甲苯一步催化硝化制备二硝基甲苯反应过程及危险性

doi:10.16085/j.issn.1000-6613.2023-0624

摘要/Abstract

摘要：

采用冷冻辅助-溶胶凝胶法制备了CuMnCoO₄三金属尖晶石氧化物，并对其结构性质进行了XRD、BET、FTIR、Raman、XPS等表征，进一步研究了该尖晶石在无硫酸条件下以硝酸为硝化剂的甲苯无溶剂硝化的催化行为。结果表明，CuMnCoO₄尖晶石催化的甲苯硝化体系对二硝基甲苯（DNT）生成具有偏好性，DNT的选择性比不含尖晶石的甲苯硝化体系高1.6倍。在此基础上，根据“替代、缓和、简化”的本质安全基本原则对传统DNT两段式硝-硫混酸硝化法生产工艺进行优化，得到最佳工艺条件：95% HNO₃、甲苯、CuMnCoO₄尖晶石催化剂的摩尔比为4∶1∶0.15，室温下滴加甲苯，结束后保持50℃反应6h，可实现甲苯一步硝化制备DNT（选择性可达67.44%）。通过全自动反应量热仪（RC1e）测试了半间歇反应下，CuMnCoO₄尖晶石催化甲苯硝化过程的热危险性参数，考察了反应过程危险性，发现了该新型多相催化体系在提高DNT选择性的同时，也降低了热失控条件下工艺合成反应可达到的最高温度（MTSR），从而提高了反应体系的安全性。

关键词: 安全, 催化剂, 选择性, 二硝基甲苯, 尖晶石, 一步催化硝化, 热危险性

Abstract:

Trimetallic spinel CuMnCoO₄ was prepared by the freezing-assisted sol-gel method, characterized by XRD, BET, FTIR, Raman and XPS, and its catalytic performance for solvent-free toluene nitration with nitric acid as nitration agent in the absence of sulfuric acid was investigated. The findings indicated that the toluene nitration system catalyzed by CuMnCoO₄ spinel had a preference for the generation of dinitrotoluene (DNT) with the selectivity of DNT being 1.6 times higher than that of the toluene nitration system without spinel. On this basis, in accordance with the fundamental principle of “substitution, mitigation and simplification” for intrinsic safety, this study optimized the conventional production process of two-stage nitrous-sulfur mixed acid nitrification of DNT and obtained the optimal process conditions as follows. With molar ratio of 95% HNO₃, toluene, CuMnCoO₄ spinel catalyst is 4∶1∶0.15, the toluene was dosed at room temperture and then the reaction was kept at 50℃ for 6h, and the DNT can be prepared by the one-step nitration of toluene (the selectivity can be up to 67.44%). In the meantime, this study tested the thermal hazard parameters of CuMnCoO₄ spinel-catalyzed toluene nitration process under semi-intermittent reaction by the reaction calorimeter(RC1e), and investigated the dangerousness of the reaction process. The calculations showed that this new heterogeneous catalytic system could improve DNT selectivity and decrease the maximum temperature which can be reached by a failure control system (MTSR), thereby enhancing the safety of the reaction system.

Key words: safety, catalyst, selectivity, dinitrotoluene, spinel, one-step catalytic nitration, thermal hazard

中图分类号:

X937

汪嘉欣, 潘勇, 熊欣怡, 万晓月, 王建超. 甲苯一步催化硝化制备二硝基甲苯反应过程及危险性[J]. 化工进展, 2023, 42(7): 3420-3430.

WANG Jiaxin, PAN Yong, XIONG Xinyi, WAN Xiaoyue, WANG Jianchao. Reaction process and hazards of dinitrotoluene preparation by one-step catalytic nitration of toluene[J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3420-3430.

图/表 8

图1 CuMnCoO4尖晶石氧化物的表征

图2 CuMnCoO4尖晶石氧化物的XPS图

图3 不同反应条件对甲苯二硝化制备DNT的选择性的影响反应条件分别为：(a) 2.5mmol甲苯，10mmol 硝酸，0.09g CuMnCoO4尖晶石催化剂；(b) 2.5mmol甲苯，10mmol 95% HNO3；(c) 36mmol甲苯，144mmol 95% HNO3，1.28g CuMnCoO4尖晶石催化剂；(d) n(95% HNO3)∶n(甲苯)∶n(CuMnCoO4尖晶石催化剂)=4∶1∶0.15，室温下滴加甲苯，滴加完毕后50℃反应6h。

图4 量热反应RC1e装置示意图1—玻璃常压反应釜；2—自动加料控制器；3—冷凝回流装置；4—搅拌装置；5—校准加热器；6—温度传感器；7—RC1e主机；8—PC终端；9—自动控温装置

表1 反应量热仪（RC1e）等温半间歇条件下CuMnCoO4尖晶石催化剂对甲苯硝化产物分布的影响

序号	甲苯/mol	催化剂/g	转化率/%	选择性/%			2,4-/2,6-DNT	碳平衡/%
序号	甲苯/mol	催化剂/g	转化率/%	2-MNT	4-MNT	DNT	2,4-/2,6-DNT	碳平衡/%
1	4.46	—	99	28. 8	23.7	45.6	4.3	95.2
2	4.46	162	99	15.4	15.9	67.4	4.3	98.7

图5 甲苯二硝化反应的放热速率、甲苯投料和RC1e反应釜温度曲线

图6 不同条件下的Tcf和MTSR曲线

表2 投料阶段CuMnCoO4尖晶石催化剂对反应热危险性参数的影响

序号

催化剂用量

c_p /kJ·kg^-1·K^-1

c_p₁

c_p₂

U₁

U₂

95% HNO₃+甲苯+CuMnCoO₄尖晶石催化剂^②

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