The degradation and mineralization of aniline (AN) using ozone combined with Fenton reagent (O₃/Fenton) in a rotating packed bed (RPB) was proposed in this study, and the process (RPB-O₃/Fenton) was compared with conventional O₃/Fenton in a stirred tank reactor (STR-O₃/Fenton) or single ozonation in an RPB (RPB-O₃). Effects of high gravity factor, H₂O₂ dosage, H₂O₂ dosing method and initial pH on the AN mineralization efficiency were investigated in the RPB-O₃/Fenton process. In addition, the behavior of Fe(Ⅱ) was monitored at different H₂O₂ dosing methods and pH values. Finally, the optimal operation conditions were determined with high gravity factor of 100, initial pH of 5, Fe(Ⅱ) concentration of 0.8 mmol·L^-1 and H₂O₂ dosage of 2.5 ml. Under these conditions, for aniline wastewater at the volume of 1 L and concentration of 200 mg·L^-1, a fast and thorough decay of AN was conducted in 10 min, and the TOC removal efficiency reached 89% in 60 min. The main intermediates of p-benzoquinone, nitrobenzene, maleic acid and oxalic acid were identified by liquid chromatography/mass spectroscopy (LC/MS), and the degradation pathways of AN in RPB-O₃/Fenton system were proposed based on experimental evidence. It could be envisioned that high-gravity technology combined with O₃/Fenton processes would be promising in the rapid and efficient mineralization of wastewater.

A new method by liquid-liquid-liquid three phase system, consisting of acidified primary amine N1923 (abbreviated as A-N1923), poly(ethylene glycol) (PEG) and (NH₄)₂SO₄ aqueous solution, was suggested for the separation and simultaneous extraction of V(V) and Cr(VI) from the acidic leach solutions of highchromium vanadium-titanium magnetite. Experimental results indicated that V(V) and Cr(VI) could be selectively enriched into the A-N1923 organic top phase and PEG-rich middle phase, respectively, while Al(Ⅲ) and other co-existing impurity ions, such as Si(IV), Fe(Ⅲ), Ti(IV), Mg(Ⅱ) and Ca(Ⅱ) in acidic leach solutions, could be enriched in the (NH₄)₂SO₄ bottom aqueous phase. During the process for extraction and separation of V(V) and Cr(VI), almost all of impurity ions could be removed. The separation factors between V (V) and Cr(VI) could reach 630 and 908, respectively in the organic top phase and PEG middle phase, and yields of recovered V(V) and Cr(VI) in the top phase and middle phase respectively were all above 90%. Various effects including aqueous pH, A-N1923 concentration, PEG added amount and (NH₄)₂SO₄ concentration on three-phase partitioning of V(V) and Cr(VI) were discussed. It was found that the partition of Cr(VI) into the PEG-rich middle phase was driven by hydrophobic interaction, while extraction of V(V) by A-N1923 resulted of anion exchange between NO₃^- and H₂V₁₀O₂₈^4-. Stripping of V(V) and Cr(VI) from the top organic phase and the middle PEG-rich phase were achieved by mixing respectively with NaNO₃ aqueous solutions and NaOH-(NH₄)₂SO₄ solutions. The present work highlights a new approach for the extraction and purification of V and Cr from the complex multi-metal co-existing acidic leach solutions of high-chromium vanadium-titanium magnetite.

The chemical stability of cefixime was determined by high-performance liquid chromatography (HPLC) under different conditions, including factors such as pH, solvents, initial concentration, temperature and additives. The degradation process follows the first-order kinetics. A pH-rate profile exhibits the U-shape and shows the maximum stability of cefixime at pH=6. The stability in different pure solvents is ranked as acetone N ethanol N methanol N water, while the degradation rate of cefixime exists a maximum at the ratio of 0.6 in water + methanol mixtures. In addition, the degradation rate increases with the temperature increasing and the activation energy of degradation was found to be 27.078 kJ·mol^-1 in acetone + water mixed solvents. The addition of different additives was proven to either inhibit or accelerate the degradation. The degradation products were analyzed using HPLC, LC-MS and infrared spectroscopy, and the possible degradation pathways in acid as well as alkaline environment were proposed to help us understand the degradation behavior of cefixime.

