低品位钛渣酸解反应试验研究

李凯茂; 王海波; 肖军

doi:10.7513/j.issn.1004-7638.2022.01.003

低品位钛渣酸解反应试验研究

doi: 10.7513/j.issn.1004-7638.2022.01.003

钒钛资源综合利用国家重点实验室, 攀钢集团研究院有限公司, 四川攀枝花617000

详细信息

作者简介:
李凯茂(1984—)，男，山西大同人，高级工程师，研究方向：钛渣冶炼相关研究，E-mail：ybni610@126.com

中图分类号: TF823
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- 被引次数: 0
出版历程
- 收稿日期: 2021-10-22
- 网络出版日期: 2022-04-24
- 刊出日期: 2022-02-28

Experimental study on the acidolysis reaction of low-grade titanium slag

State Key Laboratory for Comprehensive Utilization of Vanadium and Titanium Resources, Pangang Group Research Institute Co., Ltd., Panzhihua 617000, Sichuan, China

摘要

摘要: 针对低品位钛渣酸解率低的问题，研究了低品位钛渣和74渣的物相组成、钛渣酸解温度曲线和化学反应标准生成热之间的差异，考察了反应酸浓度、引发温度、主反应时间、酸渣比对低品位钛渣酸解率的影响。结果表明：低品位钛渣酸解率低不是由难溶于硫酸的物相引起，而是与酸解反应速率有关；引发温度高引起酸解反应速率快、主反应时间短是低品位钛渣酸解率低的主要原因之一；适当降低引发温度，可以满足低品位钛渣酸解需要外加热补充热量需求；通过降低反应酸浓度和引发温度，延长主反应时间，1^#渣的酸解率由78.98%提高至94.31%，2^#渣的酸解率由71.77%提高至91.19%；与优化前相比，酸解工艺优化后残渣物相中黑钛石相(M₂TiO₅)峰值减弱，且新增了辉石相(Ca(Mg,Fe,Al)(Si,Al)₂O₆)。
- 低品位钛渣 /
- 酸解反应 /
- 引发温度 /
- 主反应时间
Abstract: Regarding the problem that low acidolysis rate occurs frequently at the beginning of the experiment in low-grade titanium slag, an investigation was proposed to elaborate the relationship among the phase composition, acidolysis temperature curve, and standard heat of reaction for the chemical reaction in low-grade titanium slag and slag 74 (the titanium slag is 74%). Moreover, the effects of acid concentration, initiation temperature, primary reaction time, and acid-slag ratio on the acid hydrolysis rate of low-grade titanium slag were also investigated. The results show that the low acidolysis rate in low-grade titanium slag is not caused by the formation of the insoluble sulfuric acid phase but is related to the acidolysis reaction rate. One of the main reasons for the increasing acidolysis reaction rate and the decreasing primary reaction time in low-grade titanium is the increased initiation temperature. Appropriately reducing the initiation temperature can meet the demand of external heating to supplement heat for acidolysis in low-grade titanium slag. The acidolysis rate of slag 1^# increases from 78.98% to 94.31%, and that of slag 2^# increases from 71.77% to 91.19%, respectively, by reducing the concentration of reaction acid and the initiation temperature and prolonging the primary reaction time. In addition, compared with the phase of the residue obtained before optimization, the peak value about M₂TiO₅ is decreased, and a new phase (Ca(Mg,Fe,Al)(Si,Al)₂O₆) is formed in the phase of the residue.
- low-grade titanium slag /
- acidolysis reaction /
- initiation temperature /
- primary reaction time

