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.     

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.     

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.     

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.     

Heterogeneity of Adsorption Sites and Adsorption Kinetics of n-Hexane on Metal-Organic Framework MIL-101(Cr)

abstract The heterogeneity of adsorption sites and adsorption kinetics of n-hexane on a chromium terephthalate-based metal-organic framework MIL-101(Cr) were studied by gravimetric method and temperatu...     

改性超细煤粉对甲基橙的吸附行为研究

The adsorption of methyl orange onto ultrafine coal powder (UCP) and modified ultrafine coal powder (MUCP) from aqueous solutions were studied, in which the influence of contact time, dosage, temperature, pH, and methyl orange concentration in the solution were investigated. The adsorption kinetics of methyl orange by UCP and MUCP can be described by the Lagergren first-order and pseudo second-order kinetic models, respectively. The adsorption isotherms of methyl orange onto MUCP at 303, 313 and 323 K follow the Freundlich and Langmuir isotherm equation. Values of G0 for methyl orange adsorption onto MUCP are -22.55, -23.10 and -23.79 kJ•mol－1 at 303, 313, and 323 K, respectively. The values of ΔH0 and ΔS0 are -3.74 kJ•mol－1 and 61.99 J•mol－1, respectively. The adsorption process is spontaneous and exothermic.     

规整复合吸附剂真空变压吸附分离CH4/N2工艺模拟与分析

为减少甲烷排放,实现低浓度煤层气有效资源化利用,探究了使用规整复合吸附剂真空变压吸附富集低浓度煤层气的工艺。采用静态容积法测定了甲烷、氮气在规整复合吸附剂上的吸附等温线,同时建立了包括质量、热量和动量守恒在内的严格吸附床数学模型,设计了三塔连续进料的真空变压吸附工艺并进行模拟。分析了工艺达到循环稳态后吸附床层轴向温度分布和压力变化,并且探究了进料量、解吸压力、原料气中甲烷浓度和吸附压力对纯度、回收率、工艺能耗和吸附剂产率等工艺性能的影响。模拟结果表明,在进料量为100 L·min^-1,解吸压力为0.1 bar（1 bar=0.1 MPa）,原料气甲烷浓度为30%,吸附压力为3 bar时可以生产纯度为59.07%,回收率为93.64%的富CH₄产品气,同时单位能耗为18.70 kJ·mol^-1,吸附剂产率为4.56 mol·h^-1·kg^-1。表明规整吸附剂对CH₄/N₂具有良好的吸附分离效果,能够实现低浓度煤层气中甲烷高效富集。     

甲烷在成型前后活性炭上吸附的初步试验

通过对比试验,分析成型对活性炭储存甲烷特性的影响。首先,应用丙烯酸甲酯乳胶黏合剂对活性炭SAC-02成型,在温度区间268.15～338.15 K、压力范围0～15 MPa测试甲烷的吸附等温线;通过确定吸附量和等量吸附热,比较甲烷在成型前后活性炭上的吸附平衡。其次,测试储罐吸附床中心在室温、4个压力（6.5 MPa、5.5 MPa、4.5 MPa和3.5 MPa）下快速充放气过程的温度变化,分析成型对吸附过程热效应的影响。结果表明,成型活性炭的密度增大、比表面积减小、单位质量吸附剂上的甲烷吸附量减小;甲烷在成型前后活性炭上的等量吸附热均处于13～20.5kJ·mol^-1;成型活性炭吸附床中心温度在充放气过程中的变化幅度和变化速率均增大。比较试验结果时发现,选用黏合剂成型须综合考虑其对吸附床热导率、传质阻力及吸附剂微观结构的影响。     

水相中甲酸自催化制备过氧甲酸的反应动力学(英文)

Performic acid (PFA) is an oxidant used in chemical processing, synthesis and bleaching. The macro kinetic models of synthesis, hydrolysis and decomposition of PFA were investigated via formic acid-autocatalyzed reaction. It was found that the intrinsic activation energies of PFA synthesis and hydrolysis were 75.2 kJ·mol-1 and 40.4 kJ·mol-1 respectively. The observed activation energy of PFA decomposition was 95.4 kJ·mol-1. The experi-mental results indicated that the decomposition of PFA was liable to occur even at the ambient temperature. Both the spontaneous decomposition and the radical-introduced decomposition contributed to the decomposition of PFA.     

