AT522533A1 - Process for producing hydrogen with the aid of a steam plasma - Google Patents

Abstract

The inventive method for generating hydrogen H2 from formaldehyde FA, dimethyl ether DME, oxymethylene dimethyl ether OME and dibutyl ether DBE comprising a steam generator consisting of a. Water tank 2, supplied from the water to a saturated steam generator 6, 7 and a superheater 8 via a pump. The superheated steam thus obtained is fed to a plasma generator 16 in which the plasma is generated with the aid of microwaves 17, 18. The water vapor plasma is fed to a reactor 19. Dibutyl ether DBE is stored in a tank 12 and fed to an evaporator 14 by a pump 13, and the superheated vaporous dibutyl ether 15 is fed to a reactor 19. The reactor 19 has magnetic windings 21 in order to reform the water vapor plasma 20 with the vaporous dibutyl ether in the reactor 19. This reforming is also supported by catalysts in order to improve the conversion rate. The hydrogen-rich gas and vapor mixture is cooled 23,24 water obtained as condensate 25, the remaining gas mixture compressed 26 is now fed to a separation stage 28. The separation stage 28 generates a hydrogen-rich gas 29, the remaining gas mixture 33 is compressed 30, the carbon dioxide CO2 is separated in the liquid phase 31, and the remaining gas consisting of carbon monoxide CO and methane CH4 is returned to the reactor 19 via the control valve 34.

Description

The inventive method for generating hydrogen H2 from formaldehyde FA, dimethyl ether DME, oxymethylene dimethyl ether OME and dibutyl ether DBE comprising a steam generator consisting of a water tank 2, from which water is fed via a pump to a saturated steam generator 6, 7 and a superheater 8. The superheated steam thus obtained is fed to a plasma generator 16 in which the plasma is generated with the aid of microwaves 17, 18. The water vapor plasma is fed to a reactor 19.

; Dibutyl ether DBE is stored in a tank 12 and fed to an evaporator 14 by a pump 13, and the superheated vaporous dibutyl ether 15 is fed to a reactor 19. The reactor 19 has magnetic windings 21 in order to reform the water vapor plasma 20 with the vaporous dibutyl ether in the reactor 19. This reforming is also supported by catalysts in order to increase the conversion rate

,improve. The hydrogen-rich gas and vapor mixture is cooled 23,24 water obtained as condensate 25, the remaining gas mixture compressed 26 is now fed to a separation stage 28. The separation stage 28 generates a hydrogen-rich gas 29, the remaining gas mixture 33 is compressed 30, the carbon dioxide CO2 is separated in the liquid phase 31, and the remaining gas consisting of carbon monoxide CO and methane CH4 is returned to the reactor 19 via the control valve 34.

The question of hydrogen H ,, as one of the most abundant elements in the universe, was and always has been one of the driving questions in chemical processes. In the chemical process industry, the required hydrogen is obtained from natural gas (methane CH4) and steam using the well-known steam reforming process.

/ Until recently, hydrogen played a subordinate role in applications in renewable energy. Renewable energy means energy from solar radiation

(PV), wind energy, biomass and biogas. Electricity and heat were the product in the renewable energy processes.

Through the approach with new synthetic fuels, often also referred to as eFuels (FA, OME, DME, DBE), combined with the attempt to partially replace the old, well-known classic fossil fuels and fuels, hydrogen H2 is back in focus in the Use as fuel and fuel moved. In the chemical processes, hydrogen H2 is on the one hand the starting material for the production of eFuels and on the other hand the basis for chemical sub-processes such as hydrogenation.

In order to be able to generate hydrogen H2 in addition to the classic electrolysis from water H20, processes and procedures are required that. enable carbon dioxide to be stored, recycled and reused. The recycling of carbon dioxide ‘requires the implementation of the production of carbon dioxide, the storage of carbon dioxide and its reusability. The production of carbon dioxide CO2 and water H20O is a property of the zero emissions aimed for. The implementation of the property of zero emission can also be derived from the observation of the carbon assimilation during photosynthesis. The natural photosynthesis is based on the material conversion in the form of the assimilation of carbon dioxide and water with the help of radiation to an aldehyde FA and oxygen O2. -

However, the following connection should be aimed for: we use a synthetic fuel and fuel that must have a high proportion of hydrogen H2, and also a very low proportion of carbon C, so that this fuel and fuel can be liquefied to form carbon dioxide CO2 and water H20. This creates the requirement that the fuel and fuel used must be generated from carbon dioxide CO2 and water H20. Only in this way can the cycle of water H2O0 and carbon dioxide CO2 be closed and thus be called regenerative. If you look at the biogenic material flows and the biogenic waste flows to generate a regenerative fuel

