用CuO/A12O3/堇青石催化剂选择性催化还原脱硝的实验和动力学研究

The CuO/γ-Al2O3/cordierite catalyst, after being sulfated by sulfur dioxide (SO2) at 673 K, exhibits high activities for selective catalytic reduction (SCR) of nitrogen oxide (NO) with ammonia (NH3) at 573-723 K. The intrinsic kinetics of SCR of NO with NH3 over CuO/γ-Al2O3/cordierite catalyst has been measured in a fixed-bed reactor in the absence of internal and external diffusions. The experimental results show that the reaction rate can be quantified by a first-order expression with activation energy of 94.01 kJ•mol1 and the corresponding pre-exponential factor of 3.39×108 cm3•g1•s1 when NH3 is excessive. However, when NH3 is not enough, an Eley-Rideal kinetic model based on experimental data is derived with Ea of 105.79 kJ•mol1, the corresponding A of 2.94×109 cm3•g1•s1, heat of adsorption ΔHads of 87.90 kJ•mol1 and the corresponding Aads of 9.24 cm3•mol1. The intrinsic kinetic model obtained was incorporated in a 3D mathematical model of monolithic reactor, and the agreement of the prediction with experimental data indicates that the present kinetic model is adequate for the reactor design and engineering scale-up.     

氨改性的介孔二氧化硅的直接合成和CO2吸附

Amine-functionalized mesoporous silica was prepared by using lauric acid and N-stearoyl-l-glutamic acid as structure directing agents via the SN+-I mechanism and applied to CO2 adsorption at room temperature. With γ-aminopropyltriethoxysilane as co-structure directing agent and due to the direct electrostatic interaction with anionic surfactant, most of the amino groups were uniformly distributed at the inner surface of pores and the performance was stable. The amine-functionalized mesoporous silica was characterized by Fourier transform infrared spectrometer, X-ray diffraction, nitrogen physisorption and thermogravimetric analysis. The CO2 adsorption capacity was measured by digital recording balance. At the room temperature and under the atmospheric pres-sure, the adsorption capacity of LAA-AMS-0.2 for CO2 and N2 is 1.40 mmol•g1 and 0.03 mmol•g1, respectively, indicating high separation coefficient of CO2/N2.     

D318阴离子交换树脂对铼（VII）的吸附

The adsorption and mechanism of Re(VII) on resin D318 were studied using chemical methods and IR spectrometry. At pH 5.2, the static and dynamic saturation adsorption capacities were 351.4 and 366.5 mg&;#8226;g&;#61485;1, respectively. The adsorption behavior obeyed the Freundlich empirical equation and the adsorption rate constant k298 was 6.37×10&;#61485;4 s&;#61485;1. The desorption percentage was up to 99.7% when 2.0 mol&;#8226;L&;#61485;1 KSCN was used for dynamic desorption.     

硫酸铁改性颗粒活性氧化铝除氟的等温线研究

The adsorption equilibrium of a fluoride solution on 1-2 mm granular activated alumina modified by Fe2(SO4)3 solution was investigated. The experiments were conducted using a wide range of initial fluoride concentrations (0.5 to 180 mg•L1 at pH ~7.0) and an adsorbent dose of 1.0 g•L1. The application of Langmuir and Freundlich adsorption isotherm models (linear and nonlinear forms) generally showed that a single Langmuir or Freundlich equation cannot fit the entire concentration gap. Experimental data on low equilibrium concentrations (0.1 to 5.0 mg•L1) was in line with both Langmuir and Freundlich isotherm models, whereas that of high equilibrium concentrations (5.0 to 150 mg•L1) was more in line with the Freundlich isotherm model. A new Langmuir- Freundlich function was used for the entire concentration gap, as well as for low and high concentrations.     

