MECHANOCHEMICAL PROCESS

Abstract

The invention relates to a mechanochemical process for decontaminating and/or for eliminating problematic, synthetic, biogenic and biological materials A; for breaking down phosphates B; for immobilising metals and the compounds C thereof; for separating carbon dioxide and carbon monoxide D into elements; and for recovering valuable products E. The process comprises: —providing a material F to be milled containing —at least one material A, B, C and/or D and —at least one type of carbon or carbon-yielding material G, or alternatively providing the components of F and G separately from one another; —filling the material F to be milled into a mechanical mill (1), or alternatively —filling the components of the material F to be milled into a mechanical mill (1) and —milling by means of milling elements (1.2) moved by agitation means (1.4) or by means of rollers (1.4.6); after which —the resulting product I is separated from the milling elements (1.2) or the rollers (1.4.6) and is discharged from the milling chamber (1.1) and worked up. The invention also relates to the use of the products I as valuable materials E, the use of a self-cooling electric motor (4) for driving a mechanochemical mill (1), and mechanochemical mills (1) having new agitation means (1.4).

Claims

1. Mechanochemical process for the decontamination and/or elimination of problematic, synthetic, biogenic and biological materials (A), for the digestion of phosphates (B), for the immobilization of metals and their compounds (C), for the splitting of carbon dioxide (D) into the elements and for the recovery of valuable products (E), characterized in that (I) one makes available as the ground stock F at least one fluid F, at least one solution F, at least one suspension F, at least one finely divided solid mixture F and/or at least one reactive gas F, containing at least one material A, B, C and/or D and at least one material G, selected from the group consisting of pure, finely divided, mineral coal, partially pyrolyzed coal, biochar and activated carbon, contaminated or impregnated, finely divided mineral coal, partially pyrolyzed coal, biochar and activated carbon, finely divided lignite and pure and contaminated or impregnated, finely divided carbon suppliers as well as of the above-mentioned, moistened materials G, or alternatively, the components F and G are made available separately from one another, (II) one feeds the at least one fluid F, the at least one solution F, the at least one suspension F, the at least one finely divided solid mixture F and/or the at least one reactive gas F continuously or discontinuously into the grinding chamber (1.1) of at least one mechanical mill (1) or alternatively (III) one pours the components A, B, C and/or D as well as G of the ground stock F into the grinding chamber (1.1) of the at least one mechanical mill (1) one after the other or at the same time, continuously or discontinuously, and (IV) finely grinds them therein with agitation means (1.4) or moving grinding media (1.2) or with rollers (1.4.6) at constant and/or variable speed of rotation, after which one (V) separates the resulting at least one suspension H of at least one pulverulent product I and/or the at least one pulverulent product I continuously or discontinuously from the grinding media (1.2) or the rollers (1.4.6) and discharges it from the grinding chamber (1.1) and (VI) separates the at least one finely divided, solid product I from the suspension H, as a result of which at least one digested, biologically available, soluble material passes into the liquid medium as product E of value, or (VII) one washes out the at least one digested, biologically available, soluble material E present or still present in the at least one finely divided, solid product I with at least one liquid medium or leaves it in the at least one product I as product E until its further use and/or (VIII) one recycles the at least one washed, finely divided, solid product I of activated carbon G to process step (I) and/or uses it as product of value E elsewhere and/or (IX) one stores the at least one finely divided, solid product I, which contains at least one immobilized metal C and/or at least one compound C thereof, until it is reused as product E of value or disposes it and/or (X) one separates the resulting elemental nitrogen and/or oxygen.

2. Mechanochemical process according to claim 1, wherein the at least one digested material E, which is soluble in liquid media, is selected from the group consisting of lithium, sodium and potassium salts and magnesium and calcium salts and biologically available phosphates B; and/or the at least one immobilized material C is selected from the group consisting of main group elements, transition metals, lanthanides and actinides C and their compounds C.

3. Mechanochemical process according to claim 1, wherein the at least one solid, finely divided product I is at least one product E of value selected from the group consisting of activated carbons G, which are returned to process step (I) or are used otherwise, at least one phosphate-containing fertilizer E, which is applied to agricultural land, at least one safely storable material E containing at least one immobilized metal C and/or at least one of its compounds C, or at least one heterogeneous catalyst E on the basis at least one immobilized metal C and/or at least one of its compounds C.

4. Mechanochemical process according to claim 1, wherein a plasma is present during the grinding in the grinding chamber (1.1) of the mills (1).

5. Mechanochemical process according to claim 4, wherein the plasmas are generated by generating triboplasm by means of gas discharge, hotspots, electrostatic charging, emission of exoelectrons, triboluminescence, crystal lattice defects, shredding, dislocations, crystal lattice vibrations, fracture formation, cutting processes, compression, sanding, abrasion, high pressures, friction, metastable states and hotspots due to the collision of solids and/or the friction of solids against each other as well as catalytically active and/or piezoelectric particles and coatings on the grinding bodies (1.2) and/or the walls of the grinding chamber (1.1) and/or on the agitation means (1.4) and/or in the grinding chamber (1.1) of the mechanical mills (1), focused laser radiation, electron beams, radioactive radiation, X-rays, UV-Radiation, IR radiation, Microwave radiation, ultrasound, chemical and nuclear reactions, electrostatic fields, electromagnetic fields, direct voltage, capacitive electrical excitation, wire explosions, gas discharges, electric arcs, spark discharges, vacuum spark discharges, cyclotron resonance, capacitive glass tube discharge and the pinch effect.

6. Mechanochemical method according to claim 5, wherein the piezoelectric particles and/or the coatings on the grinding bodies (1.2), the drive shafts (3), the walls of the grinding chamber (1.1) and/or on the agitation means (1.4) and/or in the grinding chamber (1.1) of the mechanical mills (1) are selected from the group consisting of carbon, quartz, glass barium titanate (BTO), lead zirconate titanate (PZT), lead magnesium niobate (PMN), gallium orthophosphate, berlinite, tourmaline, seignette salt, piezoelectric thin layers of zinc oxide, aluminum nitride, silicon nitride, silicon carbide, aluminum oxide, zirconium oxide and titanium nitride, polyvinylidene fluoride (PVDF) and ferroelectric, polycrystalline ceramics, and the catalytically active particles and/or the coatings on the grinding media (1.2), the walls of the grinding chamber (1.1), the drive shafts (3) and/or on the agitation means (1.4) and/or in the grinding chamber (1.1) of the mechanical Mills (1) are selected from the group consisting of metals, metal alloys, metal compounds and microporous materials.

7. Mechanochemical method according to claim 1, wherein the at least one material A is selected from the group consisting of natural, synthetic, biogenic and biological materials that are ecologically problematic, intensely smelling, toxic, combustible, oxidizing, radioactive, carbon supplying and/or explosive materials, their mixtures and their waste as well as contaminated mineral coals, biochars, activated carbons and carbon suppliers.

8. Mechanochemical process according to claim 1, wherein the grinding of the at least one ground stock F is carried out at a temperature of the grinding media (1.2) and of the at least one ground stock F of from −273° C. to +1,200° C.

9. Mechanochemical process according to claim 8, wherein the temperatures in the hotspots and in the plasmas are up to 15,000° C.

10. Mechanochemical process according to claim 1, wherein the weight ratio (Y)=(A, B, C and/or D): (G) in the mill base F is 0.01 to 1012.

11. Use of an electric motor, comprising an electric machine component with at least one winding for generating a magnetic field which comprises at least one waveguide which has a jacket and an inner cavity through which a coolant can be conducted, the winding having two ends at which an electrical operating voltage is connected and wherein the waveguides are round tubular and have an outer diameter in a range of 1 mm to 4 mm, the ends of the winding each serve as a coolant inlet or coolant outlet and the ends of the winding are connected to a connector that has a coolant inlet and/or a coolant outlet, several waveguide connections for connecting waveguides, a distribution channel through which the coolant is fed into at least one waveguide, and/or that comprises a collecting channel into which the coolant emerging from at least one waveguide is directed to the coolant outlet of the connector, as a drive for mechanical mills for mechanochemical processes.

12. Mechanical mill (1), comprising at least one rotatable or stationary mechanochemical reactor and waveguide (1.1) containing a rotatable or stationary drum (1.5) with a grinding chamber (1.1) with at least one inlet (1.5.1) for the ground material (F; 1.3), at least one outlet (1.5.2) for the ground product I and a large number of stationary or rotatable agitation means (1.4), wherein the drum (1.5) of the rotatable mechanochemical reactor and waveguide (1.1) has a disk-shaped vertical drum wall (1.5.3) which is connected in its center to a rotatable drive shaft (3) which can be driven by a motor (4), and the drum (1.5) of the fixed mechanochemical reactor and waveguide (1.1) has agitation means (1.4) rotatable with the aid of a drive shaft (3) for mixing the grinding media (1.2) and the ground stock (1.3) or rotatable rollers aligned in the longitudinal direction of the drum (1.5) (1.4.6), the drive shaft (3) being driven by a motor (4) and being guided through the disc-shaped vertical drum wall (1.5.3) through the bushing (1.5.3.1), the agitation means (1.4) are selected from the group consisting of striking disks (1.4.2), striking holes (1.4.3), flapping or striking clubs (1.4.4) and flapping or striking wings (1.4.5), having striking holes (1.4.2.2), flapping or striking webs (1.4.2.4), mountain-and-valley profiles (1.4.3.2), connecting webs (1.4.4.2) and impact bodies (1.4.4.3) symmetrically arranged to the drive shaft (3), and wherein the rotatable rollers (1.4.6) can be rotated in opposite directions of rotation (1.4.6.1) and their axes of rotation (1.4.6.4) are parallel to one another or have an angle of inclination (1.4.6.5) or can be rotated against an abrasion surface (1.4.6.3) are.

