CA2609133A1 - Method and device and pure hydrogen generation from acidic solution - Google Patents
Method and device and pure hydrogen generation from acidic solution Download PDFInfo
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- CA2609133A1 CA2609133A1 CA002609133A CA2609133A CA2609133A1 CA 2609133 A1 CA2609133 A1 CA 2609133A1 CA 002609133 A CA002609133 A CA 002609133A CA 2609133 A CA2609133 A CA 2609133A CA 2609133 A1 CA2609133 A1 CA 2609133A1
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- Prior art keywords
- metal
- hydrogen
- organic acid
- cartridge
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000001257 hydrogen Substances 0.000 title claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000003929 acidic solution Substances 0.000 title abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 150000007524 organic acids Chemical class 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 235000000346 sugar Nutrition 0.000 claims description 2
- 150000008163 sugars Chemical class 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims 2
- 238000013022 venting Methods 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 11
- 239000000243 solution Substances 0.000 abstract description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 4
- 239000011707 mineral Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- -1 HCOOH compound Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
- C01B13/326—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process of elements or compounds in the liquid state
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Fuel Cell (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Abstract
The present development is a method for generating pure hydrogen from an organic acid solution and a zero-valent metal. By reacting the metal with the organic acid rather than a mineral acid, hydrogen generation occurs at a gradual and more consistent rate than is observed by prior art methods, making the present method suitable for fuel cell applications. A portable hydrogen-generating device using the method of generating pure hydrogen from acidic solution is further disclosed.
Description
Title Method and Device for Pure Hydrogen Generation From Acidic Solution Background The present development relates to a method and apparatus for generating pure hydrogen from an organic acid solution. The method reacts a pure metal with an organic acid and an oxidizing agent, and generates hydrogen gas having a purity greater than 99.9%. The hydrogen gas is then removed and the metal is precipitated as a metal oxide. In subsequent steps, the metal may be reduced back to zero valency by known methods, such as reaction with a hydrocarbon, and the organic acid is regenerated. Hydrogen generation is gradual and more consistent than observed by prior art methods, making the present method suitable for fuel cell applications.
In recent years, interest has been generated in fuel-cell based engines.
These engines have an energy efficiency that is two to three times higher than internal combustion engines (50-55% for fuel cell vs. 15-17% for internal combustion engines). Typically, hydrogen is a supplied directly to a fuel cell to generate electricity.
Hydrogen, however, does not exist in elemental form in nature. Rather, the hydrogen must be liberated from hydrogen-containing compounds. This requires the consumption of energy. For example, water is the most common substance on earth, covering more than 70% of the earth's surface. Water contains about 11%
hydrogen by weight, but because of the stability of water, in theory, more than 10,000 joules of energy are needed to obtain one liter of hydrogen gas from water.
For commercial operations, hydrogen is commonly derived either from hydrogen-rich chemicals, such as methanol or dimethyl ether, or from fuels, such as coal, natural gas or gasoline. In most cases, liberation of pure hydrogen from the chemicals and fuels is complex and costly.
In order to make fuel cells attractive for application in consumer products, the cost for on-board fuel processing will preferably be less than about $10 per kilowatt. However, using the technology of the prior art, on-board fuel processing costs nearly ten times more than the target. Thus, there is a need for a lower cost alternative. Further, it is highly desirable that for portable appliances fueled by fuel cells, the hydrogen can be generated instantaneously at the moment when the machine is turned on. Due to activation energy requirements for most chemical reaction systems, it is very difficult to overcome the start-up issues by conventional reforming or shift reactions.
Summary of the Invention The present development is a method for generating pure hydrogen from an organic acid solution and a portable hydrogen-generating device. A zero-valent metal is reacted with an organic acid and an oxidizing agent. Hydrogen gas generated by the reaction is removed and the metal is precipitated as a metal oxide.
In subsequent steps, the metal may be reduced back to zero valency by known methods, such as reaction with a hydrocarbon, and the organic acid is regenerated.
