钒渣亚熔盐提钒生产过程中钒铬硅分析方法研究

章伟; 王宝华; 刘超; 刘丽颖; 吕慧; 朱建岩

doi:10.7513/j.issn.1004-7638.2021.05.015

钒渣亚熔盐提钒生产过程中钒铬硅分析方法研究

doi: 10.7513/j.issn.1004-7638.2021.05.015

章伟^{1, 2,},
王宝华^{1, 2},
刘超^{1, 2},
刘丽颖^{1, 2},
吕慧^{1, 2},
朱建岩^{1, 2}

1.
河钢承德钒钛新材料有限公司, 河北承德 067102
2.
河钢集团承钢公司, 河北承德 067102

基金项目: 国家2017年绿色制造系统集成项目（钒的清洁提取与产品绿色制造产业化示范，19044011Z）。

详细信息

作者简介:
章伟（1969—），男，河北承德人，大学，高级工程师，主要从事冶金分析与试验工作。E-mail：18932879108@163.com。

中图分类号: TF841.3
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出版历程
- 收稿日期: 2021-07-26
- 刊出日期: 2021-10-30

Study on analytical method of V, Cr and Si in the process of extracting V from vanadium slag by sub-molten salt

Zhang Wei^{1, 2
,},
Wang Baohua^{1, 2},
Liu Chao^{1, 2},
Liu Liying^{1, 2},
Lv Hui^{1, 2},
Zhu Jianyan^{1, 2}

1.
Chengde Vanadium and Titanium New Material Co., Ltd., HBIS Group Co., Ltd., Chengde 067102, Hebei, China
2.
HBIS Group Chengsteel Company, Chengde 067102, Hebei, China

摘要

摘要: 研究钒渣亚熔盐提钒生产过程中钒铬硅分析方法。采用过硫酸铵氧化-硫酸亚铁铵滴定法联合测定钒铬含量：在15%～20%的硫酸酸度下，过硫酸铵氧化钒为五价，同时六价铬被还原为三价，消除铬干扰，以此测定钒量；在4%～6%的硫酸酸度下，加入银盐、过硫酸铵，同时氧化钒铬，以此测定钒铬合量，差减法计算铬量。采用硅钼蓝光度法测定结晶溶液中硅浓度，加入亚硫酸钠还原钒铬，消除钒铬干扰；以酚酞为指示剂，加入硫酸，调节硅钼黄生成时酸度为0.3 mol/L；选择波长660 nm处测量显色液吸光度，绘制工作曲线，计算硅浓度。同时进行方法精密度和加标回收试验，结果令人满意。
- 钒渣 /
- 亚熔盐提钒 /
- 钒 /
- 铬 /
- 硅 /
- 分析方法
Abstract: The analysis method of vanadium, chromium and silicon in the process of vanadium extraction from vanadium slag by sub-molten salt was studied. The content of vanadium and chromium was determined by ammonium persulfate oxidation and ammonium ferrous sulfate titration. At 15%～20% sulfuric acid acidity, ammonium persulfate oxidizes vanadium to a pentavalent state, while Cr(VI) is reduced to Cr(III) to eliminate chromium interference and determine the amount of vanadium. In 4%～6% sulfuric acid acidity, add silver salt and ammonium persulfate at the same time for oxidization of vanadium and chromium, in order to determine the amount of vanadium and chromium, and the amount of chromium is calculated by difference subtractive method. The concentration of silicon in the crystallization solution was determined by silicon molybdenum blue photometric method. Add sodium sulfite to reduce vanadium and chromium and eliminate the interference of vanadium and chromium. With phenolphthalein as indicator, sulfuric acid was added to adjust the acidity of silicon molybdenum yellow to 0.3 mol/L. The absorbance of the color solution was determined at the wavelength of 660 nm, and the working curve was drawn to calculate the silicon concentration. At the same time, the method precision and standard addition recovery tests were carried out, and the results were satisfactory.
- vanadium slag /
- vanadium extraction by sub-molten salt /
- vanadium /
- chromium /
- silicon /
- analytical method

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图 1 钒铬干扰试验

Figure 1. Vanadium chromium interference test

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表 1 钒铬共存试验结果

Table 1. Coexistence test results of vanadium and chromium

样品	加入钒量/mg	加入铬量/mg	测得钒量/mg	测得铬量/mg
1	0	50.00	0	50.00
2	50.00	0	49.98	0
3	10.00	10.00	9.90	10.11
4	25.00	25.00	25.04	24.90
5	50.00	50.00	50.08	50.13

