10] 8 Gillespite BaFe.sup.2+Si.sub.4O.sub.10 9 Sanbornite BaSi.sub.2O.sub.5 10 Bigcreekite BaSi.sub.2O.sub.5•4H.sub.2O 11 Davanite K.sub.2TiSi.sub.6O.sub.15 12 Dalyite K.sub.2ZrSi.sub.6O.sub.15 13 Fenaksite KNaFe.sup.2+Si.sub.4O.sub.10 14 Manaksite KNaMn.sup.2+[Si.sub.4O.sub.10] 15 Ershovite K.sub.3Na.sub.4(Fe, Mn, Ti).sub.2[Si.sub.8O.sub.20(OH).sub.4]•4H.sub.2O 16 Paraershovite Na.sub.3K.sub.3Fe.sup.3+.sub.2Si.sub.8O.sub.20(OH).sub.4•4H.sub.2O 17 Natrosilite Na.sub.2Si.sub.2O.sub.5 18 Kanemite NaSi.sub.2O.sub.5•3H.sub.2O 19 Revdite Na.sub.16Si.sub.16O.sub.27(OH).sub.26•28H.sub.2O 20 Latiumite (Ca, K).sub.4(Si, Al).sub.5O.sub.11(SO.sub.4, CO.sub.3) 21 Tuscanite K(Ca, Na).sub.6(Si, Al).sub.10O.sub.22(SO.sub.4, CO.sub.3, (OH).sub.2)•H.sub.2O 22 Carletonite KNa.sub.4Ca.sub.4Si.sub.8O.sub.18(CO.sub.3).sub.4(OH, F)•H.sub.2O 23 Pyrophyllite Al.sub.2Si.sub.4O.sub.10(OH).sub.2 24 Ferripyrophyllite Fe.sup.3+Si.sub.2O.sub.5(OH) 25 Macaulayite (Fe.sup.3+, Al).sub.24Si.sub.4O.sub.43(OH).sub.2 26 Talc Mg.sub.3Si.sub.4O.sub.10(OH).sub.2 27 Minnesotaite Fe.sup.2+.sub.3Si.sub.4O.sub.10(OH).sub.2 28 Willemseite (Ni, Mg).sub.3Si.sub.4O.sub.10(OH).sub.2 29 Pimelite Ni.sub.3Si.sub.4O.sub.10(OH).sub.2•4H.sub.20 30 Kegelite Pb.sub.4Al.sub.2Si.sub.4O.sub.10(SO.sub.4)(CO.sub.3).sub.2(OH).sub.4 31 Aluminoseladonite K(Mg, Fe.sup.2+)Al[(OH).sub.2|Si.sub.4O.sub.10] 32 Ferroaluminoseladonite K(Fe.sup.2+, Mg)(Al, Fe.sup.3+)[(OH).sub.2|Si.sub.4O.sub.10] 33 Seladonite K(Mg, Fe.sup.2+)(Fe.sup.3+, Al)Si.sub.4O.sub.10(OH).sub.2 34 Chromseladonite KMgCr[(OH).sub.2|Si.sub.4O.sub.10] 35 Ferroseladonite K(Fe.sup.2+, Mg)(Fe.sup.3+, Al)[(OH).sub.2|Si.sub.4O.sub.10] 36 Paragonite NaAl.sub.2(Si.sub.3Al)O.sub.10(OH).sub.2 37 Boromuskovite KAl.sub.2(Si.sub.3B)O.sub.10(OH, F).sub.2 38 Muskovite KAl.sub.2(Si.sub.3Al)O.sub.10(OH, F).sub.2 39 Chromphyllite K(Cr, Al).sub.2[(OH, F).sub.2|AlSi.sub.3O.sub.10] 40 Roscoelithe K(V, Al, Mg).sub.2AlSi.sub.3O.sub.10(OH).sub.2 41 Ganterite (Ba, Na, K)(Al, Mg).sub.2[(OH, F).sub.2|(Al, Si)Si.sub.2O.sub.10] 42 Tobelithe (NH.sub.4, K)Al.sub.2(Si.sub.3Al)O.sub.10(OH).sub.2 43 Nanpingite CsAl.sub.2(Si, Al).sub.4O.sub.10(OH, F).sub.2 44 Polylithiontie KLi.sub.2AlSi.sub.4O.sub.10(F, OH).sub.2 45 Tainiolithe KLiMg.sub.2Si.sub.4O.sub.10F.sub.2 46 Norrishite KLiMn.sup.3+.sub.2Si.sub.4O.sub.12 47 Shirokshinite KNaMg.sub.2[F.sub.2|Si.sub.4O.sub.10] 48 Montdorite KMn.sub.0.5.sup.2+Fe.sub.1.5.sup.2+Mg.sub.0.5[F.sub.2|Si.sub.4O.sub.10] 49 Trilithionite KLi.sub.1.5Al.sub.1.5[F.sub.2|AlSi.sub.3O.sub.10] 50 Masutomilithe K(Li, Al, Mn.sup.2+).sub.3(Si, Al).sub.4O.sub.10(F, OH).sub.2 51 Aspidolithe-1M NaMg.sub.3(AlSi.sub.3)O.sub.10(OH).sub.2 52 Fluorophlogopite KMg.sub.3(AlSi.sub.3)O.sub.10F.sub.2 53 Phlogopite KMg.sub.3(Si.sub.3Al)O.sub.10(F, OH).sub.2 54 Tetraferriphlogopite KMg.sub.3[(F, OH).sub.2|(Al, Fe.sup.3+)Si.sub.3O.sub.10] 55 Hendricksite K(Zn, Mn).sub.3Si.sub.3AlO.sub.10(OH).sub.2 56 Shirozulithe K(Mn.sup.2+, Mg).sub.3[(OH).sub.2|AlSi.sub.3O.sub.10] 57 Fluorannit KFe.sub.3.sup.2+[(F, OH).sub.2|AlSi.sub.3O.sub.10] 58 Annite KFe.sup.2+.sub.3(Si.sub.3Al)O.sub.10(OH, F).sub.2 59 Tetraferriannite KFe.sup.2+.sub.3(Si.sub.3Fe.sup.3+)O.sub.10(OH).sub.2 60 Ephesite NaLiAl.sub.2(Al.sub.2Si.sub.2)O.sub.10(OH).sub.2 61 Preiswerkite NaMg.sub.2Al.sub.3Si.sub.2O.sub.10(OH).sub.2 62 Eastonite KMg.sub.2Al[(OH).sub.2|Al.sub.2Si.sub.2O.sub.10] 63 Siderophyllite KFe.sub.2.sup.2+Al(Al.sub.2Si.sub.2)O.sub.10(F, OH).sub.2 64 Anandite (Ba, K)(Fe.sup.2+, Mg).sub.3(Si, Al, Fe).sub.4O.sub.10(S, OH).sub.2 65 Bityite CaLiAl.sub.2(AlBeSi.sub.2)O.sub.10(OH).sub.2 66 Oxykinoshitalithe (Ba, K)(Mg, Fe.sup.2+, Ti.sup.4+).sub.3(Si, Al).sub.4O.sub.10O.sub.2 67 Kinoshitalithe (Ba, K)(Mg, Mn, Al).sub.3Si.sub.2Al.sub.2O.sub.10(OH).sub.2 68 Ferrokinoshitalithe Ba(Fe.sup.2+, Mg).sub.3[(OH, F).sub.2|Al.sub.2Si.sub.2O.sub.10] 69 Margarite CaAl.sub.2(Al.sub.2Si.sub.2)O.sub.10(OH).sub.2 70 Chernykhite BaV.sub.2(Si.sub.2Al.sub.2)O.sub.10(OH).sub.2 71 Clintonite Ca(Mg, Al).sub.3(Al.sub.3Si)O.sub.10(OH).sub.2 72 Wonesite (Na, K,)(Mg, Fe, Al).sub.6(Si, Al).sub.8O.sub.20(OH, F).sub.4 73 Brammallite (Na, H.sub.3O)(Al, Mg, Fe).sub.2(Si, Al).sub.4O.sub.10[(OH).sub.2, H.sub.2O] 74 Illite (K, H.sub.3O)Al.sub.2(Si.sub.3Al)O.sub.10(H.sub.2O, OH).sub.2 75 Glaukonite (K, Na)(Fe.sup.3+, Al, Mg).sub.2(Si, Al).sub.4O.sub.10(OH).sub.2 76 Agrellite NaCa.sub.2Si.sub.4O.sub.10F 77 Glagolevite NaMg.sub.6[(OH, O).sub.8|AlSi.sub.3O.sub.10]•H.sub.2O 78 Erlianite Fe.sup.2+.sub.4Fe.sup.3+.sub.2Si.sub.6O.sub.15(OH).sub.8 79 Bannisterite (Ca, K, Na)(Mn.sup.2+, Fe.sup.2+, Mg, Zn).sub.10(Si, Al).sub.16O.sub.38(OH).sub.8•nH.sub.2O 80 Bariumbannisterite (K, H.sub.3O)(Ba, Ca)(Mn.sup.2+, Fe.sup.2+, Mg).sub.21(Si, Al).sub.32O.sub.80(O, OH).sub.16•4-12 H.sub.2O 81 Lennilenapeite K.sub.6-7(Mg, Mn, Fe.sup.2+, Fe.sup.3+, Zn).sub.48(Si, Al).sub.72(O, OH).sub.216•16H.sub.2O 82 Stilpnomelane K(Fe.sup.2+, Mg, Fe.sup.3+, Al).sub.8(Si, Al).sub.12(O, OH).sub.27•2H.sub.2O 83 Franklinphilite (K, Na).sub.1−x(Mn.sup.2+, Mg, Zn, Fe.sup.3+).sub.8(Si, Al).sub.12(O, OH).sub.36•nH.sub.2O 84 Parsettensite (K, Na, Ca).sub.7.5(Mn, Mg).sub.49Si.sub.72O.sub.168(OH).sub.50•nH.sub.2O 85 Middendorfite K.sub.3Na.sub.2Mn.sub.5Si.sub.12(O, OH).sub.36•2H.sub.2O 86 Eggletonite (Na, K, Ca).sub.2(Mn, Fe).sub.8(Si, Al).sub.12O.sub.29(OH).sub.7•11H.sub.2O 87 Ganophyllite (K, Na).sub.xMn.sup.2+.sub.6(Si, Al).sub.10O.sub.24(OH).sub.4•nH.sub.2O {x = 1-2}{n = 7-11} 88 Tamaite (Ca, K, Ba, Na).sub.3-4Mn.sup.2+.sub.24[(OH).sub.12|{(Si, Al).sub.4(O, OH).sub.10}.sub.10]•21H.sub.2O 89 Ekmanite (Fe.sup.2+, Mg, Mn, Fe.sup.3+).sub.3(Si, Al).sub.4O.sub.10(OH).sub.2•2H.sub.2O 90 Lunijianlaite Li.sub.0.7Al.sub.6.2(Si.sub.7AlO.sub.20)(OH, O).sub.10 91 Saliotite Na.sub.0.5Li.sub.0.5Al.sub.3[(OH).sub.5|AlSi.sub.3O.sub.10] 92 Kulkeite Na.sub.0.35Mg.sub.8Al(AlSi.sub.7)O.sub.20(OH).sub.10 93 Aliettite Ca.sub.0.2Mg.sub.6(Si, Al).sub.8O.sub.20(OH).sub.4•4H.sub.2O 94 Rectorite (Na, Ca)Al.sub.4(Si, Al).sub.8O.sub.20(OH).sub.4•2H.sub.2O 95 Tarasovite (Na, K, H.sub.3O, Ca).sub.2Al.sub.4[(OH).sub.2|(Si, Al).sub.4O.sub.10].sub.2•H.sub.2O 96 Tosudite Na.sub.0.5(Al, Mg).sub.6(Si, Al).sub.8O.sub.18(OH).sub.12•5H.sub.2O 97 Corrensite (Ca, Na, K)(Mg, Fe, Al).sub.9(Si, Al).sub.8O.sub.20(OH).sub.10•nH.sub.2O 98 Brinrobertsite (Na, K, Ca).sub.0.3(Al, Fe, Mg).sub.4(Si, Al).sub.8O.sub.20(OH).sub.4•3.5H.sub.2O 99 Montmorillonite (Na, Ca).sub.0.3(Al, Mg).sub.2Si.sub.4O.sub.10(OH).sub.2•nH.sub.2O 100 Beidellite (Na, Ca.sub.0.5).sub.0.3Al.sub.2(Si, Al).sub.4O.sub.10(OH).sub.2•4H.sub.2O 101 Nontronite Na.sub.0.3Fe.sub.2.sup.3+(Si, Al).sub.4O.sub.10(OH).sub.2•4H.sub.2O 102 Volkonskoite Ca.sub.0.3(Cr.sup.3+, Mg, Fe.sup.3+).sub.2(Si, Al).sub.4O.sub.10(OH).sub.2•4H.sub.2O 103 Swinefordite (Ca, Na).sub.0.3(Al, Li, Mg).sub.2(Si, Al).sub.4O.sub.10(OH, F).sub.2•2H.sub.2O 104 Yakhontovite (Ca, Na, K).sub.0.3(CuFe.sup.2+Mg).sub.2Si.sub.4O.sub.10(OH).sub.2•3H.sub.2O 105 Hectorite Na.sub.0.3(Mg, Li).sub.3Si.sub.4O.sub.10(F, OH).sub.2 106 Saponite (Ca|.sub.2, Na).sub.0.3(Mg, Fe.sup.2+).sub.3(Si, Al).sub.4O.sub.10(OH).sub.2•4H.sub.2O 107 Ferrosaponite Ca.sub.0.3(Fe.sup.2+, Mg, Fe.sup.3+).sub.3[(OH).sub.2|(Si, Al)Si.sub.3O.sub.10]•4H.sub.2O 108 Spadaite MgSiO.sub.2(OH).sub.2•H.sub.2O 109 Stevensite (Ca|.sub.2).sub.0.3Mg.sub.3Si.sub.4O.sub.10(OH).sub.2 110 Sauconite Na.sub.0.3Zn.sub.3(Si, Al).sub.4O.sub.10(OH).sub.2•4H.sub.2O 111 Zinksilite Zn.sub.3Si.sub.4O.sub.10(OH).sub.2•4H.sub.2O 112 Vermiculite Mg.sub.0.7(Mg, Fe, Al).sub.6(Si, Al).sub.8O.sub.20(OH).sub.4•8H.sub.2O 113 Rilandite (Cr.sup.3+, Al).sub.6SiO.sub.11•5H.sub.2O 114 Donbassite Al.sub.2.3[(OH).sub.8|AlSi.sub.3O.sub.10] 115 Sudoite Mg.sub.2Al.sub.3(Si.sub.3Al)O.sub.10(OH).sub.8 116 Klinochlore (Mg, Fe.sup.2+).sub.5Al(Si.sub.3Al)O.sub.10(OH).sub.8 117 Chamosite (Fe.sup.2+, Mg, Fe.sup.3+).sub.5Al(Si.sub.3Al)O.sub.10(OH, O).sub.8 118 Orthochamosite (Fe.sup.2+, Mg, Fe.sup.3+).sub.5Al(Si.sub.3Al)O.sub.10(OH, O).sub.8 119 Baileychlore (Zn, Fe.sup.2+, Al, Mg).sub.6(Si, Al).sub.4O.sub.10(OH).sub.8 120 Pennantite Mn.sup.2+.sub.5Al(Si.sub.3Al)O.sub.10(OH).sub.8 121 Nimite (Ni, Mg, Fe.sup.2+).sub.5Al(Si.sub.3Al)O.sub.10(OH).sub.8 122 Gonyerite Mn.sup.2+.sub.5Fe.sup.3+(Si.sub.3Fe.sup.3+O.sub.10)(OH).sub.8 123 Cookeite LiAl.sub.4(Si.sub.3Al)O.sub.10(OH).sub.8 124 Borocookeite Li.sub.1-1.5Al.sub.4-3.5[(OH, F).sub.8|(B, Al)Si.sub.3O.sub.10] 125 Manandonite Li.sub.2Al.sub.4[(Si.sub.2AlB)O.sub.10](OH).sub.8 126 Franklinfurnaceite Ca.sub.2(Fe.sup.3+Al)Mn.sup.3+Mn.sub.3.sup.2+Zn.sub.2Si.sub.2O.sub.10(OH).sub.8 127 Kämmererite(Var. v. Mg.sub.5(Al, Cr).sub.2Si.sub.3O.sub.10(OH).sub.8 Klinochlore) 128 Niksergievite (Ba, Ca).sub.2Al.sub.3[(OH).sub.6|CO.sub.3|(Si, Al).sub.4O.sub.10]•0.2 H.sub.2O 129 Surite Pb.sub.2Ca(Al, Mg).sub.2(Si, Al).sub.4O.sub.10(OH).sub.2(CO.sub.3, OH).sub.3•0.5 H.sub.2O 130 Ferrisurite (Pb, Ca).sub.2-3(Fe.sup.3+, Al).sub.2[(OH, F).sub.2.5-3|(CO.sub.3).sub.1.5-2|Si.sub.4O.sub.10]•0.5 H.sub.2O 131 Kaolinite Al.sub.2Si.sub.2O.sub.5(OH).sub.4 132 Dickite Al.sub.2Si.sub.2O.sub.5(OH).sub.4 133 Halloysite-7Å Al.sub.2Si.sub.2O.sub.5(OH).sub.4 134 Sturtite Fe.sup.3+(Mn.sup.2+, Ca, Mg)Si.sub.4O.sub.10(OH).sub.3•10 H.sub.2O 135 Allophane Al.sub.2O.sub.3•(SiO.sub.2).sub.1.3-2•(H.sub.2O).sub.2.5-3 136 Imogolithe Al.sub.2SiO.sub.3(OH).sub.4 137 Odinite (Fe.sup.3+, Mg, Al, Fe.sup.2+, Ti, Mn).sub.2.4(Si.sub.1.8Al.sub.0.2)O.sub.5(OH).sub.4 138 Hisingerite Fe.sub.2.sup.3+Si.sub.2O.sub.5(OH).sub.4•2H.sub.2O 139 Neotokite (Mn, Fe.sup.2+)SiO.sub.3•H.sub.2O 140 Chrysotile Mg.sub.3Si.sub.2O.sub.5(OH).sub.4 141 Klinochrysotile Mg.sub.3Si.sub.2O.sub.5(OH).sub.4 142 Maufite (Mg, Ni)Al.sub.4Si.sub.3O.sub.13•4H.sub.2O 143 Orthochrysotil Mg.sub.3Si.sub.2O.sub.5(OH).sub.4 144 Parachrysotil Mg.sub.3Si.sub.2O.sub.5(OH).sub.4 145 Antigorite (Mg, Fe.sup.2+).sub.3Si.sub.2O.sub.5(OH).sub.4 146 Lizardite Mg.sub.3Si.sub.2O.sub.5(OH).sub.4 147 Karyopilite Mn.sup.2+.sub.3Si.sub.2O.sub.5(OH).sub.4 148 Greenalithe (Fe.sup.2+, Fe.sup.3+).sub.2-3Si.sub.2O.sub.5(OH).sub.4 149 Berthierine (Fe.sup.2+, Fe.sup.3+, Al).sub.3(Si, Al).sub.2O.sub.5(OH).sub.4 150 Fraipontite (Zn, Al).sub.3(Si, Al).sub.2O.sub.5(OH).sub.4 151 Zinalsite Zn.sub.7Al.sub.4(SiO.sub.4).sub.6(OH).sub.2•9H.sub.2O 152 Dozyite Mg.sub.7(Al, Fe.sup.3+, Cr).sub.2[(OH).sub.12|Al.sub.2Si.sub.4O.sub.15] 153 Amesite Mg.sub.2Al(SiAl)O.sub.5(OH).sub.4 154 Kellyite (Mn.sup.2+, Mg, Al).sub.3(Si, Al).sub.2O.sub.5(OH).sub.4 155 Cronstedtite Fe.sub.2.sup.2+Fe.sup.3+(SiFe.sup.3+)O.sub.5(OH).sub.4 156 Karpinskite (Mg, Ni).sub.2Si.sub.2O.sub.5(OH).sub.2 157 Népouite (Ni, Mg).sub.3Si.sub.2O.sub.5(OH).sub.4 158 Pecoraite Ni.sub.3Si.sub.2O.sub.5(OH).sub.4 159 Brindleyite (Ni, Mg, Fe.sup.2+).sub.2Al(SiAl)O.sub.5(OH).sub.4 160 Carlosturanite (Mg, Fe.sup.2+, Ti).sub.21(Si, Al).sub.12O.sub.28(OH).sub.34•H.sub.2O 161 Pyrosmalithe-(Fe) (Fe.sup.2+, Mn).sub.8Si.sub.6O.sub.15(Cl, OH).sub.10 162 Pyrosmalithe-(Mn) (Mn, Fe.sup.2+).sub.8Si.sub.6O.sub.15(OH, Cl).sub.10 163 Brokenhillite (Mn, Fe).sub.8Si.sub.8O.sub.15(OH, Cl).sub.10 164 Nelenite (Mn, Fe.sup.2+).sub.16Si.sub.12As.sup.3+.sub.3O.sub.36(OH).sub.17 165 Schallerite (Mn.sup.2+, Fe.sup.2+).sub.16Si.sub.12As.sup.3+.sub.3O.sub.36(OH).sub.17 166 Friedelite Mn.sup.2+.sub.8Si.sub.6O.sub.15(OH, Cl).sub.10 167 Mcgillite Mn.sup.2+.sub.8Si.sub.6O.sub.15(OH).sub.8Cl.sub.2 168 Bementite Mn.sub.7Si.sub.6O.sub.15(OH).sub.8 169 Varennesite Na.sub.8(Mn, Fe.sup.3+, Ti).sub.2[(OH, Cl).sub.2|(Si.sub.2O.sub.5).sub.5]•12H.sub.2O 170 Naujakasite Na.sub.6(Fe.sup.2+, Mn)Al.sub.4Si.sub.8O.sub.26 171 Manganonaujakasite Na.sub.6(Mn.sup.2+, Fe.sup.2+)Al.sub.4[Si.sub.8O.sub.26] 172 Spodiophyllite (Na, K).sub.4(Mg, Fe.sup.2+).sub.3(Fe.sup.3+, Al).sub.2(Si.sub.8O.sub.24) 173 Sazhinit-e(Ce) Na.sub.2CeSi.sub.6O.sub.14(OH)•nH.sub.2O 174 Sazhinite-(La) Na.sub.3La[Si.sub.6O.sub.15]•2H.sub.2O 175 Burckhardtite Pb.sub.2(Fe.sup.3+Te.sup.6+)[AlSi.sub.3O.sub.8]O.sub.6 176 Tuperssuatsiaite Na.sub.2(Fe.sup.3+, Mn.sup.2+).sub.3Si.sub.8O.sub.20(OH).sub.2•4H.sub.2O 177 Palygorskite (Mg, Al).sub.2Si.sub.4O.sub.10(OH)•4H.sub.2O 178 Yofortierite Mn.sup.2+.sub.5Si.sub.8O.sub.20(OH).sub.2•7H.sub.2O 179 Sepiolithe Mg.sub.4Si.sub.6O.sub.15(OH).sub.2•6H.sub.2O 180 Falcondoite (Ni, Mg).sub.4Si.sub.6O.sub.15(OH).sub.2•6H.sub.2O 181 Loughlinite Na.sub.2Mg.sub.3Si.sub.8O.sub.16•8H.sub.2O 182 Kalifersite (K, Na).sub.5Fe.sub.7.sup.3+[(OH).sub.3|Si.sub.10O.sub.25].sub.2•12H.sub.2O 183 Minehillite (K, Na).sub.2-3Ca.sub.28(Zn.sub.4Al.sub.4Si.sub.40)O.sub.112(OH).sub.16 184 Truscottite (Ca, Mn).sub.14Si.sub.24O.sub.58(OH).sub.8•2H.sub.2O 185 Orlymanite Ca.sub.4Mn.sub.3.sup.2+Si.sub.8O.sub.20(OH).sub.6•2H.sub.2O 186 Fedorite (Na, K).sub.2-3(Ca, Na).sub.7[Si.sub.4O.sub.8(F, Cl, OH)2|(Si.sub.4O.sub.10).sub.3]•3.5H.sub.2O 187 Reyerite (Na, K).sub.4Ca.sub.14Si.sub.22Al.sub.2O.sub.58(OH).sub.8•6H.sub.2O 188 Gyrolithe NaCa.sub.16Si.sub.23AlO.sub.60(OH).sub.8•14H.sub.2O 189 Tungusite Ca.sub.14Fe.sub.9.sup.2+[(OH).sub.22|(Si.sub.4O.sub.10).sub.6] 190 Zeophyllite Ca.sub.4Si.sub.3O.sub.8(OH, F).sub.4•2H.sub.2O 191 Armstrongite CaZr(Si.sub.6O.sub.15)•3 H.sub.2O 192 Jagoite Pb.sub.18Fe.sup.3+.sub.4[Si.sub.4(Si, Fe.sup.3+).sub.6][Pb.sub.4Si.sub.16(Si, Fe).sub.4]O.sub.82Cl.sub.6 193 Hyttsjöite Pb.sub.18Ba.sub.2Ca.sub.5Mn.sub.2.sup.2+Fe.sub.2.sup.3+[Cl|(Si.sub.15O.sub.45).sub.2]•6H.sub.20 194 Maricopaite Ca.sub.2Pb.sub.7(Si.sub.36, Al.sub.12)(O, OH).sub.99•n(H.sub.2O, OH) 195 Cavansite Ca(VO)Si.sub.4O.sub.10•4H.sub.2O 196 Pentagonite Ca(VO)Si.sub.4O.sub.10•4H.sub.2O 197 Weeksite (K, Ba).sub.2[(UO.sub.2).sub.2|Si.sub.5O.sub.13]•4H.sub.2O 198 Coutinhoite Th.sub.0.5(UO.sub.2).sub.2Si.sub.5O.sub.13•3H.sub.2O 199 Haiweeite Ca[(UO.sub.2).sub.2|Si.sub.5O.sub.12(OH).sub.2]•6H.sub.2O 200 Metahaiweeite Ca(UO.sub.2).sub.2Si.sub.6O.sub.15•nH.sub.2O 201 Monteregianite-(Y) KNa.sub.2YSi.sub.8O.sub.19•5H.sub.2O 202 Mountainite KNa.sub.2Ca.sub.2[Si.sub.8O.sub.19(OH)]•6H.sub.2O 203 Rhodesite KHCa.sub.2Si.sub.8O.sub.19•5H.sub.2O 204 Delhayelithe K.sub.7Na.sub.3Ca.sub.5Al.sub.2Si.sub.14O.sub.38F.sub.4Cl.sub.2 205 Hydrodelhayelithe KCa.sub.2AlSi.sub.7O.sub.17(OH).sub.2•6H.sub.2O 206 Macdonaldite BaCa.sub.4Si.sub.16O.sub.36(OH).sub.2•10H.sub.2O 207 Cymrite Ba(Si, Al).sub.4(O, OH).sub.8•H.sub.2O 208 Kampfite Ba.sub.12(Si.sub.11Al.sub.5)O.sub.31(CO.sub.3).sub.8Cl.sub.5 209 Lourenswalsite (K, Ba).sub.2(Ti, Mg, Ca, Fe).sub.4(Si, Al, Fe).sub.6O.sub.14(OH).sub.12 210 Tienshanite (Na, K).sub.9-10(Ca, Y).sub.2Ba.sub.6(Mn.sup.2+, Fe.sup.2+, Ti.sup.4+, Zn).sub.6(Ti, Nb) [(O, F, OH).sub.11|B.sub.2O.sub.4|Si.sub.6O.sub.15].sub.6 211 Wickenburgite Pb.sub.3CaAl[Si.sub.10O.sub.27]•3H.sub.2O 212 Silhydritee Si.sub.3O.sub.6•H.sub.2O 213 Magadiite Na.sub.2Si.sub.14O.sub.29•11H.sub.2O 214 Strätlingite Ca.sub.2Al[(OH).sub.6AlSiO.sub.2(OH).sub.4]•2.5 H.sub.2O 215 Vertumnite Ca.sub.4Al.sub.4Si.sub.4O.sub.6(OH).sub.24•3H.sub.2O 216 Zussmanite K(Fe.sup.2+, Mg, Mn).sub.13(Si, Al).sub.18O.sub.42(OH).sub.14 217 Coombsite K(Mn.sup.2+, Fe.sup.2+, Mg).sub.13[(OH).sub.7|(Si, Al).sub.3O.sub.3|Si.sub.6O.sub.18].sub.2 .sup.a) vgl. Mineralienatlas, Mineralklasse VIII/H - Schichtsilikate (Phyllosilikate), Strunz 8 Systematik

