DE1417102A1 - Process for the oxidation of substances under the influence of electrical gas and glow discharges - Google Patents

Description

Electrophysical Institute

Bernhard Berghaus

.BB-2S9-0H-

Learn about the oxidation of substances

the influence of electrical, gas and glow discharges »

DI® Superficial invention relates to look Yerfahren implementation "^ on chemical reactions Sem" Einflsi® © Isktrisshei 'gas and Glimaientladungexi ₈ and in particular dl * oxidation of gaseous ^ vaporous AAFL fine = members liquids and solids in a Reaktiöns "space with electrodes at least one gas inlet and at least one gas outlet device

Various methods and devices of this type are known ₉ in which a glow discharge is generated in a suitable vessel with intermediate voltage-carrying electrodes ₉ which acts on and in a gas flow

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In the known processes of this type, the electric field acts either through insulating layers, whereby the pressure in the reaction space can then be selected as desired ₉ but the energy density of the glow discharge forming on the surfaces of the insulating layers is not above relatively low values for thermal reasons can be increased, or those discharge vessels _f in which the spanmmgführenden electrodes facing free, the energy of the glow discharge on a ₉ limits the voltage leading parts be coated Glimmhaut by welshe which must be passed materials to be treated "if not used the very low-energy positive Entladurigssäule In any case, the energy is mostly only in the immediate vicinity of body surfaces, but this is often undesirable when carrying out reactions on gaseous * vaporous or finely dispersed substances. However, they are to some extent High-energy gas or glow discharges in the free space between the electrodes, which were previously unknown. Another known method for carrying out Gasregfctionen in a narrow gap between voltage-carrying metal walls has been found to be inexpedient in that, due to the high flow resistance, the residence time of the reactants can only be influenced little "-.

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Accordingly, for large-scale purposes, electrical Methods for carrying out chemical reactions have hitherto only been used with arc-like discharges, which the well-known disadvantages such as high temperature, relatively low yield, poor purity of the end products, etc. « cling o.

In contrast, the present invention relates to a method may be used in which chemical reactions with a good yield arc without light · and, accordingly, carried out at much lower temperatures _o The method according to the present invention serves ^ for displaying Rich st off-compounds of metals, metalloids "elements and compounds from gas" shaped, vaporous and t © inverteilten liquid oä @ r solid starting materials under the egg @ .flu © electrical gas and glow discharges in a Esafeti & nsra & ai slt 'LLEK ^ Rose''of at least one * Gasjsuführung waae least .a "gas outlet infiltration", and is thereby gekenazeictenet that with the starting materials oxygen or at least one oxygen-containing reactant in the form of at least one jet is introduced into the reaction space and at least this jet is guided into a part of the room in which an electrical © gas- or _o glow discharge is maintained, and that during the passage of the reactants through the reaction space, they are allowed to act on one another for a period of time adapted to the desired end products with a supply of electrical energy adapted to this »

The invention is illustrated below in some examples explained in more detail with reference to Hg * 1 to 13 »From these pointers

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1 shows the basic diagram of an exemplary embodiment of a system for carrying out the method according to the invention;

ilgo 2 a reaction vessel for two jets directed against one another;

Figo 3 to 6. each an embodiment for a magnetic

'Influencing the method according to the invention;

7p, 8 and 9 each show a longitudinal section through different exemplary embodiments for nozzle-like feed members j

Figo 10 and 11 a plan baw _o longitudinal section for one with

several nozzle-like openings provided feed member;

üig. 12 and 13 a transverse or longitudinal section through another Embodiment for a feed element with a large number of nozzles *

A device for carrying out the method is _o schematically shown in Fig «1 Here is enclosed on all sides by metal walls 2 of the reaction chamber 1, the Sindo double-walled and arranged for passing a cooling medium flow in the arrow direction through the intermediate space 4 of the inner space 1 is top by a cover 5 of electrically insulating material is sealed airtight, which carries a feed member 6 made of metal, the inner channel 7 'of a nozzle 8 opens into the reaction space .1 ο the inner channel 7 and the nozzle 8 enclosing wall is provided with cooling channels 9 or ₀ 10 provided that from one entering in direction 11 around the nozzle 8

8 0 9 8 0 ΐ / 0 2 8 6

flowing and escaping in directivity 12 Long coolant, such as water or liquid air flows through the crossing points _o metal / insulating material are respectively on the cover 5 in a known v'eise by gaps 13, 14 protected-.

An electrical field is generated in front of the part of the metallic feed element 6, together with the nozzle 8, which protrudes into the discharge space, for which purpose a ring 15a that can be adjusted along the nozzle axis is arranged as a counterelectrode, which is connected to the inner conductor of the insulated current inlet 17a is held o The inside diameter of the ring 15a, which is arranged coaxially to the nozzle axis, is sufficient not to obstruct a gas jet emerging freely from the nozzle orifice _c The Hing 15a is connected via the switch 16a to one pole of a voltage source 18, the other pole via the holder 16 at the feeding member 6 is ₀ Preferably, a Gleichepannungsquelle used 18, whose negative pole via the switch 16, the feed element fed _o the other hand, the switches 16a sin pole of the voltage source 19 ° Bo z for DC "voltage, legendary center tap through the switch I6h and the current inlet 17b on the ring 15b and its other pole ~ via the switch 16c and di e Current inlet 17c is connected to ring 15c ο It has proven to be advantageous if electrode 15n is positive compared to electrode 15a *

_{To the supply element 6, the starting products, for example an atomized liquid 9,} possibly together with a carrier gas, are fed in via the pipe 21, which can be shut off with a valve 20 arrives, a f @ indlsDerae ,, YBKfceilune

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the liquid in the funnel 25 generates ,, so that the liquid mist with the carrier gas stream can pass together over the line 21 to the nozzle 8, as soon as the valve 20 is opened wirdο The pressure P ₂ can be read from the manometer 26th

