Preparation of Co–MgO mixed oxide nanocatalysts for low temperature CO oxidation: Optimization of preparation conditions

In this study, a series of Co–MgO mixed oxides (30 wt.% Co) were prepared by co-precipitation method and employed as catalyst in low temperature CO oxidation reaction. The preparation conditions were optimized by the Taguchi method of experimental design to synthesize a sample with high catalytic performance toward CO oxidation reaction. The effects of four variables, pH of solution, aging temperature, aging time and molarity of precursor solution at three levels were investigated. The optimized sample was characterized by X-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed desorption of oxygen (O₂-TPD), N₂ adsorption/desorption, thermal gravimetric and differential thermal analysis (TGA/DTA), and transmission electron microscopy (TEM) techniques. The results revealed that the optimized sample showed a mesoporous structure with a narrow pore size distribution centered in the range of 7–17 nm and particle size about 5.5 nm. It was found that the molarity of solution and aging time had the most influence on the CO conversion, respectively. The catalytic results showed that the highest CO conversion obtained from samples synthesized by Taguchi orthogonal array was about 90% at 200 °C, while the CO conversion for optimized sample was 95%. In addition, the effect of operational conditions was studied over optimized sample.     

Study of Fe–Co mixed metal oxide nanoparticles in the catalytic low-temperature CO oxidation

Iron–cobalt mixed metal oxide nanoparticles (Co/Fe molar ratio: 1/5) have been prepared by a simple co-precipitation method and employed as catalyst in low-temperature CO oxidation. The prepared catalysts were characterized by thermal gravimetric and differential thermal gravimetric analyses (TGA/DTG), X-ray diffraction (XRD), temperature programmed reduction (TPR), N₂ adsorption (BET) and transmission electron microscopy (TEM) techniques. The results revealed that inexpensive iron–cobalt mixed metal oxide nanoparticles have a high potential as catalyst in low temperature CO oxidation. The results showed that increasing in calcination temperature increased the crystallite and particle size and decreased the specific surface area, which caused a decrease in catalytic activity of prepared catalysts. In addition, the pretreatment conditions affect the catalytic activity and catalyst pretreated under oxidative atmosphere showed the higher activity than those pretreated under reductive and inert atmospheres.     

Effect of ultrasound irradiation and Ni-loading on properties and performance of CeO2-doped Ni/clinoptilolite nanocatalyst used in polluted air treatment

In this research nanocatalysts containing 5, 10 and 15 wt.% of Ni, dispersed by sonication over CeO₂–clinoptilolite composite support were compared toward total oxidation of toluene. Their catalytic performance at different temperatures between 150 and 350 °C was studied based on the oxidative destruction of toluene. The results indicated that the activity of Ni/CeO₂–clinoptilolite nanocatalyst for toluene oxidation increased from 33 to 44% at 250 °C by employing sonochemical method in synthesis of catalyst. Meanwhile, the catalytic activity was also improved when Ni content was increased from 5 to 10 and 15 wt.%. With the aid of several characterization techniques like XRD, FESEM, PSD, EDX, BET and FTIR, the correlation between nanocatalyst structure and its activity was addressed. It is indicated that sonochemical method can lift the catalytic activity due to the better dispersion of catalyst active components and also higher surface area. Among sonicated samples, 15 wt.% Ni nanocatalyst showed the highest toluene oxidation due to the better dispersion of catalyst active components and hence to more effective catalytic sites.     

Low temperature CO oxidation over Pd–Ce catalysts supported on ZSM-5 zeolites

A series of Pd–Ce supported ZSM-5 zeolite catalysts for CO oxidation at low temperature were prepared by co-impregnation method. The effect of Pd–Ce synergistic function, Ce loadings, and properties of ZSM-5 zeolite on low temperature CO catalytic oxidation was investigated in detailed. The results showed that the Pd and Ce loading on ZSM-5 zeolite support at the same time enhanced catalytic activity compared with only Pd or Ce loading on ZSM-5 zeolite support. The properties of ZSM-5 zeolite had a strong influence for CO oxidation. Through the research, the ZSM-5 zeolite with high silicon aluminum ratio and small size also was helpful for CO oxidation. Among these catalysts, the catalyst with 19 wt% Ce loading displayed the highest catalytic activity. Chemical and physical properties of catalysts were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). XRD and TEM showed that Pd species were highly dispersed on the surface of ZSM-5 zeolite, which was strongly dependent on the amounts of Ce loading and the interaction among Pd species, Ce promoter and ZSM-5 support. The addition of CeO₂ improved the dispersion of Pd species over ZSM-5, and synergistic function of Pd and CeO₂ enhanced the catalytic activity. XPS characterization indicated that as the addition of Ce increased, Pd species was easy to enrich on the surface of the catalyst.     

