苯加氢制环己烯装置能量系统集成及催化剂再生周期优化

doi:10.11949/0438-1157.20221213

摘要/Abstract

摘要：

苯选择性加氢制环己烯是工业上大规模生产环己烯的最佳方法，该反应的关键在于高活性和高选择性催化剂的选用。受各种因素影响，催化剂活性随生产系统运行时间的延长不断下降，影响反应器参数及换热网络（HEN）集成。从物料平衡和能量平衡出发，基于对温焓图的分析构建反应-换热网络耦合模型，揭示催化剂失活对能量系统集成的影响。据该模型分析苯加氢制环己烯生产过程，确定催化剂活性与反应关键参数及换热网络能耗的关系，并以催化剂活性为自变量构建反应-换热网络耦合性能图，直观反映反应转化率、反应器进/出口温度、反应器热负荷、系统能耗、系统运行时间及单位产品成本随催化剂失活的变化趋势。以单位产品平均生产成本为评价指标可以确定，Ru-Zn-B/ZrO₂催化剂的最佳再生活性为0.5，最佳再生周期为0.92年。再生周期优化后，单位产品平均生产成本可降低19.9%。

关键词: 环己烯, 集成, 催化剂活性, 再生, 优化

Abstract:

The selective hydrogenation of benzene to cyclohexene is the best way for industrial large-scale production of cyclohexene. The key to this reaction is the selection of catalysts with high activity and selectivity. Under the influence of various factors, the catalyst activity deteriorates with time, affecting reactor parameters and the integration of the heat exchanger network (HEN). A coupling model of the reactor-HEN system is established based on the material balance, the energy balance, and the analysis of the temperature-enthalpy diagram, revealing the influence of catalyst deactivation on energy system integration. This model is applied to analyze the hydrogenation process of benzene to cyclohexene, and correlations among the catalyst activity, the parameters of reactor, and energy consumption of the HEN are deduced. Based on these equations, the reactor-HEN coupling performance diagram is constructed with catalyst activity as the independent variable. It can directly reflect the variation trend of conversion, inlet and outlet temperatures of reactor, heat load of reactor, system energy consumption, system running time, and unit product cost with catalyst deactivation. The optimal regeneration activity of the Ru-Zn-B/ZrO₂ catalyst is determined to be 0.5, and the optimal regeneration cycle is 0.92 a by taking the unit product cost as an evaluation index. After the optimization, the average production cost per unit product can be reduced by 19.9%.

Key words: cyclohexene, integration, catalyst activity, regeneration, optimization

中图分类号:

TQ 021.8

赵丽文, 刘桂莲. 苯加氢制环己烯装置能量系统集成及催化剂再生周期优化[J]. 化工学报, 2022, 73(12): 5494-5503.

Liwen ZHAO, Guilian LIU. Energy system integration and catalyst regeneration cycle optimization of benzene hydrogenation to cyclohexene process[J]. CIESC Journal, 2022, 73(12): 5494-5503.

图/表 6

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流股位置	流股属性		公用工程变化量
流股位置	进料	出料	加热公用工程	冷却公用工程
夹点上	源	源	-ΔH₁+ΔH₂	0
	源	阱
	阱	源
	阱	阱
夹点下	源	源	0	ΔH₁-ΔH₂
	源	阱
	阱	源
	阱	阱
跨夹点	源	源	-ΔH₃	ΔH₄-ΔH₂
	源	阱	-ΔH₄	ΔH₃-ΔH₂
	阱	源	ΔH₂-ΔH₃	ΔH₄
	阱	阱	ΔH₂-ΔH₄	ΔH₃

流股位置	流股属性		公用工程变化量
流股位置	进料	出料	加热公用工程	冷却公用工程
夹点上	源	源	-ΔH₁+ΔH₂	0
	源	阱
	阱	源
	阱	阱
夹点下	源	源	0	ΔH₁-ΔH₂
	源	阱
	阱	源
	阱	阱
跨夹点	源	源	-ΔH₃	ΔH₄-ΔH₂
	源	阱	-ΔH₄	ΔH₃-ΔH₂
	阱	源	ΔH₂-ΔH₃	ΔH₄
	阱	阱	ΔH₂-ΔH₄	ΔH₃

物流	换热器	入口温度/K	出口温度/K	热容流率/ (kW∙K^-1)
H1	E101, E103	411.7	289.8	28.4
H2	E104, E105	395.0	288.2	3.7
H3	E106	454.0	313.2	10.1
H4	E107	313.2	288.2	0.2
H5	E108, E109	360.9	324.2	7.8
H6	E302, E201, E202	431.2	337.9	32.0
H7	E203	369.7	343.2	38.5
H8	E303, E304	438.4	370.0	18.8
H9	E401	310.5	310.2	0.6
H10	E403	364.0	313.2	0.9
C1	E101, E102	305.2	423.2	4.9
C2	E108	307.0	333.2	6.0
C3	E201	318.2	391.7	11.7
C4	E304	353.9	384.8	41.6
C5	E402	287.2	356.2	0.7
C6	E303	375.2	400.7	48.1
C7	E302	375.2	401.6	62.6
C8	E301	375.2	377.2	3424.6

物流	换热器	入口温度/K	出口温度/K	热容流率/ (kW∙K^-1)
H1	E101, E103	411.7	289.8	28.4
H2	E104, E105	395.0	288.2	3.7
H3	E106	454.0	313.2	10.1
H4	E107	313.2	288.2	0.2
H5	E108, E109	360.9	324.2	7.8
H6	E302, E201, E202	431.2	337.9	32.0
H7	E203	369.7	343.2	38.5
H8	E303, E304	438.4	370.0	18.8
H9	E401	310.5	310.2	0.6
H10	E403	364.0	313.2	0.9
C1	E101, E102	305.2	423.2	4.9
C2	E108	307.0	333.2	6.0
C3	E201	318.2	391.7	11.7
C4	E304	353.9	384.8	41.6
C5	E402	287.2	356.2	0.7
C6	E303	375.2	400.7	48.1
C7	E302	375.2	401.6	62.6
C8	E301	375.2	377.2	3424.6

活性	进口流股H1	出口流股H3
0.75<φ≤1	跨夹点	T^S增加；CP不变
0.5<φ≤0.75	跨夹点	T^S不变；CP增加
0<φ≤0.5	夹点上	T^S不变；CP增加