超临界氨合成

Ammonia synthesis at supercritical conditions was first studied over iron and active carbonsupported ruthenium catalysts in a fixed-bed reactor. The influences of 15 kinds of different supercritical media, such as alkanes of C7-C13, 1, 2, 3, 4-tetrahydronaphthalene, cis-decalin, o-xylene,ethylbenzene, quinolin, n-hexane and aniline etc. and reaction conditions (catalyst, temperature, space velocity, particial pressure of media) on ammonia at supercritical condition were investigated.Supercritical medium was decomposed under reaction conditions over Fe and Ru/AC catalysts. The decomposition products deactivated the catalysts. Alkane decomposed the least, and the rate of deactivation was the slowest. Therefore alklane was a relatively good medium. The decomposion of supercritical medium was the key for the deactivation of catalysts. Another important reason for the decrease of ammonia concentration was that the effective pressure of syngas decreased because of the presence of supercritical media. The active temperature of catalyst was the decisive factor in supercritical ammonia synthesis. Supercritical catalytic reaction was viable only at a lower temperature. Ammonia ynthesis at supercritical conditions is possible if a catalyst with active temperature lower than 573 K could e developed and the decomposition of supercritical media could be prevented.     

微通道反应器内异辛醇混硝化过程行为

In this paper, the nitration characteristic of alcohols with mixed acid for the synthesis of energetic materials in a stainless steel microreactor was investigated experimentally. The nitration of iso-octanol with HNO3-H2SO4 mixed acid was chosen as a typical model reaction which involved fast and strong exothermic liquid-liquid heterogeneous reaction process. The influences of mixed acid composition, flow rate, organic/aqueous flow ratio and reaction temperature have been investigated. The results indicated that the reaction could be conducted safely and stably in the microreactor at 25-40°C, which are enhanced compared to 15°C or below for safe operating conditions in the conventional reactors. Moreover, the 98.2% conversion of iso-octanol could be obtained and no by-products were detected in all cases.     

Enzymatic glycerolysis of soybean oil

Enzymatic glycerolysis of soybean oil was studied. Of the nine lipases that were tested in the initial screening, Pseudomonas sp. resulted in the highest yield of monoglycerides. Lipase from Pseudomonas sp. was further studied for the influence of temperature, thermal stability, enzyme/oil ratio, and glycerol/oil ratio. A full factorial optimization approach was performed. The following conditions were tested over the specified ranges: temperature (30–70°C), thermal stability (30–70°C), enzyme/oil ratio (0.05–0.2 g enzyme/10 g oil), glycerol/oil ratio (1:1–3:1 glycerol/oil molar ratio) and 1 h reaction time. The stability of the enzyme at the reaction temperature was also incorporated as a separate variable. At temperatures above 40°C enzyme denaturation offset the higher activity. The optimal conditions were selected to be the basis for a continuous process: 40°C, a glycerol/oil molar ratio of 2:1, and an enzyme/oil ratio of 0.1 g enzyme/10 g oil. A definition for glycerolysis activity was adopted. The glycerolysis activity (1 GU) was defined as the amount of enzyme necessary to consume 1 μmol of substrate (glycerol and oil) per minute. This research is intended to explore the reaction parameters that are important in a continuous enzymatic glycerolysis process.     

The influence mechanism of solvent on the hydrogenation of dimethyl oxalate

The hydrogenation of dimethyl oxalate(DMO) for the producing of C2-C4 alcohols with methanol as solvent was researched at the temperature of 270 °C to 310 °C. Ethylene glycol(EG) was the main product at low temperature and the selectivity of which was 61.9% at 230 °C. However, EG selectivity decreased sharply with the increase of temperature while ethanol became the main liquid products with the selectivity of 43.5% at 270 °C. It can be ascribed to a thorough hydrogenation of DMO at a high temperature. In addition, the promotion of Guerbet reaction led to the production of propanol and butanol. Simultaneously, the amount of gas products including CO, CO_2 and dimethyl ether(DME) also increased, which became a competition factor in the conversion of DMO to liquid products including C2-C4 alcohols. The blank test was carried out with pure methanol as feedstock with and without Cu/SiO_2 catalyst, which revealed that methanol was involved in the formation of gas products and higher alcohols on Cu-based catalyst, and the main gas product was CO.     

