椰油丙基酰胺甜菜碱/聚乙二醇水溶液的分相研究

Phase separation behavior of cocamidopropyl betaine/water/polyethylene glycol (PEG) system was studied. The effects of concentration and molecular weight of PEG on the phase separation behavior were investigated. Clouding occurred when the con-centration of PEG was large enough in the betaine aqueous solution, and the concentration of PEG at cloud point decreased with the increase of PEG molecular weight for a constant betaine concentration. The bottom phase was the PEG-rich phase, and the upper phase was the betaine-rich phase. The volumetric ratio of PEG-rich phase to betaine-rich phase, at the same difference between the PEG concentration and the one at the cloud point, Ccp (0.1 g•ml－1), decreased as the PEG molecular weight increased and approached 1 for higher PEG molecular weight (about 20000), which was similar to the typical aqueous two-phase system. This volumetric ratio depended on the initial PEG concentration, but independent of PEG molecular weight. The concentration ratio of betaine to PEG in both phases depended on the Ccp, independent of PEG molecular weight.     

P507溶于煤油作为载体的一种新型分散组合液膜对Eu3+的分离

The separation of Eu3+ is studied with a dispersion combined liquid membrane (DCLM), in which polyvinylidene fluoride membrane (PVDF) is used as the liquid membrane support, dispersion solution containing HCl solution as the stripping solution, and 2-ethyl hexyl phosphonic acid-mono-2-ethyl hexyl ester (P507) dissolved in kerosene as the membrane solution. The effects of pH value, initial concentration of Eu3+ and different ionic strength in the feed phase, volume ratio of membrane solution to stripping solution, concentration of HCl solution, concentration of carrier, different stripping agents in the dispersion phase on the separation are investigated. The optimum condition for separation of Eu3+ is that concentration of HCl solution is 4.0 mol•L1, concentration of carrier is 0.16 mol•L1, and volume ratio of membrane solution to stripping solution is 30︰30 in the dispersion phase, and pH value is 4.2 in the feed phase. The ionic strength has no significant effect on separation of Eu3+. Under the optimum condition, when the initial concentration of Eu3+ is 0.8×104 mol•L1, the separation percentage of Eu3+ is 95.3% during the separation time of 130 min. The kinetic equation is developed in terms of the law of mass diffusion and the theory of interface chemistry. The diffusion coefficient of Eu3+ in the membrane and the thickness of diffusion layer between feed phase and membrane phase are obtained and their values are 1.48×107 m2•s1 and 36.6 μm, respectively. The results obtained are in good agreement with literature data.     

生物活性泡沫乳液反应器处理被苯、甲苯、二甲苯污染的空气

A novel bioactive foam emulsion bioreactor for benzene, toluene and xylene (BTX) contaminated air streams treatment has been developed. The gas-liquid interfacial area by biocompatible foam and driving force for mass transfer by a water immiscible organic phase were increased in this reactor. The effect of several parameters such as gas residence time, oxygen content, and organic phase concentration on bioreactor performance was studied. Experimental results showed an average elimination capacity (EC) of 220 g&;#8226;m－3&;#8226;h－1 with removal efficiency (RE) of 89.59% for BTX inlet concentration of 1 g&;#8226;m－3 at 15 s gas residence time in the bioreactor. The statistical developed model predicted that the maximum elimination capacity of the reactor for BTX could be reached to 423.45 g&;#8226;m－3&;#8226;h－1. Continues operation of the bioreactor with high EC and RE was demonstrated by optimizing the operational parameters of the bioreactor. Overall the results suggest that the bioreactor developed can be very effective systems to treat BTX vapors.     