‚And fuel used, then a maximum use of the biogenic material flows and residual material flows has been achieved. ;

The task now is to find a method that the liquid substances dimethyl ether DME, dibutyl ether. DBE, formaldehyde FA, methanol MeOH, and oxymethylene dimethyl diether OME converts into hydrogen H2 and carbon dioxide CO2. The method used for this should be simple and compact, and the known steam reforming method should simplify, be scalable, and the method

shows the separation and storage of carbon dioxide CO2 and water H20 as a basic property. a

The process presented in patent WO 0029364 describes the production of formaldehyde FA from methanol MeOH. The resulting dimethyl ether DME is reformed to methanol MeOH in order to increase the yield of MeoH. Oxymethylene dimethyl ether OME is produced from methanol MeOH and formaldehyde FA. The disadvantage of this process is the low yield of oxymethylene dimethyl ether OME, and the known polyoxymethylene dimethyl ethers are also higher.

The method presented in the patent PL 209944 describes the generation of a synthetic gas mixture from methane CH4 with the aid of a plasma generated by microwaves. Nitrogen is needed to generate a plasma. The methane is recombined to ethine C2H2. Only a small proportion remains as usable hydrogen H2. Another disadvantage is the high proportion of nitrogen N2, which has to be laboriously separated from the synthetic gas.

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The device shown in patent WO 2014 051366 A1 describes the generation of a synthetic gas mixture from methane CH4 and carbon dioxide CO2 with the aid of a plasma generated by microwaves. This device is intended to enable the dry reforming of methane.

In the following section, the properties of the eFuels are discussed. EFules - means: formaldehyde FA, - dimethyl ether DME,% dibutyl ether DBE, oxymethylene dimethyl ether OME. .

Formaldehyde FA can be obtained from methanol by catalytic oxidation with the help of a silver oxide:

* CH3OH + Jo2-2a: n / a. CH20 + H20

Formaldehyde FA has the following chemical and physical properties

Formaldehyde (methanal)

Phase gaseous _;

Molar mass 30.03 g / mol

Density; 0.815; g / cm®

Enthalpy of formation | -106.7 kJ / mol

Soluble in water Soluble in diesel Table 1: Properties of formaldehyde FA

Dimethyl ether DME is obtained from methanol MeOH by dehydration (elimination of water)

ZCH3IOH -4202-00-200 CH3OCH3 + H20

Dimethyl ether has the following chemical and physical properties

Dimethyl ether; (Methoxymethane)

Phase gaseous

Molar mass 46.06 _g / mol

Density 1.967 g / cm?

Enthalpy of formation -184.1 kJ / mol

Soluble in water Soluble in diesel Table 2: Properties of dimethyl ether DME

Dibutyl ether DBE is obtained from dimethyl ether DME, carbon monoxide CO and hydrogen H2. This produces methanol MeOH and ethanol EtOH. Butanol BtOH is polymerized from ethanol EtOH. Subsequently, butanol BtOH dibutyl ether DBE is generated by dehydration (elimination of water).

CH3OCH3 + CO + H2 - t »CH3CH2OH + CH3OH ZCH3ICH2O0H - 4 CH3 (CH2) 4 - oH + H20 CH3 (CH2) 4 - OH - CH3 (CH2) 4 - 0 - (CH2) 4 - CH3

Dibutyl ether has the following chemical and physical properties:

Dibutyl ether (di-n-butyl ether)

Phase liquid; Molar mass. 130.01 g / mol density "0.77 g / cm?

Enthalpy of formation -378.7 kJ / mol. 1 Slightly soluble in water Very soluble in diesel, Table 3: Properties of dibutyl ether DBE

(Poly) oxymethylene dimethyl ether OME is obtained through the synthesis of dimethyl ether DME and formaldehyde FA with the help of catalytic synthesis:

CH3OCH3 + CH20 - CH3 - (OCH2) - OCH3

Oxymethylene dimethyl ether OME has the following properties:

Oxymethylene dimethyl ether | (Methylal)

Phase liquid

Molar mass 130.23 g / mol

Density _ 0.81; g / cm®

Enthalpy of formation -378.7 kJ / mol

Soluble in water Soluble in diesel Table 4: Properties of oxymethylene dimethyl ether OME

If you compare the eFuels listed here, you can see that the higher the molecular weight, the higher the calorific value and the higher the proportion of molecularly bound hydrogen H2.

eFuel FA _ | DME OME DBE carbon 1 2 3 8 hydrogen 2 6 8 18

Calorific value; 4.8kWh / kg 8.5kWh / kg 7.05kWh / kg 10.1kWh / kg phase liquid_ vapor liquid liquid Miscibility yes no no no water

Miscibility Yes Yes Yes Yes

Diesel;

Table 5: Comparison of the different eFuels

In order to obtain the hydrogen from the eFuels, the process of steam plasma reforming is used according to the invention.

