加氧对碳化渣低温氯化选择性影响的热力学分析

岳东; 温良英; 陈荣; 王建鑫; 杨仰军

doi:10.7513/j.issn.1004-7638.2023.05.009

加氧对碳化渣低温氯化选择性影响的热力学分析

doi: 10.7513/j.issn.1004-7638.2023.05.009

岳东^1,,
温良英^1, ,,
陈荣¹,
王建鑫^{1, 2},
杨仰军²

1.
重庆大学材料科学与工程学院, 重庆400044
2.
攀钢集团攀枝花钢铁研究院有限公司, 四川攀枝花617000

基金项目: 国家自然科学基金（51974046）。

详细信息

作者简介:
岳东,1998年出生，男，重庆忠县人，博士，主要从事冶金过程表界面反应模拟研究，E-mail：cquyue133@163.com

通讯作者:
温良英，1966年出生，女，博士，教授，研究领域为资源综合利用、多相表界面反应与传递等相关研究，E-mail：cquwen@cqu.edu.cn

中图分类号: TF823,X758
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出版历程
- 收稿日期: 2023-08-11
- 网络出版日期: 2023-11-04
- 刊出日期: 2023-10-31

Thermodynamic analysis of the effect of oxygenation on the low-temperature chlorination selectivity of carbonized slag

1.
College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China
2.
Pangang Group Panzhihua Iron and Steel Research Institute Co., Ltd., Panzhihua 617000, Sichuan, China

摘要

摘要: 利用Factsage热力学软件及数据库，计算分析了引入氧气对碳化钛渣中TiC和钙镁氧化物氯化的影响，以及加氧选择性强化碳化渣中TiC氯化反应的同时减少或抑制钙镁氧化物氯化反应的调控方案。结果表明，加氧低温氯化可促进渣中TiC的氯化反应进程，提高TiC的氯化率；当低温氯化反应温度为500 ℃时，在Cl₂/TiC摩尔比为1.80～3.50范围内，MgO不发生氯化反应，氧气的引入可以使CaO氯化反应受到抑制，降低CaO氯化率；氯氧气体摩尔比为4.00:1.00，氯化反应使碳化渣中TiC质量分数减小至4.02%时，可将氯化气体切换为氯气与氮气的混合气体，进一步氯化渣中残留的TiC直至2.50%以下；此加氧分步氯化与不加氧直接氯化相比，氯气总消耗量可减少25.69%，CaO总氯化率可减少37.74%。
- 碳化钛渣 /
- 加氧氯化 /
- 低温氯化 /
- 选择性 /
- 热力学分析
Abstract: Based on the Factsage thermodynamic software and database, the effects of introducing oxygen on the TiC and calcium magnesium oxide chlorination in titanium carbide slag are analyzed, and the regulatory scheme of adding oxygen to selectively enhance the chlorination reaction of TiC in the slag while reducing or inhibiting the chlorination reaction of calcium and magnesium oxides are studied. The results show that the oxygenated low-temperature chlorination can promote the chlorination process and increase the chlorination rate of TiC in the slag. When the low-temperature chlorination reaction temperature is 500 ℃ and the molar ratio of Cl₂/TiC is 1.80～3.50, MgO does not chlorinate, and the introduction of oxygen can inhibit the CaO chlorination reaction and reduce the CaO chlorination rate. When the molar ratio of chlorine-oxygen gas is 4.00:1.00, and the mass fraction of TiC with chlorination reaction in carbonization slag is reduced to 4.02%, the chlorinated gas can be switched to a mixture of chlorine gas and nitrogen gas to further chlorinate the residual TiC in the slag to less than 2.50%. Compared with direct chlorination without adding oxygen, the total chlorine consumption can be reduced by 25.69% and the total chlorination rate of CaO can be reduced by 37.74%.
- carbonized titanium slag /
- oxychlorination /
- low temperature chlorination /
- selectivity /
- thermodynamic analysis

