WO2019174679A1

WO2019174679A1 - Method and arrangement for methanol synthesis

Info

Publication number: WO2019174679A1
Application number: PCT/DE2019/100230
Authority: WO
Inventors: Dieter Erwin SCHULZE
Original assignee: Karl Bau Gmbh
Priority date: 2018-03-15
Filing date: 2019-03-14
Publication date: 2019-09-19
Also published as: DE102018106076A1

Abstract

The invention relates to a method for methanol synthesis comprising the steps: providing a fluid mixture of methanol and water; catalytically reforming the mixture of methanol and water by supplying heat to form 3H₂ and C0₂; separating H₂ and C0₂ into two type-unique gas streams; supplying the thus obtained hydrogen together with oxygen to a fuel cell (9); converting the hydrogen and the oxygen in the fuel cell (9) to reaction water in delivering electrical energy, while, parallel to the hydrogen processing, the thus obtained CO₂ is mixed with newly fed H₂O and catalytically synthesized to form a mixture of methanol and water while emitting heat and re-supplied to the first method step. The invention further relates to an arrangement for methanol synthesis, wherein a mixture of methanol and water is stored in a tank (70), wherein a steam reformation reactor (8) having a first catalyst (8) is provided, in which the mixture of methanol and water is reformed by supplying heat to form 3H₂ and CO₂, wherein a gas separation means (84) is provided, which separates the reformed 3H₂ and CO₂ gas mixture into one gas line each (85, 91) and, downstream of the H₂ gas line (91) a fuel cell (9) is arranged and, downstream of the CO₂ gas line (85) a methanol synthesis reactor (7) having a second catalyst (72) is arranged, wherein a water supply line (76) to the methanol synthesis reactor (7) and a synthesis line (73) from the methanol synthesis reactor (7) to the tank (70) are provided so that, in the methanol synthesis reactor (7), CO₂and H₂O are synthesized under the influence of the second catalyst (72) to form the CH₃OH and H₂O mixture while emitting heat.

Description

DESCRIPTION

Process and arrangement for methanol synthesis

The invention relates to a process for the synthesis of methanol and an arrangement therefor, in which a mixture of methanol and water in a

Steam reforming reactor is reformed with a first catalyst with heat to hydrogen and carbon dioxide.

Bases for the methanol synthesis have been described for example in the

US 3,790,505 described in the catalysts of copper, zinc and

Aluminum oxides are used. These catalysts are used for

Methanol production from a synthesis gas at 200 ° C to 300 ° C or the steam reforming of methanol to hydrogen as their reverse reaction. The reaction in the steam reforming of methanol is given by

CH ₃ OH + H ₂ 0 -> 3H ₂ + C0 _2, as is carried out for example in DE 698 08 983 T2. In this document, special embodiments for the methanol synthesis and reforming catalyst, which causes the reactivity of the mixtures are described. It also describes the conversion of carbon dioxide into methanol as a measure to alleviate the problem of global warming from the increase in carbon dioxide in the atmosphere.

Likewise, DE 196 44 684 A1 describes a method for storing hydrogen energy, in which a mixture of hydrogen and carbon dioxide is reacted in a reactor in methane, methanol or ethanol.

In US 6 090 312 A a reforming process is described in which steam is carried out with a hydrocarbon compound such as methane, natural gas or the like. The method uses inorganic

Membrane permeators for the separation of hydrogen (H ₂ ) - and Carbon dioxide (C0 ₂ ) molecules, which can then be fed directly for methanol synthesis fuel cells or other chemical synthesis methods. In this case, pure hydrogen can be recovered from the mixture of H ₂ and C0 ₂ by removing C0 ₂ and used in chemical synthesis processes or as a fuel for fuel cells.

From US 4,772,634 A is an apparatus and a method for

Methanol production by means of a fuel cell is known in which the injected into the methanol synthesizer gas composition is regulated.

US Pat. No. 4,309,359 A describes a catalytic process for the dehydrogenation of an alcohol or hydrocarbon or a hydrogenation process with the following steps:

a) passing the reactants over a process catalyst;

b) condensation and separation of a liquid product; and

c) removal of a carbon monoxide and / or hydrogen-containing

Exhaust gas, wherein electricity is generated by oxidation of the exhaust gas in a fuel cell.

