Treating n-butane by activated carbon and metal oxides

In order to reduce environmental pollution and regulatory issues, the adsorption of n-butane from vehicle exhaust is one of the necessary requirements. When active carbon was mixed with different proportions of metal oxides, the adsorption capacity of n-butane was markedly improved. Infrared spectroscopy data provided information on functional groups derived from activated carbon composite metal oxide indicating that one of the best adsorption capacities for n-butane was obtained by mixing 3 g TiO₂, 2.7 g CuO, and 2.1 g NaBO₃·4H₂O with 30 g activated carbon. However, more effective results were obtained by mixing 6 g TiO₂, 2.1 g CuO, and 0.9 g NaBO₃·4H₂O with 30 g activated carbon. Data suggest that these chemical complexes may be effective in lowering n-butane pollution.     

Metal-free oxidation of aldehydes to acids using the 4Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>·2H<Subscript>2</Subscript>O<Subscript>2</Subscript>·NaCl adduct

Oxidation of aldehydes to carboxylic acids is a major reaction. Conventionally, this reaction is carried out with oxidants and metal catalysts, thus producing unwanted metal waste. Recently, aqueous media have been used as an alternative for toxic organic solvents. Here, we tested the clathrate-structured, neutral hydrogen peroxide adduct 4Na₂SO₄·2H₂O₂·NaCl for the oxidation of aldehydes to acids in aqueous solution. We found that various aromatic, heteroaromatic and aliphatic aldehydes were selectively oxidized to corresponding acids in 70–98% yields. This simple acid–base treatment allows to separate easily the acid product in high purity without any organic solvent. Moreover, the adduct is produced using 25% H₂O₂, with inexpensive sodium sulphate, Na₂SO₄, and sodium chloride, NaCl. The adduct is a non-toxic white crystalline solid, readily soluble in water, and easy to handle.     

Cement industry: sustainability, challenges and perspectives

Cement-based materials, such as concrete and mortars, are used in extremely large amounts. For instance, in 2009 concrete production was superior to 10 billion tons. Cement plays an important role in terms of economic and social relevance since it is fundamental to build and improve infrastructure. On the other hand, this industry is also a heavy polluter. Cement production releases 5–6% of all carbon dioxide generated by human activities, accounting for about 4% of global warming. It can release huge amounts of persistent organic pollutants, such as dioxins and heavy metals and particles. Energy consumption is also considerable. Cement production use approximately 0.6% of all energy produced in the United States. On the other hand, the chemistry underlying cement production and its applications can be very helpful to overcome these environmental issues. In terms of manufacture, there are many alternative materials that can be used to minimize carbon dioxide production and reduce energy consumption, such as calcium sulfoaluminates and β-Ca₂SiO₄—rich cements. Using residues from other industrial sectors can also improve the sustainability of cement industry. Under adequate conditions, waste materials such as tyres, oils, municipal solid waste and solvents can be used as supplementary fuel in cement plants. Concrete can be used for encapsulation of waste materials such as tyres, plastics and glasses. In this review, we discuss some aspects of the cement industry associated with environmental science. Other issues such as economic aspects, the chemistry of cement manufacture and its properties are also presented. Special attention is given to the role that cement chemistry can play in terms of sustainability. The most relevant aspects are outlined, such as the use of alternative materials, new possibilities and also the recycling of materials. It is also argued that an important aspect is the role of research and development necessary to improve cement sustainability.     

Preparation and characterization of poly (vinylidene fluoride)/TiO2 hybrid membranes

Poly(vinylidene fluoride) (PVDF)/titanium dioxide (TiO₂) hybrid membranes were prepared using nano-TiO₂ as the modifier, and characterized by Transmission Electron Microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), atomic force microscope (AFM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The characterization results demonstrated that nano-sized TiO₂ particles dispersed homogeneously within the PVDF matrix, contributing to more hydroxyls and smoother surfaces. Moreover, permeate flux, retention factor, porosity, contact angle and anti-fouling tests were carried out to evaluate the effect of TiO₂ concentration on the performance of PVDF membranes. Among all the prepared membranes, PVDF/TiO₂ membrane containing 10 vol.% TiO₂ exhibited the best hydrophilicity with an average pure water flux up to 237 L·m^?2·h^?1, higher than that of unmodified PVDF membranes (155 L·m^?2·h^?1). Besides, the bovine serum albumin rejection of the hybrid membrane was improved evidently from 52.3% to 70.6%, and the contact angle was significantly lowered from 83° to 60°, while the average pore size and its distribution became smaller and narrower.     

