Fluidized bed reactor simulation for hydrochlorination of metallurgical silicon based on MP-PIC method

doi:10.11949/0438-1157.20220701

Abstract

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

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

CLC Number:

TQ 127.2

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.

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.

Figures/Tables 17

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

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

Fig.1 Sketch of fluidized bed reactor

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

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

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

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

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

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

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

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

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

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

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%

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

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

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

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

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

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

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