Heterogeneous photo-assisted Fenton catalytic removal of tetracycline using Fe-Ce pillared bentonite简

In the present work, a novel heterogeneous photo-Fenton catalyst was prepared by iron and cerium pillared bentonite. The catalyst Fe-Ce/bentonite was characterized by X-ray diffraction （XRD）, X-ray fluorescence （XRF）, Brunauer-Emmett-Teller （BET） and scanning electron microscopy （SEM） methods. It is found that Fe and Ce intercalate into the silicate layers of bentonite successfully. Tetracycline was removed by heterogeneous photo-Fenton reaction using the catalyst in this work. The effects of different reaction systems, hydrogen peroxide concentration, initial pH, catalyst dosage, UV power and introduction of different anions on degradation were investigated in details. The stability of catalyst was investigated through recycling experiment. The results show that removal rate of tetracycline is 98.13% under the conditions of 15 mmol/L H202, 0.50 g/L catalyst dosage, initial pH 3.0, 11 W UV lamp power and 60 min reaction time. However, the removal rate decreases after adding some anions. The hydroxyl radical plays an important role in heterogeneous photo-assisted Fenton degradation of tetracycline. The catalyst is very stable and can be recycled many times.     

Degradation of n-butyl xanthate using fly ash as heterogeneous Fenton-like catalyst

Heterogeneous Fenton-like process using fly ash as a catalyst was studied to degrade n-butyl xanthate form aqueous solution. The different reaction parameters on the degradation efficiency of the process were investigated. The fly ash/H2O2 catalyst possesses a high oxidation activity for n-butyl xanthate degradation in aqueous solution. It is found that both the dosage of catalyst and initial solution pH significantly affect the n-butyl xanthate conversion efficient. The results indicate that by using 1.176 mmol/L H2O2 and 1.0 g/L fly ash catalyst with mass fraction of 4.14% Fe（III） oxide at pH 3.0, almost 96.90% n-butyl xanthate conversion and over 96.66% COD removal can be achieved within 120 min with heterogeneous catalysis by fly ash. CS2 as an intermediate of n-butyl xanthate oxidation. Finally, it is demonstrated that the fly ash/H2O2 catalytic oxidation process can be an efficient method for the treatment of n-butyl xanthate containing wastewater.     

Three controllable factors of steady operation of EGSB reactor

The bench-scale EGSB (expanded granular sludge bed) reactor was operated to study the effect of sludge loading rate, pH value and nutrient element on the operation of the EGSB reactor and the control rule of these factors. Continuous flow was used to treat synthetic wastewater containing dextrose and beer, and the temperature of reactor was controlled at mesophiles temperature (33 ℃). The experimental results demonstrated that the proper sludge loading rate was 0.9-1.42 kg COD/(kg VSS·d); the pH value in the reactor was controlled by adding sodium bicarbonate, the proper additive quantity was 1000-1200 mg/L; the additive quantity of nutrient element was as follows: 41.3 mg/(SS·d) of FeCl2·4H2O, 4.3 mg/(SS·d) of CoCl2·6H2O, 8.2 mg/(SS·d) of NiCl2·6H2O, 7.5-13 mg/(SS·d) of CaCO3,and 56.7-22.7 mg/(SS·d) of 7Na2S·9H2O, respectively. When these parameters were properly determined, the EGSB reactor could treat wastewater with 400-5000 mg/L COD concentration. The COD removal efficiency was over 85%. The operation of the EGSB reactor was steady and the EGSB reactor had strong anti-shock load ability.     

Preparation of superabsorbent by graft copolymerization of acrylic acid onto corn starch using K_2S_2O_8 and rare earths as initiators

K2 S2 O8 and rare earths （RE） were used as initiators to prepare superabsorbents by graft copolymerization of acrylic acid （ AA ） onto corn starch. The effects of monomer concentration, initiator K2 S2 O8 concentration, cross-linker concentration, reaction temperature and the concentration ratio of RE and K2 S2O8 on the graft copolymerization were studied in terms of the water absorption capacity of superabsorbents. Results indicate that the optimum conditions obtained for the grafting of AA onto 5g starch are as follows： AA of 75. 773 g/L, K2S20s of 0. 437 g/L, RE of 0. 874 g/L, cross-linker of 0. 381 g/L and temperature of 70 ℃. The maximum water absorption capacity obtained is 740 g/g. The new method of graft polymerization is easily proceeded and controlled. The graft copolymers were characterized by infra-red spectroscopy, scanning electron microscopy and TG. Results characterized by IR and SEM give strong evidence for grafting of AA onto corn starch, and those characterized by TG reveal that the grafting of AA improves the theimostability of corn starch.     

