Microalgae as a renewable fuel source: Fast pyrolysis of Scenedesmus sp.

Herein we report the fast pyrolysis of dried, ground Scenedesmus sp. at two different reactor scales. Pyrolysis was performed at 480 °C and 1 bar in both an isothermal spouted bed reactor and a dynamic pyrolysis-GC/MS unit, each with 2 s vapor residence times. Bio-oil products were characterized on the basis of GC-MS, simulated distillation GC, elemental analysis, calorific content and total acid number. The ratio of crude oil: char obtained from the spouted bed reactor was 3.76 by weight, the average calorific content of the oil being 18.4 MJ/kg. The average total acid number (68 mg KOH/g) was lower than typical bio-oil produced via wood pyrolysis. Simulated distillation results indicated that a significant proportion of the oil corresponded to the boiling range typical for heavy gas oil (343 °C–524 °C). Elemental analysis showed the oil contained an average of 27.6 wt.% oxygen and 8.6 wt.% nitrogen, the relatively high nitrogen content being a consequence of the high protein content of the algae. According to GC-MS data, the oil consisted of various hydrocarbons as well as oxygenated and nitrogenous species, including indoles, fatty acids and amides. Pyrolysis-GC-MS was also performed on Scenedesmus sp. in order to provide insights into the nature of the primary pyrolysis products.     

Hydrogen-rich syngas production by the three-dimensional structure of LaNiO3 catalyst from a blend of acetic acid and acetone as a bio-oil model compound

Converting biomass bio-oil to hydrogen is valuable strategy. In this study, a blend of acetic acid and acetone has been utilized as a bio-oil model compound, where perovskite in a three-dimensional structure (3D-LaNiO₃) synthesized by a silica template method used as a catalyst. The result shows that the main phase of perovskite at 3D-LaNiO₃ catalyst has lower crystal size, resulting in decrease possibility of agglomeration. The amount of oxygen vacancies and higher ratio of Ni³⁺/Ni²⁺ are produced, enhancing the redox of catalyst. The stronger basic site and lager surface indicated the ability of improving coke deposition resistance. These results explained great activity of 3D-LaNiO₃ catalyst in producing hydrogen-rich syngas. The different steam/carbon mole ratios (S/C) have been discussed at 1 to 4, and the gas yield of H₂ (93.5%) shows highest at 600 °C and S/C = 3. Meanwhile, under this condition, the H₂ gas yield was stable and over 90% throughout 15 h of reaction. By analysis of spent 3D-LaNiO₃ catalyst, the result indicated that it has ability to resist the production of graphite coke deposition which is one of reasons for keeping catalyst activity. On the other hand, the stable of perovskite structure help in produce lattice oxygen for oxidizing coke deposited.     

Biomass to hydrogen-rich syngas via catalytic steam reforming of bio-oil

Hydrogen-rich syngas production from the catalytic steam reforming of bio-oil from fast pyrolysis of pinewood sawdust was investigated by using La_1−xK_xMnO₃ perovskite-type catalysts. The effects of the K substitution, temperature, water to carbon molar ratio (WCMR) and bio-oil weight hourly space velocity (W_bHSV) on H₂ yield, carbon conversion and the product distribution were studied in a fixed-bed reactor. The results showed that La_1−xK_xMnO₃ perovskite-type catalysts with a K substitution of 0.2 gave the best performance and had a higher catalytic activity than the commercial Ni/ZrO₂. Both high temperature and low W_bHSV led to higher H₂ yield. However, excessive steam reduced hydrogen yield. For the La_0.8K_0.2MnO₃ catalyst, a hydrogen yield of 72.5% was obtained under the optimum operating condition (T = 800 °C, WCMR = 3 and W_bHSV = 12 h⁻¹). The deactivation of the catalysts mainly was caused by coke deposition.     

