CO催化偶联制草酸二乙酯催化剂的宏观反应动力学

采用固定床积分反应器,研究了自制的负载型钯系催化剂上CO气相催化偶联主、副反应的宏观动力学模型.所采用的催化剂是经过模式1000 h连续运转、性能稳定的φ1.5 mm×（3～5）mm圆柱状催化剂.在适宜的反应条件下测定了动力学实验数据,并采用一维拟均相模型建立了微分方程组.使用了幂函数宏观动力学模型,采用Runge-Kutta法解微分方程组,并用单纯形法确定动力学模型参数,同时进行了残差分析和统计检验.结果表明,所得的动力学模型与实验数据吻合良好,可以为草酸二乙酯合成反应器设计和放大提供依据.     

CO气相催化偶联合成草酸二乙酯动力学

以工业应用为背景,研究了CO在钯系双金属催化剂上气相催化偶联合成草酸二乙酯的动力学特性。得出其速率控制步骤为CO吸附控制,并且认为在催化剂表面上存在烷氧羰基中间体COOR,进一步缔合生成草酸二乙酯,提出了机理型的动力学方程,并据此对反应历程做了探讨。     

CO气相偶联制草酸二乙酯工艺流程模拟

采用流程模拟软件PRO/II,对一氧化碳与亚硝酸乙酯合成草酸二乙酯工艺过程进行模拟。建立了工业过程设计详细流程,提供了模拟使用的主要物性参数、动力学模型及流程数据及其来源。流程模拟计算结果与实际生产数据吻合证明了模拟的可靠性。模拟考察了一氧化氮再生反应设计转化率对主要过程参数,如循环比、放空气中一氧化氮含量及乙醇补充量的影响。结果表明提高再生过程一氧化氮设计转化率,可以降低循环比,提高偶联过程CO的转化率,但亚硝酸乙酯利用率下降,乙醇补充量需相应提高。再生反应器较为适宜设计条件为:一氧化氮再生转化率为(92±2)%,压力为101.3～150kPa及温度为(308±2)K。     

CO常压气相催化偶联法合成草酸脂新工艺

介绍一氧化碳常压气相催化偶联合成草酸二乙酯的基本原理、工艺流程、原材料及产品的规格、公用工程及消耗定额,分析该工艺的特点以及经济和社会效益.该工艺环境友好、技术先进,可供国内化肥企业开发新产品参考.     

CO常压气相催化偶联法合成草酸酯新工艺

介绍一氧化碳常压气相催化偶联合成草酸二乙酯的基本原理、工艺流程、原材料及产品的规格、公用工程及消耗定额 ,分析该工艺的特点以及经济和社会效益。该工艺环境友好、技术先进 ,可供国内化肥企业开发新产品参考     

一氧化碳气相催化偶联制草酸二乙酯的动力学研究

在固定床反应器内，测定了一氧化碳气相催化偶联制草酸二乙酯的动力学数据，建立了相应的幂函数型动力学方程式中ｋ符合Ａｒｒｈｅｎｉｕｓ关系，ｋ＝３２．３ｅｘｐ（－２．１２×１０~４／ＲＴ），检验结果表明：模型的置信度在９９％以上。     

一氧化碳偶联再生反应动力学研究

采用常压连续流动气液反应器,测定了CO气相偶联亚硝酸乙酯再生反应的宏观动力学数据,建立了相应的宏观动力学模型R_A=K_(pNO)反应的活化能E_a=19.46kJ/mol,指前因子A=0.341mol/(m~3·Pa·s).根据气液反应双膜理论,对反应过程进行了分析和参数计算.结果表明,再生反应为一级快反应,反应区在液膜内,反应速率主要受液膜传质控制.求出“本征”反应的活化能为E_a=22.86kJ/mol,指前因子A=1.741×10~8s~(-1).     

