丁酸硝化衍生物的合成及与硝酸反应的绝热量热分析

    Synthesis of Butyric Acid Nitrification Derivatives and Adiabatic Thermal Analysis of Reaction With Nitric Acid

    • 摘要: 通过合成获得硝化衍生物4-硝基丁酸,采用红外光谱、核磁共振波谱等手段对合成样品进行结构分析,通过绝热加速量热仪探究硝基丁酸与硝酸的放热行为,并改变硝酸与反应物的摩尔比和硝酸浓度等条件进行对比分析,采用热危险性综合评估指数(THI 指数)法评估体系危险性。结果表明:合成样品结构与目标产物相对应;绝热条件下,纯硝基丁酸有明显放热反应,加入硝酸后起始放热温度降低至75.6 ℃左右,随着硝酸与硝基丁酸摩尔比的提高,终止放热温度和绝热温升呈现整体升高的趋势,反应热则随样品质量增加而下降;硝酸浓度的提高使体系反应过程逐渐加剧,样品最高放热温度、最大温升速率和放热量等数据均呈现上升的趋势,当硝酸浓度为10.0 mol/L时,最大温升速率达到457.9 ℃/min,最大压升速率可达76.1 bar/min(1 bar=100 kPa),绝热温升达到130.5 ℃;硝基丁酸- 硝酸体系普遍处于较高危险性水平。

       

      Abstract: Tributyl phosphate(TBP) undergoes stepwise degradation in the post-treatment system to produce butanol, which is ultimately converted into butyric acid. Butyric acid can gradually accumulate in the system and undergo nitration reactions triggered by free radicals such as · \mathrmOH to produce nitration derivatives. The formation of “red oil” during the post-treatment process is inseparable from the production of nitro compounds. In this work, tert-butyl acrylate and nitromethane were used as raw materials to obtain the typical nitration product of butyric acid, 4-nitrobutyric acid(hereinafter referred to as nitrobutyric acid), through synthetic methods. Its structural formula is (CH2NO2)(CH2)2COOH. The synthesized sample was structurally analyzed using infrared spectroscopy and nuclear magnetic resonance spectroscopy. The exothermic behavior of nitrobutyric acid and nitric acid was explored using an adiabatic accelerating calorimeter. Comparative analysis was conducted by varying the molar ratio(r) of nitrobutyric acid to nitric acid and nitric acid concentration. The THI index method is used to assess the risk of the system. The results indicate that the infrared spectrum of the synthesized sample bears carboxyl and nitro groups, and the structure shown in the nuclear magnetic resonance spectrum corresponds to the target product. Under adiabatic conditions, pure nitrobutyric acid undergoes self oxidation heat release within the set temperature range, and the heat release process first accelerates and then slows down; the starting temperature of the self exothermic process of the sample is 90.4 ℃, and the ending temperature is 153.6 ℃. The adiabatic temperature rise during the self exothermic process is 63.2 ℃, and the reaction heat reaches 1485.65 J/g. At 126.5 ℃, the temperature rise rate reaches the maximum value of 1.7 ℃/min, and the maximum pressure rise rate is 0.1 bar/min(1 bar=100 kPa). After adding nitric acid, the initial exothermic temperature decreases to around 75.6 ℃. As the molar ratio of nitrobutyric acid to nitric acid increases, the termination exothermic temperature and adiabatic temperature rise show an overall increasing trend, while the reaction heat decreases with increasing sample mass. The increase in nitric acid concentration gradually intensifies the reaction process of the system. The highest exothermic temperature, maximum temperature rise rate, and heat release rate of the sample all show an upward trend. When the nitric acid concentration is 10.0 mol/L, the maximum temperature rise rate reaches 457.9 ℃/min, the maximum pressure rise rate can reach 76.1 bar/min, and the adiabatic temperature rise reaches 130.5 ℃. According to the thermal risk assessment results, the THI values of samples with different molar ratios of nitrobutyric acid to nitric acid system are generally above 0.3, which is at a high risk level. The system samples are also generally at a high risk level under different nitric acid concentrations, and the THI values of the samples increase with the increase of nitric acid concentration, indicating that the increase of nitric acid concentration will make the reaction more intense and increase the risk.

       

    /

    返回文章
    返回