Projects / Programmes
Development of transition metal catalyst for efficient dry reforming of biogas to syngas
| Code |
Science |
Field |
Subfield |
| 2.02.04 |
Engineering sciences and technologies |
Chemical engineering |
Catalysis and reaction engineering |
| Code |
Science |
Field |
| T350 |
Technological sciences |
Chemical technology and engineering |
| Code |
Science |
Field |
| 2.04 |
Engineering and Technology |
Chemical engineering
|
transition metal catalysts, biogas, reforming, syngas
Researchers (1)
| no. |
Code |
Name and surname |
Research area |
Role |
Period |
No. of publicationsNo. of publications |
| 1. |
28557 |
PhD Petar Djinović |
Chemical engineering |
Head |
2013 - 2015 |
246 |
Organisations (1)
| no. |
Code |
Research organisation |
City |
Registration number |
No. of publicationsNo. of publications |
| 1. |
0104 |
National Institute of Chemistry |
Ljubljana |
5051592000 |
21,007 |
Abstract
A promising process of syngas production is catalytic reforming of methane using carbon dioxide, also known as methane dry reforming (CH4 + CO2 ↔ 2H2 + 2CO).
Transition metals are especially attractive as potential catalysts due to their low price and good activity. The development of transition metal catalysts, capable of transforming biogas to syngas with good resistance to carbon accumulation would represent an important scientific discovery. This is the primary reason for their investigation during the proposed basic postdoctoral research project. During the course of the project, attention will be focused towards synthesis, characterization, understanding the performance and optimization of transition metal catalysts in the methane dry reforming reaction.
Beside the active catalytic component (metallic nanoparticles), the catalyst support also plays an important role. Cerium dioxide exhibits an extraordinary property of acting as an oxygen reservoir in oxidative and reductive atmosphere, which results in oxidation of carbon, accumulated during reaction. This is the primary reason for selection of CeO2 as the catalyst support. In order to overcome the low surface area and low thermal stability of ceria, its refractory properties will be improved by addition of zirconia (ZrO2). Different synthesis procedures will be tested with the aim of preparing a CeO2/ZrO2 mixed oxide with high specific surface area, good thermal stability in the temperature range between 500 and 800° C and highly defective structure.
After identification of the most appropriate synthesis protocol for the CeO2/ZrO2 catalyst support, research activity will be devoted to deposition of active components: nickel and cobalt.
Different loadings of active metals, as well as different ratios between the two metals will be deposited and tested in the methane dry reforming reaction. Based on their catalytic performance and affinity for carbon accumulation, best performing catalysts will be selected for further investigation. By combining results of catalyst characterization and activity tests, the optimal catalyst composition for further testing and their key properties for effective catalytic performance will be identified.
Catalyst formulation which will exhibit the highest catalytic activity and lowest carbon accumulation, will be further tested to determine the width of the temperature interval, most appropriate for the reforming reaction. Additional tests will be performed on the reforming of model biogas streams with surplus methane, as is often the case in real biogas streams.
Improved resistance toward carbon accumulation during reforming of nonstoichiometric CH4/CO2 streams will be attempted by doping the prepared catalyst using various loadings of tin, K2O, MgO and CaO.
Doped NiCo/CeO2ZrO2 bimetallic catalyst which will exhibit best performance in the simulated biogas streams, will be further tested under real biogas streams. Special attention will be given to improving long term catalytic performance in the time scale, longer than 200 hours.
One of the fundamental goals of the proposed research project is the identification of the methane dry reforming reaction mechanism, which will be carried out using the combination of various catalyst characterization techniques, catalytic activity tests and in situ spectroscopic techniques. Characterization and identification of active centers and reaction intermediates will substantially increase the level of understanding of the investigated processes, occurring on the catalyst surface during the methane dry reforming reaction.
Significance for science
Research activities performed during the course of this research project resulted in new knowledge regarding synthesis of complex multicomponent materials in order to improve their required characteristics, namely redox properties. We have demonstrated that despite the identical chemical composition, morphology and physico-chemical properties are considerably different. With the goal of improving thermal and redox properties of CeO2, doping with ZrO2 was discovered as an efficient technique, whereas glycothermal and combustion synthesis methods were discovered as highly appropriate. Silicon carbide and alumina as refractory auxilarry supports efficiently prevent catalyst sintering during prolonged exposure to reaction conditions. Besides the redox support, the size of the deposited bimetallic clusters influences the catalytic activity, but even more importantly determines the extent of undesired side reactions, namely carbon accumulation. High activity with simultaneous absence of carbon accumulation could only be achieved using bimetallic clustres below 10 nm in size. The principle of operation was proven on nickel and cobalt, but was extended also to tungsten and iron.
Significance for the country
Slovenia is rich in renewable energy resources and a vast potential for biogas production. Developed catalysts during the course of this research proposal are the cornerstone for development of advanced, green technologies which are based on renewables for syngas production (H2 and CO), which can, using the existing well established technologies be upgraded to fuels and added value chemicals. The research project enabled sistematic investigation of an important katalitic process, which has not previously been investigated in Slovenia. The leading scientist in this project, dr. Petar Djinović would like to express his sincere gratitude to ARRS for the financial support which enabled realization of this process.
Most important scientific results
Annual report
2013,
2014,
final report,
complete report on dLib.si
Most important socioeconomically and culturally relevant results
Annual report
2013,
2014,
final report,
complete report on dLib.si