(132) Most preferably, bentonite from the group of montmorillonites ((Na,Ca).sub.0.3(Al,Mg).sub.2Si.sub.4O.sub.10(OH).sub.2.Math.nH.sub.2O) is used. Bentonite is a mixture of various clay minerals containing as the main components montmorillonites. Sodium bentonite can take up large amounts of water, and calcium bentonite can take up fats and/or oils.

(133) The layered silicate microparticles and/or nanoparticles are functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and/or non-supported. For example, they can be functionalized, agglomerated and supported. However, they can also be non-functionalized and aggregated. They can act as catalysts and/or support the dehalogenation.

(134) Additionally examples of suitable additives are heteropolyacids and isopolyacids, as well as their isomers, lacunar structures and parts of the structures (designated summarily as polyoxometalates POM), in the form of their molecules with the largest molecular diameter of less than or equal to 2 nm, preferably less than or equal to 1.5 nm and, most preferably, equal to or less than 1 nm (designated summarily as POM molecules) as well as in the form of nanoparticles and microparticles of on average particle size of from 1 nm to less than 1000 μm, preferably from 2 nm to 500 μm, more preferably 5 nm to 250 μm, even more preferably 5 nm 150 μm, and, in particular, 5 nm to 100 μm. Hereinafter, they are designated as “POM microparticles” or “POM nanoparticles”.

(135) It is emphasized that the indications less than or equal to 2 nm, less than or equal to 1.5 nm and less than or equal to 1 nm does not include a molecular diameter of 0 nm so that the lower limit of the molecular diameter is equal to the largest diameter of the smallest existing POM molecule.

(136) The average particle size of the POM microparticles and POM nanoparticles measured with the help of transmission electron microscopy (TEM), scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), atomic force microscopy (AFM) or scanning tunnel microscopy (STM) can vary very broadly and, therefore, can be excellently adapted to the requirements of the individual case.

(137) The POM microparticles and POM nanoparticles can have the most diverse morphologies and geometrical forms so that they can be adapted to the requirements of the individual case in this regard.

(138) Thus, they can be compact or they can have at least one hollow and/or any core-shell-structure, wherein the core and the shell can contain or consist of different materials. They also can have most diverse geometrical forms, such as spherules, ellipsoids, cubes, cuboids, pyramides, cones, cylinders, rhomboids, dodecahedrons, blunted dodecahedrons, icosahedrons, blunted icosahedrons, dumbbells, tori, platelets or needles all having circular, oval, elliptic, square, triangular, rectangular, pentagonal, hexagonal, heptagonal, octagonal or starshaped (threepronged, fourpronged, fivepronged, sixpronged or more pronged, the prongs having the same or different lengths) outlines. The corners and the edges can be rounded. Two or more POM microparticles and/or POM nanoparticles can form aggregates or agglomerates. The POM microparticles and/or POM nanoparticles can be of the same type or of different types. For example, spherical POM microparticles and/or POM nanoparticles can have sharp conical outgrowths. Two or three cylinder shaped POM microparticles and/or POM nanoparticles can adhere to each other to form T-shaped or Y-shaped particles. Furthermore, their surface can have indentations so that strawberry-, raspberry- or blackberrylike morphologies result. Last but not least, the dumbbells, tori, platelets or needles can be bent in at least one direction of the space.

(139) For example, the categorization of the POMs according to the following structures is known: Lindquist hexamolybdate anion, Mo.sub.6O.sub.19.sup.2−, decavanadate anion, V.sub.10O.sub.28.sup.6−, paratungstate anion B, H.sub.2W.sub.12O.sub.42.sup.10−, Mo.sub.36-polymolybdate anion, Mo.sub.36O.sub.112(H.sub.2O).sup.8−, Strandberg structure, HP.sub.2Mo.sub.5O.sub.23.sup.4−, Keggin structure, XM.sub.12O.sub.40.sup.n−, Dawson structure, X.sub.2M.sub.18O.sub.62.sup.n−, Anderson structure, XM.sub.6O.sub.24.sup.n−, Allman-Waugh structure, X.sub.12M.sub.18O.sub.32.sup.n−, Weakley-Yamase structure, XM.sub.10O.sub.36.sup.n−, und Dexter-Silverton structure, XM.sub.12O.sub.42.sup.n−.

(140) The exponent n is an integer from 3 to 20 and designates the valency of an anion which varies according to the variables X und M.

(141) The general formula I to XIII can serve as another principle of classification:
(BW.sub.12O.sub.40).sup.5−  (I),
(W.sub.10O.sub.32).sup.4−  (II),
(P.sub.2W.sub.18O.sub.62).sup.6−  (III),
(PW.sub.11O.sub.39).sup.7−  (IV),
(SiW.sub.11O.sub.34).sup.8−  (V),
(HSiW.sub.9O.sub.34).sup.9−  (VI),
(HPW.sub.9O.sub.34).sup.8−  (VII),
(TM).sub.4(PW.sub.9O.sub.34).sup.t−  (VIII),
(TM).sub.4(P.sub.2W.sub.15O.sub.56).sub.2.sup.t−  (IX),
(NaP.sub.5W.sub.30O.sub.110).sup.14−  (X),
(TM).sub.3(PW.sub.9O.sub.34).sub.2.sup.12−  (XI) und
(P.sub.2W.sub.18O.sub.6).sup.6−  (XII).

(142) In the formulas I to XII, TM designates a bivalent or trivalent transition metal ion like Mn.sup.2+, Fe.sup.2+, Fe.sup.2+, Co.sup.2+, Co.sup.3+, Ni.sup.2+, Cu.sup.2+ and Zn.sup.2+. The exponent t is an integer and designates the valency of an anion, which varies in dependency of the variable TM.

(143) Moreover, POM of the general formula XIII come into consideration:
(A.sub.xGa.sub.yNb.sub.aO.sub.b).sup.z−  (XIII).

(144) In the formula XIII, the variable A designates phosphorus, silicon or germanium, and the index x designates 0 or an integer from 1 to 40. The index y designates an integer from 1 to 10, the index a designates an integer of 1 to 8, and the index b is an integer of 15 to 150. The exponent z varies in dependency of the nature and the degree of oxidation of the variable A. Moreover, aqua complexes, and the active fragments of the POM XIII come into question.

(145) When the index x equals 0, y is preferably 6-a, wherein the index a equals an integer of 1 to 5, and the index b equals 19.

(146) When the variable A is silicon or germanium, the index x equals 2, the index y equals 18, the index a equals 6, and the index b equals 77.

(147) When the variable A designates phosphorus, the index x equals 2 or 4, the index y equals 12, 15, 17 or 30, the index a equals 1, 3, or 6, and the index b equals 62 or 123.

(148) Moreover, the isomers of the POM come into question. Thus, the Keggin structure has five isomers: the alpha, beta, gamma, delta, and epsilon structure. Furthermore, defective structures or lacunar structures as well as partial structures come into consideration.

(149) Preferably, the anions I to XIII are used as salts with cations which are approved for cleaning, personal hygiene and pharmaceutical applications.

