EP3513121B1 - Method and combustion oven for conversion of hydrogen and atmospheric oxygen to water or hho gas to water - Google Patents

Description

The invention relates to a method for converting hydrogen and atmospheric oxygen to water or HHO gas to water in a combustion furnace, the combustion chamber being surrounded by a cooling jacket in which a heat transfer fluid is circulated. The invention also relates to a combustion furnace for converting hydrogen and oxygen into water or HHO gas into water, having a combustion chamber with at least one gas supply line with an outlet nozzle through which the gas to be burned is fed, and a cooling jacket enclosing the combustion chamber with a heat transfer fluid circulating therein . HHO gas is a mixture of hydrogen and oxygen in exactly the same atomic ratio of twice H to once O as is produced as a reaction product in the electrolysis of water.

The production and use of hydrogen (H ₂ ) has a long tradition. Hydrogen (H ₂ ) was and is used primarily in the chemical and petroleum industries for the reduction of chemical compounds, for the hydrogenation of unsaturated hydrocarbons, the production of high-quality petrol, etc.

• einerseits als chemischer Energiespeicher, dessen Energie im Bedarfsfall durch Umsetzung mit Luftsauerstoff (O₂) zu Wasser (H₂O) mit angeschlossener Stromgewinnung abgerufen und benutzt werden oder
• andererseits in Gasleitungen den Verbrauchern zugeführt werden.

Recently, the production of hydrogen (H ₂ ) and its use has also gained importance in connection with the use of electrical energy from wind power and solar power systems. Hydrogen (H ₂ ) can thus be produced ecologically from water (H ₂ O) using electrical energy through electrolysis. The hydrogen (H ₂ ) obtained in this way can

• on the one hand as a chemical energy store, the energy of which can be called up and used when _{required by converting it with atmospheric oxygen (O 2} ) to form water (H _{2 O) with connected power generation or}
• on the other hand, are supplied to consumers in gas lines.

The combustion of hydrogen (H ₂ ) with atmospheric oxygen (O ₂ ) and the conversion of HHO gas from water electrolysis is associated with problems in that the heat of reaction of the water-formation reaction from hydrogen (H ₂ ) and from HHO gas is very high, which can lead to material damage in the incinerators or, if the incineration temperatures are reduced, to an interruption in the incineration reaction and a reduction in the energetic efficiency.

During the combustion of fossil fuels, reaction temperatures of approx Combustion of hydrogen (H ₂ ) with oxygen (O ₂ ) and the combustion of HHO gas present a different picture.

Also known are the H ₂ combustion furnaces from Xerion Advanced Heating GmbH, which contain graphite elements in the reactor space, which are used to electronically heat the combustion reaction. These furnaces are used for the production of special steels and ceramics as well as for research purposes, whereby the service life of the graphite electrodes is very limited due to combustion reactions.

In DE 20 2013 005411 U1 H ₂ combustion in the fluidized bed process is described, which requires substances containing metal oxides to be fluidized; here, the efficiency of heat generation is described as > 80%. The property of hydrogen (H ₂ ) to diffuse through steel at higher temperatures and pressures _{is also known, which makes handling of hydrogen (H 2} ) difficult or impossible under such conditions.

In DE 10 2006 047222 A1 is called the combustion of hydrogen (H ₂ ), which is obtained by thermolysis of water (H ₂ O). The burner device required for this was not described in detail. An energetic efficiency is not specified. The thermolysis of the water (H ₂ O) is achieved by injecting water (H ₂ O) under pressure onto a hollow body that has been heated to approx. 2000 - 3000 °C by previous chemical reactions.

From the U.S. 2004/013988 A1 a method for converting hydrogen and atmospheric oxygen to water or HHO gas to water in a combustion furnace is known, in which a combustion furnace is cooled with a heat transfer fluid and hydrogen and atmospheric oxygen or HHO gas are heated at temperatures of 1300 °C or higher in the range from sleeve-shaped arranged ceramic elements are implemented to form water of reaction.

Furthermore, in the KR 10 2000 0040478 A a burner for the combustion of HHO gas is described, in which, in addition to the HHO gas supplied in the nozzle, compressed air is additionally supplied to the combustion.