13. Mechanochemical mill (1) according to claim 14, wherein the mill (1) has an agitation means (1.4) of the same type and/or at least two different types of agitation means (1.4), the agitation means (1.4) being selected from the group, consisting of striking disks (1.4.2), striking fans (1.4.3), striking clubs (1.4.4) and flapping or striking wings (1.4.5), wherein the striking holes (1.4.2.2), the flapping or striking webs (1.4.2.4), the mountain and valley profiles (1.4.3.2), the connecting webs (1.4.4.2) and the striking bodies (1.4.4.3) are arranged symmetrically to the drive shaft (3), which agitation means (1.4) seen in the direction of the drive shaft (3) are in congruence and/or on gap.

14. Mechanical mill (1) according to claim 12, wherein the drum wall (1.5.4) of both the stationary and the rotatable mechanochemical reactor and waveguide (1.1) opposite of the disk-shaped vertical drum wall (1.5.3) is provided with one impact-resistant grid or window (1.5.5) which is permeable for electromagnetic radiation and/or corpuscular radiation (2.1) and which separates the mechanochemical reactor and waveguide (1.1) from the at least one radiation source (2).

15. Mechanochemical mill (1) according to claim 12, wherein the grinding chamber (1.1) has at least two spherical-shaped grinding chambers (1.1.1) arranged one behind the other, which are formed by at least one circular constriction (1.1.2), wherein drive shaft (3) runs centrally through the spherical section-shaped grinding chambers (1.1.1) and the circular constrictions (1.1.2) and the dimensions of the agitation means (1.4) are adapted to the periodically changing diameter of the grinding chambers (1.1.1).

Description

[0481] The mechanochemical process according to the invention and the mechanical mill according to the invention are explained in more detail below with the aid of Examples and Figures. The examples and figures are not restrictive, but are intended to specify the mechanochemical method according to the invention and the mechanochemical device according to the invention.

[0482] FIGS. 1 to 24 are schematic representations which are intended to illustrate the essential features of the mechanochemical process according to the invention and its use according to the invention. Some of the figures are not true to scale:

[0483] FIG. 1 shows a mechanical mill 1 according to the invention with a rotating drum 1.5 for grinding of the ground stock under irradiation with microwave radiation;

[0484] FIG. 2 shows a mechanical mill 1 according to the invention with a fixed drum 1.5 and an attritor 1.4 for grinding the ground stock under irradiation with microwave radiation 2.1;

[0485] FIG. 3 shows a flow diagram of the mechanochemical process for the decontamination of contaminated, phosphate-containing biomass and for the recovery of phosphate in a biologically available form;

[0486] FIG. 4 is a flow diagram of the mechanochemical process for obtaining regenerated activated charcoal from moist and contaminated activated charcoal and sludge of the fourth purification stage;

[0487] FIG. 5-1 (a) shows a plan view of the true-to-scale surface of the striking disk 1.4.2, (b) a true-to-scale side view of the striking disk 1.4.2 and (c) a perspective illustration of the striking disk 1.4.2;

[0488] FIG. 5-2 (a) shows a plan view of the true-to-scale surface of the striking disk 1.4.2, (b) a true-to-scale side view of the striking disk 1.4.2 and (c) a perspective illustration of the striking disk 1.4.2;

[0489] FIG. 6 (a) shows plan view of the true-to-scale surface of striking disk 1.4.2, (b) true-to-scale side view of striking disk 1.4.2 and (c) perspective illustration of striking disk 1.4.2;

[0490] FIG. 7 (a) shows a plan view of the true-to-scale surface of the striking disk 1.4.2 with the striking webs 1.4.2.4, (b) a true-to-scale side view of the striking disc 1.4.2, (c) a profile of a striking web 1.4.2.4 and (d) a perspective view of the striking disc 1.4.2;

[0491] FIG. 8 (a) shows a plan view of the true-to-scale surface of the striking disk 1.4.2 with the striking webs 1.4.2.4, (b) a true-to-scale side view of the striking disc 1.4.2, (c) a profile of a striking web 1.4.2.4 and (d) a perspective view of the striking disc 1.4.2;

[0492] FIG. 9 (a) shows a plan view of the true-to-scale surface of the striking disk 1.4.2 with the striking webs 1.4.2.4, (b) a true-to-scale side view of the striking disc 1.4.2, (c) a profile of a striking web 1.4.2.4 and (d) a perspective view of the striking disc 1.4.2;

[0493] FIG. 10 (a) shows a plan view of the true-to-scale surface of the fan 1.4.3 with the striking webs 1.4.2.4, (b) true-to-scale side view of the striking fan 1.4.2, and (c) a perspective view of the striking fan 1.4.2;

[0494] FIG. 11 (a) shows a plan view of the true-to-scale surface of the fan 1.4.3 with the striking webs 1.4.2.4, (b) a true-to-scale side view of the striking fan 1.4.2, (c) a profile of a striking web 1.4.2.4 and (d) a perspective view of the striking fan 1.4.2;

[0495] FIG. 12 shows a plan view of the true-to-scale surface of the fan 1.4.3 with the impact webs 1.4.2.4, (a) and (b) show a true-to-scale side views of the striking fan 1.4.2, (c) shows a profile of a striking web 1.4.2.4 and (d) a perspective view of the striking fan 1.4.2;

[0496] FIG. 13 (a) shows a plan view of the true-to-scale surface of the double striking fan 1.4.3 with the mountain and valley profiles 1.4.3.2 and the U-shaped columns 1.4.3.3, (b) and (d) show true-to-scale side views of the double striking fan 1.4.3, (c) shows a section through the mountain-and-valley profile 1.4.3.2 and (e) a perspective view of the double striking 1.4.3;

[0497] FIG. 14 shows a top view of a striking club 1.4.4 with symmetrically arranged striking bodies 1.4.4.3;

[0498] FIG. 15 shows a top view of a striking wing 1.4.5;

[0499] FIG. 16 shows a plan view of a further embodiment of the striking wing 1.4.5;

[0500] FIG. 17 shows the grinding by two counter-rotating rollers 1.4.6;

[0501] FIG. 18 shows the grinding with two counter-rotating rollers 1.4.6 with surface structures 1.4.6.2;

[0502] FIG. 19 shows the grinding with a roller 1.4.6 and an abrasion surface 1.4.6.3;

[0503] FIG. 20 shows the milling with two counter-rotating inclined rollers 1.4.6 rotating against each other at a certain angle 1.4.6.5

[0504] FIG. 21 shows the grinding with two counter-rotating rollers 1.4.6 with resilient surfaces 1.4.6.6;

[0505] FIG. 22 shows a drum 1.5 comprising several grinding chambers 1.1.1;

[0506] FIG. 23 is a flow diagram of a reverse osmosis system; and

[0507] FIG. 24 shows a grain size classifier KS comprising a mechanochemical mill 1, an acoustophoresis device 7 for agglomerating activated carbon particles G and a cyclone 8 for separating the agglomerated activated carbon particles G from the gas phase.

