富镧稀土镍-苯浆液体系中液相苯加氢反应动力学研究

The kinetics of liquid-phase hydrogenation of benzene in misch metal nickel-five (MlNi5) and benzene slurry system was studied by investigating the influences of the reaction temperature, pressure, alloy concentration and stirring speed on the mass transfer-reaction processes inside the slurry. The results show that the whole process is controlled by the reaction at the surface of the catalyst. The mass transfer resistance at gas-liquid interface and that from the bulk liquid phase to the surface of the catalyst particles are negligible. The apparent reaction rate is zero order for benzene concentration and first order for hydrogen concentration in the liquid phase. The kinetic model obtained fits the experimental data very well. The apparent activation energy of the hydrogen absorption reaction of MlNi5-C6H6 slurry system is 42.16 kJ.mol-1.     

异丙基萘的分子间烷基转移及其在制备2,6-二异丙基萘中的应用

Isopropylation of naphthalene with propene resulted in a variety of isomers having different alkylation levels. The most important isomer is 2,6-DIPN, which is the precursor of important monomer 2,6-naphthalene dicarboxylic acid used for making liquid crystal polymers. In order to increase the yield of 2,6-DIPN, the intermolecular transalkylation with naphthalene was applied to the mixture of other DIPNs and PIPN to obtain MIPN enriched product, which underwent isopropylation with propene to produce 2,6-DIPN in a higher yield. The experimental study showed that the preferable conditions for transalkylation were reaction temperature of 325℃, the molar ratio of isopropyl group to naphthyl group （IP/N） of 0.8 ： 1-0.9 ： 1, reaction time of 4h and 5% of amorphous silica-alumina by mass. The conversions of DIPN and PIPN in its mixture were 62%-69% and 87%-88% respectively and the yield of MIPN was greater than 40%. The mixture of MIPN enriched product and recovered MIPN from rectification was subject to isopropylation with propene at 275℃ over a shape-selective catalyst to produce 2,6-DIPN in a yield up to 38%. A recycled process of recovered components was established, through one cycle the yield of 2,6-DIPN based on naphthalene may be 2.8 times higher than before, and the utilization ratio of raw naphthalene was increased by 46%.     

芳香族羧酸溶解度的测定与关联

Solubility of benzoic acid, terephthalic acid and 2,6-naphthalene dicarboxylic acid in water, acetic acid, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulphoxide and N-methyl-2-ketopyrrolidine were measured by dynamic method. The solubilities were calculated by UNIFAC group contribution method, in which new groups, BCCOOH and NCCOOH, were introduced to express the activity coefficients of aromatic acids and new interaction parameters of the new groups were expressed as the function of temperature, which were determined from the experimental data. The new interaction parameters provided good calculated result. The experimental data were also correlated with Wilson and A-h models, and results were compared with present UNIFAC model.     

矿物均相酸催化剂催化甲醇和乙酸酯化反应动力学(英文)

In this work, esterification of acetic acid and methanol to synthesize methyl acetate in a batch stirred reactor is studied in the temperature range of 305.15–333.15 K. Sulfuric acid is used as the homogeneous catalyst with concentrations ranging from 0.0633 mol·L?1 to 0.3268 mol·L?1. The feed molar ratio of acetic acid to methanol is varied from 1:1 to 1:4. The influences of temperature, catalyst concentration and reactant concentration on the reaction rate are investigated. A second order kinetic rate equation is used to correlate the experimental data. The forward and backward reaction rate constants and activation energies are determined from the Arrhenius plot. The developed kinetic model is compared with the models in literature. The developed kinetic equation is useful for the simulation of reactive distillation column for the synthesis of methyl acetate.     

甲基-酰基-萘在庚烷、辛烷和十二烷中溶解度的测定与关联

The solubilities of 2-methyl-6-acetylnaphthalene (2,6-MAN) and 2-methyl-7-acetylnaphthalene (2,7-MAN) in n-heptane, n-octane, and n-dodecane were measured, respectively, from 273.15 to 319.15K using an analytical method. On the basis of the thermodynamics theory of solid-liquid equilibrium, a model was derived to relate the solubilities with temperature. Using the least square method, the parameters of the model, the fusion enthalpies ΔfusH and the Margules equation coefficients A12 and A21 of 2,6-MAN and 2,7-MAN in n-heptane, n-octane, and n-dodecane—were obtained by regressing the experimental data. The average deviation of the model was 1.70%.     

