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.     

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.     

PDMS/陶瓷复合膜用于正丁醇-水体系的渗透汽化分离

Pervaporation has attracted considerable interest owing to its potential application in recovering biobutanol from biomass acetone-butanol-ethanol (ABE) fermentation broth. In this study, butanol was recovered from its aqueous solution using a polydimethylsiloxane (PDMS)/ceramic composite pervaporation membrane. The effects of operating temperature, feed concentration, feed flow rate and operating time on the membrane pervaporation per-formance were investigated. It was found that with the increase of temperature or butanol concentration in the feed, the total flux through the membrane increased while the separation factor decreased slightly. As the feed flow rate increased, the total flux increased gradually while the separation factor changed little. At 40 C and 1% (by mass) butanol in the feed, the total flux and separation factor of the membrane reached 457.4 g•m2•h1 and 26.1, respec-tively. The membrane with high flux is suitable for recovering butanol from ABE fermentation broth.     

以正硅酸乙酯和1,2-二(三乙氧基硅基)乙烷为前驱体制备微孔SiO2复合膜及其气体分离性能

This paper reports on ¬¬¬a new microporous composite silica membrane prepared via acid-catalyzed polymeric route of sol-gel method with tetraethylorthosilicate (TEOS) and a bridged silsesquioxane [1, 2-bis(triethoxysilyl)ethane, BTESE] as precursors. A stable nano-sized composite silica sol with a mean volume size of ~5 nm was synthesized. A 150 nm-thick defect-free composite silica membrane was deposited on disk support consisting of macroporous α-Al2O3 and mesoporous γ-Al2O3 intermediate layer by using dip-coating ap-proach, followed by calcination under pure nitrogen atmosphere. The composite silica membranes exhibit molecular sieve properties for small gases like H2, CO2, O2, N2, CH4 and SF6 with hydrogen permeances in the range of (1-4)107 mol•m2•s1•Pa1 (measured at 200 C, 3.0×105 Pa). With respect to the membrane calcined at 500 C, it is found that the permselectivities of H2 (0.289 nm) with respect to N2 (0.365 nm), CH4 (0.384 nm) and SF6 (0.55 nm) are 22.9, 42 and >1000, respectively, which are all much higher than the corresponding Knudsen values (H2/N2 3.7, H2/CH4 2.8, and H2/SF6 8.5).     

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.     

响应面方法分析代谢产物对类人胶原蛋白表达的影响

Recombinant Escherichia coli BL21 is used to produce human-like collagen. The key constituents of media are optimized using response surface methodology (RSM). Before thermal induction, the highest biomass production and the lowest production of some hazardous by-products, especially acetic acid, were obtained in the media containing 0.085 mol∙L1 glucose and 0.019 mol∙L1 nitrogen (carbon-nitrogen ratio, 4.47︰1). After thermal induction, when the concentrations of glucose and nitrogen in the media were 0.065 mol∙L1 and 0.017 mol∙L1, respectively (carbon-nitrogen ratio, 3.82︰1), the productivity of human-like collagen per cell was the highest while that of acetic acid was the lowest. The extended analysis showed that the production of lactic acid and propionic acid increased while that of some intermediate acids of the tricarboxylic acid cycle decreased if the dose of glucose in-creased.     

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.     

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.     

突变株CTM2降解苯酚和4-氯酚的生物降解特性

The biodegradations of phenol and 4-chlorophenol (4-cp) were studied using the mutant strain CTM 2 obtained by the He-Ne laser irradiation on wild-type Candida tropicalis. The results showed that the capacity of the CTM 2 to biodegrade 4-cp was increased up to 400 mg•L－1 within 59.5 h. In the dual-substrate biodegradation, both velocity and capacity of the CTM 2 to degrade 4-cp increased with low-concentration phenol. A total of 400 mg•L－1 4-cp was completely degraded within 50.5 h in the presence of 300 mg•L－1 phenol. The maximum 4-cp biodegradation could reach 440 mg•L－1 with 120 mg•L－1 phenol. Low-concentration 4-cp caused great inhibition on the CTM 2 to degrade phenol. In addition, the kinetic behaviors were described using the kinetic model proposed in this lab.     