P507溶于煤油作为载体的一种新型分散组合液膜对Eu3+的分离

The separation of Eu3+ is studied with a dispersion combined liquid membrane (DCLM), in which polyvinylidene fluoride membrane (PVDF) is used as the liquid membrane support, dispersion solution containing HCl solution as the stripping solution, and 2-ethyl hexyl phosphonic acid-mono-2-ethyl hexyl ester (P507) dissolved in kerosene as the membrane solution. The effects of pH value, initial concentration of Eu3+ and different ionic strength in the feed phase, volume ratio of membrane solution to stripping solution, concentration of HCl solution, concentration of carrier, different stripping agents in the dispersion phase on the separation are investigated. The optimum condition for separation of Eu3+ is that concentration of HCl solution is 4.0 mol•L1, concentration of carrier is 0.16 mol•L1, and volume ratio of membrane solution to stripping solution is 30︰30 in the dispersion phase, and pH value is 4.2 in the feed phase. The ionic strength has no significant effect on separation of Eu3+. Under the optimum condition, when the initial concentration of Eu3+ is 0.8×104 mol•L1, the separation percentage of Eu3+ is 95.3% during the separation time of 130 min. The kinetic equation is developed in terms of the law of mass diffusion and the theory of interface chemistry. The diffusion coefficient of Eu3+ in the membrane and the thickness of diffusion layer between feed phase and membrane phase are obtained and their values are 1.48×107 m2•s1 and 36.6 μm, respectively. The results obtained are in good agreement with literature data.     

利用两级UASB消化处理实现木薯燃料乙醇的水循环型生产

Considering limited success in target-hitting discharge from alcohol industry, our attention was directed toward a recycling use of distillery spentwash (DS) in cassava bioethanol production by using a two-stage up-flow anaerobic sludge blanket bioremediation (TS-UASBB). With the TS-UASBB, , COD, N and P in the effluent from the DS degraded significantly and their concentrations were kept at 0.2 g•L1, 2.0 g•L1, 1.0 g•L1 and 15 mg•L1, respectively, in 13 batch processes for water-recycled ethanol fermentation. With the effluent used directly as dilution water, no heat-resistant bacteria were found alive. The thirteen-batch ethanol production individually achieved 10% after 48 h fermentation. The starch utilization ratio and total sugar consumption were 90% and 99.5%, respectively. The novel water-recycled bioethanol production process with ethanol fermentation and TS-UASBB has a considerable potential in other starchy and cellulosic ethanol production.     

超临界萃取技术结合超声强化技术提取鹿茸中性激素和IGF-1

Supercritical CO2 (SC-CO2) extraction technology and ultrasonic technology were used to extract two active sex hormones, estradiol and progesterone, and insulin-like growth factor-1 (IGF-1) from antler velvet. The effects of SC-CO2 extraction condition on the extraction yield and content of sex hormones, the ultrasonic extraction condition on the content of IGF-1 and the SC-CO2 extraction condition on the activity remaining of IGF-1 were studied. The optimal conditions were obtained. The experimental results showed that, in presence of 75% ethanol as the co-solvent, the mean yield and content of estradiol and progesterone were 87.67 pg•g－1 and 1224.10 pg•g－1, 12.38 ng•g－1 and 354.06 ng•g－1, respectively, with extraction pressure of 30 MPa, temperature of 35°C, extraction time of 30 min and CO2 consumption of 15 L•g－1 at the flow rate of 2.0 L•min－1. The highest content of IGF-1 was 7425.75 ng•g－1 antler velvet residue, when the pH10 ammonia-ammonium chloride buffer solution was used as the solvent, the ratio of solvent to sample was 20/1 (volume/mass), the extraction temperature was 0-35°C, and the ex-traction time was 4×15 min. Under these conditions, 93.68% activity remaining of IGF-1 in the residue was ob-tained, while little IGF-1 activity exists in traditional residue. The experimental results indicate that the technology of SC-CO2 with co-solvent is of advantage for getting high content sexual hormones and keeping high activity of IGF-1 in the residue, which can not be achieved by traditional extraction methods.     

