CN113968684B - Method for treating stainless steel pickling sludge and preparing slag cement - Google Patents
Method for treating stainless steel pickling sludge and preparing slag cement Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 148
- 238000005554 pickling Methods 0.000 title claims abstract description 59
- 239000010802 sludge Substances 0.000 title claims abstract description 59
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 56
- 239000010935 stainless steel Substances 0.000 title claims abstract description 56
- 239000004568 cement Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000003607 modifier Substances 0.000 claims abstract description 22
- 238000010791 quenching Methods 0.000 claims abstract description 13
- 230000000171 quenching effect Effects 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000003469 silicate cement Substances 0.000 claims abstract 2
- 229910052804 chromium Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011398 Portland cement Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000010881 fly ash Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 22
- 229910052596 spinel Inorganic materials 0.000 description 10
- 239000011029 spinel Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 238000002386 leaching Methods 0.000 description 7
- 230000036571 hydration Effects 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/48—Clinker treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Abstract
Description
技术领域technical field
本发明涉及冶金技术领域，具体涉及一种处理不锈钢酸洗污泥并制备矿渣水泥的方法。The invention relates to the technical field of metallurgy, in particular to a method for treating stainless steel pickling sludge and preparing slag cement.
背景技术Background technique
不锈钢酸洗污泥是不锈钢生产过程中为保证表面光洁度而用酸洗产生的废水加石灰后沉淀出的固体废弃物，因其Cr(Ⅵ)浸出超过国家标准，被明确归类为危险固体废弃物。以硫酸为酸洗介质产生的不锈钢酸洗污泥主要成分为Fe2O3 20～35wt％，CaSO4 45～60wt％，Cr2O3 1～6wt％，SiO2 2～3wt％，针对这类酸洗污泥，目前尚无有效的处理途径。企业常规做法是堆存，或少量配加到烧结工序，但带来烧结矿产品质量下降、过程污染严重(CaSO4分解产生SO2)等恶劣影响，急需有效的规模化处理途径。因此，本发明针对不锈钢酸洗污泥的处理难点，利用物理化学固化法率先提出将熔融高炉渣与不锈钢酸洗污泥相结合来制备矿渣水泥，在不改变高炉渣物相及应用途径的前提下合理处置危废。Stainless steel pickling sludge is a solid waste precipitated by adding lime to wastewater produced by pickling in order to ensure surface smoothness in the production process of stainless steel. Because its Cr(VI) leaching exceeds the national standard, it is clearly classified as hazardous solid waste. thing. The main components of stainless steel pickling sludge produced by using sulfuric acid as pickling medium are Fe 2 O 3 20-35wt%, CaSO 4 45-60wt%, Cr 2 O 3 1-6wt%, SiO 2 2-3wt%. There is no effective treatment method for acid-washing sludge. The common practice of the enterprise is to store it, or add a small amount to the sintering process, but it will bring bad influences such as the decline of the quality of the sintered ore product and the serious process pollution (CaSO 4 decomposition produces SO 2 ). Therefore, in view of the difficulties in the treatment of stainless steel pickling sludge, the present invention takes the lead in proposing to combine molten blast furnace slag and stainless steel pickling sludge to prepare slag cement by using a physical and chemical solidification method, without changing the phase and application route of blast furnace slag. Properly dispose of hazardous waste.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种处理不锈钢酸洗污泥并制备矿渣水泥的方法，将不锈钢酸洗污泥与熔融高炉渣混合，再冷淬为粒化渣，之后将粒化渣磨细的矿渣粉作为水泥掺加料制备矿渣水泥，提供了一种资源化、无害化处理不锈钢酸洗污泥的有效途径。The object of the present invention is to provide a method for treating stainless steel pickling sludge and preparing slag cement, mixing stainless steel pickling sludge with molten blast furnace slag, then quenching into granulated slag, and then grinding the granulated slag into fine slag The powder is used as a cement admixture to prepare slag cement, which provides an effective way to recycle and harmlessly treat stainless steel pickling sludge.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
本发明提供了一种处理不锈钢酸洗污泥并制备矿渣水泥的方法，包括以下步骤：The invention provides a method for treating stainless steel pickling sludge and preparing slag cement, comprising the following steps:
将不锈钢酸洗污泥、熔融高炉渣和改质剂混合，得到熔渣；Mixing stainless steel pickling sludge, molten blast furnace slag and modifier to obtain molten slag;
将所述熔渣进行冷淬，得到粒化渣；The molten slag is quenched to obtain granulated slag;
将所述粒化渣进行研磨，得到矿渣粉；The granulated slag is ground to obtain slag powder;
将所述矿渣粉和硅酸盐水泥熟料混合，得到矿渣水泥。The slag powder and Portland cement clinker are mixed to obtain slag cement.