MoO3/SO4^2- —TiO2 catalyst for transesterification of dimethyl cabonate with phenol

A new MoO3/SO4^2- -TiO2 catalyst was prepared by a conventional impregnation of SO42-/TiO2 as carrier with an aqueous solution of ammonium molybdate and used for the synthesis of transesterification of dimethyl carbonate （DMC） with phenol.A series of MoO3/SO42--TiO2 catalysts with different MoO3 loadings were investigated and characterized using X-ray diffraction （XRD）,Fourier transform infrared spectrometer （FTIR）,NH3-temperature programmed desorption （NH3-TPD） and X-ray photoelectron spectroscopy （XPS）.The results show that MoO3 loading is related to the activity of transesterification reaction.With the increase of MoO3 loading,the activity of transesterification reaction increases.The sulfur species in the catalyst have an influence on the molybdenum species,and lead to an increase in the electropositive of molybdenum,which promotes the catalytic activity of MoO3/SO42--TiO2.Among the series of catalysts prepared,MoO3/SO42--TiO2 with 10% MoO3 and 823 K calcinated is found to be the most active catalyst for transesterification reaction.Under the reaction conditions of 453 K and 12 h,the conversion of DMC is 30.5 %,and the yields of MPC and DPC reach 21.2 % and 8.7 %,respectively.     

Sorption of Pb(II) from aqueous solution by konjac glucomannan beads

Konjac glucomannan beads have been investigated as metal biosorbent for Pb(II) from aqueous solu-tions. The effect of contact time, solution pH, initial metal concentration, and desorption were studied in batch experiments at 20℃±2℃. Maximum mental sorption was found to occur at initial pH 4.0―5.5. Kinetic studies revealed that the initial uptake was rapid and equilibrium was established in 3 h and that the data followed the prseudo-second order reaction. The equilibrium sorption data at initial pH 4.0 were described by the Langmuir and Freundlich isotherm models; however, Langmuir isotherm model has been found to provide the best correlation. The highest value of Langmuir maximum uptake (qmax) was found to be 105.71 mg·g-1. Similar Freundlich empirical constant (KF) was obtained to be 1.98 for lead. Adsorption-complexation may be involved in the sorption process of lead. Desorption experi- ments showed evidence that after two contacts neither HCl nor EDTA solutions were able to desorb lead from the konjac glucomannan beads, but the desorbtion efficacy of HCl solution was higher than EDTA solution. The results obtained show that konjac glucomannan beads may be used for the treat-ment of wastewater contaminated with lead.     

Electrochemical degradation of acidified reed pulp black liquor with three-dimensional electrode reactor

The electrochemical degradation of reed pulp black liquor containing lignin pretreated by acidification method was investigated using a three-dimensional electrode reactor. Using activated carbon as particle electrode, the effects of p H value, reaction temperature, electrolysis time and current on residual concentration of total organic carbon(TOC) were discussed in detail. The optimal conditions were obtained: pH 2.5, influent flow rate of 200 mL/min, 25 °C, 300 mA and 2h of electrolysis time, and the removal efficiency of TOC maintains at 35.57 %. The results of the electrochemical method indicate that ·OH radicals are produced in activated carbon anode in the electrolysis process and then adsorbed on the activated carbon surface. Microcell consists of ·OH radicals and the absorbed lignin. With the microcell reaction, the lignin is degraded, while the anodic polarized curve illustrates that the lignin is obviously oxidized in the anode. The contributions of direct and indirect electrolyses to the TOC removal ratio are about 50%, respectively.     

Study on the removal of urea in wastewater using Fenton reagent

The great amount of NH3-N produced in biological hydrolysis process of high concentration urea can inhibit the growth of microorganisms. In allusion to this problem,the Fenton reagent was used to treat high concentration urea wastewater. And the optimum conditions of this experiment were employed as follows: Fe(Ⅱ)-H2O2mole ratio was 1/3.53,H2O2 was 4 mL (corresponding to 35.30 mmol),pH was 3.0-3.5. Then the experiment shows that the urea concentration decreases from 500 mg/L to less than 2 mg/L,or is even not detected; under the same dose of H2O2,repetitious addition does better than one-off addition; the reaction time within one minute or to be prolonged has little influence on removal effect. The results verify feasibility of this method.     