大团囊虫草L2分离鉴定及其发酵工艺优化

A strain isolated from the fruiting body of a fungus parasitized on Elaphomyces was identified as Cordyceps ophioglossoides based on the morphological characteristics and the analysis of ITS-5.8s rDNA sequence. The optimal medium composition (g•L－1), containing sucrose 66.0, yeast powder 10.0, silkworm chrysalises digest 30.0, MgSO4•7H2O 0.4, and KH2PO4 0.4, was found using fractional factorial design and a central composite design, and the optimization of cultural conditions obtained a result of seed age 6 days, inoculum size 6% (by volume), initial pH 5.6, temperature 24°C, shaking speed 160 r•min－1 by one-factor-at-a-time method. The maximum biomass reached about 20.2 g•L－1 after 90 hours culture under the optimal conditions. Elementary pharmacological activities showed that mycelia of C. ophioglossoides L2 from submerged culture promoted uterus growth in estrogen- depleted mice. In the 15-litre scale-up fermentation, the mycelial biomass was around 19.1 g•L－1, indicating a promising prospect for this biotechnology and the potency to develop its medical value.     

ZnAl类水滑石制备温度对吸附剩余污泥脱水液中磷酸根的影响

A group of Zn-Al layered double hydroxides (LDHs) were synthesized at different temperatures from 25–90 °C in order to investigate the influence of synthesis temperature on characteristics of the LDHs and their phosphate adsorption behaviour. The results reveal that an increase in the synthesis temperature generally improves the specific surface area of the sample and the phos-phate adsorption capacity. The significantly enhanced crystallinity of the Zn-Al-30, synthesized at 30 °C, leads to a remarkable de-crease in the specific surface area and consequently a poor phosphate adsorption capacity. It is suggested that the surface adsorption plays an important role in the phosphate uptake by the Zn-Al LDHs. Zn-Al-70 presents a relatively higher crystallinity and a lower specific surface area, compared with Zn-Al-60 and Zn-Al-80, but the highest phosphate adsorption capacity, indicating that surface adsorption is only one of the pathways for phosphate removal. The phosphate adsorption by the Zn-Al follows a pseudo-second-order kinetic equation. The adsorption isotherms fit Langmuir models, and the maximum adsorption capacities of the Zn-Al-25, Zn-Al-50 and Zn-Al-70 are estimated to be 17.82, 21.01 and 27.10 mg•g1 adsorbent, respectively.     

苯为前驱体的稠环芳烃的自由基反应机理的量子化学研究

The free-radical growth mechanisms for the formation of polycyclic arenes (PCAs) were constructed based on the block unit of benzene, and were calculated by the quantum chemistry PM3 method. Two kinds of reaction paths are proposed and discussed. The calculation results show that the formation of PCAs is only controlled by the elimination of H atom from benzene, and the corresponding activation energy is 307.60 kJ•mol－1. H2 is only the ef-fluent gas in our proposed reaction mechanism, and the calculation results are in accord with the experimental facts.     

D72树脂对镨(Ⅲ)的吸附性能(英文)

In this work, the feasibility of using a macroporous strong acid ion exchange resin (D72) as an adsorbent for praseodymium (Ⅲ) was examined. The adsorption behavior and mechanism were investigated with various chemical methods and IR spectrometry. The results showed that the loading of Pr (III) ions was strongly dependent on pH of the medium and the optimal adsorption condition is in HAc-NaAc medium with pH value of 3.0. Adsorption kinetics of Pr (III) ions onto D72 resin could be best described by pseudo-second-order model. The maximum adsorption capacity of D72 for Pr (Ⅲ) was evaluated to be 294 mg·g 1 for the Langmuir model at 298K. The apparent activation energy, E a , was 14.71 kJ·mol 1 . The calculated data of thermodynamic parameters, ΔSΘ value of 100 J·mol 1 ·K 1 and ΔHΘ value of 8.89 kJ·mol 1 , indicate the endothermic nature of the adsorption process, while a decrease of ΔGΘ with increasing temperature indicates the spontaneous nature of the adsorption process. Finally, Pr (Ⅲ) can be eluted by using 1.00 mol·L 1 HCl-0.50 mol·L 1 NaCl solution and the D72 resin can be regenerated and reused. Thomas model was successfully applied to experimental data to predict the breakthrough curves and to determine the characteristic parameters of the column useful for process design. The characterization before and after adsorption of Pr (Ⅲ) ions on D72 resin was conformed by IR.     

