粗钨酸钠溶液亚铁盐沉淀法除铬、钒的热力学分析及实验验证

doi:10.16085/j.issn.1000-6613.2022-1170

摘要/Abstract

摘要：

废硬质合金再生利用过程中得到的粗钨酸盐溶液Cr、V含量容易超标，由于Cr、V与W具有十分相似的水溶液性质，粗钨酸盐溶液除铬、钒一直是个技术难题。本文针对亚铁盐沉淀法从粗钨酸钠溶液中除铬、钒工艺过程进行热力学分析研究，分别绘制了298K时Cr-Fe-H₂O体系和V-Fe-H₂O体系的Eh-pH图、Cr⁶⁺-Fe³⁺-V⁵⁺-H₂O体系和Cr³⁺-Fe²⁺-Fe³⁺-V⁵⁺-H₂O体系的热力学平衡图。热力学分析结果表明：粗钨酸钠溶液中Cr(Ⅵ)在酸性和碱性体系下均能够被Fe²⁺或Fe(OH)₂沉淀还原，V(Ⅴ)则会与Fe²⁺或Fe(OH)₂反应生成Fe(VO₃)₂沉淀；在Cr³⁺-Fe²⁺-Fe³⁺-V⁵⁺-H₂O体系中存在Fe(VO₃)₂+Fe(OH)₃+Cr(OH)₃+Fe(OH)₂共沉淀稳定区，为亚铁盐沉淀法同时除铬、钒提供了热力学可行性，并获得了沉淀法最佳条件控制区间。验证实验结果表明：控制溶液的pH为9、以n(Fe²⁺)∶n(V+Cr)=15∶1加入硫酸亚铁沉淀剂时，粗钨酸钠溶液的除铬率高达99.85%、除钒率为95.05%、钨损失率仅为0.33%，实验效果与热力学分析结论基本相符；滤渣的SEM-EDS分析结果，进一步证实了Fe-Cr-V共沉淀的技术可行性。

关键词: 亚铁盐沉淀法, 热力学分析, 钒铬同步脱除, 钨酸盐溶液

Abstract:

The content of Cr and V in the crude tungstate solution obtained in the recycling process of waste cemented carbide is easy to exceed the standard. Because Cr, V and W have very similar properties of aqueous solution, the removal of chromium and vanadium from the crude tungstate solution has always been a technical problem. In this paper, the thermodynamic analysis and research on the process of removing chromium and vanadium from the crude sodium tungstate solution by ferrous salt precipitation method were carried out. The Eh-pH diagrams of Cr-Fe-H₂O System and V-Fe-H₂O system at 298K and the thermodynamic equilibrium diagrams of Cr⁶⁺-Fe³⁺-V⁵⁺-H₂O system and Cr³⁺-Fe²⁺-Fe³⁺-V⁵⁺-H₂O system at 298K were drawn, respectively. Thermodynamic analysis results showed that Cr(Ⅵ) in crude sodium tungstate solution could be reduced by Fe²⁺or Fe(OH)₂ precipitation in both acidic and alkaline systems, and V(Ⅴ) would react with Fe²⁺ or Fe(OH)₂to form Fe(VO₃)₂ precipitation. In Cr³⁺-Fe²⁺-Fe³⁺-V⁵⁺-H₂O system, there was a stable coprecipitation zone of Fe(VO₃)₂+Fe(OH)₃+Cr(OH)₃+Fe(OH)₂, which provided thermodynamic feasibility for the simultaneous removal of chromium and vanadium by ferrous salt precipitation method, and obtained the control range of the best conditions of precipitation method. The experimental results indicated that when the pH value of the solution was controlled to be 9 and ferrous sulfate precipitant was added with n(Fe²⁺)∶n(V+Cr)=15∶1, the chromium removal rate of crude sodium tungstate solution was as high as 99.85%, the vanadium removal rate was 95.05% and the tungsten loss rate was only 0.33%. The experimental effect was basically consistent with the thermodynamic analysis conclusion. The SEM-EDS analysis results of the filter residue further confirmed the technical feasibility of Fe-Cr-V coprecipitation.

