WO2020048556A1

WO2020048556A1 - Hydrogen reactor and regenerative chemical method

Info

Publication number: WO2020048556A1
Application number: PCT/DE2018/000255
Authority: WO
Inventors: Christoph Gregor WANDZIK
Original assignee: Wandzik Christoph Gregor
Priority date: 2018-09-05
Filing date: 2018-09-05
Publication date: 2020-03-12
Also published as: DE112018007957A5

Abstract

The invention relates to a thermal method with the aid of a pressure pipe reactor for carrying out, under continuous flow conditions, some chemical reactions on the surface of at least one solid reactant in a gas/solid phase reaction. The core of the invention is a solar-thermal method based on concentrated solar energy with trough collectors, and the product is a pressure pipe reactor for continuous production of split hydrogen gas (H₂) from water vapour gas (H₂O_g). Owing to the absorption and/or adsorption on the surface of metal mixtures of certain metals, the following reactions are performed at temperatures ranging from 500°C to 1350°C: cleaving, autooxidation, substitution, decomposition. The method has four main processes: water splitting, regeneration, roasting, flushing and evacuation. Problem: Hydrogen first has to be produced artificially and with lower degrees of efficacy from other energy sources (fossil energy, nuclear energy, or renewable energies). By contrast, concepts for future hydrogen economies usually provide for hydrogen recovery from renewable energies. Solution: The pressure pipe reactor and the regenerative above method; my invention. The costs of hydrogen manufacture are thus reduced, and in the long term large-scale production is made possible. My innovation constitutes the new generation of renewable energies and is devoid of harmful emissions. Merely schematic regeneration sequence (no reaction equation) (I)

Description

Title: Hydrogen reactor and the regenerative chemistry process

Topic: Gas / solid phase reaction of water with elemental iron and sulfur.

• [0001]

The invention relates to a thermal process with the aid of a pressure tube reactor for the continuous flow of some chemical

Reactions on the surface of at least one solid reactant in one

Gas / solid phase reaction. The essence of the invention is a solar thermal process based on concentrated solar energy with trough collectors, and the product is a pressure tube reactor for the continuous production of

Hydrogen fission gas from water vapor gas on the surface of at least one metal in a gas / solid phase reaction at temperatures in the range from 500 ° C to 1350 ° C. The solar chemical process has six production steps, which can be divided into four main processes: water splitting, regeneration, roasting and rinsing.

• [0002]

Hydrogen, like electric current, is not a primary energy source, but must first be artificial and with lower efficiencies and yields from others

Energy sources (fossil energy, nuclear energy or renewable energies) are generated.

Today, most of the hydrogen is made from fossil primary materials (coal, oil, natural gas). Concepts for future hydrogen economies, on the other hand, mostly provide for hydrogen generation from renewable energies, which means that such an energy supply could be emission-free. However, require one

Restricting resources and calling for an increasing reduction in greenhouse gases (especially carbon dioxide) tapping alternative sources. Splitting water with the help of electrolysis using solar power is possible, but has the disadvantage that the costs for the solar thermal systems are very high. The direct use of concentrated solar radiation for thermochemical Splitting water avoids high costs and is more efficient. This reduces the costs of hydrogen production and enables large-scale production in the long term.

. [0003]

A number of methods are available for the thermal production of hydrogen. These are either expensive or impractical to use and therefore complicated or generate harmful emissions. My idea was one

Large-scale production of hydrogen without harmful emissions

(Carbon dioxide, chlorine, etc.) to develop. I have my goal through mine

Work experience, as a state-certified chemical technician and specialist literature

"Chemietechnik Europa Verlag E: No.: 70415 page 415, finally I have alone, carried out experiments on the subject of my idea using a small one

Experimental apparatus on a laboratory scale in my basement. My invention is new because it does not correspond to the current state of the art.

[0004]

According to a press release by the German Aerospace Center on October 15, 2004, hydrogen was first generated in the solar oven by solar thermal

Water splitting generated. In the process described here, the hydrogen is generated discontinuously by splitting the water vapor over metal oxides and partially regenerating the metal oxide by reduction. A reduced iron oxide is formed which can be oxidized again. State of the art with a little hydrogen gas yield (pilot plant scale).

. [0005]

JP 03205302 A describes the production of high-purity hydrogen using activated magnetite as a reactive catalyst. • [0006]

JP 2001270701 A produces hydrogen by reacting metallic zinc, magnetite and water with each other at 600 ° C.

. [0007]

In DE 42 26 496 A1, hydrogen is generated in a modified continuous iron-water vapor process. The resulting iron oxide is then fed back to steelmaking. Cumbersome recycling of the iron ^oxide's.

[0008]

M. Inoue et al. from Solar Energy (2003) describe the production of hydrogen using a water-Zn0-MnFe2S04 system. The corresponding ferrite powder of the type M _x ²⁺ Zni _-x ²⁺ Fe2S04 can be produced by the method of S. Lorentzou et al., Presented at the Partec 2004 conference. Too complicated in my opinion.

• [0009]

In DE 44 10 915 A1, hydrogen is formed by the reaction of iron with carbonic acid with the addition of solar thermal energy. The iron oxide formed is reduced again by means of carbon monoxide and is available for the process. Disadvantage of carbon dioxide.

