WO1988001253A1

WO1988001253A1 - Process for producing nitrogen dioxide rich gas or pure oxygen

Info

Publication number: WO1988001253A1
Application number: PCT/EP1987/000442
Authority: WO
Inventors: Zbigniew Boguslawski
Original assignee: Zbigniew Boguslawski
Priority date: 1986-08-13
Filing date: 1987-08-12
Publication date: 1988-02-25
Also published as: DE3627429A1

Abstract

In a process for producing nitrogen dioxide rich gas, (NO2?-rich gas) useful for the production of hydroxylamine or nitric acid for example, and/or reaction gas with a high content of oxygen or nitrogen, a nitrogen monoxide (NOx?) containing gas, for example flue gas from combustion processes, is passed over or through a reaction mass essentially composed of dimanganese trioxide at a temperature of between 20 and 80C, and the resulting manganese nitrate is subjected in a second stage to heat treatment at a temperature of between 200 and 450, in order to regenerate the dimanganese trioxide. To obtain oxygen-free nitrogen dioxide, stages of nitrogen dioxide separation and deoxidation can be carried out separately with a preliminary stage at 80. The oxygen produced in the deoxidation stage can be used for enriching with oxygen the combustion air, thus helping to purify the exhaust fumes of combustion engines. The absorption in an exchangeable container located near the combustion engine and the regeneration of the manganese oxide after the recovery of the manganese nitrate produced can also be centrally carried out on a large scale in bigger units. To produce pure oxygen and pure nitrogen, atmospheric oxygen is added to dimanganese trioxide at a temperature of between 300 and 450C and the resulting sorbate is thermally desorbed at a temperature of between 480 and 560C, thus releasing pure oxygen.

Description

Process for the production of nitrogen dioxide rich gas or pure oxygen

The invention relates to a process for the production of nitrogen oxide rich gas (N02 rich gas) for example for the production of hydroxylamine or nitric acid and / or useful gas with a high content of oxygen or nitrogen.

In industry, for example for the production of hydroxylamine or nitric acid and for the nitriding workup of organic and inorganic compounds, for example the digestion of. Manganese dioxide and ore containing manganese, large amounts of nitric acid have been obtained to date by the combustion of ammonia. The disadvantage of this method is, in particular, that on the one hand the resulting gas contains a large proportion of nitrogen from the combustion oil, i. H. the active component begins in only a low concentration and, on the other hand, contains a high proportion of moisture, so that incineration - unless processing to nitric acid takes place - requires a complex drying step. A process by means of which nitrogen dioxide gas can be mass-produced industrially in a high concentration which is close to 100% is not yet known.

Very often the nitric acid must be combined with a reduction - -

agents are used to achieve the full chemical effect, i.e. to show the necessary responsiveness. For example, the manganese dioxide is not soluble in nitric acid, whereas the water-soluble nitrogen oxides (N203) easily dissolve manganese dioxide in water-soluble slurries, which have the reduction properties associated with nitrogen monoxide. The N02 rich gas thus becomes a competitor for nitric acid.

The present invention is accordingly based on the object of creating a method by means of which nitrogen dioxide gas can be produced in a high concentration in a simple manner. D invention is that nitrogen oxide (NOx) containing gas, for example flue gases from -combustion processes at a temperature between 20 ° and 80 ° C above or. passed through a reaction mass consisting essentially of dimangan triox (Mn0xMn02 = Mn203) and then d 5 manganese nitrate formed for the purpose of splitting off the N02 rich gas (regeneration) and the recovery of the dimangan trioxide (deoxidation in a second stage at a temperature between 200 ° and 450 ° a heat treatment is applied.

Z0

The great technical-economic advantage of this process is primarily that the N02 rich gas is an alternative to nitric acid as a cheap waste product and, depending on the type and method of production, has a 30 to 70% lower market price. For economic reasons, the methods that could be implemented with Salpet 5 acid for technical reasons are fa had to be left. This includes, for example, the chlorine production method from waste salts such as NaCl, CaC12, MgC12 waste hydrochloric acid.