Catalytic effects of ferric chloride and sodium hydroxide on supercritical liquefaction of thistle (Cirsium yildizianum)

Cirsium yildizianum stalks were liquefied in organic solvents under supercritical conditions with and without catalyst in a cylindrical reactor at temperatures of 260, 280 and 300 °C. The effects of liquefaction temperature, catalyst type and solvent on product yields were investigated. The liquid products (bio-oils) were extracted with diethyl ether and benzene using an extraction procedure. The liquid yields in supercritical methanol, ethanol and acetone were found to as 45.66%, 49.34% and 60.05% in the non-catalytical runs at 300 °C, respectively. The highest conversion (liquid + gaseous products) was obtained in acetone with 10% ferric chloride at 300 °C in the catalytic runs. The produced liquids at 300 °C were analyzed and characterized by elemental, GC–MS and FT-IR. 85, 79 and 60 different types of compounds were identified by GC–MS obtained in methanol, ethanol and acetone, respectively. The liquid products were composed of various organics including aromatics, nitrogenated and oxygenated compounds.     

Upgrading of bio-oil distillation bottoms into biorenewable calcined coke

Depleting fossil fuel sources necessitate renewable substitutes for petroleum-based co-products. Fast pyrolysis of biomass generates a hydrocarbon liquid (“bio-oil”) amenable to distillation and/or hydrotreatment into hydrocarbon blendstocks. Biorefineries must add value through parallel generation of co-products. We demonstrated a straightforward conversion of bio-oil distillate bottoms into calcined coke. The solid residue was subjected to calcination at 1200 °C for 1 h under N₂ atmosphere. The dry calcined product contained 96–99% carbon, was free from sulfur (<0.05% mass fraction), and contained a mass fraction of 0.2–1.1% ash. XRD confirmed steady increases in crystallite size with both devolatilization and calcination. FTIR spectroscopy indicated a loss of functional groups after calcination, except two broad peaks representing C–C and C–O. Temperature programmed oxidation (TPO) of the bottoms before and after calcination illustrates an increasing structural order via the increasing temperature(s) necessary to oxidize the samples. SEM images reveal bubbly morphologies similar to the industrially-favored sponge coke. The electrical resistivity of calcined coke samples measured to be < 1.6 mΩ-m, which closely falls in line with specifications for carbon anodes. Due to the aforementioned qualities and biomass origin, biorenewable calcined coke is an improved alternative to petroleum coke and can find application in carbon anodes, steel carburization, and graphite synthesis.     

Bio-oil production via fast pyrolysis of shrub residues in a fluidized-bed reactor

In this article, the shrub residues as raw materials were produced to fast pyrolysis oil (called bio-oil) in a 5-kg/h fluidized-bed reactor. The optimum conditions were obtained at 500°C, flow rate of fluidizing gas of 4 m³/h, and feed rate of 3 kg/h. The liquid yield was up to 60% at the optimum conditions. The bio-oil was easy to divide into two phases: oil phase and aqueous phase. The high heat value of the oil phase was up to 18.55 MJ/kg, but the high heat value of the aqueous phase was only 0.72 MJ/kg. The oil phase and aqueous phase both have lower pH values. The oxygen content was up to 50%, while the sulfur and nitrogen content were very low. Owing to the higher oxygen content and lower pH value in liquid products, it must be further upgraded to bio-oil before application.     

Experimental and DFT studies on catalytic reforming of acetic acid for hydrogen production over B-doped Co/Al2O3 catalysts

Steam reforming of bio-oil for hydrogen production is a promising green technology. Acetic acid was used as the bio-oil model compound. Experimental and density functional theory calculations were carried out to study the performance of Co/Al₂O₃ catalysts doped with boron (B) with a 1 wt.%–5 wt.% content. Catalyst characterization by BET, XRD, XPS, NH₃-TPD, H₂-TPR, TEM, and TG-DTG was performed. We found that the catalyst performance improved significantly by B doping. Under the reaction conditions of T = 500 °C, steam-to-carbon ratio (S/C) = 5, and liquid hourly space velocity (LHSV) = 4.3 h^?1, the catalyst with a B doping ratio of 1 wt.% had the highest hydrogen yield of 85% and a maximum acetic acid conversion rate of 95%. The corresponding hydrogen productivity was 0.8 mmol/min. The stability of this catalyst exceeded 29 h. Density functional theory calculations showed that the interactions between the reaction intermediates and the surface were strengthened with B addition.     

