INSTITUTUL NAŢIONAL DE CERCETARE DEZVOLTARE PENTRU TEHNOLOGII IZOTOPICE SI MOLECULARE

Str. Donat 67-103, 400293, Cluj-Napoca, Romānia

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Email: itim@itim-cj.ro, web: www.itim-cj.ro

Unitatea Executiva pentru Finantarea Invatamantului Superior, Cercetarii, Dezvoltarii si Inovarii

 

Syngas from biogas using combined steam and dry reforming on Ni based bimodal pore catalysts

 - SynCat-

PN-III-P2-2.1-PED-2016-0349

- 177 PED/2017 -

 

Project Leader: Dr. Mihaela D. Lazar

 

Project financed by UEFISCDI

Program PN III: Cresterea competitivitatii economiei romanesti prin cercetare, dezvoltare si inovare

Project type: Proiect experimental-demonstrativ - PED

 

 

Project Timespan: 01. 09. 2017 - 31. 12. 2018 (16 months)

 

Research Team of INCDTIM, Cluj Napoca (CO):

Institutul National de Cercetare-Dezvoltare pentru Tehnologii Izotopice si Moleculare - INCDTIM

Dr. Mihaela D. Lazar, Project leader (CV)

Dr. eng. Maria Mihet, Team member

Dr. Monica Dan, Team member

Eng. Valentin Mirel, Team member

Tehn. Sorin Oltean, Team member

 

Research Team of UB, Bucharest (P1):

Universitatea Bucuresti (P1)

Dr. Mihaela Florea, Principal Investigator

Mihaela Trandafir, PhD Student

Dr. Gheorghita Mitran, Team member

 

Summary & Objectives:

Biogas is one of the most important renewable biofuels produced at large scales from a wide range of biological wastes. It consists in a mixture of multiple gases with CH4 and CO2 as main components in different ratios depending on the starting raw materials and conditions used for its production. The biogas is not used to generate fuels (methanol or superior liquid fuels), although it contains the necessary constituents, mainly due to the low economic efficiency of the reformation process. The main objective of the present proposal is to develop a laboratory scale validated method to transform simulated biogas in synthesis gas with appropriate composition for methanol and liquid fuels synthesis (with H2:CO ratio 2:1) using new bimodal Ni based catalysts. The research will combine: (a) combined steam and dry reforming of methane process, (b) CH4:CO2 ratio from the real biogas and (c) Ni based bimodal catalysts, to give a reliable, laboratory scale validated method to produce syngas from biogas. Silica and alumina based bimodal catalysts promoted with a second oxide (MgO, CaO, ZrO2, CeO2, La2O3) will be prepared and characterized by several methods (BET, XRD, TEM-SEM, temperature programed processes, in-situ DRIFT). The bimodal pore structure is expected to improve the catalytic process because large pores provide rapid access of the reagents to active sites and the small pores provide higher surface area, while the second oxide is expected to contribute to a better metal dispersion and better metal-support interaction. NH3-TPD, CO2-TPD, in-situ DRIFT measurements will give information about the catalytic process related to catalyst structure. Catalytic tests will be developed to establish the optimum catalyst and reaction conditions to make the reformation process more energetic efficient. The catalyst deactivation will be studied in terms of carbon deposition and metal sintering.

The main objective of the project is to develop a laboratory scale method to transform simulated biogas in synthesis gas with H2 : CO ratio 2:1 using new bimodal Ni based catalysts.

The specific objectives of the project are:

O1 - Preparation and characterization of new Ni based bimodal pore catalysts, correlation of catalysts structural properties with preparation method.

O2 - Determination of the catalysts performances in combined steam and dry reforming of methane: determination of catalytic activity, selectivity for desired products, catalysts deactivation, etc.

O3 - Development of the method to produce syngas (H2 : CO = 2) by combined steam and dry reforming of methane catalyzed by bimodal pore Ni based catalysts.

 

Results:

The results obtained in the first phase of the project consist in the development of preparation methods for 2 series of oxide supported Ni catalysts with bimodal pore structure. Using these methods, 6 catalysts were prepared and completely characterized (from the structural and functional point of view).