From US 2014/0308597 A1 a steam reforming of methanol is known in which a gas phase containing CH ₃ OH and H ₂ 0 with a

Solid catalyst is brought into contact, wherein the catalyst of

Metal mixed oxides containing copper, zinc and gallium.

US 2013/0025192 A1 describes a solar thermal system. The system includes a solar thermal system for receiving concentrated solar energy. The heat from the solar energy is used for a first

Plant unit, a methane reforming reactor used. The first

Plant unit also receives a first set of reactants and generates a first set of products. A second unit receives the first set of products from the first unit and produces a second set of products in an exothermic reaction in a hydrocarbon synthesis reactor. A third unit, an evaporator, receives heat from the operation of the second unit to produce a portion of the first set of reactants. US 2009/0014336 A1 describes a process for producing methanol by recirculation and reductive conversion of an available one

Carbon dioxide source comprising:

electrochemically reducing the carbon dioxide in a divided electrochemical cell comprising an anode in a first

Cell compartment and a metal cathode in a second cell compartment containing an aqueous solution with methanol and an electrolyte, wherein the electrolyte contains one or more Alkylammoniumhalide, alkali metal carbonates or combinations thereof, in the second cell compartment

Reaction mixture to produce the carbon monoxide and

Contains hydrogen gas while oxygen is also produced in the first cell compartment at the anode;

Obtaining the carbon monoxide and the hydrogen gas from the reaction mixture from the second cell compartment and

Reacting the carbon monoxide and the hydrogen of the reaction mixture to produce methanol.

US 2009/0012332 A1 describes a process for the production of methanol, comprising:

Supplying hydrocarbon and oxygen and optionally carbon dioxide for a partial oxidation reactor and an optional reformer to produce a partial oxidation reactor effluent comprising hydrogen, carbon monoxide and carbon dioxide;

Performing an electrolysis of water to produce

Hydrogen and oxygen and

- recovering at least a portion of the hydrogen by one

To generate hydrogen flow;

Adding hydrogen from which at least part of the

Hydrogen stream is obtained, to the partial oxidation reactor effluent for generating a synthesis gas stream having a predetermined ratio of hydrogen to carbon monoxide and optionally to carbon dioxide;

Subjecting the synthesis gas to methanol synthesis to produce a methanol product stream and an exhaust gas stream; - Separating the exhaust gas stream into at least two streams comprising a purge stream and a recirculation stream, wherein the

Recirculation flow comprises a substantial part of the exhaust gas and

- Returning the recirculation flow in the partial oxidation reactor.

From WO 2013/007 993 A2 a process for the production of H ₂ by steam reforming of methanol is known, wherein the method

Contact with a solid catalyst comprises a gas phase of CH ₃ OH and H ₂ 0 and the solid catalyst comprises a copper, zinc and gallium comprehensive metal mixed oxide. In addition, a fuel cell, for example, a proton exchange membrane (PEM) fuel cell and a

Methanol reformer for the production of methanol by hydrogenation of

Carbon dioxide containing the aforementioned catalyst.

From WO 00/58 421 A1 a method for generating energy is known with the following steps:

1) burning fuel in an internal combustion engine to produce mechanical energy and carbon dioxide and water vapor-containing exhaust gas,

2) reduction of the exhaust gas components carbon dioxide and water in an organic material-containing environment to a synthesis gas containing carbon monoxide and hydrogen,

3) feeding the synthesis gas generated in step 2 into the

Internal combustion engine. To generate methanol, a methanol synthesis is inserted between steps 2 and 3 of the process.

