β-环糊精水中催化氧化肉桂醛合成天然苯甲醛(英文)

A facile and efficient procedure has been developed systematically for the oxidative cleavage of cinna-maldehyde to benzaldehyde by sodium hypochlorite with water as the only solvent in the presence of β-cyclodextrin (abbreviated as β-CD). Different factors influencing cinnamaldehyde oxidation e.g. reaction temperature, the amount of catalyst and oxidant, have been investigated. The yield of benzaldehyde reaches 76% under the optimum conditions (333 K, 4 h, molar ratio of cinnamaldehyde to β-CD is 1:1). Furthermore, a feasible reaction mecha-nism including the formation of benzaldehyde and the two main byproducts (phenylacetaldehyde and epoxide of cinnamaldehyde) has been proposed.     

水溶性β-环糊精反应萃取分离苯基琥珀酸对映体的平衡研究

This paper deals with the enantioseparation of phenylsuccinic acid (H2A) enantiomers by liquid-liquid reactive extraction using β-CD derivatives as aqueous selectors. Cyclodextrin and its derivatives can interact with guest molecules selectively to form complexes with different stabilities. Cyclodextrin derivatives are not soluble in organic liquids, but highly soluble in water. In this work, hydroxypropyl-β-cyclodextrin (HP-β-CD), hydroxyethyl- β-cyclodextrin (HE-β-CD) and methyl-β-cyclodextrin (Me-β-CD) were selected as chiral selectors in aqueous phase for the reactive extraction of phenylsuccinic acid enantiomers from organic phase to aqueous phase. The results show that the efficiency of the extraction depends, often strongly, on a number of process variables, including the types of organic solvents and β-CD derivatives, the concentrations of the extractants and H2A enantiomers, pH and temperature. HP-β-CD, HE-β-CD and Me-β-CD have stronger recognition abilities for R-phenylsuccinic acid than for S-phenylsuccinic acid. Among the three kinds of β-CD derivatives, HP-β-CD has the strongest separation ability. Excellent enantio-separation was achieved under the optimal conditions of pH of 2.5 and temperature of 5°C with a maximum enantioselectivity (a) of 2.38. Reactive extraction of enantiomers with hydrophilic β-CD derivatives is of strong chiral separation ability and can be hopeful for separations of various enantiomers at a large-scale.     

Production of biodiesel from palm fatty acid distillate using sulfonated-glucose solid acid catalyst:Characterization and optimization

A palm fatty acid distillate (PFAD) has been used for biodiesel production. An efficient sulfonated-glucose acid catalyst (SGAC) was prepared by sulfonation to catalyze the esterification reaction. The effect of three variables i.e. methanol-to-PFAD molar ratio, catalyst amount and reaction time, on the yield of PFAD esters was studied by the response surface methodology (RSM). The optimum reaction conditions were:12.2:1 methanol-to-PFAD molar ratio, 2.9%catalyst concentration and 134 min of time as predicted by the RSM. The reaction under the optimum conditions resulted in 94.5%of the free fatty acid (FFA) conversion with 92.4%of the FAME yield. The properties of the PFAD esters were determined according to biodiesel standards.     

MoVPO型催化剂上氨氧化合成2-氰基吡嗪

The mechanism of 2-cyanopyrazine prepared from 2-methylpyrazine （2-MP） by catalytic ammoxidation has been explained by the theory of appropriate structure of group. A new catalyst of MoVPO was developed. The effects of catalyst promoter phosphorus and supports were investigated. The catalyst containing P, V and Mo in molar ratio of 1.4 ： 1 ： 0.02 and supported on activated alumina and prepared by impregnation method exhibits good activity and selectivity. Reaction factors such as reaction temperature, space velocity, feed composition and service life of catalyst were investigated. Optimum reaction conditions （the volume space velocity of 0.2h-1, the reaction temperature of 380 ~C and molar ratio of 1 ： 7.8 ： 8 ： 8 for 2-MP, water, oxygen and ammonia） were obtained. Selectivity of 93% and yield of 86% could be achieved under these conditions.     