硫酸铁改性颗粒活性氧化铝除氟的等温线研究

The adsorption equilibrium of a fluoride solution on 1-2 mm granular activated alumina modified by Fe2(SO4)3 solution was investigated. The experiments were conducted using a wide range of initial fluoride concentrations (0.5 to 180 mg•L1 at pH ~7.0) and an adsorbent dose of 1.0 g•L1. The application of Langmuir and Freundlich adsorption isotherm models (linear and nonlinear forms) generally showed that a single Langmuir or Freundlich equation cannot fit the entire concentration gap. Experimental data on low equilibrium concentrations (0.1 to 5.0 mg•L1) was in line with both Langmuir and Freundlich isotherm models, whereas that of high equilibrium concentrations (5.0 to 150 mg•L1) was more in line with the Freundlich isotherm model. A new Langmuir- Freundlich function was used for the entire concentration gap, as well as for low and high concentrations.     

PDMS/陶瓷复合膜用于正丁醇-水体系的渗透汽化分离

Pervaporation has attracted considerable interest owing to its potential application in recovering biobutanol from biomass acetone-butanol-ethanol (ABE) fermentation broth. In this study, butanol was recovered from its aqueous solution using a polydimethylsiloxane (PDMS)/ceramic composite pervaporation membrane. The effects of operating temperature, feed concentration, feed flow rate and operating time on the membrane pervaporation per-formance were investigated. It was found that with the increase of temperature or butanol concentration in the feed, the total flux through the membrane increased while the separation factor decreased slightly. As the feed flow rate increased, the total flux increased gradually while the separation factor changed little. At 40 C and 1% (by mass) butanol in the feed, the total flux and separation factor of the membrane reached 457.4 g•m2•h1 and 26.1, respec-tively. The membrane with high flux is suitable for recovering butanol from ABE fermentation broth.     

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.     

甲苯与叔丁醇在补铝HM沸石催化剂上的烷基化反应

The realuminated H-mordenite catalysts (HM1-4) treated with different concentrations of NaOH and NaAlO2 aqueous solutions were prepared, and characterized by inductively coupled plasma (ICP), X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FT-IR) and temperature-programmed desorption of ammonia, They are of lower Si/Al ratio and higher acid amount while keeping a high relative crystallinity. Their catalytic performances were evaluated with the liquid-phase tert-butylation of toluene with tert-butyl alcohol in a 100 ml stainless steel batch reactor equipped with a stirrer. HM2 zeolite catalyst, obtained by treating HM in 0.1 mol•L－1 NaOH followed by 0.05 mol•L－1 NaAlO2 aqueous solution, shows a higher catalytic activity because of its highest acid amount. For HM2 catalyst the influences of reaction conditions on catalytic performance were investigated. The conversion of toluene is 50.3% and the selectivity of p-tert-butyltoluene is 74.7% at a temperature of 180°C, 2 of molar ratio of tert-butyl alcohol to toluene, 4h of reaction time and 0.2 of M(catalyst)/M(toluene).     

突变株CTM2降解苯酚和4-氯酚的生物降解特性

The biodegradations of phenol and 4-chlorophenol (4-cp) were studied using the mutant strain CTM 2 obtained by the He-Ne laser irradiation on wild-type Candida tropicalis. The results showed that the capacity of the CTM 2 to biodegrade 4-cp was increased up to 400 mg•L－1 within 59.5 h. In the dual-substrate biodegradation, both velocity and capacity of the CTM 2 to degrade 4-cp increased with low-concentration phenol. A total of 400 mg•L－1 4-cp was completely degraded within 50.5 h in the presence of 300 mg•L－1 phenol. The maximum 4-cp biodegradation could reach 440 mg•L－1 with 120 mg•L－1 phenol. Low-concentration 4-cp caused great inhibition on the CTM 2 to degrade phenol. In addition, the kinetic behaviors were described using the kinetic model proposed in this lab.     

氨改性的介孔二氧化硅的直接合成和CO2吸附

Amine-functionalized mesoporous silica was prepared by using lauric acid and N-stearoyl-l-glutamic acid as structure directing agents via the SN+-I mechanism and applied to CO2 adsorption at room temperature. With γ-aminopropyltriethoxysilane as co-structure directing agent and due to the direct electrostatic interaction with anionic surfactant, most of the amino groups were uniformly distributed at the inner surface of pores and the performance was stable. The amine-functionalized mesoporous silica was characterized by Fourier transform infrared spectrometer, X-ray diffraction, nitrogen physisorption and thermogravimetric analysis. The CO2 adsorption capacity was measured by digital recording balance. At the room temperature and under the atmospheric pres-sure, the adsorption capacity of LAA-AMS-0.2 for CO2 and N2 is 1.40 mmol•g1 and 0.03 mmol•g1, respectively, indicating high separation coefficient of CO2/N2.     

