鉻元素固化機理及利用不銹鋼工業含鉻固廢制備無機材料研究進展

武紹文; 張延玲; 張帥; 高朝輝

doi:10.13374/j.issn2095-9389.2021.09.15.007

鉻元素固化機理及利用不銹鋼工業含鉻固廢制備無機材料研究進展

doi: 10.13374/j.issn2095-9389.2021.09.15.007

北京科技大學鋼鐵冶金新技術國家重點實驗室，北京 100083

基金項目: 國家重點研發計劃資助項目（2019YFC1905701）

詳細信息

通訊作者:
E-mail:zhangyanling@metall.ustb.edu.cn

中圖分類號: TF09
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- 文章訪問數: 1448
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- 被引次數: 0
出版歷程
- 收稿日期: 2021-05-31
- 網絡出版日期: 2021-10-21
- 刊出日期: 2021-12-24

Research progress of chromium solidification mechanism and preparation of inorganic materials by Cr-containing solid wastes from stainless steel industry

State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083, China

More Information

Corresponding author: E-mail: zhangyanling@metall.ustb.edu.cn

摘要

摘要: 我國不銹鋼工業近年來飛速發展，產生大量含鉻固廢。含Cr固廢的綜合利用工藝技術的開發，Cr元素的解毒/固化機理是需要考慮的關鍵問題。本文綜述了前人在該領域的相關研究工作，包括國內外不銹鋼工業固廢的化學和物相組成、鉻在不同含鉻固廢中的存在形式、鉻在環境中的循環富集規律和毒性。探討了含Cr礦相的演變規律、Cr在不同礦相中的固化機理。總結了目前利用不銹鋼工業含鉻固廢制備水泥、微晶玻璃和燒結陶瓷等各類無機材料的研究進展。分析了目前利用不銹鋼工業含鉻固廢制備各類無機材料過程中存在的瓶頸問題。以期為未來中國無害化、高值化、資源化處理不銹鋼含鉻固廢并實現產業化應用提供基礎借鑒。
- 含鉻固廢 /
- 固化機理 /
- 無機材料 /
- 安全性能 /
- 不銹鋼渣
Abstract: In recent years, with the rapid development of the stainless steel industry in China, a large number of Cr-containing solid wastes are produced. Chromium resources in China are very scarce, and China mainly dependent on imported chromium. In the current situation of a limited supply of chromium ore in the world, determining the efficient utilization of chromium resources will become very important. The recovery of chromium in various solid wastes produced by the stainless steel industry has practical economic significance. In addition, an uncontrolled emission of Cr-containing solid wastes will endanger the ecological environment and hamper biological safety. Further, the large scale of China’s stainless steel industry has caused urgent environmental problems, i.e., the whole manufacturing process has produced a large number of Cr-containing solid wastes, including stainless steel slag, stainless steel dust, stainless steel rolled iron scale, and pickling sludge. The detoxification/solidification of Cr to obtain long-term safety performance is an important factor that must be considered in the development of a comprehensive utilization process technology for a large amount of Cr-containing solid wastes generated by the stainless steel industry. This paper reviewed the previous research work in this field, including the work regarding the chemical and phase compositions of the stainless steel industrial solid waste, the existing forms of chromium in different Cr-containing solid wastes, the cycle enrichment rule, and the toxicity of chromium in the environment. The evolution law of Cr-bearing mineral phases and the solidification mechanism of Cr in different mineral phases were discussed. The research progress of various inorganic materials such as cement, glass ceramics, and sintered ceramics prepared using Cr-containing solid wastes in the stainless steel industry was summarized. Bottleneck problems in the preparation of various inorganic materials from chromium-containing solid wastes in the stainless steel industry were analyzed to provide a basis for the future harmless, high-value, resource-based treatment of stainless steel Cr-containing solid wastes and the realization of industrial applications in China.
- Cr-containing solid waste /
- solidification mechanism /
- inorganic materials /
- safety performance /
- stainless steel slag

HTML全文

圖 1 鉻元素的循環示意圖。(a)自然環境中的鉻循環^[45]；(b)土壤中的鉻氧化/還原循環^[44]

Figure 1. Schematic diagram of Chromium cycle: (a) chromium cycle in the natural environment^[45]; (b) chromium oxidation/reduction cycle in soil^[44]

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圖 2 (a) Fe/Si摩爾比為0.19 單晶尖晶石顯微結構^[61]; (b) Fe/Si摩爾比為0.39單晶尖晶石顯微結構^[61]; (c) 尖晶石冷卻過程形成示意圖^[62]

Figure 2. (a) Microstructure of a single crystal spinel with Fe/Si mole ratios of 0.19^[61]; (b) microstructure of a single crystal spinel with Fe/Si mole ratios of 0.39^[61]; (c) growth diagram of the spinel during the cooling process^[62]

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圖 3 含鉻結晶相在硅?氧網絡結構的賦存狀態^[53]

Figure 3. Occurrence state of the Cr-containing crystalline phase in the Si–O network structure^[53]

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圖 4 碳化γ-C₂S固化Cr原理圖^[87]

Figure 4. Principle diagram of immobilization Cr from carbonization γ-C₂S^[87]

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圖 5 一步法微晶玻璃/鑄石的形核析晶原理^[98]

Figure 5. Nucleation and crystallization mechanism of the one-step method for glass ceramics/cast stone^[98]