Key words: ferrous salt precipitation method, thermodynamic analysis, simultaneous removal of vanadium and chromium, tungstate solution

中图分类号:

TF 841.1

贺山明, 潘界昌, 徐国钻, 李文君, 梁勇. 粗钨酸钠溶液亚铁盐沉淀法除铬、钒的热力学分析及实验验证[J]. 化工进展, 2023, 42(4): 2171-2179.

HE Shanming, PAN Jiechang, XU Guozuan, LI Wenjun, LIANG Yong. Thermodynamic analysis and experimental verification of chromium and vanadium removal by ferrous salt precipitation from crude sodium tungstate solution[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 2171-2179.

图/表 11

表 1 相关化学反应、热力学平衡方程及其在298K下的平衡常数[11-14]

序号	化学反应	lgK	平衡方程
(1)	Cr³⁺+OH^- $̿$ CrOH²⁺	9.969	[CrOH²⁺][Cr³⁺]^-1[OH^-]^-1=10^9.969
(2)	Cr³⁺+2OH^- $̿$ Cr(OH)₂⁺	15.384	[Cr(OH)₂⁺][Cr³⁺]^-1[OH^-]^-2=10^15.384
(3)	Cr³⁺+4OH^- $̿$ Cr(OH)₄^-	38.054	[Cr(OH)₄^-][Cr³⁺]^-1[OH^-]^-4=10^38.054
(4)	HCrO₄^- $̿$ H⁺+CrO₄^2-	-6.49	[H⁺][CrO₄^2-][HCrO₄^-]^-1=10^-6.49
(5)	2HCrO₄^- $̿$ Cr₂O₇^2-+H₂O	1.52	[Cr₂O₇^2-][HCrO₄^-]^-2=10^1.52
(6)	Fe²⁺+OH^- $̿$ FeOH⁺	6.892	[FeOH⁺][Fe²⁺]^-1[OH^-]^-1=10^6.892
(7)	Fe²⁺+2OH^- $̿$ Fe(OH)_2(aq)	9.77	[Fe(OH)_2(aq)][Fe²⁺]^-1[OH^-]^-2=10^9.77
(8)	Fe²⁺+3OH^- $̿$ Fe(OH)₃^-	12.143	[Fe(OH)₃^-][Fe²⁺]^-1[OH^-]^-3=10^12.143
(9)	Fe³⁺+OH^- $̿$ FeOH²⁺	11.825	[FeOH²⁺][Fe³⁺]^-1[OH^-]^-1=10^11.825
(10)	Fe³⁺+2OH^- $̿$ Fe(OH)₂⁺	21.103	[Fe(OH)₂⁺][Fe³⁺]^-1[OH^-]^-2=10^21.103
(11)	Fe³⁺+3OH^- $̿$ Fe(OH)_3(aq)	29.67	[Fe(OH)_3(aq)][Fe³⁺]^-1[OH^-]^-3=10^29.67
(12)	Fe³⁺+4OH^- $̿$ Fe(OH)₄^-	35.561	[Fe(OH)₄^-][Fe³⁺]^-1[OH]^-4=10^35.561
(13)	2Fe³⁺+2OH^- $̿$ Fe₂(OH)₂⁴⁺	20.779	[Fe₂(OH)₂⁴⁺][Fe⁺³]^-2[OH^-]^-2=10^20.779