At the lower end of the reaction space 1, an outlet line 27 is connected, which leads via a shut-off valve 28 to an absorption device 29a and the pump device 29, which is dimensioned such that in the reaction space 1 at the mouth of the line 27 a pressure gauge 34 readable predetermined pressure P ^ can be maintained, even if a gas stream with the pressure P ^ is fed through the nozzle 9, the pressure ratio P ₂ : P ^ should be able to be increased up to high values »

If P ^ is in the pressure range of 1 to 500 mm Hg, that is Carrying out a start-up process expediently The valves and 28 are closed for this purpose and via the in the pipe opening line 30 and the valve 31 is an auxiliary gas in the Reaction chamber 1 initiated and the same through the valve 32 on. the line 27 connected pump 33 except for evacuated a desired negative pressure »

The end product of the glow discharge process can partly be removed from the discharge chamber 1 via the absorption device 29a, partly via a suitable discharge device 35, which is of no further interest here ₀ If the gas inflow via the nozzle 8 takes place with sufficient pressure, normal atmospheric pressure can also be used in the reaction vessel rule so that one

.A,

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Pump 29 is dispensable,

P ₁ maintained at least in the unmittelbaren.Umgebung the mouth of the pipe 27: in the present process is an essential feature that in the reaction chamber 1, the reaction partners in the form of at least one beam are introduced 36 "To this end, in the reaction chamber 1, a predetermined pressure and at the same time via the nozzle-like opening 8 in the supply element 6 with the pressure Pg, a gas flow, initiated with suitable coordination of the pressure P ₂ at the mouth of the nozzle 8, its clearance and the pumping capacity on the line 27, a steady state is established In the % m reaction space between the mouth of the nozzle 8 and the outlet line 27 the pressure difference (Po- J ^) prevailed can have different shapes. In FIG is indicated, but the radial extension of the spindle-like shaped boundary surfaces is exaggerated compared to the actual shape for the sake of clarity.

If the gas flow spreads in the interior of the reaction space 1 unhindered, then the individual gas particles or * vapor-like, liquid or solid particles carried along by the jet most of the distance between the diisenmüng 8 *

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and pass through the counter electrodes 15 at high speed. By suitable choice of the total pressure gradient (P ₂ -P ₁ ), the speed and thus the passage time of the reactants can be set to the desired value within wide limits.

In the case of a negative voltage at the feed member j6 develops within the beam from the usual glimmer on the Cathode out a luminous phenomenon "which is far in the gas space extends out »mostly in the form of a lumin = However, in terms of its structure, Strahls9 is different from all those known so far Gas and glow discharge phenomena. Different «. The appearance and shape of the luminous zone is apparent determined by the gas jet, but is also occasional to perceive a stratification within the luminous phenomenon. " The spectral range of the light emission is determined to some extent by the reactions going on in the beam The light-emitting areas within the beam are of course not the only ones for the present one • Purpose of carrying out reactions in the relevant parts of the room; rather, the actual reaction zone can also include non-luminous parts of the beam, as well as its immediate surroundings and extend into the nozzle opening 8 ...

The shape of the reaction zone depends largely on the flow velocity of the jet, although the ReactiäaszonQ need not extend entirely over the same au * An essential feature of the present form of discharge be ~

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but is on the relatively sharp Abgrenzaag ier reactionary zone against ihr® environment on the steilea pressure drop from I & Neren of the beam to its edge and on the known laws g after which the energy conversion of gas- »= - charges after an approximately cubic function increases with the gas pressure 'and is based on the different concentration of the reactants inside and outside the jet '. should _o .

Depending on the pressure conditions and nozzle dimensions, the gas flow leaves the nozzle mouth at a speed »which is in the order of magnitude of about a tenth of the speed of sound to several times the speed of sound« Selection of a suitable voltage between the feed element 6 and the counter electrode 15a _e or _{0 of} the counter electrode 15a _s 15b, 15e among one another, an energy supply to the beam adapted to the duration and the desired reaction can be set = apparently the reaction partners are already at the beginning of the actual reaction zone, So in the nozzle 8 or after leaving it dissociated by electrical action and possibly broken down into atomic or "ionized components". When passing through the beam 36, the desired reaction should then come about and by tuning the major Runtime and electrical energy can be achieved so that the desired reaction products leave the jet before a reverse reaction and a breakdown of the desired end products can occur - outside the jet, however, the conditions with regard to pressure are ₉ concentrations.

'80980170286 BAD ORIGINAL ■ - ■ ■

tration ₉ temperature ₉ ionization, uewu so different than in the jet that a disintegration of the end products is largely suppressed ο.

Dicias properties of the described electric beam discharge have proven to be advantageous for the oxidation of gaseous, vapor-like or finely divided solid and liquid starting materials? wherein hydrogen gas or at least one hydrogen-containing starting material is supplied to the reaction chamber "In particular, in one method Esch ride from starting materials that can form more than one oxygen compound _f desired higher oxygen compounds are prepared"

If desired, this can be done behind the separator 29a or * am Exhaust pipe of the pump 29 escaping gas which should already be largely free of the desired reaction product? again the same process are thus subjected to approximately the vessel 22 and from there to the feed member 6 o This is particularly advantageous if an auxiliary or carrier gas not involved in the reaction is fed in via line 23 is, for example, a noble gases

The between the nozzle orifice 8 and the counter electrode 15a The prevailing electric field strength can be adjusted by shifting the electrode 15a, as well as by regulating the current source B. are influenced * In the present procedure for the power source 18 voltages between 100 and 2000 volts, preferably 300 to 1100 volts favorable »It can be equal to =

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voltage as well as half-wave and pulse voltage are used »in some cases also alternating voltage.» By designing and setting the distance between the counter-electrode 15a ^, the immediate environment can be favored in terms of discharge energy at a desired gas pressure.