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表 2 钒渣和尾渣精密度试验结果

Table 2. Precision test results of vanadium slag and tailings

样品	方法	成分	w/％		相对标准偏差 RSD /％
样品	方法	成分	测定值	平均值	相对标准偏差 RSD /％
钒渣	化学法	V	10.69，10.71，10.66，10.75，10.68，10.65，10.72，10.61	10.68	0.41
钒渣	化学法	Cr	1.55，1.56，1.51，1.54，1.54，1.56，1.51，1.49	1.53	1.70
尾渣	化学法	全V	1.05，0.98，1.01，0.99，0.98，1.04，1.04，0.99	1.01	2.90
		全Cr	0.64，0.62，0.66，0.62，0.64，0.63，0.62，0.63	0.63	2.20
		可溶V	0.13，0.14，0.13，0.12，0.14，0.12，0.14，0.11	0.13	8.66
		可溶Cr	0.051，0.048，0.051，0.052，0.052，0.053，0.055，0.056	0.052	4.79

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表 3 结晶溶液精密度试验结果

Table 3. Precision test results of crystalline solution

样品	方法	成分	测定值 /（g·L⁻¹）	平均值 /（g·L⁻¹）	相对标准偏差 RSD/％
结晶溶液1^#	化学法	V	25.45，25.36，25.49，25.28，25.41，5.38，25.34，25.29	25.38	0.29
		Cr	43.25，43.46，43.58，43.31，43.45，43.39，43.28，43.39	43.39	0.25
		Si	1.36，1.46，1.40，1.42，1.32，1.39，1.40，1.38	1.39	2.90
结晶溶液2^#	化学法	V	16.48，16.29，16.33，16.29，16.36，16.28，16.39，16.54	16.37	0.58
		Cr	23.54，23.78，23.68，23.46，23.54，23.67，23.58，23.64	23.61	0.43
		Si	0.59，0.58，0.59，0.57，0.58，0.59，0.59，0.59	0.59	1.29

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表 4 钒渣和尾渣加标回收试验结果

Table 4. Recovery test results of vanadium slag and tailings

样品	方法	成分	本底值/%	加入量/%	测定总值 /%	回收率/％
钒渣	化学法	V	10.66	1.00	11.95	102.49
钒渣	化学法	Cr	0.96	1.00	1.99	101.53
尾渣	化学法	全V	1.01	1.00	1.98	98.51
		全Cr	0.63	1.00	1.65	99.82
		可溶V	0.13	1.00	1.15	101.76
		可溶Cr	0.052	1.00	1.065	101.23

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表 5 结晶溶液加标回收试验结果

Table 5. Recovery test results of crystalline solution

样品	方法	成分	本底值 /（g·L⁻¹）	加入量 /（g·L⁻¹）	测定总值 /（g·L⁻¹）	回收率 /％
结晶溶液1^#	化学法	V	25.38	1.00	26.59	100.79
		Cr	43.39	1.00	44.30	99.80
		Si	1.39	0.50	1.866	98.73
结晶溶液2^#	化学法	V	16.37	1.00	17.57	101.15
		Cr	23.61	1.00	24.49	99.51
		Si	0.59	0.50	1.073	98.44

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参考文献(16)