(14)	VO₂⁺+2H₂O $̿$ VO₄^3-+4H⁺	-29.38	[VO₄^3-][H⁺]⁴[VO₂⁺]^-1=10^-29.38
(15)	VO₄^3-+H⁺ $̿$ HVO₄^2-	13.36	[HVO₄^2-][VO₄^3-]^-1[H⁺]^-1=10^13.36
(16)	VO₄^3-+2H⁺ $̿$ H₂VO₄^-	21.31	[H₂VO₄^-][VO₄^3-]^-1[H⁺]^-2=10^21.31
(17)	2VO₄^3-+2H⁺ $̿$ V₂O₇^4-+H₂O	27.38	[V₂O₇^4-][H⁺]^-2[VO₄^3-]^-2=10^27.38
(18)	2VO₄^3-+4H⁺ $̿$ H₂V₂O₇^2-+H₂O	45.4	[H₂V₂O₇^2-][VO₄^3-]^-2[H⁺]^-4=10^45.4
(19)	3HVO₄^2-+2H⁺ $̿$ HV₃O₁₀^4-+2H₂O	20.96	[HV₃O₁₀^4-][HVO₄^2-]^-3[H⁺]^-2=10^20.96
(20)	4VO₄^3-+8H⁺ $̿$ V₄O₁₂^4-+4H₂O	95.11	[V₄O₁₂^4-][VO₄^3-]^-4[H⁺]^-8=10^95.11
(21)	4HVO₄^2-+2H⁺ $̿$ V₄O₁₃^6-+3H₂O	20.55	[V₄O₁₃^6-][HVO₄^2-]^-4[H⁺]^-2=10^20.55
(22)	4HVO₄^2-+3H⁺ $̿$ HV₄O₁₃^5-+3H₂O	31.33	[HV₄O₁₃^5-][HVO₄^2-]^-4[H⁺]^-3=10^31.33
(23)	5VO₄^3-+10H⁺ $̿$ V₅O₁₅^5-+5H₂O	118.69	[V₅O₁₅^5-][VO₄^3-]^-5[H⁺]^-10=10^118.69
(24)	2VO₄^3-+3H⁺ $̿$ HV₂O₇^3-+H₂O	37.17	[HV₂O₇^3-][VO₄^3-]^-2[H⁺]^-3=10^37.17
(25)	6HVO₄^2-+6H⁺ $̿$ V₆O₁₈^6-+6H₂O	60.79	[V₆O₁₈^6-][HVO₄^2-]^-6[H⁺]^-6=10^60.79
(26)	10VO₄^3-+24H⁺ $̿$ V₁₀O₂₈^6-+12H₂O	264.82	[V₁₀O₂₈^6-][VO₄^3-]^-10[H⁺]^-24=10^264.82
(27)	10VO₄^3-+25H⁺ $̿$ HV₁₀O₂₈^5-+12H₂O	270.89	[HV₁₀O₂₈^5-][VO₄^3-]^-10[H⁺]^-25=10^270.89
(28)	10VO₄^3-+26H⁺ $̿$ H₂V₁₀O₂₈^4-+12H₂O	274.49	[H₂V₁₀O₂₈^4-][VO₄^3-]^-10[H⁺]^-26=10^274.49
(29)	10HVO₄^2-+17H⁺ $̿$ H₃V₁₀O₂₈^3-+12H₂O	150.38	[H₃V₁₀O₂₈^3-][HVO₄^2-]^-10[H⁺]^-17=10^150.38
(30)	Cr(OH)_3(s) $̿$ Cr³⁺+3OH^-	-29.554	[Cr³⁺][OH^-]³=10^-29.554
(31)	Fe(OH)_2(s) $̿$ Fe²⁺+2OH^-	-15.042	[Fe²⁺][OH^-]²=10^-15.042
(32)	Fe(OH)_3(s) $̿$ Fe³⁺+3OH^-	-37.94	[Fe³⁺][OH^-]³=10^-37.94
(33)	Fe(VO₃)_2(s)+2H₂O $̿$ Fe²⁺+2H₂VO₄^-	-15.524	[Fe²⁺][H₂VO₄^-]²=10^-15.524

表 1 相关化学反应、热力学平衡方程及其在298K下的平衡常数[11-14]

