Nanofiltration and reverse osmosis thin film composite membrane module for the removal of dye and salts from the simulated mixtures

Nanofiltration (NF) and reverse osmosis (RO) thin film composite polyamide membrane modules were used to remove the color from the contaminated solution mixture. The feasibility of membrane processes for treating simulated mixture by varying the feed pressures (100-400 psi) and feed concentrations was studied to assess the separation performance of both NF and RO membranes. It was found that the efficiency of NF and RO membranes used in the treatment of colored water effluents was greatly affected by the presence of salts and dyes in the mixture. Color removal by NF with a high rejection of 99.80% and total dissolved solids (TDS) of 99.99% was achieved from RO by retaining significant flux rate compared to pure water flux, which suggested that membranes were not affected by fouling during the simulated wastewater process operation. The effect of varying concentrations of Na₂SO₄ salt and methyl orange (MO) dye on the performance of spiral wound membranes was determined. Increasing the dye concentration from 500 to 1000 mg/L resulted in a decrease of salt rejection at all operating pressures and for both concentrations of 5000 and 10,000 mg/L as the feed TDS. Increasing the salt concentration from 5000 to 10,000 mg/L resulted in a slight decrease in dye removal.     

Desulfurization of digester gas: prediction of activated carbon bed performance at low concentrations of hydrogen sulfide

Three chemically modified/impregnated activated carbons (supplied by manufactures) were used for adsorption–catalytic removal of hydrogen sulfide from digester gas. The performance of samples was studied in dynamic conditions at 1000, 2000 and 5000 ppm of H₂S in digester gas. The results showed differences in the H₂S removal capacities related to the type of carbon and conditions of the experiment. A decrease in H₂S concentration resulted in an increase in a breakthrough capacity, which is linked to slow kinetics of oxidation process. No significant changes were observed when the oxygen content increased from 1 to 2% and the temperature from 38 to 60 °C. On the surface of carbons studied hydrogen sulfide was oxidized predominantly to sulfur, which was deposited in micropores, either on the walls or at the pore entrances. The capacities at low concentrations, 50 and 100 ppm, of H₂S were determined using an approach based on known theoretical solution of a dynamic model where the parameters of the model were determined from the experimental data at a high concentration of an adsorbate.     

聚电解质静电沉积改性制备高性能反渗透膜

利用次氯酸钠溶液对商品反渗透膜表面进行氯化处理,然后将聚阳离子电解质壳聚糖通过静电吸附作用沉积在RO膜的表面,系统地研究了氯化过程的pH、氯化时间、次氯酸钠浓度、壳聚糖浓度及其沉积时间对膜性能的影响,以制备出高通量、高截留率的RO膜。在压力1.55 MPa、原料液温度（298±1）K的条件下,测定RO膜处理2000 μg·g^-1氯化钠溶液的水通量和截留率。结果表明,当pH=9、氯化时间为30 min、次氯酸钠浓度为1000 mg·L^-1时,水通量较原膜提高了约19.89%,截留率略有提高;当壳聚糖浓度为0.1%（质量分数）、沉积时间为30 min时,改性膜的接触角降低到34.88°,亲水性提高,水通量较氯化后的RO膜几乎保持不变,为60.55 L·m^-2·h^-1,截留率达到了99.56%。经过氯化和沉积改性后的RO膜水通量和截留率均得到了提高。     

Photocatalytic activity of TiO2/ZSM-5 composites in the presence of SO4 ion

TiO₂/ZSM-5 composites were prepared from SiO₂ of rice husk ash and TiO₂ sol from hydrolyzed TiOSO₄ salt. The combined effect of these two materials greatly enhanced the photocatalytic decolorization of methylene blue dye solution. The instant decolorization of the dye solution in the dark by the composite, TiO₂/ZSM-5 (wt ratio 1:1), resulted from the combination of the adsorption by ZSM-5 zeolite and TiO₂ nano-particles, and of Na₂SO₄ salt adhering to the composite surface. As a strong flocculating agent, the SO₄²⁻ ion caused the precipitation of the dye onto the composite surface which consequently enhanced the photocatalytic decolorization of the dye under UV irradiation. The composite, TiO₂/ZSM-5 (wt ratio 1:5), completely decolorized the methylene blue dye in 2.5 h, giving an equivalent performance to that of TiO₂, P-25 powder.     