游离静止细胞中腈水合酶的失活动力学

Nitrile hydratase (NHase) is an important industrial enzyme used for acrylamide production from acrylonitrile. The deactivation kinetics of NHases in free resting cells of Rhodococcus sp. was presented based on a bi-steady state assumption. Effects of hydration temperature, product concentration and substrate concentration on NHase deactivation were investigated experimentally and correlated with a first order deactivation kinetics. The results showed that the hydration temperature and product concentration were major factors governing the deactivation of NHases under substrate-feeding conditions. When acrylamide concentration was higher than 250 g•L－1, the deactivation of NHases became serious and the bi-steady state assumption was not applicable. When the hydration temperature was controlled at a relatively higher level such as 28°C, the total deactivation rate constant was about 2.8-fold of that at 20°C.     

Extraction of potassium from K-feldspar via the CaCl2 calcination route☆

The extraction of potassium from K-feldspar via a calcium chloride calcination route was studied with a focus on the effects of the calcination atmosphere, calcination temperature and time, mass ratio of CaCl2 to K-feldspar ore and particle size of the K-feldspar ore. The results demonstrated that a competing high-temperature hydrolysis reaction of calcium chloride with moisture in a damp atmosphere occurred concurrently with the conversion reaction of K-feldspar with CaCl2, thus reducing the amount of potassium extracted. The conversion reaction started at approximately 600 °C and accelerated with increasing temperature. When the temperature rose above 900 °C, the extraction of potassium gradually decreased due to the volatilization of the product, KCl. As much as approximately 41%of the potassium was volatilized in 40 min at 1100 °C. The mass ratio of CaCl2/K-feldspar ore significantly affected the extraction. At a mass ratio of 1.15 and 900 °C, the potassium extraction reached 91%in 40 min, while the extraction was reduced to only 22%at the theoretical mass ratio of 0.2. Optimal process conditions are as follows:ore particle size of 50–75μm, tablet forming pressure of 3 MPa, dry nitrogen atmosphere, mass ratio of CaCl2/ore 1.15:1, calcination temperature of 900 °C, and calcination time of 40 min. The XRD analysis revealed that a complex phase transition of the product SiO2 was also accompanied by the con-version reaction of K-feldspar/CaCl2. The SiO2 product formed at the initial stage was in the quartz phase at 900 °C and was gradually transformed into cristobalite after 30 min.     

0℃以下含SDS的甲烷水合物生成方式及过程对其分解速率的影响

The dissociation rates of methane hydrates formed with and without the presence of sodium dodecyl sulfate(methane-SDS hydrates),were measured under atmospheric pressure and temperatures below ice point to investigate the influence of the hydrate production conditions and manners upon its dissociation kinetic behavior.The experimental results demonstrated that the dissociation rate of methane hydrate below ice point is strongly dependent on the manners of hydrate formation and processing.The dissociation rate of hydrate formed quiescently was lower than that of hydrate formed with stirring;the dissociation rate of hydrate formed at lower pressure was higher than that of hydrate formed at higher pressure;the compaction of hydrate after its formation lowered its stability,i.e.,increased its dissociation rate.The stability of hydrate could be increased by prolonging the time period for which hydrate was held at formation temperature and pressure before it was cooled down,or by prolonging the time period for which hydrate was held at dissociation temperature and formation pressure before it was depressurized to atmospheric pressure.It was found that the dissociation rate of methane hydrate varied with the temperature(ranging from 245.2 to 272.2 K) anomalously as reported on the dissociation of methane hydrate without the presence of surfactant as kinetic promoter.The dissociation rate at 268 K was found to be the lowest when the manners and conditions at which hydrates were formed and processed were fixed.     