[0010]

The aim of the present invention is therefore a process engineering cycle process for the production of hydrogen gas, which in particular in one

Reaction pressure tube can be carried out, in which no solid has to be exchanged. Mixing with mechanical methods may be advantageous, whereby the metals are kept porous. The metals are elementary and are mixed through the cooling pipes on a ring line, after which they can be reacted again.

The process runs optimally in a continuous flow at the lowest possible temperatures. Another object is to provide a solar-powered pressure tube reactor with a parabolic mirror in a vertical design, in which above all

Hydrogen gas is continuously produced as a product. The four

Process stages of water splitting (splitting, regeneration, roasting and

Rinsing) necessarily run in succession or in parallel in several modules simultaneously.

. [001 1]

The problem on which the invention is based and the associated object are solved on the one hand with a specific method and on the other hand with a specific apparatus: a thermal method must be brought about for

Production of hydrogen gas from water vapor on a surface of a metal in a solid phase gas reaction. A pressure tube reactor reaction space is to be provided as apparatus. Due to the specific subject matter of the invention, my invention is not general and is also not the latest state of the art in chemical engineering today. use. In the process step, water vapor is thermally split by the addition of oxygen to the highly excited metals by auto-oxidation. It will

Hydrogen gas (H2g) released. In a second process step at a lower temperature than the first step, the metal oxide is regenerated with sulfur gas (S (2-) _g ). Bound oxygen is released as sulfur dioxide and sulfur trioxide so that the metal is reduced. In a third process step, the remaining metal pyrite is increased compared to the second process step

Temperature roasted metallic; the reaction chamber is then flushed with nitrogen and the elemental metals are available for further production.

The underlying task, a solar powered pressure tube reactor

To provide, in which two products (especially hydrogen) are continuously produced in four process steps (cleavage, regeneration, roasting and rinsing) should necessarily take place in succession. [0012]

The hydrogen synthesis by water vapor gas splitting is mainly carried out in the process according to the invention in the DRR. The regeneration of the metal redox system takes place in a second reaction space. In the following

Production cycle, the roasting process is carried out at a higher temperature and then new reaction steps can then be carried out again in the regenerated reaction space. Thus, the thermal production of hydrogen can flow continuously and realized on an industrial scale and simply defined as the unknown technological background of the area. The information disclosed in my invention is not prior art because it is not obvious and has not been derived from other patents. Thus, as disclosed in the description, the knowledge and skill of this invention significantly exceeds the knowledge and skills of one of ordinary skill in the art.

. [0013]

The invention consists of a method of thermally splitting water vapor in a multi-stage cycle process by using concentrated light irradiation or by waste heat and, as a result, to generate solar hydrogen gas (H2g).

[0014]

The object of the invention has been shown to thermally split water vapor by means of concentrated sunlight and to bind oxygen in an auto-oxidation reaction and thereby generate hydrogen gas (H2g).

This basic fact of chemistry forms the basis for the development of the present invention of a method for the solar thermal generation of

Hydrogen gas. Regeneration with sulfur gas (S (2-) g) or

Phosphorus gas. This chemical process describes a situation as it corresponds to a “catalyst” in chemical engineering. This chemical process does not correspond to the current state of the art. The basic evidence or feature of my invention was disclosed here in the article. In contrast to direct thermal water splitting, which only takes place at approx. 2700 ° C, water vapor and hydrogen gas are generated in advance in a four-stage cycle process at temperatures between 600 ° C and 1350 ° C. A metal-vanadium system is used in the production cycle so that the oxygen can be split off from water molecules and reversibly incorporated into a gas compound. According to my research, my chemical process and the object of the invention, that WANDZIK ^' s pipe, are nowhere known on planet Earth. However, this fact does not prevent the commercial production of my invention, because with chemical engineering it can be produced commercially by an industrial mechanic at any time according to my instructions. And can be operated by a chemist.

• [0015]

There are mainly elemental metals (metal elements) with high

Melting points (from 1500 ° C) are used, which have an auto-oxidizing effect one after the other and are reduced by a reducing agent (sulfur gas or phosphorus gas). Vanadium catalysts help accelerate the reactions. In the first

In the production step, the hot steam flowing past the metal in a turbulent manner is split by binding the oxygen to the excited metal grid at temperatures of predominantly 500 ° C to 900 ° C. Hydrogen gas (hteg) is released. In the second production step, at temperatures of preferably 450 ° C. to 650 ° C., the oxygen previously incorporated into the metal lattice is released again to the double molecular sulfur gas (S (2-) g) or phosphorus gas (Pg) (substitution reaction); the metal oxide is partially regenerated or reduced back to the more energetic state.

In the third production step, the metal pyrite lattice is broken up by a roasting process at somewhat higher temperatures of approx. 1200 ° C to 1350 ° C, whereby sulfur dioxide and sulfur trioxide are produced again. The reaction space is then flushed with nitrogen and the gases are separated off.

Overall, with the help of the metals acting as a phantom catalyst

Splitting water vapor into its elements. The metals used are in elementary state optimally with vanadium particles homogeneously distributed iron particle beds.