CO2, NOx and SO2 emissions from the combustion of coal with high oxygen concentration gases

The emissions of CO₂, NO_x and SO₂ from the combustion of a high-volatile coal with N₂- and CO₂-based, high O₂ concentration (20, 50, 80, 100%) inlet gases were investigated in an electrically heated up-flow-tube furnace at elevated gas temperatures (1123–1573 K). The fuel equivalence ratio, φ, was varied in the range of 0.4–1.6. Results showed that CO₂ concentrations in flue gas were higher than 95% for the processes with O₂ and CO₂-based inlet gases. NO_x emissions increased with φ under fuel-lean conditions, then declined dramatically after φ=0.8, and the peak values increased from about 1000 ppm for the air combustion process and 500 ppm for the O₂(20%)+CO₂(80%) inlet gas process to about 4500 ppm for the oxygen combustion process. When φ>1.4 the emissions decreased to the same level for different O₂ concentration inlet gas processes. On the other hand, NO_x emission indexes decreased monotonically with φ under both fuel-lean and fuel-rich combustion. SO₂ emissions increased with φ under fuel-lean conditions, then declined slightly after φ>1.2. Temperature has a large effect on the NO_x emission. Peak values of the NO_x emission increased by 50–70% for the N₂-based inlet gas processes and by 30–50% for the CO₂-based inlet gas process from 1123 to 1573 K. However, there was only a small effect of temperature on the SO₂ emission.     

矿井水脱盐过程中卷式反渗透膜性能的数值模拟研究

为了更好地研究矿井水中无机盐组分对于反渗透过程产水、结垢及脱盐效果的影响,以内蒙古某煤矿矿井水水质组分作为进水水质条件,采用计算流体力学（CFD）模拟单支商用标准8寸卷式反渗透膜元件（陶氏BW30-400）内部的传质以及局部浓差极化的分布,预测实际运行情况下微溶盐结垢的风险。进水通道采用以阿基米德螺旋曲线为卷制轨迹的几何模型。无机盐的混盐作用通过混盐渗透压模型模拟。从全尺度卷式反渗透膜元件的模拟结果可以看出,卷式反渗透膜内的水流主要以轴向流速为主,沿切向阿基米德螺旋线的流速较低,对整体盐度分布的影响较小（<1%）,可以忽略不计,在后续模拟中采用简化模拟单元或几何模型或网格。在模拟操作条件下,卷式膜元件的浓水网产生的水头损失占整体水头损失约86%,为卷式膜元件中的主要水头损失来源。在没有安装浓水网的进水流道中最高Na₂SO₄浓度位于元件浓水出口处,高达3594 mg/L,约为有浓水网情况下的1.8倍。而且有浓水网的进水流道内,浓差极化现象主要发生在浓水网背水侧局部区域,影响范围较小。该模型模拟得到的产水量与实测产水量做对比,误差小于5%,同时模拟结果也接近ROSA9.1模拟数据（误差<4.4%）,因此可以对卷式反渗透膜的无机盐脱盐过程进行较精确的模拟仿真。与商业设计软件如ROSA（反渗透系统分析）相比,其只提供产水和浓水中的盐浓度信息,本文开发的模型可以提供浓度极化的特征信息,加深了对卷式反渗透膜在不同位置的潜在结垢风险的理解。     

Microstructure, Conductivity, and NO2 Sensing Characteristics of α-Al2O3-Doped (8 mol% Sc2O3)ZrO2 Composite Solid Electrolyte

α-Al₂O₃-doped (8 mol % Sc₂O₃)ZrO₂ composite solid electrolyte has been investigated in the fabrication of solid-state ceramic gas sensors. The microstructure and electrical conductivity of the composite solid electrolyte have been measured over a range of temperature from 240°C to 596°C. The composite solid electrolyte has been found to exhibit a higher conductivity compared with the commonly used (8 mol% Y₂O₃)ZrO₂ at temperatures above ∼448°C. The sensing characteristics for NO₂ detection have been studied in the temperature range of 500–650°C at the low concentration from 10 to 30 ppm and at high concentration from 100 to 500 ppm of NO₂. The NO₂ sensor was found to respond reproducibly and rapidly to the variations of NO₂, concentration, indicating that the composite solid electrolyte has promising application as a solid electrolyte for on-board exhaust gas monitoring.     