Furthermore, it has proven to be advantageous that at least one of the reaction pariners is pre-ionized before it is fed to the nozzle 8, for example in a known manner by a glow, arc or spark resist charge which is in a suitable form directly at the connection of the Line 2Jä and the container 22 arranged discharge vessel 22a »through which the relevant starting material is hindui'cageleätet ο

In some reactions kami © ss effwüsssehis © sin, in dea Reakticns space 1 via a separate Saführorgsia _P line @twa 37 "Md, the check valve 38 to initiate a © as or vapor, for example a the desired © reaction favoring gas such as chlorine _p or a substance with a catalytic effect, such as mercury vapor _n

Further details about appropriate execution forms of systems for the implementation of the present process are described in patent no ₀ (patent application -6§4 ^ described ^

© The starting material may not necessarily as described anßand Figo 1, all of which are initiated by the same feeding organ in the reaction space _o Even at illustrates installation according to Fig _o 1 can also be one or more of the Äpsgaßgsetoffe ugefihrt also through line 37 to the reaction chamber 1 ' be o

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Embodiment of a reaction vessel with two nozzle-like feed organs 40 or 41 made of metal is shown by Pigβ Io against the reaction vessel 42 made of metal, the two feed organs 40 and 41 are isolated, as indicated in FIG 40 and 41 is each an annular counter electrode 45 · provided or _c 46, respectively via insulating inlets 47 are mounted in the wall of the vessel 1 _o 48th The voltage source 49 is on the one hand at the feed member 40 and can be connected to the ring electrode 45 via the switch 50. Likewise, a further voltage source 51 is on the one hand connected to the other supply element 41 and on the other hand is connected to the ring electrode 16 when the switch 52 is closed. There is also a third voltage source

55 is provided, which can generate a voltage difference between the ring electrodes 15 and 16 when the switch 54 is closed «

Ia operation can, for example, each have a starting material via the Nozzles 40 bsw «41 introduced into the reaction space 55 and that Generated gaseous or vaporous end product via the pipe socket

56 ο By adjusting the voltage sources and 51 to different values can be achieved that the two effective reaction zones of the two rays the optimal energy is supplied, which would not be possible if the two starting materials were fed by a common supply organ were initiated. In addition, however, it can also be achieved that the two beams or the one guided by the same gaseous and vaporous or finely divided liquid and solid particles, different electrical properties are imparted, which favor a desired reaction

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or a higher affinity of the reaction partners to one another give. Dursireiae, caused by the voltage source 53 potential difference between the. Ring electrodes 15 and 16 the last-mentioned effect can be intensified *

The voltage sources 49 and 51 should preferably supply an adjustable DC voltage and the ring electrodes 15 and 16 should bring about a negative potential compared to the associated supply organ 40 or 41. However, wavy or impwlsaftig® equal voltages _p and, in some cases, alternating voltages can also be used _c

The tone dsm ZuführOrganen 40 and 41 beams generated in Figo 2 are directed towards one another "which need not necessarily be the case ο Rather, several individual beams may be parallel, convergent or divergent to one another extend ^ More _B daw present method also usable Ausführunge-

JgBt arrangements are in Patent No. _e Y

Bg Ire, ') described in more detail in such /; noj? D £ HVgeii T ₁ J ⁵ . more than one "introduced into the reaction space" is also possible, by adding an h-2, it is possible to create such conditions in the one jet that the particles entrained by this jet are markedly different. electrical properties compared to those in the other beam are given even if the speed of the

a Stj * ahlsn _? can the par-. due to a longer or shorter residence time within exerts effective beam zones with different electrical characteristics ,, & Fitted wercl n _o BAD ORIGINAL

'809801/0286.

When carrying out the present method, it has proven to be advantageous if the ionized gas jet in the The reaction space is not left to its own devices, it is controlled will o This is due to magnetic influence on the ionized Gas jet possible

An exemplary embodiment for magnetic focusing of an ionized gas jet is shown schematically in FIG. 3, in which the nozzle is designated by 6Q and the gas jet emerging from it is designated by 61. The jet is ionized by suitable means from the plane 62 running perpendicular to the jet axis what is indicated by the hatching- «. Length of the beam axis is arranged coaxially with the magnetic lens 65, which is drawn in longitudinal section and consists of a misshapen iron ring 64 ₉ and a winding 65 arranged in it ο If the winding 65 is excited with direct current via the connections 66 and 67, this results In the center plane of the lens 63, which is perpendicular to the beam axis, a magnetic field runs parallel to the beam axis and penetrates this center plane perpendicularly. Under the influence of this magnetic "field will obliquely to the beam axis moving ions in the direction of the beam axis bent, so that the ionized portion of the gas jet _o united in one focal point 68 on the ijtrahlachse Of course, the magnetic lens 63 can" uf non-ionized gas particles do not act, which accordingly continue unaffected by the diverging path indicated by the line 69. Furthermore, the sharp focusing of the ionized gas beam indicated schematically in FIG

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Mass are present, "Is this not ⁷ Her Pall, eo result e'ich different focal points along the Strahlaohse for ions of the same polarity over unterachiedlieheffl ratio of charge asu Maeee" ·. ·

In addition to such a focusing by magnetic lens systems, as indicated in Hg. 4, the eleventh magnetic bundling can also take place by a transverse field, the magnet 70, in which the magnetic force field, for example, between the poles 71 9 72 perpendicular to the beam axis and parallel to the plane of the drawing in Fig. 4 runs "in such a magnetic field dl · charge carriers in the Ga" describe jet 61 is known, spiral paths whose diameter by a sufficiently strong "magnetic field so klela can be ge hold <* * that the gas stream bsw ₀ Ionized hawks thereof; maintains the shape of a ray approximated.