• [0016]

• Facts of the production process / reactions (background information)

1st production step in the thermochemical cycle process in the FERROHYDRO-PORYLESER TUBE REACTOR

At temperatures of 560 ° C to 1350 ° C, iron (II, III) and iron gas (H2) † are formed from iron and water vapor.

3 fat test + 4 H20 gas † —► Fe304 solid + 4 H2 gas † (exothermic)

Iron water iron (ll) oxide hydrogen

2. Production step in the thermochemical cycle process in the FERROHYDRO-PORYLESER TUBE REACTOR

At temperatures above 1200 ° C the iron (III) oxide reacts to iron (II) oxide and oxygen (O2).

6 Fe203 solid 4 Fe304 solid + 02gas † (endothermic) iron (III) oxide iron (II) oxide oxygen 3rd production step in the thermochemical cycle process in the FERROHYDRO-PORYLESER TUBE REACTOR

At temperatures above 1200 ° C to 1350 ° C, pyrite (FeS2) is formed from iron (II) oxide and sulfur gas (S2-). From SO2 † + vanadium (V) SO3 † should be approx.

below 600 ° C to 450 ° C (exothermic). In the further course of the reaction, the pyrite reacts to the elemental iron.

4. Production step in the thermochemical cycle process in the FERROHYDRO-PORYLESER TUBE REACTOR

Various iron sulfur and its oxide compounds are regenerated at Tl = x <650 ° C (equilibrium reaction exothermic) and roasted at TU † = 1200 ° C to 1350 ° C, whereby elemental iron and vanadium (IV) oxide are formed. The reaction requires energy and is therefore endothermic in the second regeneration step.

5th production step in the thermochemical cycle process in the FERROHYDRO-PORYLESER TUBE REACTOR

After the regeneration has taken place, a rinsing process is carried out under vacuum and then under an inert gas atmosphere until the sulfur trioxide residual gas (SO3) finally passes through an H20 scrubber. The by-product converts to sulfuric acid (H2S04 solution) via sulfuric acid (H2S03 solution) + H20 (demin.). In the end, the oleum (H2S207 solution) is formed.

S03 (gas) † + H2OJ, - »H2SO3 + H2SO4 (both in solution) -> H2S2O7 (exothermic)

Sulfur trioxide water sulfuric acid sulfuric acid oleum 6. Process step in the thermochemical cycle process in the FERROHYDRO-PORYLESER TUBE REACTOR

The reactor is flushed completely with nitrogen and thereby for the rest

Hydrogen fission cycle (production) prepared.

All of the process steps mentioned can be summarized as follows.

Splitting step: M (elementary) + H20 (eq) —► M30 ₄ (oxidized) + 4 H2 (gas)

Regeneration steps: M304 (oxidized) + S (gas) - MxS2 (reduced) + MS04 + S03 (gas)

Roasting and washing: MS2 (reduced) + M2S2 (reduced) + S03 (gas) - M (elementary) + H2SO4

Rinsing and drying: Nitrogen gas (N2) flushes and dries the iron in the pipe without water.

In the end, the elemental metals are available for the further production of hydrogen in the evacuated DRR

. [0017]

A significant innovation of the process is the combination of a metal bed made of at least two metals - firstly made of iron and secondly made of vanadium

Pressure tube reactor module or double jacket pressure reactor can be heated.

Inside these devices are the metal redox system and the vanadium catalyst, which are able to reversibly split water vapor and can be self-regenerated. For this purpose, primarily porous, finely divided metals in particle form (x <50pm), which act as heat radiation absorbers, are mixed with the vanadium catalyst and brought to auto-oxidation. This process has advantages over comparable processes, since here the complete production cycle process can be carried out in a single pressure tube reactor room. This means that no solids have to be circulated; and by binding the oxygen to the metals, product separation is reduced to two gas separations. This synthesis system also enables the

Let the water splitting process take place at significantly lower, technically controllable temperatures. In particular, the iron-vanadium system used as a catalyst is recovered, so that only water vapor and

Sulfur is consumed. All of these technical advantages also open up economic and ecological advantages over other production processes

Hydrogen production. An additional benefit is that the heat required for the reactions can also be supplied from the particle bed.

. [0018]

The iron and vanadium powder fill, which is evenly distributed with metals, forms the mixture in a modular pressure tube reactor, which is fixed in a cylindrical basket. By coupling to a light concentrating solar system (preferably a solar gutter collector in a vertical design), the metal powder filling in the

Porylysed ruckroh rreaktor brought to the required temperature by the concentrated sunlight. The reactions take place on the surface of the

Metal powder filling takes place inside the pressure tube reactor. The pressure tube reactor is preferably in a small pilot plant for checking and optimizing the

Operating behavior integrated during water splitting and regeneration as well as during roasting and rinsing. This pilot plant primarily comprises

Fittings and mass flow controllers for supplying the required gases

Water vapor dosing system, the data acquisition and control systems and measuring systems for pressure and temperature as well as for the product gas aftertreatment. The analysis of the concentrations of hydrogen gas produced or of released sulfur dioxide gas and sulfur trioxide gas is carried out by a mass spectrometer. . [0019]

For optimal use of the pressure tube reactor, it is necessary that a

continuous flow operation to produce the product hydrogen can take place. The three reactions are with different physical conditions

to be carried out one after the other: There must be a periodic change of the time

Reaction conditions or the gases and the required amounts of thermal energy (temperatures).