Preparation of TiO2/MCM-41 by plasma enhanced chemical vapor deposition method and its photocatalytic activity

Titanium dioxide is coated on the surface of MCM-41 wafer through the plasma enhanced chemical vapor deposition (PECVD) method using titanium isopropoxide (TTIP) as a precursor. Annealing temperature is a key factor affecting crystal phase of titanium dioxide. It will transform an amorphous structure to a polycrystalline structure by increasing temperature. The optimum anatase phase of TiO₂ which can acquire the best methanol conversion under UV-light irradiation is obtained under an annealing temperature of 700°C for 2 h, substrate temperature of 500°C, 70 mL·min^?1 of oxygen flow rate, and 100W of plasma power. In addition, the films are composed of an anatase-rutile mixed phase, and the ratio of anatase to rutile varies with substrate temperature and oxygen flow rate. The particle sizes of titanium dioxide are between 30.3 nm and 59.9 nm by the calculation of Scherrer equation. Under the reaction conditions of 116.8 mg·L^-1 methanol, 2.9 mg·L^?1 moisture, and 75°C of reaction temperature, the best conversion of methanol with UV-light is 48.2% by using the anatase-rutile (91.3/8.7) mixed phase TiO₂ in a batch reactor for 60 min. While under fluorescent light irradiation, the best photoactivity appears by using the anatase-rutile (55.4/44.6) mixed phase TiO₂ with a conversion of 40.0%.     

The effects of different methods of catalyst preparation on the hydro-electric plasma TiO2-catalyzed degradation of 2,4-dinitrophenol

Hydro-electric plasma technology in the presence of TiO₂ catalyst used to treat 2,4-dinitrophenol (2,4-DNP) simulated wastewater is reported. The catalytic activity of TiO₂ prepared by ammonia precipitation was greater than the activity of the TiO₂ prepared by NaOH precipitation. The presence of chloride ions during the preparation process of TiO₂ had a large negative effect on the catalytic activity. The catalytic activity of TiO₂ calcined at 673 K was significantly higher than the activity of the TiO₂ that was calcined at higher and lower temperatures. After being calcined at 673 K, TiO₂ was mainly in the anatase phase and degraded 81% of the 2,4-DNP after 10 min of treatment.     

Titanium dioxide nanoparticles: synthesis,characterisations and aquatic ecotoxicity effects

Little information is available on the potential ecotoxicity of nanomaterials in the marine environment. In particular, the aquatic ecotoxicity impact of titanium dioxide (TiO₂) has been rarely reported. To carefully address this issue, we report on the synthesis of TiO₂ NPs using solvothermal process. The structure and morphology of the prepared TiO₂ nanoparticles were characterised using different techniques. To study the potential ecotoxicity effect of TiO₂, antioxidant system of mediterranean bivalves (Mytilus galloprovincialis) was used, measuring three oxidative biomarkers (ROS production, SOD activity and GSH/GSSG level). No considerable effect was found in the digestive glands of any of the groups treated with TiO₂ with concentration gradients ranging from 1 to 100?mg/L. Thus, the level of the superoxide anion, the activity of an antioxidant enzyme superoxide dismutase (SOD) and the GSH/GSSG ratio showed no significantly differences in digestive glands of all treated groups compared to the control. However, slight modifications were observed in the gills at high concentrations. These results demonstrated that TiO₂ appears to exert little toxicity on marine mussels after a short-term exposure at high concentration. However, before considering the use of this nanomaterial in various applications, further complementary studies are required in order to ensure the environmental safety of these NPs.     

