WO2010057875A1 - Metal tablet for use as a corrosion element or as an anode in gas generation cells for generating hydrogen for conveying flow-capable materials in mechanical spraying - Google Patents
Metal tablet for use as a corrosion element or as an anode in gas generation cells for generating hydrogen for conveying flow-capable materials in mechanical spraying Download PDFInfo
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- WO2010057875A1 WO2010057875A1 PCT/EP2009/065288 EP2009065288W WO2010057875A1 WO 2010057875 A1 WO2010057875 A1 WO 2010057875A1 EP 2009065288 W EP2009065288 W EP 2009065288W WO 2010057875 A1 WO2010057875 A1 WO 2010057875A1
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- Prior art keywords
- metal
- powder
- composition according
- zinc
- hydrogen
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 52
- 239000002184 metal Substances 0.000 title claims abstract description 52
- 239000001257 hydrogen Substances 0.000 title claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000007789 gas Substances 0.000 title description 15
- 238000005260 corrosion Methods 0.000 title description 12
- 230000007797 corrosion Effects 0.000 title description 12
- 239000000463 material Substances 0.000 title description 2
- 238000005507 spraying Methods 0.000 title 1
- 239000000843 powder Substances 0.000 claims abstract description 24
- 230000000737 periodic effect Effects 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000002923 metal particle Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 40
- 229910052725 zinc Inorganic materials 0.000 claims description 29
- 239000011701 zinc Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 238000011109 contamination Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 229910000365 copper sulfate Inorganic materials 0.000 claims 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims 1
- 150000002815 nickel Chemical class 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 210000004027 cell Anatomy 0.000 description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000005662 Paraffin oil Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000007868 Raney catalyst Substances 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000009969 flowable effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- XTPJLNSARGBDNC-UHFFFAOYSA-N 3-[diethyl(prop-2-ynyl)azaniumyl]propane-1-sulfonate Chemical compound C#CC[N+](CC)(CC)CCCS([O-])(=O)=O XTPJLNSARGBDNC-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000528 Na alloy Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000005267 amalgamation Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 208000033921 delayed sleep phase type circadian rhythm sleep disease Diseases 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical class C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Definitions
- Metal tablet for use as a corrosion element or as an anode in gas evolution cells for generating hydrogen for the conveyance of flowable substances in mechanical syringes
- the present invention relates to means for generating hydrogen from aqueous solution in which metal particles are contaminated or coated with a nobler metal and formed into tablets with the aid of a thermoplastic.
- polytetrafluorethylene as a pressing aid. Thereafter, the preparation can be carried out so that zinc powder is introduced into the solution of a salt of a metal from the 8th column of the Periodic Table of the elements with acidic pH and that the zinc powder is then washed, dried, optionally mixed with polytetrafluoroethylene powder and then compressed into tablets.
- a variant of the method for producing an agent is characterized in that zinc powder is provided by treatment with metal formate solution or by treatment with metal formate powder on the surface with a precipitate of formate, that the powder then optionally with the aid of a thermoplastic binder to Tablets is pressed and that the formate is decomposed by heating to a temperature above its decomposition temperature at the end or before pressing. It is also described that instead of formate another thermally decomposable salt of an organic acid can be used.
- the preferred supplementary steps also include the use of paraffin oil with the variants referred to as white oil within the cell as a diaphragm-like valve disc and as a seal and covering of the metal parts of the cell vessel.
- the known hydrogen evolution cell contains a zinc anode and a porous Raney nickel cathode mixed with carbon in a metal can body of the cup and lid with an insulating plastic gasket therebetween. Potassium hydroxide as the electrolyte connects anode and cathode.
- the present invention is a metal corrosion element with a defined hydrogen evolution rate from aqueous solution.
- the element now also consists of metal powder whose particles are superficially contaminated with a foreign metal.
- the metal of the metal powder is a non-noble metal, which tends to go in contact with water to form hydrogen and metal oxides or metal hydroxides in solution.
- the invention provides the means of claim 1 and the method of claim 8. Advantageous embodiments are given in the dependent claims. The use of claim 10 is also created.
- Zinc can be used advantageously as the metal powder.
- the property of zinc as Metal corrosion element is in apparent contradiction to the industrial use of zinc as corrosion protection on iron.
- the cause of this use of zinc is the high hydrogen overvoltage, which has pure zinc metal and kinetically hinders the described solution process of zinc.
- metal impurities of zinc accelerate corrosion if they are made of low hydrogen overvoltage metals, but on the other hand metal contaminants can also hinder corrosion tendency. Accelerating effect is achieved by elements such as nickel, palladium and iron, while cadmium, lead and especially mercury improve the corrosion resistance of the zinc. Therefore, the amalgamation of zinc anodes has been a practiced practice in primary cell technology for many decades.
- liquids such as water and greases of very different consistency can be promoted by means of gas-evolving elements.
- a massive zinc disk is used, into whose central bore a cylindrical molybdenum rod is soldered in.
- this element continuously evolves a certain amount of gas, adjusted to the operating time of 1 to 12 months, due to the electrochemistry of molybdenum
- a series of operations such as soldering the molybdenum rod into the zinc bladder and amalgamating it, are required to make the element, so it was a great progress to say that, according to DSPS 36 02 214 - Hydrogen developing element with uniform properties even for a long Be could produce operating time. In this one starts from a pure zinc powder, which is superficially coated with a foreign metal and pressed into tablets.
- This invention follows some of the manufacturing steps described in DS-PS 36 02 214, but turns their philosophy on its head.
- zinc powder with a uniform grain size is coated with a nobler foreign metal.