Fischer–Tropsch synthesis over Re-promoted Co supported on Al2O3, SiO2 and TiO2: Effect of water

The activity and selectivity of rhenium promoted cobalt Fischer–Tropsch catalysts supported on Al₂O₃, TiO₂ and SiO₂ have been studied in a fixed-bed reactor at 483 K and 20 bar. Exposure of the catalysts to water added to the feed deactivates the Al₂O₃ supported catalyst, while the activity of the TiO₂ and SiO₂ supported catalysts increased. However, at high concentrations of water both the SiO₂ and TiO₂ supported catalyst deactivated. Common for all catalysts was an increase in C₅₊ selectivity and a decrease in the CH₄ selectivity by increasing the water partial pressure. The catalysts have been characterized by scanning transmission electron microscope (STEM), BET, H₂ chemisorption and X-ray diffraction (XRD).     

Sintering behavior and microwave dielectric properties of Bi2O3–ZnO–Nb2O5-based ceramics sintered under air and N2 atmosphere

The sintering behavior and dielectric properties of the monoclinic zirconolite-like structure compound Bi₂(Zn_1/3Nb_2/3)₂O₇ (BZN) and Bi₂(Zn_1/3Nb_2/3−xV_x)₂O₇ (BZNV, x = 0.001) sintered under air and N₂ atmosphere were investigated. The pure phase were obtained between 810 and 990 °C both for BZN and BZNV ceramics. The substitution of V₂O₅ and N₂ atmosphere accelerated the densification of ceramics slightly. The influences on microwave dielectric properties from different atmosphere were discussed in this work. The best microwave properties of BZN ceramics were obtained at 900 °C under N₂ atmosphere with _r = 76.1, Q = 850 and Q_f = 3260 GHz while the best properties of BZNV ceramics were got at 930 °C under air atmosphere with _r = 76.7, Q = 890 and Q_f = 3580 GHz. The temperature coefficient of resonant frequency τ_f was not obviously influenced by the different atmospheres. For BZN ceramics the τ_f was −79.8 ppm/°C while τ_f is −87.5 ppm/°C for BZNV ceramics.     

The homogeneity range and the microwave dielectric properties of the BaZn2Ti4O11 ceramics

Ceramics with a composition close to BaZn₂Ti₄O₁₁ were synthesized according to various substitutional mechanisms in order to verify an existence of a homogeneity range in the vicinity of this composition. Structural and microstructural investigations showed that the crystal structure of BaZn₂Ti₄O₁₁ was formed in the homogeneity range corresponding to the formula BaZn_2 − xTi₄O_11 − x (0 < x < 0.1). Densely sintered BaZn_2 − xTi₄O_11 − x (0 < x < 0.1) ceramics exhibited a dielectric constant around 30, τ_f = −30 ppm/K and high Q × f values, which increased from 68,000 GHz at x = 0 to 83,000 GHz at x = 0.05. Structurally, the deficiency of Zn in BaZn_2 − xTi₄O_11 − x (0 < x < 0.1) resulted in a slight decrease in the unit-cell volume. The influence of secondary phases in the BaZn₂Ti₄O₁₁-based materials on the microwave dielectric properties was also investigated. A presence of small amounts of ZnO, BaTiO₃, hollandite-type solid solutions (Ba_xZn_xTi_8 − xO₁₆) and BaTi₄O₉ caused a decrease in Q × f values.     

