WO2012056071A1 - Method for the production of hydrogen by means of the electrolysis of an aqueous solution of organic products - Google Patents
Method for the production of hydrogen by means of the electrolysis of an aqueous solution of organic products Download PDFInfo
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- WO2012056071A1 WO2012056071A1 PCT/ES2011/070725 ES2011070725W WO2012056071A1 WO 2012056071 A1 WO2012056071 A1 WO 2012056071A1 ES 2011070725 W ES2011070725 W ES 2011070725W WO 2012056071 A1 WO2012056071 A1 WO 2012056071A1
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- electrolysis
- hydrogen
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- aqueous solution
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
Definitions
- the present invention belongs to the field of hydrogen production by electrolysis of a solution of organic compounds.
- Hydrogen is generally considered as one of the fuels of the future, either to produce electricity in fuel cells (known as fuel cells) with high electrical efficiency, or in the known hydrogenation of petroleum products, fats, etc.
- fuel cells known as fuel cells
- the electrolysis of organic compounds is presented, whose electrical consumption is substantially valued as half of the consumption required in the electrolysis of water.
- a first object of this invention is a process for the production of hydrogen by electrolysis of an aqueous solution of at least one organic product. This Electrolysis reaction takes place according to the following stoichiometry:
- the organic product or products used in the process are characterized by having a total miscibility in water.
- the concentration of said organic product or products in the aqueous solution is preferably between 0.5 and 4 molar.
- the organic product used in the process may consist of a residual product or biomass derivative.
- the organic product may consist of at least one organic product derived from biomass, preferably selected from a group consisting of molasses (residues from the manufacture of cane or beet sugar), alcohols, ethers and glycols, as well as any of its combinations.
- molasses residues from the manufacture of cane or beet sugar
- alcohols ethers
- glycols as well as any of its combinations.
- glycols glycerin from biodiesel production stands out in a preferred manner.
- the organic product may consist of a product from liquefaction and / or pyrolysis of wood.
- the organic product may consist of an organic waste product from the industry, preferably taladrina, sewage from the paper industry and, in general, those waste products that are miscible in water.
- an organic waste product from the industry preferably taladrina
- sewage from the paper industry preferably taladrina
- those waste products that are miscible in water since alcohols and, in general, organic products have a certain conductivity, it is not necessary in this case to add acidic or basic electrolytes to the aqueous solution. Due to this, the effect of corrosion on the electrodes is much less, which represents an important advantage over the production of hydrogen by water electrolysis.
- the voltage used in said electrolysis cell may preferably be between 0.5 V and 0.9 V in direct current.
- voltages that represent approximately half of the voltage usually required in the electrolysis of water, generally around 1.4 V in direct current may be employed.
- the ultrasonic frequency used in the process is between 50 kHz and 3 MHz. These frequencies are achieved by applying a domestic or industrial current of higher voltage and frequency to a piezoelectric crystal, where they are transformed into mechanical energy according to the known inverse piezoelectric effect.
- the selected electrolysis cell is designed to allow the application of ultrasound, which achieves the molecular agitation necessary to increase the efficiency and productivity of the cell.
- said electrolytic cell comprises at least two compartments containing a cathode and an anode, as well as a transducer preferably located on the outer face of the cell, where the ultrasound is generated.
- the application of ultrasound to the cell is carried out by the external part of the compartments and, for this purpose, the metal wall thereof is preferably designed with a thickness of less than 1 mm, at least in its lower base, in order to achieve adequate transmission of ultrasound.
- electrolysis products are, on the one hand, those derived or obtained from biomass (renewable hydrogen generation) and, on the other hand, those derived from organic waste products from industry. This is a great advantage since, as is known, the treatment of waste is subject to a very strict environmental regulatory requirement.
- the generation of combustion products such as dioxins or furans generated in incineration or co-incineration is avoided, these methods being very socially answered from the point of view environmental.
- the described process allows obtaining high purity hydrogen, said purity being greater than 99%.
- Said hydrogen due to its high purity, can be directly consumed or stored until its consumption.
- it is worth mentioning its use in fuel cell cells, or its storage in bottles or tanks, among other examples.
- Figure 1 shows a basic design of an electrolysis cell divided into two compartments comprising an anode and a cathode, respectively, where:
- Aqueous solution inlet comprising at least one organic product
- Ultrasound
- a preferred embodiment of the process object of the invention is presented below by way of example and on a non-limiting basis.
- the electrolysis process was carried out from an aqueous solution of an organic product in a concentration in the aqueous solution of 0.5 to 4 molar.