Heterogeneous Fenton oxidation of dissolved organics in salt-laden wastewater from leather industry without sludge production

This is the first report on the heterogeneous oxidation of dissolved organics in wastewater with little consumption of Fenton’s reagent and without sludge production. The salt-laden wastewater discharged from leather industry has poor biodegradability due to the presence of high total dissolved solids. This wastewater is evaporated in solar evaporation pans. The evaporated residue faces disposal problem due to high concentration of organic and inorganic salts. The present study demonstrates the preparation, characterization and application of mesoporous activated carbon matrix along with Fenton’s reagent for the removal of dissolved organics in wastewater. Free electron-rich mesoporous activated carbon matrices (MAC₇₀₀, MAC₈₀₀ and MAC₉₀₀) were prepared and characterized for surface area, C, H, N, ash content, free electron density and energy gap value. Results show that heterogeneous catalytic oxidation of dissolved organics in the wastewater decreased biochemical oxygen demand, chemical oxygen demand, total organic carbon and dissolved protein, respectively, by 74, 69, 61 and 80% at optimum pH (3.5), H₂O₂ (7.5 mmol/l), FeSO₄.7H₂O (0.3 mmol/l) and MAC₈₀₀ (10 g/l).     

Coupled electrocoagulation–electro-Fenton for efficient domestic wastewater treatment

This article reports the first use of coupled electrocoagulation and electro-Fenton (EF-EC) to clean domestic wastewater. Domestic wastewater contains high amounts of organic, inorganic and microbial pollutants that cannot be usually treated in a single step. Here, to produce an effluent suitable for discharge in a single process step, a hybrid process combining electrocoagulation and electro-Fenton was simultaneously used to decrease chemical oxygen demand (COD), turbidity and total suspended solids (TSS) from domestic wastewater. The electrocoagulation–electro-Fenton process was firstly tested for the production of H₂O₂ using Ti–IrO₂ and vitreous carbon- or graphite electrodes arranged at the anode and the cathode, respectively. The concentration of H₂O₂ recorded at 1.5 A of current intensity during 60 min of electrolysis using vitreous carbon- and graphite electrodes at the cathode was 4.18 and 1.62 mg L^?1, respectively. By comparison, when the iron electrode was used at the anode, 2.05 and 1.06 mg L^?1 of H₂O₂ were recorded using vitreous carbon and graphite, respectively. The H₂O₂ concentration decrease was attributed to hydroxyl radical formation generated by the Fenton reaction. Electro-Fenton using iron electrode at the anode and vitreous carbon at the cathode with a current density imposed of 0.34 A dm^?2 ensures the removal efficiency of 50.1 % COD_T, 70.8 % TSS and 90.4 % turbidity. The electrocoagulation–electro-Fenton technique is therefore a promising secondary treatment to simultaneously remove organic, inorganic and microbial pollutants from domestic, municipal and industrial wastewaters.     

Investigation of the effects of humic acid and H<Subscript>2</Subscript>O<Subscript>2</Subscript> on the photocatalytic degradation of atrazine assisted by microwave

A solution of atrazine in a TiO₂ suspension, an endocrine disruptor in natural water, was tentatively treated by microwave-assisted photocatalytic technique. The effects of mannitol, oxygen, humic acid, and hydrogen dioxide on the photodegradation rate were explored. The results could be deduced as follows: the photocatalytic degradation of atrazine fits the pseudo-first-order kinetic well with k = 0.0328 s^?1, and ·OH was identified as the dominant reactant. Photodegradation of atrazine was hindered in the presence of humic acid, and the retardation effect increased as the concentration of humic acid increased. H₂O₂ displayed a significant negative influence on atrazine photocatalysis efficiency. Based on intermediates identified with gas chromatography-mass spectrometry (GC-MS) and Liquid chromatography-mass spectrometry (LC-MS/MS) techniques, the main degradation routes of atrazine are proposed.     

Removal of carbamazepine from urban wastewater by sulfate radical oxidation

The occurrence of bioactive trace pollutants such as pharmaceuticals in natural waters is an emerging issue. Numerous pharmaceuticals are not completely removed in conventional wastewater treatment plants. Advanced oxidation processes may represent an interesting alternative to completely mineralize organic trace pollutants. In this article, we show that sulfate radicals generated from peroxymonosulfate/Co^II are more efficient than hydroxyl radicals generated from the Fenton’s reagent (H₂O₂/Fe^II) for the degradation of the pharmaceutical compound, carbamazepine. The second-order rate constant for the reaction of SO₄ ^·− with carbamazepine is 1.92·10⁹ M⁻¹ s⁻¹. In laboratory grade water and in real urban wastewater, SO₄ ^·− yielded a faster degradation of carbamazepine compared to HO^· . Under strongly oxidizing conditions, a nearly complete mineralization of carbamazepine was achieved, while under mildly oxidizing conditions, several intermediates were identified by LC–MS. These results show for the first time in real urban wastewater that sulfate radicals are more selective than hydroxyl radicals for the oxidation of an organic pollutant and may represent an interesting alternative in advanced oxidation processes.     

