微波辐照相转移催化合成苹果酯

以乙酰乙酸乙酯和乙二醇为原料合成苹果酯。用单因素试验法和正交试验法探讨了催化剂、投料比、反应温度、反应时间和加热方式等因素对苹果酯合成的影响。试验结果表明 :在微波辐照下 ,最佳反应条件为 :以硫酸氢钠 /三氯化铁为催化剂、PEG -80 0为相转移催化剂、乙酰乙酸乙酯 :乙二醇 (mol)为 1 :1 .5～ 1 .8、甲苯为带水剂、微波功率为中低档、微波辐照时间为 8～ 1 2min ,产率可达 91 .5 %以上。产品经IR、1HNMR、MS和GC等测定 ,其结果与文献值一致     

Crystallization kinetics of PbTiO3 ferroelectric films: Comparison of microwave irradiation with conventional heating

Lead titanate (PTO) films were deposited onto Pt/Ti/SiO₂/Si substrates by a sol-gel method and annealed by microwave irradiation and conventional heating. In contrast to conventional heating, microwave irradiation can crystallize the PTO films at a low temperature of 450 °C or at 550 °C for only 5 min. The XRD and TEM studies reveal that microwave radiation can reduce the nucleation time, and increase the growth rate of perovskite grains in the crystallization process. Moreover, the results using the Avrami’s model show that the effective activation energy for crystallization process by microwave irradiation is 131 kJ/mol, much lower than that for the PTO films by conventional heating (216 kJ/mol). Therefore, microwave irradiation can reduce the effective activation energy for the nucleation and grain growth of the perovskite phase during the crystallization process, contributing to a low-temperature or a short-time preparation process of ferroelectric films.     

Drying kinetics of Philippine nickel laterite by microwave heating

In this study, microwave heating was used to dry nickel laterite, which contains significant quantities of free water, crystal water, and hydroxy water. The results show that the main phase of crystal water is Ca₃Al₆Si₁₀O₃₂(H₂O)₁₃, and the main phases of hydroxy water are FeO(OH) and Mg₅(Al, Cr)AlSi₃O₁₀(OH)₈. The microwave drying process of nickel laterite can be divided into two stages: the removal of free water and the coupled removal of free water, crystal water, and hydroxy water. The effect of particle size and microwave power output were studied, and these indicate that the drying time and specific energy consumption decrease with increasing particle diameter and microwave power. The effective diffusivity and activation energy were calculated, and these are larger in the second stage than that in the first stage. The activation energies are 27.66 and 32.80?W/g for the first and second stages, respectively. The phase transition of the product, schematic drying mechanism, and feasibility analysis of the microwave drying process are also discussed.     

Drying kinetics and microstructure evolution of nano-zirconia under microwave pretreatment

The effects of microwave power and sample quality on microwave drying kinetics and characteristics of zirconia were studied. It is found that by increasing the microwave power and decreasing the sample mass, the surface diffusion coefficient (D_eff) appears to an upward tendency. The corresponding value D_eff at a sample mass of 10, 20, 30, and 40g are 1.849E-14, 2.443E-14, 3.210E-14, and 3.278E-14 m²/s, respectively. The corresponding value D_eff at a microwave power of 300, 400, 500, 600, and 700W are 1.270E-14, 1.784E-14, 2.619E-14, 3.392E-14, and 4.497E-14 m²/s, respectively. Besides, the materials were characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transforms infrared spectroscopy (FT-IR) to evaluate the changes of materials before and after drying. The results show that microwave accelerates the drying of zirconia and increases its dispersibility. The heat conduction direction of microwave drying is the same as that of moisture diffusion, which avoids being affected by heat inertia and heat transfer loss. The drying process is fast and efficient, and the microwave directly penetrates the product, avoiding the disadvantage of slow evaporation caused by the temperature gradient.     

二丙炔基双酚A醚的热固化动力学研究

以双酚A和溴丙炔为原料,采用相转移催化合成法合成了二丙炔基双酚A醚,利用红外和核磁对其结构进行了表征。采用示差扫描量热法(DSC)对二丙炔基双酚A醚的固化反应历程进行了研究。分别由Kisserger方程和Ozawa方程求得二丙炔基双酚A醚聚合反应的活化能分别为127.3KJ/mol和131.6KJ/mol。用Crane经验方程求得固化反应的反应级数接近于1。研究表明,二丙炔基双酚A醚具有较低的固化反应活化能以及较宽的加工窗口,这有利于二丙炔基双酚A醚树脂的加工成型。     