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 kinetics studies of divalent manganese from phosphoric acid solution by using cationic exchange resin

There are numerous impurities in wet-process phosphoric acid, among which manganese is one of detrimental metallic impurities, and it causes striking negative effects on the industrial phosphoric acid production and downstream commodity. This article investigated the adsorption behavior of manganese from phosphoric acid employing Sinco-430 cationic ion-exchange resin. Resorting FT-IR and XPS characterizations, the adsorption mechanism was proved to be that manganese was combined with sulfonic acid group. Several crucial parameters such as temperature, phosphoric acid content and resin dose were studied to optimize adsorption efficiency. Through optimization, removal percentage and sorption capacity of manganese reached 53.12 wt%, 28.34 mg·g^-1, respectively. Pseudo-2nd-order kinetic model simulated kinetics data best and the activation energy was evaluated as 6.34 kJ·mol^-1 for the sorption reaction of manganese. In addition, the global adsorption rate was first controlled by film diffusion process and second determined by pore diffusion process. It was found that the resin could adsorb up to 50.24 mg·g^-1 for manganese. Equilibrium studies showed that Toth adsorption isotherm model fitted best, followed by Temkin and Langmuir adsorption isotherm models. Thermodynamic analysis showed that manganese adsorption was an endothermic process with enhanced randomness and spontaneity.     

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.     

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.     

Desorption isotherms and isosteric heat of anaerobic fermentation residues

This paper presents the equilibrium desorption isotherms and the isosteric heat of sorption of a mixture containing mechanically dewatered fermentation residue (obtained from a blend of chicken, swine and cattle manure) used in biogas plants and corn spoiled silage in a ratio of 2:1. The moisture desorption isotherms of the fermentation residue were determined at 32℃, 40℃ and 80℃ and in the relative humidity range of 0.057/1 using static gravimetric method. Mathematical equations were used to analyze the desorption data of Modified Henderson, Modified Halsey, Modified Oswin, Modified Chung-Pfost and Modified GAB models. The constants of the model equations were calculated by non-linear regression analysis. The Modified Henderson model fitted to the desorption isotherm data well. Using the proposed function, the final moisture content of the material can be determined as long as it can be dried in infinite time with the drying gas in the given conditions. The isosteric heat of desorption was calculated by using the Modified Henderson model in the studied temperature range based on the Clausius-Clapeyron equation. The isosteric heat varied between 46 kJ·mol^-1 and 67 kJ·mol^-1 at moisture levels 1.91 < X_e < 4.05 kg_H2O·kg_dP^-1 for the material.     

污泥含炭吸附剂的制备及其吸附模拟烟气中汞蒸汽的应用(英文)

The carbonaceous adsorbent was prepared from mixtures of dewatered sludge and sawdust with enhanced ZnCl2 chemical activation.Characteristics of the adsorbent were studied using scanning electron microscope(SEM) ,Fourier transform infrared spectroscopy(FT-IR) ,and adsorption of nitrogen.The surface analysis showed that the carbonaceous adsorbent had good specific surface and porosity(394 m 2 ·g-1of BET surface,0.12 and 0.10 ml·g-1of microporous and mesoporous volume,respectively) .The oxygen functional groups such as OH,C O and C O were found on the surface by FTIR and XPS(X-ray photoelectron spectroscopy) .The adsorption of elemental mercury(Hg0) on the carbonaceous adsorbent was studied in a fixed bed reactor.The dynamic adsorption capacity of carbonaceous adsorbent increased with influent mercury concentration,from 23.6μg·g-1at 12.58μg·m-3to 87.9μg·g-1at 72.50μg·m-3,and decreased as the adsorption temperature increased,from 246 μg·g-1 at 25°C to 61.3μg·g-1 at 140°C,when dry nitrogen was used as the carrier gas.The carbonaceous adsorbent presented higher dynamic adsorption capacity than activated carbon,which was 81.2μg·g-1and 53.8μg·g-1respectively.The adsorption data were fitted to the Langmuir adsorption model.The physical and chemical adsorption were identified on the adsorbent.     

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.     

