US20080261090A1 - Catalyst for a Catalytic Process Which is Used to Obtain Hydrogen from Bioethanol and/or Ethanol, Catalyst-Preparation Method and Use Thereof in Said Catalytic Process - Google Patents

Catalyst for a Catalytic Process Which is Used to Obtain Hydrogen from Bioethanol and/or Ethanol, Catalyst-Preparation Method and Use Thereof in Said Catalytic Process Download PDF

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US20080261090A1
US20080261090A1 US11/795,257 US79525705A US2008261090A1 US 20080261090 A1 US20080261090 A1 US 20080261090A1 US 79525705 A US79525705 A US 79525705A US 2008261090 A1 US2008261090 A1 US 2008261090A1
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catalyst
hydrogen
oxide
active phase
water
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Manuel Jesus Benito Gonzalez
Juan Luis Sanz Yague
Ruth Isabel Gomez
Loreto Daza Bertrand
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GREENCELL SA
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GREENCELL SA
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    • H—ELECTRICITY
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    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
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    • C01B2203/0465—Composition of the impurity
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    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • C01B2203/1229—Ethanol
    • H—ELECTRICITY
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    • 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
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Definitions

  • the present invention belongs to the technical field of catalysts for reforming of ethanol or bioethanol and the production of hydrogen-rich gas streams which can be used in hydrogen production plants, combustion engines, and, especially, as fuel in fuel cell systems or other alternative uses.
  • Ethanol is a renewable source of energy that is playing an ever more important role in the quality of the air, the economic security of the agricultural sector and which is inducing changes in the safety of energy policy.
  • the constant advances in enzymatic and processing technology is increasing the viability of the production of ethanol starting from low-cost raw materials.
  • the different governments of Europe and America are encouraging the ethanol market by reducing and even eliminating the taxes that are otherwise levied on conventional fuels.
  • fuel cells are an emerging technology capable of increasing the energy efficiency and of drastically reducing the emissions of systems both mobile and stationary, in which this technology finds application.
  • Fuel cells need a source of hydrogen for producing electricity, but hydrogen is difficult to store and transport.
  • Ethanol is a liquid rich in hydrogen, which means that there are no technical barriers to using ethanol as a carrier of hydrogen for applications based on fuel cells. In this way, ethanol could be used as a source of hydrogen both in stationary applications and for mobile applications by means of a reforming process.
  • the reforming reaction is a complex reaction in which numerous secondary reactions can occur, with a series of by-products being able to be obtained, among which can be cited: acetaldehyde, methane, carbon monoxide, acetic acid, ethylene, diethyl ether and acetone.
  • the essential difficulty of this reaction lies in the fact that, according to the literature, one needs to work at very high steam/carbon ratios in order to avoid the formation of carbon deposits on the catalyst, which is the essential cause of poisoning of the catalysts that have been developed to date.
  • the composition of the ethanol obtained by fermentation is usually between 8-12%.
  • ethylene is a highly reactive compound which very easily decomposes to give carbon, which is deposited on the active centres of the catalyst producing its poisoning.
  • This poisoning can be detected from the drop in ethanol conversion, and in the distribution of products obtained, increasing the concentrations of secondary products, such as acetaldehyde, ethane, acetone, ethylene and diethyl ether.
  • transition metals which display high catalytic activity and, on the other hand, using supports with low surface acidity, or supports in which their basicity is increased.
  • the literature contains catalysts in which the support, specifically alumina, is modified with calcium oxide in order to neutralise its surface acidity and avoid dehydration reactions of the ethanol, successfully reducing the dehydration rate of the catalyst.
  • Another route used consists of basic supports such as magnesium oxide, but the results obtained have not succeeded in increasing the activity and stability of the catalyst in any appreciable way.
  • the present invention has the aim of a novel catalyst for a catalytic process for obtaining hydrogen from bioethanol and/or ethanol which would overcome the drawbacks of the state of the art, a process for the preparation of such catalyst and the use of the catalyst in such catalytic process.
  • the catalyst is a calcined solid comprising a support, a promoter agent and an active phase incorporated into the support, characterised in that the catalyst is a solid preferably calcined at a temperature of above 600° C., in which