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图 1 碳化渣低温氯化各反应吉布斯自由能随温度的变化

Figure 1. Change of Gibbs free energy of each reaction of carbonized slag chlorination at low temperature with temperature

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图 2 TiC-Cl₂-O₂体系平衡物相随氯氧气体分压变化规律

Figure 2. The variation of equilibrium phase of TiC-Cl₂-O₂ system with partial pressure of oxychloride

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图 3 TiC-2.04CaO-0.87MgO-nCl₂反应体系平衡物相含量随Cl₂/TiC摩尔比变化规律

Figure 3. The variation of equilibrium phase content of TiC-2.04CaO-0.87MgO-nCl₂ reaction system with Cl₂/TiC molar ratios

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图 4 TiC-2.04CaO-0.87MgO-2.00 Cl₂-mO₂体系平衡物相含量随O₂/TiC摩尔比变化规律

Figure 4. The variation of equilibrium phase content in TiC-2.04CaO-0.87MgO-2.00 Cl₂-mO₂ system with O₂/TiC molar ratios

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图 5 TiC-Cl₂-O₂体系三元平衡相图

Figure 5. Ternary equilibrium phase diagram of TiC-Cl₂-O₂ system

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图 6 TiC-2.04CaO-nCl₂-0.25nO₂体系平衡物相含量随Cl₂含量变化规律

Figure 6. The variation of equilibrium phase contents with Cl₂ content in TiC-2.04CaO-nCl₂-0.25nO₂ system

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图 7 0.07TiC-0.33CaO-nCl₂反应体系平衡物相含量随Cl₂含量变化规律

Figure 7. The variation of equilibrium phase content of 0.07TiC-0.33CaO-nCl₂ reaction system with Cl₂ contents

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图 8 0.07TiC-0.14CaO-nCl₂反应体系平衡物相含量随Cl₂含量变化规律

Figure 8. The variation of equilibrium phase content of 0.07TiC-0.14CaO-nCl₂ reaction system with Cl₂ contents

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图 9 碳化渣加氧氯化不同反应阶段TiC质量分数、TiC氯化率和CaO氯化率随Cl₂含量变化规律

Figure 9. The variation of TiC mass fraction, TiC chlorination rate, and CaO chlorination rate with Cl₂ contents during different reaction stages of carbonized slag oxychlorination

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图 10 碳化渣直接氯化不同反应阶段TiC质量分数、TiC氯化率和CaO氯化率随Cl₂含量变化规律

Figure 10. The variation of TiC mass fraction, TiC chlorination rate, and CaO chlorination rate with Cl₂ contents during different reaction stages of direct chlorination of carbonized slag

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表 1 碳化渣的主要成分及含量

Table 1. Main components and content of carbonized slag

成分	质量分数/%	摩尔数/mol*	摩尔比*
TiC	13.80	0.23	1.00
CaO	26.57	0.47	2.04
MgO	8.09	0.20	0.87
SiO₂	25.25	0.42	1.83
Al₂O₃	14.23	0.14	0.61
MnO	0.55	0.01	0.04
Fe	1.00	0.02	0.09
V₂O₅	0.24	0.01	0.04
TiO₂	3.60	0.05	0.22
FeO	2.00	0.03	0.13
C	4.00	0.33	1.43
其它	0.67
*：以100 g碳化渣计的摩尔数和以TiC=1.00 mol为基折算的摩尔比。

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表 2 TiC-2.04CaO-0.87MgO-nCl₂-mO₂反应体系中各物相氯化率随O₂含量变化规律

Table 2. The variation of chlorination rates of various phases with O₂ contents in the TiC-2.04CaO-0.87MgO-nCl₂-mO₂ reaction system

