Formic acid as an alternative reducing agent for the catalytic nitrate reduction in aqueous media

Formic acid was used for the nitrate reduction as a reductant in the presence of Pd:Cu/γ-alumina catalysts. The surface characteristics of the bimetallic catalyst synthesized by wet impregnation were investigated by SEM, TEM-EDS. The metals were not distributed homogeneously on the surface of catalyst, although the total contents of both metals in particles agreed well with the theoretical values. Formic acid decomposition on the catalyst surface, its influence on solution pH and nitrate removal efficacy was investigated. The best removal of nitrate (50 ppm) was obtained under the condition of 0.75 g/L catalyst with Pd:Cu ratio (4:1) and two fold excess of formic acid. Formic acid decay patterns resembled those of nitrate removal, showing a linear relationship between kf (formic acid decay) and k (nitrate removal). Negligible amount of ammonia was detected, and no nitrite was detected, possibly due to buffering effect of bicarbonate that is in situ produced by the decomposition of formic acid, and due to the sustained release of H2 gas.     

MgO-based adsorbents for CO2 adsorption: Influence of structural and textural properties on the CO2 adsorption performance

A series of MgO-based adsorbents were prepared through solution–combustion synthesis and ball-milling process.The prepared MgO-based powders were characterized using X-ray diffraction,scanning electron microscopy,N_2 physisorption measurements,and employed as potential adsorbents for CO_2 adsorption.The influence of structural and textural properties of these adsorbents over the CO_2 adsorption behaviour was also investigated.The results showed that MgO-based products prepared by solution–combustion and ball-milling processes,were highly porous,fluffy,nanocrystalline structures in nature,which are unique physico-chemical properties that significantly contribute to enhance their CO_2 adsorption.It was found that the MgO synthesized by solution combustion process,using a molar ratio of urea to magnesium nitrate(2:1),and treated by ball-milling during 2.5 hr(MgO-BM2.5h),exhibited the maximum CO_2 adsorption capacity of 1.611 mmol/g at 25℃ and 1 atm,mainly via chemisorption.The CO_2 adsorption behaviour on the MgO-based adsorbents was correlated to their improved specific surface area,total pore volume,pore size distribution and crystallinity.The reusability of synthesized MgO-BM2.5h was confirmed by five consecutive CO_2adsorption–desorption times,without any significant loss of performance,that supports the potential of MgO-based adsorbent.The results confirmed that the special features of MgO prepared by solution–combustion and treated by ball-milling during 2.5 hr are favorable to be used as effective MgO-based adsorbent in post-combustion CO_2 capture technologies.     

Modified activated carbon with interconnected fibrils of iron-oxyhydroxides using Mn2 + as morphology regulator, for a superior arsenic removal from water

The arsenic removal efficiency of iron-modified activated carbons depends greatly on the number of available iron oxide surface sites, which are given by the surface area of the anchored particles. In this sense, aiming the generation of an adsorbent with superior arsenic adsorption capacity, we developed a protocol to anchor interconnected fibrils of iron oxyhydroxides, using Mn^2 + as a morphology regulator. The protocol was based on a microwave-assisted hydrothermal method, using bituminous based activated carbon and both Fe^2 + and Mn^2 + ions in the hydrolysis solution. The elemental analysis of modified carbons revealed that Mn does not anchor to the carbon. However, when Mn is included in the hydrolysis solution, the iron content in the activated carbon increased up to 3.5?wt%, without considerable decreasing the adsorbent surface area. Under specific hydrothermal conditions, the Mn^2 + promoted the formation of iron oxide nanoparticles shaped as interconnected fibrils. This material showed a superior arsenic adsorption capacity in comparison to similar iron modified activated carbons (5?mg As/g carbon, at 2?mg As/L), attributed to the increase in quantity and availability of active sites located on the novel interconnected fibrils of iron oxyhydroxides nanostructures.     