A study on Cr（VI） reduction from aqueous solutions by bauxite

The reduction of Cr（Ⅵ） in aqueous solution by using bauxite ore was investigated.Experimental results for Cr（Ⅵ）reduction in aqueous solution depending on some factors such as time,sulfuric acid amount,bauxite dosage,initial Cr（Ⅵ）concentration,formic acid concentration,daylight and temperature were presented.The obtained results show that sulfuric acid amount,bauxite dosage and initial Cr（Ⅵ） concentration of solution are most effective parameters on the reduction process.Also,it has been found that the 60 g/L of bauxite dosage is sufficient to reduce up to 100% of Cr（Ⅵ） from acidic solution under the condition of low initial Cr（Ⅵ） mass concentrations such as 10 mg/L.The reduction reaction is completed within 30 min at 25 ℃ under the experimental conditions：bauxite dosage of 60 g/L,amount of sulfuric acid 40-60 stoichiometric and initial mass concentration of Cr（Ⅵ）,10 mg/L.It was determined that reduction percentage is decreasing with increasing initial Cr（Ⅵ） concentration.The chemical oxygen demand of bauxite ore was found to be 26 mg COD/g.     

CuO-containing multi-walled carbon nanotubes:a novel catalyst for the catalytic ozonation of humic acid in water

CuO particles were attempted to fill in the channel of multi-walled carbon nanotubes (MWCNTs) as novel catalytic materials CuO@MWCNTs used for ozonation of humic acids (HA) in aqueous solution.Catalyst samples were characterized by transmission electron microscopy (TEM),X-ray diffraction (XRD),thermogravimetric analysis (TG) and X-ray photoelectron spectroscopy (XPS).The removal efficiency of HA was promoted in the presence of CuO@MWCNTs compared with that of Al2O3-supported CuO catalyst (CuO/Al2O3) and CuO-coating MWCNTs catalyst (CuO/MWCNTs).The strong synergetic effect in the confinement environment on CuO nanoparticles can attribute to the locally higher pressure due to the lower potential energy of reactants in the channels.Strong interaction happened between the catalyst and reactants,which promoted the decomposition of ozone and the generation of OH.The results of experimental and theoretical investigation confirmed that CuO@MWCNTs promotes the initiation and generation of OH,hence accelerating the degradation of organic pollutants.     

Effect of cobalt loading on reducibility, dispersion and crystallite size of Co／Al2O3 Fischer-Tropsch catalyst

Co/Al2O3 Fischer-Tropsch synthesis catalysts with different cobalt loadings were prepared using incipient wetness impregnation method. The effects of cobalt loading on the properties of catalysts were studied by means of X-ray diffraction (XRD), temperature programmed reduction (TPR), hydrogen temperature programmed desorption (H2-TPD) and O2 titration. Co-support compound formation can be detected in catalyst system by XRD.For the Co/Al2O3 catalysts with low cobalt loading, CoAl2O3 phase appears visibly. Two different reduction regions can be presented for Co/Al2O3 catalysts, which belong to Co3 O4 crystallites (reduction at 320 ““C) and cobalt oxidealumina interaction species (reduction at above 400℃). Increasing Co loading results in the increase of Co3 O4 crystallite size. The reduced Co/Al2O3 catalysts have two adsorption sites, and cobalt loading greatly influences the adsorption behavior. With the increase of cobalt loading, the amount of low temperature adsorption is increased, the amount of high temperature adsorption is decreased, and the percentage reduction and cobalt crystallite size are increased.     

New technique of comprehensive utilization of spent Al2O3 -based catalyst

A new technology was developed to recover multiple valuable elements from the spent Al2O3-based catalyst by X-ray phase analysis and exploratory experiments. The experimental results show that in the condition of roasting temperature of 750 ℃ and roasting time of 30 min, molar ratio of Na2O to Al2O3 of 1.2, the leaching rates of alumina, vanadium and molybdenum in the spent catalyst are 97.2%, 95.8% and 98.9%, respectively. Vanadium and molybdenum in sodium aluminate solution can be recovered by precipitators A and B, and the precipitation rates of vanadium and molybdenum are 94. 8% and 92. 6%. Al（OH）3 was prepared from sodium aluminate solution in the carbonation decomposition process, and the purity of Al2O3 is 99. 9% after calcination, the recovery of alumina reaches 90. 6% in the whole process; the Ni-Co concentrate was leached by sulfuric acid, a nickel recovery of 98. 2% and cobalt recovery over 98.5% can be obtained under the experimental condition of 30% H2SO4, 80 ℃, reaction time 4 h, mass ratio of liquid to solid 8, stirring rate 800 r/min.     