Starting from the considerations mentioned in the introduction to US Pat. No. 3,790,505 and DE 698 08 983 T2, it is an object of the invention to specify a method and an arrangement for the synthesis of methanol, with which an existing

Heat source can be used, on the one hand C0 ₂ in an energetically and / or material-technically usable, higher quality substance, namely methanol, to transfer and thereby to take advantage of other benefits. This object is achieved with a comparison with DE 698 08 983 T2 modified methanol synthesis, in which carbon dioxide and water react exothermically to a mixture of methanol and water. The process is characterized by the following steps: providing a liquid mixture of methanol and water, in particular with a mixing ratio of 70% to 60% CH ₃ OH to 30% to 40% H ₂ O; - Catalytic reforming of the mixture of methanol and water with heat, in particular at 180 ° C to 320 ° C, to 3H ₂ and C0 ₂ , - Separation of H ₂ and C0 ₂ in two species pure

Gas flows; - supplying the thus obtained hydrogen together with oxygen to a fuel cell; - Reacting the hydrogen and the oxygen in the fuel cell to water of reaction when emitting electrical energy; while parallel to the hydrogen processing, the thus obtained C0 ₂ mixed with newly supplied H ₂ 0 and catalytically synthesized to give a mixture of methanol and water with heat release and recycled to the first process step. Accordingly, according to the device according to the invention for methanol synthesis characterized in that a gas separation means is provided, the reformed 3H ₂ and C0 ₂ gas mixture in each one

Gas line separated, and downstream of the H ₂ gas line, a fuel cell and downstream of the C0 ₂ gas line a methanol synthesis reactor with a second catalyst are arranged, wherein a water supply to

Methanol synthesis reactor and a synthesis line from

Methanol synthesis reactor are provided to the tank, so that in the

Methanol synthesis reactor C0 ₂ and H ₂ 0 is synthesized under the influence of the second catalyst to CH3OH and H ₂ 0 mixture with release of heat and excess oxygen. Thus, at the end of the H ₂ gas line seen in the direction of flow, the fuel cell is on and in

Flow direction seen end of the C0 ₂ gas line the

Methanol synthesis reactor arranged.

In the catalytic reforming in the steam reforming reactor, the methanol-water mixture is reformed with the addition of heat to hydrogen and carbon dioxide. The heat supply is energetically sensible fed by excess heat from another process. The hydrogen obtained from this is separated with oxygen, for example from a separate process, the Fuel cell fed and converted into water of reaction when emitting electrical energy. In parallel, the carbon dioxide from the catalytic

Reforming the mixture of methanol and water mixed with newly supplied water and catalytically synthesized back to a methanol-water mixture with heat release and a low release of oxygen and fed back to the storage tank.

In order to control the synthesis of methanol as needed, the thus obtained H ₂ and C0 ₂ and the oxygen is compressed and

cached. Thus, the compressed gas in each case in small

Pressure vessels cached and thus the supply to the

Methanol synthesis process can be controlled more precisely.

Characterized in that when mixing the recovered from the steam reforming C0 ₂ with the newly supplied H ₂ 0 additionally carbon dioxide, preferably

1 to 10 wt.% Of the amount of C0 ₂ obtained, more preferably

2 to 3 wt.% Of a new source, that is supplied in addition to obtain a suitable for the catalyst used mixing ratio of C0 ₂ and H ₂ 0 ZU. The recombination is carried out at temperatures of 250 ° C to 350 ° C and it is an excess of methanol-water mixture produced so that from the tank methanol-water mixture for another

Use / recovery can be deducted. For example, after separation of the methanol from the mixture, synthetic fuels or propylene can be synthesized from the methanol. A "new source" for the supplementarily supplied C0 ₂ may be a C0 ₂ gas cylinder with C0 ₂ supplied or a parallel C0 ₂ separation process, for example from the ambient air.

When the newly added C0 ₂ is filtered out of the ambient air by absorption and fed to the methanol synthesis, the additional carbon dioxide required is extracted from the ambient air, which counteracts the greenhouse effect and is an important raw material for methanol synthesis. A procedurally particularly favorable linkage of

Methanol synthesis process results from the fact that it is carried out together with a process for the production of deuterium reduced water, injected in the HHO gas obtained from an electrolysis in a reactor and ignited and in the presence of metal oxides as a catalyst at temperatures of 2800 ° C to 3500 ° C is reacted in a plasma to emerging reaction water, wherein air is supplied to the combustion furnace, the air surrounding the plasma and thus the plasma is cooled and then cooled the plasma after combustion as exhaust air and the reaction water therein is condensed and collected, wherein the heat from the HHO gas combustion is used for the catalytic decomposition of the mixture of methanol and water.

