化工学报 ›› 2022, Vol. 73 ›› Issue (1): 284-293.DOI: 10.11949/0438-1157.20211009
毛文发1(),郑赛男2,骆念军2,周静红1(),曹约强1,周兴贵1
收稿日期:
2021-07-20
修回日期:
2021-11-07
出版日期:
2022-01-05
发布日期:
2022-01-18
通讯作者:
周静红
作者简介:
毛文发(1995—),男,硕士研究生,基金资助:
Wenfa MAO1(),Sainan ZHENG2,Nianjun LUO2,Jinghong ZHOU1(),Yueqiang CAO1,Xinggui ZHOU1
Received:
2021-07-20
Revised:
2021-11-07
Online:
2022-01-05
Published:
2022-01-18
Contact:
Jinghong ZHOU
摘要:
针对列管式固定床反应器中的单根反应管,采用在接近工业条件下获得的CO氧化偶联制草酸二甲酯动力学方程,建立了一维、二维拟均相模型,并与单管实验结果进行了对比,结果表明一维拟均相反应器模型更能准确描述单管反应器内的CO偶联反应。进一步利用一维拟均相模型模拟计算了操作参数对床层热点温度、反应转化率、产物选择性及床层压降的影响,分析了反应器热点温度对操作参数的敏感性。计算结果表明:冷却介质温度对反应管热点温度、亚硝酸甲酯转化率有较大影响,是需要严格控制的工艺指标;较低的空速容易引起反应器飞温;反应器进口压力、原料气进料温度和反应物组成在计算范围内对反应器热点温度影响相对较小。为了提高偶联反应器的负荷和强化床层内的传热效果,可以将进料空速提高至4000 h-1,同时,可以通过将反应器进口压力增大至500 kPa来降低压缩机能耗。研究结果可为现有列管式CO氧化偶联反应器的改进和工艺优化提供参考。
中图分类号:
毛文发, 郑赛男, 骆念军, 周静红, 曹约强, 周兴贵. 列管固定床反应器内CO氧化偶联制草酸二甲酯反应模拟及优化[J]. 化工学报, 2022, 73(1): 284-293.
Wenfa MAO, Sainan ZHENG, Nianjun LUO, Jinghong ZHOU, Yueqiang CAO, Xinggui ZHOU. Simulation and optimization on oxidative coupling reaction of CO to dimethyl oxalate in a tubular fixed bed reactor[J]. CIESC Journal, 2022, 73(1): 284-293.
指标 | 单管实验数据 | 一维拟均相模型计算结果 | 二维拟均相模型计算结果 |
---|---|---|---|
MN转化率/% | 59.5 | 64.89 | 76.06 |
DMO选择性/% | 95.5 | 89.76 | 87.33 |
DMC选择性/% | 3.0 | 3.60 | 3.64 |
MF选择性/% | 1.5 | 6.64 | 9.03 |
DMO时空产率/(g DMO/(g cat?h)) | 0.55 | 0.56 | 0.64 |
热点温度/K | 408.2 | 405.86 | 414.42 |
表1 单管实验数据与一维、二维拟均相模型计算结果对比
Table 1 Comparison of experimental data in single-tubular reactor with one-dimensional and two-dimensional pseudo-homogeneous model results
指标 | 单管实验数据 | 一维拟均相模型计算结果 | 二维拟均相模型计算结果 |
---|---|---|---|
MN转化率/% | 59.5 | 64.89 | 76.06 |
DMO选择性/% | 95.5 | 89.76 | 87.33 |
DMC选择性/% | 3.0 | 3.60 | 3.64 |
MF选择性/% | 1.5 | 6.64 | 9.03 |
DMO时空产率/(g DMO/(g cat?h)) | 0.55 | 0.56 | 0.64 |
热点温度/K | 408.2 | 405.86 | 414.42 |
冷却介质 温度/K | 热点 温度/K | MN 转化率/% | DMO 选择性/% | DMC 选择性/% | MF 选择性/% |
---|---|---|---|---|---|
393 | 398.91 | 53.59 | 90.84 | 3.39 | 5.77 |
398 | 405.86 | 64.89 | 89.76 | 3.60 | 6.64 |
403 | 413.86 | 76.50 | 88.50 | 3.80 | 7.70 |
408 | 423.38 | 87.63 | 87.03 | 3.99 | 8.98 |
表2 冷却介质温度对反应器内热点温度和反应器出口MN转化率及产物选择性的影响
Table 2 Effect of coolant temperature on hot-spot temperature, MN conversion and product selectivities at the outlet of reactor
冷却介质 温度/K | 热点 温度/K | MN 转化率/% | DMO 选择性/% | DMC 选择性/% | MF 选择性/% |
---|---|---|---|---|---|
393 | 398.91 | 53.59 | 90.84 | 3.39 | 5.77 |
398 | 405.86 | 64.89 | 89.76 | 3.60 | 6.64 |
403 | 413.86 | 76.50 | 88.50 | 3.80 | 7.70 |
408 | 423.38 | 87.63 | 87.03 | 3.99 | 8.98 |
空速/h-1 | 压降/kPa | DMO时空产率/ (g DMO/(g cat?h)) | 热点温度/K | MN转化率/% | DMO选择性/% | DMC选择性/% | MF选择性/% |
---|---|---|---|---|---|---|---|
1000 | 7.35 | 0.28 | 423.56 | 99.93 | 86.59 | 3.57 | 9.84 |
2000 | 27.81 | 0.47 | 409.20 | 81.60 | 88.90 | 3.52 | 7.58 |
3000 | 65.71 | 0.56 | 405.86 | 64.89 | 89.76 | 3.60 | 6.64 |
4000 | 134.93 | 0.60 | 404.28 | 51.82 | 90.10 | 3.71 | 6.12 |