Thermal hazard assessment for synthesis of 3-methylpyridine-N-oxide

The exothermic oxidation of 3-methylpyridine with hydrogen peroxide was analyzed by Reaction Calorimeter (RC1e) in semi-batch operation. Heat releasing rate and heat conversion were studied at different operating conditions, such as reaction temperature, feeding rate, the amount of catalyst and so on. The thermal hazard assessment of the oxidation was derived from the calorimetric data, such as adiabatic temperature rise (ΔT_ad) and the maximum temperature of synthesis reaction (MTSR) in out of control conditions. Along with thermal decomposition of the product, the possibility of secondary decomposition under runaway conditions was analyzed by time to maximum rate (TMR_ad). Also, risk matrix was used to assess the risk of the reaction. Results indicated that with the increase of the reaction temperature, the reaction heat release rate increased, while reaction time and exotherm decreased. With the increase of feeding time, heat releasing rate decreased, but reaction time and exotherm increased. With the amount of the catalyst increased, heat releasing rate increased, reaction time decreased and exothermic heat increased. The risk matrix showed that when the reaction temperature was 70 °C, feeding time was 1 h, and the amount of catalyst was 10 g and 15 g, respectively, the reaction risk was high and must be reduced.     

Detoxification of hexavalent chromium in wastewater containing organic substances using simonkolleite-TiO2 photocatalyst

Innovative simple method for the preparation of simonkolleite-TiO₂ photocatalyst with different Zn contents was achieved. The prepared photocatalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), FT-IR, Raman and diffuse reflectance spectroscopy techniques. The photocatalytic activities of the materials were evaluated for the simultaneous detoxification of hexavalent chromium (Cr(VI)) and oxidation of organic compounds commonly present in wastewater under simulated solar light. The best photoreduction efficiency of Cr(VI) has been achieved at 1000 ppm simonkolleite-TiO₂ photocatalyst of 5% Zn/TiO₂ weight ratio, and pH value of 2.5 to enhance the adsorption onto catalyst surface. Photoreduction was significantly improved by using formic acid as holes scavenger owing to its chemical adsorption on the catalyst surface. Finally, 100% photoreduction of Cr(VI) could be achieved using formic/simonkolleite-TiO₂ systems under sunlight.     

Absorption kinetics of NO from simulated flue gas using Fe(II)EDTA solutions

The absorption of NO encountering flue gases in aqueous solutions of Fe(II)EDTA was determined using a semi-batch stirred tank with a plane gas–liquid interface at 50 °C. The concentrations of NO, SO₂ and O₂ in the feeding stream were 300–800 ppm, 500–2200 ppm and 0–20%, respectively. The pH value of the Fe(II)EDTA solutions varied from 3 to 11. The concentrations of Fe(II)EDTA were maintained between 0.01 and 0.05 M. Experiments were performed to evaluate the effect of operating parameters on the NO absorption rate, the reaction kinetics of the reactants in gas and liquid phases, and the effect of competition between various reactants on the mass transfer rate in the NO removal system. Results indicate that the average reaction rate constant is 3.70 × 10⁷ M⁻¹ s⁻¹. Adding NaOH does not increase the absorption capability of Fe(II)EDTA. The presence of O₂ decreases the NO absorption rate with Fe(II)EDTA. The absorption rate of NO with Fe(II)EDTA decreases at low concentrations of SO₂, but increases at high concentrations.     