In the present method, there is also the option of exiting the nozzle gas jet more or less static ionize and the ionized portion magnetically eu stunning river s _p so that a separation takes place of ionised from non-ionised gas flow "Then BoBο can with the ionized gas flow alone the desired reaction can be carried out, whereby a very precise metering of the amount of gas reaching the effective Besktionezone by appropriate adjustment of the degree of ionization possible

When carrying out reactions neon the procedures The main patent often results in ionized reaction products that have both the polarity of their properties and the also bozüglidh their ratio of charge to mass

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of the reaction products / könnenο different Magnetic interference with themselves leading gas jet is in such cases a separation of ionized reaction products from the gas stream possible Either a deflection of such ionised components from the Gasstrahlachs® or a stronger bundling or ο focusing the same done ₀ The concentration Such ionized reaction products at predetermined points in the interior of the vessel then facilitate their separate removal _{or the like}

As already mentioned above, the zone of intensive ionization of the gas flow "at higher pressure and with the corresponding clear width of the sensor bore can extend into this bore o In such cases it can be advantageous _p as shown in Fig. 5 and 6" anzuordnem produce the nozzle 75 of non-magnetic material, and or in the region of a longitudinal magnetic field of the magnetic lens 76, a transverse magnetic field of the magnets 77 _P 78 _o the one hand, has thereby an increase of the energy-turnover in the gas jet on the other hand a better bundling DES = the same can be achieved ₀ Furthermore, a directional separation of differently ionized reaction products can then already take place in the gas jet emerging from the nozzle 75

The magnetic fields, which run approximately parallel or transversely to the gas jet axis, can come from sufficiently strong permanent magnets or correspondingly excited electromagnets «The electromagnets are preferably supplied with constant or pulsed direct current

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variable strength

Eb it should also be mentioned that a magnetic influence of the ionized gas jet by current intensity spark discharge along the gas jet axis causes a constriction of the ionized gas flow in the radial direction, caused by the magnetic field linked with the current flow

The electrical power to be supplied is in the present case The process depends not only on the pressure conditions inside and outside the jet and on the amount of starting materials supplied, it is also determined by the type of occurring reactions »This is particularly the case with energy consuming reactions but at the beginning of the Process the electrical energy supply is adjusted according to the most favorable conditions for the creation and maintenance of the gas and glow discharge in some cases the initiation of the actual reaction, for example, which requires much higher energy, is certain Difficulty r

In such cases it has proven to be advantageous to insert an auxiliary substance into the reaction space which facilitates the reaction without taking part in the reaction itself. Such a gas or vapor, until further notice, "a finely dispersed liquid or solid Hilfsetoff example, several reactants are fed by the same feeder element as a gas stream or jet of gas into the reaction chamber together with one or" But it is also possible _eight such aid through another feed member ,

809801/0286

about one nozzle to blow or in the one or more reactants containing main beam from the side einzuleitenο as the second "the first cross beam into the reaction chamber Further, it may be advantageous even to enrich the reaction chamber with such an example, gaseous aid material ₉ so that in the outermost Zones of the beam the desired reaction is facilitated _o

The auxiliary substance which facilitates the reaction in the main jet is expediently only added at the beginning of the process, since it is normally no longer required after the normal operating state has been achieved ο In this case, an adjuvant can be chosen with one or more Reactants enter into a connection that is not a desired end product per se, but the initiation of the the desired reaction is facilitated ο Since the auxiliary substance is only introduced temporarily, the actual process is not impaired

But there is also the possibility of starting the process with an auxiliary substance with a catalytic effect or continuously sutufführung to "cause a desired reaction su bsw _c eu easier ₀ further the introduced auxiliary substance can be selected so that the same unwanted reaction companion binds or in some other way makes harmless »

With certain reactions by means of the present method has also been shown that for the preparation of certain end products at the same time old the reaction necessary for this purpose

Help response must be carried out. The energy tone ₉

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So the energy release or energy absorption, this auxiliary function must be such ₉ that the desired reaction is supported by the energy release or absorption on the part of the auxiliary reaction.

When carrying out the present method, a design of the feed member as shown in FIG. _9, 8 or 9 has proven to be advantageous, since measures are provided to pass through the beam with charge carriers _9, preferably electrons, when exiting the nozzle orifice, from the periphery and are radially aligned to the beam from all sides

7, the nozzle 80 with the mouth 81 carries the insulating rings 82 and 83, of which a metallic intermediate ring 84 is held coaxially to the nozzle 80 in such a way that it forms an annular inner neutral gap 85 with it. The intermediate ring 84 is in turn enclosed by a metallic bush 86 which is supported on the insulating ring 83 and forms an outer neutral gap 87 with the intermediate ring 84 Generation of a concentric to the beam axis directed Eletetronenstromeeο the edge 88 is through a. Coolant conducted via the cavity 89 can be cooled. The edge 88 can be surrounded on its outside by a metal sleeve 90 which rests on the insulating piece 91 and, with the edge 88, forms a protective gap 92

In operation, the metallic socket must lead 86, together with the edge 88 at least temporarily negative potential ₀ the other hand can

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the nozzle 81 ₉ if it is made of metal, depending. according to "unachieve positive or negative potential; however, it can also be operated without any connection to the voltage sources and, if desired, consist of non-conductive or poorly conductive material *, the metallic intermediate ring 84 serves as a static screen and prevents the penetration of glow discharges into the ring-shaped Neutral gaps 8 $ and 87 <The metal sleeve 90, which can also be cooled if required, must at least temporarily have a positive potential or be connected to the reaction vessel »

A similarly constructed feed member having a plurality of nozzles schematically shows the Figo 8, wherein the metal body 100 includes a plurality Djisenbohrungen 101, 102, having 105, 104 having parallel axes, each of which respectively in a cylindrical recess 105 * 106 or _o 107 br "", 108 opens whose concentrically enclosing the Strahlachee inside should have a Glimmhaut during operation the emergent beams 109, or 110 ,, _o or 111 or 112 be _c 'a metal plate 113, each having a concentric. Port 114 ο or is "115 and 116 or _o passed 117 per beam through the terminal 118 to the metal body 100, an at least seitweise negative voltage and the terminal 119 of the metal plate 115, a likewise at least temporarily positive voltage eye leads, _e so is each Beam under the influence of the electric field between the counter-electrode 113, among other things, far from the level body 100, but also immediately after its exit from the respective nozzle opening under the junction, from the inside of the troughs 105, 10S, 107, which surrounds the center of the body , 108 outgoing electron e-tromeeo

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The counter electrode 113 can also be arranged here so as to be displaceable along the beam axes _c