The invention provides a method by means of which H nitrogen oxide (NOx) is concentrated to a high proportion of nitrogen dioxide regardless of the concentration in the starting gas. K The concentration takes place without any other material consumption insofar as the required intermediate carrier material can be recovered without loss and can be used indefinitely as an intermediate carrier material . Here, as a special advantage, possibly in divalent form - as NO - existing nitrogen is oxidized into the tetravalent form, so that. the resulting gas, regardless of the N0 / N02 ratio in the starting gas, is almost pure nitrogen dioxide gas in - as a further advantage over the known process - is obtained in dry form. It also opens up as a further essential advantage the method of the invention (in modifications) the possibility of obtaining concentrated oxygen and / or nitrogen gases within the scope of nitrogen dioxide enrichment, whereby these methods can also be used independently of nitrogen dioxide enrichment

In a particularly advantageous embodiment of the invention k for the purpose of obtaining an oxygen-free nitrogen dioxide, the generation stage of the deoxidation stage is preceded as a separate heat treatment stage at a temperature between 80 ° and 150 ° C. In this case, the upstream regeneration stage takes place Expulsion of the nitrogen dioxide with the formation of manganese dioxide and the heat treatment or deoxidation stage (200-450 ° C.), the recovery of the dimanganese trioxide from the manganese dioxide with release of oxygen.

Due to the independence of the effectiveness of the method of the invention from the figuration (N0 / N02 ratio) and concentration of nitrogen oxide in the starting gas, the use of any kind of nitrogen oxide-containing Ga is possible, the present method with excellent results also for cleaning nitrogen oxide-contaminated Gases can be used. In this sense, the higher proportion of nitrogen oxide-containing process gases of the catalytic ammonia dispersion can be used as nitrogen oxide-containing gases, as can the exhaust gas containing only small amounts of nitrogen oxide. Flue gases from internal combustion engines or engines or exhaust gases from domestic heating, industrial furnaces or the like, which are also subject to a practically quantitative cleaning of the highly toxic harmful gas components.

In an embodiment of the invention which is particularly suitable for use in cleaning the exhaust gases of internal combustion engines, in particular internal combustion engines, oxygen which accumulates in the deoxidation stage can be used for oxygenation of the combustion air in the combustion engine, as a result of which a not inconsiderable enrichment of the combustion air of up to 5% and more can be achieved. In this way, the disadvantages for the combustion of such machines can be countered with great success by one for the combustion - S ^" -

low levels of oxygen in the air, for example at high geographical heights or in heavily polluted urban areas.

Furthermore, the independence of the reaction stages of the method of the invention can be used with great results when used in conjunction with internal combustion engines in portable units, such as motor vehicles, in the case of gases with only small amounts of nitrogen oxides Absorption stage in an interchangeable container in the motor vehicle and the regeneration and deoxidation stages take place after collection of large amounts of the nitrate formed a large number of sources outside the vehicle. This has the advantage that the - basically industrially valuable - raw nitrogen dioxide over a longer period of time - in the form of manganese nitrate - can be collected in large quantities by exchanging the absorption vessel and can be used on a large technical scale in central regeneration and deoxidation plants with recovery of the manganese oxide used , d can be put back into circulation. Pure oxygen is also obtained as a usable by-product.

There is also the possibility of the method of the invention regardless of the absorption and conversion and enrichment of stic oxides. Exhaust gas purification for the production of pure oxygen and re nitrogen or - in internal combustion engines or engines - z preventive pollutant reduction in such a way that immediately atmospheric oxygen at a temperature between 300 ° and 450 ° C is added to dimanga trioxide (chemisorbed) and the sorbate formed is desorbed by heat treatment at 480 ° - 560 ° C.

In a further embodiment of the invention, the heat treatment of the deoxidation stage can be carried out in a pure oxygen atmosphere and under increased pressure between 10 and 200 atm. It has surprisingly been found that under these process conditions in the deoxidation stage by atomically developing oxygen in an extraordinarily simple and cost-saving manner with high performance ozone can be produced, which previously requires considerable investment and process on the way of electrical discharges must become.