[0508] In FIGS. 1 to 24, the reference symbols have the following meaning: [0509] 1 Mechanical mill, grinding unit [0510] 1.1 Mechanical reactor, waveguide, grinding chamber [0511] 1.1.1 Spherical grinding chamber [0512] 1.1.2 Circular constriction [0513] 1.2 Grinding media [0514] 1.3 Grist F [0515] 1.4 Agitation means [0516] 1.4.1 Attritor [0517] 1.4.2 Striking disc [0518] 1.4.2.1 Bushing for the drive shaft 3 [0519] 1.4.2.2 Striking hole [0520] 1.4.2.3 Edge [0521] 1.4.2.4 Striking bar [0522] 1.4.3 Striking fan [0523] 1.4.3.1 Ring around the drive shaft 3 [0524] 1.4.3.2 Hill and valley profile [0525] 1.4.3.3 U-shaped divide [0526] 1.4.4 Striking club [0527] 1.4.4.1 Ring around the drive shaft 3 [0528] 1.4.4.2 Connecting bar [0529] 1.4.4.3 Impactor [0530] 1.4.5 Striking wing [0531] 1.4.5.1 Striking end [0532] 1.4.6 Rotating roller, drum [0533] 1.4.6.1 Direction of rotation [0534] 1.4.6.2 Spike [0535] 1.4.6.3 Abrasion surface [0536] 1.4.6.4 Axis of rotation [0537] 1.4.6.5 Inclination angle [0538] 1.4.6.6 Roller surface [0539] 1.4.6.7 Indentation [0540] 1.4.6.8 Suspension [0541] 1.4.6.9 Sphere [0542] 1.5 drum [0543] 1.5.1 Inlet for the ground stock F; 1.3 [0544] 1.5.2 Ground product outlet I [0545] 1.5.3 Disc-shaped, vertical drum wall [0546] 1.5.3.1 Passage through 1.5.3 [0547] 1.5.4 drum wall opposite to 1.5.3 [0548] 1.5.5 Grid, radiolucent window [0549] 1.5.5.1 Opening [0550] 2 Electromagnetic radiation, corpuscular radiation [0551] 2.1 Microwave radiation [0552] 3 Drive shaft [0553] 3.1 Direction of rotation [0554] 4 Motor [0555] 5 Fan [0556] 5.0 Suction [0557] 5.1 Aspirated gas [0558] 5.2 Gas stream blown into grinding chamber 1.1 of 1 [0559] 5.2.1 Gas flow injected into the bypass BP [0560] 5.2.2 Control valve in the gas line 5.5 for the gas flow 5.2 [0561] 5.2.3 Control valve in the gas line 5.5.1 in the bypass BP for the gas flow 5.2.1 [0562] 5.3 Gas stream loaded with ground grist F [0563] 5.3.1 Control valve in the gas line 5.6 for the gas flow 5.3 [0564] 5.4 Gas flow with agglomerated particles 9.1 [0565] 5.5 Gas line from the fan 5 to the mechanical mill 1 [0566] 5.5.1 Gas line in the bypass BP [0567] 5.6 Gas line from the mechanical mill 1 to the bypass BP, acoustophoresis unit 7 and cyclone 8 [0568] 5.7 Cyclone exhaust gas 8 [0569] 6 Permeable protective grid [0570] 7 Acoustophoresis unit [0571] 7.1 Ultrasonic source [0572] 7.2 Standing wave [0573] 8 cyclone [0574] 8.1 Exhaust pipe [0575] 8.2 Solids outlet [0576] 9 Powdered solid I [0577] 9.1 Agglomerated particles [0578] A-A cutting line [0579] C-C section line [0580] D diameter of the striking disc 1.4.2 [0581] d diameter of the bushing 1.4.2.1 for the drive shaft 3 [0582] DS Dissociated acids, divalent salts [0583] EWS monovalent salts [0584] F grist, ground stock, mill base [0585] H.sub.2O water [0586] KS grain size sifter [0587] MF microfiltration [0588] MM macromolecules [0589] NF nanofiltration [0590] R radius [0591] RO reverse osmosis [0592] SP Suspended Particles [0593] SW salt water [0594] T Thickness [0595] UDS Undissociated Acids [0596] UF Ultrafiltration [0597] UO Reverse osmosis [0598] X Enlarged section [0599] ZU Sugar

[0600] In the following text, the following abbreviations which are put after the terms have the following meaning:

[0601] A Problematic, synthetic, biogenic and biological materials

[0602] B phosphates

[0603] C Metals and their compounds

[0604] D Carbon dioxide, carbon monoxide

[0605] E Valuable products

[0606] F grist, fluid, solution, suspension, finely divided solid mixture, reactive gas

[0607] G Coal, carbon suppliers

[0608] H Suspension of a powdery product I

[0609] I Powdered Product, Sifted Product I

[0610] K Catalytically active particles

[0611] Q Piezoelectric particles

[0612] Y weight ratio of (A, B, C and/or D and possibly Z) to G

[0613] Z Additive

EXAMPLES 1 TO 3 AND COMPARATIVE EXPERIMENT V1

[0614] The grinding units 1 with attritors 1.4.1 described in the German laid-open specification DE 195 04 540 A1 were used for the grinding experiments of Examples 1 to 3 and of Comparative Experiment V1. 2000 steel balls weighing 1 g each were used as grinding media 1.2 in. The weight ratio of the weight of ground stock F:weight of the steel balls 1.2 was 1:10. The grinding tests were carried out under ambient air at atmospheric pressure.

[0615] An electric motor 3 according to international patent application WO 2017/055246A2 was used to drive the grinding unit 1 with the attritors 1.4.1. This comprises an electrical motor component with at least one winding for generating a magnetic field, which comprises at least one waveguide, which has a jacket and an inner cavity through which a coolant can be fed, the winding having two ends at which an electrical operating voltage is connected and where

[0616] the waveguides are designed in the shape of a round tube and have an outer diameter in a range of 3 mm, the ends of the winding each serve as a coolant inlet or coolant outlet, and

[0617] the ends of the winding are connected to a connector that includes a coolant inlet and/or a coolant outlet, multiple waveguide connections for connecting waveguides, a distribution channel through which the coolant is fed into at least one waveguide, and/or a collecting channel in which the coolant emerging from at least one waveguide flows in and is directed to the coolant outlet of the connector.

[0618] Motors 3 of this type are sold by Dynamic E Flow GmbH, Kaufbeuren, Germany, under the Capcooltech® brand. The types HC and LC were used.

[0619] Mixtures containing potassium nitrate A were provided as millbase F for Examples 1 to 3. The mixture of Comparative Experiment V1 did not contain any potassium nitrate A. Each of the mixtures F was ground for 480 minutes at a speed of the attritor 1.4.1 of 1250 revolutions/min. Samples weighing 0.5 g were taken at 0 minutes (blank sample), after 60 minutes, after 120 minutes and after 480 minutes and eluted with 50 ml of deionized water. The respective nitrate content A according to DIN EN ISO 10304-1 and the ammonium content A according to DIN EN ISO 11732 were then measured.

[0620] Table 1 gives an overview of the mixtures F and the results of the measurements.

TABLE-US-00002 TABLE 1 Examples 1 to 3 and Comparative Experiment V1 Milling Ground stock F time Ammonium A Nitrate A No. Composition h mg/Liter mg/Liter V1 2 Gew.-% Ammonium 0 84.9 <1 chloride A 49 Gew.-% Coal G 49 Gew.-% Quartz sand Q ″ ″ 60 20.7 <1 ″ ″ 120 10.8 <1 ″ ″ 480 9.5 <1 1 2 Gew.-% Potassium 0 <1 163 nitrate A 49 Gew.-% Coal G 49 Gew.-% Quartz sand Q ″ ″ 60 <1 87.4 ″ ″ 120 <1 29.6 ″ ″ 480 <1 28.1 2 2 Gew.-% Potassium 0 67.1 129 nitrate A 2 Gew.-% Ammonium chloride A 48 Gew.-% Coal G 48 Gew.-% Quartz sand Q ″ ″ 60 19.7 67.5 ″ ″ 120 7.9 31.4 ″ ″ 480 5.8 26.5 3 2 Gew.-% Potassium 0 91.8 177 nitrate A 2 Gew.-% Ammonium chloride A 2 Gew.-% Trisodium- phosphate B 47 Gew.-% Coal G 47 Gew.-% Quartz sand Q ″ ″ 60 22.7 78.5 ″ ″ 120 8.5 36.2 ″ ″ 480 8.1 43.5

[0621] It was found that the majority of ammonium A and nitrate A had already been eliminated after 60 to 120 minutes of grinding.

EXAMPLES 4 TO 6 AND COMPARATIVE EXPERIMENT V2

[0622] The Grinding of Fermentation Residues A—Influence of the Material Compositions

[0623] The grinding tests were carried out essentially as described in Examples 1 to 3 and the comparative test C1. Table 2 gives an overview of the material compositions of the ground stock F. The weight ratio of grinding media 1.2 to ground stock F was 50:1 in all cases. The number of revolutions was 1250 rpm in all cases. After milling times of 0, 1, 2 and 3 hours, 0.5 g of each of the finely divided powdery products I was eluted with 50 ml of distilled water in accordance with DIN 38414-4 DIN EN 12457-4. The respective concentrations of the ammonium ions A were determined in mg/liter in accordance with DIN EN ISO 11732. The results can also be found in Table 2.

TABLE-US-00003 TABLE 2 The Grinding of Fermentation Residues A - Influence of the Material Compositions Example Acti- Milling Fermentatio Quartz- vated Time residue sand Coal KCl under Ammo- Comparative F Q G Z air nium Example V (g) (g) (g) (g) (h) A V2 25 25 — — 0 21.1 ″ 25 25 — — 1 10.8 ″ 25 25 — — 2 11.6 ″ 25 25 — — 3 9.1 4 25 25 25 — 0 25.1 ″ 25 25 25 — 1 3.12 ″ 25 25 25 — 2 4.43 ″ 25 25 25 — 3 2.6 5 25 — 25 — 0 11.3 ″ 25 — 25 — 1 4.19 ″ 25 — 25 — 2 3.25 ″ 25 — 25 — 3 1.55 6 25 25 25 25 0 11.3 ″ 25 25 25 25 1 4.19 ″ 25 25 25 25 2 3.25 ″ 25 25 25 25 3 1.55

[0624] The test results show that the decrease in ammonium ions A in the samples with activated carbon G or quartz Q and activated carbon A was significantly greater than in the sample without activated carbon.

