不銹鋼渣高溫改性?析晶調控解毒研究現狀及發展趨勢

張鑫; 張梅; 郭敏

doi:10.13374/j.issn2095-9389.2022.02.10.003

不銹鋼渣高溫改性?析晶調控解毒研究現狀及發展趨勢

doi: 10.13374/j.issn2095-9389.2022.02.10.003

北京科技大學冶金與生態工程學院，北京 100083

基金項目: 國家重點研發計劃資助項目（2020YFB0606205）

詳細信息

通訊作者:
E-mail: guomin@ustb.edu.cn

中圖分類號: TG142.71
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- 文章訪問數: 419
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- 被引次數: 0
出版歷程
- 收稿日期: 2022-02-10
- 網絡出版日期: 2022-03-30
- 刊出日期: 2023-04-01

Advances and trends in high-temperature modification–crystallization control detoxification of stainless steel slag

School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, China

More Information

Corresponding author: E-mail: guomin@ustb.edu.cn

摘要

摘要: 截止到目前，鋼鐵工業普通固廢（高爐鐵渣）循環利用技術取得了重要進展，但仍存在固廢頑疾亟需處理。不銹鋼冶煉產生的含鉻（Cr）渣長期以來缺乏有效的無害化處置方法，環境隱患巨大。國內外專家學者通過添加還原物質、高溫調質及調節冷卻方式等以改變渣中鉻元素的賦存狀態，控制Cr⁶⁺的溶出，進而實現不銹鋼渣的解毒。其中，高溫改性?析晶調控方法可以通過調整鋼渣組分和控制溫度制度促進含鉻尖晶石相的形成和長大，提高鉻元素在尖晶石相中的富集程度，有望成為最有效且安全的無害化處理技術，在近些年得到快速發展。本文從不銹鋼渣高溫改性?析晶調控解毒的熱力學機理和結晶動力學原理出發，針對不銹鋼渣的高溫調質改性、解毒方面的研究進展進行了綜述。基于高溫調質?選擇性析晶的核心問題，重點闡述了改善解毒效果的方法和措施。另外，針對不銹鋼渣高溫改性?析晶調控解毒存在的問題提出了今后的發展方向。
- 含鉻不銹鋼渣 /
- 高溫改性 /
- 含鉻尖晶石相 /
- 解毒 /
- 鉻溶出
Abstract: To date, the recycling technology of common solid waste (blast furnace iron slag) in the iron and steel industry has made important progress. However, persisting, stubborn solid waste problems urgently need to be solved. With the continuous growth of stainless steel production in China, the total amount of stainless steel slag has reached more than 10 million tons. This slag contains a lot of CaO, MgO, and SiO₂, which are suitable building material additives. However, the harmful element chromium (Cr) in the slag and the dissolution characteristics of Cr⁶⁺ ions limit its large-scale application. For a long time, no effective, harmless disposal method has been available for Cr-containing slag, which brings great hidden danger to the environment. Given the characteristics of stainless steel slag, the current detoxification methods mainly include the solidification method, wet reduction, high-temperature ferrosilicon reduction, and high-temperature modification–crystallization control processes. Among these methods, high-temperature modification–crystallization control can promote Cr-containing spinel phase formation by adjusting steel slag compositions (e.g., basicity and oxidation-reduction properties) to improve the enrichment degree of Cr in the spinel phase. At the same time, by adjusting the slag cooling system (e.g., the quenching temperature and holding time) and reducing the slag viscosity, the nucleation and growth of the Cr-containing spinel phase can be improved, the precipitation amounts of the spinel phase are increased, and the occurrence probability of chromium in the matrix phase is reduced; thus, the detoxification of stainless steel slag can be achieved. Compared with the other three detoxification treatment methods, high-temperature modification–crystallization control has the advantages of a simple process, stable treatment effect, and large scale. In particular, solid wastes containing silicon, aluminum, and magnesium can be used as additives to adjust the composition of steel slag to realize a coordinated treatment of various solid wastes, which has very high economic value. In addition, using waste heat to modify steel slag directly after slag picking can substantially reduce energy consumption, should become one of the most promising harmless treatment approaches, and has recently attracted extensive attention. In this paper, the research progress of high-temperature modification and detoxification of stainless steel slag is reviewed according to its thermodynamic mechanism and crystallization kinetics principles. On the basis of the core problem of melt modification-selective crystallization, the methods and measures for improving the detoxification effect are emphasized. In addition, aiming at the existing problems in the high-temperature modification–crystallization control detoxification of stainless steel slag, development directions are proposed.
- chromium-containing stainless steel slag /
- high-temperature modification–crystallization control method /
- chromium-containing spinel /
- detoxification /
- dissolution of Cr⁶⁺