The _ formed N02 rich gas ^* can be used in a variety of ways, such as in a manner known per se for the production of nitric acid or mixed acid from nitric acid and sulfuric acid by simply introducing the statu nascendi, released by heat treatment or released from the Liquid phase evaporated N02 rich gas in. What ser, further for the production of hydroxylamine or for the nitration of organic or inorganic compounds. However, the nitrogen dioxide formed can be used according to the invention with particular advantage for the digestion of insoluble phosphates, in particular calcium phosphate, in such a way that the N02 rich gas formed is introduced into a suspension of finely ground calcium phosphate and the solution formed to crystallize the calcium nitrate to a temperature is cooled below 10 ° C. It is possible in this simple manner to break down insoluble calcium phosphate into phosphoric acid and calcium nitrate, which can be used in large quantities as fertilizer. -? -

In a further embodiment of the invention, the procedure can also be carried out in such a way that, simultaneously with the N02 enrichment. using N02 rich gas, the production of chlorine gas, alkali or alkaline earth metal chlorides, preferably from the masses of sodium, potassium, magnesium, calcium and ammonium chlorides accumulating as waste products, takes place. For this purpose, the stic oxide-containing gas is advantageous. N02-Reichgas together with oxidizing oxygen introduces a slurry of manganese dioxide containing the metal halide and the nitrate solution formed with the elimination of chlorine gas is dried by spray drying at 200 ° to 300 ° C with (re) recovery of N02-Reichg and the mixture formed for washing out the Alkali or alkaline earth metal nitrates is slurried. -This method according to the invention is based on the knowledge that the manganese dioxide oxidizes the nitrogen ox to a complex corresponding to the formula N203, which, respectively, removes chlorine gas from the metal chloride and both with the alkali. Form alkaline earth metal as well as with the manganese nitrates, which can be worked up in the manner specified. The nitrate obtained in this way, for example from sodium or potassium chloride, can be used directly as a fertilizer. In the case of processing alkali or Alkaline earth metal chlorides, which form when the nitrate decomposes below 300 ° C., for example sodium nitrate, are expediently separated from the manganese nitrate by fractional crystallization before the spray drying. Both the nitrates obtained in the manner described above and those obtained naturally can also be chemically worked up to NO2 rich gas using dianthan trioxide. 'S'

The treatment of the nitrogen oxide-containing gases can be carried out in reactors connected in parallel or in series such that the reactors alternate with nitrogen oxide absorption and heat treatment. Here, in a special embodiment of the invention, the treatment of the nitrogen oxide-containing gases is carried out in series-connected reactors, the masses being rinsed in the regeneration stage with steam or oxygen heated to 480 ° to 560 ° C. and the gas thus formed after cooling and removal dried from nitrogen oxide residues and then pressurized for the purpose of condensing oxygen. With the aid of this procedure, a gas which is highly enriched with oxygen and which can be used for the production of liquid oxygen can be produced in the simplest way.

In a further advantageous embodiment of the invention when using nitrogen oxide gases e.g. From the ammonia combustion, the sorption takes place in two stages such that in the first stage the essential part of the nitrogen oxide and in the second stage the residual nitrogen oxide and residual oxygen are absorbed. It is possible in this extraordinarily simple way to produce technical nitrogen, which is present in practically pure form after the second absorption stage and can be further processed after drying to liquid nitrogen or in any other manner.

The use of dimanganese trioxide is possible in any way. However, the treatment is particularly advantageously carried out using v to pellet agglomerated dimanganese trioxide mass from a mixture of 4 60 wt .-% manganese dioxide, about 2.5 wt .-% sand, about 15 wt .-% cement, b to 3 wt .-% bentonite, 15-20 wt .-% Sawdust and / or plastic granules with a grain size of less than 20 millimeters and 10 to 12 percent by weight pelletizing water agglomerate and gradually increase after the agglomeration for two hours at temperatures of about 50 °, 100 ° and 150 ° C and then again for a period of have been heat treated for two hours each with a temperature between 350 ° and 500 ° C and in a continuously flowing air stream 53 and 580 ° C. The treatment of the green pellets is carried out after 8 to 72 hours of lying in chutes under 20 cm.