CO气相催化合成草酸二乙酯催化剂的强度研究

利用颗粒强度实验机,对CO气相催化氧化偶联制草酸二乙酯催化剂的载体和催化剂强度进行测试。结果表明,随焙烧温度的升高,载体和催化剂的破碎强度明显提高,不同类型的Al₂O₃,其强度差别较大。由不同方式得到的α-Al₂O₃的强度也不相同。断裂强度随焙烧温度的升高变化不大。焙烧温度越高,催化剂强度比载体强度增加得越多。催化剂强度随助催化剂含量增加而增大,但不随活性组分负载量发生明显变化。经1000 h实验,催化剂的强度没有变化,符合工业生产的强度要求。     

反应精馏合成草酸二乙酯的工艺研究

研究了反应精馏合成草酸二乙酯的工艺条件,在自行设计的反应精馏塔内考察了挟带剂种类及用量、塔釜温度、进料速度、回流进料比对酯化反应的影响。环己烷为较适宜的挟带剂,确定了最佳工艺条件：塔釜温度为110℃,进料速度0.8 mL/min,回流比3。在最佳工艺条件下草酯二乙酯的酯化率达到92.16%。     

CO偶联制草酸二乙酯分离工艺的开发

CO气相催化偶联法生产草酸二乙酯是目前正在开发中的一碳化工新工艺。在中试及工业装置设计中开发分离工艺是新工艺的重要组成部分。该文在实验室连续精馏塔上研究工艺条件对草酸二乙酯精制过程的影响 ,为模型参数的修正提供实验数据。通过模拟计算 ,提出了适宜的草酸二乙酯精制分离工艺流程。最佳工艺条件 :闪蒸罐操作温度 90℃ ,压力 10 1.3kPa ;精馏塔常压操作 ,理论板数 14块 ,回流比 11,第7板侧线采出 ;减压蒸馏釜操作压力 3.2kPa。     

CO偶联合成草酸二甲酯催化剂研究

采用浸渍法制备CO偶联制备草酸二甲酯用负载型Pd催化剂,考察载体、浸渍方法、Pd含量、助剂对Pd催化剂性能的影响。根据傅里叶变换红外光谱研究Pd/α-Al_2O_3负载型催化剂上CO偶联制草酸二甲酯的反应机理。结果表明,采用α-Al_2O_3载体,Pd质量分数4‰,掺杂助剂Cu的蛋壳型的Pd/α-Al_2O_3催化剂上,草酸二甲酯时空收率达到735.7 g·(L·h)~(-1)。     

Microreactor technology for synthesis of ethyl methyl oxalate from diethyl oxalate with methanol and its kinectics

This study focused on the performances and kinetics of the transesterification reaction of diethyl oxalate with methanol to prepare ethyl methyl oxalate via microreactor technology. The conversion of 79.8% of diethyl oxalate (DEO) and the selectivity of 65.9% of ethyl methyl oxalate (EMO) was obtained under the following optimized conditions: the mole ratio of methanol to diethyl oxalate was 3.3:1, the temperature was 35°C, the K₂CO₃ catalyst concentration was 15 mg/mL, and the residence time was 2.30 minutes. In the temperature range of 25°C to 38°C, the simplified dynamic model was found to obtain the reaction order (α = 2.30), frequency factor (k₀ = 2.377 × 10⁵), and apparent activation energy (E = 31.86 kJ/mol). The macroscopic dynamic equation was derived from the experimental result of the transesterification reaction of two feedstocks, which can be obtained through a series of calculations.     

CO气相偶联合成草酸二甲酯催化剂的研制

考察助剂、制备方法和还原介质对CO气相偶联合成草酸二甲酯催化剂性能的影响。结果表明,以贵金属Pd为活性组分,非贵金属C为助剂,以α-Al_2O_3为载体,采用分步等体积浸渍法制备的催化剂,在水合肼还原后,具有良好的反应活性和稳定性。在反应温度130℃,空速3 000 h^(-1)时,产物中草酸二甲酯含量90%以上,时空收率平均可达813 g·(L·h)^(-1)。催化剂PC-3反应500 h后,物理性能和反应活性变化不大。     