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圖 1 生成二元復合氧化物反應的標準吉布斯自由能變隨溫度的變化曲線^[29-32]

Figure 1. Standard Gibbs free energy variation curve with temperature for the formation of binary composite oxides^[29-32]

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圖 2 尖晶石晶體生長過程中熔體中溶質原子的濃度分布^[55]

Figure 2. Concentration distribution of the solute atoms in slag during spinel crystal growth^[55]

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圖 3 3種冷卻模式下含鉻尖晶石尺寸的增長和EDS分析^[59]

Figure 3. Cr-bearing spinel growth and EDS analysis under three cooling modes^[59]

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表 1 EAF渣和AOD渣的主要化學成分(質量分數)^[18-24]

Table 1. Main chemical compositions and contents of EAF and AOD slags (mass fraction)^[18-24] %

Slag	CaO	SiO₂	MgO	Fe_tO	Cr₂O₃	Al₂O₃	MnO	B
EAF Slag	38.64?50.39	24.01?34.73	4.80?12.63	0.54?4.30	2.92?6.40	2.30?9.55	0.20?6.00	1.20?1.76
AOD Slag	54.10?66.10	24.67?26.50	2.06?6.30	0.20?1.81	0.25?1.83	1.07?4.91	0.16?1.02	2.04?2.49

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表 2 EAF渣和AOD渣的主要礦相組成及Cr的賦存形式^[18-24]

Table 2. Main mineral compositions of EAF/AOD slags and the existence form of Cr^[18-24]

Slag	Main mineral phase	Other mineral phases	Cr-containing phase
EAF slag	Ca₂SiO₄, Ca₃MgSi₂O₈	Ca₂(Al,Mg)[(Si,Al)SiO₇], Al₂SiO₅, Fe₃O₄, (Fe,Mg)(Fe,Cr,Al)₂O₄, Cr₂O₃, CaCr₂O₄, CaCrO₄	(Fe,Mg)(Fe,Cr,Al)₂O₄, Cr₂O₃, CaCr₂O₄, CaCrO₄
AOD slag	Ca₂SiO₄,Ca₃MgSi₂O₈	(Fe,Mg)(Fe,Cr,Al)₂O₄, MgO, Fe-Cr-Ni	(Fe,Mg)(Fe,Cr,Al)₂O₄, MgO, Fe-Cr-Ni

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表 3 不銹鋼渣生成二元復合氧化物的化學反應方程及熱力學數據^[29-32]

Table 3. Chemical reaction equations and thermodynamic data of slag^[29-32]

