基于MP-PIC方法的冶金硅氢氯化流化床反应器模拟

doi:10.11949/0438-1157.20220701

摘要/Abstract

摘要：

冶金硅氢氯化流化床是目前多晶硅生产工艺中实现四氯化硅（silicon tetrachloride， STC）循环利用的关键反应器。基于MP-PIC方法建立了冶金硅氢氯化流化床反应器模型。模型中反应源项采用总包反应动力学进行计算。在网格以及计算颗粒包含的真实颗粒数量无关性检验的基础上，对反应器内三氯氢硅（trichlorosilane， TCS）初始浓度进行了无关性检验。模型验证结果表明，模拟结果与实验值符合良好。反应器特征分析结果表明：TCS产率受化学平衡与气固两相流动因素共同控制；反应器操作压力对TCS产率的影响较小；提高进口H₂/STC摩尔比，可以提高TCS产率但会降低H₂的转化率。

关键词: 多晶硅, 氢氯化, 流化床, 反应器, 计算流体力学, MP-PIC

Abstract:

Metallurgical silicon hydrochlorination fluidized bed is the key reactor to realize the recycling of silicon tetrachloride (STC) in the current polysilicon production process. Based on the MP-PIC method, a metallurgical hydrochlorination fluidized bed reactor model was established. In the model, overall kinetics was used to calculate the reaction source term. On the base of independence test of grid and the number of particles per parcel, the independence test of the initial concentration of trichlorosilane (TCS) was carried out. The model validation results showed that the simulation results were in good agreement with the experimental results. The reactor analysis showed that the yield of TCS is controlled by chemical equilibrium and gas-solid two-phase flow. From the operation condition analysis, the operation pressure of the reactor has little effect on the yield of TCS. Increasing the molar ratio of imported H₂/STC can effectively improve the yield of TCS, but reduce the conversion of H₂.

Key words: metallurgical silicon, hydrochlorination, fluidized bed, reactor, computational fluid dynamics, MP-PIC

中图分类号:

TQ 127.2

吴诗鸣, 陈皓宁, 宗原, 许志美, 赵玲. 基于MP-PIC方法的冶金硅氢氯化流化床反应器模拟[J]. 化工学报, 2022, 73(10): 4419-4428.

Shiming WU, Haoning CHEN, Yuan ZONG, Zhimei XU, Ling ZHAO. Fluidized bed reactor simulation for hydrochlorination of metallurgical silicon based on MP-PIC method[J]. CIESC Journal, 2022, 73(10): 4419-4428.

图/表 17

表1 反应动力学参数［9，14］

Table 1 Parameters of kinetic equation［9，14］

参数	数值
$k$ /(mol/(kg·s·Pa^1.086))	1.3878×10^-2
$E A$ /(kJ/mol)	109.557
$a$	2.532
$b$	0.629
$c$	2.075

表1 反应动力学参数［9，14］

Table 1 Parameters of kinetic equation［9，14］

参数	数值
$k$ /(mol/(kg·s·Pa^1.086))	1.3878×10^-2
$E A$ /(kJ/mol)	109.557
$a$	2.532
$b$	0.629
$c$	2.075

图1 流化床反应器示意图

Fig.1 Sketch of fluidized bed reactor

表2 实验数据

Table 2 Experimental data

序号	温度/K	H₂/STC 摩尔比	$d p$ /μm	$W C u$ /%(mass)	$m S i$ /g	$u 0$ /(cm/s)	$Y T C S, E X P$ /%(mol)
1	823.15	2	182	0.9	400	6	14.14
2	823.15	2	182	0.9	400	9	12.32
3	873.15	2	182	0.9	400	6	14.39
4	873.15	2	182	0.9	400	9	13.64
5	823.15	2	182	4.5	400	6	14.38
6	823.15	2	182	4.5	400	9	14.44
7	873.15	2	182	4.5	400	6	14.55
8	873.15	2	182	4.5	400	9	14.35