Photocatalytic reduction of carbon dioxide into gaseous hydrocarbon using TiO2 pellets

It has been shown that CO₂ could be transformed into hydrocarbons when it is in contact with water vapour and catalysts under UV irradiation. This paper presents an experimental set-up to study the process employing a new approach of heterogeneous photocatalysis using pellet form of catalyst instead of immobilized catalysts on solid substrates. In the experiment, CO₂ mixed with water vapour in saturation state was discharged into a quartz reactor containing porous TiO₂ pellets and illuminated by various UV lamps of different wavelengths for 48 h continuously. The gaseous products extracted were identified using gas chromatography. The results confirmed that CO₂ could be reformed in the presence of water vapour and TiO₂ pellets into CH₄ under continuous UV irradiation at room conditions. It showed that when UVC (253.7 nm) light was used, total yield of methane was approximately 200 ppm which was a fairly good reduction yield as compared to those obtained from the processes using immobilized catalysts through thin-film technique and anchoring method. CO and H₂ were also detected. Switching from UVC to UVA (365 nm) resulted in significant decrease in the product yields. The pellet form of catalyst has been found to be attractive for use in further research on photocatalytic reduction of CO₂.     

Sintering and dielectric properties of Cu2Ta4O12 ceramics

In this work, Cu₂Ta₄O₁₂ ceramic was investigated as a promising, lead-free, nonferroelectric material with high dielectric permittivity. The results of impedance spectroscopy studies carried out at frequencies 10 Hz to 2 MHz over a wide temperature range from −55 to 700 °C were analyzed in the impedance, dielectric permittivity and electric modulus formalisms. In complex impedance plots two distinct arcs were distinguished, ascribed to the semiconducting grains and to the insulating grain boundaries. Cu₂Ta₄O₁₂ ceramic was found to exhibit a high dielectric permittivity exceeding 10,000 at low frequencies in the temperature range 150–740 °C. High permittivity of this material was attributed to the formation of internal (grain boundary) barrier layer capacitors. The influence of sintering conditions on microstructure, composition and dielectric properties of Cu₂Ta₄O₁₂ ceramics was also studied.     

Reactive dye removal in dye/salt mixtures by nanofiltration membranes containing vinylsulphone dyes: effects of feed concentration and cross flow velocity

In this study, DS5 DK type nanofiltration membranes were tested to recycle the reactive dye bath effluents. Reactive black 5 (RB5), reactive orange 16 (RO16), reactive blue 19 (RB19) and NaCl were used in the experiments to prepare the synthetic dye and salt mixtures. Effects of feed concentration, pressure and cross flow velocity on the permeate flux and color removal were investigated. Permeate flux increased with increasing pressure for all NaCl solutions. Dye concentration had a significant effect on flux values. Under the fixed NaCl concentrations the flux decreased with increasing dye concentrations. Dye rejections greater than 99% were achieved. Permeate was almost colorless. A gel layer formed by the rejected dye on membrane surface operates as a resistance to the permeation of dyes due to complete rejection of high molecule weight dyes, especially for the low salt concentrations. The presence of salt concentration has an interesting effect on color removal. Color removal decreased with increasing salt concentration. Cross flow velocities had also a significant effect on flux values. The dye formed agglomerates at high NaCl concentrations. High cross flow velocities decreased this effect.     

Tailoring the Microwave Dielectric Properties of MgNb2O6 and Mg4Nb2O9 Ceramics

The columbites MgNb₂O₆, MgTa₂O₆, and corundum-type Mg₄Nb₂O₉ ceramics were prepared by the conventional solid-state ceramic route. The structure and microstructure of the sintered samples were investigated by X-ray diffraction and scanning electron microscopic techniques. The microwave dielectric properties of the samples were measured by the resonance method in the frequency range 4–6 GHz. The dielectric properties have been tailored by forming a solid solution between MgNb₂O₆ and MgTa₂O₆ and by the substitution of TiO₂ for Nb₂O₅ in both MgNb₂O₆ and Mg₄Nb₂O₉ ceramics. The Mg(Nb_0.7Ta_1.3)O₆ has ɛ_r=29, Q _u× f =67 800 GHz, and τ_f=0.8 ppm/°C and the MgO–(0.4)Nb₂O₅–(1.5)TiO₂ composition has ɛ_r=34.5, Q _u× f =81 300 GHz, and τ_f=−2 ppm/°C.     