Here HHO gas means a gas which is formed during the electrolysis of water, namely 2x "H" + 1x "O", which burns extremely reactive to water. This HHO gas is also called "Brown's gas", "hydroxide gas" or "oxyhydrogen gas".

In a further embodiment of the process combination, the reaction water from the fuel cell, which has a reduced deuterium content of <140 ppm, preferably <80 ppm, the deuterium reduced water from the

HHO gas combustion supplied. Thus, the yield of deuterium reduced water can be increased with the process combination.

By supplying the exhaust air from the HHO gas combustion, which consists essentially of oxygen, to the fuel cell, the required oxygen supply for the fuel cell can be used directly from the HHO gas combustion process conducted in parallel. A

energy-consuming oxygen separation can thus be omitted.

Further synergistic effects in the execution of the methanol synthesis process in parallel to the HHO gas combustion are achieved by using the electrical energy generated in the fuel cell for the electrolysis of water in HHO gas. In this respect, the power supply for the electrolysis at least partially achieved by the electrical energy generated in the fuel cell.

According to the device, the gas separation agent has a nanopore membrane, by which C0 ₂ molecules are separable from the H ₂ molecules, whereby a pure separation of the two gases is possible. For example, it is a developed by Stanford University membrane based on zeolites.

Alternatively, a so-called Polyabsorb material can be used in which the C0 _{2 is} stored and only the H ₂ can be supplied for further use of the fuel cell (so-called "carbon capture

technology ").

When the fuel cell is a KOH electrolyte alkaline fuel cell, an efficient and relatively non-disruptive type of fuel cell is preferred. For example, the "EloFlux fuel cell" of Gaskatel GmbH, Germany can be used.

Characterized in that the methanol synthesis reactor has a mixing section with a mixing nozzle through which the carbon dioxide and the water is mixed, wherein the water as a vapor, preferably at about 4 bar pressure, is present and on

Methanol synthesis reactor a heat carrier circuit for heat dissipation

is provided, an advantageous for methanol synthesis intensive

Mixing between the supplied components carbon dioxide and water reached. The reactivity is in conjunction with the supplied

Water vapor and the preferably pressurized carbon dioxide when injecting through the mixing nozzle significantly increased.

Preferred as a supplementary source of carbon dioxide is a

C0 ₂ -Abscheideanlage provided. This can be deposited with acceptable energy expenditure pure C0 ₂ from the ambient air. The heat required for this can also be used from parallel processes, for example HHO gas combustion or exothermic methanol synthesis. For example, an air to C0 ₂ plant under the name "Direct Aire Capture (DAC)" at Climeworks AG, Switzerland.

When the first and second catalyst metal oxides such as CuO, ZnO, Zr0 _2, Al ₂ 0 _3, NiO, Ga ₂ 0 ₃ and / or the like, or exclusively of, or consists of mixtures thereof, both the

Steam reforming reaction as well as the methanol synthesis reaction amplified or maintained. In particular, the first and / or the second catalyst consist of CuO, ZnO and Al ₂ O ₃ with a weight ratio of 50 to 80% by weight CuO, 12 to 40% by weight ZnO and 5 to 15% by weight Al ₂ O ₃ , Thus, a particularly effective catalyst is provided for both the steam reforming as well as for the synthesis of methanol, which is assembled on the basis of the catalyst from DE 698 08 983 T2.

Preferably, the mixture of methanol and water has a mixing ratio of 70 to 60 wt.% CH ₃ OH to 30 to 40 wt.% H ₂ 0. In a

Mixing ratio of 68 wt.% CH ₃ OH to 32 wt.% H ₂ 0 a complete reforming reaction in hydrogen and C0 ₂ molecules is achieved.

Hereinafter, an embodiment will be described in detail with reference to the accompanying drawings.

It shows:

Fig. 1 is a schematic arrangement plan.

