Catalytic hydrotreating of pyro-oil derived from green microalgae spirulina the (Arthrospira) plantensis over NiMo catalysts impregnated over a novel hybrid support

Upgrading of pyrolysis bio-oil by a novel catalytic hydrotreating process, including hydrodeoxygenation (HDO) and hydrodenitrogenation (HDN) was found as an effective technical method for the improvement of biofuel characteristics. In this study, for the first time, the performance of a novel meso-microporous composite material, HMS-ZSM-5, as a support on the catalytic activity of NiMo-based catalysts in the bio-oil hydrotreating was evaluated. The experiments were carried out in a flow fixed-bed reactor at the temperature range of 300–360 °C, 30 bar pressure, and LHSV = 4 h-1. Also, the results were and compared with those of HMS, ZSM-5, and γ-Al2O3 supports. For all catalysts, the increase in temperature resulted in the enhancement of HDO and HDN reactions efficiency. NiMo/HMS-ZSM-5 possessed a high acid property which contributed to the removal of oxygen and nitrogen from bio-oil, with the conversion of 84.10% and 69.60%, respectively. Therefore, the novel catalyst of this study represented much superior upgrading performances compared with those of stand-alone NiMo/HMS and NiMo/ZSM-5 catalysts and also the conventional catalyst of NiMo/γ-Al2O3.     

Upgrading the lubricity of bio-oil via homogeneous catalytic esterification under vacuum distillation conditions

In order to accelerate the application of bio-oil in the internal combustion engines, homogeneous catalytic esterification technology under vacuum distillation conditions was used to upgrade the crude bio-oil. The lubricities of the crude bio-oil (BO) and refined bio-oil with homogeneous catalytic esterification (RBO_hce) or refined bio-oil without catalyst but with distillation operation (RBO_wc) were evaluated by a high frequency reciprocating test rig according to the ASTM D 6079 standard. The basic physiochemical properties and components of the bio-oils were analyzed. The surface morphology, contents and chemical valence of active elements on the worn surfaces were investigated by scanning electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy, respectively. The results show that RBO_hce has better lubricities than those of BO, but RBO_wc has worse lubricities than those of BO. The tribological mechanisms of the bio-oils are attributed to the combined actions of lubricating films and factors that will break the film. Compared with BO, plenty of phenols in RBO_wc results in corrosion of the substrate and destroys the integrity of the lubricating films, which is responsible for its corrosive wear. However, more esters and alkanes in RBO_hce contribute to forming a complete boundary lubricating film on the rubbed surfaces which result in its excellent antifriction and antiwear properties.     

Steam reforming of propionic acid: Thermodynamic analysis of a model compound for hydrogen production from bio-oil

The thermodynamic equilibrium of steam reforming of propionic acid (HPAc) as a bio-oil model compound was studied over a wide range of reaction conditions (T = 500–900 °C, P = 1–10 bar and H₂O/HPAc = 0–4 mol/mol) using non-stoichiometric equilibrium models. The effect of operating conditions on equilibrium conversion, product composition and coke formation was studied. The equilibrium calculations indicate nearly complete conversion of propionic acid under these conditions. Additionally, carbon and methane formation are unfavorable at high temperatures and high steam to carbon (S/C) ratios. The hydrogen yield versus S/C ratio passes a maximum, the value and position of which depends on temperature. The thermodynamic equilibrium results for HPAc fit favorably with experimental data for real bio-oil steam reforming under same reaction conditions.     

Hydrogen production from a solution plasma process of bio-oil

This study examined the possibility of hydrogen production using a solution plasma process (SPP). The reactants were lignin model compounds and actual lignin oil. The highest amount of hydrogen was generated in SPP using m-cresol. The total amount of gas generated by the plasma reaction for 20 min using 23 g of m-cresol was 1.69 L, which comprised of 65.51% hydrogen and 29.85% CO. Furthermore, a maximum of 1.91 L of hydrogen was generated by a reaction between pyrolysis oil and ethanol with a weight ratio of 1:1. The presence of carbon black, a reaction byproduct, was measured by Fourier transform infrared spectroscopy, which revealed molybdenum trioxide peaks. It was confirmed that molybdenum used as an electrode was doped on carbon.     

Potentiality of combined catalyst for high quality bio-oil production from catalytic pyrolysis of pinewood using an analytical Py-GC/MS and fixed bed reactor

The aim of this study was to investigate the potential of combined catalyst (ZSM-5 and CaO) for high quality bio-oil production from the catalytic pyrolysis of pinewood sawdust that was performed in Py-GC/MS and fixed bed reactor at 500 °C. In Py-GC/MS, the maximum yield of aromatic hydrocarbon was 36 wt% at biomass to combined catalyst ratio of 1:4 where the mass ratio of ZSM-5 to CaO in the combined catalyst was 4:1. An increasing trend of phenolic compounds was observed with an increasing amount of CaO, whereas the highest yield of phenolic compounds (31 wt%) was recorded at biomass to combined catalyst ratio of 1:4 (ZSM-5: CaO - 4:1). Large molecule compounds could be found to crack into small molecules over CaO and then undergo further reactions over zeolites. The water content, higher heating value, and acidity of bio-oil from the fixed bed reactor were 21%, 24.27 MJkg⁻¹, and 4.1, respectively, which indicates that the quality of obtained bio-oil meets the liquid biofuel standard ASTM D7544-12 for grade G biofuel. This research will provide a significant reference to produce a high-quality bio-oil from the catalytic pyrolysis of woody biomass over the combined catalyst at different mass ratios of biomass to catalyst.     