序号	化学反应	lgK	平衡方程
(1)	Cr³⁺+OH^- $̿$ CrOH²⁺	9.969	[CrOH²⁺][Cr³⁺]^-1[OH^-]^-1=10^9.969
(2)	Cr³⁺+2OH^- $̿$ Cr(OH)₂⁺	15.384	[Cr(OH)₂⁺][Cr³⁺]^-1[OH^-]^-2=10^15.384
(3)	Cr³⁺+4OH^- $̿$ Cr(OH)₄^-	38.054	[Cr(OH)₄^-][Cr³⁺]^-1[OH^-]^-4=10^38.054
(4)	HCrO₄^- $̿$ H⁺+CrO₄^2-	-6.49	[H⁺][CrO₄^2-][HCrO₄^-]^-1=10^-6.49
(5)	2HCrO₄^- $̿$ Cr₂O₇^2-+H₂O	1.52	[Cr₂O₇^2-][HCrO₄^-]^-2=10^1.52
(6)	Fe²⁺+OH^- $̿$ FeOH⁺	6.892	[FeOH⁺][Fe²⁺]^-1[OH^-]^-1=10^6.892
(7)	Fe²⁺+2OH^- $̿$ Fe(OH)_2(aq)	9.77	[Fe(OH)_2(aq)][Fe²⁺]^-1[OH^-]^-2=10^9.77
(8)	Fe²⁺+3OH^- $̿$ Fe(OH)₃^-	12.143	[Fe(OH)₃^-][Fe²⁺]^-1[OH^-]^-3=10^12.143
(9)	Fe³⁺+OH^- $̿$ FeOH²⁺	11.825	[FeOH²⁺][Fe³⁺]^-1[OH^-]^-1=10^11.825
(10)	Fe³⁺+2OH^- $̿$ Fe(OH)₂⁺	21.103	[Fe(OH)₂⁺][Fe³⁺]^-1[OH^-]^-2=10^21.103
(11)	Fe³⁺+3OH^- $̿$ Fe(OH)_3(aq)	29.67	[Fe(OH)_3(aq)][Fe³⁺]^-1[OH^-]^-3=10^29.67
(12)	Fe³⁺+4OH^- $̿$ Fe(OH)₄^-	35.561	[Fe(OH)₄^-][Fe³⁺]^-1[OH]^-4=10^35.561
(13)	2Fe³⁺+2OH^- $̿$ Fe₂(OH)₂⁴⁺	20.779	[Fe₂(OH)₂⁴⁺][Fe⁺³]^-2[OH^-]^-2=10^20.779
(14)	VO₂⁺+2H₂O $̿$ VO₄^3-+4H⁺	-29.38	[VO₄^3-][H⁺]⁴[VO₂⁺]^-1=10^-29.38
(15)	VO₄^3-+H⁺ $̿$ HVO₄^2-	13.36	[HVO₄^2-][VO₄^3-]^-1[H⁺]^-1=10^13.36
(16)	VO₄^3-+2H⁺ $̿$ H₂VO₄^-	21.31	[H₂VO₄^-][VO₄^3-]^-1[H⁺]^-2=10^21.31
(17)	2VO₄^3-+2H⁺ $̿$ V₂O₇^4-+H₂O	27.38	[V₂O₇^4-][H⁺]^-2[VO₄^3-]^-2=10^27.38
(18)	2VO₄^3-+4H⁺ $̿$ H₂V₂O₇^2-+H₂O	45.4	[H₂V₂O₇^2-][VO₄^3-]^-2[H⁺]^-4=10^45.4
(19)	3HVO₄^2-+2H⁺ $̿$ HV₃O₁₀^4-+2H₂O	20.96	[HV₃O₁₀^4-][HVO₄^2-]^-3[H⁺]^-2=10^20.96
(20)	4VO₄^3-+8H⁺ $̿$ V₄O₁₂^4-+4H₂O	95.11	[V₄O₁₂^4-][VO₄^3-]^-4[H⁺]^-8=10^95.11
(21)	4HVO₄^2-+2H⁺ $̿$ V₄O₁₃^6-+3H₂O	20.55	[V₄O₁₃^6-][HVO₄^2-]^-4[H⁺]^-2=10^20.55
(22)	4HVO₄^2-+3H⁺ $̿$ HV₄O₁₃^5-+3H₂O	31.33	[HV₄O₁₃^5-][HVO₄^2-]^-4[H⁺]^-3=10^31.33
(23)	5VO₄^3-+10H⁺ $̿$ V₅O₁₅^5-+5H₂O	118.69	[V₅O₁₅^5-][VO₄^3-]^-5[H⁺]^-10=10^118.69
(24)	2VO₄^3-+3H⁺ $̿$ HV₂O₇^3-+H₂O	37.17	[HV₂O₇^3-][VO₄^3-]^-2[H⁺]^-3=10^37.17
(25)	6HVO₄^2-+6H⁺ $̿$ V₆O₁₈^6-+6H₂O	60.79	[V₆O₁₈^6-][HVO₄^2-]^-6[H⁺]^-6=10^60.79
(26)	10VO₄^3-+24H⁺ $̿$ V₁₀O₂₈^6-+12H₂O	264.82	[V₁₀O₂₈^6-][VO₄^3-]^-10[H⁺]^-24=10^264.82
(27)	10VO₄^3-+25H⁺ $̿$ HV₁₀O₂₈^5-+12H₂O	270.89	[HV₁₀O₂₈^5-][VO₄^3-]^-10[H⁺]^-25=10^270.89
(28)	10VO₄^3-+26H⁺ $̿$ H₂V₁₀O₂₈^4-+12H₂O	274.49	[H₂V₁₀O₂₈^4-][VO₄^3-]^-10[H⁺]^-26=10^274.49
(29)	10HVO₄^2-+17H⁺ $̿$ H₃V₁₀O₂₈^3-+12H₂O	150.38	[H₃V₁₀O₂₈^3-][HVO₄^2-]^-10[H⁺]^-17=10^150.38
(30)	Cr(OH)_3(s) $̿$ Cr³⁺+3OH^-	-29.554	[Cr³⁺][OH^-]³=10^-29.554
(31)	Fe(OH)_2(s) $̿$ Fe²⁺+2OH^-	-15.042	[Fe²⁺][OH^-]²=10^-15.042
(32)	Fe(OH)_3(s) $̿$ Fe³⁺+3OH^-	-37.94	[Fe³⁺][OH^-]³=10^-37.94
(33)	Fe(VO₃)_2(s)+2H₂O $̿$ Fe²⁺+2H₂VO₄^-	-15.524	[Fe²⁺][H₂VO₄^-]²=10^-15.524

