Hydrochars derived from real organic wastes as carbonaceous precursors of activated carbons for the removal of NO from contaminated gas streams.

The improvement of air quality in densely-populated urban regions constitutes an environmental challenge of increasing concern. In this respect, the abatement of NO emissions, primarily emanating from combustion processes associated with motor-vehicles, along with industrial/domestic combustion systems, represents one of the main problems. Here, three hydrochars from diverse organic residues were used as activated carbon precursors for their evaluation in the NO removal in two potential application scenarios. Hydrochars were physically activated at 800 °C with pure-CO2 or diluted-O2. These materials were tested in a lab-scale biofilter at different conditions (NO concentration, temperature, relative humidity, NO-containing gas and carbon particle size) and in a larger-scale biofilter to evaluate the long-term NO removal capacity. Hydrochar-derived carbons present a relatively well-developed micro- and mesoporous structure, with BET areas of up to 421 m2/g, and a variety of oxygen surface functionalities (carboxylic, lactone, carbonyl and quinone groups), especially concerning CO2-activated carbons. These exhibited an excellent behaviour at low NO concentration (5 ppmv) between 25 and 75 °C with removal capacities of ≈97 % and > 82 %, respectively; and still good-performance (≈66 %) in a more concentrated gas (120 ppmv). Whilst, carbons obtained by diluted-O2 activation from the same hydrochars, evidenced a higher removal capacity loss at high NO concentration. The O2 presence in the gas stream was confirmed as a crucial factor in the NO elimination, since both co-adsorb on the carbon surface favouring NO oxidation to NO2. Besides, the humidity in the airstream diminished the NO removal capacity from 0.88 to 0.51 mgNO/gcarbon, but still remained at 0.54 mgNO/gcarbon, when the carbon (in pellet) was operated at larger-scale biofilter in 9-fold longer test under humid air. Therefore, this study highlights the potential of renewable carbons to serve as cost-effective component in urban biofilters, to mitigate NO emissions from exhaust gases in biomass boilers and urban semi-close areas.

Removal of NO at low concentrations from polluted air in semi-closed environments by activated biochars from renewables feedstocks.

Efficient measures are urgently required in large cities for nitric oxide (NO) elimination from air in urban semi-closed environments (parking lots and tunnels), characterized by low NO concentrations (<10 ppmv) and temperatures. One of the most promising abatement alternatives is the NO oxidation to NO2, which can be further easily captured in an alkali solution or over a porous solid. However, most of the research devoted to this topic is focused on the elimination of NO from fuel exhaust gases, with high NO concentrations (400-2000 ppmv). In this work, sustainable and low-cost activated biochars of different origin and having very different ash contents were employed in NO removal at very low concentrations. Thus, low ash content forestry (oak woodchips, OAK) and high ash content from agriculture (oilseed rape straw, OSR) biochars were subjected to physical activation with CO2 at 900 °C (OAK550-A900CO2 and OSR700-A900CO2, respectively). The NO removal performance tests of such activated carbons were carried out at different experimental conditions: i.e., temperature, relative humidity (0-50 vol% RH), NO-containing gas (N2 or air), amount of activated carbon, and NO concentration, to assess how the activated biochar properties influence their NO removal capacity. The sample OSR700-A900CO2 contained a higher population of oxygen surface functionalities, which might play an important role in the NO removal efficiency in dry conditions since they could assist NO oxidation on carbon active sites when used above room temperature (50-75 °C). However, at room temperature (25 °C), the presence of narrow micropore size distribution at 6 Å became a more relevant property, since it facilitates an intimate contact between NO and O2. Accordingly, the activated biochar from OAK was much more efficient, achieving complete removal of NO from air flow (dry or with 50 vol% RH) at 25 °C during 400 min of testing, making it an ideal candidate as biofilter for purifying air streams of semi-closed spaces contaminated with low concentrations of NO.

Removal of NO at low concentration from air in urban built environments by activated miscanthus biochar.

This work presents an innovative and sustainable approach to remove NO emissions from urban ambient air in confined areas (underground parking areas or tunnels) using low-cost activated carbons obtained from Miscanthus biochar (MSP700) by physical activation (with CO2 or steam) at temperatures ranging from 800 to 900 °C. The NO removal capacity of the activated biochars was evaluated under different conditions (temperature, humidity and oxygen concentration) and compared against a commercial activated carbon. This last material showed a clear dependence on oxygen concentration and temperature, exhibiting a maximum capacity of 72.6% in air at 20 °C, whilst, its capacity notably decreased at higher temperatures, revealing that physical NO adsorption is the limiting step for the commercial sample that presents limited oxygen surface functionalities. In contrast, MSP700-activated biochars reached nearly complete NO removal (99.9%) at all tested temperatures in air ambient. Those MSP700-derived carbons only required low oxygen concentration (4 vol%) in the gas stream to achieve the full NO removal at 20 °C. Moreover, they also showed an excellent performance in the presence of H2O, reaching NO removal higher than 96%. This remarkable activity results from the abundance of basic oxygenated surface groups, which act as active sites for NO/O2 adsorption, along with the presence of a homogeneous microporosity of 6 Å, which enables intimate contact between NO and O2. These features promote the oxidation of NO to NO2, which is further retained over the carbon surface. Therefore, the activated biochars studied here could be considered promising materials for the efficient removal of NO at low concentrations from air at moderate temperatures, thus closely approaching real-life conditions in confined spaces.