Crude Oil Desalting Using Hydrocyclones

Dilute dispersion/emulsion of ultrafine water droplets containing a variety of salts is usually present in crude oil. It is very useful to remove the water and the dissolved salts, so that corrosion, plugging, and fouling of equipment can be prevented. Electrical desalter is an effective method in crude oil desalting. In order to overcome the shortcomings of electrical desalting system, such as larger equipment volume, complex high tension electricity system, a new process of crude desalting that are based on hydrocyclone technology is designed. Preliminary industrial experiments have been carried out to prove the feasibility of desalting using hydrocyclone. The effects of several dimensionless units, such as Reynolds number, Euler number and pressure drop ratio were studied. An increase in inlet Reynolds number will decrease the pressure drop ratio. With an increase in inlet Reynolds number, Euler number increases gradually. Under the condition that Reynolds number of inlet is ranging from 5000 to 5800, the water concentrations can decrease from 5 vol%  8 vol% to less than 0.40 vol% and the salt concentrations is reduced from less than 8 mg L⁻¹ to 3 mg L⁻¹ after handled.     

Hydrogen production by autothermal reforming of sulfur-containing hydrocarbons over re-modified Ni/Sr/ZrO2 catalysts

The catalytic autothermal reforming (ATR) of liquid hydrocarbons to provide hydrogen for mobile or stationary fuel cells was carried out over a Ni/Sr/ZrO₂ catalyst that is active for steam reforming (SR). The catalyst system was found to be active for the ATR reaction, although the hydrogen concentration obtained by ATR, under the conditions employed, was a little lower than that for SR. Addition of sulfur, introduced in the form of thiophene, reduced the catalytic stability of Ni/Sr/ZrO₂, even at 1073 K. The catalyst lifetime decreased with increasing sulfur concentration between 0 and 100 ppm. Additives for improving the sulfur-tolerance of Ni/Sr/ZrO₂ were examined, and additions of Re or La were found to be effective in improving the stability of the catalysts. The best catalyst was 5 wt.% Re–Sr/Ni/ZrO₂. This catalyst was used in the ATR of liquid hydrocarbon fuels such as commercial premium gasoline, hydrotreated FCC gasoline, reagent mixtures, and methylcyclohexane. For premium gasoline, the activity remained unchanged during 30 h, but then diminished rapidly. With the other fuels, however, the catalyst showed a much improved performance, indicating that the presence of sulfur could be associated with catalyst stability. ATR coupled with the water–gas shift reaction led to a reduction in the CO concentration by up to 2800 ppm. The catalyst's activity remained constant even after cold-start runs with 853–423–853 K temperature cycles under H₂O/O₂/N₂ conditions. Thus, the Re–Sr/Ni/ZrO₂ catalyst is effective for ATR of liquid hydrocarbon fuels. Further work is currently under way to extend the catalyst life.     

Pilot plant studies on the removal of trihalomethanes by composite reverse osmosis membranes

The effect of single trihalomethane (THM) (CHCl₃) content in various types of water on the performance of two types of reverse osmosis composite membranes (the AFC99 membrane in tubular module B1, PCI, and the FT30 membrane in a spiral-wound element BW3040, FilmTec) have been investigated. The performance of these membranes in RO tests carried out using distilled water, tap water and brackish water (1000–5000 ppm NaCl) with the addition of THM have been evaluated in terms of permeate flux and the rejection of dissolved solids and THM. The FT30 membrane provided THM rejection better than 99.5% during the reverse osmosis treatment of tap water and brackish water. The AFC99 membrane exhibited only 80% retention of THM, obtained for the transmembrane pressures in the range of 10 to 30 bars. It was found that the presence of CHCl₃ slightly affects the transport and separation properties of the composite membranes used.     

