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摘要: 典型鐵合金渣（硅錳渣，鎳鐵渣，鉻鐵渣）面臨產量大、利用率低等緊迫問題。目前，我國對鐵合金渣的利用主要集中于水泥、混凝土等傳統建筑材料，但是其能耗大和產品價值相對局限。隨著市場需求以及環保能源意識的提高，對鐵合金渣的綜合利用不斷從傳統建筑材料向具有低能耗、高附價值的新型材料方向轉型。本文簡要介紹了這三種典型鐵合金渣的來源及其分類情況，系統分析了它們的化學成分及其礦物組成的差異性，重點概述了它們在水泥、混凝土等傳統建筑材料，以及在地質聚合物、無機礦物纖維、微晶玻璃、人造輕骨料、耐火材料、新型墻體材料、特色功能陶瓷等新型材料領域應用的國內外最新研究進展，分類總結不同種類鐵合金渣應用于不同材料的優缺點，并對其今后的利用方向與途徑提出了展望，指出了要進一步研究并突破主要利用方式的限制瓶頸、制定并完善相關應用及污染控制標準、以及深入開發并推廣高附加值產品的重點發展方向。Abstract: Three typical ferroalloy slags, namely, silicon–manganese, nickel–iron, and chrome–iron slags, are produced in large quantities as by-products. This is because they are not efficiently utilized, which creates lots of pressure on environmental capacity and development of enterprises. At present, comprehensive utilization of ferroalloy slags is mainly concentrated on the traditional building materials such as cement and concrete. Although the construction industry consumes a large amount of ferroalloy slags, their high-energy consumption and relatively limited product value limit their maximum utilization. With the increasing market demand and improvement of energy and environmental awareness, the research on rational utilization of ferroalloy slags has been changing from its use as raw materials in traditional building materials to use as raw materials to produce new products with comparatively lower energy consumption and higher product value, which explores the possibility of slag reutilization in other fields. Based on the quality requirements of different ferroalloys, there are significant differences in the requirements of the raw materials and different smelting processes. As a result, different types of ferroalloy slags, having different physical and chemical properties, are produced. This study briefly presented the uses of the silicon–manganese, nickel–iron, and chrome–iron slags. It also showed how to classify these three typical ferroalloy slags. The differences of their chemical and mineral phase composition were also systematically analyzed in this study, which discussed different properties of different slags and provided the basic theoretical guidelines on how to efficiently utilize these slags. This study also emphatically summarized the latest domestic and foreign research advancements about their utilization in traditional building materials such as cement and concrete, and in new functional materials such as geopolymer, inorganic mineral fiber, microcrystalline glass, artificial light aggregate, and refractory materials required to build walls and as alternative raw materials to prepare functional ceramics. Based on the results of this study, we summarized the advantages and disadvantages of using the abovementioned ferroalloy slags as raw materials to generate different materials, and put forward the prospects for its future utilization direction and approach. The study also guided the key development areas for further studying and breaking through the bottleneck of the main utilization mode, formulating and improving the relevant application and pollution control standards, and developing and promoting high value-added products.
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圖 4 鎳渣耐火材料的耐火性能及物相轉變隨鎂砂添加量的變化示意圖[63]
Figure 4. Effect of magnesia addition on the refractoriness and phase of nickel slag refractory material
表 1 典型鐵合金渣的主要化學成分及礦物組成
Table 1. Chemical and mineral compositions of some ferroalloy slags
Type Main chemical composition/% Main mineral composition Reference CaO SiO2 Al2O3 MgO Fe2O3 MnO Cr2O3 Silicon?manganese slag 20.0 32.3 16.1 4.55 0.3 20.4 ― Bustamite (CaMnSi2O6)Anorthite (CaAl2Si2O8)Cristobalite (SiO2) Choi et al.[3] Blast furnace nickel?iron slag 24.99 26.19 34.70 6.00 1.78 1.73 1.59 Dicalcium silicate(2CaO·SiO2)Magnesium aluminum spinel (MgAl2O4) Yin et al.[4] Electric furnacenickel?iron slag 0.29 58.10 2.29 26.50 11.0 ― ― Enstatite (Mg2Si2O6)Forsterite (MgSiO4) Choi et al.[5] High carbonchrome?iron slag 2.06 29.61 22.79 37.88 1.69 ― 2.06 Forsterite (MgSiO4)Magnesium chrome spinel (Mg(Al1.5Cr0.5)O4)Magnesium aluminum
spinel (MgAl2O4)Bai et al.[6] Medium & low carbonchrome-iron slag 47.35 30.77 9.03 6.9 1.3 ― 4.15 Dicalcium silicate (2CaO·SiO2)Manganolite (3CaO·MgO·2SiO2)Gehlenite (2CaO·Al2O3·SiO2) Hao[7] 
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表 2 典型鐵合金渣用于水泥混合材的部分研究成果
Table 2. Some results of the research on the uses of some ferroalloy slags as raw materials used in cement admixture