Reactive dividing wall column (RDWC) is a highly integrated unit which combines reaction distillation (RD) with dividing wall column separation technology into one shell, and it realized the chemical reaction and the separation of multiple product fractions simultaneously. In this paper, the reaction of esterification with acetic acid and ethanol to produce ethyl acetate was used as the research system, experiments and simulations of the RDWC were carried out. This system in the traditional process mostly used the homogeneous catalyst (e.g. sulfuric acid). However, in view of the corrosion of the equipment caused by the acidity of the catalyst, we used the heterogeneous catalysts - iron exchange resins - Amberlyst15 and proposed a novel catalyst loading method. Firstly, the reliability of the model of the simulation was verified by the experimental study on the change of liquid split ratio and reflux ratio. After that, the four-column model was established in Aspen Plus to analyze the effects of the amount of azeotropic agent, reflux ratio and acetic acid concentration. Finally, for a fair comparison, the economic analysis was conducted between traditional RD column and RDWC. The results showed that RDWC can save 34.7% of total operating costs and 18.5% of TAC.

A mass transfer model in consideration of multi-layer resistances through NaA zeolite membrane and lumen pressure drop in the permeate side was developed to describe pervaporation dehydration through scaled-up hollow fiber supported NaA zeolite membrane. It was found that the transfer resistance in the lumen of the permeate side is strongly related with geometric size of hollow fiber zeolite membrane, which could not be neglected. The effect of geometric size on pervaporation dehydration could be more significant under higher vacuum pressure in the permeate side. The transfer resistance in the lumen increases with the hollow fiber length but decreases with lumen diameter. The geometric structure could be optimized in terms of the ratio of lumen diameter to membrane length. A critical value of d_I/L (R_c) to achieve high permeation flux was empirically correlated with extraction pressure in the permeate side. Typically, for a hollow fiber supported NaA zeolite membrane with length of 0.40 m, the lumen diameter should be larger than 2.0 mm under the extraction pressure of 1500 Pa.

In this paper, pyrolysis of Indonesian oil sands (IOS) was investigated by two different heating methods to develop a better understanding of the microwave-assisted pyrolysis. Thermogravimetric analysis was conducted to study the thermal decomposition behaviors of IOS, showing that 550℃ might be the pyrolysis final temperature. A explanation of the heat-mass transfer process was presented to demonstrate the influence of microwave-assisted pyrolysis on the liquid product distribution. The heat-mass transfer model was also useful to explain the increase of liquid product yield and heavy component content at the same heating rate by two different heating methods. Experiments were carried out using a fixed bed reactor with and without the microwave irradiation. The results showed that liquid product yield was increased during microwave induced pyrolysis, while the formation of gas and solid residue was reduced in comparison with the conventional pyrolysis. Moreover, the liquid product characterization by elemental analysis and GC-MS indicated the significant effect on the liquid chemical composition by microwave irradiation. High polarity substances (ε < 10 at 25℃), such as oxyorganics were increased, while relatively low polarity substances (ε > 2 at 25℃), such as aliphatic hydrocarbons were decreased, suggesting that microwave enhanced the relative volatility of high polarity substances. The yield improvement and compositional variations in the liquid product promoted by the microwave-assisted pyrolysis deserve the further exploitation in the future.

A green and efficient method for the selective aerobic oxidation of p-cresol to p-hydroxybenzaldehyde catalyzed by co-catalysts between metalloporphyrins and metal salts was investigated and developed. The relationship between the synergistic catalytic effects and the composition as well as amount of co-catalysts was investigated. Moreover, the influence of different reaction conditions was studied in details. A high p-cresol conversion (>99%) and p-hydroxybenzaldehyde selectivity (83%) were obtained using only 1.125×10^-5 mol T(p-CH₃O)PPFe^ⅢCl-Co(OAc)₂ used under mild, optimized reaction conditions. A possible mechanism for the reaction was also proposed. This work would be meaningful and instructive for the further researches and applications of co-catalyst system on oxidation of cresols and could give some enlightenment on the selectively catalytic oxidation of the side-chain alkyls of aromatics.

Pyridine has been generally synthesized by aldehydes and ammonia in a turbulent fluidized-bed reactor. In this paper, a novel riser reactor was proposed for pyridine synthesis. Experiment result showed that the yield of pyridine and 3-picoline decreased, but the selectivity of pyridine over 3-picoline increased compared to turbulent fluidized-bed reactor. Based on experimental data, a modified kinetic model was used for the determination of optimal operating condition for riser reactor. The optimal operating condition of riser reactor given by this modified model was as follows:The reaction temperature of 755 K, catalyst to feedstock ratio (CTFR) of 87, residence time of 3.8 s and initial acetaldehydes concentration of 0.0029 mol·L^-1 (acetaldehydes to formaldehydes ratio by mole (ATFR) of 0.65 and ammonia to aldehydes ratio by mole (ATAR) of 0.9, water contention of 63wt% (formaldehyde solution)).