Biodiesel production from waste oil feedstocks by solid acid catalysis

Biodiesel is a non-toxic and biodegradable substitute for petroleum-based diesel. However, it is impractical to use refined edible oils to produce biodiesel due to its high cost and priority for food products, especially in China, while waste oils with high free fatty acids (FFAs) can be considered as the raw materials. In the present work, a solid acid catalyst comprising SO₄²⁻/TiO₂–SiO₂ was prepared, characterized and studied for its activity for the production of biodiesel from several low cost feedstocks with high FFAs. The solid acid catalyst can be recycled, easily removed and can simultaneously catalyze esterification and transesterification. The influence of reaction parameters was studied, and the optimized reaction parameters are reaction temperature 200 °C, molar ratio of methanol to oil 9:1 and catalyst concentration 3 wt.%. The catalyst showed good stability. A continuous process for biodiesel production from cheap raw feedstocks was proposed, and a 10,000-tonnes/year biodiesel production demonstration plant has been built.     

Modification of Fe–Mn mixed oxide COS removal sorbent by rare-earth oxides addition

In order to develop highly active sorbent for COS removal, Fe–Mn mixed oxides doped with CeO₂, La₂O₃ or Sm₂O₃ were studied. The effects of these promoters on the structural properties of Fe–Mn oxides were investigated by XRD, BET, TPR and TEM techniques. XRD results revealed that the degree of crystallinity of Fe–Mn oxide phase decreased due to the addition of rare-earth oxides. Doping with CeO₂, La₂O₃ or Sm₂O₃ led to an increase in BET surface area of the sample. TPR studies showed that the reactivity of the reduction of doped samples increased in the temperature range of 300–450 °C. In addition, the desulfurization test was performed at 325 °C with a gas hourly space velocity of 1000 h⁻¹. It was found that the addition of 3% La₂O₃ greatly improved the absorption sulfur capacity of the sorbent, while the sorbent doped 3% CeO₂ achieved a sufficiently high purifying degree before breakthrough.     

Two-stage biodegradation coupled with ultrafiltration for treatment of municipal landfill leachate

The municipal landfill leachate was treated in a hydrolysis–acidification reactor (HAR)/aerobic bio-contact oxidation reactor (ABOR) following a pretreatment with ultrafiltration (UF) membrane. Experiments were conducted continuously for 44 days at a constant flow rate of 20 l d⁻¹ and organic loading rates (OLRs) from 0.75 to 1.5 kgCOD m⁻³ per day. The results showed that COD of the leachate steadily decreased from 20,015 mg l⁻¹ to less than 3000 mg l⁻¹, and NH₄-N decreased from 368.6 mg l⁻¹ to 259.3 mg l⁻¹ in the UF process. The COD and NH₄-N removal efficiency of HAR was 56.7% and 27.7%, and that of ABOR was 94.6% and 86.7%, respectively. The total COD and NH₄-N removal efficiency reached 99.6% and 93.2%, respectively. UF and HAR played a critical role in raising the biodegradability of the landfill leachate, while ABOR had an important function on removing the dissolved NH₄-N in leachate.     

Reaction hazard and mechanism study of H2O2 oxidation of 2-butanol to methyl ethyl ketone using DSC,Phi-TEC II and GC-MS

Methyl ethyl ketone (MEK) oxidation via H₂O₂ with tungsten-based polyoxometalate catalysts has gained much attention with an ever-growing body of knowledge focusing on the development of environmentally benign processes in chemical industry. In this study, two calorimetry techniques, differential scanning calorimetry (DSC) and Phi-TEC II adiabatic calorimetry, were employed to analyze the thermal hazards associated with the 2-butanol oxidation reaction system. Hydrogen peroxide was the oxidant and a tungsten-based polyoxometalate as the catalyst. Gas chromatography-mass spectrometry was used for identification of the organic products. Important thermal kinetic data were obtained including “onset” temperature, heat of reaction, adiabatic temperature rise and self-heat rate. From DSC results, three exothermic peaks were detected with a total heat generation of approximately 1.26 kJ/g sufficiently to induce a thermal runaway. Possible reaction pathway for three stages were proposed based on both DSC and GC-MS results. One exotherm was detected by Phi-TEC II calorimeter and the pressure versus temperature profile together with the DSC and GC-MS data demonstrate the complexity of 2-butanol reaction system under both thermal screening and adiabatic conditions.     