In the drawing, the invention is explained using some exemplary embodiments. Show it

1 shows a plant for the concentration of nitrogen dioxide-containing gas and the production of nitric acid

2 shows a device for enriching the supply air of internal combustion engines with oxygen

Fig. 3 shows another embodiment of a device for enrichment tion of the supply air of internal combustion engines with oxygen

Fig. 4 shows a plant for the production of ozone

5 shows a device for air dry fractionation into its constituents nitrogen and oxygen

Fig. 6 is a plant for processing waste metal chlorides, A fall hydrochloric acid or ammonium chloride to chlorine - to -

In the embodiment of a system shown in Fig. 1 for carrying out the method of the invention, a furnace 1 is provided for the catalytic combustion of ammonia, in its place any other arbitrary nitrogen oxide source, for example the exhaust pipe of a nitric acid production plant, an internal combustion engine , a boiler or the like. The furnace 1 is a cooler 2 and connected via a line two by series connection to a double absorber unit verbu dene absorbers 4, 5. Appropriately, however, two double absorber units connected in parallel to one another or three absorbers connected in series are provided which alternately or respectively. in the Ural run. Another line 6 branches off in front of the cooler 2 and likewise leads to the absorber units 4, 5. Via this line uncooled gas is led to the absorbers. The absorbers are followed by a nitrogen dioxide absorption column 7.

To produce an enriched nitrogen dioxide gas, furnace 1 is burned with a minimal excess of ammonia and the gas mixture formed after cooling with heat recovery in the cooler 2 is first passed into the first absorber 4, in which the manganese oxide component of the dimangan trioxide contained therein in manganese nitrite / nitrate and any traces of ammonia still present in the gas can be oxidatively destroyed. The gas then passes into the absorber 5, in which it is freed from the remaining traces of nitrogen oxide, but moreover from the remaining oxygen residues. Pure nitrogen remains which, after drying, can be further processed to liquid nitrogen in a known manner. - ιι -

After complete reaction of the dimangantrioxide active mass, reversal of the (cooled) process gas in the second absorber 5 is carried out for the purpose of regeneration and deoxidation of the mass in the absorber 4. Hi is the gas throughput through the absorber 5 for the purpose of maintaining and ensuring the purity of the nitrogen ( -ab) -gas strongly reduce while at the same time branching off a portion of the hot process gas in front of the cooler and passed into the absorber 4 for the purpose of heating the reaction mass to a temperature between 300 ° and 530 ° C. Of course, the regeneration and deoxidation can also be done successively in separate stages, which requires a corresponding temperature control and gas discharge control. After the heat has been given off, gas is also passed into the absorber unit 5.

The oxygen-containing N02 rich gas is led into the absorption colon, in which the N02 is dissolved to nitric acid. The remaining oxygen can be used as circulating oxygen or, after liberation of residual nitrogen dioxide, can be worked up to liquid oxygen.

After regeneration and deoxidation of the active mass, d absorber 4 is available for fine cleaning of the combustion gas, so that the absorber unit can now be operated at full power again. Since the regeneration time is extremely short compared to the absorption time (the time ratio is between 1:25 and 1:50, the time of reduced performance is extremely short.

Particularly good results are obtained when the absorbers are connected in series units 4, 5 achieved, in which the first unit of the series absorption function and the second unit fulfills the cleaning function. It results from such a circuit, as a particular advantage, a quasi zero emission of nitrogen oxides in the exhaust gases, as well as the achievement of practically oxygen-free exhaust gases, with large amounts of free oxygen being physically stored (sorbed) and otherwise made available in the process can, for example for the oxidation of the nitrogen monoxide component in the solid oxidation phase, then during the expulsion of the absorption phase.

This method of operation also enables the production of high-quality oxygen in such a way that when the nitrogen oxide-containing gases are treated in series-connected reactors, the mass is rinsed in the de-oxidation stage with steam or oxygen heated to 480 ° to 530 ° C and the resulting mixture is formed After cooling and releasing nitrogen oxide residues, the gas is dried and then pressurized for the purpose of condensing oxygen. With the aid of this procedure, a gas which is highly enriched with oxygen and which can be used for the production of liquid oxygen can be generated in the simplest way.