Study on extraction kinetics of α-cyclopentylmandelic acid enantiomers with hydroxyethyl-β-cyclodextrin as chiral selector

In this work,the kinetic study on reactive extraction ofα-cyclopentylmandelic acid(α-CPMA)enantiomers was performed in a Lewis cell using hydroxyethyl-β-cyclodextrin(HE-β-CD)as chiral selector.The enantioselective complexation equilibrium between HE-β-CD andα-CPMA enantiomers was studied by phase solubility method.The important process parameters affecting the initial extraction rate were separately studied and the reaction rate equations were deduced.The optimal conditions for kinetic study were as follows:stirring speed of 75 r·min~(-1),interfacial area of 12.56 cm~2,pH of 2.5,initial HE-β-CD concentration of 0.05 mol·L~(-1),initialα-CPMA concentration of 5 mmol·L~(-1),and temperature of 278 K.The reaction has been found to be first order inα-CPMA and second order in HE-β-CD with the forward rate constants of 2.056×10~(-3)m~6·mol~(-2)·s~(-1)and 1.459×10~(-3)m~6·mol~(-2)·s~(-1)for(S)-α-CPMA and(R)-α-CPMA,respectively.The complexation equilibrium constants were evaluated as 61 L·mol~(-1) and 117 L·mol~(-1)for(S)-α-CPMA and(R)-α-CPMA,and the intrinsic enantioselectivity is estimated as 1.92.     

Synthesis and characterization of poppy seed oil methyl esters

Response surface methodology(RSM) was used to determine the optimum conditions of the methanolysis of crude poppy seed oil using Na OCH3 as catalyst. The experiments were run according to five levels, four variable central composite rotatable design(CCRD) using RSM. The reaction variables, i.e., molar ratio of methanol/oil(3:1–9:1), catalyst concentration(0.5 wt%–1.25 wt% Na OCH3), reaction temperature(25–65 °C), and reaction time(20–90 min) were studied. We demonstrated that the molar ratio of methanol/oil, catalyst concentration,and reaction temperature were the significant parameters affecting the yield of poppy seed oil methyl esters(PSOMEs). The optimum transesterification reaction conditions, established using the RSM, which offered a89.35% PSOME yield, were found to be 7.5:1 molar ratio of methanol/oil, 0.75% catalyst concentration, 45 °C reaction temperature, and 90 min reaction time. The proposed process provided an average biodiesel yield of more than 85%. A linear correlation was constructed between the observed and predicted values of the yield.The gas chromatography(GC) analyses have shown that PSOMEs contain linoleic-, oleic-, palmitic-, and stearic-acids as main fatty acids. The FTIR spectrum of the PSOMEs was also analyzed to confirm the completion of the transesterification reaction. The fuel properties of the PSOMEs were discussed in light of biodiesel standards(ASTM D 6751 and EN 14214).     

The biomimetic catalytic synthesis of acetal compounds using β-cyclodextrin as catalyst

Based on the principle of biomimetic catalysis, β-cyclodextrin was applied to the acetalation reaction as a facile and efficient catalyst, and the synthesis was environmentally friendly with atomic economy. The influencing factors of the acetalation reaction e.g. the reaction time, the volume of water-carrying agent,the molar ratio of catalyst to benzaldehyde and the molar ratio of glycol to benzaldehyde had been studied.The yield of benzaldehyde glycol acetal would reach a maximum of 81.3% under the conditions approached.Six of other acetals were also synthesized. Moreover, a plausible reaction mechanism for the formation of acetal had been proposed.     

Measurement and correlation of solubility of diosmin in four pure solvents and β-cyclodextrin solution at 298.15 K to 333.15 K

The aim of present study was to measure and correlate the solubility of poorly water-soluble flavonoid diosmin in water, ethanol, isopropyl alcohol (IPA), polyethylene glycol-400 (PEG-400) andβ-cyclodextrin (β-CD) aqueous solution (0.02 mol·L-1). The solubility of diosmin was measured using the shake flask method from (298.15 to 333.15) K at atmospheric pressure. The experimental solubilities of diosmin were regressed by the modified Apelblat model with a relative deviation in the range of 0.048%to 5.940%. The correlation coefficients were observed in the range of 0.9957 to 0.9995. The solubility of diosmin was found to be increased with temperature in all sample matrices investigated. The mole fraction solubility of diosmin was found to be higher inβ-CD aqueous solution and PEG-400 as compared to water, ethanol and IPA. Based on solubility data of present study, diosmin was considered as practical y insoluble in water, insoluble in ethanol&IPA and soluble in PEG-400 andβ-CD aqueous solution.     