From the U.S. 5,190,453A discloses a staged incinerator having a casing, a first combustion stage contained within the casing for combusting a fuel-rich mixture of H ₂ and an oxidant (O ₂ ). Also contained in the housing are a plurality of sequentially arranged secondary combustion stages and disposed downstream of the first stage, each of the plurality of secondary combustion stages having means for receiving secondary streams of oxidant to the combustion exhaust gas discharged from of the first stage of combustion, with the gradual increase in oxidant/fuel ratios providing a resultant substantially stoichiometric combustion. The combustion stages have catalyst bed chambers to promote combustion in a controlled manner, with a first of the catalyst bed chambers providing the first stage of combustion. Means for cooling the combustion stages are also provided, comprising coolant passages. The housing includes vapor inlet means at a forward end thereof for introducing a flow of coolant vapor into the coolant passages, oxidant inlet means for introducing O ₂ into the plurality of combustion chambers, fuel _{inlet means for introducing H 2} into the plurality of catalyst bed chambers, and an outlet at one aft end for venting a combined stream of combustion products and coolant vapor.

The object of the invention is to specify a method and a device for a specific implementation in relation to the conversion of hydrogen (H ₂ ) and atmospheric oxygen (O ₂ ) or HHO gas to water (H ₂ O).

This object is achieved with a method for converting hydrogen and atmospheric oxygen or HHO gas to water according to claim 1 and an incinerator for it according to claim 6.

If hydrogen and atmospheric oxygen or HHO gas are injected into the combustion furnace and ignited and reacted in the presence of powdery and/or coarse-grained, metal-oxide-containing earth as a catalyst at temperatures of up to 2600 °C to form water of reaction, with the hydrogen and atmospheric oxygen or the HHO -Gas is mixed with air, the combustion flame is aimed directly at the metal oxide containing soils, and the distance of the injection point of the gas supply to the metal oxide containing soils is changed to control the combustion process, efficient and durable combustion of the mixture can be achieved Hydrogen and oxygen (or HHO gas formed from electrolysis of water) can be achieved with a high thermal energy yield. Temperatures of up to 2600 °C occur directly in the reaction area on the earth containing metal oxides. Furthermore, the intensive contact of the combustion gases with the metal oxide-containing earth acting as a catalyst is achieved. The earths containing metal oxides are preferably structured in powder form and/or coarse-grained (coarsely crystalline). The effective surface area of the catalyst that comes into contact with the combustion gases is correspondingly large. Furthermore, the influence of the catalyst on the combustion reaction can be controlled. Among other things, with this adjustability of the outlet nozzle for gas supply relative to the metal oxide-containing earths deposited in the combustion chamber, the combustion temperature can be controlled in a range of preferably 1800° C. to a maximum of 2600° C. The position of the outlet nozzle (combustion nozzle in the combustion chamber) is controlled by a mechanism that reaches outwards, with which the efficiency of the reaction heat and the heat transfer to the cooling jacket can be optimized.

Accordingly, the object is achieved according to the device in a combustion furnace with a combustion chamber with at least one gas supply line with an outlet nozzle through which the gas to be burned is fed, metal oxide-containing earth being arranged as a catalyst in the combustion chamber. An air supply line with an auxiliary nozzle is provided in the combustion chamber, which is arranged directly next to the outlet nozzle for the gases to be burned, hydrogen and oxygen or HHO gas, with which air can be mixed directly with the gases to be burned, in order to keep the combustion temperature in the desired range to keep. Since, as already explained above, the maximum reaction temperature of up to 2600 °C only occurs in the area of the catalyst (earths containing metal oxides), this combustion reaction can be carried out in a combustion furnace made, for example, of stainless steel, suitable against hydrogen embrittlement, for example the

Material no. 1.4438 317 L or other suitable steels. The enclosing cooling jacket that is usually provided in such combustion chambers is kept at a temperature well below the melting point of the steel material, for example 1400° C., by the heat transfer medium circulating in it. In addition, the incinerator can also contain ceramic components that have a higher temperature resistance. The gas to be burned, at least a mixture of hydrogen and oxygen, is injected into the combustion chamber of the combustion furnace and ignited via a gas supply line with an outlet nozzle. The earths containing metal oxides are arranged on a solid base plate, which can withstand the combustion temperature, in the center of the combustion furnace. Thus, the metal oxide-containing earths acting as a catalyst can be provided in the center of the combustion furnace without directly influencing the outer walls of the furnace and thus without any thermal overload occurring there.

In order to cause a sufficient reaction mass on the one hand and on the other hand a reaction that is not too large and can no longer be controlled, 1000 to 5000 l/h of hydrogen and atmospheric oxygen or HHO gas and 200 to 5000 l/h of air are fed in during the combustion.