- aqueous solution into the electrolytic cell was carried out by the lower part thereof by means of the use of a feed pump or a system of communicating vessels and gravity, in an amount sufficient to completely cover the cathode and The anode of the cell.
- the voltage used to carry out the electrolysis procedure was 0.9 V, resulting in a current of 3 ⁇ 4 at the anode and a CO 2 current at the cathode. Also, ultrasound was applied on the outside of the two compartments of the cell, the thickness of the metal wall of the lower base of the cell being less than 1 mm.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
PROCEDIMIENTO PARA LA PRODUCCIÓN DE HIDRÓGENO MEDIANTE ELECTRÓLISIS DE UNA SOLUCIÓN ACUOSA DE PRODUCTOS ORGÁNICOS PROCEDURE FOR HYDROGEN PRODUCTION THROUGH ELECTROLISIS OF A WATER SOLUTION OF ORGANIC PRODUCTS
Campo de la técnica Technical field
La presente invención pertenece al campo de la producción de hidrógeno mediante electrólisis de una solución de compuestos orgánicos. The present invention belongs to the field of hydrogen production by electrolysis of a solution of organic compounds.
Estado de la técnica anterior a la invención State of the art prior to the invention
De forma generalizada se considera el hidrógeno como uno de los combustibles del futuro, bien para producir electricidad en células de combustible (conocidas como fuel cells) con un elevado rendimiento eléctrico, o bien en la conocida hidrogenación de productos petrolíferos, grasas, etc. Hoy en día, la gran mayoría del hidrógeno obtenido industrialmente se genera mediante la técnica de steam reforming, a partir de gas natural. Adicionalmente, es posible generar hidrógeno a partir de la electrólisis de agua, si bien esta opción es minoritaria dado el alto consumo eléctrico que requiere el proceso. De este modo, como alternativa a la electrólisis del agua se presenta la electrólisis de compuestos orgánicos, cuyo consumo eléctrico se valora sustancialmente como la mitad del consumo requerido en la electrólisis del agua. Hydrogen is generally considered as one of the fuels of the future, either to produce electricity in fuel cells (known as fuel cells) with high electrical efficiency, or in the known hydrogenation of petroleum products, fats, etc. Today, the vast majority of industrially obtained hydrogen is generated by the steam reforming technique, from natural gas. Additionally, it is possible to generate hydrogen from water electrolysis, although this option is minority given the high electrical consumption required by the process. Thus, as an alternative to the electrolysis of water, the electrolysis of organic compounds is presented, whose electrical consumption is substantially valued as half of the consumption required in the electrolysis of water.
En el artículo del estado de la técnica "Making In the state of the art article "Making
Hydrogen by Electrolysis of Methanol" (NASA Tech Briefs, 2002, Vol. 26, No. 6) se describe la posibilidad de generar hidrógeno mediante electrólisis del metanol. Hydrogen by Electrolysis of Methanol "(NASA Tech Briefs, 2002, Vol. 26, No. 6) describes the possibility of generating hydrogen by methanol electrolysis.
De este modo, es objeto de esta invención presentar un nuevo procedimiento para la obtención de hidrógeno a partir de la electrólisis de productos orgánicos, como alternativa al tradicional proceso de electrólisis de agua. Thus, it is the object of this invention to present a new process for obtaining hydrogen from the electrolysis of organic products, as an alternative to the traditional process of water electrolysis.
Descripción detallada de la invención Detailed description of the invention
Es un primer objeto de esta invención un procedimiento para la producción de hidrógeno mediante electrólisis de una solución acuosa de al menos un producto orgánico. Esta reacción de electrólisis tiene lugar de acuerdo con la siguiente estequiometría : A first object of this invention is a process for the production of hydrogen by electrolysis of an aqueous solution of at least one organic product. This Electrolysis reaction takes place according to the following stoichiometry:
CnHmOp + (2n-p)H20 <→ nC02 + 0 , 5 ( 4n+m-2p) H2 C n H m O p + (2n-p) H 2 0 <→ nC0 2 + 0, 5 (4n + m-2p) H 2
En ella se observa que la producción de hidrógeno no sólo deriva del producto orgánico seleccionado como materia prima, sino también de las propias moléculas de agua. It shows that hydrogen production not only derives from the organic product selected as raw material, but also from the water molecules themselves.
De manera preferida, el producto o productos orgánicos empleados en el procedimiento se caracterizan por presentar una miscibilidad total en agua. Asimismo, la concentración de dicho producto o productos orgánicos en la solución acuosa se encuentra comprendida, preferentemente, entre 0,5 y 4 molar. Preferably, the organic product or products used in the process are characterized by having a total miscibility in water. Also, the concentration of said organic product or products in the aqueous solution is preferably between 0.5 and 4 molar.