  • the support comprises at least one oxide with high surface mobility, such as for example, zirconium oxide, and is a support modified with the promoter agent,
  • the promoter agent comprises at least one oxide of a rare earth metal selected from the lanthanide group, preferably lanthanum oxide, cerium oxide and combinations thereof,
  • the active phase comprises at least one oxide of a transition metal from group VIII or IB, preferably nickel, cobalt, copper, iron, rhodium, palladium, ruthenium, platinum and combinations thereof.
  • This catalyst used in catalytic processes of ethanol and bioethanol reforming, displays high catalytic activity, with a total conversion of ethanol, high selectivity for the production of hydrogen, without the formation of any secondary by-products, and high stability, without any appreciable deactivation after 500 hours of continuous operation, because it contains one or more oxides of group VIII transition metals as active phase, it uses as substrate an oxide with high surface mobility and as promoter one or more oxides of rare earth metals selected from the lanthanide group.
  • the transition metal used as active phase is nickel or cobalt
  • the substrate used as support is zirconium oxide
  • the rare earth metal used as promoter is lanthanum or cerium and its oxides La 2 O 3 and CeO 2 .
  • the catalyst consists of cobalt oxide (transition metal of the active phase), zirconium oxide (high surface mobility oxide) and lanthanum oxide (promoter agent), and it displays the following X-ray diffractogram,
  • the catalyst obtained was characterised by X-ray diffraction with diffraction peaks being detected corresponding to cobalt oxide, zirconium oxide and lanthanum oxide.
  • the equipment was provided with a secondary monochromator.
  • the identification of the crystalline phases was done taking as reference the X-ray diffraction database of the Joint Committee on Powder Diffraction Standards 1971, managed by means of a computing program known as PDFWIN.
  • this can include from 1 to 30% by weight of the promoter agent and from 1 to 15% by weight of the active phase.
  • the catalyst preferably includes from 5 to 11% by weight of the promoter agent and from 3 to 10% by weight of the active phase.
  • the catalyst includes from 8 to 10% by weight of lanthanum oxide as promoter agent and from 5 to 7% by weight of cobalt as active phase.
  • the high surface mobility oxide can have been calcined prior to being modified with the promoter agent.
  • the support modified with the promoter agent can have been calcined prior to incorporating the active phase.
  • the present invention also relates to a preparation process for the catalyst with the characteristics described above. This process comprises
  • a second stage in which the active phase is incorporated into the modified support in order to obtain a precursor of the catalyst for example by means of impregnation or adsorption in solution (preferably in an inert solvent), by means of a sol-gel process, by means of microemulsion or co-precipitation, with the precursor being subjected to a drying stage as necessary, and
  • zirconium oxide powder modified with lanthanum oxide or cerium oxide which is used as support, to which is homogenously incorporated a salt of the active phase, of nickel, cobalt or copper, prior to being calcined in the third stage at high temperature, for example, at a temperature between 700° C. and 900° C.
  • the support can previously be calcined at high temperature, such as for example, at a temperature of at least 700° C., and preferably at a temperature of between 750° C. and 900° C.
  • the present invention also relates to the use of the catalyst with the properties stated above in a method for obtaining hydrogen starting from bioethanol and/or ethanol, which method is a catalytic process of reforming a carrier (donor) of hydrogen selected from the group comprising ethanol, bioethanol and mixtures thereof, in which the hydrogen carrier is made to react with water, preferably in the form of steam, in the presence of the catalyst, at a temperature between 600° C. and 800° C. in order to obtain a mixture of gases containing hydrogen.
  • a carrier (donor) of hydrogen selected from the group comprising ethanol, bioethanol and mixtures thereof, in which the hydrogen carrier is made to react with water, preferably in the form of steam, in the presence of the catalyst, at a temperature between 600° C. and 800° C. in order to obtain a mixture of gases containing hydrogen.
  • ethanol/water ratios by volume of between 1/1.25 and 1/5 and preferably between 1/1.5 and 1/4, inclusive of both.
  • the ethanol/water ratio is 1/3 v/v ⁇ 10% or 1/2 v/v+10%.
  • pressures of between 0 and 5 bar are suitable, particularly between 0 and 3 bar.
  • the water and the hydrogen carrier are made to react at atmospheric pressure.
  • the water and the hydrogen carrier can be made to react at a temperature of between 650° C. and 750° C. and particularly at a temperature of 700° C. ⁇ 5%.
  • the mixture of gases containing the hydrogen, resulting from the reaction of the hydrogen carrier with the water is fed to a high temperature fuel cell.
  • this mixture containing the hydrogen that has been produced can be fed directly to the anode of a high temperature fuel cell, for example, molten carbonate fuel cells (MCFC) or solid oxide fuel cells (SOFC, IT-SOFC) without any need for purification.
  • MCFC molten carbonate fuel cells