  • The first series contains alumina supported Ni catalysts: (i) Ni/Al2O3, Ni/CeO2-Al2O3, Ni/CeO2-MgO-Al2O3, Ni/MgO-Al2O3. All samples present pores with two distinct dimensions: for the first 3 samples, both types of pores are in the mesoporous domain, while for the last sample the smaller pores are in the mesoporous domain and the larger ones are macropores. All samples present a crystalline structure based on γ-Al2O3 with the co-existence of NiAl2O4 and MgAl2O4. The reducibility of materials depends on the calcination temperature and on the existence of the second oxide. The samples containing MgO and reduced at higher temperatures present the lowest reduction grade.

  • The second series contains silica supported Ni catalysts: Ni/MCM41 and Ni/BPS5. The first catalyst presents two types of pores, both in the mesoporous domain, while the second sample shoes pores in the mesoporous domain, as well as macropores. XRD measurements revealed that these catalysts have a high degree of amorphous oxide. The reducibility of these catalysts is better than those supported on alumina, the resulting Ni nanoparticles being around 10 nm and well dispersed.

The results obtained in the second phase of the project consist in:

  • 5 Nickel based catalyst with bi-modal pore structure: Ni/Al2O3, Ni/MgO-Al2O3; Ni/Y2O3-Al2O3; Ni/La2O3-Al2O3; Ni/CeO2-Al2O3 were tested in Combined Steam and Dry Reforming of Methane (CSDRM) using (CH4+CO2) mixture with composition similar to the real biogas. Depending on the amount of water, the reaction can be directed to the synthesis gas production or hydrogen production.

  • Synthesis gas with molar ratio H2:CO between 2 and 2.5, ideal for methanol synthesis, was obtained at temperatures ranging from 600°C to 700°C. The methane conversion is higher for the catalysts containing supplementary oxide in order: Ni/MgO-Al2O3 < Ni/Y2O3-Al2O3 < Ni/La2O3-Al2O3 < Ni/CeO2-Al2O3 < Ni/Al2O3.

  • Based on the catalytic results a method for synthesis gas production with molar ratio H2:CO between 2 and 2.5, from model biogas was developed. The method uses Ni/MgO-Al2O3 catalyst with bi-modal pore structure, reaction temperature 650°C, GHSV = 13650 h-1 and atmospheric pressure.

  • Based on the catalytic results a laboratory scale technology for hydrogen production from biogas model mixture by combined steam and dry reforming was proposed. For hydrogen production the conditions are: Ni/Al2O3 catalyst with bi-modal pore structure, reagents mol ratio CH4:CO2:H2O = 1:0.5:6, temperature 600°C, GHSV = 13650 h-1 and atmospheric pressure.

  • The method and the technology developed in this project are valuable options to add value to biogas by its transformation either in synthesis gas or in hydrogen.

Dissemination

Published papers

M. Florea, G. Postole, F.Matei-Rutkovska, A. Urda, F. Neatu, L. Massinc, P. Gelin, Catal. Sci. Technol. 8 (2018) 1333

M. Trandafir, L. Pop, N. D. Hadade, I. Hristea, C. M. Teodorescu, F. Krumeich, J.A. van Bokhoven, I. Grosu, V. I. Parvulescu, accepted paper in ChemCatChem.

Conferences

M. Dan, M. Mihet, M. D. Lazar, Nickel–alumina catalysts with bimodal pore structure and metal nanoparticles confined in the pores: preparation, structural and functional characterization, „7th EuCheMS”, Liverpool, UK, 26-30 august 2018.

M.D. Lazar, M. Dan, M. Mihet, Biogas transformation in Syngas catalyzed by alumina supported nickel catalysts with bimodal pore structure, 14th Pannonian International Symposium on Catalysis, High Tatras, Slovakia, 3-7 September 2018.

M. D. Lazar, M. Dan, M. Mihet, Biogas up-grading to Syngas catalyzed by alumina supported nickel catalysts, 22nd Conference „New Cryogenic and Isotope Technologies for Energy and Environment” - EnergEn 2018, Băile Govora, Romania, 24-26 October 2018.

 Patent Application - OSIM

Process for preparing syngas by combined steam and dry reformation of methane at low temperatures catalyzed by bimodal Ni/Al2O3.

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