废SCR脱硝催化剂钒、钛、钨选择性分离研究

张振全; 赵备备; 李兰杰; 董自慧; 白瑞国; 王海旭

doi:10.7513/j.issn.1004-7638.2021.01.004

废SCR脱硝催化剂钒、钛、钨选择性分离研究

doi: 10.7513/j.issn.1004-7638.2021.01.004

张振全^{1, 2},
赵备备³,
李兰杰^{1, 2, ,},
董自慧¹,
白瑞国³,
王海旭³

1.
河钢集团承钢公司钒钛技术研究所，河北承德 067102
2.
河北省钒钛新材料重点实验室，河北承德 067102
3.
河北省钒钛产业技术研究院，河北承德 067102

基金项目: 承德市科学技术研究与发展计划项目（项目编号：202001B007）。

详细信息

作者简介:
张振全(1974—)，男，山西文水人，硕士，高级工程师，主要从事企业管理、控制工程以及金属材料加工

通讯作者:
李兰杰，通讯联系人，正高级工程师，E-mail：lilanjie20040014@163.com

中图分类号: TF823, TQ426
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- 被引次数: 0
出版历程
- 收稿日期: 2020-12-07
- 刊出日期: 2021-02-10

Study on selective separation of vanadium, titanium and tungsten from spent SCR denitration catalyst

1.
Institute of Vanadium and Titanium Technology, HBIS Group Chengsteel Company, Chengde 067102, Hebei, China
2.
Hebei Province Key Laboratory of Vanadium and Titanium New Materials, Chengde 067102, Hebei, China
3.
Hebei Vanadium and Titanium Industrial Technology Research Institute, Chengde 067102, Hebei, China

摘要

摘要: 分别采用NaOH、HCl浸出废SCR催化剂，碳酸钠焙烧-水浸废SCR催化剂选择性分离钛。试验表明：碳酸钠焙烧-水浸废催化剂可实现钛与钒、钨高效分离。较优工艺条件：焙烧温度850 ℃，焙烧时间3 h，碳酸钠与废催化剂质量比为1.3，浸出温度95 ℃，浸出时间1 h，搅拌速度500 r/min。V、As、W的浸出率分别为52.26%，98.24%和99.9%。采用硫酸浸出废SCR催化剂钠化焙烧渣实现高效提取钛。工艺条件：上述较优条件焙烧渣，40%硫酸，液固比4∶1，浸出温度90 ℃，浸出时间3 h，搅拌速度500 r/min。钛的浸出率为93.4%。采用自生晶种水解法制备偏钛酸，钛水解率为94.05%，偏钛酸纯度为94.07%。
- 提钛 /
- 废SCR催化剂 /
- 选择性分离 /
- NaOH浸出 /
- HCl浸出 /
- 碳酸钠焙烧-水浸
Abstract: Titanium was selectively separated from waste SCR catalyst by NaOH leaching, HCl leaching and sodium carbonate roasting followed by water leaching, respectively. The results show that titanium can be separated from vanadium and tungsten by sodium carbonate roasting and water leaching of the catalyst. The optimum process conditions are as follows: roasting temperature 850 ℃, roasting time 3 h, mass ratio of sodium carbonate to waste catalyst 1.3, leaching temperature 95 ℃, leaching time 1 h, stirring speed 500 r/min. The leaching rates of V, As and W are 52.26%, 98.24% and 99.9%, respectively. High efficient titanium extraction can be achieved by leaching sodium roasting slag of the spent SCR catalyst with sulfuric acid. The optimum conditions are as follows: 40% sulfuric acid, liquid-solid ratio 4∶1, leaching temperature 90 ℃, leaching time 3 h, stirring speed 500 r/min. The leaching rate of titanium is 93.4%. Metatitanic acid was prepared by hydrolysis. The hydrolysis rate of titanium is 94.05% and the purity of metatitanic acid is 94.07%.
- titanium extraction /
- spent SCR catalyst /
- selective separation /
- NaOH /
- HCl /
- sodium carbonate roasting, water leaching

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图 1 废SCR催化剂的XRD分析结果

Figure 1. XRD pattern of spent SCR catalyst

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图 2 废SCR脱硝催化剂钒、钛、钨选择性分离研究工艺流程

Figure 2. Process flow of selective separation of V, Ti and W from spent SCR catalyst

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图 3 (a) V-Na-H₂O体系的E-pH关系；(b) W-Na-H₂O体系的E-pH关系；(c) As-Na-H₂O体系的E-pH关系

Figure 3. (a) E-pH relationship of V-Na-H₂O system; (b) E-pH relationship of W-Na-H₂O system; (c) E-pH relationship of As-Na-H₂O system

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图 4 (a) V-H₂O体系的E-pH关系；(b) W-H₂O体系的E-pH关系

Figure 4. (a) E-pH relationship of V-H₂O system; (b) E-pH relationship of W-H₂O system

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图 5 主要元素浸出率随NaOH浓度变化曲线

Figure 5. Leaching rates of main elements at different NaOH concentrations

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图 6 碳酸钠与废脱硝催化剂质量比为1.3、1.4的反应产物XRD