Finally, FIG. 9 shows an exemplary embodiment of a feed element with a nozzle body 120 which, for example, carries negative potential and has a wide end face with the central nozzle bore 121 for generating a jet 122, as well as a protruding cylindrical edge 123 which extends on its outside from the Sleeve 124 is enclosed and forms an annular, narrow protective gap 125 with it. The sleeve 124 and the nozzle body 120 are electrically isolated from each other by the insulating ring 120a. «The sleeve 124» as well as an annular counter-electrode 126 ₉ which can be cooled via the supply line 126a * lead, for example, positive potential. The ring 123 has openings 127 «which serve the purpose serve to enable the anodic sleeve 124 to reach through to the cathodic inner surface of the edge 123 and to maintain a glow discharge there, especially at high temperatures. Is compressed to facilitate ο So here are two anodes 124 and 126 exist, of which the one dee, namely 124, the cathodic surface of the ring or zugekrht 123 * adjacent and there is preferably a glow discharge gives rise "

The same effect can also be achieved by means of two annular anodes 126 _c for example, in an embodiment according to Fig 9 ₉ of which has a relatively large diameter and the edge 123 or ,, facing the inner surface or is in close proximity, while the other Downstream · is located and has a smaller opening diameter o At

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Such a design with two anodes has been shown that this second anode, which is arranged coaxially to the beam and downstream of the beam, is at a distance from the mouth of the nozzle-like opening should be adjustable, since the yield of the desired reaction product can be influenced by this distance. It is also important that the anodes are opposite to the beam axis can be centered, i.e. can be adjusted radially ο

Further usable embodiments of such a type generating a charge carrier current running transversely to the direction of the beam

r— ■

Feed members and arrangements are in the patent no. ₀ , ^c (Patentgesuoh Wr ₀ - "·""}

B <2i larger throughputs in an apparatus according to Pig ο 1 from = particular with Zuführorganen according to Figo 7 »8 and 9 is of importance ₉ that the total amount of the starting materials is not introduced into a beam of corresponding cross section in the reaction chamber" but the erforderliehe shaped overall cross-section in such a way or is divided _o that the entire amount of substance in the form of beams which Übersehreitens, is not initiated a predetermined thickness "This division can be effected either by use of multiple beams of smaller cross section by a corresponding design of the nozzle opening approximately in the form of shallow slots , intersecting slots, Ring8Chlitzen _p etc. "

An embodiment of one in the apparatus according to FIG Usable multiple nozzle are shown in Figo 10 and .11 ° Here is a cylindrical tube 140 with a nozzle-like with five Holes 141 provided end wall 142 provided as a conclusion » The axes of the ^ iÜeVriebe. through the nozzle bores 141

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The jets 143 generated run approximately parallel. Such a multi-faceted nozzle with the radius r ^ of the same bores 141 delivers approximately the same throughput rate as a circular single nozzle with the Hadius Cr ₂ Jf - 5 Cr ₁ ) °

Instead of parallel beam axes, a multiple nozzle can also be used designed for converging or diverging beam axes be c

The division of the cross-section of the dutch-like supply element serves the purpose of supplying the amount of substance, for example a gas or steam, which is adapted to the desired throughput, not in a thick jet ₉ but in a number of thinner jets to the reaction space the reaction partner (s) fed in as jets can be kept much more precisely within certain desired limits in the case of individual thinner jets than in the case of a thicker jet. because the expansion of the same takes place within the reaction space completely or at least along a rope of its path undisturbed and the dwell time of a gas particle within the individual jet is shorter and can be more precisely determined in advance? individual jets advantageous WE # ä £ ft s.Strahlen ♦ from the periphery with Xadungsträgejm, Ä ^r

trons ₉ are to be acted upon, di © . due to absorption, only a limited reichtfö.ite

BAD ORIQiNAL 80 980 1/0 ^ 86. '

This also applies to the case »that the desired subdivision was made by appropriate design of the nozzle opening (slot · = and hanging nozzles, etc. _c ) _{/ Ä} __

A further embodiment of a multiple nozzle is shown in FIGS. 12 and 13. Here, a second tube 151 of smaller diameter with a large number of nozzle-like bores 154 is located in an outer tube 150. The inner tube 151 forms one with the outer tube 150 Annular channel 152, which is used to supply one or more reactants, for example a gas mixture which is introduced into the interior 153 of the tube 151 via the nozzles 154 in the form of radially directed jets 155, one or more reactants, or an auxiliary gas , can also be blown in the direction of arrow 156 through the interior 153 and at the same time serve to discharge the reaction products _o A metal rod (not shown) extending along the central axis can be provided as a counter electrode, which has a positive potential with respect to the tube 151 the inside of the tube an electrical glow discharge and one to the ^{Ä ohrach} se directed electron flow. If desired, each of the düaenartigen holes may be provided of the recess 154 on the inside of the tube 151 with a recess 107 corresponding to the multiple nozzle shown in Figo 8 _o

The most suitable thickness of the individual beams, for example in the exemplary embodiment according to Figo 10-13 is of course on the gas density in the jet itself and on the penetration ability of the the charge carrier acting on the beam is determined. Have it

+
thicknesses between 1 mm to 10 mm, preferably 1 mm to 5 mm

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the cross-section "or η of Einae found to be useful in the design! cross sections is au consider ,, that the j ^ Strahlgeeehwindigkeit least close to the Pils mouth least 1/100 the speed of sound be MUB ₀ Most afrkCP * ^" because of the desired short residence ^ substantially higher ^ trahlgeschwindigkeiten to aum multiple of the desired speed of sound These speeds are quite achievable with suitable "for ^ the nozzle, somewhat in the manner of Lavalldüsen ₉ * ¥ I5e Druuk in the reaction chamber is according to the desired jet speed and the

Passage time of the reactants through the effective jet zones elected

It should also be mentioned ₉ that the nozzle bodies are not used in all versions! Forms must be made of metal, but z «B» in Figo 5s> 6 and 7 can also be made of insulating materials such as ceramic ₉ porcelain or ureas such as boron nitride or semiconductors such as germanium, silicon or metal / (non-metal slender bodies _o Similarly, the counter electrode 126 or the sleeve 124 may, for example, in an embodiment according to Figo 9 consist of semiconductor material _o such consisting of semiconductor material components may, in particular for corrosive reactants or reaction products advantageously be "There is also the possibility of some components even live, with a Cover a very thin but pore-free layer of insulating material, ei <wa made of silicone varnish, τη , as experience has shown that this does not completely prevent the discharge ^