面包酵母No.6催化不对称合成(2S,5S)-2,5-已二醇反应特性

Baker’s yeast number 6 was selected by screening. It showed good catalytic activity and enantioselectivity for asymmetric reduction of 2,5-hexanedione to produce (2S,5S)-2,5-hexanediol. Gas chromatography-mass spectrometry (GC-MS) revealed that the intermediate was (S)-5-hydroxyhexane-2-one. Reduction of 2,5-hexanedione proceeded in a two-step reaction. The hydroxyketone was initially formed, and this intermediate was further re-duced to the diol. Factors influencing the product yield and the enantiomeric excess of the reduction of 2,5-hexandione catalyzed by baker’s yeast number 6 were investigated. Higher concentration (≤100 mmol•L－1) of 2,5-hexandione did not influence 5-hydroxyhexane-2-one production, but 2,5-hexanediol production was inhibited by excess accumulation (＞30 mmol•L－1) of intermediate. The optimal conditions were glucose as the co-substrate at an initial glucose concentration of 20 g•L－1, 34C, pH 7.0 and cell concentration 60 g•L－1 (cell dry mass). Under the optimal condition and an initial substrate concentration of 30 mmol•L－1, the yield of 2,5-hexandiol was 78.7% and the enantiomeric excess of (2S,5S)-2,5-hexandiol was 94.4% for 24-h reduction.     

乙酰丙酮钴(Ⅱ)对甲苯液相空气氧化反应的催化性能

以乙酰丙酮钴(Co(acac)₂)为催化剂,在1 L高压搅拌反应釜中研究了其对甲苯液相空气氧化反应的催化性能和反应产物分布,考察了催化剂用量对甲苯转化率和苯甲酸收率的影响,并考察了不同温度下不同催化剂用量时的催化剂寿命。结果表明,Co(acac)₂催化甲苯液相氧化是平行连串的复杂反应,Co(acac)₂的催化活性存在"催化-抑制转换"现象,适宜的催化剂用量为0.0044%(质量分数);催化剂的寿命随反应温度变化存在一个最大值,165℃时催化剂寿命最长,反应温度较低(<165℃)时催化剂更容易失活;在165℃、Co(acac)₂用量为0.0044%时,反应4 h,甲苯转化率为19%,苯甲酸收率为80%;与醋酸钴、环烷酸钴等钴盐催化剂相比,Co(acac)₂催化剂具有用量少、催化活性时间长的优点,可有效地减缓钴盐结垢现象,Co(acac)₂催化剂对甲苯液相空气氧化反应具有良好的催化性能。     

Co/Mn/Zr复合催化剂催化甲苯液相氧化

以乙酰丙酮锆或乙酸锆与乙酸钴和乙酸锰制备乙酸钴/乙酸锰/乙酰丙酮锆或乙酸锆(Co/Mn/Zr)三元复合催化剂。比较乙酸钴(Co)、乙酸钴/乙酸锰(Co/Mn)和Co/Mn/Zr催化剂体系对甲苯液相氧化反应的催化性能。结果表明:在催化剂中添加Zr可以降低反应温度,提高甲苯转化率和苯甲酸选择性。与乙酸锆相比,采用乙酰丙酮锆制得的Co/Mn/Zr具有较好的催化活性。在Co,Mn和Zr物质的量之比为5 5 1,Co与甲苯的物质的量之比为1 10 000,溶剂乙酸与甲苯质量比为1 2.3,反应温度160℃和反应压力1.4 MPa的条件下反应3 h后,苯甲酸选择性和甲苯转化率分别为80.2%和15.4%。     

甲苯液相氧化过程中结垢的原因及其影响因素

甲苯液相空气氧化是环境友好的苯甲酸生产工艺.在SNIA苯甲酸生产过程中,CoC2O4&#8226;2H2O的生成导致甲苯氧化过程产生严重的结垢现象,严重影响生产的正常运行.通过液相色谱对反应中间产物进行检测,发现有痕量的对苯二酚、马来酸、草酸生成.对生成CoC₂O₄&#8226;2H₂O的可能途径进行了分析和研究,结果表明,通过苯、甲苯及其衍生物氧化生成草酸是导致结垢的主要原因.通过改变反应物组成及操作条件,对反应温度、操作压力、空速、催化剂用量、苯含量以及含水量等因素对结垢的影响进行了研究.结果表明,当生成苯甲酸的目标反应受到抑制时,结垢明显加剧.随着反应体系中的苯含量或含水量的增大,其结垢加剧.当催化剂浓度低于100 μg&#8226;g^-1时,随Co含量的增大,其结垢减轻.当反应体系中无苯甲酸时,反应受到抑制,结垢严重.当空气鼓气量低于4.0×10-3 m³&#8226;min^-1时,随空气鼓气量的增大,其结垢减轻.操作压力对结垢的影响较小.反应温度低于155 ℃时,反应受到抑制同时结垢加剧.     

锰卟啉-醋酸钴复合催化体系对甲苯氧气氧化的催化作用

研究了在无溶剂体系中,对氯四苯基锰卟啉［T(p-Cl)PPMnCl］和醋酸钴［Co(OAc)2］复合催化下,空气氧化甲苯制苯甲醛、苯甲醇和苯甲酸的新工艺。实验发现,T(p-Cl)PPMnCl/Co(OAc)2为复合催化剂时比单独使用T(p-Cl)PPMnCl 或Co(OAc)2时有更高的甲苯转化率和苯甲醛、苯甲醇、苯甲酸的收率,表现出明显的复合催化作用。研究表明,反应温度、反应时间和催化剂比例对T(p-Cl)PPMnCl/Co(OAc)2的复合催化效果有影响。     

槽外法苯甲酸催化甲苯电合成苯甲醛

以苯甲酸作相转移催化剂,Mn3+/Mn2+为媒介,甲苯为原料,采用槽外法电合成苯甲醛。利用正交实验研究了H2SO4浓度、反应温度和苯甲酸用量对苯甲醛生成速率和产率的影响。结果表明,当每升甲苯含8 g苯甲酸、水相H2SO4浓度为51.6%和反应温度85℃时,苯甲醛的收率大于93%。     

Micellar catalysis for partial oxidation of toluene to benzoic acid in supercritical CO2: effects of fluorinated surfactants

One of the key hindrances on development of solid catalysts containing cobalt species for partial oxidation of organic molecules at mild conditions in conventional liquid phase is the severe metal leaching. The leached soluble Co species with a higher degree of freedom always out-performs those of solid supported Co species in oxidation catalysis. However, the homogeneous Co species concomitantly introduces separation problems. We have recently reported for the first time, a new oxidation catalyst system for the oxidation of organic molecules in supercritical CO₂ using the principle of micellar catalysis. [CF₃(CF₂)₈COO]₂Co·xH₂O (the fluorinated anionic moiety forms aqueous reverse micelles carrying water-soluble Co²⁺ cations in scCO₂) was previously shown to be extremely active for the oxidation of toluene in the presence of sodium bromide in water–CO₂ mixture, giving 98% conversion and 99% selectivity to benzoic acid at 120 °C. In this study, we show that the effects of varying the type of surfactant counterions and the length of the surfactant chains on catalysis. It is found that the use of [CF₃(CF₂)₈COO]₂Mg·yH₂O/Co(II) acetate is as effective as the [CF₃(CF₂)₈COO]₂Co·xH₂O and the fluorinated chain length used has a subtle effect on the catalytic rate measured. It is also demonstrated that this new type of micellar catalyst in scCO₂ can be easily separated via CO₂ depressurisation and be reused without noticeable deactivation.     