Ni/Al_2O_3催化剂的CO_2-TPD表征

Ni/Al_2O_3催化剂是甲烷二氧化碳重整反应制取合成气研究最多、最具应用潜力的一种催化剂。通过对催化剂进行CO_2-TPD研究,考察还原态Ni/Al_2O_3催化剂的CO_2脱附特性。结果表明,浸渍法制备的Ni/Al_2O_3催化剂CO_2脱附曲线呈现双峰,分别在(60~65)℃和(350~380)℃出现高低温两个活性位;高温CO_2吸附量为3.0 cm~3·g~(-1),低温CO_2吸附量为24.0 cm~3·g~(-1)。催化剂的CO_2吸附量与其Ni含量无关。考察选用不同载体的CO_2脱附行为,发现以Al_2O_3为载体的催化剂CO_2吸附量是MgO和SiO_2为载体催化剂的2~4倍,以TiO_2为载体的催化剂几乎不吸附CO_2。     

The effect of different Co phase structure (FCC/HCP) on the catalytic action towards the hydrogen storage performance of MgH2

High hydrogen desorption temperature and sluggish reaction kinetics are the major limitations for the practical application of MgH₂. In this study, Co particles with a face centered cubic (FCC) structure and a hexagonal close packed (HCP) structure were prepared facilely and proved to be good catalysts for magnesium hydride. Co particles with FCC structure presented better catalytic effect on MgH₂ than that with HCP structure. Both 7% (mass) Co FCC and HCP particle modified MgH₂ decreased the initial dehydrogenation temperature from 301.3 ℃ to approximately 195.0 ℃, but 7% (mass) Co with FCC structure modified MgH₂ has a faster desorption rate, and around 6.5% (mass) H₂ was desorbed in 10 min at 325 ℃. Hydrogen uptake was detected at 70 ℃ under 3.25 MPa hydrogen pressure and 6.0% (mass) H₂ was recharged in 40 min at 150 ℃. The hydrogen desorption and absorption activation energy for 7% (mass) FCC Co modified MgH₂ was significantly decreased to (76.6±8.3) kJ·mol^-1 and (68.3±6.0) kJ·mol^-1, respectively. Thermodynamic property was also studied, the plateau pressures of MgH₂ + 7% (mass) FCC Co were determined to be 0.14, 0.28, 0.53 and 0.98 MPa for 300 ℃, 325 ℃, 350 ℃ and 375℃. The decomposition enthalpy of hydrogen (ΔH) for MgH₂ + 7% (mass) FCC Co was (80.6±0.1) kJ·mol^-1, 5.8 kJ·mol^-1 lower than that of as-prepared MgH₂. Moreover, cycling performance for the first 20 cycles revealed that the reaction kinetics and capacity of MgH₂-FCC Co composite remained almost unchanged. The result of density functional theory calculation demonstrated that cobalt could extract the Mg—H bond and reduced the decompose energy of magnesium hydride. Our paper can be presented as a reference for searching highly effective catalysts for hydrogen storage and other energy-related research fields.     

Direct synthesis of single-phase α-CaSO4·0.5H2O whiskers from waste nitrate solution

Single-phase α-CaSO₄·0.5H₂O whiskers were directly synthesized from waste Ca(NO₃)₂ solution using a hydrothermal method, and HNO₃ was synchronously regenerated. The effects of reaction temperature and Ca²⁺ concentration on the phase composition and morphology of products were determined by X-ray diffraction and optical microscopy. On the basis of the experimental results, the formation diagram of α-CaSO₄·0.5H₂O was plotted within the range of 5-35 g·L^-1 Ca²⁺ and 115℃-150℃. In addition, the conditions of the direct synthesis of α-CaSO₄·0.5H₂O were determined. Well-crystallized, single-phase α-CaSO₄·0.5H₂O whiskers with high aspect ratios (length, 1785 μm; diameter, 10.63 μm; aspect ratio, 168) and HNO₃ (70.25 g·L^-1) were obtained at the optimal conditions of 25 g·L^-1 Ca²⁺ and 125℃.     