The inventive method is also excellent z use in motor vehicles, where on the one hand a quantitative purification of the exhaust gases from the nitrogen oxides and carbon monoxide and d hydrocarbons formed and on the other hand an enrichment of the expansion air with oxygen can be achieved. This can be especially Operation of internal combustion engines at high geographical heights or areas prone to smog may be advantageous in which, according to the invention, the air has a below-average oxygen content. Such an installation is shown in FIG. 2, for example. It consists of three reactors, each of which consists of a reaction chamber 11a, 12a, 13a and a heat exchanger 11b, 12b, 13b and are connected in parallel to an exhaust inlet line 14. From the reaction chambers we further branch each a nitrogen dioxide line 15, an oxygen line and an exhaust line 17, each of which lead to a common collecting device. The oxygen line 16 leads into the air intake line d enn machine. Furthermore, there is a manipulation line on the input side and on the output side, respectively - in the drawing for the sake of clarity only schematically indicated. 19 provided, through which the reactors can be controlled according to operating conditions.

When operating the device, the individual reactors are controlled in such a way that the - in functional order - the first chamber as a deoxidation chamber (reacting from Mn02 to Mn203), the two chambers as a regeneration chamber (decomposition of the nitrates to form Mn02) and the third chamber serves as an absorption chamber (absorption of stic oxides on Mn203). In this sense, for example in the first stage be in the heat exchanger 11b of the reactor 11, the directly elbow derived exhaust gas is introduced, so that under the high heat v about 500 ° to 530 ° C, the manganese dioxide contained in the reaction chamber 11a with release of Oxygen is reduced to dimangan trioxide. The sow ~ m ~

Substance is fed into the combustion air via the oxygen line 16 for the purpose of oxygen enrichment. The exhaust gas then arrives at a temperature between 80 ° and 150 ° C. in the heat exchanger 12b d second reactor and here causes the nitrogen dioxide a to split off the manganese nitrate contained therein, with the formation of manganese dioxide. then finally reaches at a temperature below 80 ° C in the reaction chamber 13 a of the reactor 13, in which the nitrogen oxide is absorbed from the gas in direct contact with the dimethane trioxide. The manipulation lines 18, 19 are used to guide the gas in the specified manner and to supply oxidation air in the stripping phase. D The system is reversed in circulation after each. Consumption of the D mangantrioxids in the para ^* orptionsstufe in such a manner that the bisheri reduction chamber to the absorption chamber, the previous Austreibungskamm to the reduction chamber and the previous absorption chamber to expel will chamber.

In the alternative to the device according to FIG. 2 shown in FIG. 3, the oxygen enrichment takes place independently of the cleaning of the exhaust gas from its nitrogen oxide impurities. In this case, the combustion engine 21 is followed by a heat exchanger 22 and upstream of two containers 23, 24 filled with dimangantr oxide, which serve to alternate the combustion air with oxygen. For this purpose, a Te is taken from the combustion air flow supplied via line 25, preheated in the heat exchanger 22 to a temperature of between 20 and 450 ° C. and then passed in the first phase via the lines 26, 27 into the reactor 23. At the specified temperature - i s- -

the dimangan trioxide absorbs the oxygen contained in the air by sorption. The remainder, consisting essentially of nitrogen, is discharged into the atmosphere via line 28.

After sufficient loading of the dimanganese trioxide with oxygen e, the reversal follows in such a way that the reactor 24 is filled with preheated air, while the reactor 23 is heated to a temperature of 480 ° -560 ° by supplying a partial stream of the exhaust gas. The D manganese trioxide of the reactor 23 is desorbed accordingly and gives its oxygen via the line 29 to the combustion air of the engine 21 a To keep the concentration of oxygen in the combustion air constant, the device is expediently set up for a number of cycles between ^• and 12 changes per hour , which corresponds to a time of 5-10 minutes per cycle.

Below is an overview of the amounts of material required for oxygen enrichment of up to 5% by volume:

% Sour off kg oxygen kg ctivm

1 1, 4 5, 6 5

2 2.8 11, 2 10

3 4, 2 16, 8 15

4 5, 6 22, 4 20

5 7.0 28, 0 25 - ι

Depending on the number of cycles, the amounts of the active composition decrease to 1 to 1/12 of the stated amounts.