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图 1 钛渣酸解温度曲线

Figure 1. Acidolysis temperature curve of titanium slag

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图 2 酸渣比与1^#渣酸解率关系

Figure 2. Relationship between acid slag ratio and acidolysis rate of slag 1^#

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图 3 酸渣比与2^#渣酸解率关系

Figure 3. Relationship between acid slag ratio and acidolysis rate slag 2^#

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图 4 优化前后酸解残渣XRD图谱

Figure 4. XRD patterns of acidolysis residue before and after optimization

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表 1 钛渣主要化学成分

Table 1. Main chemical compositions of titanium slag %

编号	TiO₂	FeO	MgO	Al₂O₃	CaO	SiO₂
1^#渣	63.95	21.61	6.24	1.99	1.22	4.12
2^#渣	68.33	12.99	8.51	2.47	1.52	4.59
3^#渣	74.86	8.88	7.06	2.53	1.66	5.54

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表 2 不同品位钛渣物相组成

Table 2. Phase composition of titanium slag in different grades %

编号	黑钛石	黑钛石 +钛辉石	钛辉石	金属铁	金属钛(铁)	硫化铁	钛铁矿	金红石
1^#渣	77.64	1.39	12.14	1.09	6.68	0.16	0.73
2^#渣	81.25	1.06	11.09	3.36	2.41	0.11	0.22	0.07
3^#渣	80.29		13.72	0.65		0.69	0.11	2.17

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表 3 低品位钛渣和74渣酸解反应放热量

Table 3. Heat releases of acidolysis reactions in low-grade titanium slag and slag 74 kJ

编号	二氧化钛与硫酸反应放热	氧化亚铁与硫酸反应放热	氧化镁与硫酸反应放热	氧化铝与硫酸反应放热	氧化钙与硫酸反应放热	酸解反应总放热
1^#渣	19.50	36.38	20.33	2.53	5.90	84.64
2^#渣	20.84	21.87	27.73	3.14	7.35	80.93
3^#渣	22.83	14.95	23.00	3.22	8.03	72.03

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表 4 不同反应酸浓度的1^#渣酸解率

Table 4. Acidolysis rates of slag 1^# in different reaction acid concentrations

反应酸浓度/%	酸渣比	引发温度/℃	熟化温度/℃	酸解率/%
92	1.74∶1	210	175	78.98
89	1.74∶1	210	175	80.80
86	1.74∶1	210	175	84.81

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表 5 不同引发温度的1^#渣酸解率

Table 5. Acidolysis rates of slag 1^# in different initiation temperatures

引发温度/℃	酸渣比	反应体系最高温度/℃	主反应时间/min	熟化温度/℃	酸解率/%
210	1.86∶1	218	2.4	175	70.64
135	1.86∶1	177	0.5	175	82.53
185	1.86∶1	203	2.5	175	83.35
注：反应体系温度180 ℃至浆料完全固化时温度区间定义为“主反应时间”。

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表 6 不同主反应时间的1^#渣酸解率

Table 6. Acidolysis rates of slag 1^# in different main reaction times

试验编号	引发温度/ ℃	酸渣比	反应体系最高温度/℃	主反应时间/ min	熟化温度/ ℃	浆料完全固化温度/℃	开始熟化时浆料温度/℃	酸解率/ %	待反应体系温度下降时，是否继续外部加热
SH-1	185	1.86:1	203	2.5	175	205	205	83.35	是
SH-2	185	1.86:1	203	8.0	175	未固化	180	77.45	否
SH-3	185	1.86:1	203	9.0	160	158	158	93.72	否
注：反应体系温度180 ℃至浆料完全固化时温度区间定义为“主反应时间”；由于SH-2开始熟化时浆料未固化，故其主反应时间是指反应体系温度180 ℃至熟化前浆料温度。

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表 7 不同引发温度的2^#渣酸解率

Table 7. Acidolysis rates of slag 2^# in different initiation temperatures

引发温度/℃	反应酸浓度/%	酸渣比	反应体系最高温度/℃	主反应时间/min	浆料完全固化温度/℃	熟化温度/℃	酸解率/%
200	86	1.74∶1	218	2.5	205	175	73.16
185	86	1.74∶1	209	2.6	200	175	74.19
160	86	1.74∶1	198	7.2	172	175	87.81
注：反应体系温度180 ℃至浆料完全固化时温度区间定义为“主反应时间”。

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