(150) Examples of suitable cations are: H.sup.+, Na.sup.+, K.sup.+ and NH.sub.4.sup.+, mono-, di-, tri- oder tetra-(C.sub.1-C.sub.20-alkylammonium) like pentadecyldimethyl-ferrocenylmethyl ammonium, undecyldimethylferrocenylmethyl ammonium, hexadecyltrimethyl ammonium, octadecyltrimethyl ammonium, didodecyl-dimethyl ammonium, ditetradecyldimethyl ammonium, dihexadecyldimethyl ammonium, dioctadecyldimethyl ammonium, dioctadecylviologen, trioctadecylmethyl ammonium und tetrabutyl ammonium, mono-, di-, tri- oder tetra-(C.sub.1-C.sub.20-alkanol ammonium) like ethanolammonium diethanolammonium und triethanolammonium, and monocations of naturally occurring amino acids like histidinium (hish+), argininium (argh+) or lysinium (lysh+) or oligo- or polypeptides with one or more protonated basic amino acid residue(s).

(151) [cf. U.S. Pat. No. 6,020,369, column 3, line 6, to column 4, line 29].

(152) Natural, modified natural and synthetic cationic oligomers and polymers, i.e., oligomers and polymers, which carry primary, secondary, tertiary and quaternary ammonium groups, primary, secondary and tertiary sulfonium groups and/or primary, secondary and tertiary phosphonium groups come into question. Such synthetic oligomers and polymers are customary and known and are used, for example, in electrodeposition paints. Examples for natural oligomers and polymers are polyaminosaccharides like polyglucoseamine and chitosan.