BATH ORIGINAL

80980 1/0286

■ - 26 -

Further, ₉ particularly "in reactions with large throughput = · quantities of barren high Energiebedai-f, in the nozzle bore 8 (Figo bawT the bores 141" 154 * (Fig = 1O ₉ 11 respectively "12, 13}, a ^ electrical hollow discharge known Kind of generated _o alien in the immediate vicinity of the mouth of the nozzle 8 <^ so in the space strab! Up from the ring electrode "15a (Figo 1) the creation of such a hollow discharge can be advantageous *

The described system according to FIG. VI can be used, for example, for the synthetic production of ¥ ^ 0 from air. Here, an air flow is passed via the control element 20 to the nozzle 8, which here has, for example, a cylindrical opening τοπ 1 mm in diameter _o In the reaction chamber 1 is by means of. the immpe 29 or 33 initially created a negative pressure of about 1 mm Hg -Now the controllable DC voltage source 18 is connected with its negative pole via the switch 16 to the supply element, 6 and with its positive pole via the switch 16a to the ring electrode 15a is slowly increased from about 200 volts to 300 to 500 volts until an electrical glow discharge occurs between the metallic nozzle body 6 and the counter electrode 15a _{or the like}

Then, by means of the controller 20, the amount of air supplied increased and the pump output decreased, so that the pressure in the container slowly rises to 40 to 50 mm Hg. electrical power supplied steadily increased »up to finally a brightly shining »green-yellow light emitting

BAD ÖRK5INM

80 9 80 1/0286

■ - 27 -

fe-'icer approx. ray arises, which is a length of more than one % '"in-er and downstream. has a thickness of 10 to 20 mm. _Ä | Heg;. ·: · Setting, outputs from 1 to 3 kW are timed

.--. ' ^ lSmfi 3 he steel discharge is perfectly calm and constant

Since ·. · Irtif1 ^ «, g_e is about 3 liters per minute _o

It was initially expected NOgHßildung and au3trs2 from the pump ^ t; nde.Gas tested for seJ.nVParbe - neither on leaving the free air xti still beimMnleiten into a glass container was the characteristic of Braimfärbung ΝΟλ found werdenc r "- in initiating. Gas in line 27 in 4 liters of HoO were initially largely absorbed and resulted in a strongly acidic liquid; after some time arose over ^v OCE fluid a brown gas, the smell

'ta? After the gas produced was reduced to the content of TiO, an aqueous FeSO * solution was introduced into an aqueous FeSO * solution in order to separate out the NO as black-brown perronitrosulfate, from which S3 loh " amm when heated If the NO gas evolved, the expected f * chwax'Fb: i-aune precipitate was obtained in the PeSO "From the solution, which in turn became clear as water and reacted strongly acidic. If the gases from the outer line 27 were introduced for a long time into an FeSO ^ solution, the entire content of the same fm Kxsezu precipitated into it." trivalent form and a water-clear de: r liöBun.ii _r , which reacted strongly acidic, but did not decolorize the KMnO.-solution, also not in the case of a large excess, a sign "that no nitrous acid had formed *

809801/0286. ^SA0

Aue of these experiments it was possible to infer the formation of a higher-value oxidation product of nitrogen. The formation of N ₃ O ₅ after the reaction

2NO + 3O ₃ »N ₂ O ₅ +

appeared likely, whereby the dissociation of the air in the jet discharge could lead to the formation of the 0, « Accordingly, the introduction of the gases from line 27 was made in titrated NaOH solution in order to by. NgO ^ a amount which can be determined by means of a subsequent re-titration to neutralize from NaOH ".

As a result of this introduction in NaOH solution, the presence of NgOc could be determined correctly and in considerable quantities to be determined ο

_{The tests Nos 0} , 5, 6, 7 and 8 compiled in Table 1 below were _{carried out 9 in} each case for a period of approximately 30 minutes also previously calculated by titration of NaOH content of the absorption liquid. Every attempt * with KMnO. Solution _{checked for the presence of HHO 2} j no HNQ _{2 was} found in any case,

In addition, the gas flow emerging from the vessel was experimentally frozen in line 27 by means of liquid air ο Ee solid N ₂ Oc was found, but this

■ ■ '■ ■■ - ■' '■■ BAD ORIGlHAL

j 02 8 *

* '.' 14171.0?

.- 29 ■ - -

" ^r 1-.Ui thawing rapidly decomposes, because this possibility was initially not pursued further

BAD ORJGINAt

80 980 1/0286

IHI, / IUt

-.30 -ζ Table 1

No ο NaOH content (gr / 1) 4th VJI 6th 7th 8th NaOH in absorber 29a (oar *) 100 100 100 100 100 Operating voltage (volts) - 5000 6520 6155 6605 Amperage (Amp) 205 300 305 345 310 Elefctr «power (watt) 1.30 1.25 1.30 1.90 1.30 Duration (min ») 266.5 375 397 656 400 Energy consumption (kWh) 30th 32 30th 30th 30th Gas pressure P ^ (mm Hg) 0.134 0.196 0.198 0.328 0.200 Injected air volume (liters) 3.0 3.0 3.0 3.5 3.0 In the absorption liquid
determined amount of weight
on ENT ₂ (gr) 90 93 104 108.5 108 on ENT ₅ (gr) 0 0 0 0 0 Yield in gr ENT, per
W'h energy expenditure * » 14.65 22.68 25.40 20.50 29.12 Energy requirement in kWh for
Production of 1 kg ENT, 109 115, i 128 63 145.6 Utilization (in fi) of the Ge
stop at Og in the air stream 9.2 8.7 7.8 16.2 ■ -. · 6.9 - 64.6 64.0 48.0 67.9

BATH ORIGINAL 80980 1/0 286

The Versuchsergebniiee set forth in Ziffο 4 demonstrate the astonishing Tateache that let produced by means of a radiation discharge from an air stream immediately N 'O ^ and no NO or NO "occurs _o An electrical recovery of N ^ Oc without going through NO has hitherto apparently unknown

Except for the evidence of a novel direct. NgO, generation from air, the high yield of 145 gr _o HNO per fcwh is important from the results.

