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 2015

Title of Phase 4: Laboratory scale catalytic technology and experimental set-up for hydrogen production by steam reforming of hydroxylic compounds obtained as biomass processing wastes; techno-economic and environmental impact evaluations, dissemination activities (patent application, articles etc.).
Results: (1) purified glycerol; (2) catalytic reactor; (3) purification method for waste glycerol in order to remove all compounds which are incompatible with the catalytic steam reforming process; (4) analysis method for the compounds to be removed from waste glycerol; (5) mathematical model of the catalytic steam reforming process of glycerol, and its adaptation to the experimental conditions employed in the project; (6) Scientific and technical report including the experimentation reports for the purification and analysis of waste glycerol; catalytic studies for the determination of hydrogen production from glycerol; technological scheme for the purification of waste glycerol; project of the catalytic reactor.	Dissemination: - 4 published papers - 3 papers presented at international conferences; - 1 paper presented at national conference; (see papers)
(1) The purification method of waste glycerol was established, in order to remove the inorganic salts, mono, di-, and triglycerides and free fatty acids. The method consists in three steps and is presented in Annex 1 of the in extenso scientific report. The obtained purified glycerol has a 84% degree of purity, and was obtained pursuing the following sequence of operations: (i) neutralization of the alkaline pH with H2SO4 (98%), at 70°C, for 60 min (until a pH level of 1 ÷ 1.5 was reached); (ii) distillation under vacuum (approximatively 20 mm H2O) at 80°C, followed by a temperature raise up to 100°C; (iii) purification on active carbon, using an adsorption column with an internal diameter of D = 0.15 m and a fixed bed height of H = 0,60 m, under a total flow of ~13000 mL/h (13 L/h). (2) Analysis methods were established and validated for the constituents of waste glycerol mixture: mono, di- and triglycerides, content of FAMES, or methanol. (3) The mathematical model of the steam reforming process of glycerol was developed. For this purpose, the kinetic model found in the literature was adapted to our experimental conditions, and new values of the kinetic constants were determined for the parallel reactions considered. The correlation between the mathematical model and the experimental data was studied, which leads to a good fit for the maximum temperature and gas hourly space velocities employed. (4) The variation of hydrogen production with the operating parameters and the used catalyst was studied. In case of Ni/Al2O3, the best hydrogen production of 255 mL/min/gNi­ (STP) was obtained at 650°C, with 0.1 mL/min feed of glycerol – water mixture in the molar ratio of 1:9, and 133 mL/min Ar as eluent gas. Due to optimization costs, the working temperature was established at 550°C, for which the production of hydrogen was estimated at 210 mL/min/gNi­ (STP). It was observed that promotion with Sn and Cu of the alumina supported Ni catalyst does not improve the production of hydrogen under the investigated operating conditions, although an enhancement of glycerol conversion was observed for these catalysts. However, promotion with basic oxides slightly improves the production of hydrogen. (5) Based on the experimental results obtained until now, a larger catalytic reactor was calculated, designed and realized with an internal diameter twice as large as for the one used until now, intended to be integrated in the plant for the catalytic reforming of glycerol. This reactor will be tested in the next phase of the project.