CAJ | 학술논문

己二酸氨化法是工业上生产己二腈的重要方法之一，其中和反应步骤受气液相传质影响很大。采用体积为1 L的半间歇式反应釜，对己二酸中和反应的宏观动力学进行了研究。在磷酸质量分数为0.2%、搅拌速率为1800 r·min?1、氨气流量为600 L·h?1的条件下，实验考察了210～260℃范围内温度对己二酸浓度随时间变化的影响。由实验数据拟合结果表明：在250℃己二酸浓度大于0.1 mol·L?1时为传质控制阶段，中和反应对于己二酸为一级，反应活化能为42.9 kJ·mol?1；在250℃己二酸浓度小于0.1 mol·L?1时为反应控制阶段，中和反应对于己二酸为二级，反应活化能为52.7 kJ·mol?1。模型计算值与实验值相吻合，并结合理论模型得出对己二酸的本征反应级数为二级。保持总压（略大于常压）、温度260℃、搅拌速率1800 r·min?1和磷酸质量分数0.2%保持不变，在氨气流量为200～600 L·h?1的范围内考察了氨气分压对己二酸浓度随时间变化的影响，动力学拟合结果表明对氨气分压的本征反应级数为一级。
기이산안화법시공업상생산기이정적중요방법지일，기중화반응보취수기액상전질영향흔대。채용체적위1 L적반간헐식반응부，대기이산중화반응적굉관동역학진행료연구。재린산질량분수위0.2%、교반속솔위1800 r·min?1、안기류량위600 L·h?1적조건하，실험고찰료210～260℃범위내온도대기이산농도수시간변화적영향。유실험수거의합결과표명：재250℃기이산농도대우0.1 mol·L?1시위전질공제계단，중화반응대우기이산위일급，반응활화능위42.9 kJ·mol?1；재250℃기이산농도소우0.1 mol·L?1시위반응공제계단，중화반응대우기이산위이급，반응활화능위52.7 kJ·mol?1。모형계산치여실험치상문합，병결합이론모형득출대기이산적본정반응급수위이급。보지총압（략대우상압）、온도260℃、교반속솔1800 r·min?1화린산질량분수0.2%보지불변，재안기류량위200～600 L·h?1적범위내고찰료안기분압대기이산농도수시간변화적영향，동역학의합결과표명대안기분압적본정반응급수위일급。
Ammoniation of adipic acid is an important method for the production of adiponitrile in industry. The neutralization reaction step is largely affected by the gas-liquid phase mass transfer. The neutralization reaction macrokinetic experiments were conducted in a 1 L semi-continuous stirred reactor. The variation of adipic acid concentration with reaction time was investigated from 210 to 260℃ with 0.2% (mass) phosphoric acid, 600 L·h?1 ammonia and 1800 r·min?1 stirring speed. When the concentration of adipic acid was higher than or equal to 0.1 mol·L?1 at 250℃, the neutralization reaction was controlled by mass transfer and it was first-order with respect to adipic acid with activation energy of 42.9 kJ·mol?1. When the concentration of adipic acid in the reactor was lower than 0.1 mol·L?1 at 250℃, the reaction was controlled by reaction and it was second-order under reaction control with activation energy of 52.7 kJ·mol?1. The calculation values and experimental results were matched well, and the intrinsic reaction kinetic order with respect to adipic acid was two according to the theoretical model. Besides, at 260℃, 0.2% (mass) phosphoric acid, 1800 r·min?1 stirring speed and the same total pressure (slightly greater than the atmospheric pressure), the variation of adipic acid concentration with reaction time was investigated at a volume flow rate of ammonia between 200 to 600 L·h?1. The results uncovered that the intrinsic reaction kinetic order with respect to ammonia was one.