表2 质量守恒方程式[13]

序号	反应方程式
(34)	[Cr⁶⁺]_T $̿$ [CrO₄^2-]+[HCrO₄^-]+2*[Cr₂O₇^2-]
(35)	[Cr³⁺]_T $̿$ [Cr³⁺]+[CrOH²⁺]+[Cr(OH)₂⁺]+[Cr(OH)₄^-]
(36)	[Fe²⁺]_T $̿$ [Fe²⁺]+[FeOH⁺]+[Fe(OH)_2(aq)]+[Fe(OH)₃^-]
(37)	[Fe³⁺]_T $̿$ [Fe³⁺]+[FeOH²⁺]+[Fe(OH)₂⁺]+[Fe(OH)_3(aq)]+[Fe(OH)₄^-]+2*[Fe₂(OH)₂⁴⁺]
(38)	[V⁵⁺]_T $̿$ [VO₄^3-]+[VO₂⁺]+[HVO₄^2-]+[H₂VO₄^-]+2[V₂O₇^4-]+2[H₂V₂O₇^2-]+3[HV₃O₁₀^4-]+4[V₄O₁₂^4-]+4[V₄O₁₃^6-]+4[HV₄O₁₃^5-]+ 5[V₅O₁₅^5-]+6[HV₂O₇^3-]+6[V₆O₁₈^6-]+10[V₁₀O₂₈^6-]+10[HV₁₀O₂₈^5-]+10[H₂V₁₀O₂₈^4-]+10*[H₃V₁₀O₂₈^3-]
(39)	[Cr⁶⁺]_T $̿$ [Cr⁶⁺]_Tⁱ
(40)	[Cr³⁺]_T $̿$ [Cr³⁺]_Tⁱ
(41)	[Fe²⁺]_T $̿$ [Fe²⁺]_Tⁱ
(42)	[Fe³⁺]_T $̿$ [Fe³⁺]_Tⁱ
(43)	[V⁵⁺]_T $̿$ [V⁵⁺]_Tⁱ
(44)	[Fe²⁺]_Tⁱ-[Fe²⁺]_T $̿$ [V]_Tⁱ-[V]_T