By combining the photochemical reaction and liquid-liquid extraction (PODS), we studied desulfurization of model fuel and FCC gasoline. The effects of air flow, illumination time, extractants, volume ratios of extractant/fuel, and catalyst amounts on the desulfurization process of PODS were analyzed in detail. Under the conditions with the air as oxidant (150 ml·min^-1), the mixture of DMF-water as extractant (the volume ratio of extractant/oil of 0.5) and photo-irradiation time of 2 h, the sulfur removal rate reached only 42.63% and 39.54% for the model and FCC gasoline, respectively. Under the same conditions, the sulfur removal rate increased significantly up to 79% for gasoline in the presence of Cu₂O catalyst (2 g·L^-1). The results suggest that the PODS combined with a Cu₂O catalyst seems to be a promising alternative for sulfur removal of gasoline.

The densities and surface tensions of[Bmim] [TFO]/H₂SO₄,[Hmim] [TFO]/H₂SO₄ and[Omim] [TFO]/H₂SO₄ binary mixtures were measured by pycnometer and Wilhelmy plate method respectively. The results show that densities and surface tensions of the mixtures decreased monotonously with increasing temperatures and increasing ionic liquid (IL) molar fraction. IL with longer alkyl side-chain length brings a lower density and a smaller surface tension to the ILs/H₂SO₄ binary mixtures. The densities and surface tensions of the mixtures are fitted well by Jouyban-Acree (JAM) model and LWW model respectively. Redlich-Kister (R-K) equation and modified Redlich-Kister (R-K) equation describe the excess molar volumes and excess surface tensions of the mixtures well respectively. Adding a small amount of ILs (χ_IL < 0.1) into sulfuric acid brings an obvious decrease to the density and the surface tension. The results imply that the densities and surface tensions of ILs/H₂SO₄ binary mixtures can be modulated by changing the IL dosage or tailoring the IL structure.

In this work, SiO₂ nanoplates with opened macroporous structure on carbon layer (C-mSiO₂) have been obtained by dissolving and subsequent regrowing the outer solid SiO₂ layer of the aerosol-based C-SiO₂ double-shell hollow spheres. Subsequently, triple-shell C-mSiO₂-C hollow spheres were successfully prepared after coating the CmSiO₂ templates by the carbon layer from the carbonization of sucrose. When being applied as the anode material for lithium-ion batteries, the C-mSiO₂-C triple-shell hollow spheres deliver a high capacity of 501 mA·h·g^-1 after 100 cycles at 500 mA·g^-1 (based on the total mass of silica and the two carbon shells), which is higher than those of C-mSiO₂ (391 mA·h·g^-1) spheres with an outer porous SiO₂ layer, C-SiO₂-C (370 mA·h·g^-1) hollow spheres with a middle solid SiO₂ layer, and C-SiO₂ (319.8 mA·h·g^-1) spheres with an outer solid SiO₂ layer. In addition, the battery still delivers a high capacity of 403 mA·h·g^-1 at a current density of 1000 mA·g^-1 after 400 cycles. The good electrochemical performance can be attributed to the high surface area (246.7 m²·g^-1) and pore volume (0.441 cm³·g^-1) of the anode materials, as well as the unique structure of the outer and inner carbon layer which not only enhances electrical conductivity, structural stability, but buffers volume change of the intermediate SiO₂ layer during repeated charge-discharge processes. Furthermore, the SiO₂ nanoplates with opened macroporous structure facilitate the electrolyte transport and electrochemical reaction.

In this work, phenol and oxalic acid (OA) degradation in an ozone and photocatalysis integrated process was intensively conducted with Fe³⁺/TiO₂ catalyst. The ferrioxalate complex formed between Fe³⁺ and oxalate accelerated the removal of OA in the ozonation, photolysis and photocatalytic ozonation process, for its high reactivity with ozone and UV. Phenol was degraded in ozonation and photolysis with limited TOC removal rates, but much higher TOC removal was achieved in photocatalytic ozonation due to the generation of·OH. The sequence of UV light and ozone in the sequential process also influences the TOC removal, and ozone is very powerful to oxidize intermediates catechol and hydroquinone to maleic acid. Fenton or photo-Fenton reactions only played a small part in Fe³⁺/TiO₂ catalyzed processes, because Fe³⁺ was greatly reduced but not regenerated in many cases. The synergetic effect was found to be highly related with the property of the target pollutants. Fe³⁺/TiO₂ catalyzed system showed the highest ability to destroy organics, but the TiO₂ catalyzed system showed little higher synergy.

