A. ERDÕHELYI a and V. Z. SASCA b a Institute of Physical Chemistry and Material Science-University of Szeged b Institute of Chemistry Timisoara-Romanian

A. ERDÕHELYIa and V. Z. SASCAb

a Institute of Physical Chemistry and Material Science-University of Szeged b Institute of Chemistry Timisoara-Romanian Academy

Catalysts for bio-ethanol and bio-methane conversion

NEW TRENDS AND STRATEGIES IN THE CHEMISTRY ... 3-4 NOV 2011 TIMISOARA

Two countries, one goal, joint success!

Cross Border Cooperation Programme 2007-2013 Project HURO 0901/090/2.2.2:

History



Protocol of Scientific Cooperationbetween Reaction Kinetics Research Group of the HungarianAcademy of Sciences, Departement of Solid State and Radiochemistry-Szeged University and HeteregenousCatalysis Group, Inorganic Laboratory-Chemistry Institute Timisoara of Romanian Academy Timisoara, concerning to establish a cooperation relationship in the field of kinetics of solid state reactions and catalitic reactions regarding to: preparation methods of design at molecular level for controlled catalytic activity; thermal behavior; catalysts characterization as chemical composition, structure and texture; chemisorption studies by IR spectroscopy and temperature programmed desorption (TPD); redox properties studies by temperature programmed reduction and oxidation (TPR and TPO); catalytic activity testing using microreactor in line with gas-chromatograph technique and/or mass spectrometer detector.The scientific topics for cooperation will be aligned to the directives of „A European Technology Platform for SUSTAINABLE CHEMISTRY: The vision for 2020 and beyond.Szeged, 30.09.2005

Head of R. K. R. Group: Head of H. C . Group:Prof. János Kiss (D.Sc.) Dr. Eng. Viorel SascaHead of Department S. S. R.: Director of Ch. Institute of R. A.:Prof.András Erdõheyi (D.Sc.) Dr. Chim. Otilia Costisor

Project short summary



The project proposal is a research of solutions for bio-ethanol and bio-methane

processing into hydrogen or intermediary substances used in organic synthesis in respect to

criteria for sustainable chemistry using catalysts with high catalytic activity and selectivity

at low temperatures.

The syntheses of catalysts based on atomic/molecular level design concepts of

solid systems like:

- oxide supported mono- and bimetallyc catalysts, where the active phases' extension and

distribution are controlled at atomic level;

- heteropoly oxometalates with Keggin structure, where catalytic, redox and acidity

properties are controlled by substitution of the addenda atoms and protons. The most active

samples will be modified to improve their catalytic efficiency.

The kinetics of reaction are studied and the mechanism of the catalytic conversion

of ethanol and methane will be proposed.

Important project data



Sources of funding: 268478 EUR

Target area: South great plain area-Hungary and Western plain-Romania Csongrad-Hu and Timis-Ro counties

Timeframe: 01.04.2011-01.08.2012

Project acronym:

CATBIOETAMETCON

Key of intervention: 2.2. Promotion of co-operation in the filed of R&D and

innovation

Priority axe: 2. Strengthen social and economic cohesion of the border area

PartnershipLP: Dr. András Erdőhelyi-Hungarian research team (HRT) contact and coordinator person of

the LP, member of project staff, involved in all project activities.

PP: Dr. eng. Viorel Sasca-Romaniam research team (RRT) coordinator and contact person for the Partner, member of project staff, involved in all project research activities of RRT.



Partnership

LP team: Dr. László Óvári-internal expert of HRT, involved in electron spectoscopic analysis and model studies

Dr. Albert Oszkó-internal expert of HRT, involved in spectroscopic analysis for catalyst characterization

Dr. Márta Dömök-internal expert of HRT, involved in catalytic tests by gas chromatography and mass spectrometry

Mariann Tóth-internal expert of HRT, involved in catalytic tests by gas chromatography

Kornélia Ábrahámné Baán-internal expert of HRT, involved in FTIR spectroscopic analysis and catalyst preparation

Kata Markó-internal expert of HRT, invoved in catalytic tests by gas chromatography

István Sarusi-internal expert of HRT, involved in catalytic tests by gas chromatography

Hajnalka Novák-administrative tasks at the LP



Partnership

PP team: Dr. eng. Alexandru Popa -internal expert of RRT, involved in supported catalyst preparation, characterization and catalytic activity tests, results interpretation and preparing materials for visibility;

Drd. chim. Orsina Verdeş,-internal expert of RRT, involved in catalyst preparation, characterization and catalytic activity tests;

Drd. eng Livia Avram,-internal expert of RRT, involved in the catalyst preparation, characterization and catalytic activity tests;

Dr. chim. Valentin Careja-internal expert of RRT, Web page, catalysts computational modeling;

Drd. eng. Catalin Ianasi -internal expert of RRT, involved in the catalyst texture characterization.