表3 空速对反应器内压降、热点温度和反应器出口MN转化率及产物选择性的影响
Table 3 Effect of gas hourly space velocity on pressure drop, hot-spot temperature, MN conversion and product selectivities at the outlet of reactor
空速/h-1 | 压降/kPa | DMO时空产率/ (g DMO/(g cat?h)) | 热点温度/K | MN转化率/% | DMO选择性/% | DMC选择性/% | MF选择性/% |
---|---|---|---|---|---|---|---|
1000 | 7.35 | 0.28 | 423.56 | 99.93 | 86.59 | 3.57 | 9.84 |
2000 | 27.81 | 0.47 | 409.20 | 81.60 | 88.90 | 3.52 | 7.58 |
3000 | 65.71 | 0.56 | 405.86 | 64.89 | 89.76 | 3.60 | 6.64 |
4000 | 134.93 | 0.60 | 404.28 | 51.82 | 90.10 | 3.71 | 6.12 |
进口压力/kPa | 压降/kPa | 热点温度/K | MN转化率/% | DMO选择性/% | DMC选择性/% | MF选择性/% |
---|---|---|---|---|---|---|
400 | 90.35 | 404.76 | 58.96 | 89.16 | 3.92 | 6.91 |
450 | 65.71 | 405.86 | 64.89 | 89.76 | 3.60 | 6.64 |
500 | 50.91 | 407.03 | 69.87 | 90.20 | 3.35 | 6.44 |
550 | 40.97 | 408.26 | 74.19 | 90.56 | 3.15 | 6.29 |
表4 进口压力对反应器内压降、热点温度和反应器出口MN转化率及产物选择性的影响
Table 4 Effect of inlet feed pressure on pressure drop, hot-spot temperature, MN conversion and product selectivities at the outlet of reactor
进口压力/kPa | 压降/kPa | 热点温度/K | MN转化率/% | DMO选择性/% | DMC选择性/% | MF选择性/% |
---|---|---|---|---|---|---|
400 | 90.35 | 404.76 | 58.96 | 89.16 | 3.92 | 6.91 |
450 | 65.71 | 405.86 | 64.89 | 89.76 | 3.60 | 6.64 |
500 | 50.91 | 407.03 | 69.87 | 90.20 | 3.35 | 6.44 |
550 | 40.97 | 408.26 | 74.19 | 90.56 | 3.15 | 6.29 |
MN-CO-NO/ %(vol) | 热点 温度/K | MN 转化率/% | DMO 选择性/% | DMC 选择性/% | MF 选择性/% |
---|---|---|---|---|---|
12-25-4 | 408.88 | 71.53 | 90.42 | 3.55 | 6.03 |
12-25-8 | 405.25 | 62.98 | 89.55 | 3.61 | 6.84 |
12-25-12 | 403.67 | 56.58 | 88.77 | 3.66 | 7.57 |
12-20-8 | 403.53 | 53.41 | 87.36 | 4.67 | 7.97 |
12-10-8 | 400.64 | 31.8 | 77.47 | 9.61 | 12.92 |
表5 反应组成对反应器热点、转化率和选择性的影响
Table 5 Effect of reactant composition on hot-spot temperature, MN conversion and product selectivities at the outlet of reactor
MN-CO-NO/ %(vol) | 热点 温度/K | MN 转化率/% | DMO 选择性/% | DMC 选择性/% | MF 选择性/% |
---|---|---|---|---|---|
12-25-4 | 408.88 | 71.53 | 90.42 | 3.55 | 6.03 |
12-25-8 | 405.25 | 62.98 | 89.55 | 3.61 | 6.84 |
12-25-12 | 403.67 | 56.58 | 88.77 | 3.66 | 7.57 |
12-20-8 | 403.53 | 53.41 | 87.36 | 4.67 | 7.97 |
12-10-8 | 400.64 | 31.8 | 77.47 | 9.61 | 12.92 |
进料 温度/K | 热点 温度/K | MN 转化率/% | DMO 选择性/% | DMC 选择性/% | MF 选择性/% |
---|---|---|---|---|---|
390 | 405.62 | 64.52 | 89.79 | 3.59 | 6.61 |
395 | 405.86 | 64.89 | 89.76 | 3.6 | 6.64 |
400 | 406.38 | 65.34 | 89.71 | 3.61 | 6.68 |
405 | 407.64 | 65.9 | 89.64 | 3.63 | 6.72 |
表6 进料温度对反应器热点温度、转化率和选择性的影响
Table 6 Effect of feed gas temperature on hot-spot temperature, MN conversion and product selectivities at the outlet of reactor
进料 温度/K | 热点 温度/K | MN 转化率/% | DMO 选择性/% | DMC 选择性/% | MF 选择性/% |
---|---|---|---|---|---|
390 | 405.62 | 64.52 | 89.79 | 3.59 | 6.61 |
395 | 405.86 | 64.89 | 89.76 | 3.6 | 6.64 |
400 | 406.38 | 65.34 | 89.71 | 3.61 | 6.68 |
405 | 407.64 | 65.9 | 89.64 | 3.63 | 6.72 |
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