Optimization and evaluation of a bottom substrate denitrification tank for nitrate removal from a recirculating aquaculture system

A bottom substrate denitrification tank for a recirculating aquaculture system was developed. The laboratory scale denitrification tank was an 8 L tank (0.04 m2 tank surface area), packed to a depth of 5 cm with a bottom substrate for natural denitrifying bacteria. An aquarium pump was used for gentle water mixing in the tank; the dissolved oxygen in the water was maintained in aerobic conditions (e.g. > 2 mg/L) while anoxic conditions predominated only at the bottom substrate layer. The results showed that, among the four substrates tested (soil, sand, pumice stone and vermiculite), pumice was the most preferable material. Comparing carbon supplementation using methanol and molasses, methanol was chosen as the carbon source because it provided a higher denitrification rate than molasses. When methanol was applied at the optimal COD:N ratio of 5:1, a nitrate removal rate of 4591 ± 133 mg-N/m2 tank bottom area/day was achieved. Finally, nitrate removal using an 80 L denitrification tank was evaluated with a 610 L recirculating tilapia culture system. Nitrate treatment was performed by batch transferring high nitrate water from the nitrification tank into the denitrification tank and mixing with methanol at a COD:N ratio of 5:1. The results from five batches of nitrate treatment revealed that nitrate was successfully removed from water without the accumulation of nitrite and ammonia. The average nitrate removal efficiency was 85.17% and the average denitrification rate of the denitrification tank was 6311 ± 945 mg-N/m2 tank bottom area/day or 126 ± 18 mg-N/L of pumice packing volume/day.     

Bio-reduction of nitrate from groundwater using a hydrogen-based membrane biofilm reactor

A hydrogen-based membrane biofilm reactor(MBfR) using H2 as electron donor was investigated to remove nitrate from groundwater.When nitrate was first introduced to the MBfR,denitrification took place on the shell side of the membranes immediately,and the effluent concentration of nitrate continuously decreased with 100% removal rate on day 45 under the influent nitrate concentration of 5 mg NO3--N/L,which described the acclimating and enriching process of autohydrogenotrophic denitrification bacteria.A series of short-term experiments were applied to investigate the effects of hydrogen pressures and nitrate loadings on denitrification.The results showed that nitrate reduction rate improved as H2 pressure increasing,and over 97% of total nitrogen removal rate was achieved when the nitrate loading increased from 0.17 to 0.34 g NO3--N/(m2 ·day) without nitrite accumulation.The maximum denitrification rate was 384 g N/(m3 ·day).Partial sulfate reduction,which occurred in parallel to nitrate reduction,was inhibited by denitrififcation due to the competition for H2 .This research showed that MBfR is effective for removing nitrate from the contaminated groundwater.     

Photocatalytic removal of NO and NO2 using titania nanotubes synthesized by hydrothermal method

In this study, the photocatalysts of titania nanotubes(TNTs) were synthesized at different calcination temperatures using commercial Degussa TiO2(P25) as a precursor. The materials were then characterized by BET, SEM, TEM, and XRD analyses. The photocatalytic reactions with NO and NO2 under UV-A irradiation were both performed. The results showed that the photocatalytic reaction rate of NO was much faster than that of NO2, and the conversion of NO2 to nitrate was the rate-limiting step for photocatalytic removal of NOx if the nitrate produced cannot be removed continuously from the photocatalyst surface. For TNTs calcined at different temperatures, a significant enhancement was observed on the total NOx removal efficiency by TNT calcined at 500°C for both NO and NO2 photocatalytic reaction, which could be attributed to its high anatase crystallinity as well as high surface area. These two factors affect primarily on the NO2conversion step in which the high anatase crystallinity could be responsible for the high efficiency at the beginning, while the high surface area could be accounted for retaining this high efficiency from nitric acid poisoning during the test period.     

Unraveling the size distributions of surface properties for purple soil and yellow soil

Soils contain diverse colloidal particles whose properties are pertinent to ecological and human health, whereas few investigations systematically analyze the surface properties of these particles. The objective of this study was to elucidate the surface properties of particles within targeted size ranges(i.e. 10, 1–10, 0.5–1, 0.2–0.5 and 0.2 μm) for a purple soil(Entisol) and a yellow soil(Ultisol) using the combined determination method. The mineralogy of corresponding particle-size fractions was determined by X-ray diffraction.We found that up to 80% of the specific surface area and 85% of the surface charge of the entire soil came from colloidal-sized particles( 1 μm), and almost half of the specific surface area and surface charge came from the smallest particles( 0.2 μm). Vermiculite,illite, montmorillonite and mica dominated in the colloidal-sized particles, of which the smallest particles had the highest proportion of vermiculite and montmorillonite. For a given size fraction, the purple soil had a larger specific surface area, stronger electrostatic field, and higher surface charge than the yellow soil due to differences in mineralogy.Likewise, the differences in surface properties among the various particle-size fractions can also be ascribed to mineralogy. Our results indicated that soil surface properties were essentially determined by the colloidal-sized particles, and the 0.2 μm nanoparticles made the largest contribution to soil properties. The composition of clay minerals within the diverse particle-size fractions could fully explain the size distributions of surface properties.     

