Progress and challenges in valorisation of biomass waste from ornamental trees pruning through pyrolysis processes. Prospects in the bioenergy sector.

Nowadays, the scarcity of energy resources is promoting the search for alternative energy sources, boosting interest in the use of forest lignocellulosic residue in the energy sector. In this study, the focus is on the energy recovery from two lignocellulosic residues originated during the pruning of ornamental trees (Horse Chestnut, CI, and False Acacia, FA). Both conventional and flash pyrolysis techniques were applied. The experimental pyrolysis variables were obtained from the study of the thermal behaviour of the pruning residues in thermogravimetric analysis. It was carried out under 5 heating rates and kinetic parameters were estimated using Flynn-Wall-Ozawa method. Results denoted higher maximum mass loss rate values for the same release temperature regions under FA experiments. Also, FA samples had lower final residues for the processes. However, activation energy values were so close for both species. FA was also linked to the faster reactions according frequency factor outcomes. Conventional pyrolysis of pruning residues was carried out in a horizontal oven of original design at a heating rate of 25 °C/min, at 750 °C and 60 min of permanence at that temperature; flash pyrolysis was tested in that oven at 750 and 850 °C. In these pyrolysis processes, three fractions were obtained: bio-char, bio-oil and gas. The physicochemical attributes of the bio-chars suggested their potential utility as biofuels (28.4-29.8 MJ/kg), adsorbent precursors or soil additives. Conventional pyrolysis bio-oils had a dominant monoaromatic hydrocarbons nature, with phenols being the most abundant (≥60%), while flash bio-oils contain mainly polycyclic aromatic hydrocarbons. Conventional pyrolysis gases contained up to 60 vol% of CO2; flash pyrolysis gases had high combustible gas content (CO, CH4, H2) and a low CO2 content (<25 vol%). As a result, their calorific value (18.06 MJ/kg) exhibited a threefold increase compared to the gas produced through conventional pyrolysis (6.04 MJ/kg).

An experimental investigation of sewage sludge gasification in a fluidized bed reactor.

The gasification of sewage sludge was carried out in a simple atmospheric fluidized bed gasifier. Flow and fuel feed rate were adjusted for experimentally obtaining an air mass : fuel mass ratio (A/F) of 0.2 < A/F < 0.4. Fuel characterization, mass and power balances, produced gas composition, gas phase alkali and ammonia, tar concentration, agglomeration tendencies, and gas efficiencies were assessed. Although accumulation of material inside the reactor was a main problem, this was avoided by removing and adding bed media along gasification. This allowed improving the process heat transfer and, therefore, gasification efficiency. The heating value of the produced gas was 8.4 MJ/Nm, attaining a hot gas efficiency of 70% and a cold gas efficiency of 57%.

Gasification of rice straw in a fluidized-bed gasifier for syngas application in close-coupled boiler-gasifier systems.

The feasibility and operation performance of the gasification of rice straw in an atmospheric fluidized-bed gasifier was studied. The gasification was carried out between 700 and 850 °C. The stoichiometric air-fuel ratio (A/F) for rice straw was 4.28 and air supplied was 7-25% of that necessary for stoichiometric combustion. Mass and power balances, tar concentration, produced gas composition, gas phase ammonia, chloride and potassium concentrations, agglomeration tendencies and gas efficiencies were assessed. Agglomeration was avoided by replacing the normal alumina-silicate bed by a mixture of alumina-silicate sand and MgO. It was shown that it is possible to produce high quality syngas from the gasification of rice straw. Under the experimental conditions used, the higher heating value (HHV) of the produced gas reached 5.1 MJ Nm(-3), the hot gas efficiency 61% and the cold gas efficiency 52%. The obtained results prove that rice straw may be used as fuel for close-coupled boiler-gasifier systems.

Modelling N mineralization from bovine manure and sewage sludge composts.

Nitrogen mineralization kinetics were compared in three different soils (pH values: 5.2, 7.1 and 8.6) when treated with bovine manure (BM) and sewage sludge (SS) composts. The soil-compost mixtures were kept at a controlled moisture content of 60% of their water holding capacity (WHC) and were incubated in the dark at 25 °C for 2 years. Five mathematical models were compared (simple exponential, double exponential, special model, hyperbolic and parabolic), using as experimental data the mineralized N accumulated during 360 and 720 days of incubation. The results showed that the best fit for describing the mineralization of organic N from the compost after 1 year of experimentation was obtained with the simple exponential model. However, the special model showed the best fit for data from 2 years of incubation and thus better reflected organic N mineralization over a longer time-span. This suggested that the organic N in the two composts was made up of two organic pools of different degrees of stability.

Co-combustion of different sewage sludge and coal: a non-isothermal thermogravimetric kinetic analysis.