. [0020]

In the process engineering process according to the invention, all reversible steps of the chemical reactions are successively in the same in the same

Reaction space carried out. Thus, the separation or isolation from

Intermediate products take place in succession. The process parameters can

can be set according to the driving style.

[0021]

The process parameters can be carried out by adapting the energy heating output, the recurring, cyclical temperature and by several gas changes in one reaction chamber.

. [0022]

It is necessary that the steam gas is split at a temperature in the range of 500 ° C to 900 ° C and the metal oxide is regenerated at a temperature of 450 ° C to 650 ° C with sulfur gas (S2-) or phosphorus gas. The metal pyrite is then roasted at a temperature of 900 ° C to 1350 ° C, producing elemental metal. With conventional thermal water splitting so far

Temperatures of a few thousand degrees can be used. The lesser now

Temperature range is technically easier to handle. [0023]

First and foremost, the required temperature in the reaction spaces of the modules is modified by periodically changing the heating output for the purpose of one

to cause continuous flow of product. The differentiated thermal positioning of the reactors and / or concave mirrors firstly causes synchronous reactions of water splitting at a given temperature and secondly causes regeneration at a lower temperature. The roasting process is carried out at higher temperatures than water splitting. The sequence of these different batch processes thus enables the continuous production of hydrogen.

. [0024]

The procedure is mainly according to the different

Energy demand quantities of the successive reactions involved are sequenced. The periodic change in the temperatures of the metals is achieved by modifying the energy heating power. First the split takes place, then the regeneration and then the roasting and rinsing.

. [0025]

Usually, the one required in this process (see point 0024)

Temperature are generated by burning fossil fuels and / or using the waste heat energy from the exhaust gas flow from vehicles, because common methods use these energy sources.

[0026]

The generation of the required temperature by means of light energy is also advantageous and essential because conventional energy generation systems by burning fossil energy is not resource-saving and light energy such as sunlight is available everywhere, even in space.

. [0027]

Primarily, sunlight can shine on the reaction modules with the aid of optical devices or arrangements in order to reach the required temperature. These optical devices can be built as paraboloid concentrators,

Solar tower systems, parabolic trough collectors, elliptical or spherical mirrors, solar ovens, or line-focusing concentrators. By means of solar-thermochemical water splitting, these optical structures can be used to generate hydrogen on a large industrial scale as a sustainable, secondary energy source without carbon dioxide emissions that are harmful to the climate.

[0028]

The reaction modules are mainly rotated on a turret device in order to align them with the radiation source and thus to change the heating power. This can be used to change the temperature at the same

Radiant heating output can be achieved easily.

. [0029]

Alternatively, the reaction paraboloid can be positioned by rotation so that the light from the radiation source is redirected to a desired module. This can also be used to change the temperature at the same

Radiant heating output take place easily.

[0030]

A third possibility for the methods listed in points 0028 and 0029 consists in the focus position of several mirrors arranged in fields or To change concave mirrors. A change in temperature can also be achieved in this way.

• [0031]

For the purpose of solar thermal heating power, mainly optical components are suitable for reducing and / or increasing the radiation of the solar energy.

For this one uses spatially displaceable or in terms of their

Light transmission variable optical half mirrors, diaphragms, deflecting mirrors or optical filters.

[0032]

It is common for the absorbed heat from the apparatus to be used to heat fluids by recycling starting materials. Ideally, pipes pass through the interior of the pressure pipe reaction space. The amount of heat that is absorbed is used to evaporate liquids or gases. It is advantageous if these fluids with other reactants, auxiliaries or

Heat transfer media are heated. With preheating, the fluids no longer require as much radiant heating power in the reactor room.

. [0033]

For the continuous flow production of hydrogen gas from water vapor on a surface of a metal and subsequent regeneration of the surface, it is advantageous if a periodically offset continuous production is carried out in at least two reaction spaces. Thus, in the process according to the invention, the hydrogen synthesis by water splitting can advantageously take place in one reactor and the regeneration of the metal oxide by sulfur and / or phosphorus gas reduction in a further reactor. These two steps are carried out simultaneously for the purpose of preparing the roasting in a further pressure tube reactor module.

The professional handling of all these steps is aligned in three vertically Pressure tube reactor modules are carried out, which hang on a turret device with a rotary motor.

. [0034]

The process is carried out in several successive production cycles in order to achieve continuous flow reproducibility. It is estimated that a production cycle takes 0.5 to 1.5 hours. With a dis-continuous flow process, this has above all economic advantages. With this method, the production cycles can also be significantly shorter or longer. By both

Production methods, the temperature and the concentration of hydrogen can be changed - until the metal filling capacity is completely exhausted.

. [0035]

The aim of the invention is achieved as follows: With the aid of a reactor for the thermal production of hydrogen from water vapor on a surface in a gas-solid phase reaction with at least two connected pipes, the gas stream of educt gases into and out of a reaction space

Product gases out of this reaction space. One is also necessary

Heat source, at least two metals being provided as reactants in a reaction space.