The generation of water vapor can take place thermally or electrically. Electrically can

you can use a chain type evaporator that generates saturated steam at a pressure of 1.5 bar. The water vapor obtained in this way is then electrically superheated. Under electric

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Heating is understood to be electrically operated heating elements that are used in an evaporator (39) and in a superheater (40).

The thermal generation of steam (6,7) takes place using waste heat to generate saturated steam and to superheat the steam (9). According to the invention, this is the use of heat in the sense of combined heat and power.

In addition to the electrical generation of water vapor, it is also possible to generate water vapor thermally. This is usually done using a flow heater, which in turn generates saturated steam that is thermally superheated. In this application, too, water vapor is generated as saturated steam at a pressure of 1.5 bar and then superheated by 50 ° C.

In order to be able to convert water vapor into plasma, microwaves can be used according to the invention. Microwaves are generated via a magnetron, which then increase to a frequency of 0.5 GHz. 10 GHz. The microwaves are then introduced onto the water vapor via a waveguide. At the end of the waveguide there is a control piston that regulates the reflected microwaves so that they are not extinguished and thus cancel one another, but rather overlay and thus superpose and thus the maximum yield of water vapor plasma is achieved. In the invention, multiple microwave plasma generators are also connected in series. This has the advantage that one can achieve such a high, dense water vapor plasma. Under dense water vapor plasma

does one understand a particle number of 10 ° N / m? up to 1027 N / cm®, with an electron temperature of 1 to 100 eV.

Alternatively, plasma can also be generated inductively using pulsed high-frequency currents. Ring-shaped coils are used, through which high-frequency currents flow in a ring-shaped arrangement, and a magnetic field is then generated which enables the water vapor to be ionized. The inductive water vapor plasma formation is supported by _ an imbalance state in which the water vapor flows through a Lavall nozzle. In the invention, multiple inductive plasma generators 37, 38 are connected in series. This has the advantage that a dense and high plasma can be generated. Under dens

Does water vapor plasma mean a particle number of 10 ° N / m? to 1027 N / cm? ®, with an electron temperature of 1 to 100 eV.

In order to maintain plasma, a magnetic field is necessary that envelops the reforming reactor. The reactor 19 is therefore surrounded by magnetic coils 21 which envelop the reactor with a magnetic field, and inside the reactor enables and supports the chemical reaction of the water vapor plasma with the fuel.

In addition to the generation of water vapor plasma, you also need a vaporous eFuel that is brought into contact with the water vapor plasma. The eFuel comes in one

Tank 12 is stored and then converted into a vapor phase by a pump 13 via an evaporator 14. ; ;

Catalytic steam reforming consists of a gaseous or vaporous material flow and the water vapor plasma which comes into contact with the material flow and the reforming process is supported catalytically. Be according to the invention

Nickel catalysts 22 are used. The following shows the hydrogen yield of the various eFuels. ;

The hydrogen yield increases with the value of the eFuel. The following table shows the various yields from the eFuel.

The following hydrogen yield H2 results for formaldehyde FA

CH20 + H20 - CO2 + 2H2

For dimethyl ether DME the following hydrogen yield H2 results

CH3OCH3 + 3H20-2C02 + 6H2

For oxomethylene dimethyl ether OME the following hydrogen yield H2 results

CH3 - (CH20O) - O - CH3 + 4H20 - 3CO02 + 8H2

For dibutyl ether DBE the following hydrogen yield H2 results

CH3 (CH2) 3 - O- (CH2) 3CH3 + 15H20 - 8C02 + 27H2

According to the invention, in addition to the hydrogen H2, there are also carbon dioxide CO2, carbon monoxide CO and methane CH4, which must be separated from the hydrogen H2.

CO2 (mol) H2 (mol) Q (kJ / mol) formaldehyde FA__ 1 {2 -49.7 dimethyl ether DME 2 16; +101.7 oxymethylene dimethyl ether | 3 8 / .1-77.0 OMR | Dibutyl ether DBE 8 27; +810.0

- Table 6: Representation. the hydrogen yield from different eFuels and the required heat (kJ / mol).

The invention comprises the generation of a water vapor plasma with the aid of microwaves 17, 18 or by inductive coils 37, 38. The water vapor plasma 20 is brought into contact with the vaporous or gaseous eFuel 15 in a reactor 19. In order not to lose the plasma, the water vapor plasma 20 is introduced into a reactor with an enveloping magnetic field. The magnetic field is generated via electromagnetic coils 21, which is then used in the reactor 19 for a recombination of water vapor plasma 20 and eFuel 15 to take place. At the end of the reactor 19, a catalyst bed 22 is also used, which additionally supports the reforming process in the implementation.