The plant shown in FIG. 4 for ozone production consists of th in this case serving as "ozonizers" 30, 31 reaction units which are equipped with an (electrical) additional heating 32 with the aid of which initially consist essentially of manganese dioxide Reaction mass to temperatures up to 550 ° C, preferably 200 ° to 45 C can be heated. The ozonizers are also connected via a compressor 33 to an oxygen tank (not shown) due to the heating and the high pressure, the manganese dioxide mediates the ozonization of the oxygen flowing through the ozonizer, while providing the atomic radical oxygen in high concentration, which chemical equilibrium of the ozonization reaction is maintained by the cooling of the reaction gas in the cooler 34. Here, the manganese dioxide is converted into dimangan trioxide. The ozone formed is passed into the silica gel absorber 35 and sorbed there. The oxygen is circulated and supplemented from the storage container (not shown).

The dimangan trioxide formed in the ozonization reaction is then regenerated with N02 rich gas by carrying out nitration in an absorption stage b 20 ° -80 ° C., followed by a regeneration stage at 80 °-150 ° C. Here, the N02 rich gas used for nitration is recovered, which is therefore in circulation g can be led. The ozone production described is simple and inexpensive in comparison with the known position processes which operate on the basis of electrical discharges.

In the plant for dry fractionation of air in its components shown in FIG. 5, two pairs 41 / 43/44 of absorber units are provided - in parallel - which are so functionally connected to one another that the ones in the heat exchanger 45 to 300 ° to 450

10 heated air is passed in succession through two absorbers, of which the first absorber 41 or. 42 of the absorption of the essential part of oxygen from the air and the second absorber 43 respectively. 44 serves to absorb the residual oxygen. The remaining residual gas is pure T, which is fed to the liquefaction plant via the heat exchanger to recover the heat. The expulsion of the stored sow material is also carried out by heat at temperatures above 530 ° C, where the fan 46 promotes oxygen through the heat exchanger 47 and superheater 48 in the reactor and again through the heat exchanger 47 recovery of heat in the liquefaction system.

0

In Fig. 6, a plant for the production of chlorine gas from example as waste material during potash processing alkaline earth metal halide (MgC12) is reproduced using N02-rich gas, the nitrogen oxide-containing gas bezw. N02 rich gas together with oxidizing acid 5 substance introduced into a slurry of manganese oxide containing the metal halide and the nitrate solution formed with the elimination of chlorine gas by spray drying at 200 ° to 300 ° C. with (recovery) recovery from - l β -

recycled N02 rich gas dried and the mixture formed for washing out the alkali or. Slurry of alkaline earth metal nitrates The remaining manganese dioxide slurry is recycled. For this purpose - see FIG. 6 - in the reaction mixer 51 the waste chlorine is slurried together with manganese dioxide and / or ore and water containing manganese dioxide and a nitrogen oxide stream enriched with nitrogen dioxide and oxygen (air) are bubbled through the sludge. Chlorine gas escapes as the reaction, which is supplied via a purification stage (not shown) to the liquefaction plant. The process is carried out in such a way that the nitrogen oxide and oxygen concentration in the chlorine gas does not exceed 1 ppm.

The resulting pumped into the refurbishment stage

The third nitrate solution is worked up as follows:

Solutions which contain metal nitrates which do not thermally decompose at 300 ° C. are worked up by spray drying dryer 53 at temperatures between 200 ° and 300 ° C., the manganese nitrate contained in the solution decomposing into manganese dioxide and nitrogen dioxide a by-products, while the others Metal nitrate ounce remains.

The dry product is separated in the separator 54, while the carrier gas is removed by means of the fan after recovery of the NO 2 rich gas. The dry residue containing manganese dioxide and water-soluble metal nitrate is brought into the solution mixer 56, in which d - / 9 -

Nitrates are removed. The sludge is conveyed by means of the pump 57 into the chamber filter press 58, in which a concentrated nitrate solution is obtained by filtering, which is used immediately as a fertilizer or can be further processed. Instead of metal chloride k, hydrochloric acid (thin acid) can also be used in the process, the processing of which still represents a considerable environmental problem which can be solved in a cost-effective manner by the process according to the invention.