- Copper is preferably used for this purpose, which is admixed to the zinc as a fine powder. Its effect is contrary to that of nickel in DS-PS 36 02 214. In contact with the zinc metal, the copper remains metallic; its surface oxides are even reduced to form zinc oxides. This is contrary to contamination with Ni, which promotes corrosion of the zinc in contact with an aqueous solution. If you press tablets out of this powder, they have good electronic conductivity. It remains intact for a long time due to the copper bridges, even if the tablet develops hydrogen when immersed in a corrosive solution.
- Hydrogen evolution is the purpose of the corrosion element: it is hindered by the coverage of the zinc surface with the copper layer, because both copper and zinc have high hydrogen overvoltage levels.
- the corrosion solution is contaminated with the salt of a metal having the following properties:
- nickel is a metal of the eighth column of the Periodic Table of Elements, for example nickel.
- copper is very suitable as a metal for porous electrode frameworks in combination with nickel as a catalyst.
- the changed handling of the metallic components of the zinc tablet also allows other manufacturing steps. So you can copper the zinc powder by entering it in a galvanic copper plating, washes and dries. As a pressing aid you can use polyethylene, polytetrafluoroethylene and other plastic powders. The mixture is reactively mixed in a high speed mixer and rolled into a ribbon. From these tablets are punched. It is also possible to strike the rolled strip once more and to form the resulting powder into tablets in a tabletting machine.
- the partially hydrophobic pore framework of the tablet Provided by the partially hydrophobic pore framework of the tablet, large hydrogen bubbles are produced in operation which dissolve from the surface from time to time. It is only important that the pressing aid obtains the powder sufficiently free-flowing, so that it can be formed in a tableting machine.
- the cell shows the open voltage of the zinc / air cell of 1.4 V. If one connects the anode and cathode with a Si diode in the direction of flow, cells present in the cell or in the cathode metal (eg Raney Nickel) reduces built-in oxygen.
- the cell voltage is reduced to the characteristic voltage of the diode, for example, 0.69 V. In this case, the current flow between anode and cathode is reduced to less than 1 ⁇ A, whereby the cell voltage remains at the characteristic lock voltage.
- the cell has the usual respiratory hole, a current equivalent to the incoming oxygen will flow. This is greatly reduced by the arrangement of paraffin oil within the cell, called the "valve disc".
- the unwanted migration of oxygen into the cell corresponds to useless self-discharge of the cell without the desired hydrogen production.
- a batch of the described cells may be immersed in a bath of white oil (paraffin oil) and mildly evacuated in a desiccator. So in the cell existing gas (air) is sucked off and replaced by paraffin oil.
- the paraffin oil seals the gas pores and also the leaks between the metal surfaces and the plastic seals against the ingress of air, without hindering the removal of the hydrogen formed in the cell.
- this device has been referred to as a "valve disc".
- metals and alloys are used which are even more negative than zinc, based on the reversible hydrogen potential, such as e.g. Aluminum, magnesium and the alkali metals.
- alloys such as e.g. an alloy of aluminum and sodium are suitable for this purpose.
- An aluminum / sodium alloy is decomposed in alkaline solution with hydrogen formation, with simultaneous formation of sodium hydroxide solution.
- Fig. 1 Schematic representation of a circuit with a gas evolution cell.
- the gas evolution cell 1 shows the circuit of a gas evolution cell 1.
- the gas evolution cell 1 has a diode 2 and a resistor 3 for conditioning.
- the cell 1 is provided with a sticker which covers an opening 7.
- the gas evolution cell 1 dips into a bath of paraffin oil 6. Even a partial immersion in a paraffin oil bath is possible.
- a switch 4 starts the hydrogen evolution.
- the gas outlet takes place through the opening 7 in the paraffin oil.
- the paraffin oil prevents the entry of water vapor or oxygen through the opening 7 in the cell first
- the two positions of the switch 1 characterize the two operating states of the gas evolution cell 1 "in” and ".”
- the diode 2 shorts the cell and allows the flow of current through the cell 1 and thus the gas evolution, but only when the cell voltage is greater than the lock voltage.
- the cell is discharged independently of the cell voltage via a resistor 5 with evolution of hydrogen.
- the comparison circuit of two hydrogen evolution cells of the same type allows the measurement of the oxygen inlet from the exhaust gas of a chemical or electrochemical reactor according to DE-AS 1 153 551 (1961).
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hybrid Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Powder Metallurgy (AREA)
Abstract
Means for generating hydrogen from aqueous solution, wherein metal particles are coated with a noble metal, wherein the metal powder is compressed into tablets after the surface of the powder is contaminated with a fraction of 0.1 to 10 atom% of a metal from the 11th column of the periodic table of the elements, said fraction relative to the total amount of metal and optionally after mixing with untreated metal powder.
Description
Metalltablette zur Verwendung als Korrosionselement oder als Anode in Gasentwicklungszellen zur Erzeugung von Wasserstoff für die Förderung von fließfähigen Stoffen in mechanischen Spritzen Metal tablet for use as a corrosion element or as an anode in gas evolution cells for generating hydrogen for the conveyance of flowable substances in mechanical syringes
Gegenstand der vorliegenden Erfindung sind Mittel zur Erzeugung von Wasserstoff aus wässriger Lösung, bei denen Metallteilchen mit einem edleren Metall kontaminiert oder beschichtet und mit Hilfe eines Thermoplasten zu Tabletten ausgeformt sind.The present invention relates to means for generating hydrogen from aqueous solution in which metal particles are contaminated or coated with a nobler metal and formed into tablets with the aid of a thermoplastic.