Chemical reaction equation	Standard reaction Gibbs free energy variation/ (J·mol^?1)
$ \left( {{\text{FeO}}} \right){\text{ + }}\left( {{\text{A}}{{\text{l}}_{\text{2}}}{{\text{O}}_{\text{3}}}} \right){\text{ = FeA}}{{\text{l}}_{\text{2}}}{{\text{O}}_{\text{4}}}\left( {\text{s}} \right) $	${\Delta _{\text{r} } }{G_{\rm{m}}^{\ominus}}= - 144225 + 53.847T$
$ \left( {{\text{FeO}}} \right){\text{ + }}\left( {{\text{C}}{{\text{r}}_{\text{2}}}{{\text{O}}_{\text{3}}}} \right){\text{ = FeC}}{{\text{r}}_{\text{2}}}{{\text{O}}_{\text{4}}}\left( {\text{s}} \right) $	${\Delta _{\text{r} } }{G_{\rm{m}}^{\ominus}} = - 204144 + 76.479T$
$ \left( {{\text{MgO}}} \right){\text{ + }}\left( {{\text{A}}{{\text{l}}_{\text{2}}}{{\text{O}}_{\text{3}}}} \right){\text{ = MgA}}{{\text{l}}_{\text{2}}}{{\text{O}}_{\text{4}}}\left( {\text{s}} \right) $	${\Delta _{\text{r} } }{G_{\rm{m}}^{\ominus}} = - 224507 + 70.710T$
$ \left( {{\text{MgO}}} \right){\text{ + }}\left( {{\text{C}}{{\text{r}}_{\text{2}}}{{\text{O}}_{\text{3}}}} \right){\text{ = MgC}}{{\text{r}}_{\text{2}}}{{\text{O}}_{\text{4}}}\left( {\text{s}} \right) $	${\Delta _{\text{r} } }{G_{\rm{m}}^{\ominus}} = - 250426 + 82.002T$
$ \left( {{\text{CaO}}} \right){\text{ + }}\left( {{\text{C}}{{\text{r}}_{\text{2}}}{{\text{O}}_{\text{3}}}} \right){\text{ = CaC}}{{\text{r}}_{\text{2}}}{{\text{O}}_{\text{4}}}\left( {\text{s}} \right) $	${\Delta _{\text{r} } }{G_{\rm{m}}^{\ominus}} = - {\text{256506} } + {\text{82} }{\text{.002} }T$
$ \left( {{\text{CaO}}} \right){\text{ + }}\left( {{\text{Si}}{{\text{O}}_{\text{2}}}} \right){\text{ = CaSi}}{{\text{O}}_{\text{3}}}\left( {\text{s}} \right) $	${\Delta _{\text{r} } }{G_{\rm{m}}^{\ominus}} = - {\text{181562} } + {\text{32} }{\text{.136} }T$
$ {\text{2}}\left( {{\text{CaO}}} \right){\text{ + }}\left( {{\text{Si}}{{\text{O}}_{\text{2}}}} \right){\text{ = C}}{{\text{a}}_{\text{2}}}{\text{Si}}{{\text{O}}_{\text{4}}}\left( {\text{s}} \right) $	${\Delta _{\text{r} } }{G_{\rm{m}}^{\ominus}} = - {\text{287358} } + {\text{43} }{\text{.179} }T$
$ \left( {{\text{CaO}}} \right){\text{ + }}\left( {{\text{A}}{{\text{l}}_{\text{2}}}{{\text{O}}_{\text{3}}}} \right){\text{ = CaA}}{{\text{l}}_{\text{2}}}{{\text{O}}_{\text{4}}}\left( {\text{s}} \right) $	${\Delta _{\text{r} } }{G_{\rm{m}}^{\ominus}} = - {\text{208581} } + {\text{53} }{\text{.750} }T$
$ {\text{2}}\left( {{\text{MgO}}} \right){\text{ + }}\left( {{\text{Si}}{{\text{O}}_{\text{2}}}} \right){\text{ = M}}{{\text{g}}_{\text{2}}}{\text{Si}}{{\text{O}}_{\text{4}}}\left( {\text{s}} \right) $	${\Delta _{\text{r} } }{G_{\rm{m}}^{\ominus}}= - {\text{232410} } + {\text{59} }{\text{.229} }T$
$ {\text{2}}\left( {{\text{FeO}}} \right){\text{ + }}\left( {{\text{Si}}{{\text{O}}_{\text{2}}}} \right){\text{ = F}}{{\text{e}}_{\text{2}}}{\text{Si}}{{\text{O}}_{\text{4}}}\left( {\text{s}} \right) $	${\Delta _{\text{r} } }{G_{\rm{m}}^{\ominus}} = - {\text{93882} } + {\text{55} }{\text{.045} }T$
$ {\text{3}}\left( {{\text{A}}{{\text{l}}_{\text{2}}}{{\text{O}}_{\text{3}}}} \right){\text{ + 2}}\left( {{\text{Si}}{{\text{O}}_{\text{2}}}} \right){\text{ = A}}{{\text{l}}_{\text{6}}}{\text{S}}{{\text{i}}_{\text{2}}}{{\text{O}}_{{\text{13}}}}\left( {\text{s}} \right) $	${\Delta _{\text{r} } }{G_{\rm{m}}^{\ominus}} = - {\text{360987} } + {\text{135} }{\text{.387} }T$

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表 4 不銹鋼渣二元堿度對于選擇性富集、析出含鉻尖晶石相的影響

Table 4. Effect of the binary basicity of stainless steel slag on selective enrichment and formation of Cr-containing spinel

