Cu-Ce-Zr基催化剂上甲苯自持燃烧贫燃极限研究

doi:10.11949/0438-1157.20190136

摘要/Abstract

摘要：

在内径4 mm的微型反应器内对两种活性不同的Cu-Ce-Zr基催化剂进行甲苯自持燃烧的贫燃极限研究和热量计算。研究结果表明，活性高的CuCe_0.75Zr_0.25O_x-BC催化剂的贫燃极限小于活性低的CuCe_0.75Zr_0.25/TiO₂催化剂的贫燃极限，当流量为200 ml/min时，其当量比?值最小，为0.024。混合气在催化剂表面的停留时间随混合气流量的增大而缩短，使得催化自持燃烧的壁温高温区向催化剂床层后端移动，且壁温高温区温度随催化剂活性的增高而降低。在散热率高达91.9%的情况下，甲苯仍可维持稳定的自持燃烧状态。同时结合微管反应实验结果和理论计算，在有效降低飞温上限对反应器和催化剂的影响下实现了甲苯在固定床反应器中的自持燃烧。

关键词: 自持燃烧, Cu-Ce-Zr基催化剂, 甲苯, 贫燃极限, 传热, 微尺寸, 固定床

Abstract:

The self-sustained combustion of toluene on the Cu-Ce-Zr based catalysts with different activity has been carried out in a micro-tube with inner diameter of 4 mm. It was shown that the lean-combustion limits over CuCe_0.75Zr_0.25O_x-BC catalyst with the higher activity were less than that on CuCe_0.75Zr_0.25/TiO₂ catalyst at the same flow rate, and the minimum of equivalence ratio (?) was 0.024 under the flow rate of 200 ml/min. The residence time of the mixed gas on the catalyst surface declined with the increasing of flow rate, making the highest surface wall-temperature range shift to the back of catalyst bed. Toluene could maintain self-sustained combustion even when the heat loss was as high as 91.9%. Combined with the theoretical model, the heat transport of toluene self-sustained combustion in micro-tube was calculated. The self-sustained combustion in a fixed-bed reactor was realized with reducing the upper limit of temperature runaway s impacts for the reactor and catalysts.

Key words: self-sustained combustion, Cu-Ce-Zr based catalyst, toluene, lean-combustion limit, heat transfer, microscale, fixed-bed

中图分类号:

TQ 032.41

赵晨晨, 郝庆兰, 闫宁娜, 杨德宇, 黄亚飞, 豆宝娟. Cu-Ce-Zr基催化剂上甲苯自持燃烧贫燃极限研究[J]. 化工学报, 2019, 70(8): 3050-3057.

Chenchen ZHAO, Qinglan HAO, Ningna YAN, Deyu YANG, Yafei HUANG, Baojuan DOU. Study on lean-combustion limit of toluene self-sustained combustion on Cu-Ce-Zr based catalysts[J]. CIESC Journal, 2019, 70(8): 3050-3057.

图/表 8

图1 甲苯催化自持燃烧微管反应实验装置

Fig.1 Schematic diagram of experimental set-up for toluene self-sustained combustion in micro-tube

图2 CuCZ/T催化剂上甲苯自持燃烧贫燃极限实验过程（实心符号代表自持燃烧，空心符号代表未实现自持燃烧）

Fig.2 Experiment process of lean-combustion limits for toluene self-sustained combustion over CuCZ/T catalyst (filled/open symbols illustrate successful/failed self-sustained combustion)

图3 CuCZ-BC和CuCZ/T催化剂在不同流量下的甲苯催化自持燃烧贫燃极限

Fig.3 Lean-combustion limits of toluene catalytic self-sustaining combustion over CuCZ-BC and CuCZ/T catalysts

图4 不同气体流量下的甲苯自持燃烧壁温分布和反应实况（内图）

Fig.4 Wall temperature distributions of toluene self-sustained combustion with different flow rates and diagram of real-time reaction(inset)

图5 不同混合气流量下甲苯催化自持燃烧的热量衡算

Fig.5 Heat balance of toluene catalytic self-sustained combustion under different flow rate

表1 不同混合气流量下甲苯催化自持燃烧时的微管反应器的平均壁温

Table 1 Mean wall temperature of micro-tube for toluene catalytic self-sustained combustion under different flow rate/K

催化剂	流量/(ml/min)
催化剂	150	200	250	300	350
CuCZ-BC	406.9	397.3	409.8	432.2	462.4
CuCZ/T	410.8	409.4	412.0	486.8	511.6

图6 甲苯催化自持燃烧稳定性实验

Fig.6 Stability experiment for toluene self-sustained combustion

图7 甲苯自持燃烧的固定床实验结果（?=0.031）

Fig.7 Experiment of toluene self-sustained combustion in fixed-bed reactor (?=0.031)

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