INSTITUTUL NAŢIONAL DE CERCETARE DEZVOLTARE PENTRU TEHNOLOGII IZOTOPICE SI MOLECULARE Str. Donat 67-103, 400293, Cluj-Napoca, Romania Tel: +40-264-584037; Fax: +40-264-420042 Email: itim@itim-cj.ro, web: www.itim-cj.ro

 

 

 

 

 

 

 

 

Design by MM

             Deadline: December 2014

Title of Phase 3: Technological parameters for hydrogen production by catalytic steam reforming of waste glycerol solutions resulted in biofuels production: characterization and partial purification of waste glycerol solutions, catalytic and reaction parameters for H2 production by waste glycerol SR;  modeling and simulation of the process, model validation; design and realization of laboratory scale experimental set-up.
Results: (1) crude bio-ethanol with enhanced concentration of ethanol, prepared from fir wood wastes; (2) glycerol wastes with high glycerol content and lower content of components difficult to be catalytically reformed; (3) samples of hydrogen prepared from glycerol; (4) analytical method for glycerol wastes including a new method for glycerol analysis; (5) method and installation for hydrogen production by glycerol steam reforming using Me1-Me2/oxid1-oxid2 catalysts; (6) laboratory scale technology for biofuel preparation which generate wastes with high glycerol content and and low content of inorganic components; (7) thermodynamic study of glycerol steam reforming (8) scientific and technical report containing experimentation reports for preparation and analysis of glycerol wastes; catalytic studies for hydrogen preparation from glycerol; technological scheme for the synthesis of biofuel by the dry technology; instalation scheme for the catalytic reformation of glycerol.	Dissemination: - 4 published papers - 1 paper presented at international conferences; - 2 papers presented at national conferences; (see papers)
The optimization of hydrogen production from fir wood wastes was performed by: (i) the optimization of hydrolysis and fermentation process having as direct consequence the increase of ethanol and acetic acid concentration in crude bio-ethanol; (ii) using the crude bio-ethanol in steam reforming which have two important benefits: reduce the cost of ethanol separation from mixture and increase the hydrogen production due to the reformation of all organic oxygenated compounds from mixture; (iii) the optimization of steam reforming process by using Ni/La2O3–Al2O3 and Ni/CeO2–Al2O3 catalysts which give good catalytic performances at low temperatures. It was developed an ungraded method to produce biofuel from vegetable oils, which generates wastes with high content of glycerol and low content of inorganic salts and water. This was possible by using a new basic catalyst to replace NaOH or KOH used in clasic technologies. The wastes generated in this way contain ~75% glycerol, the rest of components being methanol, esters, mono, di and tri glycerides and water. A series of analytical methods were developed for the analysis of glycerol wastes including a new method for glycerol analysis. In order to establish the optimum reaction conditions and catalysts for hydrogen production by glycerol steam reforming, (glycerol-water) mixture was used for catalytic tests. the tested catalysts are those prepared and characterized in the first phase of the project: Me/support Me = Ni, Ni-Cu, Ni-Sn; support = Al2O3, La2O3–Al2O3, CaO–Al2O3; reaction conditions: temperature 450–650°C; atmospheric pressure; carrier gas flow: 35–133 mL/min, (glycerol+water) flow 0.1mL/min, glycerol:water molar ratio = 1:1 – 1:9. The calculated parameters were: glycerol conversion in gaseous products, hydrogen yield and catalyst stability in 100h time on stream. The highest conversion (around 50%) was obtained at 650°C; atmospheric pressure; carrier gas flow: 133 mL/min, (glycerol+water) flow 0.1mL/min, glycerol:water molar ratio = 1:9. The addition of Cu to Ni/Al2O3 increase the glycerol conversion and hydrogen yield; The addition of La2O3 and CaO to alumina increase the glycerol conversion and hydrogen yield at 550°C, almost to the same level as at 650°C. The best hydrogen yield in the above mentioned reaction conditions was obtained for Ni/CaO–Al2O3. Catalyst stability was good for all catalysts. After 100h time on stream the deposition of crystalline filamentous carbon was observed without leading to major catalysts deactivation. The thermodynamic study of glycerol steam reforming was made using the ChemCAD process simulator in extended temperature, pressure and reagent ratio domains compared to the already reported ones.  The thermodynamic favorable conditions to obtain high hydrogen concentrations and low carbon formation are: high temperatures, low pressure and low glycerol:water ratio. Taking into account also the energy consumption costs, the recomanded reaction conditions are: 650-700°C, glycerol:water ratio 1:30 and 1 bar.