低高径比外循环气升式生物反应器带渣发酵生产有效霉素

Fermentation experiments to produce validamycins from crude substrates by Streptoniyces hygroscopi-cus were carried out in an external-loop airlift bioreactor (0.0115 m3 ) with a low ratio of height to diameter of the riser of 2.9 and a ratio of riser to downcomer diameter of 6.6. The influences of gas flow rate and liquid volume on fermentation of validamycins were investigated. Comparisons of validamycin fermentation were made among the external-loop airlift bioreactor, a mechanically stirred tank bioreactor (0.010m3 ) and shaking flasks. Under the same operation conditions including fermentation medium composition, inoculum ratio and culture temperature, the fermentation time in the external-loop airlift bioreactor (45 h) was shorter than that in the shaking flasks (100 h) and the same as that in the mechanically stirred tank bioreactor. After a total fermentation time of 45 h under optimized operation conditions, average validamycin concentration obtained in the external-loop airlift bioreactor was     

3,6-二氯吡啶甲酸电化学合成及其工业化生产

The industrialization of electrochemical synthesis of 3,6-dichloropicolinic acid(3,6-DCP) from 3,4,5,6-tetrachloropicolinic acid(3,4,5,6-TCP) in a tank-type undivided electrolytic cell with silver cathode was investigated. The experimental results showed that the electrolytic performance greatly depended on the operation parameters, such as flow rate of electrolyte, temperature, and concentration of NaOH. The reduction of 3,4,5,6-TCP to 3,6-DCP was favored by increasing temperature and flow rate of electrolyte. Industrialization tests of electrochemical synthesis of 3,6-DCP were conducted under the following conditions: silver cathode, temperature 313 K, flow rate 6 cm·s^-1, concentration of NaOH 8%(mass), concentration of 3,4,5,6-TCP 5%（mass）, cathode current density 600 A·m^-2. The current efficiency and conversion ratio of 3,4,5,6-TCP were more than 76% and 99%, respectively. The yield of 3,6-DCP was up to 90% and DC power consumption was 2. 939 kW·h·(kg 3,6-DCP)^-1. The purity of the product was higher than 95%, and its melting point was 151—153℃.     

氯化胆碱·xZnCl_2离子液体在生物柴油制备中的应用(英文)

The inexpensive and moisture-stable Lewis-acidic ionic liquids were prepared and applied for transesterification of soybean oil to biodiesel.The influences of molar ratio of methanol to soybean oil,reaction temperature and amount of ionic liquids were investigated.The transesterification of soybean oil to biodiesel catalyzed by choline chloride·xZnCl2 ionic liquids showed many advantages such as mild conditions and lower cost.On the other hand,the non-ideal yield and complicated separation between biodiesel and soybean oil were also investigated and analyzed.The improvement on the systems of choline chloride·xZnCl2 was proposed for further investigation.     

Zn–Ca–Al mixed oxide as efficient catalyst for synthesis of propylene carbonate from urea and 1,2-propylene glycol

A series of Zn–Ca–Al oxides with different CaO and ZnO contents have been prepared and evaluated in the synthesis of propylene carbonate(PC) from 1,2-propylene glycol(PG) and urea in a batch reactor. The effect of catalyst composition, basicity and reaction process parameters such as temperature, catalyst dose, molar ratio of PG to urea, purge gas flow and reaction time has been studied to find suitable reaction conditions for the PC synthesis. The PC selectivity and yield under the desired conditions could reach 98.4% and 90.8%, respectively. The best performing catalyst also exhibited a good reusability without appreciable loss in the PC selectivity and yield after five consecutive reaction runs. In addition, a stepwise reaction pathway involving a 2-hydroxypropyl carbamate intermediate was proposed for the urea alcoholysis to PC in the presence of Zn–Ca–Al catalysts, according to the time dependences of reaction intermediates and products.     