Furthermore, the earth containing metal oxides is mixed with water in a mass ratio of up to 33% of the earth containing metal oxide in order to further improve the catalytic effect of the earth containing metal oxide.

As a further means of controlling the incineration temperature to 1800°C to a maximum of 2600°C to achieve optimum heat recovery in the incinerator cooling jacket, water is injected into the incinerator during combustion. Distilled, deionized water or else sea water is preferably used. Alternatively, part of the resulting water of reaction during combustion in the returned to incinerator. It has been shown that with a throughput of combustion gas of 1000 to 5000 l/h, water injection of up to 1.5 l/h is particularly preferred.

Furthermore, to control the combustion and thus also the combustion temperature, the combustion gas hydrogen and atmospheric oxygen or the HHO gas can be mixed with air with gaseous nitrogen or gaseous carbon dioxide. These additional gaseous substances are preferably arranged in the combustion chamber via a separate auxiliary nozzle directly next to the outlet nozzle for the gases to be burned, namely hydrogen and oxygen or HHO gas.

The fact that the combustion chamber has a volume of 4 to 25 l, preferably 6 to 12 l and particularly preferably 8 l at a gas throughput of 1000 to 5000 l/h means that a combustion chamber with an ideal volume is provided for the preferred gas throughput. For example, the combustion chamber can be cubic or spherical. A particularly preferred combustion chamber has internal dimensions of 200×200×200 mm ³ , ie 8 l in a cubic form.

Because the process is controlled in such a way that the naturally occurring deuterium content in the reaction water decreases in the course of the process at reaction temperatures above 2000 °C, it is presumably achieved that a partial nuclear reaction takes place during combustion in addition to the chemical reaction, since a Nuclear fusion of deuterium occurs with significant energy release within the combustion reaction.

Accordingly, the thermal energy yield is controlled to greatly exceed the energy of the water formation reaction from HHO gas, since thus the combustion process proceeds to increase the probability of nuclear fusion within the combustion reaction.

In order to avoid the deuterium content dropping too much, it is preferable to inject fresh water into the combustion process instead of water of reaction. This ensures that the deuterium content is kept essentially stable for a consistently high energy yield. When injecting seawater, the deuterium content can even be slightly increased. The combustion temperature can thus also be influenced via the water used for injection.

If the combustion reaction produces precious stones with a Mohs hardness of 8 to 10, especially when using Al ₂ O ₃ , precious stones with a Mohs hardness of 8 to 10 can be produced as a by-product of the combustion reaction, which can be used for industrial purposes, for example. Overall, the use of aluminum oxide Al ₂ O ₃ as a catalyst for the best possible conversion of the combustion gases hydrogen and oxygen to water at combustion temperatures of 1800° C. to a maximum of 2600° C. is preferred. The catalyst is placed in the combustion chamber of the incinerator on the solid base plate, with the catalyst hardly being consumed in the continuous operation of the incinerator. With corresponding maintenance intervals of several weeks or months, the catalyst can then be supplemented or replaced and the gems that have been created can be removed.

With the subject of the application, it is thus possible to achieve a very high efficiency of heat generation in the heat transfer fluid circuit of >95% based on the energy for generating hydrogen in water electrolysis. This seems to be possible in particular through the combination of thermal conduction and thermal radiation. The high efficiency of the heat generation is achieved by a combustion process without a fluidized bed.

The resulting thermal energy can be generated according to the prior art in different high levels and directly as such specifically for Heating and cooling processes can be used or converted into electricity using classic methods via turbines and generators. Thus, the efficiency of combined heat and power generation would be around 90% without taking into account the losses from electrolysis that occur when water is broken down into hydrogen and oxygen.

An exemplary embodiment of the invention is described in detail below with reference to the accompanying drawings.

Fig. 1

schematisch den Aufbau eines Verbrennungsofens und

Fig. 2

ein Verfahrensschema der Verbrennungsreaktion.

It shows:

1

Schematically the structure of an incinerator and

2

a process scheme of the combustion reaction.

In 1 an incinerator 1 is shown schematically. In the exemplary embodiment shown, the combustion furnace 1 has a combustion chamber 11 with a cubic volume of, for example, 200×200×200 mm ³ =8 l. The cubic wall 10 of the incinerator 1 contains a cooling jacket 2 containing a plurality of channels for the passage of a heat transfer fluid. The heat transfer fluid is circulated in a circulation system by a pump, not shown here, with a corresponding heat sink to release the thermal energy and further use for heating purposes or to generate electricity is to be provided outside of the incinerator 1. These plant parts are here in the 1 and 2 not shown.