Figure 6. XRD patterns of roasting products with mass ratio of sodium carbonate to spent denitration catalyst of 1.3 and 1.4

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图 7 碳酸钠与废脱硝催化剂质量比对主要元素浸出率的影响

Figure 7. Effect of mass ratio of sodium carbonate to spent denitration catalyst on leaching rate of main elements

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图 8 焙烧熟料

Figure 8. Calcined clinker

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图 9 水解试验装置

Figure 9. Hydrolysis test device

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表 1 废SCR脱硝催化剂化学成分分析

Table 1. Chemical compositions of spent SCR denitration catalyst　　　　　　　　　　　　　　　　　%

Al	As	Fe	K	Mg	Si	Ti	V	W
1.03	0.14	0.30	0.12	0.13	4.32	45.12	0.754	2.59

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表 2 NaOH浸出废脱硝催化剂浸出液各元素含量

Table 2. Contents of elements in leaching solution of spent denitration catalyst leached by NaOH

NaOH浓度/（g·L⁻¹）	浸出液各元素含量/（mg·L⁻¹）										浸出液体积/mL
NaOH浓度/（g·L⁻¹）	Al	As	Mn	Mo	P	S	Si	Ti	V	W	浸出液体积/mL
50	330.7	148.9	0.25	8.51	10.08	1048	1415	0.41	388.2	838.2	198
100	545.1	176	0.33	11.13	9.81	1220	2409	0.91	463.4	1405	170
200	292.1	207.6	0.46	14.78	11.62	1322	3645	4.78	569.2	2418	160
300	497	184.3	0.55	12.61	8.94	1148	4185	18.93	510.2	2629	188

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表 3 盐酸浸出废脱硝催化剂浸出液各元素含量

Table 3. Concentration of elements in solution of spent denitration catalyst leached by HCl solution

盐酸质量分数/%	浸出液中各元素含量/（mg·L⁻¹）											浸出液体积/mL
盐酸质量分数/%	Al	As	Ca	K	Mg	Na	S	Si	Ti	V	W	浸出液体积/mL
10	124.7	27.57	170.4	167.9	21.93	261	792.3	69.43	115.2	276.3	0.62	230
15	146.5	33.01	183.6	170.2	23.76	232	792	33.45	218.4	290.6	2.43	219
20	114.2	27.8	169	148.9	18.78	203	699.8	18.48	360.2	270.6	5.09	240

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表 4 盐酸浸出废脱硝催化剂主要元素浸出率

Table 4. Leaching rate of main elements in waste denitration catalyst leached by hydrochloric acid

盐酸质量分数/%	浸出率/%
盐酸质量分数/%	As	V	W
10	18.12	33.71	0.02
15	20.65	33.76	0.08
20	19.06	34.45	0.19

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表 5 废SCR脱硝催化剂及浸出渣成分分析

Table 5. Chemical compositions of spent SCR denitration catalyst and the leaching residue %

	Al	As	Ca	Fe	K	Mg	Si	Ti	V	W
脱硝催化剂	1.03	0.14	1.06	0.30	0.12	0.13	4.32	45.12	0.75	2.59
浸出渣	0.02	0	0.70	0.22	0.021	0.071	0.16	38.88	0.31	0.07

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表 6 硫酸浸出Na₂CO₃焙烧渣浸出液各元素浓度

Table 6. Concentration of elements in leaching solution of Na₂CO₃ roasting residue leached by sulfuric acid mg/L

Al	As	Ca	Cr	Fe	K	Mg	Na	Si	Ti	V	W
238.3	0	827.1	3.12	210.9	15.56	156.8	22540	1441	80550	1155	52.75

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表 7 硫酸浸出Na₂CO₃焙烧渣的尾渣成分分析

Table 7. Chemical compositions of tailings from sulfuric acid leaching of Na₂CO₃ roasting slag %

Al	As	Ca	Fe	K	Mg	Si	Ti	V	W
0.13	0.007	5.53	0.10	0.044	0.025	0.36	48.88	0.42	0.43

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表 8 水解前后溶液元素含量

Table 8. Element content of solution before and after hydrolysis

	体积/L	溶液中各元素含量/（mg·L⁻¹）
	体积/L	Al	As	Ca	Fe	K	Mg	Na	Si	Ti	V	W
水解前	0.42	37.12	0.11	463.20	49.79	30.61	62.32	7 346	336.50	9 420.0	115.90	3.21
水解后	1.03	10.29		191.80	12.62	11.30	20.46	3 301	115.90	228.7	2.71	1.15

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表 9 自生晶种制备的偏钛酸成分分析

Table 9. Chemical compositions of metatitanic acid prepared by in-situ seed %

类别	Al	As	Ca	Fe	K	Mg	P	Si	Ti	V	W
自制偏钛酸	0.005	0.001	0.049	0.080	0.085	0.013	0.003	0.318	46.078	0.384	0.018
工业偏钛酸	0.003	0	0.021	0.085	0.070	0.005	0.067	0.021	49.556	0.473	0.005

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