Non-catalytic and catalytic wet air oxidation of pharmaceuticals in ultra-pure and natural waters

A wet air oxidation (WAO) process was applied to four selected pharmaceuticals (metoprolol, naproxen, amoxicillin, and phenacetin) individually dissolved in ultra-pure water, varying the temperature and oxygen pressure. Due to the moderate (amoxicillin) or low (metoprolol, naproxen, and phenacetin) efficiency found in the oxidation of these pollutants, a catalytic wet air oxidation (CWAO) process was then tested using a platinum catalyst supported on multi-walled carbon nanotubes (CNT). In this CWAO process, the pharmaceuticals were dissolved together in ultra-pure water and in four natural water matrices—a reservoir water, a groundwater, and two waters from different municipal wastewater treatment plants. On the basis of the measurements of their removals, a discussion is given of the influence of the main operating variables: the presence or absence of catalyst, type of catalyst (the synthesized Pt/CNT or a commercial Pt/AC), catalyst dosage (0.005–0.050 g), temperature (120–140 °C), and oxygen pressure (20–40 bar). In most experiments, the removals were in the sequence: amoxicillin > naproxen > phenacetin. In addition, total organic carbon (TOC) removal measurements were made of some of the natural waters tested.     

Thermal characterization of fly ash from one municipal solid waste incinerator (MSWI) in Shanghai

This study aims to develop a methodology for the thermal characterization of MSWI fly ash. We performed TGA–DTA and component variation analysis, microstructure transfer of sintered fly ash, as well as leaching toxicity, volatilization ratio and specification transformation of heavy metals as a function of temperature. It is found that content of crystal phases first increases between room temperature and 800 °C and then decreases between 800 °C and 1200 °C, while that of glass phases registers a reverse trend. Fly ash registers a SiO₂–Al₂O₃–metal oxides system and its content of glass phases is around 57%. Increase of sintering temperature between 600 °C and 1200 °C is conducive to the reduction of soluble As, Cd, Cu, Hg, Pb, Ni and Zn, while content of soluble Cr increases as temperature rises from 800 °C to 1200 °C.     

Optimizing the preparation parameters of mesoporous nanocrystalline titania and its photocatalytic activity in water: Physical properties and growth mechanisms

Titania nanomaterial with an anatase structure and 5.6 nm crystallite size and 280.7 m² g⁻¹ specific surface areas had been successfully prepared by sol–gel/hydrothermal route. The effect of pH as a type of autoclave and calcination was studied. Crystallite size and phase composition of the prepared samples were identified. X-ray diffraction analyses showed the presence of anatase with little or no rutile phases. The crystallite size of the prepared TiO₂ with acidic catalyst was both smaller than that prepared with basic catalyst, and was increasing after acidic calcinations by a factor 4–5. Basic calcinations produced a specific increase of 1.5. Rutile ratio and the particle size were increased after calcination at 500 °C. However, TiO₂ powder synthesized using a basic catalyst persisted the anatase phase and a loosely aggregation of particles. Anatase TiO₂ as prepared with acidic catalyst in Teflon lined stainless steel autoclave demonstrated the highest photocatalytic activity for degradation of 2,6-dichlorophenol-indophenol under ultraviolet irradiation with t_½ 0.8 min.     

Sources of underground CO: Crushing and ambient temperature oxidation of coal

As a harmful gas in underground coal mine, CO seriously threatened the safety of miners. Currently, the spontaneous combustion of residual coal in goaf is generally considered as the main source of underground CO. CO gas is also widely used as an indicator gas in fire prediction in mines. However, high concentrations of CO are also detected in some mines without spontaneous combustion of coal. Therefore, in the paper, with four ranks of coal, we studied other two potential CO sources: crushing and oxidation at ambient temperature. The more completely crushed coal produces more CO. The concentration of generated CO is inversely proportional to moisture content in coal. Therefore, the addition of water can inhibit the generation process of CO during the crushing process of coal. Lignite with low metamorphic grade can be oxidized to produce CO at ambient temperature (25 °C), and anthracite with high coal rank can be only oxidized to produce CO at 60 °C. Infrared spectra indicated that the coal with rich aliphatic hydrocarbons and oxygen-containing functional groups are more susceptible to oxidation at room temperature. Moreover, the smaller particle size of coal is more beneficial to the oxidation at ambient temperature to generate CO. CO generation during coal oxidation is also closely related to the ventilation rate.     