微气泡O3/H2O2深度处理某化工园区二级出水效能与机制

化工园区废水经过二级处理后,仍含有多种有毒污染物,依然对生态环境存在较大风险,为此,建立微气泡O₃/H₂O₂深度处理工艺,研究某工业园区二级出水处理效能,确定最佳工艺参数,探究污染物降解机制,并对处理出水进行毒性评价。结果表明：在pH为7.3、臭氧投加量为60 mg/L、H₂O₂初始投加量为114 mg/L、反应时间为15 min条件下,微气泡O₃/H₂O₂对二级出水中有毒污染物具有良好的降解效果,COD和TOC去除率分别达到47.41%和46.61%;微气泡O₃能够显著提高臭氧利用效率,缩短反应时间;与普通O₃曝气相比,臭氧利用率提高10%,反应时间缩短2/3;微气泡O₃/H₂O₂工艺过程中,有机物去除过程遵循表观二级反应动力学;电子顺磁共振(EPR)技术证明羟基自由基(·OH)参与有机物的降解过程,H...     

Modification of nano-TiO2 by Al2O3 in-situ coating

A novel technology of in-situ coating Al₂O₃ on the surface of H₄TiO₄ was developed to prevent the aggregation of nano-TiO₂ powders and improve the dispersibility and thermal stability in the way of forming a uniform coating layer. The heterogeneous nucleation was conducted to prepare the precursor of nano-TiO₂ and then Al₂O₃ was coated on the surface of precursor. The effects of Al₂O₃ in-situ coating on the properties of nano-TiO₂ were investigated. The results show that H₄TiO₄ can be dispersed well under alkaline condition (pH 8.5) and the heterogeneous nucleation can be controlled easily. The optimized uniform coating layer is obtained by adding 5% (mass fraction) and 10% of Al₂O₃ and the aggregation of nano-TiO₂ powders is effectively inhibited and the dispersibility is obviously improved. The crystal sizes of TiO₂ powders are 12.3, 11.4 and 8.7 nm after coating 0,5% and 10% of Al₂O₃ respectively. Al₂O₃ on the surface of particulates in amorphous phase could increase the thermal stability of nano-particles after calcined at 550 °C. Foundation item: Project(04GK2007) supported by Hunan Industrial Key Project of Science and Technology     

Preparation, characterization and photocatalytic behavior of WO3-TiO2/Nb2O5 catalysts

TiO2/Nb2O5 photocatalyst loaded with WO3 (WO3-TiO2/Nb2O5) was prepared by a modified hydrolysis process, and characterized by X-ray diffractometry, transmission electron microscopy, Raman spectra and UV-Vis diffuse refraction spectroscopy. The photocatalytic activity of WO3-TiO2/Nb2O5 was investigated by employing splitting of water for O2 evolution. The results indicate that WO3 loading can pronouncedly improve the photocatalytic activity of TiO2/Nb2O5 by using Fe3 as an electron acceptor under UV irradiation. The optimum molar fraction of the loaded WO3 is 2%, and the largest speed of O2 evolution for 2% WO3-TiO2/Nb2O5 catalyst is 151.8 μmol/(L·h).     

光催化-Fenton工艺处理废纸制浆废水

为有效处理废纸制浆废水,采用氙灯照射下的光催化-Fenton技术,研究不同反应器、曝气、草酸钾、H2O2投加方式和废水质量浓度对光-Fenton工艺去除废水中TOC或吸光度的影响.结果表明,提高光照强度可提高TOC去除率;添加适量的草酸钾可提高处理效果;H2O2分两次投加可取得较好的处理效果,大大减少对催化剂的需求;在处理过程中使废水暴露于空气可提高有机物的脱氯效果,但曝气对处理效果并无益处.对于TOC为185 mg/L左右的废纸制浆废水,在[H2O2]=1000 mg/L、[Fe(Ⅱ)]=100 mg/L、pH=3.0、温度为30℃的条件下,经过30 min处理,废水的TOC可去除63%以上.     