The kinetics of the combustion of coal, two different sewage sludge and their blends (containing different dried weight percentages of sewage sludge) was studied by simultaneous thermogravimetric analysis. Once the weight percentage of sludge in the blend was 10%, the effects on the combustion of coal were hardly noticeable in terms of weight loss. The Arrhenius activation energy corresponding to the co-combustion of the blends was evaluated by non-isothermal kinetic analysis. This showed that, though differences between coal and sewage sludge, the combustion of their blends kept kinetically alike to that of the coal. This work illustrates how thermogravimetric analysis may be used as an easy rapid tool to asses, not only mass loss, but also kinetics of the co-combustion of sewage sludge and coal blends.

Fertilization of maize with compost from cattle manure supplemented with additional mineral nutrients.

An alternative approach for cattle manure management on intensive livestock farms is the composting process. An industrial-scale composting plant has been set up in northwest Spain for producing compost from cattle manure. Manure composting involved an increase in pH, electrical conductivity (EC), cation exchange capacity (CEC) and NO3(-)--N concentration, and a decrease in temperature, moisture content, organic matter (OM) content, NH4+--N concentration and C/N ratio. Cu, Zn and Ni concentrations increased due to the reduction of pile mass during the composting process. The resulting compost was applied to a field to study the viability of applying this compost combined with a nitrogen mineral fertilizer as a replacement for the mineral fertilization conventionally used for maize (Zea mays L.). The thermophilic phase of the composting process was very prolonged in the time, which may have slowed down the decomposition of the organic matter and reduced the nitrification process, leading to an over-short maturation phase. The humification and respirometric indexes, however, determined immediately after compost application to the soil, showed it to be stable. Compost application did not decrease the grain yield. A year later, soil pH, OM content and CEC were higher with the compost treatment. Total P, K, Ca and Na concentrations in compost-amended plots were higher than in mineral-fertilized ones, and no significant differences between treatments were found in soil concentrations of NH4+--N,NO3- --N, available P, Mg and B. Compost caused no heavy metal pollution into the soil. Therefore, this compost would be a good substitute for the mineral fertilizers generally used for basal dressing in maize growing.

Pyrolysis of tyres. Influence of the final temperature of the process on emissions and the calorific value of the products recovered.

A study was made of the pyrolysis of tyre particles, with the aim of determining the possibilities of using the products resulting from the process as fuel. Three final temperatures were used, determined from thermogravimetric data. The design of the experiment was a horizontal oven containing a reactor into which particles of the original tyre were placed. After the process, a solid fraction (char) remained in the reactor, while the gases generated went through a set of scrubbers where most of the condensable fraction (oils) was retained. Finally, once free of this fraction, the gases were collected in glass ampoules. Solid and liquids fractions were subjected to thermogravimetric analyses in order to study their combustibility. The gas fraction was analysed by means of gas chromatography to establish the content of CO, CO2, H2 and hydrocarbons present in the samples (mainly components of gases produced in the pyrolysis process). A special study was made of the sulphur and chlorine content of all the fractions, as the presence of these elements could be problematic if the products are used as fuel. Tyre pyrolysis engenders a solid carbon residue that concentrates sulphur and chorine, with a relatively high calorific value, although not so high as that of the original tyre. The liquid fraction produced by the process has a high calorific value, which rises with the final temperature, up to 40 MJ/kg. The chlorine content of this fraction is negligible. Over 95% of the gas fraction, regardless of the final temperature, is composed of hydrocarbons of a low molecular weight and hydrogen, this fraction also appearing to be free of chlorine.

Dye adsorption by sewage sludge-based activated carbons in batch and fixed-bed systems.

The present research work deals with the production of activated carbons by chemical activation and pyrolysis of sewage sludges. The adsorbent properties of these sewage sludges based activated carbons were studied by liquid-phase adsorption tests. Dyes removal from colored wastewater being a possible application for sludge based adsorbents, methylene blue and saphranine removing from solution was studied. Pure and binary adsorption assays were performed in batch and fixed bed systems. In all cases studied, the adsorbents produced from sewage sludges were able to adsorb both the compounds considered here. Nevertheless, time required for reaching equilibrium, adsorptive capacity and fixed bed characteristic parameters were different for these two compounds. Methylene blue adsorption occurred faster than that of saphranine, and it was preferably adsorbed when treating binary solutions. It could be concluded that the sewage sludge-based activated carbons may be promising for dyes removal from aqueous streams.

Upgrading sewage sludges for adsorbent preparation by different treatments.

Addressing the adequate management of sludges produced at sewage plants is becoming a fundamental need as a consequence of the high production volumes, both current and forecasted, of this byproduct. European waste-treatment policies consider reuse of sludges as one of the preferred actions; along those lines this study proposes using sewage sludges as adsorbents for pollutants contained in wastewaters. As potential adsorbents, sludges dried at 105 degrees C, dried and pyrolyzed, or dried and chemically activated were tried. As adsorbate, methylene blue was used in order to characterize the adsorption capacity of the different materials. Although surface areas corresponding to pyrolyzed and chemically activated sludges were around 80 and 390 m2/g, respectively, both these materials exhibited poor levels of methylene blue adsorption which may have been due to their high proportions of micropores. Sludges only dried, on the contrary, showed significant methylene blue adsorption capacities.