Removal of chromium (VI) from aqueous solutions using quaternized chitosan microspheres

In this study, quaternized chitosan microspheres (QCMS) were prepared and its Cr(VI) removal potential was investigated. Batch experiments were conducted to examine kinetics, adsorption isotherm, pH effect, and thermodynamic parameters. Equilibrium was attained within 50 min and maximum removal of 97.34% was achieved under the optimum conditions at pH 5. Adsorption data for Cr (VI) uptake by the QCMS were analyzed according to Langmuir, Freundlich, and Temkin adsorption models. The maximum uptake of Cr(VI) was 39.1 mg·g^-1. Thermodynamic parameters for the adsorption system were determinated at 293 K, 303 K, 313 K and 323 K. (ΔH°=16.08 kJ·mol^-1;ΔG°=-5.84 to -8.08 kJ·mol^-1 and ΔS°=74.81 J·K^-1·mol^-1). So the positive values of both ΔH° and ΔS° suggest an endothermic reaction and increase in randomness at the solid-liquid interface during the adsorption.ΔG° values obtainedwere negative indicating a spontaneous adsorption process. The kinetic process was described by a pseudo-second-order rate equation very well. The results of the present study indicated that the QCMS could be considered as a potential adsorbent for Cr (VI) in aqueous solutions.     

Study of the kinetic behaviour of biomass and coal during oxyfuel co-combustion

In this study, the thermogravimetric analysis(TGA) method has been used to evaluate the kinetic behavior of biomass, coal and its blends during oxyfuel co-combustion. The thermogravimetric results have been evaluated by the Coats–Redfern method and validated by Criado's method. TG and DTG curves indicate that as the oxygen concentration increases the ignition and burn out temperatures approach a lower temperature region. The combustion characteristic index shows that biomass to coal blends of 28% and 40% respectively can achieve enhanced combustion up to 60% oxygen enrichment. In the devolatilization region, the activation energies for coal and blends reduce while in the char oxidation region, they increase with rise in oxygen concentration. Biomass, however, indicates slightly different combustion characteristic of being degraded in a single step and its activation energies increase with rise in oxygen concentration. It is demonstrated in this work that oxygen enrichment has more positive combustion effect on coal than biomass. At 20% oxygen enrichment, 28% and 40% blends indicate activation energy of 132.8 and 125.5 kJ·mol~(-1) respectively which are lower than coal at 148.1 kJ·mol~(-1) but higher than biomass at 81.5 kJ·mol~(-1) demonstrating synergistic effect of fuel blending. Also, at char combustion step, an increase in activation energy for 28% blend is found to be 0.36 kJ·mol~(-1) per rise in oxygen concentration which is higher than in 40% blend at 0.28 kJ·mol~(-1).     