Der Stand der Technik ist am nächsten durch die DE-PS 36 02 214 C l beschrieben. Darin wird Zinkpulver nach Kontaminierung seiner Oberfläche mit einem Anteil von 0.1 bis 10 Atom - % eines Metalls der 8. Spalte des Periodischen Systems der Elemente bezogen auf die Gesamtzinkmenge und ggf. nach Vermischen mit unbehandeltem Zinkpulver zu Tabletten verpresst. Weiterhin wird dort beschrieben, dass das Kontaminationsmetall vorteilhaft Nickel ist. Auch wird beschrieben, dass die Tablette aus einem Gemisch von Zinkpulver mit Raney-Nickelpulver zu Tabletten verpresst ist und dass als Press hilfsmittel ein Thermoplast enthalten ist.The prior art is described next by DE-PS 36 02 214 C l. In it zinc powder is compressed after contamination of its surface in a proportion of 0.1 to 10 atom -% of a metal of the 8th column of the Periodic Table of the Elements based on the total zinc amount and optionally after mixing with untreated zinc powder to tablets. Furthermore, it is described there that the contamination metal is advantageously nickel. It is also described that the tablet is pressed from a mixture of zinc powder with Raney nickel powder into tablets and that as a press tool a thermoplastic is included.
Als weiteres Kennzeichen wird die Verwendung von Polytetrafiuorethyien als Presshilfs- mittel beschrieben. Danach kann die Herstellung so erfolgen, dass Zinkpulver in die Lösung eines Salzes eines Metalls aus der 8. Spalte des Periodischen Systems der Elemente mit saurem pH- Wert eingetragen wird und dass das Zinkpulver danach gewaschen, getrocknet, ggf. mit Polytetrafluorethylen-Pulver vermischt und anschließend zu Tabletten verpresst wird.Another feature described is the use of polytetrafluorethylene as a pressing aid. Thereafter, the preparation can be carried out so that zinc powder is introduced into the solution of a salt of a metal from the 8th column of the Periodic Table of the elements with acidic pH and that the zinc powder is then washed, dried, optionally mixed with polytetrafluoroethylene powder and then compressed into tablets.
Auch wird eine Variante des Verfahrens zur Herstellung eines Mittels so gekennzeichnet, dass Zinkpulver durch Behandlung mit Metall formiat- Lösung oder durch Behandlung mit Metallformiat-Pulver oberflächlich mit einem Niederschlag aus Formiat versehen wird, dass das Pulver anschließend ggf. unter Zuhilfenahme eines thermoplastischen Binders zu Tabletten verpresst wird und dass das Formiat zum Schluss oder vor dem Verpressen durch Er- wärmung auf eine Temperatur oberhalb seiner Zersetzungstemperatur zersetzt wird. Auch wird beschrieben, dass anstelle von Formiat ein anderes thermisch zersetzbares Salz einer organischen Säure verwendet werden kann.Also, a variant of the method for producing an agent is characterized in that zinc powder is provided by treatment with metal formate solution or by treatment with metal formate powder on the surface with a precipitate of formate, that the powder then optionally with the aid of a thermoplastic binder to Tablets is pressed and that the formate is decomposed by heating to a temperature above its decomposition temperature at the end or before pressing. It is also described that instead of formate another thermally decomposable salt of an organic acid can be used.
Im Verlauf aufwendiger Untersuchungen zur Nutzung von Wasserstoff- Entwicklungszellen
für den Transport fließfähiger Substanzen verschiedenster Art wurde festgestellt, dass die erwarteten Systemeigenschaften von Zellen der in der DE-PS 35 32 335 (1985) und der US- PS 5,242,565 (1993) beschriebenen Art in stofflicher Hinsicht wesentlich modifiziert werden können mit der überraschenden Folge, dass auch die Verfahrens- und anwendungstechnischen Möglichkeiten modifiziert und ausgeweitet werden können. Dazu gehört die Aus- formung von Zylindern oder Hohlzylindern aus formbaren Pressmassen der betreffenden Metall- oder Legierungspulver unter Zuhilfenahme von Presshilfsmitteln, die man anschließend durch thermische Nachbehandlung verfestigt. Davon können praktisch identische Tabletten abgeschnitten werden.In the course of elaborate studies on the use of hydrogen development cells for the transport of flowable substances of various kinds has been found that the expected system properties of cells of the type described in DE-PS 35 32 335 (1985) and US Patent 5,242,565 (1993) can be substantially modified in material terms with the surprising result that also the process and application possibilities can be modified and extended. This includes the shaping of cylinders or hollow cylinders from moldable molding compounds of the relevant metal or alloy powder with the aid of pressing aids, which are then solidified by thermal aftertreatment. Of these, virtually identical tablets can be cut off.
Zu den bevorzugten Ergänzungsschritten gehört auch die Verwendung von Paraffinöl mit den als Weißöl bezeichneten Varianten innerhalb der Zelle als Diaphragma-artige Ventilscheibe und als Abdichtung und Bedeckung der Metallteile des Zellgefäßes.The preferred supplementary steps also include the use of paraffin oil with the variants referred to as white oil within the cell as a diaphragm-like valve disc and as a seal and covering of the metal parts of the cell vessel.
Doch auch die Verwendung einer Gleichrichterdiode spielt im Kontext mit der Wasserstoff- entwicklungszelle eine bedeutsame Rolle. Dieser Sachverhalt wird nachfolgend durch die Beschreibung der Bauelemente und deren funktionelle Verknüpfung kurz charakterisiert:However, the use of a rectifier diode also plays an important role in the context of the hydrogen evolution cell. This situation is briefly characterized by the description of the components and their functional linkage:
Die bekannte Wasserstoffentwicklungszelle enthält in einem metallischen Blechgehäuse aus Becher und Deckel mit einer isolierenden Kunststoffdichtung dazwischen eine Anode aus Zink und eine poröse Kathode aus Raney-Nickel in der Abmischung mit Kohlenstoff. Kalilauge als Elektrolyt verbindet Anode und Kathode.The known hydrogen evolution cell contains a zinc anode and a porous Raney nickel cathode mixed with carbon in a metal can body of the cup and lid with an insulating plastic gasket therebetween. Potassium hydroxide as the electrolyte connects anode and cathode.
