Activated biochars used as adsorbents for dyes removal

Adsorption represents one of the most interesting technique for the removal of pollutants from wastewaters. Activated carbons show the best performances on this kind of processes but their high production costs limit their applications. In this context a big challenge is to find new materials having characteristic similar to those of commercial activated carbons but being environmental friendly and cheaper. In this work the adsorption efficiency of activated biochars produced from pine wood was investigated on the removal of dyes from water. An innovative method for the activation of the biochar using deep eutectic solvents (DES) was tuned and the characteristics of the obtained adsorbent material were compared with those of biochar activated with traditional method and non-activated biochar. The best adsorption capacities were obtained with the DES activated biochar, reaching a value of 480 mg/g for the methylene blue adsorption. Adsorption isotherm and kinetic models were applied to experimental data in order to understand the adsorption mechanism of the process

Biomass gasification plant and syngas clean-up system

Gasification is recognized as one of the most promising technologies to convert low quality fuels into more valuable ones. The principal problem related with the use of biomass in gasification processes is the high amount of tar released during the pyrolysis step. It is thus necessary to recover tar and to transform it in lighter combustible gas species such as CH4, CO and H-2. In this work the experimental results of a medium industrial scale plant fed with olive husk and having a capacity of 250 kWt are presented. The gasifier is composed by a up-draft reactor which is followed by a secondary fixed bed reactor filled with alluminium oxide spheres having high porosity dedicated to the tar conversion reactions. The syngas is then used to feed an internal combustion engine with a production of 60 kWe

Methane dry reforming over nickel perovsikite catalysts

In recent years dry reforming of methane (DRM) has received considerable attention as a promising alternative to steam reforming for synthesis gas (H2 and CO) production. This process could be industrially advantageous, yielding a syngas with a H2/CO ratio close to 1, suitable for Fischer-Tropsch synthesis to liquid hydrocarbons and for production of valuable oxygenated chemicals. The major drawback of the process is the endothermicity of the reaction that implies the use of a suitable catalyst to work at relatively low temperatures (923-1,023 K). Higher temperatures would make the process unaffordable for an industrial development and would increase the risk of undesirable side reactions, such as coke formation, that are the main causes of catalyst deactivation. In this work the activity of nickel perovskite catalysts were studied and the results were compared with rhodium perovskite. It is well known that rhodium is very active and stable for dry reforming but its high cost makes its utilization limited. The Ni, due to its low cost, is a promising substitute even if it is more susceptible to coking. The perovskite structure allows a high dispersion of the metal into the catalyst increasing the catalytic activity. In this work the Ni perovskite was obtained with two methods (auto-combustion and modified citrate methods). The results pointed out that the Ni perovskite obtained with the auto-combustion method is a promising route for the use of Ni in this process. The experimental tests show that with Ni catalyst very good activity can be achieved from temperature of 973 K

Biocrude production by hydrothermal liquefaction of olive residue

Hydrothermal liquefaction (HTL) converts biomass into a crude bio-oil by thermally and hydrolytically decomposing the biomacromolecules into smaller compounds. The crude bio-oil, or biocrude, is an energy dense product that can potentially be used as a substitute for petroleum crudes. Liquefaction also produces gases, solids, and water-soluble compounds that can be converted to obtain valuable chemical species or can be used as energy vectors. The process is usually performed in water at 250°C-370°C and under pressures of 4-22 MPa: depending on the adopted pressure and temperature the process can be carried out in sub-critical or super-critical conditions. In the conditions reached in hydrothermal reactors, water changes its properties and acts as a catalyst for the biomass decomposition reactions. One of the main advantages of this process is that the energy expensive biomass-drying step, required in all the thermochemical processes, is not necessary, allowing the use of biomass with high moisture content such as microalgae or olive residue and grape mark. In this work, the feasibility of a hydrothermal process conducted under sub-critical conditions to obtain a bio-oil from the residue of olive oil production is investigated. The experimental tests were performed at 320°C and about 13 MPa, using a biomass to water weight ratio of 1:5. The influence of two different catalysts on the bio-oil yield and quality was investigated: CaO and a zeolite (faujasite-Na). CaO allows the increase of bio-oil yields, while the selected zeolite enhances the deoxygenation reactions, thus improving the bio-oil quality in terms of heating value

Influence of the catalyst support on the steam reforming performance of toluene as tar model compound

The large amount of tar produced along with the syngas during biomass gasification is one of the major obstacle for the diffusion of gasifiers at industrial scale. Catalytic cracking and reforming are the most suitable processes for the transformation of tar into lighter gases. The selection of suitable catalysts is a critical step. The catalysts must own high activity and high resistance to deactivation for coke deposition. In this work the effect of two different supports, mayenite and aluminium oxide, on the activity of the nickel was investigated in the steam reforming of toluene that was used as tar model compound. In particular, the performed experimentations aimed to test the mayenite in terms of improvement of resistance to carbon deposition in conditions similar to those of gasification reactors. The obtained results indicate that Ni /mayenite catalyst needs higher temperature to activate and leads to lower value of toluene conversion with respect to Ni / alumina. However, mayenite, which is known from literature to have higher resistance to coke deposition due to the presence of free oxygens in the lattice which oxidize the coke deposited on the catalyst surface showed higher resistance to deactivation especially for low steam to carbon ratios