Recent advances in the photocatalytic reduction of carbon dioxide

Fossil fuels are currently the major energy source and are rapidly consumed to supply the increasing energy demands of mankind. CO₂, a product of fossil fuel combustion, leads to climate change and will have a serious impact on our environment. There is an increasing need to mitigate CO₂ emissions using carbon–neutral energy sources. Therefore, research activities are devoted to CO₂ capture, storage and utilization. For instance, photocatalytic reduction of CO₂ into hydrocarbon fuels is a promising avenue to recycle carbon dioxide. Here we review the present status of the emission and utilization of CO₂. Then we review the photocatalytic conversion of CO₂ by TiO₂, modified TiO₂ and non-titanium metal oxides. Finally, the challenges and prospects for further development of CO₂ photocatalytic reduction are presented.     

Removal of methylene blue by coupling black carbon adsorption with TiO2 photodegradation

In this study, the removal of methylene blue (MB) by the coupling of black carbon (BC) and TiO₂ was investigated. The effects of different parameters such as catalyst dose, sorbent, initial concentrations of dye, pH of the solutions, recycles on discoloration, and chemical oxidation demand (COD) reduction of MB were monitored to optimize the reaction conditions. The discoloration and COD conversation rate of MB obtained by the coupling process were 100% after 90?min irradiation. The synergistic effect of MB-adsorption on BC followed by degradation through TiO₂ photocatalysis was proved by FT–IR spectrophotometer. The BC as by-product of natural materials is a promising adsorbent for waste water treatment.     

Decomposition of perfluorooctanoic acid by microwaveactivated persulfate: Effects of temperature, pH, and chloride ions

Microwave-hydrothermal treatment of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in water with persulfate (S₂O ₈ ^2? ) has been found effective. However, applications of this process to effectively remediate PFOA pollution require a better understanding on free-radical scavenging reactions that also take place. The objectives of this study were to investigate the effects of pH (pH = 2.5, 6.6, 8.8, and 10.5), chloride concentrations (0.01?C0.15 mol·L^?1), and temperature (60°C, 90°C, and 130°C) on persulfate oxidation of PFOA under microwave irradiation. Maximum PFOA degradation occurred at pH 2.5, while little or no degradation at pH 10.5. Lowering system pH resulted in an increase in PFOA degradation rate. Both high pH and chloride concentrations would result in more scavenging of sulfate free radicals and slow down PFOA degradation. When chloride concentrations were less than 0.04 mol·L^?1 at 90°C and 0.06 mol·L^?1 at 60°C, presence of chloride ions had insignificant impacts on PFOA degradation. However, beyond these concentration levels, PFOA degradation rates reduced significantly with an increase in chloride concentrations, especially under the higher temperature.     

Photocatalytic degradation of phenol with mesoporous TiO2?xBx

We report a facile approach for preparing mesoporous boron-doped TiO₂ materials by combining the sol?Cgel process with the dehydration of glucose. Specifically a high surface carbon material was formed by dehydration of glucose, then used as template. This material and the TiO₂ dry gel were calcinated to produce porous TiO₂. The as-synthesized boron-doped TiO₂ was in pure anatase crystallite phase with high surface area. X-ray photoelectron spectroscopy (XPS) results showed that boron was incorporated into the anatase TiO₂ lattice to form TiO_2?xB_x. The absorption spectra of TiO_2?xB_x extended into the visible region to 460?nm. The TiO_2?xB_x exhibited much higher photocatalytic activity on phenol degradation than pure TiO₂. It showed that the phenol degradation by-products of TiO_2?xB_x were different from that of pure TiO₂. Mechanism of the photocatalytic degradation of phenol at TiO_2?xB_x was also proposed.     