In the case of working up of solutions which contain the mix-decomposing metal nitrates at 300 ° C., the nitrate solution is conveyed by means of the pump 52 instead of in the dryer 53 into the crystallizer 59 z fractional precipitation of the manganese nitrate. The substrate wi is then brought into the chamber filter press 61 by means of the pump 60, in which the crystallized fraction is separated from the liquid phase which can be processed to form a fertilizer. The filter residue passes through the diffusion mixer 62 into the spray dryer 53 and is worked up there in the manner described above.

Claims

1. A process for the production of nitrogen dioxide rich gas (N02-Reic gas) for, for example, the hydroxylamine or nitric acid production and / or reaction gas with a high content of oxygen or nitrogen, characterized in that nitrogen oxide (NOx) containing gas, for example from flue gases Combustion processes at a temperature between 20 ° and 80 ° C above or ^"passed through a reaction mass consisting essentially of dimangan trio ^ (Mn0xMn02) and then the manganese nitrate formed for the purpose of splitting off the N02 rich gas (regeneration) and recovering the dimanganese trioxide (deoxidation) in a second stage at one temperature is subjected to a heat treatment between 200 ° and 450 °.

2. The method according to claim 1, characterized in that for the Zw the elimination of an oxygen-free nitrogen dioxide, the regeneration stage of the deoxidization stage is connected upstream as a separate heat treatment step at a temperature between 80 ° and 150 ° C.

3. The method according to claim 1 or 2, characterized in that in the second heat treatment stage resulting oxygen to liquid - 7. 1 -

Oxygen is worked up.

4. The method according to claim 1 or 2, characterized in that nitrogen oxide-containing gases process gases of the catalytic ammonia combustion, the production of nitric acid or the agreement between the existing exhaust gases or flue gases from domestic heating, combustion engine or respectively. engines, industrial firing or the like. Use.

5. The method according to claim 2 or 4, characterized in that in the deoxidation stage oxygen - for example when cleaning exhaust gases in combustion engines. Engines - for the oxygen enrichment of the combustion air is added to the combustion engine.

6. The method according to claim 5 for increasing the oxygen content of supply air to internal combustion engines, characterized in that the dim gantrioxide is alternately flowed through at 300-450 ° C with an air stream, oxygen sorption taking place and then with the supply air or its part at 480 ° C - 560 ° C for oxygen desorption is flowed through.

7. The method according to claim 6, characterized in that the Erw ment of the supply air flow or its part to 480-560 ° C by Rückf tion and supply of a portion of the hot exhaust gas.

8. The method according to any one of claims 1 to 7, characterized that especially when used in motor vehicles, the absorption into an interchangeable or stationary regenerable container within the motor vehicle and regeneration and deoxidation of the manganese oxide takes place after collection of the manganese nitrate formed in larger units for storage and transport and for further processing as a raw material source outside the vehicle.

9. The method according to claim 8, characterized in that the N0 rich gas is liquefied and stored, transported and used as such. 0

10. The method according to any one of claims 1 to 9, characterized in that "for the production of pure oxygen and pure nitrogen immediately atmospheric oxygen at a temperature between 300 ° and 450 ° C on Dimanga trioxide (chemisorbed), pure nitrogen is obtained, u - ^J das the sorbate formed is then desorbed by heat treatment at 480 ° - 560 ° to release the pure oxygen.

11. The method according to claim 10, characterized in that 0 An alternating double reactors are used to enrich the oxygen in the supply air of internal combustion engines, wherein b oxygen sorption the air flow by heat exchange with exhaust gas u with oxygen desorption by direct mixing with a Partial stream d exhaust gas is heated.

12. The method according to claim 10 or 11, characterized in in order to obtain a uniform oxygen concentration in the closed combustion engine, the hourly number of cycles is 6 - 12.

13. The method according to any one of claims 10 to 12, characterized in that the nitrogen flow occurring during oxygen sorption and normally to be released from the atmosphere is used for fire fighting in around the car.