The reformate is cooled 23, 24 and water is deposited as condensate 25. The

Existing residual gas consisting of carbon dioxide CO2, carbon monoxide CO and hydrogen H2 passed into a separation stage.

According to the invention, a single-stage membrane process 26, 27, 28 is used as gas separation, in which the gas is separated mechanically by a membrane 28. Mechanical separation is understood to be a membrane with a defined pore diameter. The rent (gas portion that does not diffuse through the porous membrane) is sucked in and compressed and fed to a membrane separation again. The concentrated gas mixture of carbon dioxide

CO2, carbon monoxide CO and methane CH4 are compressed 30, the liquid carbon dioxide 31 ″ is separated and stored, the residual gas from carbon monoxide CO and methane CH4 is returned to the reactor 19 in order to be recombined again with water vapor plasma 20. The permeate 29 is a hydrogen H2 enriched Gas: the single-stage membrane process sets

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Assuming that the gas mixture ’27 has to be compressed to a pressure of 20 bar, a separation of 99% is to be achieved.

According to the invention, gas separation is used. a two-stage membrane process 26, 27, 28 is used in which the gas is mechanically separated off by a membrane 28. Mechanical separation is understood to be a membrane with a defined pore diameter. The rent (gas portion that does not diffuse through the porous membrane) is sucked in and compressed and fed to a membrane separation again. The concentrated gas mixture of carbon dioxide CO2, carbon monoxide CO and methane CH4 is compressed 30, the liquid carbon dioxide 31 is separated and stored, the residual gas from carbon monoxide CO and methane CH4 is returned to the reactor 19 to be recombined again with water vapor plasma 20. The permeate 29 is a gas enriched in hydrogen H2. A second separation stage in the form of a mechanical membrane 43 is to be used in order to achieve a higher gas purity and to further reduce the proportion of contamination by gases such as carbon dioxide Co2, carbon monoxide CO and methane Ch4. The second separation stage consists of a vacuum compressor 41, which compresses to a pressure of 4 bar and thus supplies it to separation stage 43. The pension deed is returned to the first separation stage 28 via a control valve 45. The permeate 44 is a highly pure hydrogen with an impurity <10 ppm of carbon-rich residual gases.

According to the invention, a pressure swing adsorption 46, 47, 48 is used as gas separation, in that the gas is separated off by a molecular sieve, zeolite 13 X, carbon pellets 3 A. The physical. Property exploited that 'hydrogen H2 has a very small molecule diameter of 2.9 A, carbon dioxide CO2, carbon monoxide CO and methane CH4 is stored in the zeolite or molecular sieve by means of adsorption (utilization of the physical bond).' The enriched hydrogen 48 is a product . reused. Two reactors 46, 47 are used for continuous operation. While one reactor stores carbon dioxide Co2, carbon monoxide CO, methane CH4, the other reactor is desorbed and the gas obtained in this way is brought to a pressure of 70 bar via a compressor.30 and the carbon dioxide is separated in liquefied form 32,31. The residual gas from methane CH4 and carbon monoxide CO is returned to the reactor 19 via a control valve 34. ;

-The liquefaction of carbon dioxide CO2 30,31,32 serves to store the carbon dioxide CO2 in the liquid phase and thus to be able to use the carbon dioxide further. Liquid ’carbon dioxide CO2 can be combined with hydrogen H2 to form formaldehyde FA or methanol MeOH. Liquid carbon dioxide CO2 is compact and easy to store and utilize and therefore technically considered a raw material.

The invention shown here can be used in small systems of the order of magnitude from 5 kW ele to 10 kW ele up to large systems from 500 kW ele to 1000 kW ele. Decentralized energy generation plays an important role in all applications. Scalability is a crucial property to enable applications in large-scale (industry and trade) as well as in small-scale (private consumers). Another advantageous property of the invention is to support the further development of rural areas.