  • SOFC solid oxide fuel cells
  • the mixture of gases containing the hydrogen, resulting from the reaction of the hydrogen carrier with the water is subjected to a purification stage in order to convert at least part of the carbon monoxide possibly present in the gas mixture into carbon dioxide in order to obtain a purified mixture of gases, and because said mixture is fed to a fuel cell.
  • a purification stage in order to convert at least part of the carbon monoxide possibly present in the gas mixture into carbon dioxide in order to obtain a purified mixture of gases, and because said mixture is fed to a fuel cell.
  • This embodiment is especially suitable for the case of intermediate temperature fuel cells, such as for example phosphoric acid fuel cells (PAFC), or low temperature fuel cells, such as for example polymer fuel cells (PEMFC), in which it is necessary to introduce different purification stages in order to reduce the concentration of carbon monoxide to the levels required for the correct functioning of those fuel cells (1% and 50 ppm, respectively).
  • PAFC phosphoric acid fuel cells
  • PEMFC polymer fuel cells
  • a reaction known as water gas shift (WGS) can be used, in which the carbon monoxide reacts with water to produce hydrogen and carbon dioxide.
  • WGS water gas shift
  • the advantage of this reaction is dual, since, as well as eliminating the CO present in the reforming stream, the hydrogen content is also increased.
  • the surplus concentration of CO that is usually left after the WGS stage is normally higher than what can be fed to a low temperature fuel cell of the polymer type.
  • PSA Pressure Swing Adsorption
  • methanation and selective oxidation of carbon monoxide there exist various alternatives, among which can be highlighted PSA (Pressure Swing Adsorption) systems, methanation and selective oxidation of carbon monoxide.
  • PSA Pressure Swing Adsorption
  • the present invention not only permits hydrogen to be obtained from bioethanol and/or ethanol, but also the stationary and non-stationary production of that hydrogen with a yield of hydrogen production that is close to thermodynamic under the conditions employed. Moreover, the mixture of gases generated can serve as a direct feed to fuel cells at medium or high temperature.
  • FIG. 1 is an X-ray diffractogram of an embodiment of the catalyst of the present invention
  • FIG. 2 is a diagram showing the results of the determination of the pore size of samples of the catalyst characterised in FIG. 1 ;
  • FIG. 3 shows the results of ethanol conversion tests conducted with the catalyst corresponding to FIGS. 1 and 2 ;
  • FIG. 4 shows the results of ethanol conversion tests conducted with the catalyst corresponding to FIGS. 1 and 2 ;
  • FIG. 5 shows the results of ethanol conversion tests conducted with another embodiment of the catalyst of the present invention.
  • FIG. 6 shows the results of ethanol conversion tests conducted with the same catalyst as that referred to in FIG. 5 .
  • Preparation of the catalyst 5 g of support were weighed out consisting of zirconium oxide modified with 10% of lanthanum oxide at 800° C. 1.299 g of cobalt nitrate hexahydrate were weighed out and dissolved in 100 ml of distilled water. The mixture was subjected to a vacuum of 0.5 to 0.7 bar, an approximate temperature of 70° C. and to a rotation at a speed of 20 rpm for 4 hours until complete dryness. The resulting powder was dried in an oven at 110° C. overnight. It was then calcined in air at 750° C. for 2 hours with a rate of heating of 5° C./min. Finally, the catalyst was left to cool slowly until it reached ambient temperature.
  • the catalyst obtained was characterised by X-ray diffraction with diffraction peaks being detected corresponding to cobalt oxide, zirconium oxide and lanthanum oxide.
  • the equipment was provided with a secondary monochromator.
  • the catalyst was likewise characterised texturally in order to determine the BET surface area by nitrogen adsorption, presenting a specific surface of 50 m 2 /g; the nitrogen adsorption/desorption isotherm is characteristic of a mesoporous solid ( FIG. 2 ).
  • 100 mg of catalyst were weighed out, obtained analogously to that stated in example 1, with particle size between sieve sizes 0.42-0.50 mm.
  • Water and ethanol were fed into a reactor in a ratio S/C 6.45 with a total flow of 0.1 ml/min without any carrier gas.
  • the reactor used in the catalytic tests is a stainless steel tube 316-L with a length of 300 mm, an internal diameter of 8.48 mm and external diameter of 14.30 mm.
  • the catalyst is borne inside the catalytic bed with a quartz wool stopper.
  • a thermocouple is introduced via the upper part of the reactor in order to measure the temperature inside the catalytic bed.
  • the reactor is placed in a heating oven of power 1000 W.
  • the array of reactor and oven is located inside a heating box which at all times prevents any condensation of the feed at the reaction outlet.
  • the ethanol reforming reaction was conducted at atmospheric pressure, at a temperature of 700° C. and spatial velocity of 76.430 h ⁇ 1 (GHSV). After 500 hours of operation under these conditions, total conversion of ethanol continued to be obtained with the appearance of H 2 , CO, CH 4 and CO 2 as sole products.
  • the composition on dry base obtained in this test is as can be seen in FIGS. 3 and 4 .