Fig. 1 shows a schematic arrangement plan according to a

Embodiment in which the methanol synthesis is combined with a process for the production of deuterium reduced water, as defined in claim 6. The method and the arrangement for the production of deuterium reduced water is the subject of a separate PCT patent application with the same filing date of the same Applicant, so that here this part of the method and the arrangement (based on the

Reference numerals 1 to 6 and their sub-items) only in the context of Linking points to the claimed here methanol synthesis is described in detail. However, the combination of the methanol synthesis with the process for the production of deuterium-reduced water by means of HHO gas combustion gives rise to extremely positive synergy effects, the effectiveness of both processes and the yield of the respective processes

Increase process products.

Of course, the methanol synthesis according to the present invention is also individually without linking with the process for the preparation of

Deuterium reduced water by HHO gas combustion can be used. The required arrangement refers to the reference numerals 7, 8 and 9 and their sub-items.

The arrangement for methanol synthesis has a storage tank 70, in which a methanol-water mixture with a mixing ratio of preferably 68 wt.% CH ₃ OH to 32 wt.% H ₂ 0 is included. From the tank 70, a methanol-water mixture feed line 82 leads to a steam reforming reactor 8, in which a first catalyst 81 consisting of a mixture of copper, zinc and aluminum oxide in crystalline or powder form is present. Since the process occurring in the steam reforming reactor 8 is endothermic, is a

Heat supply via a circulation line 52 is provided. In the embodiment shown here, the heat from the HHO gas combustion in a reactor 4 with combustion chamber 41 is provided by means circulating in the circulation line 52 heat transfer medium from a heat exchanger 5.

For the reaction product from the steam reforming reactor 8 is a

Gas line 83 is provided, is guided in the hydrogen and carbon dioxide. The gas line 83 leads to a gas separation means 84 in the form of a

Nanopore membrane, by which the C0 ₂ molecules are separable from the H ₂ molecules. Similarly, a C0 _{2 line} 85 and an H ₂ feed line 91 from the gas separation means 84 provide additional components of the overall arrangement. The H ₂ supply line 91 is connected to a fuel cell 9, preferably an alkaline fuel cell 9 (AFC fuel cell). Furthermore, a 0 ₂ supply line 92 is connected to the fuel cell 9, which in here illustrated embodiment, oxygen from an exhaust duct 53 of parallel executed HHO gas combustion supplies. For the reaction products of the fuel cell 9, a water outlet 93 and a power line 94 is connected to the fuel cell 9.

The water fed from the fuel cell 9 via the water outlet 93 has a reduced deuterium content of <140 ppm. Depending on

Fuel cell 9 and selected process parameters may preferably also a deuterium reduced water with a deuterium content of <80 ppm. The water discharge 93 is connected in the embodiment shown here to a treatment for deuterium reduced water 6, namely a filter and dosing station 62 and thus increases the yield of deuterium reduced water from the parallel executed HHO gas combustion.

The power line 94 is connected via a suitable control for power supply to the public power grid or other suitable consumers. In the embodiment shown here, the power line 94 to the

Power supply 11 of an electrolysis device 1 connected to the production of HHO gas.

The C0 _{2 line} 85 leads into a methanol synthesis reactor 7, wherein a C0 ₂ -Abscheideanlage 86 is connected to the C0 _{2 line} 85, which separates from the ambient air C0 ₂ and additionally passes into the C0 ₂ supply of the methanol synthesis reactor 7. Furthermore, a water supply line 76 via an evaporator 75 in the methanol synthesis reactor 7. The supply of both products in the methanol synthesis reactor 7 via a mixing nozzle 71. In methanol synthesis reactor 7, a second catalyst 72 is maintained, which also consists of copper, zinc and aluminum oxide. Preference is given to using a catalyst according to DE 698 08 983 T2. The im

Methanol synthesis reactor 7 proceeding methanol synthesis is exothermic, so that a heat carrier 74 is passed through the methanol synthesis reactor 7 to derive the resulting process heat. The heat transfer circuit 74 leads in the illustrated embodiment to the evaporator 75 to the supplied in the water supply line 76 water for the methanol synthesis process evaporate. In the embodiment shown here, the water comes from a water supply 21 with common for both methods

Water pretreatment 2, preferably an ion exchanger.