Acid-treated Fe-doped TiO2 as a high performance photocatalyst used for degradation of phenol under visible light irradiation

The photocatalytic activity of Fe-doped TiO2 nanoparticles is significantly increased by an acid-treatment process. The photocatalyst nanoparticles were prepared using sol–gel method with 0.5 mol% ratio of Fe:Ti in acidic pH of 3. The nanoparticles were structurally characterized by means of X-ray diffraction(XRD), high-resolution transmission electron microscope(HRTEM), energy-dispersive X-ray spectroscopy(EDX), X-ray photoelectron spectroscopy(XPS) and diffuse reflectance spectroscopy(DRS). It was observed that the photocatalytic activity suffered from an iron oxide contaminating layer deposited on the surface of the nanoparticles. This contamination layer was removed using an HCl acidtreatment process. The photocatalytic activity using 500 mg/L of Fe0.5-TiO2 in a 10 mg/L of phenol solution increased significantly from 33% to 57%(about 73% increase in the performance), within 90 min of reaction time under visible light irradiation. This significant improvement was achieved by removing the iron oxide contamination layer from the surface of the nanoparticles and adjusting p H to mild acidic and basic pHs.     

Remote sensing of the urban heat island and its changes in Xiamen City of SE China

World-wide urbanization has significantly modified the landscape, which has important climatic implications across all scales due to the simultaneous removal of natural land cover and introduction of urban materials. This resulted in a phenomenon known as an urban heat island(UHI). A study on the UHI in Xiamen of China was carried out using remote sensing technology. Satellite thermal infrared images were used to determine surface radiant temperatures. Thermal remote sensing data were obtained from band 6 of two Landsat TM/ETM^ images of 1989 and 2000 to observe the UHI changes over l l-year period. The thermal infrared bands were processed through several image enhancement technologies. This generated two 3-dimension-perspective images of Xiamen‘s urban heat island in 1989 and 2000, respectively, and revealed heat characteristics and spatial distribution features of the UHI. To find out the change of the UHI between 1989 and 2000, the two thermal images were first normalized and scaled to seven grades to reduce seasonal difference and then overlaid to produce a difference image by subtracting corresponding pixels. The difference image showed an evident development of the urban heat island in the 11 years. This change was due largely to the urban expansion with a consequent alteration in the ratio of sensible heat flux to latent heat flux. To quantitatively compare UHI, an index called Urban-Heat-Island Ratio Index(URI) was created. It can reveal the intensity of the UHI within the urban area. The calculation of the index was based on the ratio of UHI area to urban area. The greater the index, the more intense the UHI was. The calculation of the index for the Xiamen City indicated that the ratio of UHI area to urban area in 2000 was less than that in 1989. High temperatures in several areas in 1989 were reduced or just disappeared, such as those in old downtown area and Gulangyu lsland. For the potential mitigation of the UHI in Xiamen, a long-term heat island reduction strategy of planting shade trees and using light-colored, highly reflective roof and paving materials should be included in the plans of the city planers, environmental managers and other decision-makers to improve the overall urban environment in the future.     

Zeolite (Na) modified by nano-Fe particles adsorbing phosphate in rainwater runoff

Zeolite (Na) modified by self-synthesized nano-Fe particles was used as infiltration media to adsorb phosphate in rainwater runoff. The adsorption capacities increased up to 75 times that of natural zeolite at a saturated equilibrium phosphate concentration of 0.42 mg/L. The correlation of capacity and material-specific surface area indicated that specific surface area was not the key factor contributing to the capacity improvement. SEM and XRD analysis showed that chemical reaction between Fe and P to form new products like cacoxenite is the main reason for the increased capacity, and that the method of adding metal ions or particles to improve the adsorption capacity for phosphate is feasible.     