EXAMPLE 7

[0625] The Mechanochemical Degradation of Drug A as a Model for the Fourth Purification Stage of Sewage Treatment Plants

[0626] Quartz sand Q and activated carbon G (Example 7, tests numbers 1 to 4 and 13 to 16), quartz sand Q alone (example 7, tests numbers 9 to 12 and 21 to 24) and activated carbon G alone (example 7, tests 5 to 8 and 17 to 20) were each mixed with a mixture A consisting of 2 tablets propofol, 1 tablet loratidine, 2 tablets Ibuflam and one tablet ACC. The resulting mixtures F were rubbed dry once and a portion was poured over 150 ml of distilled water, then allowed to soak for 48 hours and then dried at room temperature under a water jet vacuum for 2 hours. The samples F were then milled under air and under argon. The grinding tests were carried out as described in Examples 4 to 6. Table 3 gives an overview of the test conditions used.

TABLE-US-00004 TABLE 3 The Mechanochemical Degradation of Drugs Example 7 Quartz sand Activated Milling Trial Q coal G time No . (g) (g) (min) RPM 1 20 20 30 1100 2 20 20 60 1100 3 20 20 120 1100 4 20 20 180 1100 5 0 40 30 1100 6 0 40 60 1100 7 0 40 120 1100 8 0 40 180 1100 9 40 0 30 1100 10 40 0 60 1100 11 40 0 120 1100 12 40 0 180 1100 13 20 20 30 800 14 20 20 60 800 15 20 20 120 800 16 20 20 180 800 17 0 40 30 800 18 0 40 60 800 19 0 40 120 800 20 0 40 180 800 21 40 0 30 800 22 40 0 60 800 23 40 0 120 800 24 40 0 180 800

[0627] The results of the tests can be summarized as follows:

[0628] 1. The degradation of medication A with activated carbon G alone was faster than that with quartz sand Q alone.

[0629] 2. After a longer grinding time (about 2 hours), the effect of quartz sand Q was stronger than that of activated carbon G, so adding a small amount of quartz sand Q was advantageous.

[0630] 3. The decrease followed the natural logarithm, with all compounds being decomposed after 60 minutes.

[0631] 4. Propofol A was broken down much more slowly than the other drugs A.

[0632] 5. A significant difference between the sumped-in mixtures F and the dry-mixed mixtures F could not be determined. However, there was a certain trend that the sumped mixtures F degraded somewhat more quickly.

[0633] 6. The speed of rotation was a decisive factor. The degradation of the drugs F was twice as fast at 1100 RPM as the degradation at 800 RPM.

[0634] 7. No difference could be found between the grinding under inert gas Z and under air.

EXAMPLE 8

[0635] The Recovery of Phosphate B from the Fourth Purification Stage of a Sewage Treatment Plant

[0636] Granulated loaded activated carbon G from a basin of the fourth purification stage was roughly cleaned once in a water bath. It was then dried in a commercially available drying system at elevated temperature and under reduced pressure. Thereafter, the dried activated carbon G was continuously introduced into a mechanical mill 1 with a drum 1.5 with a volume of 900 liters. The mechanical mill 1 contained 1000 steel balls 1.2 of 5 mm diameter, which were prevented by a protective grid 6 from exiting the drum 1.5. The dried activated carbon G was entered through the protective grid 6 at the upper opening (1.5.1, inlet for ground material F) and separated again centrally by means of a cyclone 8. About 100 kg of coal G ran through the mechanochemical mill 1 in 1 hour. Alternatively, the process could be carried out discontinuously as a batch process with the same quantities.

[0637] The number of revolutions of the mill 1 was 1100 rpm. The ground grist F with the reactivated activated carbon G was pressed discontinuously or continuously into pellets G in a commercially available pelletizing system. The pellets were then again added to the basin of the fourth purification stage. A loss of activated carbon G could not be observed here. Sand contamination did not interfere with the process.

[0638] The soluble phosphates B present could be eluted in a separate wash cycle before or after the activated carbon G was pelletized.

EXAMPLE 9

[0639] The Processing of Manure A into Activated Carbon G

[0640] 1000 kg of slurry A, which contained nitrates A, ammonium A, phosphates B and heavy metals C, were dried with a commercially available digestate dryer. This left 80 kg of dry matter as ground stock F. The drying was carried out at an elevated temperature, and the ammonia A which escaped was bound with sulfuric acid, as described in German patent application DE 10 2016 004 162 A1. The resulting ammonium sulfate A could be processed further together with the dry matter F. The dry matter F and the ammonium sulfate A were premilled in a separate mechanical mill 1. Then, they were continuously introduced into a mechanical mill 1 with a drum 1.5 of a volume of 900 liters together with half the amount of activated carbon G from above through a protective grid 6 which prevented the grinding media 1.2 from exiting. 1000 kg of steel balls 1.2 with a diameter of 5 mm were used as grinding media 1.2. The ground material F was separated again centrally by means of a cyclone 8. About 100 kg of dry material F ran through the mechanical mill 1 in 1 hour and were ground at a constant speed of 1100 rpm.

[0641] The resulting solid, finely divided product I contained significantly fewer nitrate ions A and ammonium ions A than the starting products F. In addition, the heavy metals C were immobilized.

[0642] In addition or as an alternative to carbon G, sheet silicates Z such as bentonite or montmorillonite could be introduced to immobilize the heavy metals C.

[0643] The solid, finely divided product I was pressed in a commercially available pelletizing plant and used as an alternative E to terra preta as a phosphate fertilizer E and a coal fertilizer E, which promoted humus formation and microbial growth.

[0644] Alternatively, the phosphate B could also be removed from the pellets G. The remaining material was excellently suitable as a substitute for activated carbon G to bind VOCs (volatile organic compounds), as a filler for the production of panels and as a substitute for wood and sand.

EXAMPLE 10

[0645] The Recovery of Iridium C from Spent Nafion Membranes A

[0646] 500 kg of used Nafion membranes A were shredded and dry mixed with 100 kg of activated carbon G and 20 kg of solid sodium hydroxide solution Z and pre-ground. The mixture F was then introduced continuously into a mechanochemical mill 1 as described in Examples 8 and 9 and ground for 2 hours at a speed of 1100 rpm. The finely divided solid powder I separated with the aid of a cyclone 8 was eluted with water, whereby the resulting sodium fluoride I was washed out. The remaining powder I contained the immobilized iridium C. This was recovered by burning the powder I.

EXAMPLE 11 TO 15

[0647] The Mechanochemical Processing of Biomass A, the Elimination of Nitrates A and Ammonium A and the Recovery of Phosphate B

[0648] Biomass A, quartz sand Q and activated carbon G were mixed together in various amounts. Sodium nitrate A, ammonium chloride A and glassy ultraphosphate B were added in varying amounts to the mixtures. The resulting mixtures F were rubbed dry. Part of each of these was poured over once with 150 ml of distilled water, soaked for 48 hours, then dried at room temperature under a waterjet vacuum for 2 hours and then ground. In parallel, the dry mixed mixtures F were ground. All experiments were carried out once under air and once under argon Z. The devices 1 described in Examples 1 to 3 were used for this purpose. In all cases, after 30 minutes, 60 minutes, 120 minutes and 180 minutes, samples I were taken from the resulting ground mixtures F and eluted with distilled water. The solutions were then analyzed.

[0649] Tables 4 to 8 give an overview of the materials used and their proportions.

TABLE-US-00005 TABLE 4 Mechanochemical grinding of biomass A with the additives Sodium Nitrate A, Ammonium chloride A and Ultraphosphate B under Air and under Argon Z Ex. 11 Acti- Ultra- Quartz- vated Bio- phos- Mill- Sand Coal mass NaNO.sub.3 NH.sub.4Cl phate ing Tri. Q G A A A B time No. [g] [g] [g] [g] [g] [g] [min] RPM 1 30 30 30 5 5 5 30 1100 2 30 30 30 5 5 5 60 1100 3 30 30 30 5 5 5 120 1100 4 30 30 30 5 5 5 180 1100 5 0 45 45 5 5 5 30 1100 6 0 45 45 5 5 5 60 1100 7 0 45 45 5 5 5 120 1100 8 0 45 45 5 5 5 180 1100 9 45 0 45 5 5 5 30 1100 10 45 0 45 5 5 5 60 1100 11 45 0 45 5 5 5 120 1100 12 45 0 45 5 5 5 180 1100 13 30 30 30 5 5 5 30 800 14 30 30 30 5 5 5 60 800 15 30 30 30 5 5 5 120 800 16 30 30 30 5 5 5 180 800 17 0 45 45 5 5 5 30 800 18 0 45 45 5 5 5 60 800 19 0 45 45 5 5 5 120 800 20 0 45 45 5 5 5 180 800 21 45 0 45 5 5 5 30 800 22 45 0 45 5 5 5 60 800 23 45 0 45 5 5 5 120 800 24 45 0 45 5 5 5 180 800 Ex. = Example; Tri. = Trial