Polyaniline supported 12-tungstosilicic acid as the catalyst for acetals and ketals synthesis

A novel environmental friendly catalyst, H₄SiW₁₂O₄₀/PAn was prepared and identified by FT-IR, XRD and TG/DTA. The optimal synthetic protocol was a PAn to H₄SiW₁₂O₄₀ mass ratio of 1: 1, a 20 mL of methanol and a reaction time of 2 h at reflux. It was used in catalytic synthesis of ten important ketals and acetals with a high catalytic activity. With an aldehyde/ketone to glycol molar ratio of 1: 1.5 and a 1 wt% catalyst loading, the yields of ketals and acetals could reach 60.0%–93.8 % after 1 h. Funded by the Natural Science Foundation of Hubei Province (No. 2005ABA053), Hubei Key Laboratory of Pollutant Analysis & Reuse Technology, and the National Natural Science Foundation of China (No. 20471044)     

Synthesis of γ-Al2O3 nanoparticles by chemical precipitation method

Highly pure active γ-Al₂O₃ nanoparticles were synthesized from aluminum nitrate and ammonium carbonate with a little surfactant by chemical precipitation method. The factors affecting the synthesis process were studied. The properties of γ-Al₂O₃ nanoparticles were characterized by DTA, XRD, BET, TEM, laser granularity analysis and impurity content analysis. The results show that the amorphous precursor Al(OH)₃ sols are produced by using 0.1 mol/L Al(NO₃)₃ · 9H₂O and 0.16 mol/L (NH₄)₂CO₃ · H₂O reaction solutions, according to the volume ratio 1.33, adding 0.024% (volume fraction) surfactant PEG600, and reacting at 40 °C, 1 000 r/min stirring rate for 15 min. Then, after stabilizing for 24 h, the precursors were extracted and filtrated by vacuum, washed thoroughly with deionized water and dehydrated ethanol, dried in vacuum at 80°C for 8 h, final calcined at 800 °C for 1 h in the air, and high purity active γ-Al₂O₃ nanoparticles can be prepared with cubic in crystal system, O _H ⁷ -FD3M in space group, about 9 nm in crystal grain size, about 20 nm in particle size and uniform size distribution, 131. 35 m²/g in BET specific surface area, 7 – 11 nm in pore diameter, and not lower than 99.93% in purity. Foundation item: Project(03JJY3015) supported by the Natural Science Foundation of Hunan Province     

Synthesis,characterization and catalytic application of H<Subscript>3</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript>/MCM-48 in the esterification of methacrylic acid with n-butyl alcohol

A novel environmental friendly catalyst, H3PW12O40/MCM-48, was prepared by impregnation method. The catalysts were characterized by means of XRD and FT-IR. The synthesis of n-butyl methacrylate catalyzed by H3PW12O40/MCM-48 was studied with methacrylic acid and n-butyl alcohol as reactants. H3PW12O40/MCM-48 is an excellent catalyst for synthesizing n-butyl methacrylate and Keggin structure of H3PW12O40 kept unchanged after being impregnated on surface of the molecular sieve support. Effects of n（methacrylic acid）：n（n-butyl alcohol）, catalyst dosage, cyclohexane（water-stripped reagent） and reaction time on yields of the product were investigated. The optimum conditions have been found, that is, molar ratio of acid to alcohol is 1：1.6, mass ratio of catalyst used to the reactants is 0.5% and reaction time is 2.0 h. Under these conditions, the yield of n-butyl methacrylate can reach 93.7%.     

复合活性钎料钎焊Cu与Al2O3的接头组织及性能

为改善紫铜与Al_2O_3陶瓷的连接强度,采用纳米-Al_2O_3增强的AgCuTi复合钎料(Ag Cu Tip)对紫铜与Al_2O_3陶瓷进行了真空钎焊.采用扫描电镜、能谱分析以及剪切试验对钎焊接头微观组织及力学性能进行了分析.钎焊接头典型界面组织为紫铜/扩散层/铜基固溶体+银基固溶体+Ti_2Cu+Ti_3(Cu,Al)3O/Al_2O_3.纳米-Al_2O_3的添加抑制了Al_2O_3侧反应层的生长,并促进钎缝中形成弥散分布的Ti_2Cu相.随着保温时间的延长,铜侧扩散层和Ti_3(Cu,Al)_3O反应层的厚度逐渐增大.保温时间为20 min时,铜母材向钎料过度溶解,降低了接头性能.当钎焊温度为880°C,保温10 min时,接头抗剪强度最高为82 MPa.纳米颗粒的加入细化了钎缝组织并降低了母材与钎缝热膨胀系数的不匹配,因此提高了接头的连接性能.保温时间可影响界面组织及反应层的厚度,进而影响接头的连接强度.