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  • 专利说明
  • 权利要求
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    • 专利摘要:
    Photocatalyst for the production of hydrogen, which is based on a combination of oxides of copper, iron, titanium and tin, the new photocatalyst being represented by the following formula (1): Cu2O (a)/Fe2O3/ TiO2/ SnO (I) where (a) represents the amount of copper oxide, an ingredient that acts as an electron acceptor, with respect to the rest of the oxides, and having a value of 0.5 to 1% by weight based on the total weight of the compound; and method of obtaining said photocatalyst. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2653694A1
    申请号:ES201731437
    申请日:2017-12-20
    公开日:2018-02-08
    发明作者:Alvaro Jose ARENAS GINÉS；Grigory Miller；Valerii ADAMOVICH KOVALCHUK
    申请人:Alvaro Jose ARENAS GINÉS；Grigory Miller；Valerii ADAMOVICH KOVALCHUK；
    IPC主号:
    专利说明:

    image 1
    PHOTOCATALIZER FOR THE PRODUCTION OF HYDROGEN AND METHOD FOR OBTAINING SUCH PHOTOCATALIZER DESCRIPTION
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    Photocatalyst for hydrogen production and method for obtaining said photocatalyst. OBJECT OF THE INVENTION
    The object of the present invention is the description of a new photocatalyst that can be used for the production and production of hydrogen, composed of different oxides and obtained from the combination of different metal sulfates. This method also defines the method by which said photocatalyst is obtained.
    The field of application of the present invention is the industrial sector related to the production of photocatalysts, more especially with photocatalysts whose objective is to produce hydrogen. 20 STATE OF THE INVENTION TECHNIQUE
    It is known within the industrial sector of hydrogen production, that obtaining it from photocatalytic processes is one of the most promising options for obtaining hydrogen from sunlight. However, studies of specialized journals such as Nature
    25 Chemistry show that the efficiency of known photocatalysts for this type of system is still very low and economically expensive to achieve.
    In this sense, photocatalysts for hydrogen production are known within the state of the art, but all of them are based on a composition and base elements that differ from the
    30 which is described in the present invention, and with which the production costs rise, and the process or method of obtaining it not only differs, but technically and
    image2
    Economically it is more complex.
    The existence of cadmium sulphide (CdS) based photocatilizers is known, as for example disclosed in patent EP1127614 where the photocatalyst is represented by the following formula:
    m (A) / Cd [M (B)] S where m represents an impurified metal element such as an electron accelerator, and M is a catalyst element.
    It is also known what is disclosed in patent EP0778793 where a photocatalyst for the production of hydrogen is exposed consisting of a catalytically active ingredient such as Cesium (Cs) with which a support K4Nb6O17 is impregnated so that the photocatalyst is represented by the following formula:
    Cs (a) / K4Nb6O17
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    The existence of photocatalysts for the production of hydrogen based on a mixture of zinc sulphide and molybdenum sulphide, as disclosed in EP2867169, is known.
    20 Photocatalysts for the production of hydrogen based on ZnS are also known, as disclosed in EP0930939 and having the following formula:
    Pt (a) / Zn [M (b)] S and where hydrogen generation is based on a mixture of the photocatalyst in an aqueous medium with Na2S and NaH2PO2.
    25
    Also related to the present invention it is emphasized that the existence of photocatalysts based solely on titanium dioxide; for example the photocatalyst disclosed in EP1713726 where hydrated titanium dioxide is precipitated from an aqueous solution of titanium oxychloride by adding particles of titanium dioxide 30 in the form of crystalline nuclei and isolating and calcining the resulting product of the precipitation stage; what is disclosed in document EP1681370 where a photocatalyst is prepared
    image3
    based on TiO2 powder with the aim of improving protection for substrates or surface layers sensitive to the photocatalytic layer; or procedures for obtaining hydrogen from TiO2 photocatalysts doped with Platinum as disclosed in patent ES2524492.
    5
    Given the solutions and background in the state of the art, the present invention describes a new photocatalyst for the production of hydrogen, composed of a mixture of different oxides and based on the combination of metal sulfates, essentially iron, titanium and tin, as well as for obtaining said photocatalyst
    10 a method is required that causes improved performance compared to the previous ones, with lower costs and times, and in which components with better ecological performance are used, which makes its industrial implementation more favorable with respect to existing processes in the state of the art. 15 DESCRIPTION OF THE INVENTION
    The present invention consists of a new photocatalyst composed of different oxides and based on different metal sulfates in combination, this new photocatalyst being used for the production of hydrogen, since the combination of this in low liquid water
    20 the influence of energy or sunlight generates a reaction that produces hydrogen.