优选地，所述不锈钢酸洗污泥的含水量在5wt％以下。Preferably, the water content of the stainless steel pickling sludge is below 5wt%.
优选地，所述不锈钢酸洗污泥总量为熔融高炉渣的1～10wt％。Preferably, the total amount of the stainless steel pickling sludge is 1-10 wt % of the molten blast furnace slag.
优选地，所述熔融高炉渣的温度为1400～1450℃。Preferably, the temperature of the molten blast furnace slag is 1400-1450°C.
优选地，所述不锈钢酸洗污泥、熔融高炉渣和改质剂混合的时间为 3～10min。Preferably, the mixing time of the stainless steel pickling sludge, the molten blast furnace slag and the modifier is 3-10 minutes.
优选地，所述冷淬的冷却速率为300～500℃/min。Preferably, the cooling rate of the quenching is 300˜500° C./min.
优选地，所述矿渣粉的粒径小于0.1mm；所述矿渣粉的比表面积为 500m2/kg以上。Preferably, the particle size of the slag powder is less than 0.1 mm; the specific surface area of the slag powder is more than 500 m 2 /kg.
优选地，所述矿渣粉和硅酸盐水泥熟料的质量比为40～50：50～60。Preferably, the mass ratio of the slag powder and the Portland cement clinker is 40-50:50-60.
优选地，所述改质剂为含硅质改质剂；所述改质剂的总添加量为熔融高炉渣的1～5wt％。Preferably, the modifier is a siliceous modifier; the total addition amount of the modifier is 1-5 wt% of the molten blast furnace slag.
优选地，所述不锈钢酸洗污泥为不锈钢生产企业内以硫酸为酸洗介质产生的酸洗污泥；所述不锈钢酸洗污泥的成分包括CaSO4 45～60wt％，Fe2O3 20～35wt％，Cr2O3 1～6wt％，SiO2 2～3wt％。Preferably, the stainless steel pickling sludge is the pickling sludge produced by using sulfuric acid as the pickling medium in a stainless steel production enterprise; the components of the stainless steel pickling sludge include CaSO 4 45-60wt%, Fe 2 O 3 20 ~35wt%, Cr2O3 1 ~6wt%, SiO2 2 ~3wt%.
本发明提供了一种处理不锈钢酸洗污泥并制备矿渣水泥的方法，包括以下步骤：将不锈钢酸洗污泥、熔融高炉渣和改质剂混合，得到熔渣；将所述熔渣进行冷淬，得到粒化渣；将所述粒化渣进行研磨，得到矿渣粉；将所述矿渣粉和硅酸盐水泥熟料混合，得到矿渣水泥。本发明在高炉出渣后加入不锈钢酸洗污泥，之后进行冷淬处理，冷淬后的粒化渣99％以上为玻璃相，极小部分为细小弥散的镁铬尖晶石相(部分情况下高炉渣中含有少部分MgO，熔融状态下加入含Cr2O3的酸洗污泥会产生相应少量的镁铬尖晶石相)，玻璃相和镁铬尖晶石相为固铬效果最好的矿相，冷淬后的粒化渣能够作为掺加料制备矿渣水泥；制备成矿渣水泥后玻璃相和镁铬尖晶石相均被包裹在水泥水化所产生的凝胶相中，Cr元素固化效果显著，远低于GB 30760-2014规定的烧成熟料中Cr浸出0.2mg/L标准值。The invention provides a method for treating stainless steel pickling sludge and preparing slag cement, comprising the following steps: mixing stainless steel pickling sludge, molten blast furnace slag and modifier to obtain molten slag; cooling the molten slag Quenching to obtain granulated slag; grinding the granulated slag to obtain slag powder; mixing the slag powder and Portland cement clinker to obtain slag cement. In the present invention, stainless steel pickling sludge is added after blast furnace slag removal, and then cold quenching is performed. More than 99% of the granulated slag after cold quenching is a glass phase, and a very small part is a finely dispersed magnesia-chromium spinel phase (in some cases). The lower blast furnace slag contains a small amount of MgO, and the addition of pickling sludge containing Cr 2 O 3 in the molten state will produce a corresponding small amount of magnesia-chromium spinel phase), and the glass phase and magnesia-chromium spinel phase are the most effective for fixing chromium. Good mineral phase, the granulated slag after quenching can be used as an admixture to prepare slag cement; after preparing slag cement, both the glass phase and the magnesia-chromium spinel phase are encapsulated in the gel phase produced by cement hydration, and the Cr element solidifies. The effect is remarkable, which is far lower than the standard value of 0.2mg/L of Cr leaching in burnt clinker stipulated in GB 30760-2014.