Gegenstand der vorliegenden Erfindung ist ein Metall-Korrosionselement mit definierter Wasserstoff- Entwicklungsrate aus wässriger Lösung. Das Element besteht auch jetzt aus Metallpulver, dessen Teilchen oberflächlich mit einem Fremdmetall kontaminiert sind. Dabei ist das Metall des Metallpulvers ein unedles Metall, das bestrebt ist, im Kontakt mit Wasser unter Bildung von Wasserstoff und Metalloxiden bzw. Metallhydroxiden in Lösung zu gehen.The present invention is a metal corrosion element with a defined hydrogen evolution rate from aqueous solution. The element now also consists of metal powder whose particles are superficially contaminated with a foreign metal. In this case, the metal of the metal powder is a non-noble metal, which tends to go in contact with water to form hydrogen and metal oxides or metal hydroxides in solution.
Die Erfindung schafft das Mittel des Anspruchs 1 und das Verfahren des Anspruchs 8. Vorteilhafte Ausgestaltungen sind den Unteransprüchen zu entnehmen. Geschaffen wird auch die Verwendung des Anspruchs 10.The invention provides the means of claim 1 and the method of claim 8. Advantageous embodiments are given in the dependent claims. The use of claim 10 is also created.
Als Metallpulver kann vorteilhaft Zink verwendet werden. Die Eigenschaft von Zink als
Metallkorrosionselement steht in scheinbarem Widerspruch zur großtechnischen Verwendung des Zinks als Korrosionsschutz auf Eisen. Ursache für diese Verwendungsmöglichkeit des Zinks ist die hohe Wasserstoffüberspannung, die reines Zinkmetall besitzt und die den geschilderten Lösungsvorgang des Zinks kinetisch behindert. Es ist bekannt, dass Metallverunreinigungen des Zinks die Korrosion beschleunigen, wenn sie aus Metallen mit niedri- ger Wasserstoffüberspannung bestehen, dass aber andererseits auch Metallverunreinigungen die Korrosionsneigung behindern können. Beschleunigende Wirkung erzielt man durch E- lemente wie Nickel, Palladium und Eisen, während Cadmium, Blei und insbesondere Quecksilber die Korrosionsbeständigkeit des Zinks verbessern. Deshalb ist die Amalgamie- rung der Zinkanoden seit vielen Jahrzehnten geübte Praxis in der Primärzellen Technik.Zinc can be used advantageously as the metal powder. The property of zinc as Metal corrosion element is in apparent contradiction to the industrial use of zinc as corrosion protection on iron. The cause of this use of zinc is the high hydrogen overvoltage, which has pure zinc metal and kinetically hinders the described solution process of zinc. It is known that metal impurities of zinc accelerate corrosion if they are made of low hydrogen overvoltage metals, but on the other hand metal contaminants can also hinder corrosion tendency. Accelerating effect is achieved by elements such as nickel, palladium and iron, while cadmium, lead and especially mercury improve the corrosion resistance of the zinc. Therefore, the amalgamation of zinc anodes has been a practiced practice in primary cell technology for many decades.
Aus der GB 14 37 689 ist bekannt, dass Metalle, die Aminkomplexe auf Zinkkörnern bilden, in ammoniakalischer Lösung Wasserstoff entwickeln, jedoch nicht in lang anhaltender und kontinuierlicher Weise. Für den letzteren Fall ist sogar ausdrücklich vorgesehen, den direkten Kontakt zwischen Zink und dem 2. Metall zu vermeiden, und das 2. Metall separat in die Elektrolytlösung zu geben. Ein Einsatz von Zinkpulver in Tablettenform war also vor der DEPS 36 02 214 nicht nahegelegt.It is known from GB 14 37 689 that metals which form amine complexes on zinc grains develop hydrogen in ammoniacal solution, but not in a long-lasting and continuous manner. For the latter case, it is even expressly intended to avoid the direct contact between zinc and the second metal, and to add the second metal separately into the electrolyte solution. A use of zinc powder in tablet form was therefore not suggested before DEPS 36 02 214.
