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Dry reforming - from understanding the elementary steps to better catalysts
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Details of project |
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| Identifier |
107170 |
| Type |
NN |
| Principal investigator |
Horváth, Anita |
| Title in Hungarian |
Száraz reformálás: út az elemi lépésektől a hatékony katalizátorig |
| Title in English |
Dry reforming - from understanding the elementary steps to better catalysts |
| Keywords in Hungarian |
methane dry refoming, carbon formation, isotope tracing, elementary steps, nanostructured catalysts, |
| Keywords in English |
methane dry refoming, carbon formation, isotope tracing, elementary steps, nanostructured catalysts, |
| Discipline |
| Chemical Engineering (Council of Physical Sciences) | 50 % | | Ortelius classification: Applied chemistry | | Material Science and Technology (chemistry) (Council of Physical Sciences) | 40 % | | Physical Chemistry and Theoretical Chemistry (Council of Physical Sciences) | 10 % | | Ortelius classification: Surface chemistry |
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| Panel |
Chemistry 1 |
| Department or equivalent |
Institute for Energy Security and Environmental Safety (Centre for Energy Research) |
| Participants |
Guczi, László
Győrffy, Nóra
Horváth, Anita
Károlyi, Johanna
Nagy, Norina
Németh, Miklós László
Sáfrán, György
Schay, Zoltán
Somodi, Ferenc
Srankó, Dávid Ferenc
Tompos, András
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| Starting date |
2012-07-01 |
| Closing date |
2016-12-31 |
| Funding (in million HUF) |
43.851 |
| FTE (full time equivalent) |
13.32 |
| state |
closed project |
Summary in Hungarian A kutatás összefoglalója, célkitűzései szakemberek számára
Itt írja le a kutatás fő célkitűzéseit a témában jártas szakember számára.
Catalytic dry reforming of methane is an important, highly endothermic route to CO rich synthesis gas.
Because carbon formation is thermodynamically favored under all conditions, the reaction can only be
stabilized by kinetic control. We propose a collaborative study of laboratories at the Institute of Isotopes of
the Hungarian Academy of Sciences (IoI), the Technische Universität Wien (TUW) and the Technische Universität München (TUM) to elucidate and understand the elementary reactions of methane reforming
with CO2 on supported Pt and Ni catalysts (modified with Au) under a wide variety of reaction conditions
and to use this knowledge in the quest for a new generation of highly active and stable catalysts. UHV model studies (TUW) address the specific properties of oxide supports and metal nanoparticles via surface science methods, focusing on the nature of interaction and reaction with reactants and products. Novel robust and stable nanostructured catalysts will be synthesized using traditional and sol-based approach (IoI) and are expected to facilitate a successful transition from noble to base metals. The kinetic and spectroscopic characterization (TUM) of dispersed catalysts will provide the necessary quantitative information on the dispersed catalysts at the main stages of preparation and reaction.The kinetic evaluation under stationary and transient conditions will provide a rigorous kinetic model to explain catalytic behavior and give feedback to catalyst synthesis.
Mi a kutatás alapkérdése?
Ebben a részben írja le röviden, hogy mi a kutatás segítségével megválaszolni kívánt probléma, mi a kutatás kiinduló hipotézise, milyen kérdéseket válaszolnak meg a kísérletek.
The most significant problem is that under nearly all reaction conditions, carbon is thermodynamically stable and its formation can lead even to a the blockage of the reactor. In consequence, the (catalyzed) formation of carbon can only be kinetically retarded via adjusting the properties of the catalyst. We propose to explore, (I) how the reactants CH4 and CO2 interact with the metal and the supports and (II) how the primary species react further to generate CO and H2, but also surface carbonaceous species that eventually lead to carbon formation. This will be complemented by studying (III) how the surface carbonaceous species react with varying concentrations of CO2 (and potentially H2O) and (IV) how these carbon species change in morphology and nature growing more refractory with reaction time. Based on the insight into these elementary reactions, we propose to use advanced synthesis techniques to modify catalysts to achieve reduced coke formation and stabilize the catalytic performance. We will use a combination of surface science studies under UHV conditions with model catalysts (TU Vienna), advanced catalyst synthesis and isotope labeling studies, which allow us to trace the importance of the coupled reactions (Institute of Isotopes, Budapest), as well as scalable material preparation of thermally stable catalysts and spectroscopic and kinetic reaction studies up to high pressures (TU München). If successful, we expect to be able to understand
the impact of the individual reactions under the various operating regimes and to experimentally
realize this in the synthesis of catalysts.