Problems and chalenges



The alternative solutions for fossil fuels (methane gas, coal, gasoline, diesel oil) and intermediary for the organic industry of synthesis based on methane or crude oil derivatives are the renewable source of energy and raw materials. A study on renewable energy sources of Timis county (Fraunhofer Institute) proposes biomass for production of bio-methane or a bio-ethanol as main energy sources of renewable energy. There is a project for a Technological Park in Timisoara for technologies and equipment production in purpose to use renewable source of energy and raw materials in stage of Feasibility Study. The euro region DCMT (Danube-Cris-Mures-Tisa) for economic development needs of renewable sources for energy and raw materials for the chemical industry.

The Timis, Arad and Bihor counties in Romania are known as producers of high quantities of cereals, technical plants and agricultural byproduct, but now just a half of it is cultivated. The neighbouring counties in Hungary (Csongrád, Békés, Hajdú-Bihar, Szabolcs-Szatmár-Bereg) are also known as great producers of these agricultural products and the farmers in both countries have difficulties with their commercializing. The farmers who contribute to biomass production will obtain important gains.

Objectives



General:

►To increase the utilization of the bio-ethanol and bio-methane as hydrogen and raw material sources: - Knowledge exchange on utilization of bio-ethanol and bio-methane as hydrogen and raw material sources; -Spread of project results on utilization of bio-ethanol and bio-methane as hydrogen and raw material sources; -Fast result presentation on project web-page.

Specific:

► To increase the level of research of both institutes: -Equipment acquisition; -PhD theses; -PhD students employed.► To specify two catalysts with high efficiency for bio-ethanol conversion:-Specification of reaction mechanism; -Relationship between the surface structure and the efficiency of the catalysts.-Method of preparation for high efficient catalyst.

Activities



The realization of the project will begin with the preparation of the catalysts to be tested in the conversion of bio-ethanol and methane. The preparative work of catalysts types-single or double oxide supported (of Zn, Al, Ce, Zr, Mg, Mo, V) mono- and bimetallic (Ni, Cu, Fe, Co) samples will be carried out by the LP. The PP will synthesize catalysts of heteropoly oxometallates with Keggin structure containing Mo, V or W as addenda cation, Cs as contracation and Cu, Ni, Co, and Pd as doping cations.

The characterization of the so prepared catalysts will be executed by the Lead Partner by X-ray photoelectron spectroscopy (XPS), temperature programmed desorption methods and SEM. The PP will characterize the catalysts by:- simultaneous TG/DTG-DTA analysis, - BET method with nitrogen for porosity and specific surface area determination, - XRD.

The catalyst samples will be tested in the catalytic reactions that will be monitored and analyzed by chromatographical methods (GC, GCMS).

Activity package 1:

Activities



To find out the mechanism of the reactions the interactions between the catalysts and the reactants will also be examined by infrared spectroscopy and XPS "in situ" by LP. Depending on the results on the catalyst characterization and catalytic tests the new catalysts will be developed and tested.

The test of catalytic activity for the best catalysts will be repetead by the other partner for double check. There are three phases of research: -1th. The best catalysts selection, the reaction mechanism and the relationship between the composition-structure-texture and their catalysts efficiency proposals; 2th. The selection of the best 2-3 catalysts; kinetics and deactivation mechanism study and modifying catalysts composition for improving resistance to deactivation; 3th.

Final evaluation of research, methods of preparation, composition, structure and texture specification; kinetics and deactivation mechanism models. The visibility actions will be done after every research phase.

Activity package 1:

Activities



The existence and the results of the co-operation will be reported in international journals as scientific publications. The results will be presented with the help of posters and lectures at Hungarian and Romanian symposiums (sessions of the Hungarian or Romanian Academies) and at the others conferences in the project application area.

A web-page will be constructed in order to inform the public about the joint work and spread its results.

http://192.129.4.165/~huro0901

http://acad-icht.tm.edu.ro/~huro0901

Activity package 2:

Images from common activities



Management risk



► There are a few risks related of the project implementation as result of using own fund for all costs until the Reimbursement for each four-month reporting period for the Romanian partner especially in case of the equipment acquisition if the Romanian government will not allocate the fund at expected level for the Romanian Academy.► The Romanian partner asked the Romanian Academy about this risk and the answer was a positive one for the realocation of fund for winning projects.► The other risk is usual one for every research, the results relate to catalytic activity, especially the catalytic selectivity or a very clear and certain explanation of reaction mechanisms could not be at the expected level. The methods of investigation for characterization of catalysts and for catalytic activity used in project and the method of results evaluation by the correlations of catalytic activity with the catalysts composition, structure and texture, minimize such risks.



Thank you for attention!

Documents

A. ERDÕHELYI a and V. Z. SASCA b a Institute of Physical Chemistry and Material Science-University of Szeged b Institute of Chemistry Timisoara-Romanian