Scaling-Up of Bio-Oil Upgrading during Biomass Pyrolysis over ZrO2 /ZSM-5-Attapulgite.

Ex situ catalytic biomass pyrolysis was investigated at both laboratory and bench scale by using a zeolite ZSM-5-based catalyst for selectively upgrading the bio-oil vapors. The catalyst consisted of nanocrystalline ZSM-5, modified by incorporation of ZrO2 and agglomerated with attapulgite (ZrO2 /n-ZSM-5-ATP). Characterization of this material by means of different techniques, including CO2 and NH3 temperature-programmed desorption (TPD), NMR spectroscopy, UV/Vis microspectroscopy, and fluorescence microscopy, showed that it possessed the right combination of accessibility and acid-base properties for promoting the conversion of the bulky molecules formed by lignocellulose pyrolysis and their subsequent deoxygenation to upgraded liquid organic fractions (bio-oil). The results obtained at the laboratory scale by varying the catalyst-to-biomass ratio (C/B) indicated that the ZrO2 /n-ZSM-5-ATP catalyst was more efficient for bio-oil deoxygenation than the parent zeolite n-ZSM-5, producing upgraded bio-oils with better combinations of mass and energy yields with respect to the oxygen content. The excellent performance of the ZrO2 /n-ZSM-5-ATP system was confirmed by working with a continuous bench-scale plant. The scale-up of the process, even with different raw biomasses as the feedstock, reaction conditions, and operation modes, was in line with the laboratory-scale results, leading to deoxygenation degrees of approximately 60 % with energy yields of approximately 70 % with respect to those of the thermal bio-oil.

Multifunctional Pd/Ni-Co catalyst for hydrogen production by chemical looping coupled with steam reforming of acetic acid.

High yield of high-purity H2 from acetic acid, a model compound of bio-oil obtained from the fast pyrolysis of biomass, was produced by sorption-enhanced steam reforming (SESR). An oxygen carrier was introduced into a chemical loop (CL) coupled to the cyclical SESR process to supply heat in situ for the endothermic sorbent regeneration to increase the energy efficiency of the process. A new multifunctional 1 %Pd/20 %Ni-20 %Co catalyst was developed for use both as oxygen carrier in the CL and as reforming catalyst in the SESR whereas a CaO-based material was used as CO2 sorbent. In the sorbent-air regeneration step, the Ni-Co atoms in the catalyst undergo strong exothermic oxidation reactions that provide heat for the CaO decarbonation. The addition of Pd to the Ni-Co catalyst makes the catalyst active throughout the whole SESR-CL cycle. Pd significantly promotes the reduction of Ni-Co oxides to metallic Ni-Co during the reforming stage, which avoids the need for a reduction step after regeneration. H2 yield above 90 % and H2 purity above 99.2 vol % were obtained.

Gasification of the char derived from distillation of granulated scrap tyres.

This work reports the effect of pressure on the steam/oxygen gasification at 1000°C of the char derived from low temperature-pressure distillation of granulated scrap tyres (GST). The study was based on the analysis of gas production, carbon conversion, cold gas efficiency and the high heating value (HHV) of the product. For comparison, similar analyses were carried out for the gasification of coals with different rank. In spite of the relatively high ash (≈12 wt.%) and sulphur (≈3 wt.%) contents, the char produced in GST distillation can be regarded as a reasonable solid fuel with a calorific value of 34MJkg(-1). The combustion properties of the char (E(A)≈50 kJ mol(-1)), its temperature of self-heating (≈264°C), ignition temperature (≈459°C) and burn-out temperature (≈676°C) were found to be similar to those of a semi-anthracite. It is observed that the yield, H(2) and CO contents and HHV of the syngas produced from char gasification increase with pressure. At 0.1 MPa, 4.6 Nm(3)kg(char)(-1) of syngas was produced, containing 28%v/v of H(2) and CO and with a HHV around 3.7 MJ Nm(-3). At 1.5 MPa, the syngas yield achieved 4.9N m(3)kg(char)(-1) with 30%v/v of H(2)-CO and HHV of 4.1 MJ Nm(-3). Carbon conversion significantly increased from 87% at 0.1 MPa to 98% at 1.5 MPa. It is shown that the char derived from distillation of granulated scrap tyres can be further gasified to render a gas of considerable heating value, especially when gasification proceeds at high pressure.