Table 2 Process yield Oldest procedure using

of horn lightning arresters. * 60 gr ENT * per kWh

Magnetically broadened arc

according to Birkeland and Eyde 70 gr ENT * per kWh

Arc-Qfen according to Schönherr 75 gr ENT * per kWh Laboratory tests with high · ^:. ~

frequency discharges (maximum value) 88 gr ENT, per kHw

Strehl discharge (experiment 8) 145 gr HWO, per kWh

• 09t · 1/02 ««

The present opinion shows an improvement in the

Sti-ah lent la dangs proceed at around 100

All previously known electrical methods (Table 2) dee to oxidize nitrogen supply exclusively NO and! Purely high-order oxidation ₀ Processing of KO auf.-nitric acid HNO, requires extensive so-called Absorptionsanlagtn that üblicberweise of eight towers, each about 5 Ό Durchmcss-ei - and 15 m high made of V2A = steel are ₀

the dir.e ktfeii Erzeugun g of N POC ^ absorption equipment at gsverfahren ^ j atrahlentladun unnecessarily when an oxidation of St'ioirstoff from the air to produce !! WO · per Wh at \ srsuch 8 _y compared to only 63 gr ENT per Wh at test T ₉ shows that the jet discharge aagGinlirte f'loktii: before energy has a great influence on the yield-is "Deinm-often but is quite unlikely that the cheapest. The conditions for the beam discharge reaction have already been found and an even better yield can be expected

BATH ORIGINAL 80980 1/0286

Claims (1)