Adsorption equilibrium and the effect of honeycomb heat exchanging device on charge/discharge characteristic of methane on MIL-101(Cr) and activated carbon

Experiments were conducted for developing suitable ANG adsorbents for vehicular applications. MIL^-101 and activated carbon samples were respectively prepared by hydrothermal and chemical activation methods. Two samples were undergone structure analysis on adsorption data of nitrogen at 77.15 K, and adsorption data of methane were then volumetrically measured within temperature-pressure range 293.15 K-313.15 K and 0-8 MPa. A conformable vessel in volume 2.5 L was employed for charge/discharge tests under the flow rate 10-30 L·min^-1. It shows that limit isostreic heat of methane adsorption is respectively about 25.15 kJ·mol^-1 and 22.94 kJ·mol^-1 on the activated carbon and the MIL-101, and isosteric heat within the experimental condition is 14-19.5 kJ·mol^-1; employing a smaller charge/discharge flow rate can weaken the temperature fluctuation of the adsorbent bed and increase the charge/discharge amount; employing honeycomb heat exchanging device enhance the thermal conductivity of the adsorbent bed by consuming a negligible part of volume of the vessel. It suggests that a smaller flow rate for charge/discharge should be employed, and MOFs together with the honeycomb heat exchanging device are promising for practical applications.     

Molecular dynamic simulation of carbon dioxide,methane, and nitrogen adsorption on Faujasite zeolite

Removing impurities such as carbon dioxide and nitrogen from natural gas is a technical challenge and one of the major concerns in natural gas treatment process. In this study, adsorption of CH₄, N₂, and CO₂ on the Faujasite(FAU) zeolite has been studied using molecular dynamics simulation at temperatures of 293, 308, and 323 K and pressures up to 1 MPa. COMPASS force field was used to model the interactions between zeolite and guest molecules. Ewald and atom-bas...     

Removal of Reactive Red 198 from aqueous solution by combined method multi-walled carbon nanotubes and zero-valent iron:Equilibrium,kinetics, and thermodynamic

Dyes often include toxic,carcinogenic compounds and are harmful to humans' health.Therefore,removal of dyes from textile industry wastewater is essential.The present study aimed to evaluate the efficiency of the combination of zero valent iron(ZVI) powder and multi-walled carbon nanotubes(MWCNTs) in the removal of Reactive Red 198(RR198) dye from aqueous solution.This applied research was performed in a batch system in the laboratory scale.This study investigated the effect of various factors influencing dye removal,including contact time,p H,adsorbent dose,iron powder dose,initial dye concentration,and temperature.The equilibrium adsorption data were analyzed using three common adsorption models:Langmuir,Freundlich and Temkin.Besides,kinetic and thermodynamic parameters were used to establish the adsorption mechanism.The results showed,in pH =3,contact time = 100 min,ZVI dose = 5000 mg·L~(-1),and MWCNTs dose = 600 mg·L~(-1)in 100 mg·L~(-1)dye concentration,the adsorption efficiency increased to 99.16%.Also,adsorption kinetics was best described by the pseudo-second-order model.Equilibrium data fitted well with the Freundlich isotherm(R2= 0.99).The negative values of ΔG0and the positive value of ΔH0(91.76) indicate that the RR198 adsorption process is spontaneous and endothermic.According to the results,the combination of MWCNTs and ZVI was highly efficient in the removal of azo dyes.     

The performance of activated carbon/NiFe2O4 magnetic composite to retain heavy metal ions from aqueous solution