Pt／C催化邻硝基氯苯加氢反应的动力学研究

The kinetics of catalytic hydrogenation of ortho-nitrochlorobenzene to 2,2‘-dichloroazoxybenzene on platinum/carbon catalyst is investigated in a slurry reactor with the temperature range of 313--343 K, and orthochloroaniline is formed as a byproduct. Models based on Rideal-Eley and Langmuir-Hinshelwood mechanism have been proposed based on the rate data and the kinetic regime. The former model can be used to fit the experimental data better. Reaction controlling steps are physical adsorption of hydrogen and adsorbed ortho-nitrochlorobenzene reacted on the surface of catalyst.     

[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.     

Kinetics of Liquid-Phase Hydrogenation of Benzene in a Metai Hydride Slurry System Formed by MlNi_5 and Benzene

The kinetics of liquid-phase hydrogenation of benzene in misch metai nickel-five (MINi5) and benzene slurry system was studied by investigating the influences of the reaction temperature, pressure, alloy concentration and stirring speed on the mass transfer-reaction processes inside the slurry. The results show that the whole process is controlled by the reaction at the surface of the catalyst. The mass transfer resistance at gas-liquid interface and that from the bulk liquid phase to the surface of the catalyst particles are negligible. The apparent reaction rate is zero order for benzene concentration and first order for hydrogen concentration in the liquid phase. The kinetic modei obtained fits the experimental data very well. The apparent activation energy of the hydrogen absorption reaction of MINi5-C6H6 slurry system is 42.16kJ·mol-1.     

小麦秸秆制备乙酰丙酸的动力学研究

Levulinic acid is considered as a promising green platform chemical derived from biomass. The kinetics of levulinic acid accumulation in the hydrolysis process of wheat straw was investigated in the study. Using dilute sulfuric acid as a catalyst, the ki-netic experiments were performed in a temperature range of 190-230C and an acid concentration range of 1%-5% (by mass). A simple model of first-order series reactions was developed, which provided a satisfactory interpretation of the experimental results. The kinetics of main intermediates including sugar and 5-hydroxymethylfurfural (5-HMF) were also established. The kinetic pa-rameters provided useful information for understanding the hydrolysis process.     

搅拌槽内液-固两相体系的数值研究(Ⅰ)流场的数值模拟

Three-dimensional solid-liquid flow is mathematically formulated by means of the “two-fluid” approach and the two-phase k-ε-Ap turbulence model. The turbulent fluctuation correlations appearing in the Reynolds time averaged governing equations are fully incorporated. The solid-liquid flow field and solid concentration distribution in baffled stirred tanks with a standard Rushton impeller are numerically simulated using an improved “inner-outer” iterative procedure. The flow pattern is identified via the velocity vector plots and a recirculation loop with higher solid concentration is observed in the central vicinity beneath the impeller. Comparison of the simulation with experimental data on the mean velocities and the turbulence quantities of the solid phase is made and quite reasonable agreement is obtained except for the impeller swept volume. The counterpart of liquid phase is presented as well. The predicted solid concentration distribution for three experimental cases with the average solid concentration up to 20% is also found to agree reasonably with the experimental results published in the literature.     

聚酯用萘系衍生物的开发技术进展

聚萘二甲酸乙二醇酯等高性能聚酯以其卓越的品质日益受到人们的关注。2,6-二甲基萘、2,6-萘二甲酸和2,6-萘二甲酸二甲酯是生产聚萘二甲酸乙二醇酯（PEN）等聚合物的重要原料和中间体,介绍了这些聚酯用萘系衍生物的生产技术和研究开发趋势,指出解决生产2,6-萘二甲酸二甲酯的原料和成本问题是工业化生产聚萘二甲酸乙二醇酯的关键。     