    In this sense, the present invention, compared to other photocatalysts known in the state of the art, introduces the possibility of relying on more abundant and less expensive products, which increases the profitability of the process, as well as based on elements
    25 more environmentally beneficial, which generates a smaller impact compared to those known to date.
    Specifically, the new photocatalyst for hydrogen production proposed in the present invention has a composition represented by the following formula (I):
    30
    Cu2O (a) / Fe2O3 / TiO2 / SnO (I)
    image4
    As can be seen, it is a metal oxide compound, in particular of oxides of copper, iron, titanium and tin; where copper oxide is an electron acceptor, and where its proportion is determined by the value (a) corresponding to 0.5-1% by weight based on
    5 the total weight of the compound
    In order to obtain the new photocatalyst, a method of obtaining is required, comprising the following stages:
    10 a) FeSO4, Ti (SO4) 2 and Sn SO4 metal sulfates are dissolved in distilled water; where the proportion by weight over the total solution of FeSO4, Ti (SO4) 2 and Sn SO4 is between:
    - FeSO4: 60-75%;
    - Ti (SO4) 2: 5-20%; and 15 - Sn SO4: 15-30%.
    b) a concentrated solution of Na (OH) 2 is added in the solution of step a) in a concentration not greater than the total mass of the solution of step a);
    C) the mixture resulting from the combination of the previous steps is rested, and where the rest time is between 6 and 24 hours;
    d) the precipitate obtained from step c) is filtered;
    E) the resulting obtained from step d) is rested, and where the rest time is between 48 and 120 hours .;
    f) the result obtained from step e) is ground and sieved;
    30 g) Cu2O is added to the result of step f); where the added Cu2O is between 0.5-1% with respect to the total mass obtained in said stage f).
    h) the product obtained in step g) is heated to a temperature of at least 400 ° C;
    image5
    i) the product obtained from step h) is ground and sieved; Y
    5 j) the photocatalyst with composition Cu2O (a) / Fe2O3 / TiO2 / SnO is obtained
    This new photocatalyst obtains its main advantage that it requires to obtain daily conditions with respect to ambient temperature and / or atmospheric pressure, adapting its production to simple means when compared to obtaining any
    10 another known photocatalyst.
    By way of example, and in greater detail with respect to what was previously indicated, separating the different base compounds from which the obtaining of the photocatalyst starts, then the method of obtaining said photocatalyst is expanded and detailed, where:
    fifteen
    a) FeSO4, Ti (SO4) 2 and Sn SO4 metal sulfates are dissolved in distilled water; where the proportion by weight over the total solution of 65% FeSO4, 15% Ti (SO4) 2 and 20% Sn SO4;
    b) a concentrated solution of Na (OH) 2 is added in the solution of step a) in a concentration not greater than the total mass of the solution of step a); c) the mixture resulting from the combination of the stages is allowed to stand for 12 hours
    previous; d) the precipitate obtained from step c) is filtered; e) the result obtained from step d) is set aside 80 hours;
    F) the resulting obtained from step e) is ground and sieved; g) Cu2O is added to the result of step f); where the added Cu2O is 0.75% in
    mass with respect to the total mass obtained in said stage f). h) the product obtained in step g) is heated to a temperature of 450 ° C; i) the product obtained from step h) is ground and sieved; Y
    30 j) the photocatalyst with composition Cu2O (a) / Fe2O3 / TiO2 / SnO is obtained where the value (a) corresponding to 0.75% by weight based on the total weight of the compound.
    image6
    Finally, it is considered that any other characteristic, advantage and type of realization of which has been described previously is easily clear to the normal technicians of this industrial sector after reading the previous arguments. In this sense, although the specific embodiment of the method of obtaining the photocatalyst has been described in great detail, it has been
    5 tried to elaborate the description from a broad and non-limiting sense, whereby slight variations and modifications can be made without departing from the scope of the invention as described and what is claimed below.