TABLE-US-00006 TABLE 5 Mechanochemical Grinding of Biomass A with the Additives Sodium Nitrate A, Ammonium Chloride A and Ultraphosphate B under Air and under Argon Z Ex. 12 Acti- Quartz- vated Ultra- sand Coal Biomass NH.sub.4Cl phosphat Milling Tri. Q G A A B time No. [g] [g] [g] [g] [g] [min] RPM 1 30 30 30 7.5 7.5 30 1100 2 30 30 30 7.5 7.5 60 1100 3 30 30 30 7.5 7.5 120 1100 4 30 30 30 7.5 7.5 180 1100 5 0 45 45 7.5 7.5 30 1100 6 0 45 45 7.5 7.5 60 1100 7 0 45 45 7.5 7.5 120 1100 8 0 45 45 7.5 7.5 180 1100 9 45 0 45 7.5 7.5 30 1100 10 45 0 45 7.5 7.5 60 1100 11 45 0 45 7.5 7.5 120 1100 12 45 0 45 7.5 7.5 180 1100 13 30 30 30 7.5 7.5 30 800 14 30 30 30 7.5 7.5 60 800 15 30 30 30 7.5 7.5 120 800 16 30 30 30 7.5 7.5 180 800 17 0 45 45 7.5 7.5 30 800 18 0 45 45 7.5 7.5 60 800 19 0 45 45 7.5 7.5 120 800 20 0 45 45 7.5 7.5 180 800 21 45 0 45 7.5 7.5 30 800 22 45 0 45 7.5 7.5 60 800 23 45 0 45 7.5 7.5 120 800 24 45 0 45 7.5 7.5 180 800 Ex. = Example; Tri. = Trial

TABLE-US-00007 TABLE 6 Mechanochemical Grinding of Biomass A with the Additives Sodium Nitrate A, Ammonium Chloride A and Ultraphosphate B under Air and under Argon Z Ex. 13 Acti- Quartz- vated Ultra- sand Coal Biomass NaNO.sub.3 phosphate Milling Tri. Q G A A B Time No. [g] [g] [g] [g] [g] [min] RPM 1 30 30 30 7.5 7.5 30 1100 2 30 30 30 7.5 7.5 60 1100 3 30 30 30 7.5 7.5 120 1100 4 30 30 30 7.5 7.5 180 1100 5 0 45 45 7.5 7.5 30 1100 6 0 45 45 7.5 7.5 60 1100 7 0 45 45 7.5 7.5 120 1100 8 0 45 45 7.5 7.5 180 1100 9 45 0 45 7.5 7.5 30 1100 10 45 0 45 7.5 7.5 60 1100 11 45 0 45 7.5 7.5 120 1100 12 45 0 45 7.5 7.5 180 1100 13 30 30 30 7.5 7.5 30 800 14 30 30 30 7.5 7.5 60 800 15 30 30 30 7.5 7.5 120 800 16 30 30 30 7.5 7.5 180 800 17 0 45 45 7.5 7.5 30 800 18 0 45 45 7.5 7.5 60 800 19 0 45 45 7.5 7.5 120 800 20 0 45 45 7.5 7.5 180 800 21 45 0 45 7.5 7.5 30 800 22 45 0 45 7.5 7.5 60 800 23 45 0 45 7.5 7.5 120 800 24 45 0 45 7.5 7.5 180 800 Ex. = Example; Tri. = Trial

TABLE-US-00008 TABLE 7 Mechanochemical Grinding of Biomass A with the Additives Sodium Nitrate A and Ammonium Chloride A under Air and under Argon Z Ex. 14 Acti- Quartz- vated Sand Coal Biomass NaNO.sub.3 NH.sub.4C1 Milling Tri. Q G A A A Time No. [g] [g] [g] [g] [g] [min] RPM 1 30 30 30 7.5 7.5 30 1100 2 30 30 30 7.5 7.5 60 1100 3 30 30 30 7.5 7.5 120 1100 4 30 30 30 7.5 7.5 180 1100 5 0 45 45 7.5 7.5 30 1100 6 0 45 45 7.5 7.5 60 1100 7 0 45 45 7.5 7.5 120 1100 8 0 45 45 7.5 7.5 180 1100 9 45 0 45 7.5 7.5 30 1100 10 45 0 45 7.5 7.5 60 1100 11 45 0 45 7.5 7.5 120 1100 12 45 0 45 7.5 7.5 180 1100 13 30 30 30 7.5 7.5 30 800 14 30 30 30 7.5 7.5 60 800 15 30 30 30 7.5 7.5 120 800 16 30 30 30 7.5 7.5 180 800 17 0 45 45 7.5 7.5 30 800 18 0 45 45 7.5 7.5 60 800 19 0 45 45 7.5 7.5 120 800 20 0 45 45 7.5 7.5 180 800 21 45 0 45 7.5 7.5 30 800 22 45 0 45 7.5 7.5 60 800 23 45 0 45 7.5 7.5 120 800 24 45 0 45 7.5 7.5 180 800 Ex. = Example; Tri. = Trial

TABLE-US-00009 TABLE 8 Mechanochemical Grinding of Biomass A with the Additives Sodium Nitrate A and Ammonium Chloride A under Air and under Argon Z Ex. 15 Acti- Quartz- vated sand Coal Biomasse NaNO.sub.3 NH.sub.4C1 Milling Tri. Q G A A A time No. [g] [g] [g] [g] [g] [min] RPM 1 30 30 30 7.5 7.5 30 1100 2 30 30 30 7.5 7.5 60 1100 3 30 30 30 7.5 7.5 120 1100 4 30 30 30 7.5 7.5 180 1100 5 0 45 45 7.5 7.5 30 1100 6 0 45 45 7.5 7.5 60 1100 7 0 45 45 7.5 7.5 120 1100 8 0 45 45 7.5 7.5 180 1100 9 45 0 45 7.5 7.5 30 1100 10 45 0 45 7.5 7.5 60 1100 11 45 0 45 7.5 7.5 120 1100 12 45 0 45 7.5 7.5 180 1100 13 30 30 30 7.5 7.5 30 800 14 30 30 30 7.5 7.5 60 800 15 30 30 30 7.5 7.5 120 800 16 30 30 30 7.5 7.5 180 800 17 0 45 45 7.5 7.5 30 800 18 0 45 45 7.5 7.5 60 800 19 0 45 45 7.5 7.5 120 800 20 0 45 45 7.5 7.5 180 800 21 45 0 45 7.5 7.5 30 800 22 45 0 45 7.5 7.5 60 800 23 45 0 45 7.5 7.5 120 800 24 45 0 45 7.5 7.5 180 800 Ex. = Example; Tri. = Trial

[0650] The following general tendencies can be derived from the test results of Examples 11 to 15.

[0651] 1. The degradation of the biomass A and the nitrogenous compounds A proceeded faster with activated carbon G than with quartz sand Q.

[0652] 2. After about 2 hours, however, the effect of quartz sand Q was stronger than that of activated carbon G, so it was advisable to add small amounts of quartz sand Q to the mixtures.

[0653] 3. The decrease in nitrogen-containing compounds A followed the natural logarithm, with all nitrogen-containing compounds A having been broken down after 60 minutes.

[0654] 4. A significant difference in the breakdown of the nitrogen-containing compounds A between the sumped-in mixtures F and the dry-prepared mixtures F could not be determined. There was only a certain trend that the sumped mixtures F showed faster degradation.

[0655] 5. The number of revolutions was the decisive factor. For example, the breakdown of the nitrogen-containing compounds A is twice as fast at 1,100 RPM as that at 800 RPM.

[0656] 6. No difference was found between the rate of degradation when grinding in air and the rate of degradation when grinding under argon.

[0657] 7. The ultraphosphate B could be converted into biologically available, water-soluble phosphate B by grinding.

[0658] 8. The different amounts of sodium nitrate A and ammonium chloride A had no influence on the degradation rates.

EXAMPLE 16

[0659] The Elimination of Nitrates A and Ammonium A and the Immobilization of Trace Elements C in Coal G and the Reuse of Coal G in Biogas Plants

[0660] 10,000 kg of slurry A, which contained nitrates A, ammonium A, phosphates B and traces of arsenic C and heavy metals C, were gradually dried using a commercially available digestate dryer. A total of 800 kg of dry matter F remained. The drying was carried out at an elevated temperature, and the ammonia A which escaped was bound with sulfuric acid, as described in German patent application DE 10 2016 004 162 A1. The resulting ammonium sulfate A could be processed further together with the dry matter F. The dry matter F and the ammonium sulfate A were premilled in a separate mechanical mill 1. Then they were entered from above together with half the amount of activated carbon G, 50 kg of bentonite Z and 10 kg of N,N,N′,N′-ethylenediaminetetra-(methylenephosphonic acid) Z continuously in a mechanical mill 1 with a drum 1.5 of a volume of 900 liters through a protective grille 6, which prevented the grinding media 1.2 from exiting. 1000 kg of steel balls 1.2 with a diameter of 5 mm were used as grinding media 1.2. The ground material F was separated again centrally by means of a cyclone 8. About 100 kg of dry material F ran through the mechanical mill 1 in one hour and were ground at a constant speed of 1,100 rpm.

[0661] The resulting solid, finely divided product I contained significantly fewer nitrate ions A and ammonium ions A than the original dry matter F. In addition, arsenic C, the heavy metals C and their compounds C were immobilized in the coal G, in the bentonite Z, and with the chelate complexing agent Z and thus could no longer get into the groundwater, which was a major benefit.

[0662] The water-soluble phosphate B was washed out of the solid, finely divided product I, and the resulting solution could be used as liquid fertilizer E.