聚萘二甲酸乙二醇酯的开发

综述了聚2，6－萘二甲酸乙二醇酯及其单体2，6－萘甲酸的生产方法，介绍了聚2，6－萘二甲酸乙二醇酯的特性及用途。     

2,6-二异丙基萘液相空气氧化制2,6-萘二甲酸

在1 L钛材反应釜内，采用Co-Mn-Br系催化剂对2,6-二异丙基萘（2,6-DIPN）液相氧化合成2,6－萘二甲酸（2,6-NDCA）的工艺条件进行了研究。采用反相高效液相色谱法分析2,6-萘二甲酸的纯度，考察了催化剂的量、反应温度、压力、原料的进料量、体系的含水量等因素对氧化反应结果的影响，得出了氧化反应较为适宜的操作条件；考察了在含氧气体中添加一定量的CO2和催化剂中加入Ni对氧化反应的影响，结果表明，CO2和Ni都可作为反应促进剂，明显提高产物的收率和纯度。在适宜的工艺条件下，实现了2,6-萘二甲酸的连续化生产，反应稳定后产品纯度可达到95%以上，随反应时间的延长，2,6-NDCA收率由69%提高到73%。     

2,6-萘二甲酸合成技术进展

综述了2,6-萘二甲酸合成技术的国内外研究进展,主要介绍了2,6-二烷基萘氧化法、β-甲基萘酰化氧化法的特点,指出2,6-二甲基萘氧化法是较具竞争力的生产方法,建议充分利用我国的萘和烷基萘资源来制备2,6-二甲基萘,以降低生产成本。     

2,6—萘二甲酸的合成探讨

叙述了高性能能聚合物聚萘酯（ＰＥＮ）的关键单体２,６－萘二甲酸（２,６－ＮＤＣＡ）合成的最近进展,以及采用２－甲基萘的酰化,氧经路线合成２,６－ＮＤＣＡ的概况。     

2,6-二甲基萘技术的研究进展

2 ,6 -二甲基萘是一种重要的有机化工原料 ,是制备高性能聚酯材料聚萘二甲酸乙二醇酯的前体。本文全面的介绍了以萘、甲基萘、甲苯及二甲苯为原料合成二甲基萘的工艺。     

PET-PEN共聚酯的合成研究

以2,6-萘二甲酸(NDA)、对苯二甲酸或2,6-萘二甲酸二甲酯(NDC)、对苯二甲酸二甲酯与乙二醇为原料,在2 L聚合反应装置上,采用直接酯化法或酯交换法合成聚对苯二甲酸乙二酯(PET)-聚2,6-萘二甲酸乙二酯(PEN)共聚酯(PETN),探讨了PETN的合成反应条件。结果表明:直接酯化法较酯交换法更加可行易控;直接酯化法反应条件:酸/醇摩尔比为1:(1.3～1.5),NDA摩尔分数(相对于酸的总量)为28%,酯化阶段无需催化剂,酯化反应温度220～250℃,缩聚反应温度280～295℃,合成的PETN特性黏数达0.65～0.85 dL/g;钛系催化剂的催化活性优于锑系催化剂,且添加比例小,添加量为8～50μg/g时,即可得到高特性黏数的PETN。     

β-甲基萘合成2-甲基-1,4-萘醌绿色氧化反应工艺

2-甲基-1,4-萘醌(2-MNQ)是K族维生素的重要中间体,广泛应用于医药、农药、饲料添加剂等领域。本工作以2-甲基萘(2-MN)为原料,(NH4)2S2O8为引发剂,用30% H2O2与冰醋酸在硫酸催化下制备过氧乙酸并滴加至反应液中,氧化合成2-甲基-1,4-萘醌(2-MNQ),通过ICIR, GC-MS, LCMS对其结构进行表征,并验证氧化反应机理及中间产物。考察了催化剂、反应温度、反应时间、氧化剂与引发剂用量对产品2-MNQ收率、转化率的影响,采用HPLC (外标法)测定产品2-MNQ的转化率和收率,得到最佳工艺条件为反应温度65℃、反应时间5 h、n(H2O2):n(2-MN)=26:1,此时,2-甲基萘的转化率为99%,产品收率为34%。本工作的创新点是使用原位红外技术验证反应机理和中间过程,即原料2-甲基萘经过氧乙酸氧化,发生环氧化反应生成中间体,之后重排生成2-甲基羟醌,继续氧化生成目标产物2-甲基-1,4-萘醌。该工艺具有简单环保、操作条件温和、原料易得等特点。