Isomerization of linoleic,linolenic, and other polyunsaturated acids with potassium tertiary butoxide and its application in the spectrophotometric estimation of these acids

Summary It has been shown that potassium tertiary butoxide isomerizes such unsaturated fatty acids as linoleic, linolenic, arachidonic, and pentaenoic at a temperature of 90°. With 5% potassium-t-butanol reagent conjugation of linoleic acid attains a maximum at the end of 2 hrs. and remains steady thereafter even up to 10 hrs. while with linolenic, arachidonic, and pentaenoic acids it is still occurring at the end of such long times of reaction as 48 and 10 hrs., respectively. This continuance of reaction at the end of such long periods with these higher unsaturated acids demonstrates that the isomerization with the tertiary butoxide reagent at 90° is not complicated by side reactions, such as polymerization and deisomerization. All the methods studied give high absorption coefficients in the lower regions of maxima—233 mμ with linolenic, 233 mμ and 268 mμ with arachidonic acids—showing thereby that isomerizations of these acids occur stepwise. Based on this study, a method using 5% potassium-t-butanol as reagent, at 90° with a time of reaction of 4 hrs., has been proposed for the estimation of linoleic and linolenic acids. The k₂₃₃ value for linoleic acid (94.0) obtained by this method compares very well with those by the 6.6% KOH-glycol and 21% KOH-glycol methods while with linolenic acid the k₂₃₃ value (63.2) is higher and k₂₆₈ value (74.2) lies intermediate between those by the other methods. The proposed method is shown to estimate the linoleic and linolenic acid contents of several typical oils with about the same degree of accuracy as either the 6.6% KOH-glycol or 21% KOH-glycol methods. Appendix. When this paper was ready to be submitted, a note (27) describing the use of tertiary butoxide reagent on the kinetic study of isomerization of linoleic and linolenic acids came to our attention. Extinction coefficients at 235 mμ and 268 mμ are reported for linolenic acid and the values (61.4, 74.2) obtained by isomerization with a molar solution of the reagent at 99.5° and 180 minutes’ time of reaction are about the same order as those reported in this paper. It is of interest to note that these authors have also noted that no destruction of the product occurs at this temperature and time of heating. Post-doctoral Fellow in Physiological Chemistry. This work was supported in part from funds granted by the Ohio State University Research Foundation to the University for aid in fundamental research.     

苯甲酸釜残液全部回收的工艺开发利用

Benzoic acid residue is solid waste produced from the production of benzoic acid by oxidizing toluene. Because it contained important chemical raw materials such as benzoic acid, benzyl benzoate and fluorenone, it is necessary to recover them from the residue. In this work the technique featured with high efficiency evaporation and vacuum distillation was developed to obtain total recovery and utilization of the benzoic acid residue. By controlling the operation temperature at 260°C and the pressure of 16 kPa in the rising and falling film evaporators, heavy components separated efficiently from the residue can be polymerized and the light components consisting of 63% of the residue entered into a benzoic acid vacuum distillation column. Keeping the temperature of polymerization at (280±10)°C, coumarone resin was produced after adjusting the softening point according to the market re-quirements. Vacuum distillation was operated under the following conditions: top temperature at 186°C, top pres-sure of 16 kPa, bottom temperature at 240-250°C, reflux ratio being 3︰1. Benzoic acid of 98% purity was distilled out from the column as a side stream and the bottom product was crude benzyl benzoate. By the developed tech-nique, the benzoic acid residue was splitted into three products, benzoic acid, crude benzyl benzoate and coumarone resin without any surplus waste.     

反应条件对钌催化剂和铁催化剂的氨合成性能影响

Activated carbon-supported Ru-based catalyst and A301 iron catalyst were prepared,and the influences of reaction temperature,space velocity,pressure,and H2/N2 ratio on performance of iron catalyst coupled with Ru catalyst in series for ammonia synthesis were investigated.The activity tests were also performed on the single Ru and Fe catalysts as comparison.Results showed that the activity of the Ru catalyst for ammonia synthesis was higher than that of the iron catalyst by 33.5%-37.6% under the reaction conditions:375-400 °C,10 MPa,10000 h-1,H2︰N2 3,and the Ru catalyst also had better thermal stability when treated at 475 °C for 20 h.The outlet ammonia concentration using Fe-Ru catalyst was increased by 45.6%-63.5% than that of the single-iron catalyst at low tem-perature (375-400 °C),and the outlet ammonia concentration increased with increasing Ru catalyst loading.     