Hydrogen generation is gradual and more consistent than observed by prior art methods, making the present method suitable for fuel cell applications. A
portable hydrogen-generating device using the method of generating pure hydrogen from acidic solution is further disclosed.
Brief Description of the Figures Figure 1 is a graphical representation of hydrogen production over time resulting from the method of the present development - reaction of iron and an organic acid - versus hydrogen production over time resulting from a prior art method - reaction of iron and a mineral acid; and Figure 2 is a drawing of a portable llydrogen-generating device made in accordance with the present development.
Detailed Description of the Preferred Embodiment The present invention is a renewable hydrogen generation system. By reacting an organic acid and metal, hydrogen generation can occur at ambient temperature, defined herein as temperatures less than about 35 C, and ambient pressure, or at pressures of about 1 bar. The purity of the hydrogen generated is greater than 99.9%, and the hydrogen can be generated continuously at an essentially steady rate.
As shown in Figure 1, when approximately one gram of iron powder is reacted with from about 100 mL to about 300 mL acid, hydrogen gas is generated.
When the iron powder is reacted with a mineral acid, such as hydrochloric acid, the initial hydrogen generation is extremely rapid and then the production rate holds steady. By contrast, when the iron powder is reacted with an organic acid, such as formic acid or acetic acid, the initial hydrogen production rate is less abrupt with a gradual increase in hydrogen production. In situations where a hydrogen storage tank is not available, it is preferable to have a gradual, consistent rate of hydrogen production. Thus, it is advantageous to have a method for harnessing the hydrogen produced by these organic acid plus metal reactions.
The method of the present invention is intended for use in a portable hydrogen-generating device. The method comprises the steps of:
(a) reacting a zero-valent metal with an organic acid, and optionally an oxidizing agent, thereby forming a metal-O-CO-R complex;
In recent years, interest has been generated in fuel-cell based engines.
These engines have an energy efficiency that is two to three times higher than internal combustion engines (50-55% for fuel cell vs. 15-17% for internal combustion engines). Typically, hydrogen is a supplied directly to a fuel cell to generate electricity.
Hydrogen, however, does not exist in elemental form in nature. Rather, the hydrogen must be liberated from hydrogen-containing compounds. This requires the consumption of energy. For example, water is the most common substance on earth, covering more than 70% of the earth's surface. Water contains about 11%
hydrogen by weight, but because of the stability of water, in theory, more than 10,000 joules of energy are needed to obtain one liter of hydrogen gas from water.
For commercial operations, hydrogen is commonly derived either from hydrogen-rich chemicals, such as methanol or dimethyl ether, or from fuels, such as coal, natural gas or gasoline. In most cases, liberation of pure hydrogen from the chemicals and fuels is complex and costly.
In order to make fuel cells attractive for application in consumer products, the cost for on-board fuel processing will preferably be less than about $10 per kilowatt. However, using the technology of the prior art, on-board fuel processing costs nearly ten times more than the target. Thus, there is a need for a lower cost alternative. Further, it is highly desirable that for portable appliances fueled by fuel cells, the hydrogen can be generated instantaneously at the moment when the machine is turned on. Due to activation energy requirements for most chemical reaction systems, it is very difficult to overcome the start-up issues by conventional reforming or shift reactions.
Summary of the Invention The present development is a method for generating pure hydrogen from an organic acid solution and a portable hydrogen-generating device. A zero-valent metal is reacted with an organic acid and an oxidizing agent. Hydrogen gas generated by the reaction is removed and the metal is precipitated as a metal oxide.
In subsequent steps, the metal may be reduced back to zero valency by known methods, such as reaction with a hydrocarbon, and the organic acid is regenerated.
Hydrogen generation is gradual and more consistent than observed by prior art methods, making the present method suitable for fuel cell applications. A
portable hydrogen-generating device using the method of generating pure hydrogen from acidic solution is further disclosed.