Production of glycerol carbonate via reactive distillation and extractive distillation:An experimental study☆

A process for the production of glycerol carbonate (GC) is proposed with the transesterification of glycerol (GL) and dimethyl carbonate (DMC) with CaO as catalyst by reactive distil ation and extractive distil ation. The perfor-mance of solvents in separating DMC-methanol azeotrope and the effects of operation parameters on the reactive distillation process are investigated experimental y. The results indicate that both the GL conversion and GC yield increase with the DMC/GL molar ratio, reflux ratio, final temperature of tower bottom, and CaO/GL molar ratio and decrease as the recycle number of CaO increases. The calcium concentration in the residual reaction mixture also decreases remarkably as the DMC/GL molar ratio increases. At DMC/GL molar ratio 4.0, reflux ratio 1.0, final temperature of tower bottom 358 K, and CaO/GL molar ratio 0.05, both the GL conversion and GC yield can reach above 99.0%, and the mass concentration of calcium in the product is less than 0.08%.     

固体超强酸催化剂SO2-4/TiO2-MoO3的制备及其催化合成缩醛（酮）

SO4^2-/TiO2-MoO3, a novel solid superacid, has been prepared and its catalytic activity at different synthetic conditions was examined with esterification of n-butanoic acid and n-butyl alcohol as probing reaction.The optimum conditions were also found, that is, the mass ratio of MoO3 used in the compound is 25%, the calcination temperature 450℃, and the soaked consistency of H2SO4 is 0.5mol.L^-1. Then it was applied in the catalytic synthesis of six similar important ketals and acetals as catalyst and revealed high catalytic activity. Under the condition that the molar ratio of aldehyde/ketone to glycol was 1:1.5, the mass ratio of the catalyst to the reactants was 0.5% and the reaction time 1.0 h, the yield of ketals and acetals reached up to 63.2%. The catalyst can be easily recovered and reused.     

Ni-Na/Zr02-Mn02-Zn0催化合成甲基异丙基酮和二乙基酮（英文）

ZrO2-MnO2-ZnO supports were prepared by the co-precipitation method,and then Ni-Na/ZrO2-MnO2-ZnO catalysts were prepared by the impregnation method.In this paper,the reactions to synthesize methyl isopropyl ketone and diethyl ketone by the one-step synthesis method over this catalyst were studied,and meanwhile,the impact of the catalyst preparation conditions and the reaction conditions on catalyst performance was also investigated.It was observed that under the conditions when Ni loading was 25%,calcination temperature was 400℃ and reduction temperature was 410℃,this catalyst had good catalytic performance on the reaction.The suitable reaction conditions were achieved:reaction temperature was 400℃;reaction at atmospheric pressure;liquid hourly space velocity of raw material of 0.5 h 1 ;and the molar ratio of(methanol)/(methyl ethyl ketone)/(water) was equal to 1/1/1.Under such conditions,the conversion of methyl ethyl ketone could achieve 41.7%,and the overall selectivity of methyl isopropyl ketone and diethyl ketone could achieve 83.3%,which was comparable to the conversion of 38.1% and the selectivity of 82.2% achieved by using palladium as the active material.The good stability made this catalyst have good prospects for industrial application.     

Insight into the degradation mechanism of cefixime under crystallization condition

The chemical stability of cefixime was determined by high-performance liquid chromatography(HPLC) under different conditions, including factors such as p H, solvents, initial concentration, temperature and additives.The degradation process follows the first-order kinetics. A p H-rate profile exhibits the U-shape and shows the maximum stability of cefixime at pH = 6. The stability in different pure solvents is ranked as acetone N ethanol N methanol N water, while the degradation rate of cefixime exists a maximum at the ratio of 0.6 in water + methanol mixtures. In addition, the degradation rate increases with the temperature increasing and the activation energy of degradation was found to be 27.078 k J·mol~(-1) in acetone + water mixed solvents. The addition of different additives was proven to either inhibit or accelerate the degradation. The degradation products were analyzed using HPLC, LC–MS and infrared spectroscopy, and the possible degradation pathways in acid as well as alkaline environment were proposed to help us understand the degradation behavior of cefixime.     