Types Research results Reference Silicon?manganese slag The authors found that the cement products with 15% slag in mass showed good chemical resistance. After 56-d of exposure to the corrosion solution, the weight of the cement products was basically the same. Besides, the addition of silicon manganese slag reduced the void structure, which is conducive to resisting the external extreme environment. Frías et al.[15] Silicon?manganese slag The authors prepared low-calorie composite cement using silico-manganese slag, fly ash and medical waste, which achieved a 28-d compressive strength of 34 MPa and a stability value of 8.95, meeting the requirements of the construction industry. Singh et al.[16] High?magnesium nickel?iron slag The authors prepared the cement slurry mixed with high magnesium nickel?iron slag, and found that the water demand and setting time did not change significantly when it was used to replace 50% cement. Under the accelerated curing at 80 ℃ for 120 d, although the magnesium content was high, the product did not expand because the magnesium existed in the form of stable Mg olivine ferrite and did not participate in the hydration reaction. Rahman et al.[17] Blast furnace nickel?iron slag The authors prepared the cement with 20% blast furnace nickel?iron slag. Compared with pure cement products, it required less water and had a longer setting time. The addition of nickel iron slag would reduce the hydration rate in the early stage, and increased the strength of its products in the later stage, achieving a 28-d compressive strength greater than 45 MPa. Katsiotis et al.[18]
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表 3 典型鐵合金渣用于混凝土的部分研究成果
Table 3. Some results of research on some ferroalloy slags used in concrete
Types Function Research Results Reference Silicon?manganese slag Admixture The authors mixed silicon manganese slag, limestone and cement grinding aids to produce composite micropowder, and found that the fluidity of the concrete prepared by replacing the cement with 30% fine powder was comparable to that of the whole cement, besides its compressive strength was far higher than that of the concrete prepared with 30% pure silicon-manganese slag. Lv et al.[32] Nickel?iron slag Admixture The author replaced part of the cement with electric furnace nickel?iron slag to prepare concrete materials with excellent performance, whose strength could meet that of full cement concrete. Besides, the composition of raw materials was reduced by 15 US dollars, and the CO2 emission was reduced by 4%?24%. Kim et al.[33] Nickel?iron slag Fine aggregate In this paper, the durability of ferronickel slag as concrete fine aggregate was studied. The results showed that when 27% nickel?iron slag replaced sand, the corrosion resistance of concrete to sulfate increased, but it had no significant effect on chloride ion corrosion. Liu et al.[34] High?carbonchrome?
iron slagFine aggregate The concrete products was prepared by cement and partial granular high?carbon chrome?iron slag which was used as fine aggregate instead of a part of natural river sand. When the amount of slag was 10%, the strength indicators of concrete products were equivalent to those of pure natural sand-based concrete. Toxic leaching experiments showed that the leaching concentration of chromium was far less than the standard concentration threshold. Dash et al.[35]
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表 4 典型鐵合金渣用于多種產品的優勢及問題
Table 4. Advantages and problems of products prepared by some ferroalloy slags
Product Slag Advantage Problem Standard Industrialization feasibility Cememnt Admixture Silicon-manganese slag; Blast furnace Nickel-iron slag; Medium & low-carbon chrome-iron slag Large dosage (40%?60%); high activity; low water demand and small hydration heat; small volume expansion and small possibility of powdering; mature technology The reaction in the early stage of hydration is slow and the intensity is low. In the later stage of hydration, the reaction is fast and the intensity is high. The setting time is longer. YB/T 4229―2010 Simple Raw meal Electric furnace nickel-iron slag; High-carbon chrome-iron slag Relatively large dosage (15%?30%); reducing the amount of free CaO in clinker Cement products have low activity and require the use of large amounts of adjuvants. The market acceptance is low. Concrete Admixture Silicon-manganese slag; Blast furnace nickel-iron slag; Medium & low-carbon chrome-iron slag Large amount (30%?60%); reducing water consumption and improving fluidity; improving the density of aggregate-slurry transition area; strong operability The MgO content is high, and the long-term stability of the concrete is potentially dangerous. The particle size of the raw material is small, and the possibility of heavy metal elements leaching is high. YB/T 4229-2010JIS A5011-2―2003 Simple Aggregate Electric furnace nickel-iron slag; High-carbon chrome-iron slag High hardness and good abrasion resistance; no need for ultra-fine processing and high operability; making up for the shortage of raw materials such as river sand If