Effects of particle sizes on performances of the multi-zone steam generator using waste heat in a bio-oil steam reforming hydrogen production system

Hydrogen production by bio-oil steam reforming is an advanced production technology. It is a good method of coupling waste heat utilization with bio-oil steam reforming to produce hydrogen, which increases the cleaning ability of the bio-oil steam reforming system. A multi-zone steam generator using waste heat has been proposed, which can produce the heat source and steam source of the hydrogen system. The DEM model of the multi-zone steam generator was set up. The model has been used to investigate the effects of particle sizes (40 mm–80 mm). With increasing particle size, the flow index and the flow uniformity gradually decrease, the vertical velocity gradient increases in the area on both side with the zone steam generator, and the vertical velocity fluctuation amplitude gradually increases. So, the hydrogen production decreases from the particle size increasing.     

Catalytic steam reforming of bio-oil aqueous fraction for hydrogen production over Ni–Mo supported on modified sepiolite catalysts

Hydrogen will be an important energy carrier in the future and hydrogen production has drawn a great deal of attention to its advantages in efficiency and environmental benefit. Catalytic steam reforming in this study was carried out in a fixed bed tubular reactor with sepiolite catalysts. Sepiolite catalysts modified with nickel (Ni) and molybdenum (Mo) were prepared using the precipitation method. Influential parameters such as temperature, catalyst, steam to carbon ratio (S/C), the feeding space velocity (WHSV), reforming length, and activity of catalyst were investigated and the yields of H₂, CO, CH₄, and CO₂ were obtained. The result of this experiment shows that the acidified sepiolite catalyst with addition of the Ni and Mo greatly improves the activities of catalyst and effectively increases the yield of hydrogen. The favorable reaction condition is as follows: reaction temperature is 700–800 °C; S/C is 16–18; the feeding space velocity is 1.5–2.2 h⁻¹, respectively.     

Upgrading of a wood-derived oil over various catalysts

The upgrading of a bio-oil using a fixed bed micro-reactor operating at 1 atm, 3.6 WHSV and 330–410°C over various catalysts is reported. The catalysts used were HZSM-5, silicalite, H-mordenite, H-Y and silica-alumina. The yield of hydrocarbons as well as the extent of deoxygenation, coke formation and conversion of the non-volatile portion of the bio-oil were used as measures of catalyst performance. The maximum hydrocarbon yield when HZSM-5 was used occurred at 370°C and was 39.3 wt% of the bio-oil. For the other catalysts, the hydrocarbon yields increased with temperature and were up to 22.1 wt% for silicalite; 27.5 wt% for H-mordenite; 21.0 wt% for H-Y; and 26.2 wt% for silica-alumina at 410°C. The hydrocarbon selectivity with HZSM-5 and silicalite catalysts was mostly for gasoline range hydrocarbons (C₆ to C₁₂) and for H-mordenite and H-Y for kerosene range hydrocarbons (C₉ to C₁₅). The hydrocarbon fraction obtained with silica-alumina did not produce any defined distribution. The pore size, catalyst acidity and catalyst shape selectively affected the product distribution. The overall performance followed the order: HZSM-5 > H-mordenite > H/Y > silica-alumina, silicalite.     

A thermodynamic equilibrium analysis of hydrogen and synthesis gas production from steam reforming of acetic acid and acetone blends as bio-oil model compounds

Thermodynamic analysis of steam reforming of blends of two model oxygenates, acetic acid and acetone, representing carboxylic acids and ketones in bio-oil is performed to investigate the effects of their potential interactions on hydrogen yield, synthesis gas composition and progress of reaction network. The results show that both acetic acid and acetone reach complete conversion at all operating conditions. Higher S/C molar ratio results in higher H₂ and CO₂ yields for both acetic acid and acetone. With the increase in pressure, H₂ and CO yields are diminished whereas CH₄ and CO₂ yields are enhanced. H₂ and CO₂ yields increase with the decrease in acetone concentration in the feed blend. CO and CH₄ production are affected adversely for acetic acid rich blends. The maximum H₂ yield values are 75.54%, 78.34%, 80.09%, 81.78% and 84.17% at 700 °C for acetic acid/acetone blends of 0.0/1.0, 0.3/0.7, 0.5/0.5, 0.7/0.3 and 1.0/0.0, respectively.     

Tailoring Cu/Al2O3 catalysts for the catalytic pyrolysis of tomato waste

In this study, pyrolysis of tomato waste has been performed in fixed bed tubular reactor at 500 °C, both in absence and presence of Cu/Al₂O₃ catalyst. The influences of heating rate, catalyst preparation method and catalyst loading on bio-oil yields and properties were examined. According to pyrolysis experiments, the highest bio-oil yield was obtained as 30.31% with a heating rate of 100 °C/min, 5% Cu/Al₂O₃ catalyst loading ratio and co-precipitation method. Results showed that the catalysts have strong positive effect on bio-oil yields. Bio-oil quality obtained from fast catalytic pyrolysis was more favorable than that obtained from non-catalytic and slow catalytic pyrolysis.