[1]	Zhang Dade, Zhang Yudong. Review and prospect of technology for vanadium recovery from hot metal in converter at PZH Steel[J]. Iron Steel Vanadium Titanium, 2001,22(1):30−33. (张大德, 张玉东. 攀钢转炉提钒工艺的回顾与展望[J]. 钢铁钒钛, 2001,22(1):30−33. doi: 10.3969/j.issn.1004-7638.2001.01.006
[2]	Wang Jinchao, Chen Housheng, Li Guisheng, et al. V₂O₅ prduction process from vanadium slag smelted in Pangang converter[J]. Iron Steel Vanadium Titanium, 1998,19(4):41−46. (王金超, 陈厚生, 李瑰生, 等. 攀钢转炉钒渣生产V₂O₅研究[J]. 钢铁钒钛, 1998,19(4):41−46. doi: 10.7513/j.issn.1004-7638.1998.04.009
[3]	Zheng Shili, Du Hao, Wang Shaona, et al. Efficient and cleaner technology of vanadium extraction from vanadium slag by sub-molten salt method[J]. Iron Steel Vanadium Titanium, 2012,33(1):15−19. (郑诗礼, 杜浩, 王少娜, 等. 亚熔盐法钒渣高效清洁提钒技术[J]. 钢铁钒钛, 2012,33(1):15−19. doi: 10.7513/j.issn.1004-7638.2012.01.003
[4]	Wang Dawei, Zheng Shili, Wang Shaona, et al. Process research of vanadium extraction for vanadium slags by NaOH sub-molten salt medium[J]. Journal of Chinese Society of Rare Earths, 2012,30(专辑):684−691. (王大卫, 郑诗礼, 王少娜, 等. 钒渣NaOH亚熔盐法提钒工艺研究[J]. 中国稀土学报, 2012,30(专辑):684−691.
[5]	Dong Bingcheng, Song Hongting, Dong Shikai. Faster and continuously the content of manganese chromium and vanadium in steel is mensurated by ferrous titration[J]. Metallurgical Standardization & Quality, 2007,(4):8−10. (董丙成, 宋洪亭, 董世凯. 亚铁滴定法连续快速测定合金钢中锰、铬、钒[J]. 冶金标准化与质量, 2007,(4):8−10.
[6]	Li Huiling, Zhang Lin. Study of measuring method for the mixture added chromium and vanadium[J]. Sichuan Nonferrous Metals, 2007,(2):37−39. (李慧玲, 张林. 混合料中钒、铬分量测定方法的研究[J]. 四川有色金属, 2007,(2):37−39. doi: 10.3969/j.issn.1006-4079.2007.02.010
[7]	Zhou Jinzhi, Li Tuo. Continuous determination of vanadium and chromium in aluminum vanadium tin chromium alloy by ammonium ferrous sulfate titrimetry[J]. Metallurgical Analysis, 2015,35(6):70−73. (周金芝, 李佗. 硫酸亚铁铵滴定法连续测定铝钒锡铬合金中钒和铬[J]. 冶金分析, 2015,35(6):70−73.
[8]	Yang Chunsheng, Yang Junhong. Ammonium ferrous sulfate volumetric method for determination of high content of Cr and V in Ti alloys[J]. Journal of Materials Engineering, 2002,(12):11−13. (杨春晟, 杨军红. 硫酸亚铁铵容量法测定钛合金中高含量钒和铬[J]. 材料工程, 2002,(12):11−13. doi: 10.3969/j.issn.1001-4381.2002.12.004
[9]	Wang Shaona, Wang Yaru, Du Hao, et al. Decomposition mechanism of vanadium slag by sub-molten salt medium with active carbon catalytic oxidation[J]. The Chinese Journal of Nonferrous Metal, 2017,27(8):1729−1735. (王少娜, 王亚茹, 杜浩, 等. 活性炭强化亚熔盐介质中钒渣分解机理[J]. 中国有色金属学报, 2017,27(8):1729−1735.
[10]	Liu Xingyi, Wei Yan, Jin Yuqing, et al. Fast determination of vanadium in vanadium-nitrogen-iron alloy by ammonium ferrous sulfate titrimetric method[J]. Shandong Metallurgy, 2009,31(1):48−49. (刘兴沂, 魏燕, 金玉清, 等. 硫酸亚铁铵滴定法快速测定钒氮铁合金中的钒[J]. 山东冶金, 2009,31(1):48−49. doi: 10.3969/j.issn.1004-4620.2009.01.019
[11]	Liang Yunsheng, Yang Yi, Mao Wenjian. Rapid determination of chromium in chromite samples by titrimetry with ammonium ferrous sulfate[J]. Rock and Mineral Analysis, 2007,26(1):73−74. (梁云生, 杨毅, 毛文剑. 硫酸亚铁铵滴定法快速测定铬铁矿中铬[J]. 岩矿测试, 2007,26(1):73−74. doi: 10.3969/j.issn.0254-5357.2007.01.018
[12]	Ying Tengyuan. Spectrophotometric determination of silicon in ferrochrome with molybdenum blue[J]. Metallurgical Analysis, 2002,22(1):58−60. (应腾远. 钼蓝光度法测定铬铁中硅[J]. 冶金分析, 2002,22(1):58−60. doi: 10.3969/j.issn.1000-7571.2002.01.022
[13]	Ma Lei, Liu Yazhen, Zhang Aimin. Study on the detemination of silico-molybdenum blue specprophotometric method and its application in metallurgical analysis[J]. Metallurgical Analysis, 2004,24(10):297−299. (马雷, 刘雅贞, 张爱民. 冶金分析中硅钼蓝光度法的研究与应用[J]. 冶金分析, 2004,24(10):297−299.
[14]	Tang Huaying. Mathematical correction to eliminate color interference in spectrophotometry study Ⅲ: Molybdenum blue specprophotometric method for direct determination of silicon content in vanadium iron[J]. Jiangxi Metallurgy, 1998,18(2):38−40. (唐华应. 数学校正消除光度法中色泽干扰的研究Ⅲ: 钼蓝光度法直接测定钒铁中硅量[J]. 江西冶金, 1998,18(2):38−40.
[15]	Xiao Mantian. Photometric determination of trivalent chromium in cr plating bath[J]. Electroplating & Pollution Control, 1987,7(5):33−35. (肖满田. 镀铬溶液中三价铬的光度测定[J]. 电镀与环保, 1987,7(5):33−35.
[16]	Li Haili. Determination of silica with spectrophotometry under presence of much phosphate[J]. Yunnan Metallurgy, 2001,30(4):45−46. (李海黎. 大量磷酸盐存在下光度法测定二氧化硅[J]. 云南冶金, 2001,30(4):45−46. doi: 10.3969/j.issn.1006-0308.2001.04.014