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US11/795,257 2005-01-14 2005-12-21 Catalyst for a Catalytic Process Which is Used to Obtain Hydrogen from Bioethanol and/or Ethanol, Catalyst-Preparation Method and Use Thereof in Said Catalytic Process Abandoned US20080261090A1 (en)

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PCT/ES2005/000696 WO2006075035A1 (es) 2005-01-14 2005-12-21 Catalizador para un proceso catalítico para la obtención de hidrógeno a partir de bioetanol y/o etanol7 procedimiento de preparación del catalizador, y su uso en el proceso catalítico

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CN112439416A (zh) * 2020-10-16 2021-03-05 大连理工大学 一种高分散铜负载二氧化钛纳米片的制备方法及其应用
US11417903B2 (en) * 2019-11-29 2022-08-16 Nissan North America, Inc. Electrode-based reformer for solid oxide electrochemical devices
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EP2193840A1 (en) * 2007-06-01 2010-06-09 Invista Technologies S.a.r.l. Catalyst and process for the conversion of nitrous oxide
BRPI0923620A2 (pt) * 2008-12-23 2019-12-10 Shell Internatioale Res Maatschappij B V catalisador de reforma a vapor de carga de alimentação bio-baseada, e, método para preparar um catalisador de reforma a vapor de carga de alimentação bio-baseada
CA2747649A1 (en) * 2008-12-23 2010-07-01 Shell Internationale Research Maatschappij B.V. Processes for hydrogen production and catalysts for use therein
KR101725293B1 (ko) * 2015-11-04 2017-04-10 한국과학기술연구원 혼합 개질 반응용 니켈 담지촉매

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US20120015266A1 (en) * 2009-01-13 2012-01-19 Melo Faus Francisco Vicente Catalyst for a process for obtaining hydrogen through reforming hydrocarbons with steam, process for preparing the catalyst and use thereof in the process
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US11417903B2 (en) * 2019-11-29 2022-08-16 Nissan North America, Inc. Electrode-based reformer for solid oxide electrochemical devices
CN112439416A (zh) * 2020-10-16 2021-03-05 大连理工大学 一种高分散铜负载二氧化钛纳米片的制备方法及其应用
US11865515B2 (en) * 2021-12-06 2024-01-09 ExxonMobil Technology and Engineering Company Catalyst for olefins generation

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