(153) Examples of suitable POM are listed in the TABLE 2

(154) TABLE-US-00002 TABLE 2 Molecular Formulas of Polyoxometalates No. Molecular Formulas Structure Family 1 [(NMP).sub.2H].sub.3PW.sub.12O.sub.40 2 [(DMA).sub.2H].sub.3PMo.sub.12O.sub.40 3 (NH.sub.4).sub.17Na[NaSb.sub.9W.sub.21O.sub.86] Inorganic cryptate 4 a- und b-H.sub.5BW.sub.12O.sub.40 ″ 5 a- und b-H.sub.6ZnW.sub.12O.sub.40 ″ 6 a- und b-H.sub.6P.sub.2W.sub.18O.sub.62 ″ 7 alpha-(NH.sub.4).sub.6P.sub.2W.sub.18O.sub.62 Wells-Dawson-structure 8 K.sub.10Cu.sub.4(H.sub.2O).sub.2(PW.sub.9O.sub.34).sub.2•20H.sub.2O ″ 9 K.sub.10Co.sub.4(H.sub.2O).sub.2(PW.sub.9O.sub.34).sub.2•20H.sub.2O ″ 10 Na.sub.7PW.sub.11O.sub.39 ″ Na.sub.7PW.sub.11O.sub.39•20H.sub.2O + 2 C.sub.6H.sub.5P(O)(OH).sub.2 ″ 11 [(n-Butyl).sub.4N].sub.4H.sub.3PW.sub.11O.sub.39 ″ 12 b-Na.sub.8HPW.sub.9O.sub.34 ″ 13 [(n-Butyl).sub.4N].sub.3PMoW.sub.11O.sub.39 ″ 14 a-[(n-Butyl).sub.4N].sub.4Mo8O26 ″ 15 [(n-Butyl).sub.4N].sub.2W.sub.6O.sub.19 ″ 16 [(n-Butyl).sub.4N].sub.2Mo.sub.6O.sub.19 ″ 17 a-(NH.sub.4).sub.nH.sub.(4−n)SiW.sub.12O.sub.40 ″ 18 a-(NH.sub.4).sub.nH.sub.(5−n)BW.sub.12O.sub.40 ″ 19 a-K.sub.5BW.sub.12O.sub.40 ″ 20 K.sub.4W.sub.4O.sub.10(O.sub.2).sub.6 ″ 21 b-Na.sub.9HSiW.sub.9O.sub.34 ″ 22 Na.sub.8H.sub.2W.sub.12O.sub.40 23 (NH.sub.4).sub.14[NaP.sub.5W.sub.30O.sub.110] Preyssler-structure 24 a-(NH.sub.4).sub.5BW.sub.12O.sub.40 ″ 25 a-Na.sub.5BW.sub.12O.sub.40 ″ 26 (NH.sub.4).sub.4W.sub.10O.sub.32 ″ ,,27 (Me.sub.4N).sub.4W.sub.10O.sub.32 ″ 28 (HISH.sup.+).sub.nH.sub.(5−n)BW.sub.12O.sub.40 ″ 29 (LYSH.sup.+).sub.nH.sub.(5−n)BW.sub.12O.sub.40 ″ 30 (ARGH.sup.+).sub.nH.sub.(5−n)BW.sub.12O.sub.40 ″ 31 (HISH.sup.+).sub.nH.sub.(4−n)SiW.sub.12O.sub.40 ″ 32 (LYSH.sup.+).sub.nH.sub.(4−n)SiW.sub.12O.sub.40 ″ 34 (ARGH.sup.+).sub.nH.sub.(4−n)SiW.sub.12O.sub.40 ″ 35 K.sub.12[EuP.sub.5W.sub.30O.sub.110]•22H.sub.2O.sup.b) ″ 36 a-K.sub.8SiW.sub.11O.sub.39 ″ 37 K.sub.10(H.sub.2W.sub.12O.sub.42) ″ 38 K.sub.12Ni.sub.3(II)(PW.sub.9O.sub.34).sub.2•nH.sub.2O ″ 39 (NH.sub.4).sub.10Co.sub.4(II)(PW.sub.9O.sub.34).sub.2•nH.sub.2O ″ 40 K.sub.12Pd.sub.3(II)(PW.sub.9O.sub.34).sub.2•nH.sub.2O ″ 41 Na.sub.12P.sub.2W.sub.15O.sub.56•18H.sub.2O Lacunare (defect) structure 42 Na.sub.16Cu.sub.4(H.sub.2O).sub.2(P.sub.2W.sub.15O.sub.56).sub.2•nH.sub.2O ″ 43 Na.sub.16Zn.sub.4(H.sub.2O).sub.2(P.sub.2W.sub.15O.sub.56).sub.2•nH.sub.2O ″ 44 Na.sub.16Co.sub.4(H.sub.2O).sub.2(P.sub.2W.sub.15O.sub.56).sub.2•nH.sub.2O ″ 45 Na.sub.16N.sub.i4(H.sub.2O).sub.2(P.sub.2W.sub.15O.sub.56).sub.2•nH.sub.2O Wells-Dawson-Sandwich-structure 46 Na.sub.16Mn.sub.4(H.sub.2O).sub.2(P.sub.2W.sub.15O.sub.56).sub.2•nH.sub.2O ″ 47 Na.sub.16Fe.sub.4(H.sub.2O).sub.2(P.sub.2W.sub.15O.sub.56).sub.2•nH.sub.2O ″ 48 K.sub.10Zn.sub.4(H.sub.2O).sub.2(PW.sub.9O.sub.34).sub.2•20H.sub.2O Keggin-Sandwich-structure 49 K.sub.10Ni.sub.4(H.sub.2O).sub.2(PW.sub.9O.sub.34).sub.2•nH.sub.2O ″ 50 K.sub.10Mn.sub.4(H.sub.2O).sub.2(PW.sub.9O.sub.34).sub.2•nH.sub.2O ″ 51 K.sub.10Fe.sub.4(H.sub.2O).sub.2(PW.sub.9O.sub.34).sub.2•nH.sub.2O ″ 52 K.sub.12Cu.sub.3(PW.sub.9O.sub.34).sub.2•nH.sub.2O ″ 53 K.sub.12(CoH.sub.2O).sub.3(PW.sub.9O.sub.34).sub.2•nH.sub.2O ″ 54 K.sub.12Zn.sub.3(PN.sub.9O.sub.34).sub.2•15H.sub.2O ″ 55 K.sub.12Mn.sub.3(PW.sub.9O.sub.34).sub.2•15H.sub.2O ″ 56 K.sub.12Fe.sub.3(PW.sub.9O.sub.34).sub.2•25H.sub.2O ″ 57 (ARGH.sup.+).sub.10(NH.sub.4).sub.7Na[NaSb.sub.9W.sub.21O.sub.86] ″ 58 (ARGH.sup.+).sub.5HW.sub.11O.sub.39•17H.sub.2O ″ 59 K.sub.7Ti.sub.2W.sub.10O.sub.40 ″ 60 [(CH.sub.3).sub.4N].sub.7Ti.sub.2W.sub.10O.sub.40 ″ 61 Cs.sub.7Ti.sub.2W.sub.10O.sub.40 ″ 62 [HISH.sup.+].sub.7Ti.sub.2W.sub.10O.sub.40 ″ 63 [LYSH.sup.+].sub.nNa.sub.7−nPTi.sub.2W.sub.10O.sub.40 ″ 64 [ARGH.sup.+].sub.nNa.sub.7−nPTi.sub.2W.sub.10O.sub.40 ″ 65 [n-Butyl.sub.4N.sup.+].sub.3H.sub.3V.sub.10O.sub.28 ″ 66 K.sub.7HNb.sub.6O.sub.19•13H2O ″ 67 [(CH.sub.3).sub.4N.sup.+].sub.4SiW.sub.11O.sub.39— Organically modified structure O[SiCH.sub.2CH.sub.2C(O)OCH.sub.3].sub.2 68 [(CH.sub.3).sub.4N.sup.+].sub.4PW.sub.11O.sub.39—(SiCH.sub.2CH.sub.2CH.sub.2CN) ″ 69 [(CH.sub.3).sub.4N.sup.+].sub.4PW.sub.11O.sub.39—(SiCH.sub.2CH.sub.2CH.sub.2Cl) ″ 70 [(CH.sub.3).sub.4N.sup.+].sub.4PW.sub.11O.sub.39—(SiCH.sub.2═CH.sub.2) ″ 71 Cs.sub.4[SiW11O.sub.39—(SiCH.sub.2CH.sub.2C(O)OCH.sub.3).sub.2].sub.4 ″ 72 Cs.sub.4[SiW11O.sub.39—(SiCH.sub.2CH.sub.2CH.sub.2CN)].sub.4 ″ 73 Cs.sub.4[SiW11O.sub.39—(SiCH.sub.2CH.sub.2CH.sub.2Cl).sub.2].sub.4 ″ 74 Cs.sub.4[SiW11O.sub.39—(SiCH.sub.2═CH.sub.2)].sub.4 ″ 75 [(CH.sub.3).sub.4N.sup.+].sub.4SiW.sub.11O.sub.39—O—(SiCH.sub.2CH.sub.2CH.sub.2Cl).sub.2 ″ 76 [(CH.sub.3).sub.4N.sup.+].sub.4SiW.sub.11O.sub.39—O(SiCH.sub.2CH.sub.2CH.sub.2CN).sub.2 ″ 77 [(CH.sub.3).sub.4N.sup.+].sub.4SiW.sub.11O.sub.39—O(SiCH.sub.2═CH.sub.2).sub.2 ″ 78 [(CH.sub.3).sub.4N.sup.+].sub.4SiW.sub.11O.sub.39—O[SiC(CH.sub.3)].sub.2 ″ 79 [(CH.sub.3).sub.4N.sup.+].sub.4SiW.sub.11O.sub.39—O[SiCH.sub.2CH(CH.sub.3)].sub.2 ″ 80 [(CH.sub.3).sub.4N.sup.+].sub.4SiW.sub.11O.sub.39— ″ O[SiCH.sub.2CH.sub.2C(O)OCH.sub.3].sub.2 81 K.sub.5Mn(II)PW.sub.11O.sub.39•nH.sub.2O With transition metals substituted structure 82 K.sub.8Mn(II)P.sub.2W.sub.17O.sub.61•nH.sub.2O ″ 83 K.sub.6Mn(II)SiW.sub.11O.sub.39•nH.sub.2O ″ 84 K.sub.5PW.sub.11O.sub.39[Si(CH.sub.3).sub.2]•nH.sub.2O ″ 85 K.sub.3PW.sub.11O.sub.41(PC.sub.6H.sub.5).sub.2•nH.sub.2O ″ 86 Na.sub.3PW.sub.11O.sub.41(PC.sub.6H.sub.5).sub.2•nH.sub.2O ″ 87 K.sub.5PTiW.sub.11O.sub.40 ″ 88 Cs.sub.5PTiW.sub.11O.sub.39 ″ 89 K.sub.6SiW.sub.11O.sub.39[Si(CH.sub.3).sub.2]•nH.sub.2O ″ 90 KSiW.sub.11O.sub.39[Si(C.sub.6H.sub.5)(tert.—C.sub.4H.sub.9)]•nH.sub.2O ″ 91 K.sub.6SiW.sub.11O.sub.39[Si(C.sub.6H.sub.5).sub.2]•nH.sub.2O ″ 92 K.sub.7SiW.sub.9Nb.sub.3O.sub.40•nH.sub.2O ″ 93 Cs.sub.7SiW.sub.9Nb.sub.3O.sub.40•nH.sub.2O ″ 94 Cs.sub.8Si.sub.2W.sub.18Nb.sub.6O.sub.77•nH.sub.2O ″ 95 [(CH.sub.3).sub.3NH.sup.