微波辐照下煤的电化学脱硫研究

以北宿煤为原料,利用微波选择性加热的特点,考察了微波辐照时间、煤样粒径、NaOH等因素对高硫煤磁性强化磁选脱硫的影响,同时考察了微波-NaOH饱和溶液联合处理对北宿煤磁选脱硫的影响。研究表明,不同粒径的煤样的最大脱硫率存在一个最佳微波辐照时间,而微波-NaOH联合处理法脱硫效果更为显著。对煤样进行微波预处理后,可以根据需要控制NaOH饱和溶液用量达到较为理想的脱硫效果。     

微波辐射相转移催化合成乙酸异戊酯

研究采用微波辐射反应技术,以三氧化二铝作载体,十六烷基三甲基溴化铵（HDTMAB）为相转移催化剂合成乙酸异戊酯,得到了高收率的产物;并考察了诸因素对产率的影响,找出了最佳反应条件。     

Comparative study of conventional and microwave sintered mullite fibres: structural study

Mullite fibres were synthesised from a mixture of aluminium, aluminium chloride and acidic silica solutions as monophasic salts using a sol–gel technique. The viscosity and rheological behaviour of the mullite precursor sol were examined. Mullite fibres were synthesised using both conventional and microwave sintering techniques. The samples were characterised by X-ray diffraction and scanning electron microscopy. Pure mullite fibres were synthesised by microwave sintering at a relatively low temperature of 1200°C. The grain size of the fibre samples sintered using the microwave technique was finer than that produced by conventional sintering. These results show that microwave sintering is a promising technique for processing mullite fibres.     

Crystal structure and morphology of CeO2 doped stabilized zirconia ceramics under high-frequency microwave field sintering

Under high-frequency microwave irradiation, zirconia ceramics were prepared by sintering nano-CeO₂ (Ce = 7 mol%) doped zirconia powder. The different effects of temperature environment on the phase structure transformation, surface functional groups, microstructure, growth process, and density of doped zirconia were analyzed, and the optimized microwave sintering process for zirconia was determined. The experimental results reveal that the tetragonal phase of zirconia is positively correlated with the temperature when the temperature reaches about 1100 °C in the studied range. The reason is that the grain grows with the increase of sintering temperature, and the surface energy of grain decreases, which leads to the fluctuation of tetragonal phase content. The density of zirconia reaches 98.03% at 1300 °C, and the growth activation energy is 27.40 kJ/mol. There is no abnormal growth of zirconia particles, and the phase transition temperature decreases, which is attributed to the efficient heating of microwave and the incorporation of nano-ceria stabilizer.     

Experimental and modeling study of the kinetics of methane hydrate formation and dissociation

In this work, several experiments were conducted at isobaric and isothermal condition in a CSTR reactor to study the kinetics of methane hydrate formation and dissociation. Experiments were performed at five temperatures and three pressure levels (corresponding to equilibrium pressure). Methane hydrate formation and dissociation rates were modeled using mass transfer limited kinetic models and mass transfer coefficients for both formation and dissociation were calculated. Comparison of results, shows that mass transfer coefficients for methane hydrate dissociation are one order greater than formation conditions. Mass transfer coefficients were correlated by polynomials as relations of pressure and temperature. The results and the method can be applied for prediction of methane production from naturally occurring methane hydrate deposits.     

The influence of structure order on the kinetics of dehydroxylation of kaolinite

The structural order of kaolinite is an important factor that shows a substantial effect on the processes which take place during the thermal treatment of kaolin. The influence of structural order on the dehydroxylation process was investigated by simultaneous thermogravimetry and differential thermal analysis (TG-DTA). The thermal analysis was performed on the samples with gradually decreasing structural order prepared by milling procedure. The apparent activation energy of dehydroxylation process decreases with decreasing structural order according to the exponential function. The extrapolation of experimental data leads to the estimation of apparent activation energy of 76.6 kJ mol^?1 and of frequency factor of 0.12 × 10⁴ s^?1 related to completely disordered form of kaolinite, while the ordered form shows the apparent activation energy of 216.17 kJ mol^?1 and the frequency factor of 9.26 × 10⁴ s^?1. The relationships between features such as the infrared pattern of treated material, the degree of structural order and the apparent activation energy were established.     

Effect of demineralization and heating rate on the pyrolysis kinetics of Jordanian oil shales

The effect of mineral matter content on the activation energy of oil shale pyrolysis has been studied. Kerogen was isolated from raw oil shale by sequential HCl and HCl/HF digestion. Oil shale and kerogen samples were pyrolyzed in a Thermogravimetric Analyzer at different heating rates (1, 3, 5, 10, 30, and 50 °C/min) up to a temperature of 1000 °C. Total mass loss of all oil shale samples remained almost constant irrespective of the heating rate employed, whereas it decreased with the increase of heating rate for kerogen (74.5 to 71.4%). From the pyrolysis profile activation energy (Ea) was found to vary between 70 and 83 kJ/mol for oil shale, while 82-112 kJ/mol has been determined for isolated kerogen. An increase of both Ea and pre-exponential factor was observed with an increasing heating rate. It is concluded that the mineral matter in oil shale enhances catalytic cracking as is evident from the reduced Ea values of oil shale compared with those for kerogen.     