. [0036]

The required temperature in the reaction rooms of the pressure tube reactors is changed by a periodic change in the heat output, which results in a continuous flow of production. The modified thermal control of sunlight on the pressure tube reactors enables the simultaneous reaction sequence of water splitting at a certain temperature and

Regeneration at a certain low temperature. The sequence of these different processes ensures a cascade-like one

continuous hydrogen gas production. The first pressure tube reactor has a connected cooling pipe system, which enables a liquid flow (permeate) into the reaction space of the first pressure pipe reactor and a flow of water vapor from the cooling system, which feeds into a second pressure pipe reactor.

• [0037]

There is yet another variant to achieve the object of the invention: the use of a double-jacket reactor for the thermal production of hydrogen from water vapor on a surface in a solid-phase gas reaction. Connected to this reactor is at least one cooling pipe system and two gas pipes which carry a gas stream of educt gases into and out of a reaction vessel

Allows product gases out of this container. A heat source (e.g. engine exhaust or turbine exhaust nozzle) is required, whereby the metal powders iron and vanadium (each <50pm) are provided as reactants in a reaction chamber.

[0038]

The metal powders are preferably of one in the double-jacket reactor

heat-resistant and scale-resistant double jacket material made of NiMo16Cr15V enclosed around the exhaust duct. This double jacket has the advantage that the metals are not destroyed, so they are always available and are optimally exposed to the heat source in the jacket reactor.

. [0039]

Feed water cooling is also required so that the operating conditions (i.e. the heating output) can be varied. In addition, the sulfur regeneration is made possible with at least one connected pipe, which allows a gas flow of starting gas into a reaction vessel and product gases out of this vessel. [0040]

The following metals are particularly popular for the metal powder fillings in the pressure tube reactor rooms: iron, manganese and nickel. Vanadium is or are added to one or more of these substances. In addition to the favorites mentioned, the following metals can also be used: Ti, Li, Cr, Er, Hf, Ho, Lu, Mo, Nb, Os, Pd, Re, Rh, Ru, Sc, Si, Ta, Tc, Tb, Th, Tm, Ti, W, Y, Zr, Co. These metals can also be used as individual substances or as mixtures, since these - both in pure form and as a mixture - can be used particularly efficiently in hydrogen splitting, the melting point temperature must be above 1400 ° C. The higher the valence of the metal ion, the more hydrogen per atom can be generated.

• [0041]

The reaction chamber is cylindrical (tube) and blackened from the outside with heat-resistant black lacquer. The tube is covered with a transparent

Thermal radiation protection, a borosilicate glass tube (evacuated).

. [0042]

Ideally, there are components between the reaction space and the energy source that weaken and / or intensify the energy flow so that better control of the reactions is made possible.

[0043]

The heat exchanger tubes primarily contain a fluid (permeate), since this enables the heat exchange to be individually tailored. The water vapor is generated in one reactor and passed into another reactor, which is used to return the water vapor to the first reactor. [0044]

The reactor is equipped with two four-way valves (left and right of the module) to enable the gaseous starting materials to be fed in and the products to be discharged.

. [0045]

These two multi-way valves are preferably switched so that the

gaseous products can be discharged separately.

[0046]

The reactor turret is ideally of modular construction - from at least two, better still three reaction pressure tube reactors, since this makes the continuous flow process described above particularly easy to handle.

. [0047]

In particular, the two reaction modules are used alternately

Steam, sulfur gas and / or phosphorus gas or nitrogen supplied. The modules are then evacuated. The switching takes place in such a way that hydrogen production is constant over time.

[0048]

A concentrating solar thermal system is mainly used as the energy supplier - this includes the following variants: a paraboloid concentrator, a solar tower system, a sun oven, an elliptical or spherical mirror and a line-focusing concentrator. As an alternative to this, an engine exhaust or a turbine exhaust gas space can be used as an energy source, as explained above. [0049]

Ideally, the required radiant light output is achieved using a group of heliostats. The radiation power required for regeneration is made possible by another group of heliostats.

. [0050]

In the following, a functional model of a flow-continuous pressure tube reactor is presented and described in more detail with the aid of a schematic representation. In addition, with the help of another schematic representation

Solar thermal pilot system presented, which is also conceivable in other model versions. At this point it should be emphasized that the patent protection claims are not limited to the two schemes presented, but also include other good, basically similar model versions. This fact enables me to realize my invention as an independent, coherent unit of invention of my ideas.

[0051]

The inventive method of solar-thermochemical water splitting based on metals with sulfur gas regeneration for continuous flow

Hydrogen gas generation can be done using the pressurized gas reactor presented

almost continuously - almost continuously. The pressure inside the pressure tube reactor will ensure even more hydrogen yield. If the pressure in the apparatus increases, the chemical equilibrium shifts in favor of the product (H2) on the right side of the reaction equation.

(see RG. [16.1]). The same procedure also works for the regeneration with sulfur gas and / or phosphorus gas products, so the pressure

Reaction speeds up, which results in faster regeneration. • [0052]

It is presented and documented:

• First, a perspective schematic representation (vertical horizontal section) of the flow-continuous pressure tube reactor module system according to the main subject of the invention

To [0053]

Drawing No .: 01 shows the pressure tube reactor module system, whereby the water vapor is fed into the apparatus with a four-way valve from the left side. The sunlight-focused radiation energy is transferred from the outside to the

Pressure tube reactor module blasted. The energy heating power of the incident light can be adjusted by means of an aperture. The pressure tube reactor is based on the already described connection of the metal-gas system with a metal powder filling inside, which consists of a finely divided, loose particle powder structure (10). The metal powder filling is in a modular cell; it is filled with the metals and installed in a cylindrical tube housing (10).