A safe and efficient process for the preparation of difluoromethane in continuous flow

Difluoromethane is typically produced vialiquid-phase fluorination as performed in a batch reactor. However,this process suffers from some problems, e.g., severe corrosion of the reactor, high safety risk, and the regeneration of the catalyst. In this paper, a flow process as performed in the tubular reactor was designed. The optimum conditions for continuous synthesis of difluoromethane were obtained as follows: the reaction temperature was 100℃, the molar ratio of dichloromethane to hydrogen fluoride was 1.6:1 and the reaction time was 300 s. The operation of the cyclic process was stable for 24 h with the conversion per pass of hydrogen fluoride up to 16.2%.The unreacted raw materials were easily reused. The deactivation of the common catalyst, antimony pentachloride, was investigated by catalyst concentration curve and XPS analysis. The approach proposed in this work is proven to be safe, efficient and low amount of catalyst.     

Optimization of a continuous ultrasound assisted oxidative desulfurization (UAOD) process of diesel using response surface methodology (RSM) considering operating cost

A continuous-flow ultrasound-assisted oxidative desulfurization(UAOD) of partially hydro-treated diesel has been investigated using hydrogen peroxide-formic acid as simple and easy to apply oxidation system. The effects of different operating parameters of oxidation stage including residence time(2–24 min), formic acid to sulfur molar ratio(10–150), and oxidant to sulfur molar ratio(5–35) on the sulfur removal have been studied using response surface methodology(RSM) based on Box–Behnken design. Considering the operating costs of the continuous-flow oxidation stage including chemical and electrical energy consumption, the appropriate values of operating parameters were selected as follows: residence time of 16 min, the formic acid to sulfur molar ratio of 54.47, and the oxidant to sulfur molar ratio of 8.24. In these conditions, the sulfur removal and the volume ratio of the hydrocarbon phase to the aqueous phase were 86.90% and 4.34, respectively. By drastic reduction in the chemical consumption in the oxidation stage, the volume ratio of the hydrocarbon phase to the aqueous phase was increased up to 10. Therefore, the formic acid to sulfur molar ratio and the oxidant to sulfur molar ratio were obtained 23.64 and 3.58, respectively, which lead to sulfur removal of 84.38% with considerable improvements on the operating cost of oxidation stage in comparison with the previous works.     

Simultaneous desulfurization and denitrification of sintering flue gas via composite absorbent

Experiments on simultaneous absorption of SO_2 and NO_X from sintering flue gas via a composite absorbent NaClO_2/NaClO were carried out. The effects of various operating parameters such as NaClO_2 concentration(ms), NaClO concentration(mp), molar ratio of NaClO_2/NaClO(M), solution temperature(TR), initial solution pH, gas flow(Vg) and inlet concentration of SO_2(CS) and NO(CN) on the removal efficiencies of SO_2 and NO were discussed. The optimal experimental conditions were determined to be initial solution pH = 6, TR=55 °C and M = 1.3 under which the average efficiencies of desulfurization and denitrification could reach99.7% and 90.8%, respectively. Moreover, according to the analysis of reaction products, it was found that adding NaClO to NaClO_2 aqueous solution is favorable for the generation of ClO_2 and Cl_2 which have significant effect on desulfurization and denitrification. Finally, engineering experiments were performed and obtained good results demonstrating that this method is practicable and promising.     

Organotemplate-free Hydrothermal Synthesis of SUZ-4 Zeolite： Influence of Synthesis Conditions

Various conditions were investigated in detail for the novel organic template-free static hydrothermal synthesis of SUZ-4 zeolite in the presence of seeds. The obtained samples were characterized by XRD （X-ray diffraction）, SEM （scanning electron microscope）, TG （thermal gravimetric analysis）, ICP （inductively coupling plasma） elemental analysis, nitrogen sorption isotherm and surface area. The results show that pure SUZ-4 zeolites with high crystallinity are obtained in a broad window of synthesis conditions： seed mass concentration 0.2%-2%, SIO2/A1203 molar ratio 21 25, KOH/SiO2 molar ratio 0.33 0.43, H20/SiO2 molar ratio 7.14-38.1, aging time 24 h, crystallization temperature 160℃, and crystallization time 6-10 d. Also, crystallinity and size of the rod-like SUZ-4 zeolite crystals are found to alter with the conditions.