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表 1 不銹鋼行業含鉻固體廢物的化學成分（質量分數）

Table 1. Chemical composition of Cr-containing solid wastes in the stainless steel industry %

Types	CaO	SiO₂	MgO	Al₂O₃	Fe₂O₃/FeO	MnO	Cr₂O₃	NiO	CaSO₄	CaF₂	Resource
EAF slag	47.78	28.68	7.67	4.83	3.57	0.21	4.73	—	—	—	[14]
	46.5	28.0	7.4	4.3	2.7	1.7	8.0	—	—	—	[15]
	46.9	33.5	6.22	2.30	1.43	2.60	2.92	—	—	—	[16]
	36	32	4.4	7.9	1.6	5.8	10.4	—	—	—	[17]
AOD slag	64.02	26.51	4.68	1.54	0.28	0.47	0.43	—	—	—	[14]
	54.1	26.5	6.30	4.91	1.81	1.02	1.83	—	—	—	[16]
	56.4	29.7	8.5	1.6	1.1	0.3	1.6	—	—	—	[18]
	55.7	33.0	7.6	1.3	0.3	0.4	0.7	—	—	—	[19]
Stainless steel dust	28.70	0.70	3.71	0.12	22.18	/	13.19	0.03	—	—	[20]
	10.8	3.42	2.12	1.45	47.6	/	11.1	2.12	—	—	[21]
	19.3	5.8	3.2	0.5	37.1	/	16.3	2.98	—	—	[8]
Stainless steel pickling sludge	14.68	0.17	0.99	11.48	20.09	/	4.12	0.96	51.61	8.92	[22]
	7.95	1.15	0.92	/	17.5	/	5.07	3.18	8.50	42.7	[4]
	14.61	2.37	0.38	0.88	15.48	/	6.12	1.03	5.32	13.86	[23]

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表 2 不銹鋼工業含鉻固廢礦相組成

Table 2. Phase composition of Cr-containing solid wastes in the stainless steel industry

Types	Phase composition	Resource
AOD slag	(Mg,Fe)Cr₂O₄, Ni?Cr metal, Ca₂SiO₄, Cuspidine, MgO, CaF₂	[16]
	MgCr₂O₄, Ca₂SiO₄, Cuspidine, Ca₃Mg₂O₈, CaO	[15]
	Ca₂SiO₄, MgO, Ni metal, Fe₃O₄	[24]
	Ca₃Mg₂O₈, Cuspidine, MgO, β-Ca₂SiO₄, CaSiO₃,CaF₂	[19]
	γ-Ca₂SiO₄, Ca₃Al₂O₆, MgAl₂O₄, Mg₂SiO₄	[25]
EAF slag	(Mg,Fe)₂SiO₄, Ca₂SiO₄, CaCrO₄, CaCr₂O₄,Ni?Cr metal, MgCr₂O₄	[26]
	glass, MgCr₂O₄, CaTiO₃,Ca₂SiO₄,	[27]
	Ca₃Mg₂O₈, MgCr₂O₄, γ-Ca₂SiO₄,	[28]
	(Mg,Fe)Cr₂O₄, Ca₃Mg₂O₈, Ca₂SiO₄,CaO	[29]
	Ca₂SiO₄, Ca₃Mg₂O₈, MgCr₂O₄, MgO, Ni?Cr metal	[30]
Stainless steel dust	Fe₂O₃, Fe₃O₄, NiO, CrO, FeCr₂O₄, NiMn₂O₄, CuFe₂O₄, ZnCr₂O₄	[31]
Stainless steel dust	Fe₂O₃, Fe₃O₄, FeCr₂O₄, NiFe₂O₄, ZnO	[32]
Stainless steel pickling sludge	Fe₂O₃, FeCr₂O₄, Cr(OH)₃, NiCr₂O₄, Cr₂O₃, Cr, Ni(OH)₂, CaF₂, CaSO₄·2H₂O, CaCO₃, CaCrO₄,	[33]
Stainless steel pickling sludge	Fe₂O₃, Fe₃O₄, FeCr₂O₄, NiO, NiFe₂O₄, CaCO₃, SiO₂	[34]

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表 3 利用不銹鋼含鉻固廢制備微晶玻璃研究現狀

Table 3. Research status of the glass ceramic prepared from Cr-containing solid wastes of the stainless steel industry

Solid waste	Main mineral phase	Cr mass content and addition mass fraction of raw material	Preparation heat treatment	Properties	Reference
AOD stainless steel slag	Diopside?akermanite?gehlenite	40%–80%AOD slag(2.1% Cr₂O₃)	Melted at 1500 ℃ for 1 h and heated at the required temperatures	Bending strength:137.83 MPa, acid and alkali resistances: 99.919% and 99.991%	[94]
Stainless steel slag	Wollastonite?augite	1.82% Cr₂O₃	Melted at 1450 ℃ for 3 h and heated at the required temperatures	Bending strength 176.21 MPa	[95]
Heavy metal gypsum and pickling sludge	Akermanite	Pickling sludge (4.55%Cr₂O₃)	Melted at 1460 ℃ for 2.5 h, nucleated at 700 ℃ for 2 h, and crystallized at 900 ℃ for 1 h	Bending strength: 206 MPa,	[96]
Fly ash and pickling sludge	Diopside	22% pickling sludge	Melted at 1400 ℃ for 3 h, nucleated and crystallized at 800 ℃ for 0.5 h	Bending strength 135.84 MPa, acid and alkali resistances 98.65% and 99.88%	[97]

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