• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    Method for obtaining palladium sulfide nanoparticles supported on carbon materials comprising simultaneously supporting the sulfur and palladium elements on the surface of such materials, where said elements are supported on the surface of the materials by means of a deposition or a anchoring of the elements and activation treatment in a reducing atmosphere; and application of the nanoparticles prepared according to this process as selective catalysts for the partial hydrogenation of polyolefins and acetylenic hydrocarbons containing between 2 and 5 carbon atoms. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2595027A1
    申请号:ES201400992
    申请日:2014-12-05
    公开日:2016-12-27
    发明作者:Antonio Guerrero Ruiz；Eva CASTILLEJOS LOPEZ；Inmaculada RODRIGUEZ RAMOS；Belén BACHILLER BAEZA；Marcos FERNANDEZ GARCIA；Ana IGLESIAS JUEZ
    申请人:Universidad Nacional de Educacion a Distancia UNED；
    IPC主号:
    专利说明:

    Within the scope of the present invention, "reducing atmosphere" or "reducing conditions" means an environment free or essentially free of oxygen. Typically, it is an atmosphere of hydrogen or a mixture of hydrogen with an inert gas (nitrogen, argon or helium). As for the "reactive atmospheres" they may be constituted by the said reducing atmosphere together with hydrocarbons
    Acetylenics or alkynes, that is to say with a triple bond between two of their carbon atoms (such as acetylene), or by hydrocarbons with several double bonds (such as 1,3-butadiene), or by mixtures of said polyunsaturated hydrocarbons with saturated hydrocarbons or with monoolefins. The present invention is directed to the preparation and identification of a new phase of nano particles of palladium sulfide (hereinafter, PdS) supported on carbon material, for example, carbon fibers, which will be applied in the partial hydrogenation of hydrocarbons with two double bonds or with a triple bond, in order to obtain mono-unsaturated olefins, inhibiting the obtaining of thermodynamically favored products. Thus, for example, in the hydrogenation of 1,3-butadiene, the undesired product is not obtained, that is to say butane saturated hydrocarbon, but different butene isomers are formed. The reactions can be carried out in the gas phase, at atmospheric pressure and at moderate operating temperatures, less than 200 oC. Finally, it should be noted that under certain reaction conditions the yield on olefin production is stable over time. A first aspect of the invention relates to the preparation of PdS nanoparticles in carbon materials comprising the step of simultaneously supporting sulfur and palladium on said material, which can be carried out either by anchoring or deposition of said elements. on the surface of the materials. To prepare the PdS nanoparticles by deposition of sulfur and palladium, it is based on a suitable precursor that can be any salt or coordination compound containing palladium, for example, PdS04. Alternatively, to prepare nanoparticles of PdS, by way of anchoring, a prior modification of the carbon material surfaces is carried out by means of functionalization (incorporation of chemical species on the surfaces) with sulfur-containing compounds, especially sulfonic groups and, then, the addition or incorporation of an active phase, for example, palladium. Optionally, the anchor comprises the generation of sulfonic groups on the surface of the carbon materials by a previous modification of the surface with the use of sulphanilic acid and the addition of isoamyl nitrite. According to another option, the preliminary modification of the surface of the carbon materials is done with smoking sulfuric acid to generate sulfur compounds and, subsequently, subsequent incorporation of palladium. According to an optional embodiment, the incorporation of palladium comprises the impregnation or adsorption of dissolved palladium ions. In the present invention, the following are used as precursors: Pd Cb, PdAc2, PdOH2.
    At the end of the deposition of sulfur and palladium on the carbon materials, an activation of the materials is carried out under reducing conditions, that is, a reduction stage is carried out, which is carried out in an atmosphere containing hydrogen, at a temperature of between 150 and 300 ° C. An additional aspect refers to the application of the PdS nanoparticles, prepared according to the procedure described above, which are used as catalysts in the selective hydrogenations of polyolefins and acetylenic hydrocarbons, containing between 2 and 5 carbon atoms. To weigh the results of the present invention, the special catalytic properties of said nanoparticles have been evaluated in the gas phase hydrogenation of 1,3-butadiene, at atmospheric pressure and at temperatures between 25 and 200 ° C. The great performance in the production of butenes is surprising when the supported nanoparticles are used as catalysts of the present invention. The nanoparticles prepared here have chemical compositions suitable for use as selective catalysts in the hydrogenation of 1,3-butadiene, exclusively in butenes, and other unsaturated olefins and with triple carbon-carbon bonds. The nanoparticles are prepared by supporting sulfur and palladium on a carbon material, by deposition or anchoring of the sulfur and palladium precursors and obtaining them on said material. Examples of carbon materials used in this invention are the following: carbon fibers with or without prior graffiti, carbon nanotubes, active carbons or graphites with a surface area between 100 and 1000 m2 / g. Any type of carbon material, for use as a support for metal catalysts (fibers, nanotubes, activated carbon, graphites, etc.), can be modified by incorporating sulfur-containing chemical species on its surface. In this invention, when using the PdS nanoparticles as selective catalysts in the hydrogenation of butadiene, it has surprisingly been found that the selectivity towards olefins is at least triple the result obtained when the palladium nanoparticles are supported in any other material, both metallic oxides and carbonaceous materials, provided that the precursors of Pd are the most conventional, that is to say that they do not have sulfur in their composition, regardless of the size of the generated nanoparticles of Pd. Likewise, it is found that, by using PdS nanoparticles as catalysts prepared from sulfur-containing precursors in its formulation, for example, palladium sulfate, selectivity results towards monoolefins in butadiene hydrogenation are improved, practically the
    Only products are butenes, compared to palladium nanoparticles prepared from other metal precursors.