D301大孔吸附树脂吸附甘氨酸

通过静态吸附法研究了树脂D301对水溶液中甘氨酸的吸附行为。采用单因素实验法确定了最佳吸附条件为pH 7.5,温度35℃,时间45 min,吸附剂用量为0.1 g,在此条件下最大平衡吸附量可达794.81 mg·g^-1。同时探究了D301对甘氨酸溶液吸附的热力学行为,测得了303.15～318.15 K温度范围内的吸附等温线数据,用Langmuir、Freundlich、Temkin方程对此进行拟合,并根据热力学原理计算得到吸附过程中ΔH^θ、ΔG^θ、ΔS^θ值和吸附表观活化能。结果表明等温吸附平衡符合Langmuir等温线模型,其ΔH^θ 134.75 kJ·mol^-1,ΔG^θ-6.312 kJ·mol^-1, ΔS^θ 450.806 J·mol^-1·K^-1,E_a为81.27 kJ·mol^-1。研究结果表明D301对甘氨酸的吸附为化学吸附和物理吸附共存且为自发进行的吸热过程。     

快速变压吸附制氢工艺的模拟与分析

目前工业上主要通过变压吸附技术从蒸汽甲烷重整气中制取氢产品气。然而,能源需求量的快速增加使得传统变压吸附技术在产量方面的不足越发明显。为此,进行了快速变压吸附从蒸汽甲烷重整气中制取氢气的模拟研究。采用活性炭和5A分子筛作为吸附剂,并以测得的原料气中各组分在两种吸附剂上的吸附数据为基础,进行了六塔快速变压吸附工艺的数值模拟与分析。在分析了塔内温度、压力和固相的浓度分布后,探究了进料流量、双层吸附剂高度比以及冲洗进料比三个操作参数对于快速变压吸附工艺性能的影响,结果表明：原料气组成为H₂/CH₄/CO/CO₂=76%/3.5%/0.5%/20%,吸附压力为22 bar（1 bar=10⁵ Pa）,解吸吹扫压力为1.0 bar,处理量为0.8875 mol·s^-1,吸附剂床层高度比为0.5∶0.5,冲洗进料比为22.37%时,可获得H₂纯度99.90%,回收率69.88%,此时H₂产量为0.4713 mol·s^-1。相比之下,氢气纯度为99.90%时,尽管PSA工艺回收率为83.40%,但处理量只有0.39 mol·s^-1,因此H₂产量仅为0.2472 mol·s^-1。     

Synthesis of spinel ferrite and its role in the removal of free fatty acids from deteriorated vegetable oil

Deterioration and loss of quality of vegetable oil is a big challenge in the food industry. This study investigated the synthesis of nickel ferrite (NiFe₂O₄) via co-precipitation method and its use for the removal of free fatty acids (FFAs) in deteriorated vegetable oil. NiFe₂O₄ was characterized using Fourier transformed infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric (TG) analysis, Brunauer–Emmett–Teller (BET) surface area, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). Synthesis of NiFe₂O₄ was confirmed by characterization, which revealed a BET surface area of 16.30 m²·g^-1 and crystallite size of 29 nm. NiFe₂O₄ exhibited an adsorption capacity of 145.20 L·kg^-1 towards FFAs with an 80.69% removal in a process, which obeys Langmuir isotherm and can be described by the pseudo-second-order kinetic model. The process has enthalpy (ΔH) of 11.251 kJ·mol^-1 and entropy (ΔS) of 0.038 kJ·mol^-1·K^-1 with negative free energy change (ΔG), which suggests the process to be spontaneous and endothermic. The quantum chemical computation analysis via density functional theory further revealed the sorption mechanism of FFAs by NiFe₂O₄ occurred via donor–acceptor interaction, which may be described by the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO). The study showed NiFe₂O₄ to be a potential means that can remove FFAs from deteriorated vegetable oil.     

累托石吸附分离水中金霉素(英文)

The removal of antibiotics from water by clay minerals has become the focus of research due to their strong adsorptive ability. In this study, adsorption of chlortetracycline (CTC) onto rectories was conducted and the effects of time, concentration, temperature and pH were investigated. Experimental results showed that adsorption equilibrium was reached in 8 h. Based on the Langmuir model, the maximum adsorption capacity of CTC on rectories was 177.7 mg·g 1 at room temperature. By the study on adsorption dynamics, it is found that the kinetic date fit the pseudo-second-order model well. The adsorption of CTC by rectories is endothermic and the free energy is in the range of 10 to 30 kJ·mol 1 . The pH value of solution has significant effects on adsorption and the optimal pH is at acidity (pH 2-6). At concentration of 2500 mg·L 1 , the intercalated CTC produces an interlayer space with a height of 1.38 nm, which is 1.12 nm in raw rectories, suggesting that the adsorption occurs between layers of rectories.