The borosilica glass (evacuated) enables high temperatures to be generated in a directly absorbing vacuum with low reflection losses (9).

Point (01): superheated steam inlet (from return)

Point (02): steam pipe made of high-alloy steel Point (03): four-way valve (heat-resistant, pressure-resistant)

Point (04): Suction line for vacuum and sulfur gas outlet Point (05): Bellows left end cap

Point (06): left flange connection to the pressure chamber or reaction chamber Point (07): nitrogen purge line entrance

Point (08): return cooling system line (water vapor from feed water)

Point (09): Borosilica glass 3.3 (evacuated)

Point (10): reactor pressure chamber line made of scale-resistant material

Filled with finely divided, loose particle powder structure of the metals iron and vanadium

Point (1 1): Feed water cooling system with ring line in the center of the chamber Point (12): Bellows right end cap

Point (13): flow of cooling system line (permeate from reverse osmosis system) Point (14): right flange connection to the pressure chamber or reaction chamber Point (15): nitrogen purge line outlet Point (16): four-way valve (heat-resistant, pressure-resistant)

Point (17): Hydrogen gas line outlet for measurement

Point (18): sulfur gas line entry

Point (19): safety valve

Point (20): Downstream processing plants

-004-

Legend of drawing no .: 01/01 (only pressure tube reactor without lines)

Dimension x-direction = 1: 20cm; Dimension y-direction = 1: 1 cm;

Name of the artist: WANDZIK, Christoph, Gregor Date: 07.07.2018

Title: Perspective schematic representation (vertical horizontal section) of the flow-continuous pressure tube reactor module system (WANDZIK ^'s tube)

(see drawing 1 / page 1/1) [0054]

The operation of the flow reactor is based on the simultaneous use of both modules. While water is split in one of the two reaction rooms, regeneration with sulfur gas takes place in the other reaction room. After the reactions have ended, the regenerated module is switched over to cleavage by changing the gas supply. Requirements for this continuous operation and the

Hydrogen production is the separate supply of nitrogen gas, which is called

Carrier gas or purge gas is used, as well as the same supply of water vapor. In addition, another line is on the one hand for the products of the cleavage and on the other hand for the regeneration gas containing regeneration gas

necessary. This is made possible by two four-way valves, each after

Completion of a reaction step can be switched. One of these valves has to withstand high temperatures up to 600 ° C.

• [0055]

The two steps of the process are carried out in the same reactor at different temperature levels with different heat requirements. The

Regeneration is endothermic and takes place at 450 ° C. The steam splitting is slightly exothermic and takes place at 900 ° C. This is why some of the modules are required

(Regeneration) a lower solar flux density than the second part for the

Water splitting, which requires a lot of energy flux density to compensate for heat losses. It is therefore necessary to change the irradiance cyclically if the cycle is switched from regeneration to fission or vice versa. For this purpose, the mirror focus is changed between two identical focal lines by a suitable adjustment of the concentrating mirrors of the solar system. The periodic change in the irradiance is achieved by time-varying optical components, e.g. B. by optical gratings as attenuators, deflecting mirrors or semi-transparent mirrors. Such a component is movable and is in front of one of the two devices. When the gas supplied is changed, its position can be switched accordingly. Also possible, but technically

It is more time-consuming to change the position of the receiver over time between locations with different levels of radiation. [0056]

Advantages and conclusion on Wandzik ^'rule pipe

1 1.0) Carbon dioxide free, chlorine free, halogen free chemistry

12.0) High yield of hydrogen

13.0) Low costs for the construction and operation of the plant

14.0) Space-saving, vertical construction possible

15.0) Conserving resources through regeneration of the reactants

16.0) Several versions of the invention in all technical fields

17.0) Use of different metals possible

I recommend this invention for humanitarian use and look forward to working with experts and the German Patent Office. Thank you very much!!!

Appendix (2 pages) -005-

• QUOTES CONTAIN IN THE DESCRIPTION (Appendix [(2 Pages)])

This list of documents listed by the applicant has been generated automatically and is only included for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

Chemical engineering Europe Teaching aids Europe no. : 70415 6th edition page: 415 DRR or DE 2438264 C2 [0004]

o EP 1019316 B1 [0005]

o DE 102005017216 A1 [0008]

o DE 2634662 C2 [0009]

Patent quotes

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Sun Ventures

DE2438264C2 8 Aug. 1974 18 Feb. 1988 Inc., St. Davids, title not available

Pa., Us

Ga Technologies

DE2634662C2 Aug. 2, 1976 March 19, 1987 Inc., San Diego, title not available

Calif., USA

German

Thermal

Center for air

Apr 14th Hydrogen production

DE102005017216A1 Oct. 19, 2006 and

2005 in a gas

Space technology

Solid phase reaction e.V.