Simultaneous photocatalytic treatment of Cr(VI), Ni(II) and SDBS in aqueous solutions: Evaluation of removal efficiency and energy consumption

Simultaneous photocatalytic reduction of poisonous Cr(VI) and Ni(II) ions, coupled with photocatalytic oxidation of sodium dodecyl benzene sulfonate (SDBS) were studied with a trace amount of commercial titania nanoparticles and by means of a direct-photo-irradiation reactor. The co-presence of metal ions and SDBS causes metal ions reduction as well as SDBS oxidation to enhance and energy efficiency to improve. XRD, XPS and FTIR analysis were used to characterize TiO₂ particles before and after usage with the aim of evaluating the mechanism of reactions. The effect of major operating parameters, pH and temperature, was investigated. Under conditions of [Cr(VI)]₀ = [Ni(II)]₀ = 5 mg/L, [SDBS]₀ = 10 mg/L, [TiO₂] = 40 mg/L, pH 6 and T = 35 °C; the removal efficiencies of 55.4%, 71.2% and 57.2% were obtained, respectively, for Cr(VI) and Ni(II) reduction, as well as for SDBS oxidation, after 110 min operation. The relevant kinetic model jointed with the Arrhenius equation was introduced. Pseudo-first-order reactions are relevant. Energy consumption (electrical and thermal) evaluations revealed that operations at higher temperatures provide significant cost reduction. Meantime, a criterion was proposed for a consistent assessment of this kind of processes.     

Effect of pyrolysis and oxidation characteristics on lauric acid and stearic acid dust explosion hazards

The effect of pyrolysis and oxidation characteristics on the explosion sensitivity and severity parameters, including the minimum ignition energy MIE, minimum ignition temperature MIT, minimum explosion concentration MEC, maximum explosion pressure P_max, maximum rate of pressure rise (dP/dt)_max and deflagration index K_st, of lauric acid and stearic acid dust clouds was experimentally investigated. A synchronous thermal analyser was used to test the particle thermal characteristics. The functional test apparatuses including the 1.2 L Hartmann-tube apparatus, modified Godbert-Greenwald furnace, and 20 L explosion apparatus were used to test the explosion parameters. The results indicated that the rapid and slow weight loss processes of lauric acid dust followed a one-dimensional diffusion model (D1 model) and a 1.5 order chemical reaction model (F1.5 model), respectively. In addition, the rapid and slow weight loss processes of stearic acid followed a 1.5 order chemical reaction model (F1.5 model) and a three-dimensional diffusion model (D3 model), respectively, and the corresponding average apparent activation energy E and pre-exponential factor A were larger than those of lauric acid. The stearic acid dust explosion had higher values of MIE and MIT, which were mainly dependent on the higher pyrolysis and oxidation temperatures and the larger apparent activation energy E determining the slower rate of chemical bond breakage during pyrolysis and oxidation. In contrast, the lauric acid dust explosion had a higher MEC related to a smaller pre-exponential factor A with a lower amount of released reaction heat and a lower heat release rate during pyrolysis and oxidation. Additionally, due to the competition regime of the higher oxidation reaction heat release and greater consumption of oxygen during explosion, the explosion pressure P_m of the stearic acid dust was larger in low concentration ranges and decayed to an even smaller pressure than with lauric acid when the concentration exceeded 500 g/m³. The rate of explosion pressure rise (dP/dt)_m of the stearic acid dust was always larger in the experimental concentration range. The stearic acid dust explosion possessed a higher P_max, (dP/dt)_max and K_st mainly because of a larger pre-exponential factor A related to more active sites participating in the pyrolysis and oxidation reaction. Consequently, the active chemical reaction occurred more violently, and the temperature and overpressure rose faster, indicating a higher explosion hazard class for stearic acid dust.     