Brief Description of the Figures Figure 1 is a graphical representation of hydrogen production over time resulting from the method of the present development - reaction of iron and an organic acid - versus hydrogen production over time resulting from a prior art method - reaction of iron and a mineral acid; and Figure 2 is a drawing of a portable llydrogen-generating device made in accordance with the present development.
Detailed Description of the Preferred Embodiment The present invention is a renewable hydrogen generation system. By reacting an organic acid and metal, hydrogen generation can occur at ambient temperature, defined herein as temperatures less than about 35 C, and ambient pressure, or at pressures of about 1 bar. The purity of the hydrogen generated is greater than 99.9%, and the hydrogen can be generated continuously at an essentially steady rate.
As shown in Figure 1, when approximately one gram of iron powder is reacted with from about 100 mL to about 300 mL acid, hydrogen gas is generated.
When the iron powder is reacted with a mineral acid, such as hydrochloric acid, the initial hydrogen generation is extremely rapid and then the production rate holds steady. By contrast, when the iron powder is reacted with an organic acid, such as formic acid or acetic acid, the initial hydrogen production rate is less abrupt with a gradual increase in hydrogen production. In situations where a hydrogen storage tank is not available, it is preferable to have a gradual, consistent rate of hydrogen production. Thus, it is advantageous to have a method for harnessing the hydrogen produced by these organic acid plus metal reactions.
The method of the present invention is intended for use in a portable hydrogen-generating device. The method comprises the steps of:
(a) reacting a zero-valent metal with an organic acid, and optionally an oxidizing agent, thereby forming a metal-O-CO-R complex;
(b) removing the hydrogen produced by the reaction of the metal and acid;
(c) regenerating the organic acid by oxidizing the metal-O-CO-R
complex by reacting the complex with an oxidizing agent;
(d) precipitating the metal as a metal oxide; and, (e) optionally, reacting the metal oxide with a hydrocarbon to reduce the metal to the zero-valent state.
The reaction occurs at essentially ambient temperature, defined herein as at a temperature of less than about 35 C. Further, the reaction occurs at essentially ambient pressure or at about 1 bar.
The metal may be any metal that can be easily oxidized in the presence of mild aqueous acid, such as iron, zinc, copper, aluminum, nickel and a combination thereof. The metal may be in the form of powder, granules or pellets and acidic aqueous solution. Iron has been found to be particularly effective for the reaction both in terms of hydrogen yield and with respect to being a relatively low cost metal source.
The organic acids are selected on the basis of a steady hydrogen production rate during a period of time and the absence of additional cations or anions in the solutions. The organic acid may be any RCOOH or HCOOH compound, including carboxylic acids, formic acid, acetic acid, oxalic acid, and combinations thereof.
The oxidizing agent may be any oxidant that can oxidize the M-O-CO-R
complex with concomitant formation of the free acid HO-CO-R. Such agents would include, without limitation, hydrogen peroxide, oxygen, ozone, starches and sugars.
(c) regenerating the organic acid by oxidizing the metal-O-CO-R
complex by reacting the complex with an oxidizing agent;
(d) precipitating the metal as a metal oxide; and, (e) optionally, reacting the metal oxide with a hydrocarbon to reduce the metal to the zero-valent state.
The reaction occurs at essentially ambient temperature, defined herein as at a temperature of less than about 35 C. Further, the reaction occurs at essentially ambient pressure or at about 1 bar.
The metal may be any metal that can be easily oxidized in the presence of mild aqueous acid, such as iron, zinc, copper, aluminum, nickel and a combination thereof. The metal may be in the form of powder, granules or pellets and acidic aqueous solution. Iron has been found to be particularly effective for the reaction both in terms of hydrogen yield and with respect to being a relatively low cost metal source.
The organic acids are selected on the basis of a steady hydrogen production rate during a period of time and the absence of additional cations or anions in the solutions. The organic acid may be any RCOOH or HCOOH compound, including carboxylic acids, formic acid, acetic acid, oxalic acid, and combinations thereof.