A novel magnetic activated carbon composite(AC/NiF) was synthesized by a precipitation method and applied in retention of Cu(Ⅱ),and Zn(Ⅱ) ions from aqueous solutions.The impact of different sorption parameters such as:equilibration time,solution pH value,competing cations and ionic strength on the amount sorbed of Cu(Ⅱ),and Zn(Ⅱ) was clarified.Results illustrated that the magnetic composite had retention ability towards both metal ions significantly higher than that of activated carbon(AC).The magnetic composite exhibited an affinity to adsorb Cu(Ⅱ) higher than Zn(Ⅱ) ions.The maximum sorption capacities(Q_(max)) of the applied magnetic composite(AC/NiF)towards Cu(Ⅱ) and Zn(Ⅱ) were 105.8 and 75.1 mg·g~(-1),respectively.Retention of Cu(Ⅱ) and Zn(Ⅱ) was proposed to be achieved though an ion exchange and surface adsorption in neutral conditions,while precipitation was believed to be the relevant mechanism in their removal from basic solutions.The kinetic studies showed that sorption process followed the kinetics of pseudo-second-order reactions with rate constant of 3 × 10~(-3) and 2 × 10~(-3) min~(-1)for sorption of Cu(Ⅱ) and Zn(Ⅱ) onto AC/NiF composite.Removal of Cu(Ⅱ) slightly decreased with increasing the ionic strength of aqueous solution,using NaCl as a background electrolyte.In contrast,presence of Mn(Ⅱ),Mg(Ⅱ)and Co(Ⅱ) in reaction solutions highly depressed the sorption of Cu(Ⅱ) and Zn(Ⅱ) with a competing efficiency followed the order:Mg(Ⅱ) Mn(Ⅱ) Co(Ⅱ).The magnetic composite was rapidly recovered from aqueous solution by an external magnetic field,and effectively regenerated using 0.1 mol L~(-1) HCl and 0.1 mol L~(-1) FeCl_3 as eluents.Sorption of Cu(Ⅱ) and Zn(Ⅱ) onto the surface of AC/NiF composite occurred via a spontaneous reaction.And thermodynamically favorable process had ΔH~o values of 30.9 kJ·mol~(-1) and 19.7 kJ·mol~(-1),respectively.The results confirm that the magnetic composite can be viewed as a promising novel composite opens new opportunities for the attainment of required adsorption and operative magnetic separation.     

Investigation on molar heat capacity,standard molar enthalpy of combustion for guaiacol and acetyl guaiacol ester

The molar heat capacities(C_p) of guaiacol(CAS 90-50-1) and acetyl guaiacol ester(AGE, CAS 613-70-7) were determinated from 290 K to 350 K by differential scanning calorimetry(DSC), and expressed as a function of temperature. Two kinds of group contribution models were used to estimate the molar heat capacities of both guaiacol and AGE, the average relative deviation is less than 10%. The standard molar enthalpies of combustion of guaiacol and AGE were- 3590.0 k J·mol~(-1)and- 4522.1 k J·mol~(-1) by a precise thermal isolation Oxygen Bomb Calorimeter. The standard molar enthalpies of formation of guaiacol and AGE in a liquid state at298.15 K were calculated to be- 307.95 k J·mol~(-1) and- 448.72 k J·mol~(-1), respectively, based on the standard molar enthalpies of combustion. The thermodynamic properties are useful for exploiting the new synthesis method, engineering design and industry production of AGE using guaiacol as a raw material.     

Adsorption of methyl orange from aqueous solution by composite magnetic microspheres of chitosan and quaternary ammonium chitosan derivative

Novel composite magnetic microspheres containing chitosan and quaternary ammonium chitosan derivative (CHMMs) were prepared by inverse suspension method, and used for the methyl orange (MO) removal from aqueous solutions. The CHMMs were characterized by a scanning electron microscope, a transmission electron microscope, and Fourier transform infrared spectroscopy, respectively. Compared with the chitosan beads, the incorporation of quaternary ammonium chitosan derivative significantly reduced the particle size. The MO adsorption by CHMMs was investigated by batch adsorption experiments. The adsorption kinetics was conformed to the pseudo second-order kinetics equation. The adsorption isotherm followed the Langmuir model better than the Freundlich model and the calculated maximum MO adsorption capacity was 266.6 mg·g^-1 at 293 K. Thermodynamic studies indicated that the MO adsorption was endothermic in nature with the enthalpy change (ΔH°) of 99.44 kJ·mol^-1. The CHMMs had a stable performance for MO adsorption in the pH range of 4-10, but high ionic strength deteriorated the MO removal due to the shielding of the ion exchange interaction. A 1 mol·L^-1 NaCl solution could be used to regenerate the exhausted CHMMs. The proposed CHMMs can be used as an effective adsorbent for dye removal or recovery from the dye wastewater.