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Figures Figure 1

Figure 1 shows a water tank 2, from which water is sucked off with a pump 3, via a control valve 4. Continuous evaporator is fed. The once-through evaporator consists of a heat exchanger 6, an evaporator 7, a superheater 9; a steam water separation bottle 8, the condensate being returned to the tank 2. The superheated steam is fed to a steam plasma converter 16. Water vapor plasma is generated with microwaves 17, 18 via a magnetron 17 and actuating piston 18. Several microwave generators are arranged in series. The water vapor plasma 20 is introduced into a reactor 19. Dibutyl ether 11 is stored in a tank 12 and sucked off by a pump 13, evaporated via the heat exchanger 14 and introduced into the reactor 19 as superheated vapor 15: The reactor 19 is surrounded by a magnetic field generated by coils 21, so that the reforming of the superheated dibutyl ether 15 can be reformed with the steam plasma 20 to carbon dioxide CO2 and hydrogen H2. The gas mixture of carbon dioxide CO2, hydrogen H2, methane CH4 and hydrocarbons CO is cooled 23, with water 25 being separated out as condensate. The remaining gas mixture of hydrogen H2, methane CH4, hydrocarbons CO, CO2 is separated into hydrogen 29 and hydrocarbons 33 via a separation system 28. The remaining gas mixture is compressed 30 and cooled, and the liquid carbon dioxide 31, 32 is separated off via a condenser 32 and the remaining gas 33 is returned to the reactor 19 via a control valve 34. The concentrated hydrogen 29 is further recovered as a product.

Figure 2

Figure 2 shows a water tank 2, from which water is sucked off with a pump 3, via a. Control valve ‘‘ 4 is fed to a once-through evaporator. The once-through evaporator consists of a heat exchanger 6, an evaporator 7; a superheater 9, a steam water separation bottle 8, the condensate being returned to the tank 2. The superheated steam is fed to a steam plasma converter 16. Water vapor plasma is generated with pulsed inductive windings in a dielectric. Several inductive generators are arranged in series. In order to support the formation of the plasma, the reactor is designed as a Lavall nozzle 36. The water vapor plasma 20 is introduced into a reactor 19. Dibutyl ether 11 is stored in a tank 12 and pumped. 13 sucked off, evaporated via the heat exchanger 14 and introduced into the reactor 19 as superheated steam 15. The reactor 19 is surrounded by a magnetic field generated by coils 21, so that the reforming of the superheated dibutyl ether 15 can be reformed with the steam plasma 20 to form carbon dioxide CO2 and hydrogen H2. The gas mixture of carbon dioxide CO2, hydrogen H2, methane CH4 and hydrocarbons CO is cooled 23, with water 25 being separated out as condensate. The remaining gas mixture of hydrogen H2, methane CH4, hydrocarbons CO, CO2 is separated into hydrogen 29 and hydrocarbons 33 via a separation system 28. The remaining gas mixture is compressed 30 and cooled, and the liquid carbon dioxide 31, 32 is separated off via a condenser 32 and the remaining gas 33 is returned to the reactor 19 via a control valve 34. The concentrated hydrogen 29 is further recovered as a product. ;

Figure 3

Figure 3 shows a water tank 2, from which water is drawn off with a pump 3. is fed to an electric evaporator 39 via a control valve 4. The once-through evaporator consists of an electric evaporator 39, a steam water separation bottle 8, the condensate being returned to the tank. The saturated steam is electrically superheated 40. The superheated steam is fed to a steam plasma converter 16.

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Water vapor plasma is generated with microwaves 17, 18 via a magnetron 17 and actuating piston 18. Several microwave generators are arranged in series. The water vapor plasma 20 is introduced into a reactor 19. Dibutyl ether 11 is stored in a tank 12 and sucked off by a pump 13, evaporated via the heat exchanger 14 and introduced into the reactor 19 as superheated vapor 15. The reactor 19 is surrounded by a magnetic field generated by coils 21, so that the reforming of the superheated dibutyl ether 15 can be reformed with the steam plasma 20 to form carbon dioxide CO2 and hydrogen H2. The gas mixture of carbon dioxide CO2, hydrogen H2, methane CH4 and hydrocarbons CO is cooled 23, with water 25 being separated out as condensate. The remaining gas mixture of hydrogen H2, methane CH4, hydrocarbons CO, CO2 is separated into hydrogen 29 and hydrocarbons 33 via a separation system 28. The remaining gas mixture is compressed, cooled and. the liquid carbon dioxide 31, 32 is separated out via a condenser 32 and the residual gas 33 is returned to the reactor 19 via a control valve 34. The concentrated hydrogen 29 is further recovered as a product.