Es ist bekannt, dass man Flüssigkeiten wie Wasser und Schmierfette sehr unterschiedlicher Konsistenz mit Hilfe von gasentwickelnden Elementen fördern kann. So wird in den auto- matischen Fettspendern des Systems „Perma" (Hersteller: Fa. Satzinger, Bad Kissingen) eine massive Zinkronde verwendet, in deren zentrale Bohrung ein zylindrischer Molybdän- Stab eingelötet ist. Je nach Größe des Durchmessers des Molybdänstabs und damit der dem Elektrolyten ausgesetzten Fläche entwickelt dieses Element, nachdem es zur Inbetriebnahme in einen kleinen Kalilauge-See gestoßen wurde, kontinuierlich eine gewisse Gasmenge, die der Betriebszeit von 1 - 12 Monaten angepasst ist. Es liegt in der Elektrochemie des Molybdäns begründet, dass dieses Kurzschlusselement in seiner Gasentwicklung schwer vorherbestimmbar ist. Außerdem sind eine Reihe von Arbeitsschritten, wie das Einlöten des Molybdänstäbchens in die Zinkronde und das Amalgamieren, erforderlich, um das Element zu fertigen. So war es ein großer Fortschritt, dass man nach der DSPS 36 02 214 ein Was- serstoff entwickelndes Element mit gleichmäßigen Eigenschaften auch für eine lange Betriebszeit herstellen konnte. Bei diesem geht man von einem reinen Zinkpulver aus, das man mit einem Fremdmetall oberflächlich belegt und zu Tabletten presst. Dabei hat es sich als vorteilhaft erwiesen, quecksilberfrei zu arbeiten, denn einerseits ist Quecksilber teuer und
umweltschädlich, es hat aber auch die unerwünschte Wirkung, dass es die Atome des Kon- taminierungsmetalls mit der Zeit bedeckt und die Wasserstoff- Abscheidung inhibiert. So hat man Zinktabletten auch schon aus Zinkpulver hergestellt, das mit Molybdänpulver kontaminiert war. Auch diese Tabletten funktionieren leidlich, doch entwickeln sie Wasserstoff, der mit dem toxischen Stibin-Gas, (SbH3 ), verunreinigt ist. Auch dies war ein Grund, nach einer anderen Zinktablette bzw. Metalltablette zu suchen. Das Ergebnis ist der Gegenstand der in dieser Erfindung beschriebene Tablette.It is known that liquids such as water and greases of very different consistency can be promoted by means of gas-evolving elements. For example, in the automatic grease dispensers of the "Perma" system (manufactured by Satzinger, Bad Kissingen), a massive zinc disk is used, into whose central bore a cylindrical molybdenum rod is soldered in. Depending on the size of the diameter of the molybdenum rod and thus the After being put into operation in a small potash lake for commissioning, this element continuously evolves a certain amount of gas, adjusted to the operating time of 1 to 12 months, due to the electrochemistry of molybdenum In addition, a series of operations, such as soldering the molybdenum rod into the zinc bladder and amalgamating it, are required to make the element, so it was a great progress to say that, according to DSPS 36 02 214 - Hydrogen developing element with uniform properties even for a long Be could produce operating time. In this one starts from a pure zinc powder, which is superficially coated with a foreign metal and pressed into tablets. It has proven to be advantageous to work mercury-free, because on the one hand mercury is expensive and harmful to the environment, but it also has the undesirable effect of covering the atoms of the contaminating metal over time and inhibiting hydrogen deposition. Zinc tablets have already been made from zinc powder contaminated with molybdenum powder. These tablets also work well, but they produce hydrogen that is contaminated with the toxic stibin gas, (SbH 3 ). Again, this was a reason to look for another zinc tablet or metal tablet. The result is the subject of the tablet described in this invention.
Diese Erfindung folgt einigen der in der DS-PS 36 02 214 beschriebenen Fertigungsschritte, stellt allerdings deren Philosophie auf den Kopf. Im ersten Verfahrensschritt wird in einer bevorzugten erfindungsgemäßen Ausführungsvariante möglichst reines Zinkpulver mit gleichmäßiger Korngröße mit einem edleren Fremdmetall belegt. Bevorzugt verwendet man hierfür Kupfer, das man als feines Pulver dem Zink zumischt. Seine Wirkung ist der des Nickels in der DS-PS 36 02 214 konträr. Im Kontakt mit dem Zinkmetall bleibt das Kupfer metallisch; seine Oberflächenoxide werden sogar unter Bildung von Zinkoxiden reduziert. Dieses ist gegensätzlich zur Kontaminierung mit Ni, das die Korrosion des Zinks im Kontakt mit einer wässrigen Lösung begünstigt. Presst man aus diesem Pulver Tabletten, so besitzen diese eine gute elektronische Leitfähigkeit. Sie bleibt aufgrund der Kupferbrücken lange erhalten, auch wenn die Tablette Wasserstoff entwickelt, wenn sie in eine korrodierende Lösung eingetaucht wird.This invention follows some of the manufacturing steps described in DS-PS 36 02 214, but turns their philosophy on its head. In the first process step, in a preferred variant of the invention as pure as possible zinc powder with a uniform grain size is coated with a nobler foreign metal. Copper is preferably used for this purpose, which is admixed to the zinc as a fine powder. Its effect is contrary to that of nickel in DS-PS 36 02 214. In contact with the zinc metal, the copper remains metallic; its surface oxides are even reduced to form zinc oxides. This is contrary to contamination with Ni, which promotes corrosion of the zinc in contact with an aqueous solution. If you press tablets out of this powder, they have good electronic conductivity. It remains intact for a long time due to the copper bridges, even if the tablet develops hydrogen when immersed in a corrosive solution.
Die Wasserstoffentwicklung ist jedoch der Zweck des Korrosionselements: Sie wird durch die Bedeckung der Zinkoberfläche mit der Kupferschicht behindert, denn Kupfer und Zink besitzen beide hohe Wasserstoffüberspannungswerte. Um die Wasserstoffentwicklung in einer vorbestimmbaren Weise einzurichten, wird die Korrosionslösung mit dem Salz eines Metalls verunreinigt, das die folgenden Eigenschaften aufweist:Hydrogen evolution, however, is the purpose of the corrosion element: it is hindered by the coverage of the zinc surface with the copper layer, because both copper and zinc have high hydrogen overvoltage levels. To establish hydrogen evolution in a predeterminable manner, the corrosion solution is contaminated with the salt of a metal having the following properties:
1. Es scheidet sich im Kontakt mit der Tablette möglichst spontan im Porensystem auf der inneren Zinkoberfläche ab.1. It separates as spontaneously in contact with the tablet in the pore system on the inner zinc surface.
2. Es inhibiert nicht die Wasserstoffentwicklung in Gegenwart von Zink und Kupfer- metall.2. It does not inhibit hydrogen evolution in the presence of zinc and copper metal.
3. Es ist ein Metall der 8. Spalte des Periodischen Systems der Elemente, zum Beispiel Nickel.
Bei Untersuchungen der Wasserstoffauflösung und -abscheidung an Gaselektroden wurde gefunden, dass Kupfer als Metall für poröse Elektrodengerüste in Kombination mit Nickel als Katalysator sehr geeignet ist. (EJusti und A. Winsel, Kalte Verbrennung Fuel Cells, Steiner Verlag, Wiesbaden 1962, Seite 64 ff.) Somit empfehle ich hier als Korrosionsbad eine wässrige Lösung von Nickelformiat.3. It is a metal of the eighth column of the Periodic Table of Elements, for example nickel. In studies of hydrogen dissolution and deposition on gas electrodes, it has been found that copper is very suitable as a metal for porous electrode frameworks in combination with nickel as a catalyst. (EJusti and A. Winsel, Cold combustion Fuel Cells, Steiner Verlag, Wiesbaden 1962, page 64 et seq.) Thus, I recommend here as a corrosion bath, an aqueous solution of nickel formate.
