The kinetic analysis of optimization and selective transportation of Cu(Ⅱ) ions with TNOA as carrier by MDLM system

This study covers the transportation of Cu(Ⅱ) ions by multi-dropped liquid membrane(MDLM) system and tri-noctylamine(TNOA) as carrier in kerosene. Batch experiments are held to obtain optimum conditions for the transportation of Cu(Ⅱ) ions such as volume of donor, organic, and acceptor phase 100 ml, p H of donor phase9.00, temperature 298.15 K, concentration of H_2SO_4 in acceptor phase 1.00 mol·L~(-1), concentration of TNOA in organic phase 5.00 × 10~(-3)mol·L~(-1)and rate of peristaltic pump 50 ml·min~(-1). Optimum circumstances of this extraction are as follows: p H of donor phase is 9.00, concentration of TNOA is 5.00 × 10~(-3)mol·L~(-1),1.00 mol·L~(-1)H_2SO_4 as acceptor phase, and flux rate is 50 ml·min~(-1). Cu(Ⅱ) ion transportation is consecutive first order irreversible reaction. Activation energy is found as 5.22 kcal·mol-1(21.82 k J·mol~(-1), this process is called as diffusion controlled system. Selective transportation of Cu(Ⅱ) ions with alkaline, alkaline earth, and different heavy metal ions at optimum conditions of single Cu(Ⅱ) extraction was conducted. According to the selective transportation Cu(Ⅱ) ions with alkaline and alkaline earth metal ions, Na~+, K~+, and Ba~(2+)ions are not detected in the acceptor phase, but 12.00% of Ca~(2+)ions is transported from donor phase to acceptor phase. At the end of the simultaneous extraction of Zn(Ⅱ), Fe(ⅡI), and Mo(VI) with Cu(Ⅱ) ions, 2.20% of Mo(VI), 0.80% of Fe(Ⅲ) and 3.60% of Zn(Ⅱ) are detected in the acceptor phase.     

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.     

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.     

Selective extraction of In(III), Ga(III) and Zn(II) using a novel extractant with phenylphosphinic acid

A new extractant, [N,N-di(2-ethylhexyl)amino]methylphenylphosphinic acid (DEAPP), was synthesized to de-velop the mutual separation techniques of In(III), Ga(III) and Zn(II). The extraction selectivity for In(III), Ga(I I) and Zn(II) with DEAPP was higher than that of the commercial phosphorus acid extractants such as D2EHPA and PC-88A. The extraction selectivity for metal ions in 1 mol·L?1 aqueous ammonium nitrate solution with DEAPP was in the following order:In(III) N Ga(III) N Zn(II). These selective extraction behaviors indicate that the amino moiety of DEAPP plays an important role in the mutual separation of In(III), Ga(III) and Zn(II). The extraction equilibria of In(I I), Ga(II ) and Zn(II) with DEAPP (=HR) were expressed by the following reactions:In3++2eHRT2?InR3eHRT+3H+, Ga3++1.5eHRT2+NO3??GaR2eHRTeNO3T+2H+, and Zn2++2eHRT2?ZnR2eHRT 2 + 2H+. The extraction equilibrium constants of In(III), Ga(III) and Zn(II) with DEAPP were determined to be Kex,M=1.7 × 104 [dm3·mol?1], 4.17 [(dm3·mol?1)0.5], and 1.55 x 10?2 [–], respectively.     

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...     

Analysis of pH-dependent Structure and Mass Transfer Characteristics of Polydopamine Membranes by Molecular Dynamics Simulation☆

Detailed atomistic structures are constructed for polydopamine membranes containing different amounts of cat-echol and quinone groups to investigate the effect of pH value in the membrane casting solut...     

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.     

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.     

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.     

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).     