For the methanol-water mixture formed in the methanol synthesis reactor 7, a synthesis line 73 is provided which leads to the tank 70 and thus closes the process run. Further, the methanol synthesis reactor 7 is a

Degassing valve 77 for excess oxygen, at the

Methanol synthesis from water and C0 ₂ is formed, provided. On the tank 70, an overflow for the methanol-water mixture is also provided, which leads to a methanol recovery 78.

For the understanding of the overall arrangement with two combined methods, the arrangement for the production of deuterium reduced water by means of HHO gas combustion in terms of its components and the

Procedure as well as the linking points with the

Methanol synthesis method with reference to Fig. 1 described below.

In the electrolyzer 1 HHO gas is generated by means of direct current electrolysis, fed by a mains power supply 11 and a

HHO gas distributor 12 supplied. Here is the HHO gas on three

HHO gas lines 13 to supply HHO gas nozzles 14 divided and, if necessary, regulated in the flow.

The HHO gas flowing into the HHO gas nozzles 14 is ignited by electric ignition systems, not shown, and burned in the combustion chamber 41 of the reactor 4. The flame is directed to a catalyst 40. The catalyst 40 consists of metal oxides, in particular Al ₂ 0 ₃ in a powdery, crystalline state. The catalyst 40 causes a plasma with a temperature of about 2800 ° C to 3500 ° C arise.

A catalyst support plate 42 in the combustion chamber 41 is rotated with the catalyst resting thereon 40 by a rotating and lifting device 43 at a speed of 1 to 3 rev / min to the entire free surface of the Catalyst 40 from the HHO gas flame to sweep, so that an intense and uniform plasma formation is formed. Furthermore, the

Combustion process of the HHO gas in the combustion chamber 41 thereby regulated by the height adjustment of the catalyst support plate 42 via the rotating and lifting device 43, the fresh air supply and possibly by additional injection of water.

At the same time, fresh air 31, which is supplied via a fan 3, an annular space 32 and air supply openings 33 directly in the area of the HHO gas nozzles 14, flows into the combustion chamber 41 and forms a plasma

Frischluftumhüllung that protects the walls of the combustion chamber 41 from overheating and further turbulence of the plasma with the

Fresh air 31 leads to a total of cooled exhaust air at a temperature of <600 ° C. This exhaust air is in an exhaust duct 45 then the

Heat exchanger 5 is supplied. In the heat exchanger 5, the exhaust air is removed by means of a circulation line 52 with a heat transfer medium. The

Circulation line 52 leads in the illustrated embodiment to the steam reforming reactor 8 and there supplies the required process heat of at least 180 ° C to 320 ° C to effect the endothermic catalytic reaction by means of the first catalyst 81. This is the over the

Methanol-water mixture feed 82 fed mixture in the

Steam reforming reactor 8 gasified and reformed according to the formula (1) listed on page 1 in hydrogen and carbon dioxide.

This gas mixture is supplied via the gas line 83 to the gas separation means 84, wherein the two gases are separated into two separate types of separate streams. The pure hydrogen gas is supplied via the H ₂ supply line 91 of the fuel cell 9. In order to supply the oxygen required for the operation of the fuel cell 7, a "waste product" of the parallel HHO gas combustion process is now used, namely the exhaust air or a partial flow of the exhaust air from the exhaust duct 53, which after combustion over the Exhaust duct 45 and the heat exchanger 5 is guided. In this heat exchanger is by cooling the exhaust air from the

Plasma HHO gas combustion Deuterium reduced water of reaction condenses, which is an essential manufacturing product of this process. This resulting water of reaction has a significantly reduced

Deuterium content <80 ppm. This condensate is fed via the condensate line 61 of the filter and metering station 62. In addition, in the filter and dosing station 62, a metered addition of minerals and trace elements to the reaction water to the deuterium reduced water for the

Nutrition, therapy or healing support to use optimally. The remaining exhaust air consists essentially of oxygen and residual moisture.