    EXAMPLES OF THE INVENTION In order to describe the present invention in an illustrative manner but in no way limiting, the following examples are shown. Example 1: Obtaining nanoparticles with palladium sulfate as a precursor Carbon material: commercial carbon fibers (Pyrograf, codes PR24-PS and PR24-HTT) supplied by Applied Sciences Inc. Their surface areas are between 30 and 40 square meters per gram . This example shows the pathway of the deposition of the sulfur and palladium elements on the carbon material. Without prior modifications to the surface of the material, they are incorporated
    or deposit, on the carbon fibers, salts of palladium sulfate containing sulfur in a proportion of between 1% and 5%, by weight, and which are the precursors of the metal Pd. Then, a reduction treatment is carried out at a temperature of 250 oC, under a reducing atmosphere current, 10 cm3 / minute of H2 along with 80 cm3 / minute of inert helium gas. Palladium Sulfide nanoparticles are generated.
    Example 2: Obtaining nanoparticles with sulfanilic acid and Pd chloride (PdCIz.}. As a precursor Here, an anchoring of sulfur-containing species on the carbon fibers is carried out. To this end, a dispersion of the fibers of carbon (PR24-PS and PR24-HHT) in dimethylfuran (according to a ratio of 1 g of fiber per 100 ml of solvent), with subsequent reflux and reaction in an inert atmosphere with 6 mmol of sulphanilic acid / g of fiber. add isoamyl nitrite (10% of the total volume of the solution) and stir continuously for 24 h. Wash with distilled water and dry in an oven at 100 oC, for more than 10 hours. Subsequently, on the functionalized fibers it is incorporated Pd by incipient impregnation.To do this, PdCI2 is dissolved in concentrated HCI, which forms H2PdCI4, which is dissolved in water.This solution is added dropwise onto the carbon fibers until the final Pd content is of the order of 1% , by weight, with respect to the support. Next, an activation stage is performed under reducing conditions (reducing atmosphere) at 200 ° C. Following this treatment, highly selective palladium sulfide nanoparticles are generated for application in partial hydrogenations of polyunsaturated hydrocarbons.
    Example 3: Obtaining nanoparticles with smoking sulfuric acid and palladium chloride (PdClz) as a precursor It is based on a carbon material, such as carbon fibers PR24-PS and PR24-HHT. 3 grams of fibers are taken and immersed in a volume of 150 ml of smoking sulfuric acid (15%, by weight, of S03), kept at 80 oC, for 7 hours, in an inert atmosphere. Then, the materials are washed with distilled water and dried in an oven at 120 oC, overnight. Thus, sulfur species are fixed in significant percentage amounts. The palladium precursor (PdCI2) is introduced, between 1 and 5%, by weight, proceeding in the same manner as in Example 2. Finally, an activation stage of the material is carried out in a reducing atmosphere at 250 oC. Thus, palladium sulfide nanoparticles are obtained that are active, selective and stable when used as catalysts in the partial hydrogenation of butadiene, generating butenes.
    Example 4: Partial hydrogenation of butadiene Between 0.01 and 0.10 g of any Pd catalyst, obtained as indicated in examples 1, 2 or 3, are placed in a glass or steel tube with an internal diameter of 4 mm, together with an inert material (glass beads or silicon carbide grains). Before the reaction, the catalyst is treated in a reducing atmosphere as specified below: 10% hydrogen in nitrogen, with a total flow rate of 50 cm3 / minute, at 250 oC, for 1 hour. The reaction mixture contains 10% hydrogen, 2% 1,3-butadiene and a total flow rate of 60 ml / min. The reaction temperatures are adjusted to have an adequate yield in butenes varying between 100 and 200 oC.