Hydrophobicity and catalytic properties of Ti-MFI zeolites synthesized by microwave and conventional heating

Ti-incorporated MFI zeolite (Ti-MFI-MW) has been synthesized with microwave heating. Their physicochemical properties such as surface hydrophobicity, and adsorption and catalytic properties have been compared with those of Ti-incorporated MFI zeolite (Ti-MFI-CH) prepared by conventional hydrothermal method. Competitive adsorption measurements with toluene and water revealed that the hydrophobicity index of Ti-MFI-MW (8.0) is higher than that of Ti-MFI-CH (6.2). IR spectra showed that Ti-MFI-MW also has a lower content of surface hydroxyl groups and adsorbs a larger amount of 1-hexene than Ti-MFI-CH. These results pointed out that Ti-MFI-MW is more hydrophobic than Ti-MFI-CH. Epoxidation reactions of 1-hexene and styrene with hydrogen peroxide have been conducted to investigate catalytic properties of the Ti-MFI zeolites according to the synthesis method. The conversions and epoxide selectivities over Ti-MFI-MW are higher than those over Ti-MFI-CH due to the enhanced surface hydrophobicity.     

Electrochemical ozone production: influence of the supporting electrolyte on kinetics and current efficiency

The nature of the electrolyte strongly influences the electrode kinetics of the oxygen evolution reaction (OER) and electrochemical ozone production (EOP) mainly by affecting the degree of coverage by the intermediates of both processes. The anomalous behaviour of the Tafel coefficient, b, as a function of temperature was attributed to surface adsorption of the electrolyte species, and the competition between them, as well as gas bubble adherence. Comparison of the current efficiencies of the EOP, Φ_EOP, determined for different temperatures and supporting electrolyte compositions, showed the presence of fluorinated anions increases Φ_EOP. The influence of the anion nature on Φ_EOP, when analysed in the light of the proposed electrode mechanism, reveals introduction into the electrolyte of anions having a high electronegativity changes the double layer structure resulting in an increase of surface concentration of the active centres leading to EOP. The inhibition of the OER in the high overpotential domain during EOP provoked by fluoro-anion adsorption is supported by the activation energy data. In situ surface characterisation before and after EOP investigation revealed that even under drastic conditions (high current density, low interfacial pH) β-PbO₂ can be considered an inert electrode material.     

Study on drying kinetics of calcium oxide doped zirconia by microwave-assisted drying

Ca–ZrO₂ is an essential structural and functional material, which is commonly used in refractories, electronic ceramics, and functional ceramics. The properties of Ca–ZrO₂ materials are depending on the quality of Ca–ZrO₂ powders. The main factors affecting the quality of powder are sintering temperature and the drying effect. This paper applied modern microwave drying technology to dry Ca–ZrO₂ powder. The impact of initial mass, microwave heating power, and initial moisture content on the drying of Ca–ZrO₂ were explored. The results showed that the average drying rate increased with the rise of initial mass, microwave heating power, and initial moisture content. Wang and Singh, Page, and Quadratic Model were applied to fit Ca–ZrO₂ with an initial moisture content of 5.6%, mass of 30 g, and microwave output power of 400 W. The results displayed that the Page model had a better fitting effect. It was also applicable to other different initial moisture content, original mass, and microwave heating power. The diffusion coefficient calculated by Fick's second law displayed that with the increase of initial mass, initial moisture content, and microwave heating power of Ca–ZrO₂, the effective diffusion coefficient increased first and then declined. When the Ca–ZrO₂ of microwave heating power was 640 W, mass was 30 g, and the moisture content was 5.65%, the effective diffusion coefficients of zirconia were 1.42533 × 10^?13, 2.91806 × 10^?13, 5.652.2471 × 10^?13 m²/s, respectively. To determine the activation energy of microwave dried zirconia, using the relationship between microwave power and activation energy, the activation energy of microwave dried zirconia was calculated to be ?23.39 g/W. This paper aims to rich experimental data for the industrial application of microwaves to strengthen dried zirconia and propose a theoretical basis.     