Cl₂含量n	TiC氯化率/%			CaO氯化率/%			最优O₂/TiC 摩尔比	Cl₂/O₂摩尔比
Cl₂含量n	未引入氧气	引入氧气	氯化率变化情况	未引入氧气	引入氧气	氯化率变化情况	最优O₂/TiC 摩尔比	Cl₂/O₂摩尔比
1.80	51.35	100.00	+48.65	50.33	0.00	−50.33	1.10	1.64
1.90	54.20	100.00	+45.80	53.12	0.00	−53.12	1.10	1.73
2.00	57.06	100.00	+42.94	55.88	0.49	−55.39	1.00	2.00
2.10	59.91	100.00	+40.09	58.82	5.39	−53.43	1.00	2.10
2.20	62.76	100.00	+37.24	61.27	10.29	−50.98	0.90	2.44
2.30	65.62	100.00	+34.38	64.22	15.20	−49.02	0.90	2.56
2.40	68.47	100.00	+31.53	67.16	20.10	−47.06	0.80	3.00
2.50	71.32	100.00	+28.68	70.10	25.00	−45.10	0.80	3.13
2.70	77.03	100.00	+22.97	75.49	34.80	−40.69	0.70	3.86
2.90	82.74	100.00	+17.26	80.88	44.61	−36.27	0.60	4.83
3.10	88.44	100.00	+11.56	86.76	54.41	−32.35	0.50	6.20
3.30	94.15	100.00	+5.85	92.16	64.22	−27.94	0.40	8.25
3.50	100.00	100.00	+0.00	98.04	74.02	−24.02	0.30	11.67

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表 3 碳化渣加氧氯化不同阶段组分含量变化（初始渣质量以100 g计）

Table 3. Changes in component of carbonized slag during different stages of oxychlorination. (The initial slag mass is calculated as 100 g)

氯化反应阶段	Cl₂/O₂ 摩尔比	混合气体中Cl₂含量/ mol	TiC初始量/g	TiC初始量/mol	TiC残余量/g	TiC残余量/mol	CaO初始量/g	CaO初始量/mol	CaO残余量/g	CaO残余量/mol	其他组分含量/g	TiC质量分数/%	TiC总氯化率%	CaO总氯化率/%
第一阶段	4.00		13.80	0.23	3.93	0.07	26.57	0.47	18.76	0.33	59.63	4.02	71.50	29.39
第二阶段		0.00	3.93	0.07	3.93	0.07	18.76	0.33	18.76	0.33	59.63	4.02	71.50	29.39
		0.02			3.59	0.06			18.11	0.32		3.67	73.99	31.84
		0.06			2.99	0.05			16.81	0.30		3.05	78.33	36.73
		0.10			2.40	0.04			15.35	0.27		2.41	82.61	42.23
		0.14			1.80	0.03			14.21	0.25		1.80	86.96	46.52

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表 4 碳化渣直接氯化不同阶段组分含量变化（初始渣质量以100 g计）

Table 4. Changes in composition and content of slag before and after the first stage chlorination reaction without introducing oxygen. (The initial slag mass is calculated as 100 g)

氯化反应阶段	混合气体中 Cl₂含量/mol	TiC初始量/g	TiC初始量/mol	TiC残余量/g	TiC残余量/mol	CaO初始量/g	CaO初始量/mol	CaO残余量/g	CaO残余量/mol	其他组分含量/g	TiC质量分数/%	TiC总氯化率%	CaO总氯化率/%
第一阶段		13.80	0.23	3.93	0.07	26.57	0.47	7.94	0.14	59.63	3.63	71.50	70.11
第二阶段	0.00	3.93	0.07	3.93	0.07	7.94	0.14	7.94	0.14	59.63	3.63	71.50	70.11
	0.02			3.59	0.06			7.37	0.13		3.31	73.99	72.26
	0.06			2.99	0.05			6.24	0.11		2.75	78.33	76.51
	0.10			2.40	0.04			4.54	0.08		2.18	82.61	82.91
	0.14			1.80	0.03			3.40	0.06		1.63	86.96	87.20

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