The oxidizing agent may be any oxidant that can oxidize the M-O-CO-R
complex with concomitant formation of the free acid HO-CO-R. Such agents would include, without limitation, hydrogen peroxide, oxygen, ozone, starches and sugars.
The present invention further includes a portable hydrogen-generating device designed around this method. With reference to Figure 2, the device proposed would include a case (D) housing a first cartridge (A) filled with the metal, a solution recycle column holding additional solution of organic acid (C) and, optionally, the oxidizing agent, and an optional a second replacement cartridge filled with metal (B). The recycle column is plumbed to both cartridges with valves to allow the recycle column to be inline with the cartridge in use. A
variable speed pump moves the solution between the active reaction cartridge and the recycle column. When fed to the active reaction cartridge, the organic acid and oxidizing agent solution is preferably fed across the metal as uniformly as possible, such as may be accomplished by using a solution distribution plate or a spray nozzle. The hydrogen gas formed in the active reaction cartridge is vented from the cartridge and case to any desired location. To minimize the risk of contamination of the hydrogen gas by mist or other gases, a hydrogen-permeable membrane is preferably mounted between the metal and the hydrogen vent.
It is noted that although there is significant prior art that teaches hydrogen generation from the reaction of iron with mineral acids, reactions between iron and organic acids are less well-known. Further, the present development includes experimental data showing surprising results - exceptionally high purity and very good yields for hydrogen production at a steady hydrogen production rate -when iron metal is reacted with an organic acid.
It is understood that the processing conditions and apparatus designs may be varied as known to those skilled in the art without exceeding the scope of this development.
variable speed pump moves the solution between the active reaction cartridge and the recycle column. When fed to the active reaction cartridge, the organic acid and oxidizing agent solution is preferably fed across the metal as uniformly as possible, such as may be accomplished by using a solution distribution plate or a spray nozzle. The hydrogen gas formed in the active reaction cartridge is vented from the cartridge and case to any desired location. To minimize the risk of contamination of the hydrogen gas by mist or other gases, a hydrogen-permeable membrane is preferably mounted between the metal and the hydrogen vent.
It is noted that although there is significant prior art that teaches hydrogen generation from the reaction of iron with mineral acids, reactions between iron and organic acids are less well-known. Further, the present development includes experimental data showing surprising results - exceptionally high purity and very good yields for hydrogen production at a steady hydrogen production rate -when iron metal is reacted with an organic acid.
It is understood that the processing conditions and apparatus designs may be varied as known to those skilled in the art without exceeding the scope of this development.
Claims (10)
1. A method for generating hydrogen using reactants and regenerating those reactants comprising the steps of:
(a) reacting a zero-valent metal, preferably selected from the group consisting of iron, zinc, copper, aluminum, nickel and a combination thereof and more preferably iron, with an organic acid, preferably selected from the group consisting of carboxylic acids, formic acid, acetic acid, oxalic acid, and combinations thereof, thereby forming a metal-O-CO-R complex;
(b) removing hydrogen produced by the reaction of the metal and acid;
(c) regenerating the organic acid by oxidizing the metal-O-CO-R
complex utilizing an oxidizing agent, preferably selected from the group consisting of hydrogen peroxide, starches, sugars, oxygen, ozone and combinations thereof; and, (d) precipitating the metal as a metal oxide.
(a) reacting a zero-valent metal, preferably selected from the group consisting of iron, zinc, copper, aluminum, nickel and a combination thereof and more preferably iron, with an organic acid, preferably selected from the group consisting of carboxylic acids, formic acid, acetic acid, oxalic acid, and combinations thereof, thereby forming a metal-O-CO-R complex;
(b) removing hydrogen produced by the reaction of the metal and acid;
(c) regenerating the organic acid by oxidizing the metal-O-CO-R
complex utilizing an oxidizing agent, preferably selected from the group consisting of hydrogen peroxide, starches, sugars, oxygen, ozone and combinations thereof; and, (d) precipitating the metal as a metal oxide.