DMFCs用SPEEK/SiOx-S复合质子交换膜

A sulfonated poly(ether ether ketone) (SPEEK) membrane with a fairly high degree of sulfonation (DS) can swell excessively and even dissolve at high temperature. To solve these problems, insolvable functionalized silica powder with sulfonic acid groups (SiOx-S) was added into the SPEEK matrix (DS 55.1%) to prepare SPEEK/ SiOx-S composite membranes. The decrease in both the swelling degree and the methanol permeability of the membranes was a dose-dependent result of addition of the SiOx-S powder. Pure SPEEK membrane swelled 52.6% at 80°C, whereas the SPEEK/SiOx-S (15%, by mass) membrane swelled only 27.3% at the same temperature. From room temperature to 80℃, all SPEEK/SPEEK/SiOx-S composite membranes had methanol permeability of about one order of magnitude lower than that of Nafion115. Compared with pure SPEEK membranes, the addition of the SiOx-S powder not only leads to higher proton conductivity, but also increases the dimensional stability at higher temperatures, and greater proton conductivity can be achieved at higher temperature. The SPEEK/SiOx-S (20%, by mass) membrane could withstand temperature up to 145°C, at which in 100% relative humidity (RH) its proton conductivity exceeded slightly that of Nafion115 membrane and reached 0.17 S•cm－1, while pure SPEEK mem-brane dissolved at 90°C. The SPEEK/SiOx-S composite membranes are promising for use in direct methanol fuel cells because of their good dimensional stability, high proton conductivity, and low methanol permeability.     

WC@TiO2核壳结构纳米复合材料制备与电催特征

Monotungsten carbide and titania nanocomposite with core-shell(WC@TiO2)structure was prepared by a new approach of spray drying and reduction-carbonization reaction,with titania nanopowder and ammonium metatungstate as precursors,methane as carbon source,and hydrogen as reduction gas.The sample was characterized by X-ray diffraction,scanning electron microscope,high resolution transmission electron microscope and X-ray energy dispersion spectroscopy.The results show that its crystal phase is composed of brookite,tungsten and monotungsten carbide.The morphology of the sample particle is irregular sphere-like,with a diameter smaller than 100 nm.Its chemical components are titanium,tungsten,carbon and oxygen.Monotungsten carbide nanoparticles lie on the surface of titania core and form an incomplete shell around titania core in the nanocomposite.The measurement with a microelectrode system of three electrodes shows that the sample is electrocatalytic active to nitrophenol in basic solution at room temperature.Its peak potential is at0.988 V(vs saturated calomel electrode (SCE)),which is more negative than the peak potential,0.817 V(vs SCE),of mesoporous monotungsten carbide, and its peak current is 8.809μA,which is higher than the peak current,4.058μA,of mesoporous monotungsten carbide.The hydrogen generation potential of the sample is at1.199 V(vs SCE),which is more negative than that of pure nanosized monotungsten carbide at1.100 V(vs SCE).These results show that the presence of titania in the sample can lower the peak potential of nitrophenol electrocatalysis and its hydrogen generation potential,and increase its peak current of nitrophenol electrocatalysis in basic solution at room temperature.This indicates a synergistic effect of titania and monotungsten carbide in electrocatalysis.     