Der veränderte Umgang mit den metallischen Komponenten der Zinktablette erlaubt auch andere Herstellungsschritte. So kann man das Zinkpulver verkupfern, indem man es in ein galvanisches Verkupferungsbad einträgt, wäscht und trocknet. Als Presshilfsmittel kann man Polyethylen, Polytetrafluorethylen und auch andere Kunststoffpulver verwenden. Die Mischung wird reaktiv in einem schnell laufenden Mischer vermischt und zu einem Band ausgewalzt. Daraus werden Tabletten gestanzt. Man kann das Walzband auch ein weiteres Mal aufschlagen und das entstandene Pulver in einer Tablettiermaschine zu Tabletten ausformen.The changed handling of the metallic components of the zinc tablet also allows other manufacturing steps. So you can copper the zinc powder by entering it in a galvanic copper plating, washes and dries. As a pressing aid you can use polyethylene, polytetrafluoroethylene and other plastic powders. The mixture is reactively mixed in a high speed mixer and rolled into a ribbon. From these tablets are punched. It is also possible to strike the rolled strip once more and to form the resulting powder into tablets in a tabletting machine.
Vorgegeben durch das teilweise hydrophobe Porengerüst der Tablette entstehen im Betrieb große Wasserstoffblasen, die sich von Zeit zu Zeit von der Oberfläche lösen. Es ist nur wichtig, dass das Presshilfsmittel das Pulver ausreichend rieselfähig erhält, so dass es in einer Tablettiermaschine ausgeformt werden kann.Provided by the partially hydrophobic pore framework of the tablet, large hydrogen bubbles are produced in operation which dissolve from the surface from time to time. It is only important that the pressing aid obtains the powder sufficiently free-flowing, so that it can be formed in a tableting machine.
Im der zuvor beschriebenen Aus führ ungs form zeigt die Zelle die offene Spannung der Zink- /Luftzelle von 1 ,4 V. Verbindet man Anode und Kathode mit einer Si-Diode in Durchflussrichtung, so wird in der Zelle vorhandener oder in das Kathodenmetall (z.B. Raney-Nickel) eingebauter Sauerstoff reduziert. Die Zellspannung vermindert sich dabei auf die charakteristische Schleusenspannung der Diode von beispielsweise 0,69 V. Dabei wird der Strom- fluss zwischen Anode und Kathode auf weniger als 1 μA reduziert, wobei die Zellspannung auf der charakteristischen Schleusenspannung stehen bleibt.In the embodiment described above, the cell shows the open voltage of the zinc / air cell of 1.4 V. If one connects the anode and cathode with a Si diode in the direction of flow, cells present in the cell or in the cathode metal (eg Raney Nickel) reduces built-in oxygen. The cell voltage is reduced to the characteristic voltage of the diode, for example, 0.69 V. In this case, the current flow between anode and cathode is reduced to less than 1 μA, whereby the cell voltage remains at the characteristic lock voltage.
Neben einer Si-Diode können auch andere Dioden eingesetzt werden, wobei jedoch die Schleusenspannung und damit auch die Wasserstoffentwicklung je nach der eingesetzten Diode variieren kann.In addition to a Si diode and other diodes can be used, but the slip voltage and thus the hydrogen evolution may vary depending on the diode used.
Besitzt die Zelle das übliche Atmungsloch, so fließt ein Strom, der dem zufließenden Sauerstoff äquivalent ist. Dieser wird durch die als „Ventilscheibe" bezeichnete Anordnung von Paraffinöl innerhalb der Zelle sehr stark reduziert.
Die unerwünschte Einwanderung von Sauerstoff in die Zelle entspricht einer nutzlosen Selbstentladung der Zelle ohne die gewünschte Wasserstoffproduktion. Diese kann man durch den beschriebenen Einbau einer Sperrscheibe schon bei der Assemblierung der Zellkomponenten oder durch eine zusätzliche Behandlung der Zelle im Paraffinölbad vermei- den.If the cell has the usual respiratory hole, a current equivalent to the incoming oxygen will flow. This is greatly reduced by the arrangement of paraffin oil within the cell, called the "valve disc". The unwanted migration of oxygen into the cell corresponds to useless self-discharge of the cell without the desired hydrogen production. These can be avoided by the described installation of a locking disc already during the assembly of the cell components or by an additional treatment of the cell in the paraffin oil bath.
Man kann zum Beispiel ein Fertigungslos der beschriebenen Zellen in ein Bad aus Weißöl (ParaffmÖl) eintauchen und in einem Exsikkator mild evakuieren. So wird in der Zelle vorhandenes Gas (Luft) abgesaugt und durch Paraffmöl ersetzt. Das Paraffinöl verschließt die Gasporen und auch die Undichtigkeiten zwischen den Metallflächen und den Kunststoffdichtungen gegen die eindringende Luft, ohne den Abtransport des in der Zelle gebildeten Wasserstoffs zu behindern. In der schon hinterlegten Patenanmeldung ist dieses Bauelement als „Ventilscheibe" bezeichnet worden.For example, a batch of the described cells may be immersed in a bath of white oil (paraffin oil) and mildly evacuated in a desiccator. So in the cell existing gas (air) is sucked off and replaced by paraffin oil. The paraffin oil seals the gas pores and also the leaks between the metal surfaces and the plastic seals against the ingress of air, without hindering the removal of the hydrogen formed in the cell. In the already filed patent application this device has been referred to as a "valve disc".