2. The method of Claim 1 further including addition of additional oxidizing agent with the organic acid.
3. The method of Claims 1 or 2 further including reacting the metal oxide with a hydrocarbon to reduce the metal to a zero-valent state.
4. The method of any of Claims 1-3 further comprising passing the hydrogen through a hydrogen-permeable membrane.
5. A portable hydrogen-generating device comprising a case housing (i) a first cartridge filled with a metal, and (ii) a recycle column filled with an organic acid solution, wherein said recycle column is plumbed to said cartridge, and wherein a variable speed pump is also connected to the device so as to move said acid solution between the first cartridge and the recycle column.
6. The device of Claim 5 further including a replacement cartridge filled with a metal plumbed to said recycle column.
7. The device of any of Claims 5-6 further including at least one valve to allow said recycle column to be in communication with each of the first cartridge and the replacement cartridge separately.
8. The device of any of Claims 5-7 wherein said recycle column contains an oxidizing agent.
9. The device of any of Claims 5-8 further including a means for uniformly dispersing said organic acid within the first cartridge.
10. The device of any of Claims 5-9 further including a means for venting gas.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68445905P | 2005-05-25 | 2005-05-25 | |
| US60/684,459 | 2005-05-25 | ||
| US11/438,595 US20060266159A1 (en) | 2005-05-25 | 2006-05-22 | Method and device for pure hydrogen generation from acidic solution |
| US11/438,595 | 2006-05-22 | ||
| PCT/US2006/020028 WO2006127775A2 (en) | 2005-05-25 | 2006-05-24 | Method and device and pure hydrogen generation from acidic solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2609133A1 true CA2609133A1 (en) | 2006-11-30 |
Family
ID=37198701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002609133A Abandoned CA2609133A1 (en) | 2005-05-25 | 2006-05-24 | Method and device and pure hydrogen generation from acidic solution |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20060266159A1 (en) |
| EP (1) | EP1899263A2 (en) |
| JP (1) | JP2008542169A (en) |
| AU (1) | AU2006250086A1 (en) |
| BR (1) | BRPI0610756A2 (en) |
| CA (1) | CA2609133A1 (en) |
| RU (1) | RU2007148689A (en) |
| WO (1) | WO2006127775A2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007015070A1 (en) * | 2005-08-02 | 2007-02-08 | Isis Innovation Limited | Initiating a reaction between hydrogen peroxide and an organic compound |
| GB2459267A (en) * | 2008-04-15 | 2009-10-21 | H2Renew Ltd | A method for producing hydrogen |
| DE102008057865B3 (en) * | 2008-11-18 | 2010-03-25 | Winsel, August, Prof. Dipl.-Phys. Dr. | 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 |
| ITRM20100700A1 (en) * | 2010-12-30 | 2012-07-01 | Roberta Gerla | ELECTRODE, IN PARTICULAR FOR THE REACTION OF WATER HYDROLYSIS. |
| RU2521632C1 (en) * | 2012-11-13 | 2014-07-10 | Федеральное государственное бюджетное учреждение "Национальный исследовательский центр "Курчатовский институт" | Method of producing hydrogen from water |
| US20230159325A1 (en) * | 2020-05-14 | 2023-05-25 | Element 1 Technologies, Llc | A system and method for producing hydrogen on demand |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US98442A (en) * | 1869-12-28 | Improvement in apparatus for producing and carbureting hydrogen gas | ||