+].sub.7SiW.sub.9Nb.sub.3O.sub.40•nH.sub.2O Substituierte Keggin-structure 96 (CN.sub.3H.sub.6).sub.7SiW.sub.9Nb.sub.3O.sub.40•nH.sub.2O ″ 97 (CN.sub.3H.sub.6).sub.8Si.sub.2W.sub.18Nb.sub.6O.sub.77•nH.sub.2O ″ 98 Rb.sub.7SiW.sub.9Nb.sub.3O.sub.40•nH.sub.2O ″ 99 Rb.sub.8Si.sub.2W.sub.18Nb.sub.6O.sub.77•nH.sub.2O ″ 100 K.sub.8Si.sub.2W.sub.18Nb.sub.6O.sub.77•nH.sub.2O ″ 101 K.sub.6P.sub.2Mo.sub.18O.sub.62•nH.sub.2O ″ 102 (C.sub.5H.sub.5N).sub.7HSi.sub.2W.sub.18Nb.sub.6O.sub.77•nH.sub.2O ″ 103 (C.sub.5H.sub.5N).sub.7SiW.sub.9Nb.sub.3O.sub.40•nH.sub.2O ″ 104 (ARGH.sup.+).sub.8SiW.sub.18Nb.sub.6O.sub.77•18H.sub.2O ″ 105 (LYSH.sup.+).sub.7KSiW.sub.18Nb.sub.6O.sub.77•18H.sub.2O ″ 106 (HISH.sup.+).sub.6K.sub.2SiW.sub.18Nb.sub.6O.sub.77•18H.sub.2O ″ 107 [(CH.sub.3).sub.4N.sup.+].sub.4SiW.sub.11O.sub.39—O(SiCH.sub.2CH.sub.3).sub.2 ″ 108 [(CH.sub.3).sub.4N.sup.+].sub.4SiW.sub.11O.sub.39—O(SiCH.sub.3).sub.2 ″ 109 [(CH.sub.3).sub.4N.sup.+].sub.4SiW.sub.11O.sub.39—O(SiC.sub.16H.sub.33).sub.2 ″ 110 Li.sub.9P.sub.2V.sub.3(CH.sub.3).sub.3W.sub.12O.sub.62 ″ 111 Li.sub.7HSi.sub.2W.sub.18Nb.sub.6O.sub.77 ″ 112 Cs.sub.9P.sub.2V.sub.3CH.sub.3W.sub.12O.sub.62 ″ 113 Cs.sub.12P.sub.2V.sub.3W.sub.12O.sub.62 ″ 114 K.sub.4H.sub.2PV.sub.4W.sub.8O.sub.40 ″ 115 Na.sub.12P.sub.4W.sub.14O.sub.58 ″ 116 Na.sub.14H.sub.6P.sub.6W.sub.18O.sub.79 ″ 117 a-K.sub.5(NbO.sub.2)SiW.sub.11O.sub.39 ″ 118 a-K.sub.5(TaO.sub.2)SiW.sub.11O.sub.39 ″ 119 [(CH.sub.3).sub.3NH.sup.+).sub.5NbSiW.sub.11O.sub.40 ″ 120 [(CH.sub.3).sub.3NH.sup.+].sub.5TaSiW.sub.11O.sub.40 ″ 121 K.sub.6Nb.sub.3PW.sub.9O.sub.40 Peroxo-Keggin-structure 122 [(CH.sub.3).sub.3NH.sup.+].sub.5(NbO.sub.2)SiW.sub.11O.sub.39 ″ 123 [(CH.sub.3).sub.3NH.sup.+].sub.5(TaO.sub.2)SiW.sub.11O.sub.39 ″ 124 K.sub.4(NbO.sub.2)PW.sub.11O.sub.39 ″ 125 K.sub.7(NbO.sub.2)P.sub.2W.sub.12O.sub.61 ″ 126 [(CH.sub.3).sub.3NH.sup.+].sub.7(NbO.sub.2).sub.3SiW.sub.9O.sub.37 ″ 127 Cs.sub.7(NbO.sub.2).sub.3SiW.sub.9O.sub.37 ″ 128 K.sub.6(NbO.sub.2).sub.3PW.sub.9O.sub.37 ″ 129 Na.sub.10(H.sub.2W.sub.12O.sub.42) ″ 130 K.sub.4NbPW.sub.11O.sub.40 ″ 131 [(CH.sub.3).sub.3NH.sub.+].sub.4NbPW.sub.11O.sub.40 ″ 132 K.sub.5NbSiW.sub.11O.sub.40 ″ 133 K.sub.5TaSiW.sub.11O.sub.40 ″ 134 K.sub.7NbP.sub.2W.sub.17O.sub.62 Wells-Dawson-structure 135 K.sub.7(TiO.sub.2).sub.2PW.sub.10O.sub.38 ″ 136 K.sub.7(TaO.sub.2).sub.3SiW.sub.9O.sub.37 ″ 137 K.sub.7Ta.sub.3SiW.sub.9O.sub.40 ″ 138 K.sub.6(TaO.sub.2).sub.3PW.sub.9O.sub.37 ″ 139 K.sub.6Ta.sub.3PW.sub.9O.sub.40 ″ 140 K.sub.8Co.sub.2W.sub.11O.sub.39 ″ 141 H.sub.2[(CH.sub.3).sub.4N.sup.+]4(C.sub.2H.sub.5Si).sub.2CoW.sub.11O.sub.40 ″ 142 H.sub.2[(CH.sub.3).sub.4N.sup.+].sub.4(iso-C.sub.4H.sub.9Si).sub.2CoW.sub.11O.sub.40 ″ 143 K.sub.9Nb.sub.3P.sub.2W.sub.15O.sub.62 ″ 144 K.sub.9(NbO.sub.2).sub.3P.sub.2W.sub.15O.sub.59 ″ 145 K.sub.12(NbO.sub.2).sub.6P.sub.2W.sub.12O.sub.56 Well-Dawson-Peroxo structure 146 K.sub.12Nb.sub.6P.sub.2W.sub.12O.sub.62 Wells-Dawson-structure continued 147 a.sub.2-K.sub.10P.sub.2W.sub.17O.sub.61 ″ 148 K.sub.6Fe(III)Nb.sub.3P.sub.2W.sub.15O.sub.62 ″ 149 K.sub.7Zn(II)Nb.sub.3P.sub.2W.sub.15O.sub.62 ″ 150 (NH.sub.4).sub.6(a-P.sub.2W.sub.18O.sub.62)•nH.sub.2O ″ 151 K.sub.12[H.sub.2P.sub.2W.sub.12O.sub.48]•.sub.24H.sub.2O ″ 152 K.sub.2Na.sub.15H.sub.5[PtMo.sub.6O.sub.24]•8H.sub.2O ″ 153 K.sub.8[a.sub.2-P.sub.2W.sub.17MoO.sub.62]•nH.sub.2O ″ 154 KHP.sub.2V.sub.3W.sub.15O.sub.62•34H.sub.2O ″ 155 K.sub.6[P.sub.2W.sub.12Nb.sub.6O.sub.62]•24H.sub.2O ″ 156 Na.sub.6[V.sub.10O.sub.28]•H.sub.2O ″ 157 (Guanidinium).sub.8H[PV.sub.14O.sub.62]•3H.sub.2O ″ 158 K8H[PV14O62] ″ 159 Na.sub.7[MnV.sub.13O.sub.38]•18H.sub.2O ″ 160 K.sub.6[BW.sub.11O.sub.39Ga(OH).sub.2]•13H.sub.2O ″ 161 K.sub.7H[Nb.sub.6O.sub.19]•13H.sub.2O ″ 162 [(CH.sub.3).sub.4N.sup.+/Na.sup.+/K.sup.+].sub.4[Nb.sub.2W.sub.4O.sub.19] ″ 163 [(CH.sub.3).sub.4N.sup.+].sub.9[P.sub.2W.sub.15Nb.sub.3O.sub.62] ″ 164 [(CH.sub.3).sub.4N.sup.+].sub.15[HP.sub.4W.sub.30Nb.sub.6O.sub.123]•16H.sub.2O ″ 165 [Na/K].sub.6[Nb.sub.4W.sub.2O.sub.19] ″ 166 [(CH.sub.3).sub.4N.sup.+/Na.sup.+/K.sup.+]5[.sub.Nb3W3O19]•6H.sub.2O ″ 167 K.sub.5[CpTiSiW.sub.11O.sub.39]•12H.sub.2O ″ 169 b.sub.2-K.sub.8[SiW.sub.11O.sub.39]•14H.sub.2O ″ 170 a-K.sub.8[SiW.sub.10O.sub.36]•12H.sub.2O ″ 171 Cs.sub.7Na.sub.2[PW.sub.10O.sub.37]•8H.sub.2O ″ 172 Cs.sub.6[P.sub.2W.sub.5O.sub.23]•7.5H.sub.2O ″ 173 g-Cs.sub.7[PW.sub.10O.sub.36]•7H.sub.2O ″ 174 K.sub.5[SiNbW.sub.11O.sub.40]•7H.sub.2O ″ 175 K.sub.4[PNbW.sub.11O.sub.40]•12H.sub.2O ″ 176 Na.sub.6[Nb.sub.4W.sub.2O.sub.19]•13H.sub.2O ″ 177 K.sub.6[Nb.sub.4W.sub.2O.sub.19]•7H.sub.2O ″ 180 K.sub.4[V.sub.2W.sub.4O.sub.19]•3.5H.sub.2O ″ 181 Na.sub.5[V.sub.3W.sub.3O.sub.19]•12H.sub.2O ″ 182 K.sub.6[PV.sub.3W.sub.9O.sub.40]•14H.sub.2O ″ 183 Na.sub.9[A-b-GeW.sub.9O.sub.34]•8H.sub.2O ″ 184 Na.sub.10[A-a-GeW.sub.9O.sub.34]•9H.sub.2O ″ 185 K.sub.7[BV.sub.2W.sub.10O.sub.40]•6H.sub.2O ″ 186 Na.sub.5[CH.sub.3Sn(Nb.sub.6O.sub.19)]•10H.sub.2O ″ 187 Na.sub.8[Pt(P(m-SO.sub.3C.sub.6H.sub.5).sub.3).sub.3Cl]•3H.sub.2O ″ 188 [(CH.sub.3).sub.3NH.sup.+].sub.10(H)[Si (H).sub.3W.sub.18O.sub.68]•10H.sub.2O ″ 189 K.sub.7[A-a-GeNb.sub.3W.sub.9O.sub.40]•18H.sub.2O ″ 190 K.sub.7[A-b-SiNb.sub.3W.sub.9O.sub.40]•20H.sub.2O ″ 191 [(CH.sub.3).sub.3NH.sup.+].sub.9[A-a-HGe.sub.2Nb.sub.6W.sub.18O.sub.78 ″ 192 K.sub.7(H)[A-a-Ge.sub.2Nb.sub.6W.sub.18O.sub.77]•18H.sub.2O ″ 193 K.sub.8[A-b-Si.sub.2Nb.sub.6W.sub.18O.sub.77] ″ 194 [(CH.sub.3).sub.3NH.sup.+].sub.8[A-B-Si.sub.2Nb.sub.6W.sub.18O.sub.77] ″ .sup.a) cf. U.S. Pat. No. 6,020,369, TABLE 1, columns 3 to 10; .sup.b)Tierui Zhang, Shaoquin Liu, Dirk G. Kurth und Chari F. J. Faul, »Organized Nanostructured Complexes of Polyoxometalates and Surfactants that Exhibit Photoluminescence and Electrochromism, Advanced Functional Materials, 2009, 19, pages 642 bis 652; n a number, in particular an integer from 1 to 50.