En una realización preferida de la invención, el producto orgánico empleado en el procedimiento puede consistir en un producto residual o derivado de la biomasa. De manera aún más preferida, el producto orgánico puede consistir en al menos un producto orgánico derivado de la biomasa, preferentemente seleccionado de un grupo que consiste en melazas (residuos de la fabricación del azúcar de caña o remolacha), alcoholes, éteres y glicoles, asi como cualquiera de sus combinaciones. De entre estos productos es posible emplear, de manera preferente, metanol, etanol (preferentemente derivado de procesos de fermentación), glucosas, fructosas y azúcares en general, asi como cualquiera de sus combinaciones. Entre los glicoles, destaca de manera preferida la glicerina procedente de la producción de biodiesel. In a preferred embodiment of the invention, the organic product used in the process may consist of a residual product or biomass derivative. Even more preferably, the organic product may consist of at least one organic product derived from biomass, preferably selected from a group consisting of molasses (residues from the manufacture of cane or beet sugar), alcohols, ethers and glycols, as well as any of its combinations. Among these products, it is possible to use, preferably, methanol, ethanol (preferably derived from fermentation processes), glucoses, fructose and sugars in general, as well as any combination thereof. Among glycols, glycerin from biodiesel production stands out in a preferred manner.
De manera adicional, el producto orgánico puede consistir en un producto procedente de la licuefacción y/o pirólisis de la madera. Additionally, the organic product may consist of a product from liquefaction and / or pyrolysis of wood.
Asimismo, en una realización adicional de la invención, el producto orgánico puede consistir en un producto residual orgánico procedente de la industria, preferentemente, taladrina, aguas negras de la industria papelera y, en general, aquellos productos residuales que sean miscibles en agua. A diferencia de la electrólisis del agua, puesto que los alcoholes y, en general, los productos orgánicos presentan una cierta conductividad, no es necesario adicionar en este caso electrolitos ácidos o básicos a la solución acuosa. Debido a ello, el efecto de la corrosión en los electrodos es mucho menor, lo que supone una importante ventaja frente a la producción de hidrógeno mediante electrólisis de agua. Also, in a further embodiment of the invention, the organic product may consist of an organic waste product from the industry, preferably taladrina, sewage from the paper industry and, in general, those waste products that are miscible in water. Unlike water electrolysis, since alcohols and, in general, organic products have a certain conductivity, it is not necessary in this case to add acidic or basic electrolytes to the aqueous solution. Due to this, the effect of corrosion on the electrodes is much less, which represents an important advantage over the production of hydrogen by water electrolysis.
Con objeto de llevar a cabo la electrólisis, es posible emplear cualquier tipo de celda de electrólisis comúnmente conocida en la técnica. In order to carry out electrolysis, it is possible to employ any type of electrolysis cell commonly known in the art.
El voltaje empleado en dicha celda de electrólisis puede estar comprendido, preferentemente, entre 0,5 V y 0,9 V en corriente continua. De este modo, es posible emplear voltajes que representan aproximadamente la mitad del voltaje habitualmente requerido en la electrólisis del agua, generalmente, en torno a 1,4 V en corriente continua. The voltage used in said electrolysis cell may preferably be between 0.5 V and 0.9 V in direct current. Thus, it is possible to employ voltages that represent approximately half of the voltage usually required in the electrolysis of water, generally around 1.4 V in direct current.