本发明针对不锈钢酸洗污泥——这类危险固体废弃物的无害化、资源化和规模化处理，提供了一种有效的途径，环境和经济效益巨大。The invention provides an effective way for the harmless, resourceful and large-scale treatment of stainless steel pickling sludge, such dangerous solid waste, with huge environmental and economic benefits.
本发明提供的处理方法实施简单，无额外装备，生产现场实施即可，成本低，实用推广价值高。The processing method provided by the invention is simple to implement, without additional equipment, and can be implemented on the production site, with low cost and high practical and popularization value.
附图说明Description of drawings
图1为实施例1制备的粒化渣的SEM图；Fig. 1 is the SEM image of the granulated slag prepared in Example 1;
图2为实施例1制备的粒化渣在高倍率下镁铬尖晶石相SEM-EDS照片；Fig. 2 is the SEM-EDS photograph of magnesia-chromium spinel phase under high magnification of the granulated slag prepared in Example 1;
图3为镁铬尖晶石的EDS面扫描能谱图；Fig. 3 is the EDS surface scanning energy spectrum of magnesia-chromium spinel;
图4为实施例1和实施例2制备的粒化渣的XRD图；Fig. 4 is the XRD pattern of the granulated slag prepared by Example 1 and Example 2;
图5为普通高炉水渣与污泥添加的粒化渣水化28天的抗压强度对比图；Figure 5 is a comparison chart of the compressive strength of ordinary blast furnace water slag and granulated slag added with sludge after hydration for 28 days;
图6为矿渣水泥的制备工艺流程图。FIG. 6 is a flow chart of the preparation process of slag cement.
具体实施方式Detailed ways
本发明提供了一种处理不锈钢酸洗污泥并制备矿渣水泥的方法，包括以下步骤：The invention provides a method for treating stainless steel pickling sludge and preparing slag cement, comprising the following steps:
将不锈钢酸洗污泥、熔融高炉渣和改质剂混合，得到熔渣；Mixing stainless steel pickling sludge, molten blast furnace slag and modifier to obtain molten slag;
将所述熔渣进行冷淬，得到粒化渣；The molten slag is quenched to obtain granulated slag;
将所述粒化渣进行研磨，得到矿渣粉；The granulated slag is ground to obtain slag powder;
将所述矿渣粉和硅酸盐水泥熟料混合，得到矿渣水泥。The slag powder and Portland cement clinker are mixed to obtain slag cement.
在本发明中，矿渣水泥的制备工艺流程图如图6所示，结合图6对本发明矿渣水泥的制备方法进行详细说明。In the present invention, the flow chart of the preparation process of the slag cement is shown in FIG. 6 , and the preparation method of the slag cement of the present invention will be described in detail with reference to FIG. 6 .