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    权利要求:
    Claims (5)
    [1]
    image 1
    1.-Photocatalyst for the production of hydrogen, which is characterized in that it is based on a combination of oxides of copper, iron, titanium and tin, and is represented in the following formula (I):
    Cu2O (a) / Fe2O3 / TiO2 / SnO (I) where (a) represents the amount of copper oxide, an ingredient that acts as an electron acceptor, with respect to the other oxides, and has a value of 0.5 to 1 % by weight based on the total weight of the compound.
    10
    [2]
    2. Method of obtaining a photocatalyst according to the characteristics of claim 1,
    characterized by comprising the following steps: a) the metal sulfates FeSO4, Ti (SO4) 2 and Sn SO4 are dissolved in distilled water; b) a concentrated solution of Na (OH) 2 is added in the solution of step a) in a
    15 concentration not greater than the total mass of the solution of step a); c) the mixture resulting from the combination of the previous steps is rested; d) the precipitate obtained from step c) is filtered; e) the result obtained from step d) is rested; f) the result obtained from step e) is ground and sieved;
    20 g) Cu2O is added to the result of step f); h) the product obtained in step g) is heated to a temperature of at least 400 ° C; i) the product obtained from step h) is ground, sieved and mixed; and j) the photocatalyst is obtained.
    3. Method according to claim 2, characterized in that in step a) the proportion by weight over the total solution of FeSO4, Ti (SO4) 2 and Sn SO4 is comprised between:
    - FeSO4: 60-75%;
    - Ti (SO4) 2: 5-20%; Y
    - Sn SO4: 15-30%.
    30
    [4]
    4. Method according to claim 2, characterized in that in step c) the time of
    8
    image2
    Rest is between 6 and 24 hours.
    [5]
    5. Method according to claim 2, characterized in that in step e) the resting time is between 48 and 120 hours.
    5
    [6]
    6. Method according to claim 2, characterized in that in stage g) the added Cu2O is comprised between 0.5-1% with respect to the total mass obtained in stage f).
    10
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    9
    image3
    SPANISH OFFICE OF THE PATENTS AND BRAND
    image4 Application number: 201731437
    SPAIN
    Date of submission of the application: 20.12.2017
    image5 Priority Date:
    REPORT ON THE STATE OF THE TECHNIQUE
    image6 51 Int. Cl.: See Additional Sheet
    RELEVANT DOCUMENTS
    Category 56 Documents citedClaims Affected
    X US 2016129432 A1 (OZAKI TAKASHI et al.) 12/05/2016, Paragraphs [0072] and [0094].1-6
    X US 2008 280750 A1 (LIU PAO-CHU) 11/13/2008, Example 3.1-6
    X WO 2004058634 A2 (HONDA MOTOR CO LTD et al.) 07/15/2004, Page 4, lines 15-27.1-6
    X WO 2013046228 A1 (COUNCIL SCIENT IND RES et al.) 04/04/2013, Pages 13-14.1-6
    TO AYUELA DÍAZ DEL RÍO, FJ, PREPARATION OF CATALYSTS FOR THE REACTION OF DISPLACEMENT OF WATER GAS AT HIGH TEMPERATURE FROM METAL SULPHATES, Final Degree Project read at the Rey Juan Carlos University in the academic year 2010/2011, 06/27 / 2013 Recovered from the Internet <URL: http://hdl.handle.net/10115/11712>. Section 4.1.1-6
    Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the date of priority submission of the application E: previous document, but published after the date of submission of the application
    This report has been prepared • for all claims □ for claims no:
    Date of realization of the report 29.01.2018 Examiner M. d. Garcia PozaPage 1/2
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    同族专利:
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    ES2653694B2|2018-11-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2004058634A2|2002-12-20|2004-07-15|Honda Giken Kogyo Kabushiki Kaisha|Catalyst formulations for hydrogen generation|
    US20080280750A1|2007-05-09|2008-11-13|Pao-Chu Liu|Catalysts for treating acid and halogen gases and production methods thereof|
    WO2013046228A1|2011-09-30|2013-04-04|Council Of Scientific & Industrial Research|A process for generation of hydrogen and syngas|
    US20160129432A1|2013-07-05|2016-05-12|Nitto Denko Corporation|Filter Element for Decomposing Contaminants, System for Decomposing Contaminants and Method Using the System|
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