Legt man an eine zuvor beschriebene bekannte Wasserstoffentwicklungszelle eine Spannung von z.B. 0,7 V an, um unter Luftausschluss die Wasserstoffentwicklung zu provozieren, so wird der Stromfluss unter Sperrung des Durchgangs durch die Wasserstoff-Kathode verringert.When applying to a previously described known hydrogen evolution cell a voltage of e.g. 0.7 V in order to provoke the hydrogen evolution in the absence of air, the current flow is reduced while blocking the passage through the hydrogen cathode.
Daher werden in einer zweiten vorteilhaften Ausführungsvariante der Erfindung in Wasserstoffentwicklungszellen auch Metalle und Legierungen eingesetzt, die bezogen auf das reversible Wasserstoffpotential noch negativer sind als Zink, wie z.B. Aluminium, Magnesium und die Alkalimetalle.Therefore, in a second advantageous embodiment of the invention in hydrogen evolution cells, metals and alloys are used which are even more negative than zinc, based on the reversible hydrogen potential, such as e.g. Aluminum, magnesium and the alkali metals.
Auch Legierungen, wie z.B. eine Legierung aus Aluminium und Natrium sind dafür geeignet. Eine Aluminium/Natrium-Legierung wird in alkalischer Lösung unter Wasserstoffbildung zersetzt, unter gleichzeitiger Bildung von Natronlauge.Also alloys, such as e.g. an alloy of aluminum and sodium are suitable for this purpose. An aluminum / sodium alloy is decomposed in alkaline solution with hydrogen formation, with simultaneous formation of sodium hydroxide solution.
Auch bei der Auflösung von Lithium-Elektroden beobachtet man an Eisenelektroden den Stopp der vollständigen Auflösung durch die Passivierung der Eisenelektrode.Also in the case of the dissolution of lithium electrodes, the complete dissolution is stopped by iron passivation of the iron electrode.
Der Sachverhalt wird nachfolgend in einem Ausführungsbeispiel anhand einer Figur näher erläutert. Sie zeigt:
Fig. 1 : Schematische Darstellung einer Schaltung mit einer Gasentwicklungszelle.The facts will be explained in more detail in an embodiment with reference to a figure. She shows: Fig. 1: Schematic representation of a circuit with a gas evolution cell.
Fig. l zeigt die Schaltung einer Gasentwicklungszelle 1. Die Gasentwicklungszelle 1 weist zu ihrer Konditionierung eine Diode 2 und einen Widerstand 3 auf. Die Zelle 1 ist mit einem Aufkleber versehen, welcher eine Öffnung 7 bedeckt. Die Gasentwicklungszelle 1 taucht in ein Bad aus Paraffmöl 6 ein. Auch ein teilweises Eintauchen in ein Paraffinölbad ist möglich.1 shows the circuit of a gas evolution cell 1. The gas evolution cell 1 has a diode 2 and a resistor 3 for conditioning. The cell 1 is provided with a sticker which covers an opening 7. The gas evolution cell 1 dips into a bath of paraffin oil 6. Even a partial immersion in a paraffin oil bath is possible.
Ein Schalter 4 setzt die Wasserstoffentwicklung in Gang. Der Gasaustritt erfolgt durch die Öffnung 7 in das Paraffmöl. Dabei verhindert das Paraffmöl den Eintritt von Wasserdampf oder Sauerstoff durch die Öffnung 7 in die Zelle 1.A switch 4 starts the hydrogen evolution. The gas outlet takes place through the opening 7 in the paraffin oil. The paraffin oil prevents the entry of water vapor or oxygen through the opening 7 in the cell first
Die beiden Stellungen des Schalters 1 charakterisieren die beiden Betriebszustände der Gasentwicklungszelle 1 in „zu'" und „auf. In Stellung „zu" schließt die Diode 2 die Zelle kurz und ermöglicht den Stromfluss durch die Zelle 1 und damit die Gasentwicklung, dies jedoch nur dann, wenn die Zellspannung größer als die Schleusenspannung ist. In der Stellung „auf4 hingegen wird die Zelle unabhängig von der Zellspannung über einen Widerstand 5 unter Wasserstoffentwicklung entladen.The two positions of the switch 1 characterize the two operating states of the gas evolution cell 1 "in" and "." In the "closed" position, the diode 2 shorts the cell and allows the flow of current through the cell 1 and thus the gas evolution, but only when the cell voltage is greater than the lock voltage. In the position "on 4, however, the cell is discharged independently of the cell voltage via a resistor 5 with evolution of hydrogen.
Die Vergleichsschaltung zweier Wasserstoffentwicklungszellen gleicher Art, die eine mit offenem Atmungsloch, die andere mit geschlossenem, erlaubt die Messung des Sauerstoff- Eintritts aus dem Abgas eines chemischen oder elektrochemischen Reaktors entsprechend DE-AS 1 153 551 (1961).
The comparison circuit of two hydrogen evolution cells of the same type, one with open breathing hole, the other with closed, allows the measurement of the oxygen inlet from the exhaust gas of a chemical or electrochemical reactor according to DE-AS 1 153 551 (1961).
Claims
1. Mittel zur Erzeugung von Wasserstoff aus wässriger Lösung, bei dem Metallteilchen eines Metallpulvers mit einem edleren Metall beschichtet sind, dadurch gekennzeichnet, dass das Melallpulver nach Kontamination seiner Oberfläche mit einem Anteil von 0,1 bis 10 Atom-% eines edleren Metalls der 1 1. Spalte des Periodischen1. means for generating hydrogen from aqueous solution, are coated in the metal particles of a metal powder with a nobler metal, characterized in that the melal powder after contamination of its surface in a proportion of 0.1 to 10 atom% of a noble metal of the 1 1st column of the periodic
Systems der Elemente bezogen auf die Gesamtmetallmenge zu Tabletten verpresst ist.Systems of elements based on the total metal amount is compressed into tablets.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, dass die Metallteilchen und das Metallpulver Zink oder eine zinkhaltige Legierung ist.2. Composition according to claim 1, characterized in that the metal particles and the metal powder is zinc or a zinc-containing alloy.