Potential-aided recovery of iodide using 2-D nanosheet CuxO coating polymer/graphene/carbon fibers composite

2-D nanosheet Cu_2O doped CuO coating poly m-phenylenediamine and melamine/graphene/carbon fibers composite(Cu_xO/MPM/GFs) was firstly fabricated by compound electrochemical method. Cu_xO/MPM/GFs was successfully used to the recovery of iodide(I~-) from salt water by lower potential-aided sorption and desorption processes. The potential-aided recovery of I~- at CuxO/MPM/GFs was characterized by FE-SEM, XRD, IR, Raman,XPS, UV–vis and electrochemical techniques in detail. The maximal adsorption capacity of 86.82 mg·g~(-1) could be obtained with a pseudo-second-order model at 0.8 V for 210 min in pH 5.0, 0.1 mol·L~(-1) NaCl, and the process accompanied the generation of CuI, CuO and I~(5-). The I-could be quickly desorbed from the electrode with a transfer of CuI to Cu_2O by cycle voltammetry from -1.0 to 0.5 V for 90 cycles in pH 9.0, 0.1 mol·L~(-1) KNO_3.Thus, CuxO/MPM/GFs was renewable in the continuous electrochemical-adsorption–desorption processes.     

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.     

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.     

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&#8226;mol&#61485;1 and the corresponding pre-exponential factor of 3.39×108 cm3&#8226;g&#61485;1&#8226;s&#61485;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&#8226;mol&#61485;1, the corresponding A of 2.94×109 cm3&#8226;g&#61485;1&#8226;s&#61485;1, heat of adsorption ΔHads of 87.90 kJ&#8226;mol&#61485;1 and the corresponding Aads of 9.24 cm3&#8226;mol&#61485;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.     

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.     

交联氧化铝-壳聚糖新杂化吸附剂的制备及去除废水中Cu(Ⅱ)(英文)

A novel biosorbent was developed by coating chitosan,a naturally and abundantly available biopolymer,on to activated alumina based on oil shale ash via crosslinking.The adsorbent was characterized by various techniques,such as Fourier transform infrared spectroscopy,scanning electron microscopy,thermogravimetric-differential thermal analysis,and X-ray photoelectron spectroscope.Batch isothermal equilibrium adsorption experiments were condcted to evaluate the adsorbent for the removal of Cu(Ⅱ) from wastewater.The effect of pH and agitation time on the adsorption capacity was also investigated,indicating that the optimum pH was 6.0.The equilibrium adsorp-tion data were correlated with Langmuir and Freundlich models.The maximum monolayer adsorption capacity of chitosan coated alumina sorbent as obtained from Langmuir adsorption isotherm was found to be 315.46 mg·g-1 for Cu(Ⅱ).The adsorbent loaded with Cu(Ⅱ) was readily regenerated using 0.1 mol?L?1 sodium hydroxide solution.All these indicated that chitosan coated alumina adsorbent not only have high adsorption activity,but also had good stability in the wastewater treatment process.     

Recovery of lithium using H4Mn3.5Ti1.5O12/reduced graphene oxide/polyacrylamide composite hydrogel from brine by Ads-ESIX process

Powdery Li⁺-imprinted manganese oxides adsorbent was widely used to the recovery of Li⁺, but there are some difficulties, such as poor stability in acid solution, inconvenience of operation and separation. In this work, a useful hydrogel composite based H₄Mn_3.5Ti_1.5O₁₂/reduced graphene oxide/polyacrylamide (HMTO-rGO/PAM) was fabricated by thermal initiation method with promising stable, conductive and selective properties. The resulting materials were characterized by field emission scanning electron microscope, infrared absorption spectrum, X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical techniques. The recovery of Li⁺ was investigated using HMTO-rGO/PAM from brine by a separated two-stage sorption statically and electrically switched ion exchange desorption process. The adsorption capacity of 51.5 mg·g^-1 could be achieved with an initial Li⁺ concentration of 200 mg·L^-1 in pH 10, at 45 ℃ for 12 h. Li⁺ ions could be quickly desorbed by cyclic voltammetry (CV) in pH 3, 0.1 mol·L^-1 HCl/NH₄Cl accompanying the exchange of Li⁺ and H⁺(NH₄⁺) and the transfer of LMTO-rGO/PAM to HMTO-rGO/PAM.     

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.     

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&#8729;L&#61485;1 glucose and 0.019 mol&#8729;L&#61485;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&#8729;L&#61485;1 and 0.017 mol&#8729;L&#61485;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.     

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.