Nitric oxide (NO) removal and sulfur dioxide (SO₂) removal by sodium persulfate (Na₂S₂O₈) were studied in a Bubble Column Reactor. The proposed reaction pathways of NO and SO₂ removal are discussed. The effects of temperatures (35-90℃), Na₂S₂O₈ (0.05-0.5 mol·L^-1), FeSO₄ (0.5-5.0 m mol·L^-1) and H₂O₂ (0.25 mol·L^-1) on NO and SO₂ removal were investigated. The results indicated that increased persulfate concentration led to increase in NO removal at various temperatures. SO₂ was almost completely removed in the temperature range of 55-85℃. Fe²⁺ accelerated persulfate activation and enhanced NO removal efficiency. At 0.2 mol·L^-1 Na₂S₂O₈ and 0.5-1.0 mmol·L^-1 Fe²⁺, NO removal of 93.5%-99% was obtained at 75-90℃, SO₂ removal was higher than 99% at all temperatures. The addition of 0.25 mol·L^-1 H₂O₂ into 0.2 mol·L^-1 Na₂S₂O₈ solution promoted NO removal efficiency apparently until utterly decomposition of H₂O₂, the SO₂ removal was as high as 98.4% separately at 35℃ and 80℃.

The drying processes are always applied prior to the transportation or utilization of lignite, and result in notable changes in the stabilities of lignite. In this paper, the study on the effects of nitrogen and MTE drying process on the physico-chemical properties and stabilities of Zhaotong lignite was carried out. The briquettes produced by MTE drying in this study were 150 mm in dimension, and so had a much larger particle size than nitrogendried samples. Nitrogen adsorption, mercury intrusion porosimetry and scanning electron microscopy all suggested that drying was accompanied by the transformation of larger pores into smaller ones. Compared to nitrogen drying, the pore structures could be stabilized by the MTE process. The soluble salts were removed during MTE drying which resulted in the decrease in ash and the concentrations of some of the major metals. The removal of water enhanced the hydrophilicity of nitrogen dried samples, but did not affect the hydrophilicity of MTE dried samples. The moisture holding capacity of MTE dried samples reduced faster than nitrogen dried samples with the decrease of residual moisture content. The moisture readsorption processes of MTE dried samples were strongly inhibited due to the much larger particle size of sample produced by MTE drying than nitrogen drying. The susceptibility to spontaneous combustion, indicated by cross point temperature and self-heating tests, of nitrogen and MTE dried samples increased with the decrease of residual moisture content. The MTE dried samples are more liable to spontaneous combustion than nitrogen dried samples with the same residual moisture and particle size. However, the larger particle size of the MTE product made it more stable with respect to spontaneous combustion and also moisture readsorption.

In this work, a coking wastewater was selected and a biochemical A²/O treatment device for fractional degradation was designed and employed. After each stage of the treatment, the products were analyzed through gas chromatography-mass spectroscopy (GC-MS) to determine their composition. Finally, AgNO₃ + K₂FeO₄ was used as an advanced deep catalytic oxidation treatment. It was concluded from the analysis that cyclic organics could be degraded and the chemical oxygen demand (COD) was controlled within 50 mg·L^-1, in line with the target value. Meanwhile, the spectra obtained from the GC-MS were in accordance with the conclusions reached based on the COD. The research results showed that all hard-degradable organics in coking wastewater could be eliminated through the A²/O bio-membrane treatment and the advanced treatment of making use of K₂FeO₄ as an oxidant and Ag⁺ as a catalyst, the catalytic efficiency with Ag⁺ as a catalyst of K₂FeO₄ was very high. Ag⁺ could evidently improve the oxidation capacity of K₂FeO₄ to wastewater in its short stability time, and this is an important innovation.

A facile eco-friendly hydrothermal route (180℃, 12.0 h) has been developed for the first time to the uniform hierarchical porous MgBO₂(OH) microspheres without the aid of any organic additive, surfactant or template, by using the abundant MgCl₂·6H₂O, H₃BO₃ and NaOH as the raw materials. The as-obtained porous microspheres exhibit a specific surface area of 94.752 mg·g^-1, pore volume of 0.814 cm³·g^-1, and ca. 84.0% of which have a diameter of 2.25-3.40 μm. The thermal decomposition of the porous MgBO₂(OH) microspheres (650℃, 2.5℃·min^-1) leads to the porous Mg₂B₂O₅ microspheres with well-retained morphology. When utilized as the adsorbents for the removal of CR from mimic waste water, the present porous MgBO₂(OH) microspheres exhibit satisfactory adsorption capacity, with the maximum adsorption capacity q_m of 309.1 mg·g^-1, much higher than that derived from most of the referenced adsorbents. This opens a new window for the facile green hydrothermal synthesis of the hierarchical porous MgBO₂(OH) microspheres, and extends the potential application of the 3D hierarchical porous metal borates as high-efficiency adsorbents for organic dyes removal.