Photodegradation of an azo dye by silver-doped nano-particulate titanium dioxide

The synthesis of silver doped nano-particulate titanium dioxide (Ag/TiO₂) using a microemulsion method and an investigation of its photocatalytic activity for the degradation of Acid Red 27 in distilled water under UV-irradiation is reported. The prepared Ag/TiO₂ is characterized using transmission electron microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy. The size of the Ag nanoparticles is around 5–15?nm, with almost uniform distribution on the TiO₂ particles. The efficiency of the photocatalytic process is evaluated to establish the optimum conditions, found to be at 2?wt% of Ag loading on TiO₂, catalyst dosage of 400?mg?L^?1, and calcination temperature of 300°C. Complete decolorization of the dye solution on Ag/TiO₂ was observed in 20?min of UV irradiation in the optimum conditions.     

Nano-titanium dioxide (TiO2)-induced changes affecting Cu2+-mediated alterations in bacterium Bacillus subtilis and α-amylase

Titanium dioxide (TiO₂) nanoparticles possess the potential to coexist with Copper (Cu²⁺) in soil. The individual and combined toxicity of these two chemicals was evaluated using the bacterium Bacillus subtilis, a known soil model bacterium. Cu²⁺ (6.25–50?µg?mL^?1) alone produced toxicity to bacteria as evidenced by the decreased cell viability and deceased α-amylase production. The addition of TiO₂ (50?mg?mL^?1) enhanced the Cu²⁺-induced decrease in cell viability but elevated amylase activity. TiO₂ did not markedly affect the growth rate and lag period. A primary cause of TiO₂ increasing Cu²⁺ toxicity is presumed to be associated with hydroxyl radical formation, while increased amylase activity is considered to arise from Cu²⁺ facilitating TiO₂ degradation ability.     

Thermochemical conversion of municipal solid waste into energy and hydrogen: a review

The rising global population is inducing a fast increase in the amount of municipal waste and, in turn, issues of rising cost and environmental pollution. Therefore, alternative treatments such as waste-to-energy should be developed in the context of the circular economy. Here, we review the conversion of municipal solid waste into energy using thermochemical methods such as gasification, combustion, pyrolysis and torrefaction. Energy yield depends on operating conditions and feedstock composition. For instance, torrefaction of municipal waste at 200 °C generates a heating value of 33.01 MJ/kg, while the co-pyrolysis of cereals and peanut waste yields a heating value of 31.44 MJ/kg at 540 °C. Gasification at 800 °C shows higher carbon conversion for plastics, of 94.48%, than for waste wood and grass pellets, of 70–75%. Integrating two or more thermochemical treatments is actually gaining high momentum due to higher energy yield. We also review reforming catalysts to enhance dihydrogen production, such as nickel on support materials such as CaTiO₃, SrTiO₃, BaTiO₃, Al₂O₃, TiO₃, MgO, ZrO₂. Techno-economic analysis, sensitivity analysis and life cycle assessment are discussed.

     

Degradation of azo dyes in water by Electro-Fenton process

The degradation of the azo dyes azobenzene, p-methyl red and methyl orange in aqueous solution at room temperature has been studied by an advanced electrochemical oxidation process (AEOPs) under potential-controlled electrolysis conditions, using a Pt anode and a carbon felt cathode. The electrochemical production of Fenton's reagent (H₂O₂, Fe²⁺) allows a controlled in situ generation of hydroxyl radicals (^·OH) by simultaneous reduction of dioxygen and ferrous ions on the carbon felt electrode. In turn, hydroxyl radicals react with azo dyes, thus leading to their mineralization into CO₂ and H₂O. The chemical composition of the azo dyes and their degradation products during electrolysis were monitored by high performance liquid chromatography (HPLC). The following degradation products were identified: hydroquinone, 1,4-benzoquinone, pyrocatechol, 4-nitrocatechol, 1,3,5-trihydroxynitrobenzene and p-nitrophenol. Degradation of the initial azo dyes was assessed by the measurement of the chemical oxygen demand (COD). Kinetic analysis of these data showed a pseudo-first order degradation reaction for all azo dyes. A pathway of degradation of azo dyes is proposed. Specifically, the degradation of dyes and intermediates proceeds by oxidation of azo bonds and aromatic ring by hydroxyl radicals. The results display the efficiency of the Electro-Fenton process to degrade organic matter. Electronic Publication