油菜秸秆高温水解液中单糖组分的高效液相色谱测定

建立了高温水中CO₂催化油菜秸秆水解体系中单糖的高效液相色谱（HPLC）分析的方法。其分析采用Prevail^TM ES糖柱,蒸发光散射检测器（ELSD）,流动相为乙腈/水（体积比80∶20）,等度洗脱,流速0.8 mL/min,柱温35 ℃,漂移管温度95 ℃,干燥空气作为载气,流速为3.0 L/min。20 min内阿拉伯糖、木糖、果糖、甘露糖、半乳糖和葡萄糖6种单糖得到了较好的分离,各物质线性回归方程的相关系数R²为0.999 1~0.999 7,其平均回收率为95.3 %~108.0 %,相对标准偏差（RSD）均小于3 %。     

Concentration control of volatile organic compounds by ionic liquid absorption and desorption

Volatile organic compounds (VOCs) are difficult to be eliminated safely and effectively because of their large concentration fluctuations. Thus, maintaining a stable concentration of VOCs is a significant study. In this research, H₂O, Tween-80,[Emim]BF₄,[Emim]PF₆, and[Hnmp]HSO₄ were applied to absorb and desorb simulated VOCs. The ionic liquid[Emim]BF₄ demonstrated the best performance and was thus selected for further experiments. As the ionic liquid acted as a buffer, the toluene concentration with a fluctuation of 2000-20000 mg·m^-3 was stabilized at 6000-12000 mg·m^-3. Heating distillation (90℃) was highly efficient to recover[Emim]BF₄ from toluene. The regenerated[Emim]BF₄ could retain its initial absorption capacity even after multiple cycles. Moreover,[Emim]BF₄ had the same buffer function on various aromatic hydrocarbons.     

阳离子三联表面活性剂/NaSS/St蠕虫状胶束及性能

引言蠕虫状胶束是基于非共价键作用的表面活性剂分子的自组装结构[1-2],胶束处于断裂-重新生成的动态平衡中[3-4]。由于其具有独特的流变性质,被广泛应用于清洁压裂中,其中使用的主剂大多为普通单链的阳离子表面活性剂、阴离子表面活性剂及两性离子表面活性剂[5-6]。然而,蠕虫状胶束对温度、离子强度、应力等[7-9]因素的变化过于敏感,     

Adsorption equilibrium for Z-ligustilide on C18-bonded silica from supercritical carbon dioxide

Adsorption equilibrium is of great importance for the preparative supercritical fluid chromatography(pre-SFC) in defining supercritical adsorption behavior and the industrial amplification.This paper presents adsorption isotherms of Z-ligustilide from supercritical carbon dioxide(SC-CO_2) on C18-bonded silica.Adsorption behavior was studied at 305.15 K,313.15 K and 323.15 K with SC-CO_2 density varying from 0.687 g·cm~(-3) to0.863 g·cm~(-3) with the elution by characteristic points(ECP) method.The adsorption amount of Z-ligustilide from SC-CO_2 on C18-bonded silica decreased with the increasing density of the mobile phase as well as the increasing temperature.Adsorption equilibrium data were fitted by Langmuir and Freundlich isotherm models,and the Langmuir isotherm model performed better for describing the whole adsorption process on the column.The monolayer saturation adsorption capacity of Z-ligustilide is in the range of 3.0 × 10~(-4) mg·cm~(-3) to5.5 × 10~(-4) mg·cm~(-3) with an average value of 4.0 × 10~(-4) mg·cm~(-3).     