14. The method according to one or more of claims 1 to 12, characterized in that the treatment of the nitrogen oxide-containing gases in reactors connected in parallel or in series is carried out in such a way that the nitrogen treatment on the one hand and the heat treatment takes place alternately on the other.

15. The method according to claim 14, characterized in that the processing of the nitrogen oxide-containing gases takes place in series-connected reactors, the active composition after the second regeneration stage being heated with steam or oxygen heated to 480 ° to 560 ° C and thus formed After the cooling and the removal of nitrogen oxide, gas is dried and then pressurized for the purpose of condensing oxygen.

16. The method according to any one of claims 1 to 15, characterized in that when using nitrogen oxide gases from the ammonia combustion absorption takes place in two phases, such that in the first phase the essential part of the nitrogen oxide and in the second phase the residual nitrogen oxide the residual oxygen can be absorbed.

17. The method according to any one of claims 1 to 16, characterized gekennzeic net that the deoxidation stage with the supply of pure oxygen b at a temperature up to 550 ° C, advantageously 200 ° to 300 ° C and a pressure between 10 and 200 ata.

18. The method according to any one of claims 1 to 17, characterized gekennzeic net that the N02 rich gas formed is introduced into a suspension of finely ground calcium phosphate and the solution formed for crystallization of the calcium nitrate and production of phosphoric acid to a temperature below 10 ° C. is cooled.

19. The method according to any one of claims 1 to 18, characterized gekennzeic net that the nitrogen oxide gases or the N02 rich gas formed z production of chlorine gas from alkali metal or alkaline earth metal chloride is used in such a way that the nitrogen oxide-containing gas. N02 rich gas together with oxidizing oxygen is introduced into a slurry of manganese dioxide containing the metal halide and the nitrate solution formed with elimination of chlorine gas is dried by spray drying at 200 ° to 300 ° with (re) recovery of N02 rich gas and the mixture formed is added Wash out the alkali or Alkaline earth metal nitrates is slurried.

20. The method according to claim 19, characterized in that the alkali metal chlorides, the waste salts NaCL, KC1, MgC1 CaC12, NH4C1 and moreover manganese dioxide with waste hydrochloric acid manganese ores are used.

21. The method according to claim 20, characterized in that in the Fa of processing alkali or. Alkaline earth chlorides, which form at 300 ° C decomposing nitrates, the alkali or. Alkaline earth metal nitrate spray drying by fractional crystallization occurred from the manganese separated.

22. The method according to any one of claims 18 to 21, characterized gekennzei net that the resulting nitrates of the alkali and alkaline earth metal chlorine thermally without or with the use of dimanganium dioxide mediator, as he and the second stage to N02 rich gas, where as Kopp products are marketable oxides or hydroxides of metals.

23. The method according to claim 22, characterized in that naturally occurring nitrates of the alkali and alkaline earth metals are worked into N02 rich gas a.

24. The method according to any one of claims 1 to 23, characterized in that the reaction is carried out using manganese trioxide agglomerated into pellets.

25. The method according to any one of claims 1 to 24, characterized in that the reaction is carried out with the aid of pellets, which from a - ~

40-60% by weight of dimangan dioxide, approximately 2.5% by weight of sand, approximately% by weight of cement, up to 3% by weight of bentonite, 15-20% by weight of sawdust and / or plastic granules Grain size below 20 mu and 10 - 12 wt. Pelletizing water agglomerated and after agglomeration for two hours gradually increasing under air or oxygen flow at temperatures of about 50 °, 100 ° and 150 ° C and then again for a time of each two hours with a temperature between 350 ° and 500 ° C respectively. 530 ° and 580 ° C have been heat treated.

26. The method according to claim 25, characterized in that d green pellets are subjected to a thermal treatment in layers below 20 cm after 8 to 72 hours of lying time.

27. The method according to claim 5, characterized in that the reactive filling deodorises the exhaust gases in the absorption stage and - laid out as a filter - retains the soot and in the heat treatment d pollutants are destroyed by the action of temperature.

28. The method according to claim 6, characterized in that the cleaning container is mounted on the cold end of the exhaust pipe.