Slag system	B	Crystallization temperature/ ℃	Heating time /h	Cr-containing phase	Cr mass fractionin spinel phase /%
CaO?SiO₂?Cr₂O₃?MgO Synthetic slag ^[37]	1.0?2.0	1600	24	(CaMg)Cr₂O₄, Ca₃MgSi₂O₈, Ca₂SiO₄,CaSiO₃	32.27
CaO?SiO₂?Cr₂O₃?MgO?FeO Synthetic slag ^[38]	0.6?2.2	1550	0.5	(Mg,Fe)(Fe,Cr)₂O₄
CaO?SiO₂?Cr₂O₃?MgO?Al₂O₃ Synthetic slag ^[39]	1.1?1.5	1400	12	Mg(Al,Cr)₂O₄, Ca₂MgSi₂O₇	46.70
CaO?SiO₂?Al₂O₃?Cr₂O₃?MgO-CaF₂?FeO Synthetic slag^[40]	1.0?2.0	1300	0.5	Mg(Cr,Al)₂O₄, glass, MgO, Ca₂SiO₄	35.23
CaO?SiO₂?Al₂O₃?CrO_x?MgO?Fe_tO Industrial slag ^[41]	0.96?1.96	1200	12	(Fe,Mg)(Cr,Al)₂O₄, CaSiO₃, Ca₂MgSi₂O₇	46.06

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表 5 不銹鋼渣的化學成分（Fe_tO、MgO、Al₂O₃）對于選擇性富集及析出含鉻尖晶石相的影響

Table 5. Effect of the chemical composition (Fe_tO, MgO, Al₂O₃) of stainless steel slag on the selective enrichment and formation of Cr-containing spinel

Slag system	Added compound (mass fraction/%)	Crystallization temperature /℃	Heating time /h	Cr-containing phase	Cr content in spinel phase/%
CaO?SiO₂?Al₂O₃?Cr₂O₃?MgO? CaF₂?FeO Synthetic slag^[44]	FeO (0?6.00)	1300	1	(Fe,Mg)(Cr,Fe,Al)₂O₄,MeO	27.21 (atom fraction)
CaO?SiO₂?Al₂O₃?Cr₂O₃?MgO? FeO Synthetic slag^[45]	FeO (0?20.00)	1550	0.5	(Mg,Fe)(Cr,Fe,Al)₂O₄	27.38 (mass fraction)
CaO?SiO₂?Al₂O₃?Cr₂O₃?MgO? Fe₂O₃ Synthetic slag^[46]	Fe₂O₃ (0?20.00)	1550	0.5	(Mg,Fe)(Cr,Fe,Al)₂O₄
CaO?SiO₂?Al₂O₃?Cr₂O₃?MgO?FeO?Fe₂O₃ Synthetic slag^[47]	Fe₂O₃ (2.00?12.00)	1550	0.5	(Mg,Fe,Ca)(Cr,Fe,Al)₂O₄	12.79 (atom fraction)
CaO?SiO₂?Cr₂O₃?MgO Synthetic slag^[48]	MgO (0?12.00)	1600	24	MgCr₂O₄,Cr₂O₃,CrO	63.98 (mass fraction)
CaO?SiO₂?Cr₂O₃?MgO?CaF₂ Synthetic slag^[35]	MgO (0?9.00)	1600	0	CaCr₂O₄,CaCrO₄,Ca₅(CrO₄)₃F, MgCr₂O₄	33.00 (mass fraction)
CaO?SiO₂?Al₂O₃?Cr₂O₃?MgO Synthetic slag^[51]	Al₂O₃ (3.00?12.00)	1400	0.5	Mg(Al,Cr)₂O₄,Ca₂SiO₄,Melilite	10.94 (atom fraction)
CaO?SiO₂?Al₂O₃?Cr₂O₃?MgO? FeO?CaF₂ Synthetic slag^[33]	Al₂O₃ (4.00?16.00)	1300	0.5	Mg(Al,Cr)₂O₄,Ca₂SiO₄	18.23(atom fraction)
CaO?SiO₂?Al₂O₃?Cr₂O₃?MgO Synthetic slag^[34]	Al₂O₃ (5.56?25.00)	1400?1600	48	Mg(Al,Cr)₂O₄

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