Mi a kutatás jelentősége?
Röviden írja le, milyen új perspektívát nyitnak az alapkutatásban az elért eredmények, milyen társadalmi hasznosíthatóságnak teremtik meg a tudományos alapját. Mutassa be, hogy a megpályázott kutatási területen lévő hazai és a nemzetközi versenytársaihoz képest melyek az egyediségei és erősségei a pályázatának!
Dry reforming of methane (CH4 + CO2 ⇌ 2CO +2H2, ΔHo = 261 kJ/mol) is not only the most endothermic reforming reaction, it leads also to the lowest concentration of hydrogen in synthesis gas. Despite these drawbacks it is an important reaction from the practical side, because of large concentrations of carbon dioxide in some of the natural gas reservoirs and because the H2/CO ratio of one is being used for the synthesis of oxygenates. The other aspect, which makes the reaction very interesting for selected cases, is related to the fact that methane and carbon dioxide are greenhouse gases. While the overall need for synthesis gas with a H2/CO = 1 may be limited, the availability of CO2 and methane at one location may make it economically very attractive to convert both to synthesis gas. As note in passing it should be mentioned that due to the projected size of an industrial implementation, the cost of the catalyst is an important element in the process development. While noble metal catalysts are less susceptible to the accumulation of deactivating carbon during the reaction, their price is prohibitive for industrial implementation at a large scale. Thus, a new generation of supported Pt, Ni catalysts with high activity and stability will be proposed based on the outcome of collaboration.
A kutatás összefoglalója, célkitűzései laikusok számára
Ebben a fejezetben írja le a kutatás fő célkitűzéseit alapműveltséggel rendelkező laikusok számára. Ez az összefoglaló a döntéshozók, a média, illetve az érdeklődők tájékoztatása szempontjából különösen fontos az NKFI Hivatal számára.
In methane dry reforming, greenhouse gases, methane and carbon dioxide are utilized to obtain a valuable feedstock, synthesis gas (CH4 + CO2 ⇌ 2CO +2H2). Synthesis gas is a mixture of hydrogen and carbon monoxide in this case with H2/CO ratio of 1 that is being used for the synthesis of oxygenates. The other economical aspect of dry reforming is that some of the natural gas reservoirs with large concentrations of carbon dioxide (low heating value) or even biogas could be converted. The first and most significant problem associated with dry reforming carried out at high temperature is related to the fact that destructive carbon formation can be significant, leading even to a complete blockage of the reactor. The cost of the catalyst is an important element in the process development. While noble metal catalysts are less susceptible to the growth of undesired carbon that may lead reactor blockage, their price is prohibitive for industrial implementation at a large scale. We aim to retarde the (catalyzed) formation of undesired carbon via adjusting the properties of the catalyst. To achieve this via a knowledge based approach, the relevant reactions and their relation to properties of the catalyst need to be understood at an elementary level. A new generation of supported Pt, Ni catalysts with high activity and stability will be proposed based on the outcome of the research.
| Summary Summary of the research and its aims for experts
Describe the major aims of the research for experts.
Catalytic dry reforming of methane is an important, highly endothermic route to CO rich synthesis gas.
Because carbon formation is thermodynamically favored under all conditions, the reaction can only be
stabilized by kinetic control. We propose a collaborative study of laboratories at the Institute of Isotopes of
the Hungarian Academy of Sciences (IoI), the Technische Universität Wien (TUW) and the Technische Universität München (TUM) to elucidate and understand the elementary reactions of methane reforming
with CO2 on supported Pt and Ni catalysts (modified with Au) under a wide variety of reaction conditions
and to use this knowledge in the quest for a new generation of highly active and stable catalysts. UHV model studies (TUW) address the specific properties of oxide supports and metal nanoparticles via surface science methods, focusing on the nature of interaction and reaction with reactants and products. Novel robust and stable nanostructured catalysts will be synthesized using traditional and sol-based approach (IoI) and are expected to facilitate a successful transition from noble to base metals. The kinetic and spectroscopic characterization (TUM) of dispersed catalysts will provide the necessary quantitative information on the dispersed catalysts at the main stages of preparation and reaction.The kinetic evaluation under stationary and transient conditions will provide a rigorous kinetic model to explain catalytic behavior and give feedback to catalyst synthesis.