Figure 4

FIG. 4 shows a water tank 2, from which water is sucked off with a pump 3 and fed to an electric evaporator 39 via a control valve 4. The once-through evaporator consists of an electric evaporator 39, a steam water separation bottle 8, the condensate being returned to the tank. The saturated steam is electrically superheated 40. The superheated steam is fed to a steam plasma converter 16. Steam plasma is generated with microwaves 17, 18 via a magnetron 17 and actuating piston 18. Several microwave generators are arranged in series. The water vapor plasma 20 is introduced into a reactor 19. Dibutyl ether 11 is stored in a tank 12 and sucked off by a pump 13, evaporated via the heat exchanger 14 and introduced into the reactor 19 as superheated vapor 15. The reactor 19 is enveloped with a magnetic field generated by coils 21, so that the reforming. of the overheated dibutyl ether 15 can be reformed with the steam plasma 20 to carbon dioxide CO2 and hydrogen H2. The gas mixture of carbon dioxide CO2, hydrogen H2, methane CH4 and hydrocarbons CO is cooled 23, with water 25 being separated out as condensate. The remaining gas mixture of hydrogen H2, methane CH4, hydrocarbons CO, CO2 is separated into hydrogen 29 and hydrocarbons 33 via a separation system 28. The remaining gas mixture is compressed 30 and cooled, and the liquid carbon dioxide 31, 32 is separated off via a condenser 32 and the remaining gas 33 is returned to the reactor 19 via a control valve 34. The concentrated hydrogen 29 is further recovered as a product. In a second separation stage 43, the permeate from the first separation stage 29 is separated again. The permeate from the second separation stage 44 is reused as a product. The pension deed is returned via the control valve ’45 of the first separation stage.

Figure 5

FIG. 5 shows a water tank 2 from which water is sucked off with a pump 3 and fed to an electrical evaporator 39 via a control valve 4. The once-through evaporator consists of an electric evaporator 39, a steam water separation bottle 8, the condensate being returned to the tank. The saturated steam is electrically superheated 40. The superheated steam is fed to a steam plasma converter 16. Water vapor plasma is generated with microwaves 17, 18 via a magnetron 17 and actuating piston 18. Several microwave generators are arranged in series. The water vapor plasma 20 is introduced into a reactor 19. Dibutyl ether 11 is stored in a tank 12 and sucked off by a pump 13, evaporated via the heat exchanger 14 and introduced into the reactor 19 as superheated vapor 15. The reactor 19 is enveloped with a magnetic field generated by coils 21 so that the reforming of the overheated

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Dibutyl ether 15 can be reformed with the steam plasma 20 to form carbon dioxide CO2 and hydrogen H2. The gas mixture of carbon dioxide CO2, hydrogen H2, methane CH4 and hydrocarbons CO is cooled 23, with water 25 being separated out as condensate. The remaining gas mixture of hydrogen H2, methane CH4, hydrocarbons CO, CO2 is separated into hydrogen 48 and hydrocarbons 33 via a separation system 28 in the form of pressure swing adsorption 46, 47. The remaining gas mixture is compressed 30 and cooled, and the liquid carbon dioxide 31, 32 is separated off via a condenser 32 and the remaining gas 33 is returned to the reactor 19 via a control valve 34. The concentrated hydrogen 29 is further recovered as a product.

1 water

2 water tank

3 pump

4 control valve

5 water

6 economizers

7 evaporators

8 water vapor separators

9 superheaters

10 Condensate return

11 fuel

12. Tank -

13 'pump

14 evaporator

15 gaseous fuel 16 plasma reactor

17 magnetron

18 microwave controls

19 reactor

20 .Water vapor plasma 21 Inductive windings 22 Catalyst; “23 capacitor

24 cooling water

25 water tank

26 compressors

27 Anhydrous gas - vapor mixture 28 Separation stage (membrane) 29 Hydrogen-rich gas 30. Compressor

31 capacitor

32 carbon dioxide tank

33 Carbon dioxide-free gas. 34 Volume flow, pressure regulator 35 Recirculated gas

36 reactor

37 Inductive windings ‘38 Inductive windings 39 electrical evaporator 40 electrical superheater 41 compressor

42 hydrogen-rich gas 43 separation stage

44 hydrogen-rich gas 45 regulator for gas recirculation 46 adsorption reactor 1

47 Adsorption reactor 2

48. Hydrogen-rich gas 49 Control fitting for eFuel

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12

DME DBE

- OME

FA

CO2

H20

H2

CH4

CH20

CH3O0CH3

CH3OH CH3I (CH2) n -O- (CH2) nCH3 CH3- (CH2O) n -O-CH3 MeOH

EtOH '.BtOH

eFuel

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Dimethyl ether dibutyl ether | Oxymethylene dimethyl ether formaldehyde

Carbon dioxide

Water . Hydrogen \ methane

Formaldehyde dimethyl ether

Methanol. Oxymethylene dimethyl dibutyl ether

Methanol

Ethanol

Butanol

Collective term for FA, DME, DBE, OME

13

Claims (1)