表2 实验数据

Table 2 Experimental data

序号	温度/K	H₂/STC 摩尔比	$d p$ /μm	$W C u$ /%(mass)	$m S i$ /g	$u 0$ /(cm/s)	$Y T C S, E X P$ /%(mol)
1	823.15	2	182	0.9	400	6	14.14
2	823.15	2	182	0.9	400	9	12.32
3	873.15	2	182	0.9	400	6	14.39
4	873.15	2	182	0.9	400	9	13.64
5	823.15	2	182	4.5	400	6	14.38
6	823.15	2	182	4.5	400	9	14.44
7	873.15	2	182	4.5	400	6	14.55
8	873.15	2	182	4.5	400	9	14.35

表3 模拟参数

Table 3 Parameters for simulation

参数	数值
颗粒密度/(kg/m³)	2329.0
操作压力/Pa	101325.0
紧密堆积空隙率	0.4696
颗粒-壁面碰撞恢复系数	0.9
颗粒-颗粒碰撞恢复系数	0.85
时间步长/s	1.0×10^-3
计算时间/s	30.0

图2 采用不同网格划分方式得到的时均气相相分率轴向分布

Fig.2 Axial distribution of time-averaged gas phase fraction for different grids

图3 采用不同计算颗粒包含的真实颗粒数量得到的时均气相相分率轴向分布

Fig.3 Axial distribution of time-averaged gas phase fraction for different number of particle per parcel

表4 TCS初始摩尔分数

Table 4 Initial mole fraction of TCS

$n S i H C l 3, 0$	$n H 2, 0$	$n S i C l 4, 0$
0.82	0.12	0.06
0.07	0.623	0.307
0.009	0.862	0.129

表4 TCS初始摩尔分数

Table 4 Initial mole fraction of TCS

$n S i H C l 3, 0$	$n H 2, 0$	$n S i C l 4, 0$
0.82	0.12	0.06
0.07	0.623	0.307
0.009	0.862	0.129

图4 不同TCS初始浓度条件下出口TCS摩尔分数随流动时间变化情况

Fig.4 Change of outlet TCS molar fraction with flow time under different initial concentration of TCS

图5 不同TCS初始浓度条件下反应器内轴向平均温度分布情况

Fig.5 Axial average temperature distribution in the reactor under different initial concentration of TCS

图6 计算得到的TCS产率与文献模拟值[14]以及实验值对比

Fig.6 Comparison of simulated TCS yield with simulated results[14] and experimental results

表5 模拟值与实验值的相对误差

Table 5 Relative error between simulated results and experimental results

序号	文献^[14]结果	本文的结果
1	-9.80%	-2.96%
2	-7.47%	4.14%
3	1.81%	5.21%
4	0.59%	7.77%
5	-2.57%	-1.18%
6	-6.37%	-1.73%
7	3.57%	4.33%
8	3.62%	5.78%
平均绝对偏差	4.48%	4.13%

图7 30 s时反应器内轴向平均表观气速分布

Fig.7 Axial average apparent gas velocity distribution in the reactor at 30 s

图8 30 s时反应器内轴向平均压力分布

Fig.8 Average axial pressure distribution in the reactor at 30 s

图9 流化床反应器中时均Qp/Kp值分布情况

Fig.9 Distribution of time-averaged Qp/Kp value in the simulated fluidized bed reactor

图10 模拟流化床反应器中时均气相相分率分布情况

Fig.10 Distribution of time-averaged gas volume fraction in simulated fluidized bed reactor

图11 不同进口表观气速下操作压力对TCS产率的影响

Fig.11 Effect of operation pressure on TCS yield under different inlet apparent gas velocity

图12 不同进口表观气速下进口H2/STC摩尔比对TCS产率的影响

Fig.12 Effect of inlet H2/STC molar ratio on TCS yield at different inlet apparent gas velocity

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