颗粒分辨的乙炔选择性加氢固定床反应器数值模拟

doi:10.11949/0438-1157.20240406

摘要/Abstract

摘要：

乙烯产量是反映国家石油化工发展水平的关键指标。构建了颗粒分辨的乙炔选择性加氢固定床反应器模型，分析了圆柱形颗粒堆积结构对传递过程以及操作条件对其反应性能的影响。结果表明，床层压降主要集中在反应器入口段，该段乙炔加氢反应速率最高，但在后半段催化剂颗粒未被充分利用，且反应器内存在明显的径向温度梯度。入口压力的增加和空速的降低均有利于提升乙炔转化率，但同时会降低乙烯选择性，其中乙烯选择性对压力更敏感，而乙炔转化率对空速更敏感；反应温度和氢炔比的提高均有利于促进乙炔生成乙烯的速率，但会导致乙烯富集在催化剂颗粒的外表面，其进一步向颗粒内部扩散时过度加氢生成乙烷，降低了乙烯的选择性。

关键词: 乙炔选择性加氢, 固定床反应器, 数值模拟, 传质, 传热

Abstract:

Ethylene production is a key indicator reflecting the development level of a country's petrochemical industry. A particle-resolved fixed-bed reactor model for selective acetylene hydrogenation process has been established. The impact of cylindrical particle packing structure on the transport processes has been analyzed and the influence of operational conditions on the reaction performance has been explored. The simulation results show that the pressure drop in the catalyst bed mainly happened in the entrance section of the reactor, where the reaction rate of acetylene hydrogenation is the highest. However, in the latter half of the bed, the catalyst particles are not fully utilized, and there is a significant radial temperature gradient within the reactor. In terms of operational conditions, increasing the inlet pressure and decreasing the gas velocity both favor the improvement of acetylene conversion rate, but at the same time, they would reduce the selectivity of ethylene, where the selectivity of ethylene is more sensitive to pressure, and the conversion of acetylene is more sensitive to gas velocity. The increase in reaction temperature and hydrogen-to-acetylene ratio both help to promote the acetylene conversion to ethylene, but it can lead to the enrichment of ethylene on the exterior surface of the catalyst particles, which when diffusing further into the interior zone, can be over-hydrogenated to ethane, thus reducing the selectivity of ethylene.

Key words: selective acetylene hydrogenation, fixed-bed reactor, numerical simulation, mass transfer, heat transfer

中图分类号:

TQ 203.2

李泓宇, 刘祥坤, 施尧, 曹约强, 钱刚, 段学志. 颗粒分辨的乙炔选择性加氢固定床反应器数值模拟[J]. 化工学报, DOI: 10.11949/0438-1157.20240406.

Hongyu LI, Xiangkun LIU, Yao SHI, Yueqiang CAO, Gang QIAN, Xuezhi DUAN. Numerical simulation of particle-resolved fixed-bed reactor for selective acetylene hydrogenation process[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240406.

图/表 13

图1 反应器几何模型

Fig. 1 Reactor geometry model

表1 模拟中所用的扩散体积［35］

Table 1 Diffusion volumes used in simulation［35］

分子	值
C₂H₂	36.42
H₂	6.12
C₂H₄	41.01
C₂H₆	45.66
C₃H₈	65.34
C₄H₈	82.08
Ar	16.1

表2 模型中所用的计算经验方程式

Table 2 Empirical equations used in simulation

物性	经验公式	文献
催化剂粉末热导率	$λ s o l i d = 79.6671 - 0.16625 T + 9.6265 × 10 - 5 T 2$	[36]
气体混合物热导率	$λ m = ∑ i = 1 N g y i λ i ∑ j = 1 N g y j Φ i j$	[37]
物质i和物质j的二元黏度	$Φ i j = 18 (1 + M i M j) - 1 / 2 [1 + (μ i μ j) 1 / 2 (M j M i) 1 / 4] 2$	[37]
气体混合物比热容	$C p, m = ∑ i = 1 N g C p, i y i$	[37]
气体混合物密度	$ρ m = p M w, m R T$	[37]
气体混合物平均摩尔质量	$M w, m = ∑ i = 1 N g M w, i y i$	[37]
反应热	$Δ H i = Δ H i θ + ∫ 298 T Δ C p d T i = 1,2, 3$	[33]

表2 模型中所用的计算经验方程式

Table 2 Empirical equations used in simulation

物性	经验公式	文献
催化剂粉末热导率	$λ s o l i d = 79.6671 - 0.16625 T + 9.6265 × 10 - 5 T 2$	[36]
气体混合物热导率	$λ m = ∑ i = 1 N g y i λ i ∑ j = 1 N g y j Φ i j$	[37]
物质i和物质j的二元黏度	$Φ i j = 18 (1 + M i M j) - 1 / 2 [1 + (μ i μ j) 1 / 2 (M j M i) 1 / 4] 2$	[37]
气体混合物比热容	$C p, m = ∑ i = 1 N g C p, i y i$	[37]
气体混合物密度	$ρ m = p M w, m R T$	[37]
气体混合物平均摩尔质量	$M w, m = ∑ i = 1 N g M w, i y i$	[37]
反应热	$Δ H i = Δ H i θ + ∫ 298 T Δ C p d T i = 1,2, 3$	[33]