3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Metallteilchen und das Metallpulver Aluminium, Magnesium, Alkalimetalle oder Legierungen daraus sind.3. Composition according to claim 1 or 2, characterized in that the metal particles and the metal powder are aluminum, magnesium, alkali metals or alloys thereof.
4. Mittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Metallpulver nach dem Kontaminieren seiner Oberfläche und nach Vermischen mit unbehandeltem Metallpulver zu Tabletten verpresst ist.4. Composition according to one of the preceding claims, characterized in that the metal powder is compressed after contaminating its surface and after mixing with untreated metal powder into tablets.
5. Mittel nach Anspruch einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass das Kontaminations- bzw. Beschichtungsmetall Kupfer ist.5. Composition according to claim one of the preceding claims, characterized in that the contamination or coating metal is copper.
6. Mittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass als Presshilfsmittel ein Thermoplast enthalten ist.6. Composition according to one of the preceding claims, characterized in that a thermoplastic is contained as a pressing aid.
7. Mittel nach Anspruch 6, dadurch gekennzeichnet, dass als Presshilfsmittel Polytet- rafluorethylen enthalten ist.7. Composition according to claim 6, characterized in that polytetrafluoroethylene is contained as pressing aid.
8. Verfahren zur Erzeugung eines Mittels nach den Ansprüchen 1 bis 7, dadurch ge- kennzeichnet, dass Metallpulver in die Lösung eines Metallsalzes der 11. Spalte des8. A process for producing a composition according to claims 1 to 7, character- ized in that metal powder in the solution of a metal salt of the 11th column of
Periodischen Systems der Elemente mit saurem pH- Wert eingetragen, gewaschen, getrocknet, ggf. mit Polytetrafluorethylcn-Pulver vermischt und anschließend zuPeriodic system of elements with acidic pH entered, washed, dried, optionally mixed with Polytetrafluorethylcn powder and then added
Tabletten verpresst wird.Tablets is pressed.
9. Mittel nach Anspruch 8, dadurch gekennzeichnet, dass die Lösung aus Kupfersulfat besteht.9. Composition according to claim 8, characterized in that the solution consists of copper sulfate.
10. Erzeugung von Wasserstoff durch Eintragung des Mittels nach einem der vorhergehenden Ansprüche in die Lösung eines Metallsalzes der achten Spalte des Periodensystems der Elemente, vorzugsweise in eine Nickelsalzlösung. 10. Generation of hydrogen by registration of the agent according to one of the preceding claims in the solution of a metal salt of the eighth column of the Periodic Table of the Elements, preferably in a nickel salt solution.
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DE102008057865.7 | 2008-11-18 | ||
DE102008057865A DE102008057865B3 (en) | 2008-11-18 | 2008-11-18 | Zinc tablet for use as a corrosion element or as an anode in gas evolution cells for the production of hydrogen for the conveyance of flowable substances in mechanical syringes |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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GB794261A (en) * | 1954-12-09 | 1958-04-30 | Bruno Friedrich Schweig | Improvements relating to coating metals with copper |
GB1437689A (en) * | 1974-02-08 | 1976-06-03 | Ishizaka O | Method of generating hydrogen |
JPS5625903A (en) * | 1979-08-08 | 1981-03-12 | Nippon Mining Co Ltd | Preparation of metallic sulfide powder coated with copper |
DE3602214C1 (en) * | 1986-01-25 | 1987-07-16 | Winsel August | Zinc corrosion element for producing hydrogen from alkaline solution at a predetermined gas evolution rate |
JP2005243617A (en) * | 2004-01-28 | 2005-09-08 | Kawaken Fine Chem Co Ltd | Hydrogen supply method, its device, and portable equipment mounting fuel cell |
WO2006127775A2 (en) * | 2005-05-25 | 2006-11-30 | Sud-Chemie Inc. | Method and device and pure hydrogen generation from acidic solution |
-
2008
- 2008-11-18 DE DE102008057865A patent/DE102008057865B3/en not_active Expired - Fee Related
-
2009
- 2009-11-17 WO PCT/EP2009/065288 patent/WO2010057875A1/en active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB794261A (en) * | 1954-12-09 | 1958-04-30 | Bruno Friedrich Schweig | Improvements relating to coating metals with copper |
GB1437689A (en) * | 1974-02-08 | 1976-06-03 | Ishizaka O | Method of generating hydrogen |
JPS5625903A (en) * | 1979-08-08 | 1981-03-12 | Nippon Mining Co Ltd | Preparation of metallic sulfide powder coated with copper |
DE3602214C1 (en) * | 1986-01-25 | 1987-07-16 | Winsel August | Zinc corrosion element for producing hydrogen from alkaline solution at a predetermined gas evolution rate |
JP2005243617A (en) * | 2004-01-28 | 2005-09-08 | Kawaken Fine Chem Co Ltd | Hydrogen supply method, its device, and portable equipment mounting fuel cell |
WO2006127775A2 (en) * | 2005-05-25 | 2006-11-30 | Sud-Chemie Inc. | Method and device and pure hydrogen generation from acidic solution |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Section Ch Week 200564, Derwent World Patents Index; Class E36, AN 2005-624272 * |
Also Published As
Publication number | Publication date |
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DE102008057865B3 (en) | 2010-03-25 |
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