Catalytic activity of porous manganese oxides for benzene oxidation improved via citric acid solution combustion synthesis

Various manganese oxides (MnO_x) prepared via citric acid solution combustion synthesis were applied for catalytic oxidation of benzene. The results showed the ratios of citric acid/manganese nitrate in synthesizing process positively affected the physicochemical properties of MnO_x, e.g., BET (Brunauer-Emmett-Teller) surface area, porous structure, reducibility and so on, which were in close relationship with their catalytic performance. Of all the catalysts, the sample prepared at a citric acid/manganese nitrate ratio of 2:1 (C2M1) displayed the best catalytic activity with T₉₀ (the temperature when 90% of benzene was catalytically oxidized) of 212℃. Further investigation showed that C2M1 was Mn₂O₃ with abundant nano-pores, the largest surface area and the proper ratio of surface Mn⁴⁺/Mn³⁺, resulting in preferable low-temperature reducibility and abundant surface active adsorbed oxygen species. The analysis results of the in-situ Fourier transform infrared spectroscopy (in-situ FTIR) revealed that the benzene was successively oxidized to phenolate, o-benzoquinone, small molecules (such as maleates, acetates, and vinyl), and finally transformed to CO₂ and H₂O.     

Purification of starch and phosphorus wastewater using core-shell magnetic seeds prepared by sulfated roasting

Core-shell magnetic seeds with certain adsorption capacity that were prepared by sulfated roasting, served as the core of a magnetic separation technology for purification of starch wastewater. XRD and SEM results indicate that magnetite's surface transformed to be porous α-Fe_2O_3 structure. Compared with magnetite particles, the specific surface area was significantly improved to be 8.361 from 2.591 m~2/g, with little decrease in specific susceptibility. Zeta potential, FT-IR and XPS experiments indicate that both phosphate and starch adsorbed on the surface of the core-shell magnetic seeds by chemical adsorption, which fits well with the Langmuir adsorption model. The porous surface structure of magnetic seeds significantly contributes to the adsorption of phosphate and starch species, which can be efficiently removed to be 1.51 mg/L(phosphate) and 9.51 mg/L(starch) using magnetic separation.     

Improving the removal of fine particles by chemical agglomeration during the limestone-gypsum wet flue gas desulfurization process

Coal-fired power plants are considered a major source of fine particle emissions in China.Aimed to improve the removal efficiency of fine particles during the limestone-gypsum wet flue gas desulfurization(WFGD) process, a novel technology using chemical agglomeration to abate the emission of fine particles is presented herein. The relationship between fine particle emission and the proportion of fine particles in the desulfurization slurry was studied.Additionally, the influence of chemical agglomeration on fine particle size distribution, both in the flue gas and slurry was experimentally investigated. When chemical agglomeration agents were added to the desulfurization slurry, the fine particle removal performance as well as the effects of the operation parameters was also explored via the simulated experimental facility.The results revealed that the fine particles in both the desulfurization slurry and flue gas were significantly enlarged after the addition of the agglomeration agents. This was more marked in the submicron particles. Thus, the proportion of fine particles( 10 μm) in the slurry decreased from 31.1% to 22.6%. An increase in the desulfurization slurry temperature and liquid-to-gas ratio aided the reduction in fine particle emission. Moreover, the addition of an agglomeration agent in the slurry did not affect the desulfurization efficiency of the desulfurization tower and even promoted the WFGD process. Thus, the proposed chemical agglomeration technique reduced the fine particle emission of the WFGD system by ～30%, while a desulfurization efficiency 90% was maintained.     