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A method for generating hydrogen, comprising a water tank (2), a pump (3) with a control valve (4), an evaporator (6,7) with a water separator (8), a superheater (9), a plasma reactor (16 ) with a microwave generator (17, 18), a tank (12), a pump (13), an evaporator (14), a reforming reactor (19), a condenser (23) with a tank (25), a compressor (25 ), a gas separation stage (28), a high pressure compressor (30) with a condenser (32) and a tank (31), a control valve (34) Characterized by the fact that - The water tank (2) is filled with distilled water (deionized water) - The water tank (2) has a minimum filling volume of 100 L to a maximum of 5000 L. - The temperature of the distilled water (1) has a minimum of 5 ° C to a maximum of 85 ° C - The water tank (2) is depressurized, - The pump (3), driven electrically by an electric motor, generates a minimum pressure of 1 bar to a maximum pressure of 5 bar - The volume flow of distilled water is regulated to a minimum value of 10 L / min to a maximum of 100 L / min via the control valve (4) ‘ - The evaporator (6,7) generates saturated steam with a temperature from a minimum of 111 ° C to a maximum of 145 ° C - The saturated steam pressure is given with a minimum pressure of 1.5 bar to a maximum of 4 bar. - The saturated steam obtained in the separation bottle (8). a superheater (9) is superheated to a minimum temperature of 120 ° C to a maximum temperature of 175 ° C, -. In the fuel tank (12) the fuel (11) dibutyl ether DBE is stored without pressure - the fuel in the tank (12) has a temperature of a minimum of 5 ° C to a maximum. 50 ° C. is stored - The fuel is compressed by the hydraulically driven pump (13) to a pressure of a minimum of 1.0 bar to a maximum of 5 bar - The fuel is evaporated via the evaporator (14) to a temperature of a minimum of 150 ° C to a maximum of 175 ° C - The vaporous fuel (15) is introduced into the reactor (19) - The superheated water vapor in a plasma reactor (16) into a water vapor plasma; is converted; - The water vapor plasma is generated with the help of microwaves with a frequency of 0.5 GHz to a maximum of 10 GHz . ® 08 a 2 0.0 0 "0i0o entered tet;» The microwaves are generated with the help of a magnetron (17) and a piston to regulate the wave reflection is set so that the water vapor can be converted into plasma in the reactor, as the incoming and reflected waves are additively amplified in the reactor core, The electrical power of a magnetron has a value of at least 1 KW, maximum 10 kW, The microwave generators are arranged in sequence along the reactor, a minimum of one microwave generator, a maximum of 10 microwave generators are used to generate a high-density water vapor plasma that has a number of charged particles at least 10 ° N / m? has up to a maximum of 10 ° N / m®, The microwave generators are arranged in sequence along the reactor, a minimum of one microwave generator, a maximum of 10 microwave generators are used to generate a high-density water vapor plasma in which the charged particles have a minimum temperature of 1 eV to a maximum of 100 eV, The water vapor plasma (20) with. the vaporous fuel (15) is brought together in a reactor (19) so as to make the steam reforming possible,; The reactor is surrounded by coils (21) that generate a magnetic field that has a minimum magnetic flux density of 0.5 T to a maximum of 10 T in order to allow the water vapor plasma to react chemically with the fuel (15) at the end of the reactor (19) a catalyst bed (22) made of pellets with a diameter of a minimum of 3 mm to a maximum of 5 mm is present in order to increase the chemical reaction conversion by a minimum of 5% to a maximum of 30%, A carrier made of ceramic aluminum oxide AI203 with nickel oxide NiO on the surface is used as the catalyst, and has a layer thickness of a minimum of 10 μm to a maximum of 100 μm, The water is obtained as condensate (25) from the reformed gas bel a ‘temperature from a minimum of 10 ° C to a maximum of 25 ° C; The reformed gas consists of a gas mixture of hydrogen, carbon dioxide, carbon monoxide and methane, The reformed dry gas is compressed by a hydraulic piston compressor to a pressure of between 4 bar and 20 bar, The gas is separated into hydrogen and carbon-containing gases in a gas separation stage. The gas separation stage consists of a membrane with a pore diameter of at least 1 Angstrom to a maximum of 3 Angstrom, . The hydrogen-rich gas (29) obtained as permeate has a fraction of carbon-containing gases at least 1% to 5%, the carbon-rich gas is fed to a hydraulic piston compressor (30) which compresses the gas to a pressure of at least 50 bar to a maximum of 70 bar, The carbon dioxide contained in the gas at a pressure of 50 bar, at a temperature of 10 ° C, at a pressure of 70 bar, with a temperature of 25 ° C is deposited as a liquid condensate, the carbon dioxide-free gas via a control valve (34) Reactor (19) is recycled to be recycled again. ; I. ° ..). ° 0082 a0 "° HH 16 .. ° ° ° .. .. 