甲苯液相氧化动力学研究

建立了一套甲苯液相空气氧化的连续反应装置,在工业条件下进行了动力学实验研究。在排除氧气、催化剂质量分数等影响因素下,建立了反应动力学模型,并回归得到模型参数。用该模型计算得到的甲苯转化率和实验结果对比,最大误差4.72%,平均误差2.36%。研究结果表明,甲苯转化率受温度和停留时间的影响较大,尤以温度影响更为明显;主产物选择性受温度和停留时间的影响较小,但停留时间延长,会加剧苯甲醛向苯甲酸转化。     

甲苯液相氧化反应过程的动力学研究

在直径Φ48mm 的鼓泡床反应器中对以醋酸钴(CO~(2+))水溶液为催化剂的甲苯液相空气氧化反应动力学进行了研究。结果表明,反应体系的活性时间随催化剂的用量的增大而线性增大,当 Co 含量大于2×10~(-2)%(mass)时,对反应影响较小。甲苯液相空气氧化反应的甲苯消耗动力学分别与甲苯浓度和氧溶解在甲苯中的浓度成一级反应.其宏观动力学活化能约为41 kJ/mol。氧在液相主体消耗的本征动力学活化能为57 kJ/mol,指前因子53.34m~3/(mol·s)。通过 Ha 数和效率因子η对反应动力学控制步骤进行分析,结果表明,Ha 小于0.1,η为0.606～0.728。反应主要发生在液相主体,受动力学控制,但传质仍对反应有影响。     

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•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•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•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•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.     

液相氧化对叔丁基甲苯合成对叔丁基苯甲酸

以对叔丁基甲苯(PTBT)为原料,醋酸钴为催化剂,无溶剂液相氧化法合成对叔丁基苯甲酸(PTBA)。引发剂乙醛明显缩短了诱导期;反应的适宜温度为170℃,反应100 min后PTBA收率为50%,其选择性为98%;确定了170℃时反应级数n为一级,仅与PTBT浓度有关,速率常数k=21.7×10-3min-1。     

甲苯液相催化氧化反应动力学

采用一套可无级调速的玻璃搅拌釜气液相反应器,通过改变搅拌速率考察了传质对甲苯液相氧化反应的影响,考察结果表明搅拌速率达到700 r/min时可基本排除传质的影响.在不同反应温度下进行了甲苯液相催化空气氧化的动力学实验研究,得到了反应物甲苯和主要反应产物苯甲酸、苯甲醛、苯甲醇和苯甲酸苄酯的浓度随反应时间变化的数据.在已有动力学研究的基础上,根据甲苯及其主要产物的情况,提出了甲苯液相氧化的反应网络和分子反应机理,建立了相应的动力学模型.根据实验数据回归获得了动力学模型参数,动力学模型计算与实验数据吻合良好,甲苯氧化生成苯甲酸反应的活化能为49.4 kJ/mo.     

甲苯液相空气催化氧化技术研究进展

介绍了甲苯液相催化氧化的反应机理、反应动力学模型和催化剂的研究进展;叙述了近年来在催化剂的研制、利用纯氧或富氧工艺、强化反应等方面的新技术.认为现有的生产技术有待于进一步改进,使用新型或复合催化剂、开发富氧或纯氧氧化工艺是降低成本、提高产品质量和生产能力的发展方向,并可借鉴其它液相氧化研究中出现新技术.     

甲苯液相空气氧化制苯甲酸扩大实验报告

文中介绍了采用重金属盐为催化剂，溴化物为促进剂，甲苯液相空气氧化制苯甲酸扩大实验结果。     

甲苯液相氧化制苯酚系列产品

比较了苯酚的各种生产方法和经济效益,重点阐明了甲苯液相氧化制取苯酚的原理和工艺;说明采用该方法制取苯酚原料价格低,工艺流程简单,可副产无氯苯甲醇、苯甲醛、苯甲酸系列产品,无必然副产物拖累,经济效益好。     

甲苯液相氧化反应过程的模拟

甲苯液相空气氧化是环境友好的苯甲酸和苯甲醛生产工艺。根据在模拟工业条件下测定的动力学数据和观察到的实验现象,提出了该反应的反应机理和反应网络,建立了相应的动力学模型。根据该动力学方程,对现有工业生产过程进行了模拟,发现现有工业过程处于严重供氧不足的情况。提出了3种强化方案并分别对其进行了模拟计算和比较。模拟结果表明,通过增大空气供给量和采用富氧空气氧化均可有效强化现有工业生产过程。采用富氧空气氧化,其甲苯转化率可提高到22.24%,甲苯反应量可增大57%。采用增大空气量的方法,可提高甲苯反应量31%,甲苯转化率可提高到18.61%。若同时增大甲苯和空气负荷,甲苯反应量可提高71%。     