[0663] The washed product I could be returned to the biogas plant as dry matter or in a moist state in any form in order to increase the methane formation.

EXAMPLE 17

[0664] The Mechanochemical Processing of Manure A and the Elimination of Nitrates A in the Presence of Catalytically Active Iron Particles K.

[0665] A slurry containing 200 mg/L nitrate ions was dried in a customary and known manner. 100 parts by weight of the dried manure A, 34 parts by weight of quartz sand Q, 34 parts by weight of activated carbon G and 2 parts by weight of catalytic iron particles K were mixed with one another and ground as described in the Examples 1 to 3. After 30 minutes, 60 minutes, 90 minutes, 120 minutes, 180 minutes and 240 minutes, samples I were removed from the mill base F and eluted with distilled water. The respective nitrate content A was then determined. It was 180 mg/L, 120 mg/L, 90 mg/L, 50 mg/L, 36 mg/L, 21 mg/L and 11 mg/L, respectively.

[0666] The example demonstrated that the mechanochemical process according to the invention was outstandingly suitable for the elimination of nitrates A in biomasses.

EXAMPLE 18

[0667] The Mechanochemical Immobilization of Carcinogenic Hexavalent Chromium A

[0668] A mill base F was prepared from 50 parts by weight of activated carbon G, 50 parts by weight of quartz sand and 10 parts by weight of potassium dichromate C and ground as described in the Examples 1 to 3. After 120 minutes, samples were taken from the powdery product I. The samples I were eluted with water and it was checked whether water-soluble chromium salts C were still present. However, the concentrations were below the detection limits of the customary and known methods for determining chromium C. For comparison, the chromium content of the powdered product I was analyzed in the customary and known manner. Almost the entire original amount of chromium C was found. Thus the original amount of hexavalent chromium C was almost completely immobilized. The small missing amounts of chromium C had apparently been taken up by the materials in cavity 1.1 of mechanical mill 1

EXAMPLES 19 AND 20

[0669] Mechanical Mills for Carrying Out Mechanochemical Processes

[0670] The mechanical mill 1 for mechanochemical processes comprised at least one rotatable (Example 18; FIG. 1) or fixed (Example 19; FIG. 2) mechanochemical reactor and waveguide 1.1, containing a variety of balls made of technical ceramic as grinding media 1.2 in a drum 1.5 made of stainless steel and lined with technical ceramic, at least one inlet 1.5.1 for the grist F; 1.3 and at least one outlet 1.5.2 for the ground product I.

[0671] The drum 1.5 of the rotatable mechanochemical reactor and waveguide 1.1 of example 19 (FIG. 1) had a disk-shaped vertical drum wall 1.5.3 which was connected in its center to a rotating drive shaft 3 driven by a motor 4.

[0672] The drum 1.5 of the stationary mechanochemical reactor and waveguide 1.1 of Example 20 (FIG. 2) had an attritor 1.4 made of stainless steel, coated with technical ceramics, for mixing the grinding media 1.2 and the ground material 1.3. The attritor was arranged to be rotatable along the longitudinal axis of the drum 1.5 by a rotatable drive shaft 3 which was driven by a motor 4 and which passed through the disk-shaped vertical drum wall 1.5.3 through a bushing 1.5.3.1.

[0673] Both in the mechanical mill 1 of Example 19 (FIG. 1) and in the mechanical mill 1 of Example 20 (FIG. 2), the disk-shaped vertical drum wall 1.5.3 and the opposing drum wall 1.5.4 consisted of a electromagnetic radiation and/or corpuscular radiation 2.1 permeable, removable, scratch-resistant and impact-resistant grid 1.5.5 made of ceramic, which separated the mechanochemical reactors and waveguides 1.1 from the microwave generators 2.

[0674] The microwave generators 2 were firmly connected to mechanochemical reactors and waveguides 1.1 by means of flanges. The openings 1.5.5.1 in the grids 1.5.5 were round and formed a pattern. The grids 1.5.5 with round openings 1.5.5.1 could be replaced by grids 1.5.5 with openings 1.5.5.1 with 3-cornered, 4-cornered, 5-cornered, 6-cornered and slot-shaped outlines.

[0675] The drum 1.5 of Example 20 (FIG. 2) could also have the shape shown in FIGS. 1 a, 1 b, 2a and 3a of the German patent application DE 195 04 540 A1, only that it had at least one grid 1.5.5 on the drive 4; 3 and the drum wall 1.5.4 opposite the drum wall 1.5.3.

[0676] The motors 4 used were electric motors from Dynamic E Flow GmbH, Kaufbeuren, Germany, under the Capcooltech® brand, type HC and type LC.

EXAMPLE 21

[0677] Embodiments of the Agitation Means 1.4 in Mechanochemical Mills 1

[0678] Mechanochemical mills 1 according to Example 20 were provided which, instead of the attritors 1.4.1, contained further embodiments of the agitation means 1.4.

[0679] The agitation means 1.4 according to FIGS. 5-1 (a), (b) and (c) were striking disks 1.4.2, each with a circular edge 1.4.2.3. The striking disks 1.4.2 each had a centrally arranged bushing 1.4.2.1 for the drive shaft 3. Six equally sized striking holes 1.4.2.2 were arranged symmetrically around the bushing 1.4.2.1. The striking disks 1.4.2 according to FIGS. 5-2 (a), (b) and (c) differ from the striking disks 1.4.2 according to FIGS. 5-1 a), (b) and (c) only in that they had four instead of six striking holes 1.4.2.2. The striking disks 1.4.2 according to FIGS. 6 (a), (b) and (c) had three striking holes 1.4.2.2 which were curved, elongated and symmetrically arranged in a circle to each other and arranged parallel to the edge 1.2.4.3.

[0680] The striking disks 1.4.2 could be arranged on the drive shaft 3 in such a way that the striking holes 1.4.2.2 were in congruence or in a gap. The striking disks 1.4.2.1 could, however, also be arranged in such a way that two or more were alternately in congruence and then two or more on gaps.

[0681] The striking disks 1.4.2 of FIGS. 7 (a), (b) and (c) had six symmetrically arranged striking webs with a triangular profile that were convexly curved in the direction of rotation on one of their opposite surfaces. 1.4.2.4. The striking webs 1.4.2.1 each ran from the bushing 1.4.2.1 to the edge 1.4.2.3. In a further embodiment, the striking webs 1.4.2.4 could be arranged on both surfaces.

[0682] The striking disks 1.4.2 of FIGS. 8 (a), (b) and (c) differ from the striking disks 1.4.2 in that the striking webs 1.4.2.4 were arranged in a straight line and had a square profile. The striking disks 1.4.2 of FIGS. 9 (a), (b) and (c) differed from those of FIGS. 8 (a), (b) and (c) only in that the striking webs 1.4.2.4 had a triangular profile.

[0683] These striking disks 1.4.2 could also be arranged on the drive shaft 3 in such a way that the striking webs 1.4.2.4 were in congruence or in a gap. The striking disks 1.4.2.1 could, however, also be arranged in such a way that two or more were alternately in congruence and then two or more on gaps.

[0684] The agitation means 1.4 of FIGS. 10 (a), (b) and (c), which are arranged symmetrically to the drive shafts 3, each had two striking fans 1.4.3 radiating from a ring 1.4.3.1 surrounding the bushing 1.4.2. Two striking webs 1.4.2.4 with a square profile were arranged radially on each of the surfaces of the two striking fans 1.4.3. The striking fans 1.4.3 of FIGS. 11 (a), (b) and (c) differed from those of FIGS. 10 (a), (b) and (c) only in that the striking webs 1.4.2.4 had a triangular profile.

[0685] The striking fans 1.4.3 of FIGS. 12 (a), (b), (c) and (d) were arranged symmetrically to the drive shafts 3 and had each a mountain-and-valley profile 1.4.3.2 which consisted of two valleys and two mountains each running parallel to the edges 1.4.2.3.

[0686] In the agitation means 1.4 of FIGS. 13 (a), (b), (c) and (e), the ring 1.4.3.1 widened symmetrically and merged into two pairs of two radiating striking fans 1.4.3, each separated by a U-shaped gap 1.4.3.3 were separated from each other, over. The each of the four compartments had also a mountain-and-valley profile running parallel to the edges 1.4.2.3.

[0687] These striking fans 1.4.3 could also be arranged on the drive shaft 3 in such a way that they were in congruence or in a gap. The striking fans 1.4.3 could also be arranged in such a way that alternately two or more were in congruence and then two or more on gaps.

[0688] The striking club 1.4.4 of FIG. 14 had three connecting webs 1.4.2.4 with a round cross section radiating symmetrically from the ring 1.4.4.1 encompassing the drive shaft 3, at each of the ends of which a spherical striking body 1.4.4.3 was attached. The striking clubs 1.4.4 could be arranged on the drive shaft 3 in such a way that they were in congruence or on gap. However, they could also be arranged in such a way that alternately two or more stood in congruence and then two or more on gap. In other embodiments, the connecting webs 1.4.2.4 could also have a quadrangular, oval or trapezoidal cross-section or a flattened cross-section the same as through a knife edge.