Iron-doped Mn-Ce/TiO2 catalyst for low temperature selective catalytic reduction of NO with NH3

The catalysts of iron-doped Mn-Ce/TiO 2(Fe-Mn-Ce/TiO 2) prepared by sol-gel method were investigated for low temperature selective catalytic reduction(SCR) of NO with NH 3.It was found that the NO conversion over Fe-Mn-Ce/TiO 2 was obviously improved after iron doping compared with that over Mn-Ce/TiO 2.Fe-Mn-Ce/TiO 2 with the molar ratio of Fe/Ti = 0.1 exhibited the highest activity.The results showed that 96.8% NO conversion was obtained over Fe(0.1)-Mn-Ce/TiO 2 at 180°C at a space velocity of 50,000 hr 1.Fe-Mn-Ce/TiO 2 exhibited much higher resistance to H 2 O and SO 2 than that of Mn-Ce/TiO 2.The properties of the catalysts were characterized using X-ray diffraction(XRD),N 2 adsorption,temperature programmed desorption(NH 3-TPD and NOx-TPD),and Xray photoelectron spectroscopy(XPS) techniques.BET,NH3-TPD and NOx-TPD results showed that the specific surface area and NH3 and NOx adsorption capacity of the catalysts increased with iron doping.It was known from XPS analysis that iron valence state on the surface of the catalysts were in Fe3+ state.The doping of iron enhanced the dispersion and oxidation state of Mn and Ce on the surface of the catalysts.The oxygen concentrations on the surface of the catalysts were found to increase after iron doping.Fe-Mn-Ce/TiO2 represented a promising catalyst for low temperature SCR of NO with NH3 in the presence of H2 O and SO2.     

Structure and flow calculation of cake layer on microfiltration membranes

Submerged membrane bioreactors(SMBR) are widely used in wastewater treatment. The permeability of a membrane declines rapidly because of the formation of a cake layer on the membrane surface. In this paper, a multiple staining protocol was conducted to probe the four major foulants in the cake layer formed on a filtration membrane. Fluorescent images of the foulants were obtained using a confocal laser scanning microscope(CLSM). The three dimensional structure of the cake layer was reconstructed, and the internal flow was calculated using computational fluid dynamics(CFD). Simulation results agreed well with the experimental data on the permeability of the cake layer during filtration and showed better accuracy than the calculation by Kozeny–Carman method. β-D-Glucopyranose polysaccharides and proteins are the two main foulants with relatively large volume fractions, while α-D-glucopyranose polysaccharides and nucleic acids have relatively large specific surface areas. The fast growth of β-D-glucopyranose polysaccharides in the volume fraction is mainly responsible for the increase in cake volume fraction and the decrease in permeability. The specific area, or the aggregation/dispersion of foulants, is less important to its permeability compared to its volume fraction.     

Effect of biomass addition on the surface and adsorption characterization of carbon-based adsorbents from sewage sludge

Sewage sludge with the additive corn cob was used as prescusor to prepare sludge-based carbon adsorbents by pyrolysis method. And then, the carbonizated products were activated with potassium hydroxide. The mixing ratio of the corn cob to sewage sludge was investigated. The surface area and pore size distribution, elemental composition, surface chemistry structure and the surface physical morphology were determined and compared. The results demonstrated that the addition of corn cob into the sewage sludge sample could effectively improve the surface area (from 287 to 591 m 2 /g) and the microporosity (from 5% to 48%) of the carbon based adsorbent, thus enhancing the adsorption behavior. The sulfur dioxide adsorption capacity was measured according to breakthrough test. It was found that the sulfur dioxide adsorption capacity of the adsorbents was obviously enhanced after the addition of the corn cob. It is presumed that not only highly porous adsorbents, but also a high metallic content of these materials are required to achieve good performances.     

Synthesis of novel adsorbent by intercalation of biopolymer in LDH for the removal of arsenic from synthetic and natural water

This study focuses on the synthesis of nanocomposites named CCA and CZA that were prepared by the incorporation of cellulose(CL) in the Ca/Al and Zn/Al layered double hydroxide(LDH),respectively.These materials were then used for the uptake of As(Ⅲ)and As(V) from aqueous medium.Characterization of both nanocomposites(CCA and CZA) was done using FTIR and Raman analysis to identify the functional groups, N_2 adsorption-desorption isotherms to determine the specific surface area and pore geometry and XPS analysis to obtain the surface atomic composition.Some other characters were investigated using simultaneous TGA and DTA and elemental chemical analysis(CHNS/O).The crystallinity of the prepared nanocomposites was displayed by XRD patterns.Furthermore,the sheet-like structure of the LDHs and the irregularity of surface morphology with porous structure were observed by TEM and SEM microphotographs.Optimization of maximum adsorption capacity was adjusted using different parameters including pH,contact time and adsorbent dosage.The pseudo-second-order model was in good fitting with kinetics results.The adsorption isotherm results showed that CZA exhibits better adsorption capacity for As(Ⅲ) than CCA and the Langmuir isotherm model described the data well for both nanocomposites.Thermodynamic studies illustrated the endothermic nature of CCA and exothermic nature on CZA,as well as the fact that the adsorption process is spontaneous.A real water sample collected from well located in Gabes(Tunisia),has also been treated.The obtained experimental results were confirmed that these sorbents are efficient for the treatment of hazardous toxic species such as.     