A gas supply line 3 with an outlet nozzle 31 is arranged inside the combustion chamber 11 for supplying the gases to be burned, in this case hydrogen and oxygen. Additional gas supply lines, for example an air supply line 32 with a corresponding auxiliary nozzle 33 , are optionally arranged in the combustion chamber 11 .

Hydrogen and oxygen are supplied in mixed form from the outside via the gas supply line 3 and injected under pressure through the outlet nozzle 31 into the combustion chamber 11 . Optionally, as shown schematically in 2 shown, air is injected into the combustion chamber via the air supply line 32 and auxiliary nozzle 33 . In addition to the supply of air, gaseous CO ₂ and/or gaseous nitrogen can also be supplied to the combustion chamber 11 .

Within the combustion chamber 11, a solid base plate 5 withstanding the combustion temperature is provided in the center. The base plate 5 is made of ceramic, for example. On the upper side of the base plate 5 metal oxide containing soils 4 are placed as a catalyst. Furthermore, an exhaust gas outlet 6 is provided at a suitable point in the combustion chamber 11, through which the "exhaust gases", essentially consisting of water vapor, can escape.

In an experimental setup, a water-aluminum oxide mixture was filled in such a combustion furnace 1 to saturation, so that no free water is present, as a catalyst 4 on the base plate 5 arranged in the center of the combustion chamber 11 . Subsequently, HHO gas was electrically ignited in the combustion chamber 11 from a water electrolysis device with the gas supply line 3 open and the exhaust gas outlet 6 open. The ignition system is in 1 not shown separately.

Due to the water formation reaction, the temperature in the area close to the flame rises to approx. 1000 to 1300 °C. Air supply line 32 is now throttled to about 50% by means of auxiliary nozzle/valve 33 and exhaust outlet 6 with associated control valve 6, so that the temperature in the combustion chamber rises to about 1500°C. Water vapor escaping via the exhaust gas outlet 6 is directed onto the aluminum oxide Al ₂ O ₃ acting as a catalyst 4 by being fed back into the combustion chamber via a corresponding supply line and auxiliary nozzle. Accordingly, the circulation is now the Heat transfer fluid in the cooling jacket 2 controls the temperature of the incinerator 1 so that overheating of the wall 10 of the incinerator 1 is avoided.

By increasing the air supply via air supply line 32 and auxiliary nozzle/valve 33, the temperature in the center of the combustion chamber 11 is now increased to 1800° C. up to a maximum of 2600° C. Continuous operation takes place at this temperature. It should be noted that the temperature of 1800 °C to max. 2600 °C only occurs in the central area of the combustion chamber 11, namely directly in the area of the metal oxide-containing earth 4 acting as a catalyst, here aluminum oxide Al ₂ O ₃ , with this catalyst on a temperature-resistant base plate 5, for example made of ceramic, is kept ready.

After prolonged continuous operation, for example 4 weeks, precious stone-like crystal structures with a Mohs hardness of about 9.5 have formed on the aluminum oxide powder acting as a catalyst. These gems can be used for industrial applications, for example.

During the continuous operation, the heat recovery efficiency based on the energy used for the water electrolysis to generate the HHO gas was measured. The efficiency was 98%. The temperature of the exhaust gases directly at the exhaust gas outlet 6 was approx. 500°C. It can therefore be assumed that the rest of the wall 10 of the combustion chamber 11 will also reach temperatures of little more than 1000°C. In the tests carried out so far, no measured values could be achieved here.

In addition, the exhaust gases contained no nitrogen oxides and no hydrocarbon compounds. The CO and CO ₂ values were each 0.00 ppm. The method is thus characterized by very low Pollutant emissions compared to conventional energy generation processes based on fossil fuels.

Particular attention should be paid to the decrease in the deuterium content in the reaction water of the test facility. The natural abundance of the isotope deuterium in hydrogen is 0.015%. This proportion could be verified at the beginning of a series of measurements. In the course of operation, in which the combustion temperature at the catalyst was always kept above 2000 °C and below 2600 °C, a decrease in the deuterium content could be detected. In this experiment, it was found that the heat energy yield significantly exceeds the energy of the water formation reaction from HHO gas. Based on the conventional calculation of the efficiency, namely the heat generation in the cooling circuit based on the energy for generating hydrogen and oxygen by means of water electrolysis, an efficiency of well over 100%, namely approx. 120%, could be determined. This efficiency, which is actually not physically possible, can only be explained by spontaneous nuclear fusion taking place in the combustion reaction. The declining deuterium content in the reaction water can serve as an indication of the actual occurrence of isolated nuclear fusion reactions.