表3 求解方程（12）、（13）、（14）、（16）和（17）使用的边界条件

Table 3 Boundary conditions for solving Eq. （12），（13），（14），（16） and （17）

位置	动量方程	质量方程	能量方程
反应器入口 ( $z = 0$ )	$u = u 0$	$c m, i = c m, i, 0$	$T m = T 0$
反应器出口 ( $z = H t$ )	$P 表压 = 0$	$∂ c m, i ∂ z = 0$	$∂ T m ∂ z = 0$
反应器管壁( $r = R t$ )	$u = 0$	$∂ c m, i ∂ r = 0$	$∂ T m ∂ r = 0$
颗粒与流体交界面	-	$c m, i = c c a t, i$	$T m = T c a t$

表3 求解方程（12）、（13）、（14）、（16）和（17）使用的边界条件

Table 3 Boundary conditions for solving Eq. （12），（13），（14），（16） and （17）

位置	动量方程	质量方程	能量方程
反应器入口 ( $z = 0$ )	$u = u 0$	$c m, i = c m, i, 0$	$T m = T 0$
反应器出口 ( $z = H t$ )	$P 表压 = 0$	$∂ c m, i ∂ z = 0$	$∂ T m ∂ z = 0$
反应器管壁( $r = R t$ )	$u = 0$	$∂ c m, i ∂ r = 0$	$∂ T m ∂ r = 0$
颗粒与流体交界面	-	$c m, i = c c a t, i$	$T m = T c a t$

图2 网格敏感性分析（a）和网格的纵截面及横截面示意图（b）

Fig. 2 Gird sensitivity analysis (a) and schematic diagrams of the gird’s longitudinal and cross sections (b)

图3 沿反应器轴向的模拟和实验结果

Fig. 3 Simulation and experimental results along the reactor axis

图4 反应器中心纵截面的流速分布（a）和轴向压降分布（b）

Fig. 4 Central longitudinal flow velocity distribution (a) and axial pressure drop distribution of reactor (b)

图5 反应器中心纵截面和横截面（30 mm处）的C2H2浓度分布（a）和反应器轴向C2H2浓度分布（b）

Fig. 5 Central longitudinal and cross-sectional (30 mm) C2H2 concentration distribution (a) and C2H2 concentration along axial direction of reactor (b)

图6 反应器中心纵截面和横截面（40 mm处）的温度分布（a）和反应器轴向温度分布（b）

Fig. 6 Central longitudinal and cross-sectional (40 mm) temperature distribution (a) and temperature distribution along axial direction of reactor (b)

图7 反应器中心纵截面的温度分布（a），反应器轴向温度（b），反应器中心纵截面的C2H2浓度分布（c），反应器轴向C2H2浓度分布（d）和C2H2转化率和C2H4选择性随压力的变化（e）

Fig. 7 Central longitudinal temperature distribution (a), temperature along axial direction of reactor (b), central longitudinal C2H2 concentration distribution (c), C2H2 concentration along axial direction of reactor (d) and C2H2 conversion and C2H4 selectivity with respect to pressure (e)

图8 反应器中心纵截面的温度分布（a），反应器轴向温度（b），反应器中心纵截面的C2H2浓度分布（c），反应器轴向C2H2浓度分布（d）和C2H2转化率和C2H4选择性随空速的变化（e）

Fig. 8 Central longitudinal temperature distribution (a), temperature along axial direction of reactor (b), central longitudinal C2H2 concentration distribution (c), C2H2 concentration along axial direction of reactor (d) and C2H2 conversion and C2H4 selectivity with respect to GHSV (e)

图9 反应器中心纵截面的温度分布（a），反应器轴向温度（b），反应器中心纵截面的C2H2浓度分布（c），反应器轴向C2H2浓度分布（d）和C2H2转化率和C2H4选择性随入口温度的变化（e）

Fig. 9 Central longitudinal temperature distribution (a), temperature along axial direction of reactor (b), central longitudinal C2H2 concentration distribution (c), C2H2 concentration along axial direction of reactor (d) and C2H2 conversion and C2H4 selectivity with respect to inlet temperature (e)

图10 反应器中心纵截面的温度分布（a），反应器轴向温度（b），反应器中心纵截面的C2H2浓度分布（c），反应器轴向C2H2浓度分布（d）和C2H2转化率和C2H4选择性随氢炔比的变化（e）

Fig. 10 Central longitudinal temperature distribution (a), temperature along axial direction of reactor (b), central longitudinal C2H2 concentration distribution (c), C2H2 concentration along axial direction of reactor (d) and C2H2 conversion and C2H4 selectivity with respect to hydrogen-acetylene ratio (e)

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