    Example 5: Obtaining nanoparticles of Pd sulfide in other carbon materials By applying the same methods described in Examples 1, 2 and 3, PdS nanoparticles can be synthesized from various commercial carbon materials. For example, and without being exclusive, multipared carbon nanotubes, active carbons or graphites with high surface are used. All of them can be obtained from external suppliers.
    Example 6: Partial hydrogenation of alguines and alguine mixtures in algenes According to the same experimental procedures described in example 4, the catalysts described in examples 1, 2, 3 and 5 can be used for reactions of mechanisms similar to that of butadiene for give butenos. Among them, and without being exclusive, are indicated: hydrogenation of acetylene to ethylene, hydrogenation of acetylene contained in mixtures rich in ethylene without ethane, hydrogenation of butadiene contained in mixtures rich in butenes without butane.
    5 Example 7: Characterization of catalytic nanoparticles The characterization of all materials, supports and catalysts has been carried out by various techniques: thermal analysis, X-ray diffraction, desorption of programmed temperature decomposition with detection of gases emitted by mass spectrometry , transmission electron microscopy and
    10 X-ray photoelectronic spectroscopy. Special mention should be made of X-ray diffraction studies performed in situ and using synchrotron radiation. These last measures have allowed us to follow the genesis of the Pd sulfide nanoparticles, confirm their structure and check their stability during the hydrogenation reaction of 1,3-butadiene.
    权利要求:
    Claims (14)
    [1]
     Claims
    one. Procedure for obtaining palladium sulfide nanoparticles supported in carbon materials, characterized by understanding the step of simultaneously supporting sulfur and palladium on the carbon materials.
    [2]
    2. Method according to claim 1, characterized in that the step of supporting the sulfur and palladium precursors on the carbon materials is carried out by deposition.
    [3]
    3. Method according to claim 1, characterized in that the step of supporting sulfur and palladium on the carbon materials is carried out by means of a previous modification of the surface of the carbon material and an anchor.
    [4]
    Four. Process according to claims 1 to 3, characterized in that the carbon materials are carbon fibers, carbon nanotubes, activated carbon or graphite with a surface area between 100 and 1000 m2.
    [5]
    5. A process according to claims 1 to 4, characterized in that the carbon fiber is a graffiti carbon fiber.
    [6]
    6. A process according to claims 1 and 2, characterized in that after the deposition of sulfur and palladium a reduction stage is performed.
    [7]
    7. A process according to claim 6, characterized in that the reduction is carried out in an atmosphere containing hydrogen, at a temperature between 150 and 300 ° C.
    [8]
    8. A method according to claim 3, characterized in that the anchor comprises the generation of sulfonic groups on the surface of the carbon materials and, subsequently, the incorporation of palladium.
    [9]
    9. A process according to claim 8, characterized in that the generation of sulfonic groups is carried out by means of a previous modification of the surface of the carbon materials with the use of sulphanilic acid and the addition of isoamyl nitrite.
    [10]
    10. A method according to claim 3, characterized in that the anchor comprises the generation of sulfur compounds by preliminary modification of the surface of the carbon materials with smoking sulfuric acid and, subsequently, incorporation of palladium.
    [11]
    eleven. A method according to claim 8, characterized in that the incorporation of palladium comprises the impregnation or adsorption of dissolved palladium ions.
    [12]
    12. A method according to claim 11, characterized in that Pd Cb, PdAc2, PdOH2 are used as precursors.
    [13]
    13. A process according to claims 1 to 12, characterized by producing PdS nanoparticles for application as catalysts in the selective hydrogenations of polyolefins and acetylenic hydrocarbons, containing between 2 and 5 carbon atoms.
    [14]
    14. A process according to claims 1 to 13, characterized by producing PdS nanoparticles that act as selective catalysts for the hydrogenation of 1,3 butadiene exclusively in butenes.
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    同族专利:
    公开号 | 公开日
    ES2595027B1|2017-10-09|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN109261170A|2018-11-12|2019-01-25|山东大学|A kind of Pd@Pd4Porous carbon nanomaterial of S- and its preparation method and application|
    法律状态:
    2016-03-01| PC2A| Transfer of patent|Owner name: UNIVERSIDAD NACIONAL DE EDUCACION A DISTANCIA Effective date: 20160224 |
    2016-03-31| FA2A| Application withdrawn|Effective date: 20160323 |
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    ES201400992A|ES2595027B1|2014-12-05|2014-12-05|Procedure for obtaining palladium sulfide nanoparticles supported on carbon materials, and their application in selective hydrogenation of polyolefins and acetylenic hydrocarbons|ES201400992A| ES2595027B1|2014-12-05|2014-12-05|Procedure for obtaining palladium sulfide nanoparticles supported on carbon materials, and their application in selective hydrogenation of polyolefins and acetylenic hydrocarbons|
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