[0689] The sheet-like striking wing 1.4.5 of FIG. 15 had an S-shape, in the two striking ends 1.4.5.1 of which striking holes 1.4.2.2 were arranged. The planar striking fan 1.4.5 16 had a more pronounced S-shape without striking holes 1.4.2.2. The striking wings 1.4.5 could be arranged on the drive shaft in such a way that they were in congruence or on gap. They could, however, also be arranged in such a way that two or more were alternately in congruence and then two or more on gap.

[0690] Instead of the agitation means 1.4 and grinding media 1.2 described above, the mechanical mills 1 could also be operated with rollers 1.4.6 rotating in the opposite direction of rotation 1.4.6.1. The grinding then took place in the nip. In the configuration according to FIG. 17, two parallel rollers were arranged in the grinding chamber 1.1. In the configuration according to FIG. 18, the surfaces of the two rollers 1.4.6 had interlocking spikes 1.4.6.2. In the configuration according to FIG. 19, the roller 1.4.6 rotated against an abrasion wall 1.4.6.3, the grinding taking place in the gap between the roller 1.4.6 and the abrasion wall 1.4.6.3. In the configuration of FIG. 20, the axes of rotation 1.4.6.4 of the two parallel rollers 1.4.6 intersected at an angle 1.4.6.5, which resulted in an additional torsion of the ground stock F.

[0691] The rollers 1.4.6 of FIG. 21 rotating in the opposite direction of rotation 1.4.6.1 had a resilient surface 1.4.6.6. This was formed by symmetrically arranged depressions 1.4.6.7, in which springs 1.4.6.8 pushed the spheres 1.4.6.9 out of the depressions 1.4.6.7. The grinding of the ground stock F then took place when the rollers 1.4.6 were rotated in the contact area between two spheres 1.4.6.9. The spheres 1.4.6.9 had a smaller diameter than the clear width of the depressions 1.4.6.7, so that the grist F that had penetrated into the depressions 1.4.6.7 could trickle out again when the rollers 1.4.6 were in a suitable position.

EXAMPLE 22

[0692] Embodiments of the Grinding Chamber 1.1 of the Mechanical Mills 1

[0693] Instead of a drum 1.5, in which the grinding chamber 1.1 had the shape of a straight cylinder, a grinding chamber 1.1 could also be used, comprising at least two spherical-shaped grinding chambers 1.1.1 arranged one behind the other, which were formed by at least one circular constriction 1.1.2. The drive shaft 3 ran centrally through the spherical section-shaped grinding chambers 1.1.1 and the circular constrictions 1.1.2. The dimensions of the agitation means 1.4 were adapted to the periodically changing diameter of the grinding chambers 1.1.1. This configuration made it possible to improve the mixing of the ground stock F.

EXAMPLE 23

[0694] Mechanochemical Process for the Decontamination of Contaminated, Phosphate-Containing Biomass A; B and for the Recovery of Phosphate B in Bioavailable Form

[0695] The mechanochemical process is explained in more detail using the flow diagram in FIG. 4.

[0696] The moist, noxious, phosphate-containing biomass A; B was dried. The resulting dry matter A; B or the solids of the biomass A; B were sieved and pre-ground. The water obtained during drying, which contained ammonia A and ammonium A, was subjected to osmosis or distillation, so that solid ammonium salts E resulted. These could be used as ammonium fertilizers (valuable product E). The ammonium salts A could also be transferred together with the solids of the biomass A; B to a mechanical mill and subjected therein to mechanochemical grinding in the presence of a plasma. This resulted in a noxious-free or noxious-reduced, immobilized heavy metals C and destroyed bacteria A and viruses A containing biomass A; B, as well as coal G and phosphates B. This mixture I could be granulated and pelletized and used as phosphate fertilizer E with coal G and non-toxic inorganic and organic components Z. The mixture I could also be ground, so that powdered phosphate fertilizer E with coal G and non-toxic inorganic and organic components Z was formed. The water-soluble, biologically available phosphate B could be extracted from the powder I and the pellets I and used as liquid fertilizer E. This way, carbon G with non-toxic organic and inorganic components Z was left behind.

EXAMPLE 23

[0697] The regeneration of Activated Carbon G for the Return to the Fourth Purification Stage

[0698] The moist, loaded activated carbon G and the sludge A of the fourth purification stage were washed out. This resulted in a washed-out, moist, loaded activated carbon G; A. This was dried so that a washed-out, dry, loaded activated carbon G resulted.

[0699] In a further embodiment, the moist, loaded activated carbon G; A and the sludge A were dried directly, so that a dry, loaded activated carbon G; A with sand Q and organic impurities A resulted.

[0700] The two dry masses could each be sieved for itself or combined and then sieved, so that sieved, dry, loaded activated carbon G; A was obtained.

[0701] The dry, loaded activated carbon G; A with sand Q and organic impurities A, the washed-out, dry, loaded activated carbon G; A and the sifted, dry, loaded activated carbon G; A could be subjected each individually or together in a mechanical mill 1 to a mechanochemical processing with grinding media 1.2 and a plasma. In all cases, the result was a ground, regenerated activated carbon G, which may also contain impurities A; C due to fibers and mineral and metallic components. This activated carbon was sieved to separate the heavy metals C. If necessary, the heavy metals C could also be separated using magnets. The resulting milled, sieved and regenerated activated carbon G could be granulated and pelletized, and the granules and pellets could be returned to the fourth purification stage.

EXAMPLE 24

[0702] The Radical Graft Copolymerization of a Mixture of Ethylene and Propylene on a Mechanochemically Treated, Thermosetting Clearcoat—Proof of Concept

[0703] A mechanical mill 1 according to Examples 1 to 3 was used for the grinding. Their metal surfaces were coated with a layer of aluminum oxide ceramic according to Example 17 (FIG. 2), and balls made of aluminum oxide ceramic were used instead of steel balls 1.2 (cf. Ulrike Wiech in the company brochure of Ceram Tec-ETEC GmbH, Lohmar, think ceramics TECHNISCHE KERAMIK, pages 211 and 212, 3.4.4.2 grinding and breaking). The weight ratio of grinding media 1.2 to ground stock F was 20:1. The inlet 1.5.1 for the ground stock F comprised an evacuable lock into which the ground stock F was poured. The lock was then evacuated. After a pressure of 0.01 mbar had been reached, the lock was filled with argon up to a pressure of 1.0 bar. The ground stock F was then dropped from the lock into the argon-filled grinding chamber 1.1 of the mechanochemical reactor and waveguide 1.1. The outlet 1.5.2 for the ground product P comprised a tangential cyclone separator 8.

[0704] A mixture of 70 g of powdered, thermally cured automobile series clearcoat A according to Table II-2.5: Automobile series clearcoat, page 142 of the textbook by Bodo Mueller and Ulrich Poth, lacquer formulations and lacquer recipes, the textbook for training and practice, Vincentz Verlag 2003, 3 g activated carbon G and 2 g quartz sand Q were used as the ground stock F. The ground stock F was ground under argon for 2 hours with an attritor speed of 1100 rpm to a fineness of an average particle size d.sub.50=500 nm. During the grinding, the waveguide 1.1 was irradiated through the grid 1.5.5 with microwaves 2.1, which were generated with the aid of a microwave generator 2. After the end of the grinding, the resulting product I was flushed with argon from the mechanochemical reactor 1.1 into the tangential cyclone separator 8 and separated therein from the gas phase under argon, transferred under inert conditions into a suitably sized fluidized bed reactor of the customary and known design and fluidized with argon. The inert gas atmosphere was displaced by a gas mixture of ethylene and propylene in a molar ratio of 1:1. The gas mixture was pumped in a circle from below through the fluidized bed reactor, and the pressure drop resulting from the graft copolymerization on the particles of the ground product I was compensated for by metering in the gas mixture. When the pressure drop could be no longer observed, the graft copolymerization was terminated by flushing the fluidized bed reactor with argon and the resulting graft copolymer was discharged. This was a finely divided, free-flowing black powder with an average particle size of d.sub.50=1.5 μm.

EXAMPLE 25

[0705] The Use of the Mechanochemical Process According to the Invention in the Production of Drinking Water H.sub.2O

[0706] FIG. 23 schematically shows the production of drinking water H.sub.2O from salt water and/or dirty water SW by reverse osmosis UO and membrane filtration.

[0707] Before the microfiltration MF, the activated carbon G was used as a preliminary stage for microfiltration in order to protect the membrane MF from dirt and particles SP. This reduced the buildup and clogging.

[0708] Common macromolecules MM were retained at the ultrafiltration stage. However, the majority of the macromolecules MM had already been removed by the activated carbon G, so that the ultrafiltration membrane UF was a guard membrane that was less clogged and lasted much longer. This was especially true for cellulose, hemicellulose, lignin, humic acids, proteins and metabolites.

[0709] In the subsequent nanofiltration, the nanofiltration membrane NF retained dissociated salts and divalent and higher-valent salts DS as well as cations and anions such as sulfates DS, phosphates B and alkaline earth metals C as well as sugars ZU. It was particularly important that phosphates B could be separated here and processed cleanly together with alkaline earth metals C.