Effects of C/N ratio on nitrate removal and floc morphology of autohydrogenotrophic bacteria in a nitrate-containing wastewater treatment process

The effects of C/N ratio of a nitrate-containing wastewater on nitrate removal performed by autohydrogenotrophic bacteria as well as on the morphological parameters of floc such as floc morphology, floc number distribution, mean particle size(MPS), aspect ratio and transparency were examined in this study. The results showed that the nitrate reduction rate increased with increasing C/N ratio from 0.5 to 10 and that the nitrogen removal of up to 95% was found at the C/N ratios of higher than 5(between 0.5–10). Besides, high C/N ratio values reflected a corresponding high nitrite accumulation after 12-hr operation, and a fast decreasing rate of nitrite in the rest of operational time. The final p H values increased with the C/N ratio increasing from 0.5 to 2.5, but decreased with the C/N ratio increasing from2.5 to 10. There were no significant changes in floc morphology with the MPSs ranging from35 to 40 μm. Small and medium-sized flocs were dominant in the sludge suspension, and the number of flocs increased with the increasing C/N ratios. Furthermore, the highest apparent frequency of 10% was observed at aspect ratios of 0.5 and 0.6, while the transparency of flocs changed from 0.1 to 0.7.     

Evidence for coupled iron and nitrate reduction in the surface waters of Jiaozhou Bay

Iron and nitrate (NO₃^?) are dominant physiologically required nutrients for phytoplankton growth, and iron may also play a key role in the marine nitrogen cycle. In this study, we investigated the temporal and spatial distributions of dissolved iron (DFe) and Fe(II) in the surface waters of Jiaozhou Bay (JZB) from April 2 to July 26, 2017. High concentrations of DFe and Fe(II) predominantly occurred in nearshore and estuarine stations and concentrations were generally higher in April and May. The highest DFe concentration was observed along the coast of Hongdao (51.55 nmol/L) in May, while the lowest concentration was observed in the western coastal region (2.88 nmol/L) in April. The highest and lowest Fe(II) concentrations were observed in the Licun estuary (22.42 nmol/L) and outer bay (0.50 nmol/L) in May, respectively. We calculated the proportions of nitrate, nitrite, and ammonium in dissolved inorganic nitrogen (DIN) as well as the ratio of Fe(II) to DFe in all four months. The mean Fe(II)/DFe ratio was 0.48 in April, 0.43 in May, 0.69 in June, and 0.32 in July. The mean ratio of NO₃^? to DIN was 0.78 in April, 0.54 in May, 0.20 in June, and 0.62 in July. NO₃^?/DIN continuously decreased in the first three months, while Fe(II)/DFe remained high, which suggests that the reduction of iron and nitrate occurred simultaneously in the surface waters of JZB.     

Effect of SO2 on the performance of Ag-Pd/Al2O3 for the selective catalytic reduction of NOx with C2H5OH

The influence of SO2 on the performance of Ag-Pd/Al2O3 for the selective catalytic reduction （SCR） of NOx with C2H5OH was investigated experimentally. The activity test results suggest that Ag-Pd/Al2O3 shows a small activity loss in the presence of SO2 when using C2H5OH as a reductant. In situ DRIFTS spectra show that the activity loss originates from the formation of surface sulphate species on the Ag-Pd/Al2O3. The surface sulphate species formation inhibits the formation of nitrate, whereas hardly changes the partial oxidation of C2H5OH. Compared with the NOx reduction by C3H6, an obvious suppression of the surface sulphate species formation was observed by DRIFTS experiment when using C2H5OH as a reductant. This phenomenon reveals the better catalytic performance and strong SO2 tolerance of Ag-Pd/Al2O3-C2H50H system.