Optimization of two bio-oil steam reforming processes for hydrogen production based on thermodynamic analysis

Thermodynamics of hydrogen production from conventional steam reforming (C-SR) and sorption-enhanced steam reforming (SE-SR) of bio-oil was performed under different conditions including reforming temperature, S/C ratio (the mole ratio of steam to carbon in the bio-oil), operating pressure and CaO/C ratio (the mole ratio of CaO to carbon in the bio-oil). Increasing temperature and S/C ratio, and decreasing the operating pressure were favorable to improve the hydrogen yield. Compared to C-SR, SE-SR had the significant advantage of higher hydrogen yield at lower desirable temperature, and showed a significant suppression for carbon formation. However excess CaO (CaO/C > 1) almost had no additional contribution to hydrogen production. Aimed to achieve the maximum utilization of bio-oil with as little energy consumption as possible, the influences of temperature and S/C ratio on the reforming performance (energy requirements and bio-oil consumption per unit volume of hydrogen produced, Q_D/H2 (kJ/Nm³) and Y_Bio-oil/H2 (kg/Nm³)) were comprehensively evaluated using matrix analysis while ensuring the highest hydrogen yield as possible. The optimal operating parameters were confirmed at 650 °C, S/C = 2 for C-SR; and 550 °C, S/C = 2 for SE-SR. Under their respective optimal conditions, the Y_Bio-oil/H2 of SE-SR is significant decreased, by 18.50% compared to that of C-SR, although the Q_D/H2 was slightly increased, just by 7.55%.     

Production of hydrogen by steam reforming of bio-oil over Ni/Al2O3 catalysts: Effect of addition of promoter and preparation procedure

Catalytic steam reforming of bio-oil was investigated in a fixed bed tubular reactor for production of hydrogen. Two series of nickel/alumina (Ni/Al₂O₃) supported catalysts promoted with ruthenium (Ru) and magnesium (Mg) were prepared. Each catalyst of the first series (Ru–Ni/Al₂O₃) was prepared by co-impregnation of nickel and ruthenium on alumina. They were examined to investigate the effect of adding ruthenium on the performance of the catalysts for hydrogen production. The effect of the temperature, the most effective parameter in the steam reforming of bio-oil, on the activity of the catalysts was also investigated. Each catalyst of the second series (Ni–MgO/Al₂O₃) was prepared by consecutive impregnation using various preparation procedures. They were tested to determine the effect of adding magnesium as well as the effect of the preparation procedure on the outlet gas concentrations. It was shown that in both series, the catalysts were more efficient in hydrogen production as well as carbon conversion than Ni/Al₂O₃ catalysts. The highest hydrogen yield was 85% which was achieved over Ru–Ni/Al₂O₃ at 950 °C. It was also found that the effect of adding a small amount of ruthenium was superior to that of nickel on the yield of hydrogen when the nickel content was equal to or greater than 10.7%.     

Optimisation of bio-oil production by hydrothermal liquefaction of agro-industrial residues: Blackcurrant pomace (Ribes nigrum L.) as an example

This work reports bio-oil production by hydrothermal liquefaction of blackcurrant pomace (Ribes nigrum L.), a fruit residue obtained after berry pressing. The bio-oil has a higher heating value of 35.9 MJ kg⁻¹ and low ash content, which makes it suitable for energy applications. We report the influence of process parameters on yields and carbon distribution between products: temperature (563–608 K), holding time (0–240 min), mass fraction of dry biomass in the slurry (0.05–0.29), and initial pH (3.1–12.8) by adding sodium hydroxide (NaOH). Depending on the experiments, the bio-oil accounts for at least 24% mass fraction of the initial dry biomass, while char yields ranges from 24 to 40%. A temperature of 583 K enhances the bio-oil yield, up to 30%, while holding time does not have a significant influence on the results. Increasing biomass concentrations decreases bio-oil yields from 29% to 24%. Adding sodium hydroxide decreases the char yield from 35% at pH = 3.1 (without NaOH) to 24% at pH = 12.8. It also increases the bio-oil yield and carbon transfer to the aqueous phase. Thermogravimetric analysis shows that a 43% mass fraction of the bio-oil boils in the medium naphtha petroleum fraction range. The bio-oil is highly acidic and unsaturated, and its dynamic viscosity is high (1.7 Pa s at 298 K), underlining the need for further upgrading before any use for fuel applications.