(155) Additional examples of suitable POM are known from the American patent U.S. Pat. No. 7,097,858 column 14, line 56 to column 17, line 19 and from TABLE 8a, column 22, line 41, to column 23, line 28, compounds No. 1-53, and TABLE 8b, column 23, line 30, to column 25, line 34, compounds No. 1 to 150.

(156) Particularly preferred are ammoniumheptamolybdate tetrahydrate {(NH.sub.4).sub.6Mo.sub.7O.sub.24].Math.4H.sub.2O, CAS-No. 13106-76-8 (wasserfrei), CAS-Nr. 12054-85-2 (Tetrahydrat), AHMT}, tungstenphosphoric acid hydrate {H.sub.3P(W.sub.3O.sub.10).sub.4].Math.xH.sub.2O, CAS-No. 1343-93-7 (free of water), CAS-No. 12067-99-1 (hydrate), Wo-Pho}, molybdatophosphoric acid hydrate, {H.sub.3P(Mo.sub.3O.sub.10).sub.4].Math.xH2O, CAS-No.: 12026-57-2 (wasserfrei), CAS-Nr. 51429-74-4 (Hydrat), Mo-Pho} und/oder tungstensilicic acid {H.sub.4[Si(W.sub.3O.sub.10).sub.4].Math.xH.sub.2O, CAS-No. 12027-43-9, WKS} and/or their salts.

(157) The POM described hereinbefore in detail are characterized by their thermal stability and they render the valuable products biocidal and virucidal. In particular, the act against mollicutes, especially, mycoplasmata.

(158) Additional examples for suitable additives are non-functionalized or amino, hydroxyl, and/or carboxyl functionalized graphenes.

(159) Further examples for suitable additives are reactive gases and liquids, which can be (co-) polymerized with the originating valuable products like acetylene, ethylene, propylene, isopropene, butadiene and further mono- or multifunctional or other olefinically unsaturated monomers, monomers for the polyaddition like diisocyanates, monomers for the polycondensation like carboxylic acid anhydrides, carboxylic acids and hydroxy compounds as well as syngas.