The kinetics of epoxidation of trimethylolpropane ester

Kinetics pertaining epoxidation reaction of a palm oil‐based synthetic lubricant trimethylolpropane (TMP) ester were investigated. The epoxidation reaction of TMP ester was carried out utilizing peracetic acid generated by an in situ technique. The analysis of the reaction kinetics was performed within the low temperature (30, 50, and 60°C) and high temperature (70, 80, and 90°C) regions, owing to the nature of the reactions. The maximum conversion of the unsaturated carbon to oxirane ring was achieved in 1 h at high temperature region, while epoxidation of TMP esters took more than 4 h to reach the maximum conversion at the low temperature region. From the experimental data, the kinetics of epoxidation of TMP esters fitted well with both the second‐order and pseudo first‐order models. The rate constants for pseudo first‐order model increased from 0.0009 to 0.0055 by increasing temperature at the low temperature region, and from 0.0129 to 0.0209 within the high temperature region. The values of activation energies at low temperature and high temperature regions were found to be 69.4 and 53.3 kJ/mol, respectively.     

A kinetic study of microwave and fluidized-bed drying of a Chinese lignite

The drying kinetics of Chinese lignite in nitrogen fluidized-bed, superheated steam fluidized-bed and microwave were investigated. The changes in the mass as a function of drying time were measured under various drying conditions. The variations of moisture ratio with time were used to test ten different thin-layer empirical drying models given in the literature. In studying the consistency of all the models, some statistical tests, such as χ², residual sum of squares (RSS) and F-value were also used as well as coefficient of determination R². In nitrogen fluidized-bed and superheated steam fluidized-bed, the Midilli–Kucuk model best described the lignite drying process. Drying data in microwave were best described by the Page model, indicative of a difference in kinetics between the two drying methods. This difference was attributed to different heat transfer mechanisms under conventional and microwave drying conditions. The effects of drying parameters in nitrogen fluidized-bed, superheated steam fluidized-bed and microwave drying on the constants and coefficients of the selected models were studied by multiple regression analysis. The apparent diffusion coefficient of moisture in samples was obtained from the kinetics data and the apparent activation energies under nitrogen fluidized-bed, superheated steam fluidized-bed and microwave drying were found to be rather similar.     

Optimisation on the stability of CaO-doped partially stabilised zirconia by microwave heating

Partially stabilised zirconia has advantages for the applications in the metallurgical processes which have special requirements in corrosion resistance and high-temperature performance. In the present work, controllable microwave heating was used for the uniform thermal field and consequent microstructure improvement to further improve the stability of partially stabilised zirconia, which was 88.14% prepared by electric arc melting. Analyses including X-ray diffraction (XRD), Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy (Raman) were used to study the effect of temperature change on the phase composition and structure of the samples. After heating at temperatures of 900 °C, 1000 °C, 1100 °C, 1200 °C and 1300 °C for 1h, the stabilities of the heated product were 88.51%, 95.02%, 95.17%, 96.31% and 97.64%, respectively. From the phase transformations based on the experimental results, the discussion indicates that the martensitic transformation temperature of zirconia from m-ZrO₂ to t-ZrO₂ during the heating stage was reduced under the radiation of microwave energy.     

Selective crystallization of CoAPO-34 and VAPO-5 molecular sieves under microwave irradiation in an alkaline or neutral condition

Syntheses of cobalt- and vanadium-incorporated aluminophosphate molecular sieves (CoAPO and VAPO) with AFI and CHA structures have been studied using an alkaline or neutral gel under microwave irradiation and conventional hydrothermal heating. Microwave synthesis gives rise to the selective crystallization of CoAPO-34 with a CHA structure and VAPO-5 with an AFI structure, while the conventional hydrothermal crystallization brings CoAPO-5 and VAPO-34 through the gradual transformation of CoAPO-34 and VAPO-5, respectively, as the crystallization time increases. These results reveal that the relative stabilities of metal-incorporated aluminophosphate (MeAPO) molecular sieves between AFI and CHA structures depend on the type of incorporated metal ions. This work also suggests that microwave syntheses of MeAPO molecular sieves preferentially induce a kinetically favorable MeAPO phase in a short period of crystallization time. The synthesis of VAPO-5 in an alkaline condition is for the first time reported in this work.     

微波促进高相对分子质量N-丁烷基壳聚糖的合成

在微波促进下首先对高相对分子质量壳聚糖碱化,再使之与溴代正丁烷进行烷基化反应,合成出了高取代度的N-丁烷基化壳聚糖.在n(氢氧化钠)∶n(壳聚糖)=4∶1,(壳聚糖粘均相对分子质量为1.49×106)、60℃下微波碱化处理1h、n(溴代正丁烷)∶n(碱化壳聚糖)=1.4∶1、80℃烷基化反应4h的较佳反应条件下,所得产...