| US971206A (en) * | 1908-12-02 | 1910-09-27 | Corp Internationale Wasserstoff Ag | Process of producing hydrogen. |
| US1002366A (en) * | 1911-01-18 | 1911-09-05 | Merle G Campau | Cream-tester. |
| US1109447A (en) * | 1912-06-26 | 1914-09-01 | Anton Messerschmitt | Generation of hydrogen by means of iron. |
| US1059818A (en) * | 1912-08-26 | 1913-04-22 | Friedrich Bergius | Process for the manufacture of hydrogen from metals and water. |
| US1109448A (en) * | 1913-03-14 | 1914-09-01 | Anton Messerschmitt | Manufacture of hydrogen. |
| US1102716A (en) * | 1913-07-07 | 1914-07-07 | Basf Ag | Producing hydrogen and apparatus therefor. |
| US1129559A (en) * | 1913-12-06 | 1915-02-23 | Berlin Anhaltische Maschb Aktien Ges | Reducing and oxidizing apparatus for generating hydrogen from iron ore and steam. |
| US1617965A (en) * | 1924-04-11 | 1927-02-15 | Alais & Froges & Camarque Cie | Process for the manufacture of hydrogen |
| US3969495A (en) * | 1975-06-26 | 1976-07-13 | The United States Of America As Represented By The United States Energy Research And Development Administration | Thermochemical production of hydrogen |
| US4547356A (en) * | 1980-08-05 | 1985-10-15 | Unique Energy Systems, Inc. | Method of generating hydrogen and using the generated hydrogen |
| US4988486A (en) * | 1985-08-02 | 1991-01-29 | The Boeing Company | Hydrogen generator |
| US4842844A (en) * | 1985-08-02 | 1989-06-27 | The Boeing Company | Method of generating hydrogen |
| US5510201A (en) * | 1992-04-24 | 1996-04-23 | H Power Corporation | Method of operating a fuel cell wherein hydrogen is generated by providing iron in situ |
| US6468499B1 (en) * | 2000-06-09 | 2002-10-22 | Argonne National Laboratory | Method of generating hydrogen by catalytic decomposition of water |
| US20020090539A1 (en) * | 2000-09-29 | 2002-07-11 | Getty John Paul | Hydrogen-powered energy-producing device and system for continous production of hydrogen |
| US6395252B1 (en) * | 2000-09-29 | 2002-05-28 | Ut-Battelle, Llc | Method for the continuous production of hydrogen |
| JP2003020201A (en) * | 2001-07-06 | 2003-01-24 | Yoshiro Tanaka | Apparatus and element for generating hydrogen |
| ITMI20020567A1 (en) * | 2002-03-18 | 2003-09-18 | Sud Chemie S R L | PROCESS FOR THE PREPARATION OF IRON OXIDES |
| JP2005243617A (en) * | 2004-01-28 | 2005-09-08 | Kawaken Fine Chem Co Ltd | Hydrogen supply method, its device, and portable equipment mounting fuel cell |
-
2006
- 2006-05-22 US US11/438,595 patent/US20060266159A1/en not_active Abandoned
- 2006-05-24 BR BRPI0610756-7A patent/BRPI0610756A2/en not_active Application Discontinuation
- 2006-05-24 RU RU2007148689/15A patent/RU2007148689A/en not_active Application Discontinuation
- 2006-05-24 JP JP2008513648A patent/JP2008542169A/en not_active Withdrawn
- 2006-05-24 CA CA002609133A patent/CA2609133A1/en not_active Abandoned
- 2006-05-24 AU AU2006250086A patent/AU2006250086A1/en not_active Abandoned
- 2006-05-24 WO PCT/US2006/020028 patent/WO2006127775A2/en active Application Filing
- 2006-05-24 EP EP06771027A patent/EP1899263A2/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006127775A2 (en) | 2006-11-30 |
| JP2008542169A (en) | 2008-11-27 |
| BRPI0610756A2 (en) | 2011-11-08 |
| AU2006250086A1 (en) | 2006-11-30 |
| US20060266159A1 (en) | 2006-11-30 |
| RU2007148689A (en) | 2009-06-27 |
| EP1899263A2 (en) | 2008-03-19 |
| WO2006127775A3 (en) | 2007-02-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |