循环微反应系统内间甲基苯甲醚的合成

间甲基苯甲醚是一种染料中间体,其传统合成方法是通过低温控制反应物混合,生产效率低下,通过微反应器改善反应物混合具有重要的研究价值。本文系统研究了微反应器辅助下的间甲基苯甲醚合成过程,发现体系内间甲酚与氢氧化钠可快速发生反应,形成间甲酚钠,进而发现间甲酚钠与硫酸二甲酯间的氧烷基化反应随着反应温度的提升而获得强化,60~80℃的高温更有利于氧烷基化反应与硫酸二甲酯水解反应的竞争。通过实验考察了反应物流量比、计量比、浓度等因素对间甲基苯甲醚收率的影响,发现微反应器保证两相反应物的快速均匀混合是成功实施高温快反应的关键。相对优化的实验结果表明：当硫酸二甲酯/间甲酚摩尔比大于1.05时,使用质量分数为30%的氢氧化钠溶液实施间甲基苯甲醚的合成反应的产率可达99%以上。     

油酚分离过程低共熔溶剂的筛选及萃取性能研究

低温煤焦油中酚类化合物的高效分离在工业上具有重要意义。采用COSMO-RS模型对40种用于间甲酚-异丙苯分离的低共熔溶剂进行筛选,结合σ-profile和σ-potential对筛选得到的低共熔溶剂的高萃取性能进行分析。并采用液液相平衡实验对筛选结果进行验证,优化了萃取工艺条件。结果表明,COSMO-RS模型筛选得到的氯化胆碱(ChCl)∶乙二醇(EG)(1∶2)、ChCl∶丙三醇(Gly)(1∶2)、ChCl∶乳酸(LA)(1∶2)三种低共熔溶剂与间甲酚之间存在较强的氢键相互作用,与异丙苯之间存在排斥作用。液液相平衡实验证实了COSMO-RS筛选结果的可靠性,其中ChCl∶EG(1∶2)具有最高的分配系数和选择性系数,且黏度最低,被选定为最佳的低共熔溶剂。在25℃、ChCl∶EG(1∶2)与模型油质量比为1∶1时,ChCl∶EG(1∶2)对间甲酚萃取率高达98.41%,同时异丙苯夹带量仅为8.41%,并且具有良好的循环使用性能。     

油酚分离过程低共熔溶剂的筛选及萃取性能研究

低温煤焦油中酚类化合物的高效分离在工业上具有重要意义。采用COSMO-RS模型对40种用于间甲酚-异丙苯分离的低共熔溶剂进行筛选,结合σ-profile和σ-potential对筛选得到的低共熔溶剂的高萃取性能进行分析。并采用液液相平衡实验对筛选结果进行验证,优化了萃取工艺条件。结果表明,COSMO-RS模型筛选得到的氯化胆碱(ChCl)∶乙二醇(EG)(1∶2)、ChCl∶丙三醇(Gly)(1∶2)、ChCl∶乳酸(LA)(1∶2)三种低共熔溶剂与间甲酚之间存在较强的氢键相互作用,与异丙苯之间存在排斥作用。液液相平衡实验证实了COSMO-RS筛选结果的可靠性,其中ChCl∶EG(1∶2)具有最高的分配系数和选择性系数,且黏度最低,被选定为最佳的低共熔溶剂。在25℃、ChCl∶EG(1∶2)与模型油质量比为1∶1时,ChCl∶EG(1∶2)对间甲酚萃取率高达98.41%,同时异丙苯夹带量仅为8.41%,并且具有良好的循环使用性能。     

Heterogeneous basic catalysts as alternatives to homogeneous catalysts: reactivity of Mg/Al mixed oxides in the alkylation of m-cresol with methanol

Mg/Al mixed oxides, obtained by decomposition of hydrotalcite-like precursors, represent interesting heterogeneous catalytic systems for basic-catalyzed reactions, as an alternative to environmentally unfriendly homogeneous catalysts. The reactivity of these oxides was evaluated using the methylation of m-cresol as a test reaction and relationships between catalytic performance and chemical–physical features were established. The basicity of the samples was evaluated by CO₂ adsorption and thermal-programmed-desorption. The presence of Al in the mixed oxides considerably affected the density and the strength of the basic sites with respect to MgO. These basic properties in turn influenced the catalytic performance of the materials. Under the reaction conditions used in the present work, medium strength basic sites played the major role in the reaction.     

HIGH PRESSURE DENSITIES OF MIXTURES OF COAL CHEMICALS

Densities of seven coal chemicals (benzene, toluene, letralin, quinoline, m-cresol, bicyctohexyl and 1-methylnapthalene) and their binary mixtures at temperatures between 298 K and 338 K and pressures between 0.1 MPa and 34.5 MPa were measured using a high-pressure vibrating tube densitometer and are reported in this paper. The pure component densities were correlated using a modified Tail equation. The pure components were then used as reference fluids in a corresponding stales method for the prediction of the densities of the mixtures. @KEYWORDS High pressure Densities Mixtures Coal chemicals.     

Interdiffusion in blends of polystyrene and polymethylstyrene studied by light scattering after temperature jumps across the phase boundary

We describe a simple light scattering set-up for measuring interdiffusion coefficients D in polymer blends by generating spinodal decomposition and subsequent dissolution after temperature jumps across the phase boundary. In blends of polystyrene and polymethylstyrene (random copolymer of 60% m-methylstyrene and 40% p-methylstyrene) D values were obtained between 10⁻¹¹ and 10⁻¹⁵ cm²s⁻¹ at temperatures up to 50 K above the upper critical solution temperature. The results are discussed in relation to tracer diffusion in the same system.     

Synthesis and photo-induced solution properties of new rigid-rod polyimides

A series of new, substituted pyromellitic dianhydrides were synthesized from 1,2,4,5-tetramethylbenzene. New soluble rigid-rod polyimides were obtained from the dianhydrides and 2,2′-bis(trifluoromethyl)-4,4′-biphenyl (PFMB) in phenolic solvents in the presence of isoquinoline as a catalyst. The polyimides are soluble in N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), m-cresol and other solvents, in spite of having no bending in their rigid structures.

UV irradiation changed color of the polyimide solutions and also their viscosity. We observed new absorbance in the 700-nm region and an ESR signal by UV irradiation. The new visible absorbance and the ESR signal are derived from the same origin. They are attributed to the anion radical of the diimide moiety in the polyimide as deduced from the hyper fine structure of the ESR signal. In addition, UV irradiation diminishes the solution viscosity.     

有机溶剂浸取湿法磷酸脱氟渣制备磷酸的研究

脱氟渣是湿法磷酸化学沉淀脱氟过程产生的固体废渣。分别用甲醇、乙醇和丙酮浸取脱氟渣来回收脱氟渣中的磷酸,研究了浸取时间、温度和液固比对于五氧化二磷、氟的浸取率以及浸出液磷氟比［m（五氧化二磷）/m（氟）］的影响,得到了适宜的浸取条件。浸取液经蒸发浓缩回收浸取剂后,浓缩液均可满足饲料级磷酸氢钙生产对于湿法磷酸磷氟比的要求。综合考虑浸取剂成本、五氧化二磷浸取率和浸出液磷氟比,确定甲醇为优选浸取剂,并用响应面法对甲醇浸取工艺条件进行优化。优化工艺条件下五氧化二磷的浸取率为97.13%、浸出液磷氟比为51.62,甲醇在5次循环回收利用后对脱氟渣仍有较好的浸取效果。     

Investigation of conformational transitions in polyamide-6 macromolecules in mixtures of m-cresol and methanol

The intrinsic viscosity of polyamide-6 (PA-6) solutions in mixtures of m-cresol and methanol decreases with increasing methanol concentration. A conformational transition occurs in the 50–60% methanol concentration range. This phenomenon has been studied by viscometric measurements for various methanol concentrations, a two-fold decrease of intrinsic viscosity having been observed. The results are interpreted by assuming that the observed decrease in intrinsic viscosity is due to a coil-globule conformational change in the polyamide-6 molecules. A decrease of intrinsic viscosity also occurs on increasing the temperature at which the viscometric measurements are carried out. This is explained by the possibility of occurrence of a cis-trans isomerisation, and of a partial helix-coil conformational change.     

Biodegradability enhancement of phenolic compounds by Hydrogen Peroxide Promoted Catalytic Wet Air Oxidation

The aim of this work is to study the viability of the H₂O₂ Promoted Catalytic Wet Air Oxidation (PP-CWAO) process, using activated carbon (AC) as catalyst, to increase the biodegradability of phenolic aqueous solutions. Seventy-two hours experiments were performed in a trickle bed reactor at 140 °C and 2 bar of oxygen partial pressure. Feed concentrations, in terms of theoretical chemical oxygen demand (ThCOD), were 11.8 g COD l⁻¹ for phenol, 12.6 g COD l⁻¹ for o-cresol and 8.0 g COD l⁻¹ for p-nitrophenol. Air was used as main oxidant and 20% of the stoichiometric amount of H₂O₂ needed for pollutant complete mineralisation was added as oxidation promoter. Adding H₂O₂ to the CWAO process not only increases pollutant removal but also leads to higher mineralisation of the remaining oxidation products. For instance, removal of phenol, o-cresol and p-nitrophenol increase from 45, 33 and 15% in the CWAO process to 64, 64 and 49% in the PP-CWAO process. In addition, the PP-CWAO process leads to better biodegradability enhancements, when compared to CWAO, as demonstrated by the respirometric tests. However, it is still necessary to improve the oxidation step in order to assure more biodegradable effluents that could be combined with a subsequent biological wastewater plant.     

Direct NO decomposition over La2−xBaxNiO4 catalysts containing BaCO3 phase

Catalytic and in situ Fourier Transform Infrared (FTIR) spectroscopic studies were conducted to investigate the adsorption and oxidation of o- and p-chlorophenol over a 3.6 wt.% V₂O₅/TiO₂ catalyst. At a space velocity of approximately 53,000 cm³ g⁻¹ h⁻¹, this catalyst was found to be active for the oxidation of o- and p-chlorophenol at temperatures as low as 200 °C, yielding CO₂ and HCl as the main products. Trace amounts of higher molecular weight products were also detected at the reactor outlet indicating the operation of additional condensation, coupling and chlorination/dechlorination side reactions in parallel to the main complete oxidation scheme. The in situ FTIR studies revealed that different phenols adsorb on the V₂O₅/TiO₂ catalyst through their hydroxyl group. Furthermore, the formation of similar surface species (i.e., maleates, acetates, formates and an aldehyde-type species) was observed. The results were compared with those of previous studies on the oxidation of m-dichlorobenzene (m-DCB) and benzene and suggest that a similar reaction mechanism is operating in all cases, although the relative kinetic significance of the different steps varies with the presence and the position of the hydroxyl and chlorine groups on the aromatic ring.     

硝酸法磷酸脱氟工艺研究

针对以硝酸法湿法磷酸直接制备饲料级磷酸氢钙存在磷氟比（五氧化二磷与氟的质量比）较低的问题,采用化学沉淀法,以钙盐作为脱氟剂,通过间歇实验考察了反应时间、反应温度、反应pH、酸解液中五氧化二磷和氧化钙浓度等因素对酸解液中磷沉淀率和磷氟比的影响。结果表明,反应时间和反应温度的变化对溶液的磷沉淀率和磷氟比影响不大,而降低五氧化二磷和氧化钙的浓度能够有效地提高溶液的磷氟比、降低磷沉淀率。通过对比脱氟溶液制备饲料级磷酸氢钙的收益变化可得出较优操作条件：反应温度为40 ℃,反应时间为20 min,酸解液中五氧化二磷质量分数为7.6%、氧化钙质量分数为3.4%,钙盐中和溶液pH为2.4。在此条件下,脱氟溶液的磷氟比达到230以上、磷损失率小于30%,可为后续饲料级磷酸氢钙的制备提供合格的原料。     

Carbon-based monolithic supports for palladium catalysts: The role of the porosity in the gas-phase total combustion of m-xylene

Three different carbon-based monoliths have been studied in their performance as Pd catalyst supports in the total gas-phase combustion of m-xylene at low temperatures. The first monolithic support (HPM) was a classical square channel cordierite modified with -Al₂O₃, blocking the macroporosity of the cordierite and rounding the channel cross-section, on which a carbon layer was applied by carbonization of a polyfurfuryl alcohol coating obtained by dipcoating. The other two monolithic supports were composite carbon/ceramic monoliths (MeadWestvaco Corporation, USA), microporous (WA) and a mesoporous (WB) sample.

All the catalysts have a comparable total Pd loading and very similar Pd particle size (around 5–6 nm). In sample Pd/WA the Pd is situated only in the macropores, while in the case of Pd/WB the Pd is distributed throughout the mesoporous texture. In the case of Pd/HPM, Pd particles are clearly situated at the external surface of the carbon layer.

The catalytic activities of the samples were very different, decreasing in the order: Pd/WB > Pd/WA > Pd/HPM. These results show that the carbon external surface area, the macropores and mainly mesopores, play an important role in this kind of gas-phase reactions, improving the contact between the Pd particles and the m-xylene molecules. The catalytic activity of the Pd supported on carbon-based monoliths correlates with the surface area developed in macro- and mesopores of the monolithic support.     

咪唑类离子液体催化合成抗氧剂BHT

2,6-二叔丁基对甲酚（BHT）是一种受阻酚类抗氧化剂,因其抗氧化性强、挥发性低、稳定性高、耐用性好等优点被广泛应用于化工、食品、医药等领域。本文以对甲酚和异丁烯为原料,对咪唑类离子液体1-（3-磺酸基丙基）-3-甲基咪唑（IL1）催化合成BHT的反应进行了研究,得到的最优反应条件为：对甲酚与催化剂IL1的摩尔比为5：1,在80℃下反应8h。BHT粗品的含量达到99.1%,收率为93.0%,且IL1重复使用4次后仍具有较高的催化活性。与传统酸性催化剂如浓硫酸和对甲苯磺酸比较,IL1具有催化活性高、易于分离、可重复使用、对设备腐蚀性小等优点,在BHT的工业制备中具有良好的应用前景。     

工业生产氟硅酸镁工艺探究

为了寻求工业生产氟硅酸镁的最佳工艺条件,降低能耗并提高产品质量,系统研究并优化了利用磷肥工业副产氟硅酸和氧化镁粉生产氟硅酸镁晶体颗粒产品的工艺参数。列举了氟硅酸镁产品的粒径以及粒度分布等物化性能指标,得到了氟硅酸镁产品最大产率的最佳工艺参数：直接将氧化镁粉计量加入合成槽,并确定其加入的顺序,氟硅酸质量分数为16%,m（氧化镁）/m（氟硅酸）为0.244~0.260,合成温度控制在40~50 ℃,得到浓度较高的产品溶液;蒸发温度为35~45 ℃,蒸发浓缩的晶浆进入MSMPR冷却结晶槽;冷却结晶温度控制在30 ℃,结晶槽搅拌器的转动频率控制在20~40 Hz,产品粒径可以控制在0.16~0.37 mm,该研究可为相关生产企业提供工艺技术方面的借鉴。     

Determination and correlation solubility of m-phenylenediamine in (methanol,ethanol, acetonitrile and water) and their binary solvents from 278.15 K to 313.15 K

In this study, the solubility of m-phenylenediamine in four pure solvents(methanol, ethanol, acetonitrile and water) and three binary solvent(methanol + water),(ethanol + water) and(acetonitrile + water) systems were determined in the temperature ranging from 278.15 K to 313.15 K by using the gravimetric method under atmospheric pressure. In the temperature range of 278.15 K to 313.15 K, the mole fraction solubility values of m-phenylenediamine in water, methanol, ethanol, and acetonitrile are 0.0093–0.1533, 0.1668–0.5589,0.1072–0.5356, and 0.1717–0.6438, respectively. At constant temperature and solvent composition, the mole fraction solubility of o-phenylenediamine in four pure solvents was increased as the following order:water b ethanol b methanol b acetonitrile; and in the three binary solvent mixtures could be ranked as follows:(ethanol + water) b(methanol + water) b(acetonitrile + water). The relationship between the experimental temperature and the solubility of m-phenylenediamine was revealed as follows: the solubility of mphenylenediamine in pure and binary solvents could be increased with the increase of temperature. The experimental values were correlated with the Jouyban–Acree model, van't Hoff–Jouyban–Acree model, modified Apelblat–Jouyban–Acree model, Sun model and Ma model. The standard dissolution enthalpy, standard dissolution entropy and the Gibbs energy were calculated based on the experimental solubility data. In the binary solvent mixtures, the dissolution of m-phenylenediamine could be an endothermic process. The solubility data,correlation equations and thermodynamic property obtained from this study would be invoked as basic data and models regarding the purification and crystallization process of m-phenylenediamine.     

钒酸铋晶面调控制备及其降解四环素类抗生素性能研究

采用溶剂热法合成了单斜白钨矿型钒酸铋（m-BiVO₄）催化材料,采用XRD、BET、SEM、TEM等对其进行了表征。研究发现m-BiVO₄的形貌和晶面可以通过反应溶液的pH进行调控,在pH=7条件下制备出了具有（010）晶面择优暴露的m-BiVO₄（BVO-010）。以盐酸金霉素（CTC-HCl）、土霉素（OTC）、四环素（TC）和盐酸四环素（TCN）溶液为目标污染物,评价了制备材料的光催化降解性能。结果发现,与主要暴露热力学稳定的（-121）面的m-BiVO₄（BVO-121）相比,BVO-010的降解性能明显提高,光照150 min后对CTC-HCl、OTC、TC和TCN的降解率分别为77.9%、79.2%、63.6%和73.9%,可用于处理含抗生素类药物的污水。     

Mechanism of N2O decomposition over a Rh black catalyst studied by a tracer method: The reaction of N2O with O(a)

N₂O decomposition on an unsupported Rh catalyst has been studied using tracer technique in order to reveal the reaction mechanism. N₂¹⁶O was pulsed onto ¹⁸O/oxidized Rh catalyst at 220°C and desorbed O₂ molecules (m/e=32,34,36) were monitored by means of mass spectrometer. The ¹⁸O fraction in the desorbed dioxygen was the same value as that on the surface oxygen. The result shows that the O₂ molecules desorb via Langmuir–Hinshelwood mechanism, i.e., the desorption of dioxygen through the recombination of adsorbed oxygen. On the other hand, TPD measurements in He showed that desorption of oxygen from the Rh black catalyst occurred at the higher temperatures. Therefore, reaction-assisted desorption of oxygen during N₂O decomposition reaction at the low temperature was proposed.     

Thermoregulated phase transfer ligands and catalysis. III. Aqueous/organic two-phase hydroformylation of higher olefins by thermoregulated phase-transfer catalysis

A series of poly(ethylene oxide)-substituted triphenylphosphines, Ph_3−mP[C₆H₄-p-(OCH₂CH₂)_nOH]_m (PEO-TPPs; 1a m=1, 1b m=2, 1c m=3; N=m×n=8–25), have been prepared by the ethoxylation of mono-, di-, and tri-p-hydroxytriphenylphosphines. PEO-TPPs demonstrate an inverse temperature-dependent solubility in water, and possess distinct cloud points range from 26°C to 90°C.

Based on the clouding property of PEO-TPPs, a new line of aqueous/organic two-phase catalysis termed the thermoregulated phase-transfer catalysis (TRPTC) has been described. That is, the catalyst transfers into the organic phase to catalyze a reaction at a higher temperature, and returns to the aqueous phase to be separated from the products at a lower temperature. Application of this novel strategy to the rhodium-catalyzed two-phase hydroformylation of higher olefins gave desirable results with an average turnover frequency of 180 h⁻¹ for 1-dodecene. The TRPTC is suitable for carrying out a reaction with extremely water-immiscible substrate in the aqueous/organic two-phase system. Thus, the application scope of the classical two-phase catalysis has been widened.