Liquid Phase Oxidation of Toluene to Benzaldehyde with Molecular Oxygen over Copper‐Based Heterogeneous Catalysts

We conducted the liquid phase oxidation of toluene with molecular oxygen over heterogeneous catalysts of copper‐based binary metal oxides. Among the copper‐based binary metal oxides, iron‐copper binary oxide (Fe/Cu=0.3 atomic ratio) was found to be the best catalyst. In the presence of pyridine, overoxidation of benzaldehyde to benzoic acid was partially prevented. As a result, highly selective formation of benzaldehyde (86% selectivity) was observed after 2 h of reaction (7% conversion of toluene) at 463 K and 1.0 MPa of oxygen atmosphere in the presence of pyridine. These catalytic performances were similar or better than those in the gas phase oxidation of toluene at reaction temperatures higher than 473 K and under 0.5–2.5 MPa. It was suggested from competitive adsorption measurements that pyridine could reduce the adsorption of benzaldehyde. At a long reaction time of 4 h, the conversion increased to 25% and benzoic acid became the predominant reaction product (72% selectivity) in the absence of pyridine. The yield of benzoic acid was higher than that in the Snia‐Viscosa process, which requires corrosive halogen ions and acidic solvents in the homogeneous reaction media. The catalyst was easily recycled by simple filtration and reusable after washing and drying.     

Catalytic Liquid Phase Oxidation of Toluene to Benzoic Acid

The production of benzoic acid from toluene in the liquid phase with pure oxygen was studied. Investigations have been carried out with a view to determining the most suitable reaction conditions with respect to operating variables including oxygen flow rate, reaction temperature, batch time and catalyst loading. In a series of batch experiments carried out at 4 atm, the optimum values of mole ratio of oxygen to toluene, temperature, reaction time, and catalyst loading were found to be 2, 157 °C, 2 h and 0.57 g/L, respectively. In addition, a kinetic study was carried out by taking into consideration the optimum reaction conditions. The model dependent on the formation of benzyl radical was found to be feasible for describing the catalytic oxidation of toluene to benzoic acid in the liquid phase. The activation energy was determined as 40 kJ/mol.     

异丙苯液相催化氧化

在500 mL钛制间歇釜中,以异丙苯为原料,醋酸为溶剂,醋酸钴、醋酸锰和溴化氢为催化剂,空气为氧化剂,考察催化剂浓度和反应温度对产物组成和反应速率的影响,并分析异丙基氧化产物结构.结果表明,比较适宜的反应条件为180℃,催化剂Co和Mn与反应物异丙苯物质的量之比为0.05,该条件下,异丙苯可以完全转化,苯甲酸的收率为95%.异丙苯氧化产物主要为α-甲基苯乙烯、苯乙酮、α-甲基苯乙烯的聚过氧化物以及苯甲酸;整个氧化过程中,α-甲基苯乙烯与氧气作用形成聚过氧化物的反应是影响苯甲酸收率的关键因素;提高反应温度和增加催化剂浓度都能改变口-甲基苯乙烯的聚过氧化物的稳定性,使其开裂并最终转化为苯甲酸.     

醋酸液相氧化燃烧反应动力学

以醋酸钴、醋酸锰为主催化剂,溴化钾为促进剂,乙酸钾为助催化剂,在半连续搅拌釜式钛材反应器中通过测定尾气中CO2和CO的生成量,对醋酸的液相催化氧化动力学进行了研究. 分别考察了空气流量、温度、催化剂总浓度、[Co]/[Mn]比、溴离子浓度、水含量等因素对醋酸燃烧损失速率的影响. 实验结果表明,增加催化剂总浓度和[Co]/[Mn]比能明显加快CO2和CO的生成速率常数,提高溴离子浓度和降低反应温度可显著抑制醋酸的燃烧损失,同时根据实验结果得出CO2和CO的反应活化能分别为88.11和127.31 kJ/mol.