Adsorption of congo red on mesoporous activated carbon prepared by CO2 physical activation

This research demonstrates the production of mesoporous activated carbon from sargassum fusiforme via physical activation with carbon dioxide. Central composite design was applied to conduct the experiments at different levels by altering three operating parameters. Activation temperature(766–934 ℃), CO_2 flow rate(0.8–2.8 L·min(~-1)) and activation time(5–55 min) were the variables examined in this study. The effect of parameters on the specific surface area, total pore volume and burn-out rate of activated carbon was studied,and the influential parameters of methylene blue adsorption value were identified employing analysis of variance. The optimum conditions for maximum methylene blue adsorption value were: activation temperature = 900 ℃, activation time = 29.05 min and CO_2 flow rate = 1.8 L·min(~-1). The activated carbon produced under optimum conditions was characterized by BET, FTIR and SEM. The adsorption behavior on congo red was studied. The effect of parameters on the adsorbent dosage, temperature, PH and initial congo red concentration was investigated. The adsorption properties of the activated carbon were investigated by kinetics. The equilibrium removal rate and maximum adsorption capacity reaches up to 94.72%, 234 mg·g-1,respectively when initial congo red concentration is 200 mg·L~(-1) under adsorbent dosage(0.8 g · L~(-1)),temperature(30℃), PH7.     

Amine-immobilized HY zeolite for CO2 capture from hot flue gas

Solid amine-based adsorbents were widely studied as an alternative to liquid amine for post-combustion CO₂ capture (PCC). However, most of the amine adsorbents suffer from low thermal stability and poor cyclic regenerability at the temperature of hot flue gases. Here we present an amine loaded proton type Y zeolite (HY) where the amines namely monoethanolamine (MEA) and ethylenediamine (ED) are chemical immobilized via ionic bond to the zeolite framework to overcome the amine degradation problem. The MEA and ED of 5%, 10% and 20% (mass) concentration – immobilized zeolites were characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, and N₂ -196 ℃ adsorption to confirm the structure integrity, amine functionalization, and surface area, respectively. The determination of the amine loading was given by C, H, N elemental analysis showing that ED has successfully grafted almost twice as many amino groups as MEA within the same solvent concentration. CO₂ adsorption capacity and thermal stability of these samples were measured using thermogravimetric analyser. The adsorption performance was tested at the adsorption temperature of 30, 60 and 90 ℃, respectively using pure CO₂ while the desorption was carried out with pure N₂ purge at the same temperature and then followed by elevated temperature at 150 ℃. It was found that all the amine@HY have a substantial high selectivity of CO₂ over N₂. The sample 20% ED@HY has the highest CO₂ adsorption capacity of 1.76 mmol·g^-1 at 90 ℃ higher than the capacity on parent NaY zeolite (1.45 mmol·g^-1 only). The amine@HY samples presented superior performance in cyclic thermal stability in the condition of the adsorption temperature of 90 ℃ and the desorption temperature of 150 ℃. These findings will foster the design of better adsorbents for CO₂ capture from flue gas in post-combustion power plants.     

Infrared thin layer drying of saffron (Crocus sativus L.) stigmas: Mass transfer parameters and quality assessment

Saffron is the most precious and expensive agricultural product. A dehydration treatment is necessary to convert Crocus sativus L. stigmas into saffron spice. To the best of our knowledge, no information on mass transfer parameters of saffron stigmas is available in the literature. This study aimed at investigating the moisture transfer parameters and quality attributes of saffron stigmas under infrared treatment at different temperatures(60,70, …, 110 °C). It was observed that the dehydration process of the samples occurred in a short accelerating rate period at the start followed by a falling rate period. The effective moisture diffusivity and convective mass transfer coefficient were determined by using the Dincer and Dost model. The diffusivity values varied from1.1103 × 10~(-10)m~2·s~(-1)to 4.1397 × 10~(-10)m~2·s~(-1) and mass transfer coefficient varied in the range of 2.6433 × 10~(-7)–8.7203 × 10~(-7)m·s~(-1). The activation energy was obtained to be 27.86 k J·mol~(-1). The quality assessment results showed that the total crocin content increased, when the temperature increased up to90 °C but, in higher temperatures, the amount of crocin decreased slightly. The total safranal content of the samples decreased slightly when drying temperature increased from 60 °C to 70 °C and then continuously increased up to 110 °C. Also, the amount of picrocrocin increased from 83.1 to 93.3 as the drying temperature increased from 60 °C to 100 °C.