Optionally, additionally completely desalinated water can be used in the combustion chamber 41, which is injected via the water pretreatment 2, in particular by means of an ion exchanger, and a water distributor 22 with cycle control via water nozzles 24 directly in the region of the plasma. The additional water injection achieves a greater yield of deuterium-reduced water. In addition to an additional hydrogen production and a concomitant plasma stabilization, the

Water injection can be used for additional cooling of the reactor 4, if in the combustion monitoring in the combustion chamber 41 excessively high temperatures should arise. The temperature monitoring is preferably carried out via a pyrometer to ensure a fast reaction and non-contact temperature measurement. As a result of the described control possibilities in the case of HHO combustion, the ionized plasma can breathe, so that the exhaust air in the region of the exhaust air duct 45 has already cooled below 600 ° C. before entering the heat exchanger 5.

Interestingly, in the combustion of the HHO gas in the plasma in addition to the electrolytically previously split amount of water additionally water is formed, which is obviously supplied by the in the fresh air 31

Humidity comes from. It is also assumed that in the

Fresh air 31 contained substances, such as nitrogen, noble gases and carbon dioxide are digested in the plasma, and it is not clear what exactly happens with these substances, whether they are split, converted or deposited. This still requires a scientific investigation. It is, however, of it assumed that the carbon accumulates in the catalyst 40 and the oxygen forms the exhaust air together with the reaction water vapor. The measured oxygen content in the exhaust air is 18% to 20.5%. The remainder consists of the reaction water vapor and is within the scope of

Emission accuracy emission-free, with the reaction water vapor largely separated by condensation and the product of manufacture Deuterium forms reduced water. The carbon taken up in the catalyst 40 leads to the formation of gems under the extreme conditions in the plasma. Therefore, the catalyst 40 should be replaced from time to time, for example, once or twice a year. Basically, the catalyst 40 of metal oxides, especially Al ₂ 0 ₃ , does not consume in the combustion process. The procedure can thus be used in addition to the production of deuterium reduced water for the production of gemstones and thus for C0 ₂ reduction.

LIST OF REFERENCE NUMBERS

Electrolysis device 5 heat exchanger

Power supply 52 Circulation line HHO gas distributor 53 Exhaust air duct

HHO gas line

HHO gas nozzle Water pretreatment, 6 Treatment for deuterium ion exchanger Reduced water Water supply 61 Condensate line

Water distributor, cycle control 62 Filtering and dosing station Water line 63 Filling line

Water Injector Fan 7 Methanol Synthesis Reactor Fresh Air 70 Methanol Water Tank Annular Space 71 Mixing Nozzle

Air supply port 72 second catalyst

73 synthesis line

Reactor 74 Heat transfer circuit Catalyst 75 Evaporator

Combustion chamber 76 Water supply line Catalyst support plate 77 Degassing valve

Turning and lifting device 78 Methanol recovery drive means

exhaust duct Steam reforming reactor 9 Fuel cell first catalyst 91 H ₂ supply line methanol-water mixture 92 0 ₂ feed line

supply

Gas line 93 Water drainage Gas separator 94 Power line C0 ₂ line

C0 ₂ separation plant

Z cylinder axis

Claims

PATENT APPLICATIONS

1. Process for the synthesis of methanol with the steps:

Providing a liquid mixture of methanol and water; catalytic reforming of the mixture of methanol and water with addition of heat to 3H ₂ and C0 ₂ ;

Separation of H ₂ and C0 ₂ into two pure gas streams;

Supplying the thus obtained hydrogen together with oxygen to a fuel cell (9);

Reacting the hydrogen and the oxygen in the fuel cell (9) to water of reaction when emitting electrical energy;

- While parallel to the hydrogen processing, the thus obtained C0 ₂ mixed with newly fed H ₂ 0 and catalytically synthesized to give a mixture of methanol and water with heat release and fed back to the first process step.

2. A process for the synthesis of methanol according to claim 1, characterized

characterized in that the thus obtained H ₂ , the C0 ₂ and / or the oxygen are compressed and cached.

3. A process for methanol synthesis according to claim 1 or 2, characterized in that during mixing of the thus obtained C0 ₂ with the newly supplied H ₂ 0 additionally 1 to 10 wt% C0 _{2 is} supplied from a new source, wherein the recombination at

Temperatures from 250 ° C to 350 ° C and excess takes place

Methanol-water mixture is withdrawn for another recovery.