Effect of pH, inorganic ions, organic matter and H2O2 on E. coli K12 photocatalytic inactivation by TiO2: Implications in solar water disinfection

The effect of different chemical parameters on photocatalytic inactivation of E. coli K12 is discussed. Illumination was produced by a solar lamp and suspended TiO₂ P-25 Degussa was used as catalyst. Modifications of initial pH between 4.0 and 9.0 do not affect the inactivation rate in the absence or presence of the catalyst. Addition of H₂O₂ affects positively the E. coli inactivation rate of both photolytic (only light) and photocatalytic (light plus TiO₂) disinfection processes. Addition of some inorganic ions (0.2 mmol/l) like HCO₃⁻, HPO₄²⁻, Cl⁻, NO₃⁻ and SO₄²⁻ to the suspension affects the sensitivity of bacteria to sunlight in the presence and in absence of TiO₂. Addition of HCO₃⁻ and HPO₄²⁻ resulted in a meaningful decrease in photocatalytic bactericidal effect while it was noted a weak influence of Cl⁻, SO₄²⁻ and NO₃⁻. The effect of counter ion (Na⁺ and K⁺) is not negligible and can modify the photocatalytic process as the anions. Bacteria inactivation was affected even at low concentrations (0.2 mmol/l) of SO₄²⁻ and HCO₃⁻, but the same concentration does not affect the resorcinol photodegradation, suggesting that disinfection is more sensitive to the presence of natural anions than photocatalytic degradation of organic compounds. The presence of organic substances naturally present in water like dihydroxybenzenes isomers shows a negative effect on photocatalytic disinfection. The effect of a mixture of chemical substances on photocatalytic disinfection was also studied by adding to the bacterial suspension nutrient broth, phosphate buffer and tap water.     

Effect of Bi2O3 Addition on the Sintering Temperature and Microwave Dielectric Properties of Zn2SiO4 Ceramics

Bi₂O₃ was added to a nominal composition of Zn_1.8SiO_3.8 (ZS) ceramics to decrease their sintering temperature. When the Bi₂O₃ content was <8.0 mol%, a porous microstructure with Bi₄(SiO₄)₃ and SiO₂ second phases was developed in the specimen sintered at 885°C. However, when the Bi₂O₃ content exceeded 8.0 mol%, a liquid phase, which formed during sintering at temperatures below 900°C, assisted the densification of the ZS ceramics. Good microwave dielectric properties of Q × f =12,600 GHz, ɛ_r=7.6, and τ_f=−22 ppm/°C were obtained from the specimen with 8.0 mol% Bi₂O₃ sintered at 885°C for 2 h.     

A study on the characteristics of the SO2 reduction using coal gas over SnO2-ZrO2 catalysts

SO₂, which is an air pollutant causing acid rain and smog, can be converted into elemental sulfur in direct sulfur recovery process (DSRP). SO₂ reduction was performed over catalyst in DSRP. In this study, SnO₂-ZrO₂ catalysts were prepared by a co-precipitation method, and CO and coal gas, which contains H₂, CO, CO₂ and H₂O, were used as reductants. The reactivity profile of the SO₂ reduction over the catalysts was investigated at the various reaction conditions as follows: reaction temperature of 300–550 °C, space velocity of 5000–30,000 cm³/g_-cat. h, [reductant]/[SO₂] molar ratio of 1.0–4.0 and Sn/Zr molar ratio of SnO₂-ZrO₂ catalysts 0/1, 2/8, 3/5, 5/5, 2/1, 3/1, 4/1 and 1/0. SnO₂-ZrO₂ (Sn/Zr = 2/1) catalyst showed the best performance for the SO₂ reduction in DSRP on the basis of our experimental results. The optimized reaction temperature and space velocity were 325 °C and 10,000 cm³/g_-cat. h, respectively. The optimal molar ratio of [reductant]/[SO₂] varied with the reductants, that is, 2.0 for CO and 2.5 for coal gas. SO₂ conversion of 98% and sulfur yield of 78% were achieved with the coal gas.