甲苯液相氧化制苯酚系列产品

比较了苯酚的各种生产方法和经济效益,重点阐明了甲苯液相氧化制取苯酚的原理和工艺;说明采用该方法制取苯酚原料价格低,工艺流程简单,可副产无氯苯甲醇、苯甲醛、苯甲酸系列产品,无必然副产物拖累,经济效益好。     

Effects of Oxygen Partial Pressure on the Oxidation of Silicon Carbide

The rate of oxidation of silicon carbide was studied at different partial pressures of oxygen. The diffusion rate constant was found to vary with the logarithm of the partial pressure of oxygen according to the theory of oxidation of thin films as proposed by Engell and Hauffe. An alternative explanation based on the change of free energy with surface coverage was also found to fit the data.     

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.     

甲苯液相均相选择性催化氧化研究进展

将甲苯液相均相选择性催化氧化反应的催化剂分为：过渡金属盐、杂多化合物、过渡金属配合物、非金属化合物、复合催化剂等,对反应条件、结果和机理进行了总结。杂多化合物或金属卟啉参与反应时,反应条件较温和,对苯甲醛和苯甲醇的选择性高。复合催化剂通常表现出更好的催化性能,而且,当催化剂由非金属催化剂和金属催化剂组成时,对产物的选择性主要取决于金属催化剂部分。此外,以甲苯侧链的氧化为重点阐述了反应机理,指出开发更高效的复合催化剂和粗甲苯的氧化工艺是今后的发展重要方向。     

甲苯液相氧化法制取苯甲醛的改进研究

文章研究了用气-液-固非均相反应器进行的甲苯液相空气氧化法制取苯甲醛,采用自制的主催化剂ME05(氧化铜和丁酸锰的混合物)和助催化剂ME12(摩尔比为1的氯化铵和氯化钾)、溶剂丁酸、引发剂苯甲醛。获得的最佳反应工艺条件是主催化剂ME05、助催化剂ME12、溶剂丁酸、引发剂苯甲醛的用量分别占甲苯质量的0.1%、0.002%、10%和0.001%,反应温度110℃,反应压力0.8MPa,反应时间2h,此时苯甲醛的单程收率可达到21.1%。     

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.     

甲苯液相氧化制苯甲醛工艺的产品质量控制

简述了甲苯液相氧化制苯甲醛的工艺过程,详细介绍了苯甲醛在生产过程中存在的产品质量问题、影响因素,并提出了解决方案及优化过程,从而使苯甲醛产品纯度从99%提高到99.5%,优级品率达到95%以上。     

Effect of Temperature and Oxygen Partial Pressure on the Oxidation of Titanium Carbide

The oxidation of powdered titanium carbide was followed by weight gain measurement, using a thermogravimetric apparatus, between 600° and 850°C. The oxygen partial pressure effect was investigated between 6.5 and 645 mm Hg. The oxidation was parabolic with an activation energy of 46 ± 2 kcal/mole which was essentially independent of the overpressure. The rate of oxidation was dependent on p o₂¼ below approximately 800°C. Above this temperature the rate was proportional to p o₂¼. The oxidation of single-crystal TiC above 850° C produced porous rutile films. The rates of oxidation were between linear and parabolic time dependence.     

Effects of Oxygen Transfer Limitation and Kinetic Control on Biomimetic Catalytic Oxidation of Toluene

Under oxygen transfer limitation and kinetic control, liquid-phase catalytic oxidation of toluene over metalloporphyrin was studied. An improved technique of measuring dissolved oxygen levels for gas-liquid reaction at the elevated temperature and pressure was used to take the sequential data in the oxidation of toluene catalyzed by metalloporphyrin. By this technique the corresponding control step of toluene oxidation could be obtained by varying reaction conditions. When the partial pressure of oxygen in the feed is lower than or equal to 0.070 MPa at 463 K, the oxidation of toluene would be controlled by oxygen transfer, otherwise the reaction would be controlled by kinetics. The effects of both oxygen transfer and kinetic control on the toluene conversion and the selectivity of benzaldehyde and benzyl alcohol in biomimetic catalytic oxidation of toluene were systematically investigated. Three conclusions have been made from the experimental results. Firstly, under the oxygen transfer limitation the toluene conversion is lower than that under kinetic control at the same oxidation conditions. Secondly, under the oxygen transfer limitation the total selectivity of benzaldehyde and benzyl alcohol is lower than that under kinetic control with the same conversion of toluene. Finally, under the kinetics control the oxidation rate of toluene is zero-order with respect to oxygen. The experimental results are identical with the biomimetic catalytic mechanism of toluene oxidation over metalloporphyrins.