EP1019316B1 May 5, 1999 March 24, 2004 Shec Labs - Method for

Solar Hydrogen Manufacturing Patent cited Registered Date of publication Applicant Title

Energy hydrogen through

Corporation thermal

water decomposition

Classifications

International classification C01 B3 / 22. C01 B21 / 082. C01 B31 / 30

Y02E60 / 364. C01 B3 / 042. C01B3 / 045. C01 B13 / 0207.

Company classification

CO 1 B21 / 0828. C01 B3 / 22

Legal events

Date Code Event Description

4th Sept. Change of Representative = name: SCHNEIDER, CLAUDIA,

R082

2014 representative DIPL.-ING., DE

Oct. 23 Utility model

R207 Effective date: 20141023

2014 specification

Process for the production of hydrogen by thermal water decomposition EP 1019316 B1

Claims

Claims [(31) 8 pages] -001 -

1. The invention relates to a method by means of a reactor for the continuous flow of several chemical reactions on the

Surface of two solid reactants in a gas-solid phase reaction whereby, the invention is based in particular on a thermal process with the aid of a pressure tube reactor for the continuous flow production of hydrogen from water vapor, which is based on the surfaces of a metal powder filling, which is composed of elemental iron and vanadium thermal sulfur gas or phosphorus gas regeneration, is provided to restore the basic educt metals.

Abbr .: DRR: pressure tube reactor

2. The invention relates to a thermal process for the production of hydrogen from water vapor. On an enlarged, porous surface of a metal bed, which consists of at least two metals, a gas / solid phase reaction occurs relatively quickly in flowing operation

Pressure tube reactor realized, which is characterized in that

2.1) In a reaction pressure tube reactor, the first step

Steam gas generated with an energy source. Two processes are now taking place inside the reactor, which is filled with at least two metals (iron and vanadium):

2.2) In the pyrolysis reaction, the addition of

Oxygen on the thermally highly excited

Metal surfaces. The chemical compound (H20g) is broken down. Hydrogen gas (H2) is released and oxygen gas (O2) is bound to the metal surfaces. In a second step, the metal oxide is regenerated with sulfur gas (S2-) or phosphorus gas (P) at a lower temperature than the first process step.

3.1) Through a substitution conversion reaction, the bound oxygen is replaced by sulfur oxides or phosphorus oxides. The bound gases are created from the converted metal oxide fill: sulfur dioxide and sulfur trioxide.

3.2) The released sulfur dioxide is at the

excited metal surface of a vanadium catalyst accelerated to react, so that the metal pyrite formed is available for further reactions. In a third step, the solid phase gas reactor for carrying out this process is again - as in

Process step one - brought to an elevated temperature, whereby the pyrites are roasted and only

Sulfur trioxide remains. (Traces of sulfur dioxide) At the end of the cyclical cycle, sulfur trioxide and elementary metals iron and

Vanadium.

5.1) The sulfurous gases are fed out with inert gas nitrogen and dissolved in the gas scrubber to sulfuric acid.

5.2) The reactor is evacuated and brought to temperature

brought. The regeneration of the solid phase is only completed after the third process step. Now the elementary are Redox metals are available for further hydrogen production.

3. The method according to claim 1 and 2, are characterized in that one

1) Steam gas in DRR. splits at a temperature in the supercritical range of 500 ° C to 900 ° C,

2) and with the metal oxide at a temperature of 450 ° C to 650 ° C

molecular sulfur gas (S2-) or phosphorus gas regenerates and,

3) then roasted at 1000 ° C to 1350 ° C and flushed with nitrogen and evacuated.

4. The method according to claim 1 and / or 2, wherein according to the

different amounts of heat for the reactants involved

has to ensure different individual reactions to be carried out by means of a periodic change in the temperature of the metal powder in the pressure tube reactor by adjusting the solar heating power.

5. The method according to any one of claims 1 to 3, wherein the required temperature is generated on the blackened DRR surface by focusing solar energy by means of solar systems and / or using waste heat energy from internal combustion engines.

6. The method according to any one of claims 1 to 3, wherein the required temperature is generated by light energy from channel collectors via internal combustion engines with an exhaust system and / or up to the radiant heat of nuclear reactors.

7. The method according to any one of claims 1 to 6, characterized in that

following features:

1) the sunlight shines onto the blackened surface of the pressure tube reactor with the aid of optical devices or arrangements, 2) until the required temperature is reached. The heat transfer should transport the necessary amount of heat to the inside of the DRR.

8. The method according to claim 5 or 6, wherein the pressure tube reactor

aligned with the radiation source on a turret device in order to change the heating power, thereby advantageously the

Circulation process optimally used.

9. The method according to any one of claims 5 to 7, wherein the optical

Devices (mirrors and / or lenses or light screens) for

Pressure tube reactor adjusted to or away to vary the radiant heating power.

10. The method according to any one of claims 1 to 8, wherein optical lenses and / or mirrors are used which maximize the radiation or minimize it by means of diaphragms and thereby change the solar thermal heating power.

11. The method according to claim 9, wherein one of the focused light energy

optical components or by rotating the turret, the required heating of return liquids is achieved.

12. Thermal process first for the continuous production of

Hydrogen gas (H2g) from water vapor gas (H20g) on the surface of a homogeneous metal powder filling and secondly to the subsequent one

Regeneration of the surfaces according to the preceding claims 1 to 10, wherein the production of hydrogen gas (H2g) is carried out in at least two pressure tube reactor modules.