CO氧化偶联反应器模拟与优化

CO与亚硝酸甲酯(MN)氧化偶联制草酸二甲酯(DMO)是合成气制乙二醇过程的关键步骤,现有工业装置存在效率低的问题。采用包括副反应(生成碳酸二甲酯和甲酸甲酯)动力学的动力学模型和二维两相反应器模型,对CO氧化偶联的移热式固定床反应器进行建模,研究了换热方式及操作条件对反应器性能和安全性的影响。结果表明,以温度的二阶导数作为飞温的判据是灵敏和可靠的。与常规的逆流和恒温移热方式相比,并流移热使反应器形成更为均匀的温度分布,有利于提高反应器产能。增加入口MN含量会升高反应器MN转化率和热点温度;但是,由于CO、NO和反应物MN之间存在竞争吸附,增加入口CO和NO含量会导致MN转化率和热点温度降低,所以增加入口压力导致MN转化率降低。且热点温度对MN和NO的含量更为敏感,应严格控制入口MN和NO的含量。采用遗传算法进行反应器工况寻优,确定了最优的反应条件,可提高单台反应器对应的乙二醇(EG)年产能至12万吨。     

CFD modeling of gas flow in porous medium and catalytic coupling reaction from carbon monoxide to diethyl oxalate in fixed-bed reactors

A comprehensive two-dimensional heterogeneous reactor model was developed to simulate the flow behavior and catalytic coupling reaction of carbon monoxide (CO)–diethyl oxalate (DEO) in a fixed-bed reactor. The two-temperature porous medium model, which was revised from a one-temperature porous medium model, as well as one equation turbulent model, and exponent-function kinetic model was constructed for the turbulent velocity scale comparing with laminar flow and simulation of the catalytic coupling reaction. The simulation results were in good agreement with the actual data collected from certain pilot-plant fixed bed reactors in China. Based on the validated approach and models, the distributions of reaction parameters such as temperature and component concentrations in the reactor were analyzed. The simulations were then carried out to understand the effects of operating conditions on the reactor performance which showed that the conduction oil temperature in the reactor jacket and the CO concentration are the key impact factors for the reactor performance.     

Synthesis of diethyl carbonate from ethanol through different routes: A thermodynamic and comparative analysis

In this study, thermodynamic analysis of various possible synthesis routes of diethyl carbonates (DEC), a benign organic carbonate, was carried out and a comparative analysis was performed. Chemical equilibrium constants at standard conditions were calculated using Gibbs free energy of the system. The Benson group contribution method was used to estimate standard heat of formation and standard entropy change of some raw materials/components like dimethyl carbonate. Variation of heat capacity (C_p) with temperature was estimated for different components from the Rozicka‐Domalski model. Variation of chemical equilibrium constants with temperature and pressure was studied for various routes. Synthesis of DEC from ethylene carbonate (EC) was also found to be better considering equilibrium constants at room temperature. The CO₂ route was found to be the most unfavourable route for DEC synthesis due to stability of CO₂ molecules. Moreover, DEC synthesis through the urea route was found to be best at high temperatures since the equilibrium constants were found to increase exponentially. Experiments were conducted for DEC synthesis using the EC route at two temperatures. Activity coefficients were calculated using the UNIFAC model. Experimentally and theoretically determined chemical equilibrium constant values were found to be similar. PRO/II was also used to minimize Gibbs free energy of the system and estimate the equilibrium constants and the results were comparable with those obtained by the equilibrium constant method and the trend was found to be the same for both the methods.     

碳酸二乙酯联产碳酸甲乙酯技术开发及产业化

阐述了碳酸二乙酯联产碳藏甲乙酯的工艺路线和开发过程，预测市场情况。     

草酸二乙酯加氢制乙二醇产品精馏试验研究

通过减压间歇精馏对草酸二乙酯加氢制乙二醇产品进行精制.试验表明该方法切实可行,获得了纯度≥99.8％的乙二醇产品;同时探讨了塔顶压强、回流比变化对产品纯度的影响,获得了试验条件下的最佳操作条件,为工业化提纯草酸二乙酯加氢制乙二醇产品提供了有益信息.