Therefore, it is preferable that the chemical combustion of hydrogen and oxygen in the incinerator is controlled so that the heat energy yield exceeds the energy of the water formation reaction from the gas to be burned. In this way, an additional source of energy from the suspected nuclear fusion that is partially taking place can be utilized in a process that is relatively simple in terms of equipment and can be carried out economically.

With regard to the longevity of the incinerator 1, it should be pointed out that the desired incineration reaction must be maintained at temperatures of 1800° C. to a maximum of 2600° C., particularly taking into account possible (cold) nuclear fusion above 2000° C. The flame geometry is narrow limited to the center of the combustion chamber 11 in which the aluminum oxide serving as a catalyst 4 rests on the ceramic base plate 5, for example. The combustion flame is aimed directly at this catalytic converter and thus at most at the base plate 5 . However, the walls 10 of the combustion chamber 11 are not directly touched by the flame. Accordingly, it is possible to be able to keep the wall 10 of the combustion chamber 11 at temperatures <1250° C. even in continuous operation. Suitable steels for such temperatures are known in the prior art. For example, stainless steel with material no. 1.4438 317 L can be used, which has a melting point of over 1400 °C and is also resistant to hydrogen embrittlement.

Reference List

1

incinerator

10

wall

11

combustion chamber

2

cooling jacket

3

gas supply line

31

outlet nozzle

32

air supply line

33

Auxiliary nozzle/valve

4

earth containing metal oxides; catalyst

5

base plate

6

exhaust outlet

61

control valve

Claims (8)

1. A method for converting hydrogen and atmospheric oxygen to water, or HHO gas to water, in a combustion furnace (1), wherein

   - the combustion furnace (1) is cooled using a heat transfer fluid, where a combustion chamber (10) is surrounded by a cooling jacket (2) in which the heat transfer fluid is circulated,

   - hydrogen and atmospheric oxygen or HHO gas is injected into the combustion furnace (1) and ignited and converted to water of reaction that forms in the presence of metal-oxide-containing earths (4) at temperatures of up to 2600°C, and

   - the hydrogen and atmospheric oxygen or the HHO gas is mixed with air, characterised in that the metal-oxide-containing earths (4) are present in powdered form and/or with a coarse-grained structure as a catalyst, in that the combustion flame is directed directly on to the metal-oxide-containing earths (4), and in that the distance from the injection point of the gas supply to the metal-oxide-containing earths (4) is varied to control the combustion process.
2. The method according to claim 1, characterised in that during the combustion, 1000 to 5000 l/h hydrogen and atmospheric oxygen or HHO gas and 200 to 5000 l/h air are supplied.
3. The method according to one of the preceding claims, characterised in that water, preferably up to 1.5 l/h, is injected into the combustion furnace (1) during the combustion.
4. The method according to one of the preceding claims, characterised in that the hydrogen and atmospheric oxygen or the HHO gas is mixed with gaseous nitrogen or gaseous carbon dioxide.
5. The method according to one of the preceding claims, characterised in that the metal-oxide-containing earths (4) are mixed with water in a mass ratio of up to 33% of the mass of the metal-oxide-containing earths (4).
6. A combustion furnace (1) for converting hydrogen and oxygen to water or HHO gas to water, having a combustion chamber (11) with at least one gas supply line (3) with an outlet nozzle (31), through which the gas to be combusted is supplied, and a cooling jacket (2) surrounding the combustion chamber (11) with a heat transfer fluid circulating therein, wherein an air supply line (32) is provided in the combustion chamber (11) with an auxiliary nozzle (33), which is arranged in the combustion chamber (11) immediately adjacent to the outlet nozzle (31) for the gases to be combusted, hydrogen and oxygen or HHO gas, characterised in that metal-oxide-containing earths in powdered and/or coarsely crystalline form are arranged in the combustion chamber (11) as the catalyst (4), and in that the metal-oxide-containing earths (4) are arranged on a solid base plate (5), which is resistant to the combustion temperature, in the centre of the combustion furnace (1).
7. The combustion furnace (1) according to claim 6, characterised in that the combustion chamber (11) has a volume of 4 to 25 I, preferably 6 to 12 I and particularly preferably 8 I with a gas throughput of 1000 to 5000 l/h.
8. The combustion furnace (1) according to claim 7, characterised in that the combustion chamber (11) is of cubic or spherical configuration.

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