the content of glass phase is high, the expansion of concrete may be caused by the strong alkali silica reaction. Geopolymer Silicon-manganese slag; Blast furnace nickel-iron slag; Medium & low-carbon chrome-iron slag No high temperature sintering and hydration reactions are required, and the preparation method is simple. There is no transition area of ordinary cement concrete. The three-dimensional network structure gel makes the corrosion resistance stronger. The gel needs to be thermally cured at high pH values, which is not difficult in actual operation.It is necessary to develop simple and efficient solid activators to replace highly alkaline solutions; No Simple Inorganic mineral fiber Silicon-manganese slag; Blast/electric furnace nickel-iron slag; Medium & low/high carbon chrome-iron slag The combination of product preparation and slag sensible heat recovery has the advantages of low cost and low energy consumption; It is widely used and has high added value. Due to the difference in composition and temperature, the slag viscosity and acidity match fluctuate greatly. The high MgO and Al2O3 of high carbon ferrochrome slag and electric furnace nickel iron slag make the viscosity difficult to control. No Moderate Glass ceramic Silicon-manganese slag; Blast/electric furnace nickel-iron slag; Medium & low/high carbon chrome-iron slag High fluctuation range of raw material composition;use with a variety of ferroalloy slag; high degree of solid waste utilization (50%?80%); high market acceptance It is prepared by high-temperature melting method with high energy consumption, and the energy consumption is high. The procedure is relatively complicated and the preparation time is long. It will take a long time to observe whether the stability problems of powdered glass and other glass ceramics have been used for a long time. No Moderate Artificial light aggregate Silicon-manganese slag; Electric furnace nickel-iron slag; High-carbon chrome-iron slag The porous structure increases the density of the aggregate slurry. The water absorption is small, which is conducive to later stability. Large amount of solid waste doping (60%?80%). The requirements for raw material composition and firing system are relatively strict to ensure the best balance of pores and liquid phase. The strength is relatively limited, and it is relatively lagging behind for structural engineering research. No Simple Refractory material Electric furnace nickel-iron slag; High-carbon chrome-iron slag Easier formation of forsterite phase and spinel phase because of the high content of magnesium and aluminum; variety of products; high degree of solid waste utilization and large added value of products Affected by products and processes, the magnesium and aluminum content fluctuates greatly, which causes trouble for actual operation.After being corroded by gas and liquid for a long time, heavy metals are easily dissolved out and cause pollution. No Moderate New wall materials (autoclaved brick, autoclaved aerated concrete) Silicon-manganese slag; Blast/electric furnace nickel-iron slag;Medium & low/high carbon chrome-iron slag The preparation method is relatively simple, low cost, and low energy consumption.The utilization degree of solid waste is high and the added value of products is large.The technical guidance of high efficiency, high sound insulation, and high thermal resistance is conducive to the promotion and use of energy-saving non-bearing wall materials. The general cementitious material has a long gelation time, which is not conducive to rapid demoulding treatment. The study of fast high-strength gelling materials is the key.Because of the contradiction between light weight and high strength, mineral fiber can be added to increase the performance. GB/T 32989―
2016Simple Featured functional materials (structural ceramics, porous ceramics, porous polymer particles) Electric furnace nickel-iron slag; High-carbon chrome-iron slag (structuralceramics); Silicon-manganese slag; High-carbon chrome-iron slag (porous ceramics) The incorporation of slag will reduce the sintering temperature without affecting its performance. The utilization degree of solid wastes and the added value of products are relatively higher. Porous polymer particles are used in sound-absorbing materials, which are not easy to pulverize and settle, and the preparation method is simple and operable. For spinel corundum structural ceramics, the requirements for raw materials are relatively strict, and the preparation process is relatively complex, and the preparation time is long.The development of slag-based sound-absorbing materials is not yet perfect, and lacks in-depth theoretical and technical support. No Difficult
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