13. The method according to claim 1 1, wherein one adjusts the required temperature in the reaction spaces by a periodic change in the radiant light heating power and thus a continuous flow

Product mass flow that enables DRR.

14. The method of claim 1, wherein the radiant energy is heated

Pressure tube reactors are identified as internal reaction spaces and can be produced in a modular, commercial manner by a specialist.

15. The method according to claim 1 and 2, wherein the temperature is first regulated to a range of 500 ° C to 900 ° C. Is characterized in that

7.0) as soon as the capacity of the metals is exhausted

8.0) the temperature is set in a second step in a further reaction space to a range from 450 ° C to 650 ° C.

9.0) Subsequently, the

Temperature brought to 1350 ° C.

10.0) Furthermore, the

Temperature sank with nitrogen to a range of 500 ° C to 900 ° C.

16. The method according to claim 1 1 and / or 14, wherein a cyclical change in the temperature of the metals is brought about by careful gradation and gradation of the heating power - depending on the different

Energy requirements of the reactions involved are set by means of counterflow cooling installed inside the DRR.

17. The method according to claim 1 to 15, wherein the exchange of gas flows in and out is regulated by means of two pipes with two four-way valves.

18. The invention relates to a hydrogen pressure tube reactor

(Wandzik ^'s pipe), which is said to cause a gas / solid phase reaction.

The pressure tube reactor is characterized according to the following features:

1.0) is made of hydrogen scale resistant alloys such as NiMo16Cr15V or NiMo16Cr15W,

2.0) which is covered by a borosilicate glass tube,

3.0) There is a vacuum of between the glass envelope and the pressure pipe

X S10 - 3 mbar,

4.0) the surface of the pressure pipe is covered with a layer

heat-resistant carbon lacquer intensely blackened.

5.0) Inside the pressure tube reactor there is a homogeneously distributed iron-vanadium powder reaction medium bed

(Grain size x <50 pm),

6.0) On the left and right at the pipe inlet and outlet there are four-way pressure valves (x> 20 bar / x> 600 ° C),

7.0) There is a pressure relief valve at the pipe outlet

(corresponding to the nominal pressure of the reactor).

19. Reactor for the thermal production of hydrogen gas (H2g)

Steam gas (H20g) on a surface in a solid-phase gas reaction with at least two connected pipes, which allow a gas flow of educt gas into a reaction chamber and out of product gases. The inner tube is provided with distribution holes and serves to introduce the regeneration gases, the reaction space comprising at least one metal as a reactant.

20. Reactor according to claim 18 and 19, wherein the metal is present in a homogeneously distributed, loose metal powder bed, which is fixed in a permeable container (basket) or on a coated membrane.

21. The reactor of claim 20, wherein the metal structure is a porous

Vanadium powder addition (x> 50 pm) included.

22. A reactor according to any one of claims 18 to 21, wherein the metals comprise iron, manganese and vanadium.

23. Reactor according to one of claims 18 to 22, wherein the metals of the

elementary properties and the operating conditions must correspond. These are all metallic elements that stably correspond to the temperature range from 500 ° C to 1350 ° C and do not melt or evaporate.

24. Reactor according to one of claims 18 to 23, wherein the metals are mixtures of the elemental metals.

25. Reactor according to one of claims 18 to 24, wherein the pressure tube reactor contains a temperature sensor and a pressure sensor, and a

Product volume measuring device included after the product flow.

26. Reactor according to one of claims 18 to 25, which comprises a four-way valve for supplying the gaseous starting materials.

27. A reactor according to any one of claims 18 to 25, which comprises a four-way valve for separating the gaseous products.

28. Reactor according to one of claims 18 to 27, wherein the reactor has a modular structure:

- With screwable parts of a pressure pipe, in the

inside a metal powder filling is fixed.

- A fold bar is installed at the beginning and end of the DRR to compensate for the linear expansion of the DRR.

- The DRR has pipes with suitable flanges for the unmistakable joining of the four-way valves and the connection lines, the upstream and downstream systems.

29. A reactor according to any one of claims 18 to 28, which comprises two four-way valves. These valves can alternately supply the reaction spaces with water vapor and nitrogen or sulfur, phosphorus or vacuum.

- There is a metering circuit at the tube outlet, which enables hydrogen to be produced at a constant rate.

- In addition, a pressure safety valve (x> 25 bar) is available at the pipe outlet to avoid pressure peaks and to ensure safety.

30. Reactor according to one of claims 18 to 29, wherein according to the following

Features of the reactor as an energy source one of the following

uses solar thermal systems:

- solar tower systems,

Paraboloid channel concentrators

Solar ovens - elliptical or spherical mirrors,

- line focusing concentrators,

Alternatively, the use of any is possible

Internal combustion engines with exhaust system, all turbine engines with exhaust system, all electric motors, all fuel cells, all chemical production systems such as galvanic cells, electrolysis or arc furnaces, etc.

31. A reactor according to claim 30, wherein the reactor uses heliostats to achieve the radiant heating power and heliostats for the regeneration of the required radiant heating power, the latter heliostats being convertible to individual reaction fields.