What is the major research question?
Describe here briefly the problem to be solved by the research, the starting hypothesis, and the questions addressed by the experiments.
The most significant problem is that under nearly all reaction conditions, carbon is thermodynamically stable and its formation can lead even to a the blockage of the reactor. In consequence, the (catalyzed) formation of carbon can only be kinetically retarded via adjusting the properties of the catalyst. We propose to explore, (I) how the reactants CH4 and CO2 interact with the metal and the supports and (II) how the primary species react further to generate CO and H2, but also surface carbonaceous species that eventually lead to carbon formation. This will be complemented by studying (III) how the surface carbonaceous species react with varying concentrations of CO2 (and potentially H2O) and (IV) how these carbon species change in morphology and nature growing more refractory with reaction time. Based on the insight into these elementary reactions, we propose to use advanced synthesis techniques to modify catalysts to achieve reduced coke formation and stabilize the catalytic performance. We will use a combination of surface science studies under UHV conditions with model catalysts (TU Vienna), advanced catalyst synthesis and isotope labeling studies, which allow us to trace the importance of the coupled reactions (Institute of Isotopes, Budapest), as well as scalable material preparation of thermally stable catalysts and spectroscopic and kinetic reaction studies up to high pressures (TU München). If successful, we expect to be able to understand
the impact of the individual reactions under the various operating regimes and to experimentally
realize this in the synthesis of catalysts.
What is the significance of the research?
Describe the new perspectives opened by the results achieved, including the scientific basics of potential societal applications. Please describe the unique strengths of your proposal in comparison to your domestic and international competitors in the given field.
Dry reforming of methane (CH4 + CO2 ⇌ 2CO +2H2, ΔHo = 261 kJ/mol) is not only the most endothermic reforming reaction, it leads also to the lowest concentration of hydrogen in synthesis gas. Despite these drawbacks it is an important reaction from the practical side, because of large concentrations of carbon dioxide in some of the natural gas reservoirs and because the H2/CO ratio of one is being used for the synthesis of oxygenates. The other aspect, which makes the reaction very interesting for selected cases, is related to the fact that methane and carbon dioxide are greenhouse gases. While the overall need for synthesis gas with a H2/CO = 1 may be limited, the availability of CO2 and methane at one location may make it economically very attractive to convert both to synthesis gas. As note in passing it should be mentioned that due to the projected size of an industrial implementation, the cost of the catalyst is an important element in the process development. While noble metal catalysts are less susceptible to the accumulation of deactivating carbon during the reaction, their price is prohibitive for industrial implementation at a large scale. Thus, a new generation of supported Pt, Ni catalysts with high activity and stability will be proposed based on the outcome of collaboration.
Summary and aims of the research for the public
Describe here the major aims of the research for an audience with average background information. This summary is especially important for NRDI Office in order to inform decision-makers, media, and others.
In methane dry reforming, greenhouse gases, methane and carbon dioxide are utilized to obtain a valuable feedstock, synthesis gas (CH4 + CO2 ⇌ 2CO +2H2). Synthesis gas is a mixture of hydrogen and carbon monoxide in this case with H2/CO ratio of 1 that is being used for the synthesis of oxygenates. The other economical aspect of dry reforming is that some of the natural gas reservoirs with large concentrations of carbon dioxide (low heating value) or even biogas could be converted. The first and most significant problem associated with dry reforming carried out at high temperature is related to the fact that destructive carbon formation can be significant, leading even to a complete blockage of the reactor. The cost of the catalyst is an important element in the process development. While noble metal catalysts are less susceptible to the growth of undesired carbon that may lead reactor blockage, their price is prohibitive for industrial implementation at a large scale. We aim to retarde the (catalyzed) formation of undesired carbon via adjusting the properties of the catalyst. To achieve this via a knowledge based approach, the relevant reactions and their relation to properties of the catalyst need to be understood at an elementary level. A new generation of supported Pt, Ni catalysts with high activity and stability will be proposed based on the outcome of the research.