表2 质量守恒方程式[13]

序号	反应方程式
(34)	[Cr⁶⁺]_T $̿$ [CrO₄^2-]+[HCrO₄^-]+2*[Cr₂O₇^2-]
(35)	[Cr³⁺]_T $̿$ [Cr³⁺]+[CrOH²⁺]+[Cr(OH)₂⁺]+[Cr(OH)₄^-]
(36)	[Fe²⁺]_T $̿$ [Fe²⁺]+[FeOH⁺]+[Fe(OH)_2(aq)]+[Fe(OH)₃^-]
(37)	[Fe³⁺]_T $̿$ [Fe³⁺]+[FeOH²⁺]+[Fe(OH)₂⁺]+[Fe(OH)_3(aq)]+[Fe(OH)₄^-]+2*[Fe₂(OH)₂⁴⁺]
(38)	[V⁵⁺]_T $̿$ [VO₄^3-]+[VO₂⁺]+[HVO₄^2-]+[H₂VO₄^-]+2[V₂O₇^4-]+2[H₂V₂O₇^2-]+3[HV₃O₁₀^4-]+4[V₄O₁₂^4-]+4[V₄O₁₃^6-]+4[HV₄O₁₃^5-]+ 5[V₅O₁₅^5-]+6[HV₂O₇^3-]+6[V₆O₁₈^6-]+10[V₁₀O₂₈^6-]+10[HV₁₀O₂₈^5-]+10[H₂V₁₀O₂₈^4-]+10*[H₃V₁₀O₂₈^3-]
(39)	[Cr⁶⁺]_T $̿$ [Cr⁶⁺]_Tⁱ
(40)	[Cr³⁺]_T $̿$ [Cr³⁺]_Tⁱ
(41)	[Fe²⁺]_T $̿$ [Fe²⁺]_Tⁱ
(42)	[Fe³⁺]_T $̿$ [Fe³⁺]_Tⁱ
(43)	[V⁵⁺]_T $̿$ [V⁵⁺]_Tⁱ
(44)	[Fe²⁺]_Tⁱ-[Fe²⁺]_T $̿$ [V]_Tⁱ-[V]_T

图1 298K下Cr-Fe-H2O体系Eh-pH图

图2 298K下V-Fe-H2O体系Eh-pH图

图3 298K下Cr6+-Fe3+-V5+-H2O体系相关组分分布图

图4 298K下Cr3+-Fe2+-Fe3+-V5+-H2O体系溶解组分的lgc-pH曲线

图5 298K下不同 [Fe2+]Ti对Cr3+-Fe2+-Fe3+-V5+-H2O体系的影响

图6 不同的硫酸亚铁添加量对粗钨酸钠溶液除铬、除钒率以及钨损率的影响

图7 不同pH条件下对粗钨酸钠溶液除铬、除钒率以及钨损率的影响

图8 pH分别为9和11条件下滤渣的SEM-EDS分析

图9 pH为9条件下滤渣的XRD谱图分析

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