BB-2Ö9 P d t e η t a η a ρ r U ΰ h e ^ Learn about the production of oxygen compounds in metals? Me * salloid _p elements and compounds, from gaseous, vapor-like and finely divided "liquid or solid starting materials under the influence of electrical gas and glow discharges in a reaction space with an electrode, at least one gas supply and at least one gas inlet elnrichtungp characterized in that _s eingeleitel Ausgangsstofffen with the oxygen or at least one oxygen-Rsaktionspartner Ία ί'ΌΚΊη at least one jet in the Reactionsraum; and at least this beam is passed through a part in which an electrical gas- heating, glow discharge is properly obtained ₉ and that during the passage the partner acts through the reaction chamber in the same one The final products are adapted to suit the electrical energy supply that interacts with one another: /! ge la eis on vns BATH ORIGINAL Π O Π 1 / A ""} O ί a ο ui I U JL Ö Q 2 ·>) Method according to Claim 1, characterized in that the Jets are injected at a speed in the range from one tenth to two times the speed of sound 3 °) Method according to Claim I _9, characterized in that at least one, n part of the surfaces forming the reaction space and / or surfaces arranged in the reaction space is cooled 4o) Method according to claim 1, characterized in that da® Mixture derived from the reaction space, if appropriate after the reaction products have been separated off again the same Subject to trial * 5o) Method according to claim 1, characterized in ₉ that the gas and glow discharge is maintained with a voltage in the range 100 to 2000 YoIt. Method according to claim 1 "characterized in that at least, one of the reactants received a pretreatment ionized and connect! into the reaction chamber single site is o Procedure naaia Anaprueh I ₉ datlure-h characterized ₉ that the opening of a feed organ is cooled ) Method according to Claim 1 _9, characterized in that at least one of the electrodes is cooled. BATH ORIGINAL «03801/0283 ^! ! _(! Method according to claim 1, characterized in * that the operational state of discharge for the Durehführung Her desired reaction is provided a start-up operation ,, in which in the reaction chamber at the beginning at sufficiently low pressure and relatively low gas flow creates a low-energy gas discharge _f whereupon the pressure , the gas inflow and the supplied electrical energy are gradually increased ^ until the operational discharge state is reached _{o (} 10o) The method of claim 1 _P characterized ₉ that the starting materials are passed through a reaction zone in the beam passing »and passed into a space part at the outlet from the reaction zone ₉ in which such temperature and / or DruckYerhältnisse created that egg;" 55fcr ^ if the desired reaction products produced are largely intertwined _; 1)? Out according to claim 1 _r ^ characterized in that di "starting materials are introduced into sand over a voltage-carrying electrode as a gas jet into άβη ReaktionsriiUffi at least one bore, an effective reaction zone from the interior of Bore is created right into the beam ο 12,) 'method na nh claim 1, characterized in that _p of Reaktionspartnemund suitable counter electrodes eil electric field is created in the vicinity of the nozzle orifice formed between an electrode of a nozzle for introducing, ÖÄD ORIGINAL 809801/0286. 15'ο5 method according to claim 1, characterized ₉ that an electrical hollow discharge is generated at least in parts of the nozzle bore or the vicinity thereof. 14 «, -) Process according to claim 1 _9, characterized in that the desired mean residence time of the substances to be treated in the reaction zone is set by regulating an introduced gas stream 15 «) The method according to claim 1, characterized in that in introduced hydrogen into the reaction space and the supplied material to be hydrogenated to that present in the reaction space amount of hydrogen is coordinated such that by the Binding of the gaseous hydrogen, the maintenance of the negative pressure in the reaction space is facilitated 16 «) Method according to claim 1 _9, characterized in that substances are fed to the reaction space to promote the reaction _{17ο) Method according to claim 1 9,} characterized in that the immediate vicinity of the gas supply element is favored in terms of discharge energy by selecting the distance and shape of a live counter-electrode, as well as by regulating the gas pressure, 18o) Method according to claim 1, characterized in that the gas atmosphere ₉ in which the jet spreads, catalytically active substances are added in finely dispersed distribution "■■" BAD ORIGINAL • 80 9 80 1/0 286 "190 Vex ^ drive according to claim I ₉ characterized ₉ that a gas flow is introduced and the electrically charged gaseous, liquid and solid particles carried along by the gas flow are influenced by magnetic force fields in a predetermined manner at least in part of their path 2Go) method according to claim 1, characterized in that at least one of the jets immediately before its exit from the nozzle-like opening of the gas supply through which »'Changes to the gas consisting of non-magnetic material» feed through is magnetically influenced " 21c) ancestors according to claim 1, characterized in that particles carried along in a beam are influenced by magnetic force fields running at least in places approximately parallel to the beam axis _{or the like} 22ο) Method according to claim 1, characterized in that WOXi particles entrained in a beam are influenced by magnetically focusing force fields. ο) Method according to claim I _9, characterized in that electrically charged particles carried along by a beam are influenced by force fields running at least in places transversely to the gas beam axis » 24-o) Method according to claim 1, characterized in that a part of at least one ray "an approximately -t parallel The spark discharge running on the beam axis is superimposed BADOBIGINAL '80 980 1/0286;. Be 25o) A method according to claim 1 "characterized in that diffracted by a magnetic influence in a given beam ionized different components in different direction and characterized components from the other grain · = separated at least in part ₀ 26p) Method according to claim 1 _9, characterized in that at least one of the reactants is electrically influenced independently of other reactants and is only then combined with other reactants The method of claim 1 ₉ characterized in that at least one of the reactants introduced as a separate jet into the reaction space and is provided in this case άμΓΟίι electrical impact with electrical characteristics · ■ 'j is compared with at least one of • remaining in the reaction vessel reactants increased through which he Affinity is exercised o 28.) The method according to claim 1, characterized in that at least two beams with different electrical properties and beam directions are introduced into the reaction chamber _o 29o) Method according to claim 1 ₉ characterized; that in at least two rays different electrical properties are produced by different substances in them " 80980 1/0286 '5oC) A method according to claim 1, characterized in that at least two beams different in electrical properties are generated by different velocities when passing through beam effective areas ₀ ο) method according to claim 1> characterized in that in addition to the reaction partner, at least one at least at times Auxiliary substance is introduced into the reaction space, by means of which a reaction is facilitated c. 32 «) The method according to claim 1, characterized in that except the reactant is introduced at least intermittently at least one auxiliary substance into the reaction space through which unwanted reaction companions are at least partially rendered harmless » 33ο) The method according to claim 1, characterized in that the Gas atmosphere in the reaction chamber with at least enriched with an auxiliary substance and through the same the desired reaction in the outskirts of at least one jet facilitates vvirdo 34a) Method according to Atis claim 1, characterized in that besides an adjustable amount of air is introduced into the reaction space as an auxiliary material for the reactants » ο X method according to claim 1, characterized in that apart from An adjustable amount of mercury in finely divided form is introduced into the reaction chamber as an auxiliary material for the reactants c BATH ORIGINAL 80 980 1/0286: · ■ 1-7102 36o) Method according to claim 1, characterized in that except at least one auxiliary reaction is carried out at the same time during the reaction to produce the desired end products, whose energy tint is such that through the energy release or energy consumption of the auxiliary reaction the desired reaction is supported ο 37ο) Method according to claim 1 _S, characterized in that at least one beam is guided through a part of the reaction space in which it is penetrated from the periphery with charge carriers directed onto the beam. 38 ₄ ) Method according to claim 1, characterized in that at least one beam is passed through a part of the reaction space * in which it is penetrated by a charge carrier stream directed transversely to the beam, consisting predominantly of electrons, - ■ the one at the periphery of the Beams generated by an electrical gas and glow discharge on a metal surface facing the beam and at least partially coaxially surrounding the same * 39 *) Method according to claim V, characterized in that min- = ' deeteη »one beam through one coaxially narrowed to the beam path. arranged, enclosing it at least partially, approximately cylindrical, at least at times one cathodic ,: Glow discharge is passed through the metal wall having the surface facing the beam, which metal wall is at least partially cooled _c -ΐ / ■. * ■ * ORIGINAL BATHROOM 809801/0286. 40ο.) Method according to claim 1 *, characterized in that at least one jet into the reaction chamber via a nozzle initiated and immediately after the exit ■ from the nozzle mouth from all sides radially onto the jet directed charge carrier flow is penetrated, which is at a the metal wall enclosing the nozzle axis coaxially an electrical, at least temporarily cathodic, glow discharge is generated o • ■. 41c) Method according to claim 1, characterized in that at least a beam is introduced via a nozzle-like electrode and further in the reaction chamber through at least one Electrode with at least approximately concentric sur Beam axis arranged through opening for the beam. hindu is passed, and that between the electrodes a ¥ a manageable electric field is generated « 4S) method _{according to claim H 9,} characterized in that at least one beam is introduced into the reaction space via an electrode with a metal wall concentrically enclosing the beam at a distance and is influenced by electrical fields between the nozzle-like electrode and counter-electrodes, and that at least one counter-electrode facilitates the formation of an electrical glow discharge on the surface of the metal wall facing the beam. 43-0 procedure close to claim. L ₉ characterized «that a feed member with narrow protective gaps running coaxially to the Büsenachee is seen o BAD ORIGINAL • 8 0 9801/0286 U17102 44c) Method according to claim 43 »characterized in that the components forming the respective protective gap are relative are designed to be movable relative to one another and are adjusted relative to one another to achieve a constant gap width " 45o) Method according to claim I _9, characterized in that, in at least one feed member, the total cross-section adapted to the predetermined throughput is designed and subdivided in such a way that the added amount of substance is introduced into the reaction chamber in the form of at least one jet of predetermined thickness ο 46a) Method according to claim 1 _9, characterized in that, in the case of at least one feed member, the total cross-section adapted to the predetermined throughput is divided into several openings ο 47 o) Method according to claim 1, characterized in that a nitrogen-containing gas is introduced as the starting material and NgOc is produced as at least one of the end products » 48c) Method according to claim 1, characterized in that a Air flow introduced and produced as at least one of the end products NgOc ο Elektrophyaikalische Anstalt Bernhard Berghaus » BATH ORIGINAL 809801/0286