Influence of thermal environment on metallographic structure characteristics of the electric arc bead pattern

Electrical apparatuses are prone to arc, which generally causes a fire, even an explosion hazard, when a flammable gas mixture is present, especially during industrial processes. Terrible fire scenes are challenging for fire investigations. In this work, by performing a simultaneous thermal analysis test we simulated a fire environment and found that as the oxygen concentration decreased, the oxidation/exothermic peak temperature of ‘cause’ bead became higher, but the melting temperature was unaffected. Results indicated that the bead pattern underwent oxidation at approximately 831 °C, melting initiated at approximately 1060 °C, and the pattern then disappeared. The melted pattern grain changes were divided into three critical temperature stages: Approximately 600 °C, the onset temperature at which the melted pattern grains began to be equiaxed; approximately 831 °C, at which the grains were interspersed with oxygen-containing material; and 831–1060 °C, when the grains disappeared, which is a criterion for identifying electrical fires. However, the boundaries remained throughout the thermal environment process. Moreover, the bead pattern demonstrated three metallographic regions: Deep layer (Region I), the intermediate layer (Region Ⅱ), and surface layer (Region Ⅲ). Region I was the most thermally sensitive, in which equiaxed crystals first appeared. Region Ⅲ was the thermal reaction lag zone, in which the typical branching crystals finally disappeared, and Region Ⅱ was intermediate between Regions I and Ⅲ. The results may help fire investigators determine the fire scene temperature stages and provide support for fire evidence extraction.     

Preoptimal analysis of phase characteristic indicators in the entire process of coal spontaneous combustion

To accurately predict the development degree of coal spontaneous combustion (CSC), the CSC process was investigated using a programmed high-temperature-heating experimental system, and the variation law of index gas concentration in the holistic process of CSC and oxidation is formulated. Additionally, the accuracy of the experimental system was evaluated using experimental design for thermal analysis, and the correlation between gas index and apparent activation energy was determined using grey correlation analysis. The results indicated the following. In the critical temperature stage (0–100 °C), φ(CO)/φ(CO₂) should serve as the main index and C₂H₄ should serve as the auxiliary index; in the crack-active-speedup temperature stage (100–260 °C), CO and φ(C₂H₄)/φ(C₂H₆) should serve as the main index and R₁, the Graham index, and φ(C₂H₄)/φ(CH₄) should serve as auxiliary indexes; in the speedup-ignition temperature stage (260–370 °C), R₂ and the Graham index should serve as main indexes and φ(CO)/φ(CO₂), C₂H₄, and R₁ should serve as auxiliary indexes; in the ignition temperature (370–500 °C), R₃ should serve as the main index and R₂, the Graham index and C₂H₄ should serve as auxiliary indexes. Among them, the grey correlation degrees among the Graham index, Grignard fire coefficient, and apparent activation energy were the highest, reaching 0.91.     

High nitrite accumulation and strengthening denitrification for old-age landfill leachate treatment using an autocontrol two-stage hybrid process

An autocontrol two-stage hybrid process was developed to treat landfill leachate. Biological nitrogen removal with nitrification and denitrification via nitrite pathway was split into two stages. The first stage was designed for the high nitrite accumulation and was composed of two hybrid bed reactors (Hybrid I and Hybrid II) and a coagulation–flocculation reactor having effective volumes of 120 L and 80 L, respectively. The second stage was designed for strengthening denitrification and included a single 80 L reactor. The carriers of the hybrid bed reactors were composed of fixed multiple flexible carriers and suspended particle carriers. Dissolved oxygen (DO), pH value, oxidation–reduction potential (ORP) and temperature were used as online fuzzy control parameters of the automatic control system. The concentration of nitrite in Hybrid I and Hybrid II could reach 411 mg L⁻¹ and 604 mg L⁻¹, respectively. Ammonia removal has reached maximal rates of 0.061 kgNH₄⁺-N (m³ h)⁻¹ and 0.041 kgNH₄⁺-N (m³ h)⁻¹, respectively. A maximum nitrite removal rate of 0.211 kgNO₂⁻-N (m³ h)⁻¹ was observed during the strengthening denitrification. The running time of one cycle was not fixed and was actually controlled by the system. The results indicated that the running period was more closely related to influent ammonia concentration than influent COD concentration. The aeration times could be shortened and the energy could be saved. The autocontrol two-stage hybrid process is therefore an economical and effective way for landfill leachate treatment.