(160) More examples for suitable additives are oxygen activated by actinic radiation, wherein actinic radiation is understood to be UV radiation, x-rays and electron beams, organic and inorganic peroxides like the customary and known thermal radical initiators and peroxosulfuric acid, peroxodisulfuric acid, peroxoacetic acid, sodium peroxide and barium peroxide as well as ozone.

(161) A particularly broad range of valuable products can be produced with the help of the mechanochemical process of the invention. In the context of the present invention, valuable products can be understood to mean materials, which are not down-recycled but up-recycled or, in other words, which are not less valuable than their starting products, but have a higher value.

(162) Thus, the following valuable products which are free from persistent organic contaminants (POP) and/or other organic halogen compounds, can be produced: Plastics, wherein the organic halogen compounds are at least reduced or completely eliminated, such as completely dehalogenated PVC or PVDC, polymers which form copolymers, blockcopolymers, graftcopolymers, combcopolymers and polymer blends from otherwise incompatible polymers, polymers having a modified surface which is significantly stronger cross-linked by radical reactions at the ends of the polymers, polymers with a diamondoidal reinforcement, polymers with a graphene insertion which causes a particularly high stabilization, polymer composite materials with the aforementioned fibers, nanoparticles and additives, which are activated by the mechanochemical processing and enter into very strong bonds in a particularly highly dispersed embedded state with the polymers, which effect cannot not be achieved by mechanical or chemical treatment alone and which renders the valuable products significantly more stable, microcrystalline and nanocrystalline co-crystals of the polymers with the aforementioned nanoparticles and microparticles which are built up during the mechanochemical treatment by selforganization, polymer composite materials, polymer alloys and microcrystalline and nanocrystalline co-crystals, which are doped with impurity atoms, such as, for example, scandium, yttrium, lanthanum, the lanthanides, uranium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury, boron, aluminium, gallium, indium, thallium, silicon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulfur, selenium and/or tellurium; the respective valuable products are valuable catalysts and can have mesoporous properties, copolymers with superabsorbers, superabsorbers by addition of oxygen radicals, peroxides and/or ozone, which can enter into reactions with the radicals at the end groups of the polymers, MOFs, rotoxanes, cage-like compounds, metalorganic lattice works and self organizing systems, mesoporous materials with different pore sizes, pore size distributions, degrees of cross-linking, mesh-values, hydrophobic, superhydrophobic, hydrophilic, superhydrophilic and hydrophilic-hydrophobic polarities and/or thermal and electric conductivities and/or magnetic properties, polymer additives which are particularly homogeneously distributed in the valuable polymeric products and have novel applicational properties, such as a reinforcement against pressure, shearing forces and/or tensile forces, resilience towards weathering, radiation and/or chemicals, a denser cross-linking, a low solubility, a lower swelling because of a dense cross-linking and/or a better capability to bind water or lipids, composites for building materials filled with sand, in particular with desert sand, and topological materials (cf. Technology Review, November 2017, page 83).

(163) The broad range of valuable products which is obtained by the mechanochemical process of the invention, corresponds to the numerous possibilities to use the valuable products. Thus, they can be used as high-grade polymeric engineering materials, polymer additives, reversible and irreversible absorbents for water or oils, for the desalination of seawater and of oversalted soils, as catalysts, as electrode materials for batteries, as building materials and for the manufacture of shielding of electrical and magnetic fields.

(164) The essential advantage of these valuable products is that they are no longer a source for persistent contaminants (POP) and organic halogen compounds.

EXAMPLES

Example 1: The Mechanochemical Preparation of a High Temperature Stable, Sterilizable Polymer Composite from POP-Contaminated Polymer Wastes

(165) Discarded moldings of polyether ketone (PEK) and polyether sulfone (PES), to which residues of metal-plastic pieces still adhered, were mixed with each other in a weight ratio of 1:1 and were shredded in a shredder to an average particle size of 100 μm. The portion of coarse parts of a particle size larger than 500 μm was again shredded until the desired average particle size of 100 μm was achieved.

(166) In a ball mill of corresponding size, wherein 80% of the volume were filled with tungsten carbide balls of a diameter of 20 mm, 2 kg of the shredded PEK-PES-mixture were contaminated with 0.1 g PCB (about 0.005% by weight) by milling for 30 minutes at room temperature. Thereby, the average particle size was reduced to 1 μm.

(167) Thereafter, 40 g (4% by weight) of tungstensilicic acid {H.sub.4[Si(W.sub.3O.sub.10).sub.4].Math.xH.sub.2O, CAS-No. 12027-43-9} were added to the contaminated PEK-PES mixture, whereafter the resulting mixture was again milled for 30 minutes at room temperature. This way, the average particle size was further reduced to 500 nm. Thereafter, 30 g of butyl amine and 50 g tetraethyleneglycol dimethylether were admixed during 5 minutes by milling at room temperature. The resulting mixture was milled at room temperature for 3 hours with magnesium chips.

(168) The resulting valuable product was separated from the tungsten carbide balls and was freed from the water-soluble components (magnesium chloride, butyl amine, tetraethyleneglycol dimethylether and by-products). The valuable product involved a powder-like, thermoplastic PEK-PES alloy, wherein the otherwise incompatible polymers did not form separate PEK and PES domains. The average particle size was 100 nm and the content of tungstensilicic acid was 4.2% by weight. It was confirmed by gas chromatographic measurements with an electron capturing detector and decachlorobiphenyl as an internal standard that 99.7% of the original amount of PCB had been removed.

(169) The resulting valuable product could be moulded to yield high temperature resistant, shock-resistant, sterilizable parts, like hilts for surgical devices. These hilts were permanently protected from the contamination with mollicutes, in particular, with mycoplasmata.

Example 2: The Mechanochemical Preparation of a Biochar Filled Thermoplastic Material which is Free from Organic Halogen and Organic Bromine

(170) In a ball mill of corresponding size, wherein 80% of the volume were filled with tungsten carbide balls of a diameter of 20 mm, 2 kg of shredded parts of a bilayer aluminum-EPDM foil, the polymer part of which contained 1.5% by weight of dekabromodiphenylether (approximately 25 g) as a flame retardant were contaminated with 0.1 g PCB (approximately 0.005% by weight) by grinding at room temperature for 30 minutes. This way, the average particle size was reduced to 1 μm.

(171) The PCB-contaminated parts were mixed with 10% by weight, based on the polymer parts, of husks by grinding at room temperature for 1 hour. This way, the husks were converted into biochar, and the average particle size of the resulting mixture sank to 600 nm.

(172) A dispersion or solution of 30 g finally divided sodium in 50 g tris(hydroxyethyl)amine and 10 g of tetraethyleneglycol was prepared separately under argon and added to the ball mill under argon. The resulting mixture was milled at room temperature for 3 hours. The resulting product mixture was separated from the tungsten carbide balls and, if necessary, metallic sodium still present was carefully destroyed with ethanol. Thereafter, the product mixture was freed from water-soluble compounds (sodium chloride, sodium bromide, aluminum chloride, tris(hydroxyethyl)amine and triethyleneglycol with water and dried.

(173) The resulting dried valuable product was free from aluminum. The bio charcoal which was formed in situ was homogeneously distributed in the EPDM. It was confirmed by gas chromatographic measurements with an electron capturing detector and decachlorobiphenyl as an internal standard that 99.7% of the original amounts of the PCB and 99.9% of the original amounts of the dekabromodiphenylether had been removed.

(174) The EPDM highly filled with biochar could be processed thermoplastically, exhibited excellent elasticity and absorbed contaminants from the air. Because of this, the valuable product could be used advantageously in interiors.

Example 3: The Mechanochemical Preparation of a Polymer Concrete Filled with Desert Sand and Having a Particularly Low Content of Polymeric Binders

(175) In a ball mill of corresponding size, wherein 80% of the volume were filled with tungsten carbide balls of a diameter of 20 mm, 10 kg of the desert sand from a sand dune was contaminated with 0.5 g PCB (approximately 0.005% by weight) by milling for 1 hour at room temperature. This way, the average particle size of the desert sand was reduced to 500 μm. A sieve analysis showed a narrow monomodal particle size distribution. Under the microscope the sand particles showed fissures. 0.50 kg of shredded polymer wastes of an average particle size of 1 mm were added. The polymer wastes consisted of 0.2 kg polyethylene terephthalate, 0.2 kg polyepoxide and 0.1 kg polyoxymethylene. The resulting mixture was milled for 30 minutes. Thereafter, 50 g of the graphite intercalation compound C.sub.8K were added under dried nitrogen, and the resulting mixture was milled for 2 hours.

(176) The resulting gray valuable product was separated from the milling balls and its chlorin content was determined. It turned out that nearly 100% of the organically bound chlorine had been converted into inorganic chloride. For further use, it was not necessary to separate the inorganic chlorides. The grey valuable product was a free-flowing powder, with an average particle size of 400 μm as determined by sieve analysis. It contained only 5 5% by weight of organic polymers. Nevertheless, the valuable product could be compressed under bars at a temperature of 100° C. to give stable molded parts.