A database-based strategy of candidate generation was proposed for molecular design of new de-phenol extractants following the idea of finding new applications of existing commercial compounds. The strategy has the advantage that the environmental, safety and health risks of candidate compounds are known and controllable. In this work, the Existing Commercial Compounds (ECC) database and special combined search strategy were developed as the base for the proposed CAMD method following such idea, and molecules for phenol extraction used in coking wastewater treatment were selected from the ECC database. The candidate solvents cover the following categories:ketones, esters, ethers, alcohols, anhydrides and benzene compounds, which are consistent with the de-phenol extractants commonly used in the industry or experiment. The compounds with higher partition coefficient and selectivity than widely used methyl isobutyl ketone (MIBK) are mainly ketones. 26 obtained molecules show higher partition coefficient and selectivity than MIBK, which are suggested to be further investigated by experiment. Furthermore, analysis of these potential molecules may present the effective functional groups as the initial group set to generate new molecular structures of de-phenol extractants. The results show that the proposed method enables us to efficiently generate chemicals with benefits of less time, less economical cost, and known environmental impact as well.

The synthesis of inorganic materials with special morphologies with the assistance of biological molecules is a potential development in the field of controllable growth and assembly of nanomaterials. In this paper, BaF₂ nanocrystals in patterns of well-defined linear and erythrocyte-shaped structure were synthesized with the assistance of Escherichia coli DNA. Morphology and the arrangement of BaF₂ particles on DNA were controllable by altering the reaction condition. Square nanoparticles arranged in linear chains were gained with the assistance of normal DNA; while, erythrocyte-shaped BaF₂ nanospheres were synthesized with the assistance of denatured DNA. Besides, the influences of solvent, reaction temperature, concentration of reactants and the heating time on the morphology of the BaF₂ particles were studied.

Vapreotide acetate (Vap) was used as a biotemplate to synthesize silver nanocages through direct co-incubation of a AgNO₃ solution, following by reduction using fresh NaBH₄. The characterized vapreotide-templated silver nanocages (Vap-AgNCs) presented a wide and red shifted absorption band with a maximum between 480 nm and 800 nm and possessed a uniform structure with a face-centered cubic crystal structure. The biocompatibility of Vap-AgNCs was assessed using the MTT method, indicating Vap-AgNCs had better biocompatibility when its concentration was lower than 2.5×10-4 mmol·L^-1. The photothermal characteristics of Vap-AgNCs were analyzed with laser irradiation (808 nm, 1.5 W·cm^-2) and the results showed that the temperature of the VapAgNCs solution reached 45℃ starting from 25℃ within 5 min. Additionally, Vap-AgNCs with a laser led to HeLa cell death. Therefore, the prepared Vap-AgNCs is expected to be an effective photothermal therapy agent.

The rare ginsenoside Compound K (C-K) is attracting more attention because of its good physiological activity and urgent need. There are many pathways to obtain ginsenoside C-K, including chemical and biological methods. Among these, the conversion of PPD-type ginsenosides by enzymatic hydrolysis is a trend due to its high efficiency and mild conditions. For effectively extracting from the other panaxadiol saponins, the conversion process for ginsenoside C-K was investigated using snailases in this study. The univariate experimental design and response surface methodology were used to determine the optimal hydrolysis conditions for the conversion of ginsenoside Rb1 into ginsenoside C-K by snailases. The optimum conditions were as follows:pH 5.12, temperature 51℃, ratio of snailase/substrate 0.21, and reaction time 48 h. On the basis of these parameters, the addition of 1.0 mmol·L^-1 ferric ion was found to significantly improve the enzymolysis of snailases for the first time. With the above conditions, the maximum conversion rate reached 89.7%, suggesting that the process can obviously increase the yield of ginsenoside C-K. The bioassay tests indicated that the ginsenoside C-K showed anti-tumor activity in a series of tumor cell lines. Based on these results, we can conclude that the process of rare ginsenoside CK production by enzymolysis with snailase is feasible, efficient, and suitable for the industrial production and application.