Thermo-economic assessment of a olive pomace gasifier for cogeneration applications

A thermo-economic analysis of a combined heat and power (CHP) plant fed by syngas produced through the gasification of dry olive pomace is presented. The plant is composed by a 800 kWtdowndraft gasifier, a gas clean-up system, a 200 kWemicroturbine (MGT) and a heat recovery system to cogenerate hot water. Surplus heat is used to dry olive pomace from 50% to 17% wb moisture content. The plant is modeled in ASPEN Plus. Real data from experimental tests are used to calibrate the gasifier model, while the technical specification and performance of the CHP plant are collected from commercial plants in operation and data from manufacturers. Mass and energy balances are reported throughout the paper. The thermodynamic simulation of the biomass gasifier coupled to the MGT, the thermal and electrical conversion efficiency and temperature of cogenerated heat available are also presented. A thermo-economic assessment is then proposed, to investigate the economic profitability of this small scale CHP plant in the Italian energy policy scenario and considering the subsidies available for renewable electricity in the form of feed-in tariffs. For this purpose, the case study of base load CHP plant operation and heat supplied to different typologies of energy end user is assumed. The results allow quantifying the most influencing economic and technical factors that affect the performance and profitability of such investment and the bottlenecks that should be faced to facilitate a broader implementation of such CHP schemes for on site generation

Use of low-cost materials for tar abatement process

In the present work char, olivine and mayenite were used as bed materials to study ability to remove tar produced in biomass thermal processing. The tar gases formed from the pyrolysis reactions of the olive pomace biomass were forced to pass through the bed material. Nitrogen was used as carrier gas. The temperature of the bed was set at 660 °C and no oxidizing agent was added during the tests. The char was produced from the pyrolysis of olive pomace biomass. Olivine was used without any pre-treatment. Mayenite was synthesized in laboratory using CaCO3 and Al2O3 as precursors. Among the tested materials, mayenite showed the best tar removal capacity and stability, with a total tar removal of about 60% after 60 min time on stream, while in the case of char and olivine the attained value was 15%. The measured average nitrogen-free gas flow value in the tests carried out with mayenite was 0.84 NL min-1, whereas in the case of char and olivine the obtained average gas flow values were 0.65 and 0.55 NL min-1, respectively. Accordingly, the higher average hydrogen amount was measured in the tests using mayenite as bed material (36%)

Improved photocatalytic properties of doped titanium-based nanometric oxides

Photocatalysis is considered one of the most promising technologies for applications in the environmental field especially in the abatement of water-soluble organic pollutants. In this field, titanium dioxide nanoparticles have drawn much attention recently; however, the use of this oxide presents some limitation since it allows to obtain high photoresponse and degradation efficiency only under UV light irradiation, that represents the 3 to 4% of the solar radiation, so preventing its environmental large-scale applications under diffuse daylight. In this work the photocatalytic efficiencyoftitanium-based oxides systems containing alkaline earth metals such as barium and strontium, prepared by a simple sol-gel method was investigated, evaluating the degradation of methylene blue as model compound under UV and visible light irradiation. The results were compared with those obtained with Degussa P25 titanium dioxide. The achieved degradation percentage of methylene blue are very promising showing that under visible light irradiation it is possible to obtain a maximum dye removal percentage ~ 50 % higher than that obtained with the Degussa P25

Hydrothermal liquefaction of mixed plastic waste to obtain bio-crude and a residue composed by pure poly-olefins

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Simulation on hydrothermal liquefaction of pinewood to produce bio-crude in a zero-waste process scheme

Hydrothermal liquefaction (HTL) is one of the advanced biomass conversion technologies to produce bio-crude from wet lignocellulosic feedstocks. Hydrochar and water phase containing organics are always generated as by-products and their efficient re-use could be fundamental to decrease the whole energy consumption. Hydrogen producers like Fe are often added to the HTL reactor to maximize the bio-crude yields and quality. Furthermore, Fe can be easily recovered from the biochar at the end of the reaction and re-used, after a reduction treatment. In this work, the feasibility to produce bio-crude through HTL of pinewood in a continuous zero-waste process scheme is evaluated in an Aspen Plus® simulation. The zero- waste configuration was carried out using the water phase containing organics instead of distillate water in the HTL reactor and the hydrochar as renewable reductant of iron oxides. Experimental data were used to model the HTL (Ryield) while the iron oxide reduction and the combustion of the side streams were simulated in the Gibbs reactor (Rgibbs). Red mud, a waste stream of the Bayern process for aluminium production, containing 50 wt % of hematite (Fe2O3), was selected as low-cost iron source. The iron oxides reduction with hydrochar was performed at different temperature (400-1200 °C) to determine the optimal value (complete conversion to Fe). Based on the simulation results, hydrochar allows the complete red mud reduction at 780 °C but the separation of the carbon excess before Fe recirculation must be considered. The proposed continuous zero-waste HTL plant consumed a total energy of 5080 J s-1, mostly of it related to the HTL (4945 J s-1) and iron oxide reduction (640.2 J s-1). However, the combustion of both off gases and hydrochar excess can approximately provide the heat needed to plant (-5012 J s-1). Finally, the results demonstrated that the proposed HTL scheme might be a zero-waste process in terms of both mass and energy flows