De manera adicional, con la finalidad de facilitar el proceso y mejorar la disolución y miscibilidad de los productos orgánicos, es posible emplear ultrasonidos como agente agitador molecular de la disolución, durante el tiempo en que transcurra la reacción. De manera preferida, la frecuencia de ultrasonidos empleada en el procedimiento se encuentra comprendida entre 50 kHz y 3 MHz . Estas frecuencias se alcanzan mediante la aplicación de una corriente doméstica o industrial de mayor voltaje y frecuencia a un cristal piezoeléctrico, donde son transformados en energía mecánica según el conocido efecto piezoeléctrico inverso. De este modo, de manera preferida, la celda de electrólisis seleccionada es diseñada de modo que permita la aplicación de ultrasonidos, los cuales logran la agitación molecular necesaria para incrementar la eficacia y productividad de la celda. De manera preferente, dicha celda electrolítica comprende al menos dos compartimentos que contienen un cátodo y un ánodo, así como un transductor situado preferentemente en la cara externa de la celda, donde se generan los ultrasonidos. De este modo, de manera preferida, la aplicación de ultrasonidos a la celda se lleva a cabo por la parte externa de los compartimentos y, a tal efecto, la pared metálica de los mismos se diseña preferentemente con un espesor inferior a 1 mm, al menos en su base inferior, con objeto de lograr una transmisión adecuada de los ultrasonidos. Additionally, in order to facilitate the process and improve the dissolution and miscibility of organic products, it is possible to use ultrasound as the molecular agitator of the solution, during the time the reaction takes place. Preferably, the ultrasonic frequency used in the process is between 50 kHz and 3 MHz. These frequencies are achieved by applying a domestic or industrial current of higher voltage and frequency to a piezoelectric crystal, where they are transformed into mechanical energy according to the known inverse piezoelectric effect. Thus, preferably, the selected electrolysis cell is designed to allow the application of ultrasound, which achieves the molecular agitation necessary to increase the efficiency and productivity of the cell. Preferably, said electrolytic cell comprises at least two compartments containing a cathode and an anode, as well as a transducer preferably located on the outer face of the cell, where the ultrasound is generated. Of this mode, preferably, the application of ultrasound to the cell is carried out by the external part of the compartments and, for this purpose, the metal wall thereof is preferably designed with a thickness of less than 1 mm, at least in its lower base, in order to achieve adequate transmission of ultrasound.
De este modo, a diferencia de la electrólisis del agua, en la que se genera oxigeno en el cátodo, en la electrólisis de productos orgánicos el producto resultante de la oxidación es CO2. Por lo tanto, los productos de la electrólisis son, por una parte, los derivados u obtenidos a partir de la biomasa (generación renovable de hidrógeno) y, por otra parte, los derivados de los productos residuales orgánicos procedentes de la industria. Ello supone una gran ventaja puesto que, como es sabido, el tratamiento de residuos se encuentra sometido a una exigencia normativa ambiental muy rigurosa. De este modo, mediante el método de electrólisis objeto de la presente invención, se consigue evitar la generación de productos derivados de la combustión como las dioxinas o los furanos generados en la incineración o coincineración, siendo estos métodos muy contestados socialmente desde el punto de vista ambiental . Thus, unlike water electrolysis, in which oxygen is generated in the cathode, in the electrolysis of organic products the product resulting from oxidation is CO 2 . Therefore, electrolysis products are, on the one hand, those derived or obtained from biomass (renewable hydrogen generation) and, on the other hand, those derived from organic waste products from industry. This is a great advantage since, as is known, the treatment of waste is subject to a very strict environmental regulatory requirement. Thus, by means of the electrolysis method object of the present invention, the generation of combustion products such as dioxins or furans generated in incineration or co-incineration is avoided, these methods being very socially answered from the point of view environmental.
Asimismo, el procedimiento descrito permite obtener hidrógeno de alta pureza, siendo dicha pureza superior al 99%. Dicho hidrógeno, por su elevada pureza, puede ser directamente consumido o almacenado hasta su consumo. Entre las distintas aplicaciones del hidrógeno generado cabe mencionar su empleo en celdas de pilas de combustible, o su almacenamiento en botellas o tanques, entre otros ejemplos. Likewise, the described process allows obtaining high purity hydrogen, said purity being greater than 99%. Said hydrogen, due to its high purity, can be directly consumed or stored until its consumption. Among the different applications of the hydrogen generated, it is worth mentioning its use in fuel cell cells, or its storage in bottles or tanks, among other examples.
Breve descripción de las figuras Brief description of the figures
La figura 1 muestra un diseño básico de una celda de electrólisis dividida en dos compartimentos que comprenden un ánodo y un cátodo, respectivamente, donde: Figure 1 shows a basic design of an electrolysis cell divided into two compartments comprising an anode and a cathode, respectively, where:
1. Entrada de solución acuosa que comprende al menos un producto orgánico; 2. Ultrasonidos; 1. Aqueous solution inlet comprising at least one organic product; 2. Ultrasound;
3. Ánodo ; 3. Anode;
4. Cátodo ; 4. Cathode;
5. Hidrógeno ; 5. Hydrogen;
6. Dióxido de carbono; 6. Carbon dioxide;
Descripción preferida de la invención Preferred Description of the Invention
A continuación se presenta, a modo de ejemplo y con carácter no limitante, una realización preferida del procedimiento objeto de la invención. En dicha realización particular, el procedimiento de electrólisis se llevó a cabo a partir de una solución acuosa de un producto orgánico en una concentración en la solución acuosa de 0.5 a 4 molar. A preferred embodiment of the process object of the invention is presented below by way of example and on a non-limiting basis. In said particular embodiment, the electrolysis process was carried out from an aqueous solution of an organic product in a concentration in the aqueous solution of 0.5 to 4 molar.