常温及热态通气条件下多层桨三相搅拌反应器中局部气含率分布

Vertical distributions of void fraction in gas-liquid and gas-liquid-solid stirred tanks have been measured in a fully baffled dished base vessel of 0.48 m diameter, using a conductivity probe. The impeller configuration (a hollow half elliptical blade dispersing turbine below two up-pumping wide blade hydrofoils, identified as HEDT+2WHU) recommended in previous work has been used in this work. The operating temperatures were 24°C and 81°C, identified as cold and hot respectively. The effects of superficial gas velocity, agitator speed and the corresponding power input on the local void fraction in two-phase systems are investigated and discussed. Results show that the increasing of agitator speed or gas flow rate leads to an increase in local void fraction at the majority of measurement points in both cold and hot systems. However, the uniformity of gas dispersion does not always increase as the rais-ing of agitator speed and power input. In either cold or hot sparged conditions, the two- and three-phase systems have similar vertical profiles for void fraction, with maxima in similar locations; however, the void fractions are significantly lower in hot sparging than with cold. In cold operation the presence of particles leads to a lower void fraction at most points, although the local void fractions increase a little with the addition of solid particles at high temperature, in good agreement with the global gas holdup results, and the possible reasons are discussed in this paper. This work can give a better understanding of the differences between cold-gassed and hot-sparged three phase stirred tanks.     

Integration of coal pyrolysis process with iron ore reduction:Reduction behaviors of iron ore with benzene-containing coal pyrolysis gas as a reducing agent☆

An integrated coal pyrolysis process with iron ore reduction is proposed in this article. As the first step, iron oxide reduction is studied in a fixed bed reactor using simulated coal pyrolysis gas with benzene as a model tar compound. Variables such as reduction temperature, reduction time and benzene concentration are studied. The carbon deposition of benzene results in the retarded iron reduction at low temperatures. At high temperatures over800 °C, the presence of benzene in the gas can promote iron reduction. The metallization can reach up to 99% in20 min at 900 °C in the presence of benzene. Significant increases of hydrogen and CO/CO2 ratio are observed in the gas. It is indicated that iron reduction is accompanied by the reforming and decomposition of benzene. The degree of metallization and reduction increases with the increasing benzene concentration. Iron oxide can nearly completely be converted into cementite with benzene present in the gas under the experimental conditions. No sintering is found in the reduced sample with benzene in the gas.     

掺杂的阳离子缺陷型磷灰石 La9.33－2x/3MxSi6O26 (M=Mg,Sr,Ca)的合成及离子导电特性

Apatite-type lanthanum silicate with special conduction mechanism via interstitial oxygen has attracted considerable interest in recent years. In this work, pure powder of La9.33－2x/3MxSi6O26 (M＝Mg, Ca, Sr) is prepared by the sol-gel method with sintering at 1000°C. The powder is characterized by X-ray diffraction (XRD) and scan-ning electron micrograph (SEM). The apatite can be obtained at relatively low temperature as compared to the con-ventional solid-state reaction method. The measurements of conductivity of a series of doped samples La9.33－2x/3MxSi6O26 (M＝Ca, Mg, Sr) indicate that the type of dopant and the amount have a significant effect on the conductivity. The greatest decrease in conductivity is observed for Mg doping, following the Ca and the Sr doped apatites. The effect is ultimately attributed to the amount of oxygen interstitials, which is affected by the crystal lat-tice distortion arising from cation vacancies.     

热辅助紫外光催化氧化方法用于总磷检测的实验研究和动力学分析(英文)

A novel thermal-assisted ultra-violet (UV) photocatalysis digestion method for the determination of total phos-phorus (TP) in water samples was introduced in this work. The photocatalytic experiments for TP digestion were conducted using a 365 nm wavelength UV light and TiO2 particles as the photocatalyst. Sodium tripolyphosphate and sodium glycerophosphate were used as the typical components of TP and the digested samples were then determined by spectrophotometry after phosphomolybdenum blue reaction. The effects of operational parameters such as reaction time and temperature were studied for the digestion of TP and the kinetic analysis of two typical components was performed in this paper. The pseudo-first-order rate constants k of two phosphorus compounds at different temperatures were obtained and the Arrhenius equation was employed to explain the effect of temperature on rate constant k. Compared with the conventional thermal digestion method for TP detection, it was found that the temperature was decreased from 120 °C to 60 °C with same conversion rate and time in this thermal-assisted UV digestion method, which enabled the digestion process work at normal pressure. Compared with the individual ultra-violet (UV) photocatalysis process, the digestion time was also decreased from several hours to half an hour using the thermal-assisted UV digestion method. This method wil not lead to secondary pol ution since no oxidant was needed in the thermal-assisted UV photocatalysis digestion process, which made it more compatible with electrochemical detection of TP.     

基于FTIR分析的稻草热解机理

The pyrolysis mechanism of rice straw (RS) was investigated using a tube reactor with Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analyzer. The results show that the maximum pyrolysis rate increases with increasing heating rate and the corresponding temperature also increases. The three-pseudocomponent model could describe the pyrolysis behavior of rice straw accurately. The main pyrolysis gas products are H2O, CO2, CO, CH4, HCHO (formaldehyde), HCOOH (formic acid), CH3OH (methanol), C6H5OH (phenol), etc. The releasing of H2O, CO2, CO and CH4 mainly focuses at 220-400°C. The H2O formation process is separated into two stages corresponding to the evaporation of free water and the formation of primary volatiles. The release of CO2 first increases with increasing temperature and gets the maximum at 309°C. The releasing behavior of CO is similar to H2O and CO2 between 200 and 400°C. The production of CH4 happens, compared to CO2 and CO, at higher temperatures of 275-400°C with the maximum at 309°C. When the temperature exceeds 200°C, hydroxyl and aliphatic C H groups decrease significantly, while C O, olefinic C C bonds and ether structures increase first in the chars and then the aromatic structure develops with rising temperature. Above 500°C, the material becomes increasingly more aromatic and the ether groups decreases with an increase of temperature. The aromatization process starts at ≈350°C and continues to higher temperatures.     

生物油中乙酸和乙醇共裂化获取汽油产物的研究简

Abstract Acetic acid was selected as the model compound representing the carboxylic acids present in bio-oil. This work focuses the co-cracking of acetic acid with ethanol for bio-gasoline production. The influences of reaction temperature and pressure on the conversion of reactants as well as the selectivity and Conaposition of the crudegasoline phase were investigated. It was found that increasing reaction temperature benefited the conversion of reactants and pressurized cracking produced a higher crude gasoline yield. At 400 ℃ and 1 MPa, the conversion of the reactants reached over 99% and the selectivity of the gasoline phase reached 42.79% （by mass）. The gasoline phase shows outstanding quality, with a hydrocarbon content of 100%.     

煤矸石盐酸浸溶出铝铁的动力学研究（英文）

The extraction of aluminum from coal mining waste (CMW) is an important industrial process. The two major problems in applications are low aluminum dissolution efficiency and high iron content in the raw material, which affect the quantity and quality of products. To improve the aluminum recovery process, the leaching kinet-ics of CMW with hydrochloric acid was studied. A shrinking core model was used to investigate aluminum and iron dissolution kinetics. Based on the kinetic characteristics, a process for recovering aluminum was proposed and tested experimental y. It is found that the aluminum leaching reaction is controlled by surface reaction at low temperatures (40–80 °C) and by diffusion process at higher temperatures (90–106 °C). The iron dissolution process is dominated by surface reaction at 40–100 °C. The results show that iron could be dissolved or separated by concentrated hydrochloric acid. Fine grinding wil improve aluminum dissolution significantly.     

[bupy]BF4-AlCl3离子液体上甲苯和间戊二烯的烷基化反应

The alkylation of toluene with 1,3-pentadiene to produce pentyltoluene was carded out to obtain 2,6-dimethylnaphalene, which is an important intermediate during the production of 2,6-naphthalene dicarboxylic acid. Based on our previous work using anhydrous AlCl3 as catalyst, [bupy]BF4-AlCl3 ionic liquids were employed to catalyze the reaction of 1,3-pentadiene with toluene. The experimental results show that [bupy]BF4-AlCl3 ionic liquids are suitable for the reaction especially when the molar ratio of AlCl3 to [bupy]BF4 is 1.75 ： 1, and the reaction could proceed at the temperature as low as 0℃. It could be as active as pure AlCl3, but much more environmentally friendly.