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.     

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).     

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.     

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.     

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.     

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.     

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...     

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.     

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.     

Synthesis and kinetics of 2,5-dicyanofuran in the presence of hydroxylamine ionic liquid salts

2,5-Dicyanofuran (DCF) is an important biomass-derived platform compound primarily used to prepare bio-based adiponitrile, which is the key precursor for the synthesis of nylon 66 and 1,6-hexanediisocyanate (HDI). In this study, one-pot, green and safe synthesis of DCF from 2,5-diformylfuran (DFF) and hydroxylamine ionic liquid salts was proposed. Eco-friendly hydroxylamine ionic liquid salts were used as the nitrogen source. Ionic liquid exhibited three-fold function of cosolvent, catalysis and phase separation. The conversion of DFF and yield of DCF reached 100% under the following optimum reaction conditions: temperature of 120 ℃ for 70 min, volume ratio of paraxylene: [HSO₃-b-Py]·HSO₄ of 2:1, and molar ratio of DFF:(NH₂OH)₂·[HSO₃-b-Py]·HSO₄ of 1:1.5. The reaction mechanism for the synthesis of DCF was proposed, and the kinetic model was established. The reaction order with respect to DFF and intermediate product 2,5-diformylfuran dioxime (DFFD) was 1.06 and 0.16, and the reaction activation energy was 64.07 kJ·mol^-1 and 59.37 kJ·mol^-1 respectively. After the reaction, the ionic liquid was easy to separate, recover and recycle.     

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.     

环氧树脂和环氧/环硫树脂与胺的固化反应动力学

采用非等温DSC法对低黏度体系CY184/IPDA环氧树脂体系及对CY184/ES184/IPDA环氧/环硫树脂体系的固化反应动力学进行了研究。用高级等转化率Vyazovkin积分法求取活化能E_a,通过Málek法确定了固化反应机理函数和动力学参数,得到固化反应动力学方程。结果表明:CY184/IPDA环氧树脂体系的平均活化能为47.04 kJ·mol^-1;CY184/ES184/IPDA环氧/环硫树脂体系的活化能为48.97 kJ·mol^-1。两种体系的模型拟合曲线与实验得到的DSC曲线吻合得较好,均符合esták-Berggren(m,n)模型。     

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...     

H2, CO, N2, O2和CH4在碳膜中的扩散

Diffusion of pure H2, CO, N2,O2 and CH4 gases through nanoporous carbon membrane is investigated by carrying out non-equilibrium molecular dynamics （NEMD） simulations. The flux, transport diffusivity and activation energy for the pure gases diffusing through carbon membranes with various pore widths were investigated. The simulation results reveal that transport diffusivity increases with temperature and pore width, and its values have a magnitude of 10^-7 m^2·s^-1 for pore widths of about 0.80 to 1.21 nm at 273 to 300 K. The activation energies for the gases diffusion through the membrane with various pore widths are about 1-5 kJ·mol^-1, The results of transport diffusivities are comparable with that of Rao and Sircar （J. Membr. Sci., 1996）, indicating the NEMD simulation method is a good tool for predicting the transport diffusivities for gases in porous materials, which is always difficult to be accurately measured by experiments.     

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.     

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.     

EQUILIBRIUM CONSTANTS FOR ETHYL tert-BUTYL ETHER LIQUID-PHASE SYNTHESIS

Thermodynamic equilibrium constants for the liquid-phase synthesis of ethyl terl-butyl ether (ETBE) were determined experimentally in the temperature range 40-80°C (313-353 K) at 1.6 MPa for an initial molar ratio of ethanol to isobutene ranging from 1 to 1.5. To reach etherification equilibrium a macroporous sulphonic acid resin (K-2631, Bayer) was used as a catalyst. The thermodynamic equilibrium constant and the enthalpy, free energy, and entropy changes are given as a temperature function. At 298 K, ΔH° = -34.8 kj mol^-1, ΔG° = -11.7kJmol^-1, and ΔS° = -77.3J mol^-1 K^-1. A comparison with the values obtained for MTBE is also included.     

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.     

Fabrication of nickel oxide functionalized zeolite USY composite as a promising adsorbent for CO2 capture

Adsorption process is considered to be the most promising alternative for the CO₂ capture to the traditional energy-intensive amine absorption process, and the development of feasible and efficient CO₂ adsorbents is still a challenge. In this work, the NiO@USY (ultrastable Y) composites with different NiO loadings were prepared for the CO₂ adsorption using Ni(NO₃)₂ as the precursor. The composites were characterized by X-ray photoelectron spectroscopy, X-ray diffraction, nitrogen adsorption–desorption test, scanning electron microscopy analysis, and thermogravimetric analysis, and were evaluated for the CO₂ adsorption capacity, CO₂/N₂ adsorption selectivity and CO₂ cycle adsorption capacity. The characterization results show that after the activation at 423 K, the Ni(NO₃)₂ species were well dispersed into the surface of zeolite USY, and after the further activation at 823 K, Ni(NO₃)₂ could be converted into highly dispersed NiO. The adsorption results show that the presence of the active component NiO plays an important role in improving the CO₂ adsorption performance, and the NiO@USY composite with a NiO loading of 1.5 mmol·g^-1 USY support displays a high adsorption capacity and adsorption selectivity for CO₂, and shows a good cycle stability. In addition, the Clausius–Clapeyron equation was used to evaluate the isosteric heat of adsorption of CO₂ on the NiO(1.5)@USY composite, and the heat of adsorption was 17.39–38.34 kJ·mol^-1.     

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.