La introducción de dicha solución acuosa en la celda electrolítica se llevó a cabo por la parte inferior de la misma mediante el empleo de una bomba de alimentación o por un sistema de vasos comunicantes y gravedad, en una cantidad suficiente para cubrir por completo el cátodo y el ánodo de la celda. The introduction of said aqueous solution into the electrolytic cell was carried out by the lower part thereof by means of the use of a feed pump or a system of communicating vessels and gravity, in an amount sufficient to completely cover the cathode and The anode of the cell.
El voltaje empleado para llevar a cabo el procedimiento de electrólisis fue de 0,9 V, dando como resultado una corriente de ¾ en el ánodo y una corriente CO2 en el cátodo. Asimismo, se aplicaron ultrasonidos por la parte externa de los dos compartimentos de la celda, siendo el espesor de la pared metálica de la base inferior de la celda inferior a 1 mm. The voltage used to carry out the electrolysis procedure was 0.9 V, resulting in a current of ¾ at the anode and a CO 2 current at the cathode. Also, ultrasound was applied on the outside of the two compartments of the cell, the thickness of the metal wall of the lower base of the cell being less than 1 mm.
De este modo, se obtuvo una corriente de hidrógeno con una pureza superior al 99%. In this way, a stream of hydrogen with a purity greater than 99% was obtained.
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES201031560A ES2381231B1 (en) | 2010-10-26 | 2010-10-26 | PROCEDURE FOR THE PRODUCTION OF HYDROGEN BY ELECTROLYSIS OF A WATER SOLUTION OF ORGANIC PRODUCTS. |
| ESP201031560 | 2010-10-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2012056071A1 true WO2012056071A1 (en) | 2012-05-03 |
Family
ID=45993206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/ES2011/070725 Ceased WO2012056071A1 (en) | 2010-10-26 | 2011-10-20 | Method for the production of hydrogen by means of the electrolysis of an aqueous solution of organic products |
Country Status (2)
| Country | Link |
|---|---|
| ES (1) | ES2381231B1 (en) |
| WO (1) | WO2012056071A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4395316A (en) * | 1981-02-17 | 1983-07-26 | Institute Of Gas Technology | Hydrogen production by biomass product depolarized water electrolysis |
| US5417817A (en) * | 1994-06-15 | 1995-05-23 | Dammann; Wilbur A. | Biomass gasification process and apparatus |
| US20030226763A1 (en) * | 1997-09-10 | 2003-12-11 | California Institute Of Technology | Hydrogen generation by electrolysis of aqueous organic solutions |
| ES2299388A1 (en) * | 2006-11-08 | 2008-05-16 | Consejo Superior De Investigaciones Cientificas | REACTOR FOR THE ELECTROCHEMICAL TREATMENT OF BIOMASS. |
-
2010
- 2010-10-26 ES ES201031560A patent/ES2381231B1/en active Active
-
2011
- 2011-10-20 WO PCT/ES2011/070725 patent/WO2012056071A1/en not_active Ceased
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4395316A (en) * | 1981-02-17 | 1983-07-26 | Institute Of Gas Technology | Hydrogen production by biomass product depolarized water electrolysis |
| US5417817A (en) * | 1994-06-15 | 1995-05-23 | Dammann; Wilbur A. | Biomass gasification process and apparatus |
| US20030226763A1 (en) * | 1997-09-10 | 2003-12-11 | California Institute Of Technology | Hydrogen generation by electrolysis of aqueous organic solutions |
| ES2299388A1 (en) * | 2006-11-08 | 2008-05-16 | Consejo Superior De Investigaciones Cientificas | REACTOR FOR THE ELECTROCHEMICAL TREATMENT OF BIOMASS. |
Non-Patent Citations (3)
| Title |
|---|
| HU ET AL.: "Pt-WC/C as a cathode electrocatalyst for hydrogen production by nethanol electrolysis", JOURNAL OF POWER SOURCES, vol. 166, 2007, pages 458 - 461 * |
| MARSHALL ET AL.: "Production of hydrogen by the electrochemical reforming of glycerol-water solutions in a PEM electrolysis cell.", INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 33, 2008, pages 4649 - 4654 * |
| SASIKUMAR ET AL., INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 33, 2008, pages 5905 - 5910 * |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2381231A1 (en) | 2012-05-24 |
| ES2381231B1 (en) | 2013-04-26 |
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