原料粒度对合成碳化硅的影响研究

doi:10.11949/0438-1157.20200981

摘要/Abstract

摘要：

以轮胎半焦为碳源，石英砂为硅源，在1520℃下通过碳热还原法制备了碳化硅。采用XRD、SEM和红外光谱仪等对不同原料粒度条件下制备的碳化硅进行了表征，探究了原料粒度对合成碳化硅物相、形貌、粒度和反应程度的影响规律。结果表明：原料粒度对碳化硅的合成反应进行程度及产物碳化硅的物相组成、形貌、粒度均有十分重要的影响。在一定粒度范围内，随着石英砂粒度的减小，碳化硅晶型变完整，且晶须逐渐减少，碳化硅的粒径分布没有明显变化；随着轮胎半焦粒度的增大，产物物相逐渐变为单一，碳化硅的粒径和晶须所占的比例逐渐减小。此外，通过对产物中C/Si 比的测定和存在中间产物SiO的证实，推测出了碳化硅颗粒的生成机理为气-固（VS）反应，而碳化硅晶须的生成机理为气-气（VV）反应。

关键词: 轮胎半焦, 碳化硅, 粒度分布, 碳热还原, 生成机理

Abstract:

Using tire semi-coke as carbon source and silicon sand as silicon source,silicon carbide(SiC) was prepared by carbothermal reduction method at 1520℃. XRD, SEM and FTIR spectrometer were used to characterize the SiC prepared under different raw material particle size conditions. The influence law of raw material particle size on the phase, morphology, particle size and reaction degree of the synthesized SiC was investigated. The results show that the size of the raw material has a very important influence on the degree of synthesis reaction and the phase composition, morphology and size of the product.Within a certain particle size range, with the decrease of silicon sand particle size, SiC crystal type becomes complete and SiC whisker decreases gradually, while the SiC particle size distribution does not change significantly.With the increase of semi-coke size of tire, the product phase gradually becomes single, and the proportion of SiC particle size and whisker decreases gradually. In addition, by measuring the C/Si ratio in the product and confirming the presence of the intermediate product SiO, it is inferred that the formation mechanism of SiC particles is gas-solid (VS) reaction, while the formation mechanism of SiC whiskers is gas-gas(VV) reaction.

Key words: tire carbocoal, SiC, particle size distribution, carbothermic reduction, generation mechanism

中图分类号:

TB 321

陆鹏飞, 金志浩, 崔彦斌, 许光文, 武荣成. 原料粒度对合成碳化硅的影响研究[J]. 化工学报, 2021, 72(4): 2300-2308.

LU Pengfei, JIN Zhihao, CUI Yanbin, XU Guangwen, WU Rongcheng. Effect of raw material size on the synthesis of silicon carbide[J]. CIESC Journal, 2021, 72(4): 2300-2308.

图/表 12

图1 轮胎半焦的SEM图

Fig.1 SEM image of tire semi-coke

表1 轮胎半焦的工业分析结果和元素分析

Table 1 Industrial analysis results and elemental analysis of tire semi-coke

Proximate analysis w_ar/%

BET/

(m2/g)

Ultimate analysis w_ar/%

表2 石英砂的化学分析结果

Table 2 Results of chemical analysis of silicon sand

Compositin	Content w_d/%
SiO₂	99.54
CaO	0.06
Fe₂O₃	0.13
Al₂O₃	0.11
MgO	0.08
burn reduces	0.08

图2 碳化硅制备流程

Fig.2 Flow chart for SiC preparation

图3 不同粒度的原料合成的碳化硅的XRD谱图

Fig.3 XRD patterns of SiC synthesized by raw materials with different particle sizes

表3 不同粒度石英砂对应的样品烧失率和产率

Table 3 The burning loss rate and yield of silicon sand samples with different particle size

Silica sand size/mesh	Reaction loss rate, w_tf/%	Reaction loss rate, w_mf/%	Productive rate, w/%
20—40	28.31	40.48	52.33
50—80	66.99	0.58	91.05
100—120	65.03	2.41	86.41
140—160	63.05	7.53	81.65

图4 不同粒度的原料合成的碳化硅的SEM图

Fig.4 SEM images of SiC synthesized by raw materials with different particle size

图5 不同粒度的原料合成的碳化硅粒径分布

Fig.5 SiC particle size and size distribution of raw materials with different particle size

图6 不同粒度的原料合成的碳化硅的SEM图

Fig.6 SEM images of SiC synthesized by raw materials with different particle size

表4 不同粒度的原料制备的碳化硅的平均粒径

Table 4 Average particle size of SiC prepared from raw materials with different particle size

Materials	Raw material particle size/mesh	Average particle size of SiC/μm
tire semi-coke	20—35	161.8
	140—160	53.353
	270—325	42.106
silica sand	50—80	37.679
	100—120	40.015
	140—160	38.473

图7 产物中白色物质与SiO的红外谱图

Fig.7 FT-IR spectra of the white substance in the product and SiO

图8 产物碳化硅粉体的能谱图

Fig.8 EDS of prepared SiC

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