4. A process for the synthesis of methanol according to claim 3, characterized

characterized in that the newly supplied C0 ₂ by absorption The ambient air is filtered out and fed to the methanol synthesis.

5. A process for the synthesis of methanol according to claim 3 or 4, characterized in that the methanol is separated from the excess methanol-water mixture and converted into propylene and / or synthetic fuels.

6. Process for the synthesis of methanol according to one of the preceding

Claims, characterized in that it is carried out together with a process for the production of deuterium reduced water, in which obtained from an electrolysis

HHO gas in a reactor (4) injected and ignited and in

The presence of metal oxides as a catalyst (40) at temperatures of 2800 ° C to 3500 ° C in a plasma zugebem to

Reaction water is reacted, wherein air is supplied to the combustion furnace, the air surrounds the plasma and thus the plasma is cooled and then cooled the plasma after combustion as exhaust air and the reaction water therein

is condensed and collected, with the heat from the

HHO gas combustion is used for the catalytic decomposition of the mixture of methanol and water.

7. A process for the synthesis of methanol according to claim 6, characterized

characterized in that the reaction water from the fuel cell (9), which has a reduced deuterium content of <140 ppm, the

Deuterium reduced water from the HHO gas combustion is supplied.

8. A method for methanol synthesis according to claim 6 or 7, characterized in that the exhaust air from the HHO gas combustion, which consists essentially of oxygen, the fuel cell (9) is supplied.

9. A method for methanol synthesis according to claim 6, 7 or 8, characterized in that in the fuel cell (9) generated electrical energy for the electrolysis of water in HHO gas is used.

10. Arrangement for the synthesis of methanol, in which a mixture of methanol and water in a tank (70) is stored, wherein a

Steam reforming reactor (8) with a first catalyst (81)

is provided, in which the mixture of methanol and water with the addition of heat to 3H ₂ and C0 _{2 is} reformed, characterized in that a gas separation means (84) is provided, the reformed 3H ₂ and C0 ₂ gas mixture in each line (85 , 91), and downstream of the H ₂ supply line (91) a fuel cell (9) and downstream of the C0 _{2 line} (85) a methanol synthesis reactor (7) with a second catalyst (72) are arranged, wherein a

Water supply line (76) to the methanol synthesis reactor (7) and a synthesis line (73) from the methanol synthesis reactor (7) to the tank (70) are provided so that in the methanol synthesis reactor (7) C0 ₂ and H ₂ 0 under the influence of the second catalyst (72) to CH ₃ OH and H ₂ 0 mixture is synthesized with the release of heat.

11 arrangement for the synthesis of methanol according to claim 10, characterized

characterized in that the gas separation means (84) is a

Nanopore membrane has, through the C0 ₂ molecules of the

H ₂ molecules is separable.

12. Arrangement for the synthesis of methanol according to claim 10 or 11, characterized in that the fuel cell (9) is an alkaline

Fuel cell (9) with KOH electrolyte is.

13. Arrangement for the synthesis of methanol according to claim 10, 11 or 12,

characterized in that the methanol synthesis reactor (7) has a mixing section with a mixing nozzle (71) through which the carbon dioxide and water are mixed, the water being in the form of vapor and the methanol synthesis reactor (7) a heat transfer circuit (74) is provided for heat dissipation.

14. An arrangement for methanol synthesis according to any one of claims 10 to 13, characterized in that for the production of carbon dioxide from the ambient air, a C0 ₂ -Abscheideanlage (86) is provided.

15. Arrangement for methanol synthesis according to one of claims 10 to 14, characterized in that the first and second catalyst (81, 72) contains metal oxides.

16. Arrangement for methanol synthesis according to claim 15, characterized

characterized in that the first and second catalysts (81, 72) are made of

CuO, ZnO and Al ₂ O ₃ consist of a weight ratio of 50 to 80 wt.% CuO, 12 to 40 wt.% ZnO and 5 to 15 wt.% Al ₂ O ₃ .

17. An arrangement for methanol synthesis according to any one of claims 10 to 16, characterized in that the mixture of methanol and water, a mixing ratio of 70 to 60 wt.% CH ₃ OH to

30 to 40 wt.% H ₂ 0 has.