08000 00 0 ... .o ° 2. The method according to claim 1, comprising a plasma reactor (36) with. an induction generator (37,38), Characterized by the fact that - The reactor (36) is designed in the form of a Lavall nozzle and thus a negative pressure of a minimum of 0.1 bar to a maximum of 0.3 bar can be generated, - The water vapor in the Lavall nozzle of the reactor (36) is in a thermodynamic imbalance, T - The water vapor plasma is generated inductively in the reactor (36) with the help of windings ‘, With a magnetic flux density of a minimum of 0.5 T to a maximum of 10 T is used, - The current in the windings has a frequency from a minimum of 1 kHz to a maximum of 1 MHz - The number of windings is a minimum of one to a maximum of 10, are arranged in series, so that a high, dense water vapor plasma is generated that has a number of charged particles at least 10 ° N / m? up to a maximum of 1027 N / m? Has, - The number of windings is a minimum of one to a maximum of 10, arranged in series, so that a high, dense water vapor plasma is generated in which the charged particles have a minimum temperature of 1 eV to a maximum of 100 eV. 3. The method of claim 1, comprising an electric evaporator (39), an electric superheater (40), Characterized by the fact that - The saturated steam is electrically heated with an electrical output of a minimum of 5 KW to a maximum of 500 kW, - The steam pressure is a minimum of 1.5 bar and a maximum of 4 bar, - The saturated steam temperature is a minimum of 111 ° C to a maximum of 143 ° C, - The saturated steam is brought to a temperature of a minimum of 145 ° C to a maximum of 175 ° C in an electrically heated superheater, - The electrically heated superheater has an electrical output of at least 5 kW to a maximum of 500 kW, e 4. The method according to claim 1, comprising a second gas separation stage (43), a compressor (41), a control valve (45),; Characterized by the fact that _- The second gas separation stage (43) is mechanically separated by a membrane with a pore diameter of at least 1 A to a maximum of 3 A, DELETE ". 9 17 0. .. * 0500 0 ° 000 .. - The second gas separation stage (43) is operated at a pressure of a minimum of 4 bar to a maximum of 15 bar, - The second gas separation stage (43) is operated at a temperature of a minimum of 5 ° C to a maximum of 25 ° C, ‚= A hydraulic piston compressor (41) is used to generate the pressure before the gas separation, a gas pressure of at least 4 bar to a maximum of 16 bar is generated, - The hydrogen separated in the second gas separation stage (43) has an impurity in the form of carbon-containing gases of a minimum of 0.001% to a maximum of 0.1%, - The carbon-containing gas not separated in the second gas separation stage (43) is reduced via a control valve (45) to the pressure upstream of the first gas separation stage from a minimum of 4 bar to a maximum of 15 bar,; - The carbon-containing gas of the first that is not separated in the second gas separation stage _ Separating stage (28) is fed. ; ; 5. The method according to claim 1, comprising a pressure swing adsorption (46,47) characterized in that - The gas mixture of hydrogen H2, carbon dioxide CO2, carbon monoxide CO and methane CH4 is separated in the form of pressure swing adsorption (46,47), - The pressure swing adsorption is operated at a pressure of minimum 8 bar, maximum 16 bar, - the molecular sieve used as zeolite 13X has a pore diameter of at least 3 Angstroms, maximum 5 Angstroms, and so the carbon compounds such as carbon dioxide CO2, carbon monoxide CO, methane CH4 can be physically bound in the sieve, - The adsorption takes place at a temperature of a minimum of 10 ° C to a maximum of 25 ° C, - The desorption takes place at a pressure of minimum 0.1 bar, maximum 0.3 bar, - Desorption takes place at a temperature of at least 50 ° C to a maximum of 100 ° C. ‚6. A method according to claim 1, comprising a tank (12) for the fuel dimethyl ether (DME) S Characterized by the fact that - Dimethyl ether (DME) is used as fuel in the tank (12), - The fuel dimethyl ether (DME) is stored in the liquid phase at a pressure of a minimum of 10 bar and a maximum of 15 bar, - The fuel dimethyl ether (DME) has a temperature of minimum 5 ° C, maximum 50 ° C. 7. The method according to claim 1, comprising a tank (12) for the fuel oxymethylenedimethyl ether (OME) Characterized by the fact that. - Oxymethylene dimethyl ether (OME) is used as fuel in the tank (12), The fuel oxymethylene dimethyl ether (OME) at one. Pressure of 1 bar is stored in the liquid phase; The fuel oxymethylene dimethyl ether (OME) has a temperature of at least 5 ° C, has a maximum of 50 ° C.