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.     

铁基载氧体辅助无烟煤焦富氧燃烧动力学分析

流化床铁基载氧体辅助富氧燃烧下传统石英砂床料被铁基载氧体替代,铁基载氧体扩展了传统床料的“热载体”的功能,另承担了“氧载体”的角色,为调节炉内氧分布与煤燃烧过程匹配提供了新思路。本文在热重实验平台探究了10%O₂/90%CO₂气氛下分析纯Fe₂O₃、赤铁矿及钢渣三种铁基载氧体辅助无烟煤焦燃烧特性及动力学。结果表明,相较于纯无烟煤焦燃烧,铁基载氧体辅助燃烧下无烟煤焦的燃烧特性得到显著改善,其中燃烧速率提高29%以上,燃尽温度降低65℃以上,综合燃烧指数提升2倍以上,活化能与指前因子同步增加且表现出“补偿效应”。三种铁基载氧体中分析纯Fe₂O₃对无烟煤焦燃烧特性的改善略优于赤铁矿和钢渣,钢渣可作为流化床铁基载氧体辅助富氧燃烧的床料替代石英砂。     

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.     

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.     

1-丁基-3-甲基咪唑二氰胺盐离子液体的热稳定性和热分解动力学(英文)

Thermal stability and thermal decomposition kinetics of 1-butyl-3-methylimidazolium dicyanamide ([bmin+][N(CN) ]2-) were investigated using both isothermal and non-isothermal thermogravimetric analyses (TGA) under high pure nitrogen as carrier gas. The long-term thermogravimetric studies revealed that the highest temperature used should be 110 °C, at which [bmin+][N(CN)2-] lost less than 10% by mass in 10 hours. The non-isothermal activation energy values determined using Friedman and ASTM methods were (150±13) and (147±2) kJ·mol –1 , respectively. Multivariate non-linear-regression methods showed that expanded Fn and CnB models were the best fit models with highest correlation coefficient of 0.9994, and the apparent activation energies were consistent with iso-conversional methods.     

Thermogravimetric assessment of combustion characteristics of blends of a coal with different biomass chars

In connection to future energy demand and fossil fuel crisis particularly in India, biomass is gaining its importance for possible use as co-fuel. In India varieties of biomass products are available which do have tremendous potentiality for co-combustion with pulverized coal. Based on the emerging need, detailed investigations are felt necessary to examine the compatibility of different kind of biomass with coal and to select suitable blend composition(s) before utilizing those biomass products in utility operation as co-fuels. This study elaborates the lab scale findings of combustion experiments in DSC-TGA apparatus with a typical Indian coal, two biomass samples and low temperature biomass chars (300 and 450 °C) as well as with ‘blends of low temperature chars and coal’. Conventional TGA parameters, activation energy and ignition index of different blends were estimated which provided elaborate information on their basic combustion features. Results of non-isothermal combustion studies in general depict that blends containing less than 50% biomass char are better performing as compared those with higher biomass char content. Lowering of activation energy and improvement of reactivity in major combustion zone were also observed in the coal/biomass-char blends. Improvement of ignition index of the blends of coal with 300 °C chars over expected weighted mean values was noticed. Such attempts may help to identify appropriate biomass-type, blend proportion for a given coal and to derive some specific advantages with respect to particular combustion practice.     

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.     

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...     

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。     

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 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.     

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.     

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.     

硫酸-糖蜜酒精废液浸出软锰矿的动力学(英文)

The kinetics of reductive leaching of manganese from low grade pyrolusite in dilute sulfuric acid in the presence of molasses alcohol wastewater was investigated. The shrinking core model was applied to quantify the effects of reaction parameters on leaching rate. The leaching rate increases with reaction temperature, concentrations of H 2 SO 4 and organic matter in molasses alcohol wastewater increase and ore particle size decreases. The leaching process follows the kinetics of a shrinking core model and the apparent activation energy is 57.5 kJ·mol –1 . The experimental results indicate a reaction order of 0.52 for H2SO4 concentration and 0.90 for chemical oxygen demand (COD) of molasses alcohol wastewater. It is concluded that the reductive leaching of pyrolusite with molasses alcohol wastewater is controlled by the diffusion through the ash/inert layer composed of the associated minerals.     

微型流化床与热重测定煤焦非等温气化反应动力学对比

利用微型流化床反应分析仪(MFBRA)和热重分析仪(TGA)比较煤焦与CO₂的非等温气化反应特性,并利用单一升温速率法和组合升温速率法计算反应动力学数据。结果表明:升温速率对半焦非等温气化过程有重要影响,随着升温速率的增大,起始反应温度和最大反应速率对应的气化温度增加,同一气化温度下的碳转化率降低,而且利用单一升温速率法求取气化反应的活化能逐渐减小。与TGA相比,同一升温速率下,MFBRA中半焦气化反应的起始反应温度和最大反应速率对应的反应温度明显较小,而且升温速率越大差异越显著。无论是单一升温速率法(升温速率≥5℃·min^-1)还是组合升温速率法,TGA测得的动力学数据均明显小于MFBRA测得的动力学数据。高升温速率下(升温速率≥5℃·min^-1)半焦在TGA和MFBRA中非等温气化行为和动力学数据的差异很可能与MFBRA内较好的热量传递和受扩散的抑制作用较小有关。     

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.     

A comparative reactivity and kinetic study on the combustion of coal-biomass char blends

The combustion behavior and kinetics of various biomass chars, a lignite and a hard coal char and their blends were investigated. Pure fuel chars were compared to blended chars with respect to their performance during combustion. Non-isothermal thermogravimetry experiments were performed in air atmosphere, over a temperature range of 25-850 °C and at a heating rate of 10 °C/min. Kinetic evaluation was performed using a power law model. Reaction kinetic parameters were obtained by modeling the combustion of biomass and coal chars as a single reaction, with the exception of lignite and olive kernel chars, the combustion of which was modeled by two partial reactions. A single reaction model was used in the case of coal-wood char blends, while for the lignite-biomass char blends two partial reactions were used. Reactivity was assessed using the specific reaction rate, as a function of conversion. Biomass chars were generally more reactive than those of hard coal and lignite. The combustion behavior of the blends was greatly influenced by the rank of each coal (hard coal or lignite) and the proportion of each component in the blend. Combustion performance of the blends showed some deviation from the expected weighted average of the constituent chars. An attempt was made to estimate the kinetics of the blends using, as a basis, the parameters estimated for the individual components. In this case, because of the interactions between the components of the blends, the kinetic parameters needed to be slightly modified. Alteration in reactivity was more pronounced in the case of lignite-biomass chars than coal-wood chars.