[0710] In the final reverse osmosis or reverse osmosis RO, monovalent and undissociated salts EWS; UDS were withheld. This resulted in a highly enriched solution or suspension that contained a lot of ammonium A and nitrate A as well as chlorides, bromides and alkali metal cations C. These salts C could be thickened separately or sold as fertilizer concentrate E or, if there was an oversupply, simply converted mechanochemically into atmospheric nitrogen after drying. This made it possible to increase the concentration of cations C, such as potassium C, that were not destroyed, in the mechanical mill. The activated carbon as a prefilter was mechanochemically recycled after drying and used again as a prefilter.

[0711] Overall, this process enabled the production of pure water effectively and efficiently due to the pre-filtration and the mechanochemical reprocessing of the activated carbon.

EXAMPLE 26

[0712] The Binding of Noxae A with the Help of Impregnated Activated Carbons G and the Reprocessing of the Loaded Impregnated Activated Carbons G

[0713] The exhaust air filters of cattle barns, digestion towers, biogas plants and closed waste disposal sites were equipped with multi-layer impregnated activated carbon filters A. The individual layers were impregnated with potassium iodide, carbon dioxide, carbon monoxide, hydrogen sulfide and other sulfur compounds. This significantly increased the adsorption capacity of activated carbon G, because noxae A such as ammonia, amines, fine dust, ultrafine dust, arsenic and mercury were not only bound by adsorption, but also by chemical sorption or catalyzed reactions. The activated carbons G impregnated with potassium iodide were particularly effective in this regard.

[0714] The impregnated activated carbons G loaded with noxae A could then be recycled and reactivated with the aid of the mechanochemical process according to the invention.

EXAMPLE 27

[0715] The Classification of Activated Carbon Particles G with a Particle Size of 1 μm to 3 μm

[0716] A further advantageous application of the mechanochemical method according to the invention was the sifting, the separation and sifting of activated carbon particles G with an average particle size d.sub.50 of 1 μm 3 μm in the device according to FIG. 24. For this purpose, cleaned, dried nitrogen 5.1 was sucked in through a suction pipe 5.0 with the aid of a blower 5 and blown as a gas flow 5.2 through a first pipe 5.5 into the grinding chamber 1.1 of a mechanical 1 mill. Before entering the grinding chamber 1.1, the gas 5.2 flowed through a gas-permeable protective grid 6, which prevented grinding balls 1.2 from entering the tube 5.5 during the operation of the mechanical mill 1. The gas flow 5.2, viewed in the direction of flow, was regulated with the aid of a control valve 5.2.2 immediately before entering the grinding chamber 1.1.

[0717] The finely divided, powdery activated carbon particles G were discharged from the grinding chamber 1.1 with the gas stream 5.3 with an average particle size <1 μm through a further protective grid 6 via a second tube 5.6. The gas flow 5.3 was regulated by a control valve 5.3.1.

[0718] The gas flow 5.3 was passed in the further course of the pipe 5.6 through a bypass BP with a pipe 5.5.1 and combined with a gas flow 5.2.1 regulated with the aid of a control valve 5.2.3. The combined gas streams 5.3; 5.2.1 was led into an acoustophoresis unit 7 according to the international patent application WO 2017/153038, in which the finely divided activated carbon particles G were agglomerated by means of standing ultrasonic waves 7.2, which were generated by mutually opposing ultrasonic sources 7.1, so that they had the desired mean particle size d.sub.50. The exiting gas stream 5.4 with the agglomerated activated carbon particles G was blown into the cyclone 8 via the gas feed line 5.6, in which the agglomerated activated carbon particles G; 9.1 were separated from the gas phase (exhaust gas 5.7), which was discharged via the exhaust gas line 8.1, and discharged as a powdery solid 9 via the solids outlet 8.2.

[0719] A major advantage of this device was that the bypass BP, which fluidly connected the gas line 5.5 and the gas line 5.6, ensured that a stronger gas flow 5.4 flowed through the cyclone 8 than through the grinding chamber 1.1.

EXAMPLE 28

[0720] The Mechanochemical Elimination of the Slip of Organic Gases and Carbon Dioxide in the Exhaust Gases from Biogas Plants and Gas Engines

[0721] The slip of organic gases F and carbon dioxide D, in particular the methane slip F in biogas plants and in gas engines operated with methane and/or natural gas, could be effectively and efficiently eliminated by mechanochemically converting the slip gases into carbon G using the mechanochemical method according to the invention in the presence of activated carbon G so that they no longer entered the atmosphere, where they would have acted as particularly strong greenhouse gases. Thus, not only could the emission of greenhouse gases be effectively prevented by the mechanochemical process according to the invention, but the resulting coal G could be used again for grinding.

EXAMPLES 29 AND 30

[0722] The Splitting of Carbon Dioxide into the Elements—Proof of Concept

EXAMPLE 29: CARBON DIOXIDE WITH C-13 ON NORMAL ACTIVATED CARBON

[0723] 20 g of activated carbon with a typical isotope ratio of 98.9% C-12 and 1.1% C-13 were treated with C-13-labeled carbon dioxide (Sigma Aldrich 364592-1 L EU, 99% atom C-13) until saturation in a mechanical mill with a volume of 1 L for 12 hours at room temperature. The activated carbon was first dried at 1100 C. for 12 hours and then degassed under reduced pressure. The reduced pressure was a high vacuum of 10.sup.3 hPa (mbar).

[0724] Thereafter, the coal was mixed with 5% by weight of silica and treated mechanochemically at room temperature at 1200 RPM in a mechanical mill with a grinding chamber of 1 L with 1250 g of chrome steel balls of 5 mm diameter. The C-13 content of the activated carbon was then determined by means of mass spectrometry. The measurements indicated that 3.4% C-13 was present. This means that 3.4×100/3.854=88.2% C-13 had been incorporated into the activated carbon during the grinding.

[0725] Calculation:

[0726] 1 Liters of C-13 CO.sub.2 contained 0.04461 moles of C-13 CO.sub.2

[0727] 0.04461 mol with a molar mass of M=45 g/mol (O-16=99%) contained n×M=m, m=2.0076 g

[0728] Of this, 13/45 percentages would have been converted into coal with 100% conversion. That would have been 0.579 g of C-13.

[0729] A theoretical implementation of 100% would have resulted in:

[0730] 20 g activated carbon AK with 98.9% C-12 and 1.1% C-13

[0731] Making 0.006 g and 0.573 g

[0732] Yielding 19.780 g Activated Carbon AK and 0.220 g with C-13 and 99% C-12

[0733] In total: 19.786 g of C-12 and 0.793 g of C-13

[0734] In total: 19.786 g+0.793 g=20.579 g

[0735] Which is 96.146% C-12 and 3.854% C-13

[0736] Previously, the mass ratio in the activated carbon AK=98.9 C-12/1.1% C-13

[0737] After a 100% adsorption and conversion, the ratio in the activated carbon AK would have been 96.146% C-12/3.854% C-13.

EXAMPLE 30

[0738] Carbon Dioxide Labeled with 13-C on Activated Carbon Loaded with Ammonia

[0739] 20 g of activated carbon with a typical isotope ratio of 98.9% C-12 and 1.1% C-13 were treated in a mechanical mill with a volume of 1 L for 12 hours at room temperature with C-13-labeled carbon dioxide (Sigma Aldrich 364592-1 L EU, 99%—atom C-13) and the same stoichiometric amount of ammonia until saturation. The activated carbon was first dried at 110° C. for 12 hours and then degassed under reduced pressure. The reduced pressure was a high vacuum of 10.sup.−3 hPa (mbar).

[0740] Thereafter the coal was mixed with 5% by weight of silicon dioxide and treated mechanochemically at room temperature at 1200 rpm in a mechanical mill with a grinding chamber of 1 L with 1250 g of chrome steel balls of 5 mm diameter. The C-13 content in the ground coal was then determined by means of mass spectrometry. The measurements showed that it contained 3.4% C-13. This means that 3.6×100/3.854=93.4% C-13 had been incorporated into the activated carbon.

[0741] 1 Liters of C-13 CO.sub.2 contained 0.04461 moles of C-13 CO.sub.2

[0742] 0.04461 mol with a molar mass of M=45 g/mol (O-16=99%) contained n×M=m, m=2.0076 g

[0743] Of this, 13/45 percentages would have been converted into coal with 100% conversion. That would have been 0.579 g of C-13.

[0744] A theoretical implementation of 100% would have resulted in:

[0745] 20 g activated carbon AK with 98.9% C-12 and 1.1% C-13

[0746] Making 0.006 g and 0.573 g

[0747] Yielding 19.780 g Activated Carbon AK and 0.220 g with C-13 and 99% C-12

[0748] In total: 19.786 g of C-12 and 0.793 g of C-13

[0749] In total: 19.786 g+0.793 g=20.579 g

[0750] Which is 96.146% C-12 and 3.854% C-13

[0751] Previously, the mass ratio in the activated carbon AK=98.9 C-12/1.1% C-13

[0752] After a 100% adsorption and conversion, the ratio in the activated carbon AK would have been 96.146% C-12/3.854% C-13.

CONCLUSION

[0753] In the presence of ammonia, the incorporation of C-13 into the activated carbon was significantly increased. The incorporation of C-13 into the activated carbon was evidence that the carbon dioxide had been split into the elements.