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List of publications |
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| Miklós Németh, Zoltán Schay, Dávid Srankó, Johanna Károlyi, György Sáfrán, István Sajó, Anita Horváth: Impregnated Ni/ZrO2 and Pt/ZrO2 catalysts in dry reforming of methane: Activity tests in excess methane and mechanistic studies with labeled 13CO2, Appl. Catal. A.: Gen., 504 pp. 604-620., 2015 | | Johanna Károlyi, Miklós Németh, Claudio Evangelisti, György Sáfrán, Zoltán Schay, Anita Horváth, Ferenc Somodi: Carbon dioxide reforming of methane over Ni-In/SiO2 catalyst without coke formation, Journal of Industrial and Engineering Chemistry , accepted for publication, 2017 | | Yue Liu, Yu Lou, Matthias Steib, Qi Zhang, Konrad Tiefenbacher, Anita Horváth, Andreas Jentys, Johannes A. Lercher: Design of stable Ni/ZrO2 catalysts for dry reforming of methane, Journal of Catalysis, submitted, now under minor revision, 2017 | | M. Németh, D. Srankó, J. Károlyi, F. Somodi, Z. Schay, G. Sáfrán, I. Sajó and A. Horváth: Na-promoted Ni/ZrO2 dry reforming catalyst with high efficiency: details of Na2O–ZrO2–Ni interaction controlling activity and coke formation, Catalysis Science and Technology, DOI: 10.1039/c7cy01011g, 2017 | | A. Horváth, L. Guczi, N. Nagy, G. Sáfrán, V. La Parola, L. F. Liotta, G. Pantaleo, A. Venezia: The effect of preparation on the structure of Au-modified Ni/MgAl2O4 catalysts and its methane dry reforming activity, The 10th Natural Gas Conversion Symposium, poster#708, Doha, Qatar, 2-7 March, 2013 | | A. Horváth, L. Guczi, N. Nagy, A. Kocsonya, G. Sáfrán, V. La Parola, L. F. Liotta, G. Pantaleo, A. M. Venezia: Gold effect on dry reforming activity of MgAl2O4 supported Ni catalysts, submitted to Appl. Catal. A, 2013 | | Nagyné Horváth Anita, előadás: Katalízis az energiatermelésben: a Felületkémiai és Katalízis Laboratórium (FKKL) kutatásai, MTA Székház, nyilvános KÖTEB ülés, 2013. február 27., 2013 | | Nagyné Horváth Anita, előadás: A metán száraz reformálása, újabb eredmények és kutatási irányok, MTA Székház, EK iskola, 2013. április 29-30., 2013 | | A. Horváth, Gy. Stefler, V. La Parola, L. F. Liotta, G. Pantaleo, A. Venezia, L. Guczi, Institute of Isotopes, Budapest, Hungary.: Comparative study on Au-modified Ni/MgAl2O4 catalysts for dry reforming of methane, 15th International Congress on Catalysis, poster presentation, 1 - 6 July, 2012, Munich, Germany, 2012 | | A. Horváth, L. Guczi, A. Kocsonya, G. Sáfrán, V. La Parola, L. F. Liotta, G. Pantaleo, A. M. Venezia: Sol-derived AuNi/MgAl2O4 catalysts: Formation, structure and activity in dry reforming of methane, Applied Catalysis A, Volume 468, 2013, Pages 250–259, 2013 | | A. Horváth, M.L. Németh, N. Nagy, Z. Schay, Zs. Kasztovszky, I. Sajó, G. Sáfrán: CARBON DIOXIDE REFORMING OF METHANE ON NANOSTRUCTURED NICKEL-BASED CATALYSTS, 3rd European Energy Conference, poster presentation, Budapest, October 27 – 30, 2013., 2013 | | Anita Horváth, Miklós László Németh, Johanna Károlyi, Norina Nagy, György Sáfrán, Zoltán Schay: Dry reforming of methane on Ni, Pt and NiPt/ZrO2 catalysts: mechanistic studies with 13C labeled reactants, 12th Pannonian Symposium on Catalysis, oral presentation, Trest, Czech Republic, September 16 to 20, 2014, 2014 | | Miklós László Németh, Zoltán Schay, Zsolt Kasztovszky, István Sajó, György Sáfrán, Anita Horváth: Dry reforming of methane on Ni, Pt and NiPt/ZrO2 catalysts: preparation method versus catalytic activity in large excess of methane, 12th Pannonian Symposium on Catalysis, poster presentation, Trest, Czech Republic, September 16 to 20, 2014, 2014, 2014 | | Anita Horváth, Miklós László Németh, Johanna Károlyi, Norina Nagy, Zsolt Kasztovszky, István Sajó, György Sáfrán, Zoltán Schay: Dry reforming of methane on Ni, Pt and NiPt/ZrO2 catalysts prepared by sol adsorption or impregnation: mechanistic studies with 13C labeled reactants, (before submission to) Special issue of the J. Applied Catalysis A, celebrating Jacques C. VEDRINE 75 th Birthday, 2014 | | A. Horváth, L. Guczi, N. Nagy, G. Sáfrán, V. La Parola, L. F. Liotta, G. Pantaleo, A. Venezia: The effect of preparation on the structure of Au-modified Ni/MgAl2O4 catalysts and its methane dry reforming activity, The 10th Natural Gas Conversion Symposium, poster#708, PO1.13, Doha, Qatar, 2-7 March, 2013 | | A. Horváth, L. Guczi, A. Kocsonya, G. Sáfrán, V. La Parola, L. F. Liotta, G. Pantaleo, A. M. Venezia: Sol-derived AuNi/MgAl2O4 catalysts: Formation, structure and activity in dry reforming of methane, Applied Catalysis A, Volume 468, Pages 250–259, 2013 | | Nagyné Horváth Anita, előadás: Katalízis az energiatermelésben: a Felületkémiai és Katalízis Laboratórium (FKKL) kutatásai, MTA Székház, nyilvános KÖTEB ülés, február 27., 2013 | | Nagyné Horváth Anita, előadás: A metán száraz reformálása, újabb eredmények és kutatási irányok, MTA Székház, EK iskola, április 29-30., 2013 | | A. Horváth, Gy. Stefler, V. La Parola, L. F. Liotta, G. Pantaleo, A. Venezia, L. Guczi, Institute of Isotopes, Budapest, Hungary.: Comparative study on Au-modified Ni/MgAl2O4 catalysts for dry reforming of methane, 15th International Congress on Catalysis, 1.11_1605 poster, 1 - 6 July, Munich, Germany, 2012 | | A. Horváth, M.L. Németh, N. Nagy, Z. Schay, Zs. Kasztovszky, I. Sajó, G. Sáfrán: CARBON DIOXIDE REFORMING OF METHANE ON NANOSTRUCTURED NICKEL-BASED CATALYSTS, 3rd European Energy Conference, poster T1-P5, Budapest, October 27 – 30, 2013 | | Anita Horváth, Miklós László Németh, Johanna Károlyi, Norina Nagy, György Sáfrán, Zoltán Schay: Dry reforming of methane on Ni, Pt and NiPt/ZrO2 catalysts: mechanistic studies with 13C labeled reactants, 12th Pannonian Symposium on Catalysis, oral presentation O41, Trest, Czech Republic, September 16 to 20, 2014 | | Miklós László Németh, Zoltán Schay, Zsolt Kasztovszky, István Sajó, György Sáfrán, Anita Horváth: Dry reforming of methane on Ni, Pt and NiPt/ZrO2 catalysts: preparation method versus catalytic activity in large excess of methane, 12th Pannonian Symposium on Catalysis, poster presentation P21, Trest, Czech Republic, September 16 to 20, 2014 | | Miklós Németh, Zoltán Schay, Dávid Srankó, Johanna Károlyi, György Sáfrán, István Sajó, Anita Horváth: Impregnated Ni/ZrO2 and Pt/ZrO2 catalysts in dry reforming of methane: Activity tests in excess methane and mechanistic studies with labeled 13CO2, Appl. Catal. A.: Gen., doi: 10.1016/j.apcata.2015.04.006, 2015 | | Miklós Németh, Johanna Károlyi, Ferenc Somodi, Dávid Srankó, Zoltán Schay, Anita Horváth: Comparison of different Ni/ZrO2 catalysts in CO2 reforming of methane using isotope-labeled experiments, 17th International Symposium on Relations between Homogeneous and Heterogeneous Catalysis, poster P69, Utrect, July 12-15, 2015 | | M. Németh, Z. Schay, D. Srankó, J. Károlyi, Gy. Sáfrán, I. Sajó, A. Horváth: Mechanistic Studies With Labeled 13CO2 on Ni/ZrO2 and Pt/ZrO2 dry reforming catalysts, 12th European Congress on Catalysis, poster, Kazan, Russia, 30 August – 4 September, 2015 | | Miklós Németh, Zoltán Schay, Dávid Srankó, Johanna Károlyi, György Sáfrán, István Sajó, Anita Horváth: A metán száraz reformálásának (CH4+CO2⇌2CO+2H2) vizsgálata hordozós katalizátorokon, MKE 2. Nemzeti Konferencia, előadás, Hajdúszoboszló, aug. 31. – szept. 2., 2015 | | Miklós Németh, Johanna Károlyi, Ferenc Somodi, Dávid Srankó, Zoltán Schay, Anita Horváth: Comparison of different Ni/ZrO2 catalysts in CO2 reforming of methane using isotope-labeled experiments, 17th International Symposium on Relations between Homogeneous and Heterogeneous Catalysis, poster P69, Utrect, July 12-15, 2015 | | M. Németh, Z. Schay, D. Srankó, J. Károlyi, Gy. Sáfrán, I. Sajó, A. Horváth: Mechanistic Studies With Labeled 13CO2 on Ni/ZrO2 and Pt/ZrO2 dry reforming catalysts, 12th European Congress on Catalysis, poster #I-PP27, Kazan, Russia, 30 August – 4 September, 2015 | | Miklós Németh, Zoltán Schay, Dávid Srankó, Johanna Károlyi, György Sáfrán, István Sajó, Anita Horváth: A metán száraz reformálásának (CH4+CO2⇌2CO+2H2) vizsgálata hordozós katalizátorokon, MKE 2. Nemzeti Konferencia, presentation #SZ-O-14, Hajdúszoboszló, August 31 – Sept. 2, 2015 | | M. Németh, J. Károlyi, F. Somodi, D. Srankó, Gy. Safran, I. Sajó, A. Horváth: CO2 reforming studies in excess methane using Ni/ZrO2 catalysts, 13th Pannonian International Symposium on Catalysis, presentation (pp. 70. ISBN 978-963-9970-56-4) Siófok, September 19-23, 2016 | | M. Németh, J. Károlyi, D. Srankó, F. Somodi, Gy. Sáfrán, A. Horváth: Low temperature dry reforming of methane over Ni/ZrO2 catalysts: the effects of sodium promotion, 13th Pannonian International Symposium on Catalysis, (pp. 115. ISBN 978-963-9970-56-4) poster, Siófok, Sept. 19-23, 2016 | | M. Németh, J. Károlyi, F. Somodi, D. Srankó, Gy. Safran, I. Sajó, A. Horváth: Dry reforming studies in excess methane using Ni/ZrO2 catalysts, 16th International Congress on Catalysis, poster PA098, Peking, July 3-8, 2016 | | M. Németh, J. Károlyi, D. Srankó, F. Somodi, Gy. Sáfrán, I. Sajó, A. Horváth: Tracking of carbon species during dry reforming of methane on different Ni/ZrO2 catalysts, 11th Natural Gas Conversion Symposium, Topic 1 pp.1-2. poster #1314, Tromso, június 6-9, 2016 | | Anita Horváth, Ferenc Somodi, Johanna Károlyi, Dávid Srankó, Miklós Németh, György Sáfrán: Low temperature dry reforming of methane over Ni/ZrO2 catalysts: details of the beneficial sodium promotion, 13th European Congress on Catalysis, poster #P3.115 , Florence, 27-31 August, 2017 | | Ferenc Somodi, Johanna Károlyi, Miklós Németh, Anita Horváth: Dry reforming of methane without coke formation over indium promoted Ni/SiO2 catalysts, 13th European Congress on Catalysis, poster #P3.78 Florence, 27-31 August, 2017 |
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