本发明将不锈钢酸洗污泥、熔融高炉渣和改质剂混合，得到熔渣。在本发明中，所述不锈钢酸洗污泥为不锈钢生产企业内以硫酸为酸洗介质产生的酸洗污泥。在本发明中，所述不锈钢酸洗污泥的成分优选包括CaSO4 45～60wt％，Fe2O3 20～35wt％，Cr2O3 1～6wt％，SiO2 2～3wt％。在本发明中，所述不锈钢酸洗污泥的成分更优选包括CaSO4 55～60wt％，Fe2O3 25～30wt％， Cr2O3 1～3wt％，SiO2 2～3wt％。In the present invention, stainless steel pickling sludge, molten blast furnace slag and modifier are mixed to obtain molten slag. In the present invention, the stainless steel pickling sludge is the pickling sludge produced by using sulfuric acid as the pickling medium in a stainless steel production enterprise. In the present invention, the components of the stainless steel pickling sludge preferably include CaSO 4 45-60 wt %, Fe 2 O 3 20-35 wt %, Cr 2 O 3 1-6 wt %, and SiO 2 2-3 wt %. In the present invention, the components of the stainless steel pickling sludge more preferably include CaSO 4 55-60 wt %, Fe 2 O 3 25-30 wt %, Cr 2 O 3 1-3 wt %, and SiO 2 2-3 wt %.
在本发明中，所述不锈钢酸洗污泥的含水量优选在5wt％以下，更优选为2wt％。在本发明中，熔渣的制备过程是高温，如果水分含量高，高温热解后会发生喷溅，甚至爆炸，因此将不锈钢酸洗污泥的含水量控制在上述范围。In the present invention, the water content of the stainless steel pickling sludge is preferably below 5 wt %, more preferably 2 wt %. In the present invention, the preparation process of slag is high temperature, if the water content is high, splashing or even explosion will occur after high temperature pyrolysis, so the water content of stainless steel pickling sludge is controlled within the above range.
在本发明中，所述不锈钢酸洗污泥优选由原始不锈钢酸洗污泥经干燥后得到。在本发明中，所述原始不锈钢酸洗污泥的含水量为10～55％。在本发明中，所述干燥的温度优选为300～500℃，更优选为400℃；所述干燥的时间优选为2～4h，更优选为3h。In the present invention, the stainless steel pickling sludge is preferably obtained by drying the original stainless steel pickling sludge. In the present invention, the water content of the raw stainless steel pickling sludge is 10-55%. In the present invention, the drying temperature is preferably 300-500°C, more preferably 400°C; the drying time is preferably 2-4h, more preferably 3h.
在本发明中，所述熔融高炉渣的温度优选为1400～1450℃。在本发明中，所述熔融高炉渣为高炉出渣后的高温液态渣。在本发明中，所述熔融高炉渣中MgO的质量含量优选为1～8％。本发明控制熔融高炉渣的温度区间为 1400～1450℃，可保证熔渣流动性，同时该温度是硫化物分解温度的下限，且在熔渣的混冲下分解受阻，避免了SO2气体大量逸出。In the present invention, the temperature of the molten blast furnace slag is preferably 1400 to 1450°C. In the present invention, the molten blast furnace slag is high temperature liquid slag after blast furnace slag tapping. In the present invention, the mass content of MgO in the molten blast furnace slag is preferably 1-8%. The invention controls the temperature range of the molten blast furnace slag to be 1400-1450°C, which can ensure the fluidity of the molten slag. At the same time, the temperature is the lower limit of the decomposition temperature of the sulfide, and the decomposition is hindered under the mixed flushing of the molten slag, thereby avoiding a large amount of SO 2 gas. escape.
在本发明中，所述不锈钢酸洗污泥总量为熔融高炉渣的1～10wt％，更优选为5～8wt％。In the present invention, the total amount of the stainless steel pickling sludge is 1-10 wt % of the molten blast furnace slag, more preferably 5-8 wt %.
在本发明中，所述改质剂优选含硅质改质剂；所述含硅质改质剂优选包括粉煤灰和废玻璃中的一种或两种；在本发明中，所述改质剂的总添加量优选为熔融高炉渣的1～5wt％，更优选为3～4wt％。本发明添加改质剂能够促进更多玻璃相生成。In the present invention, the modifier is preferably a siliceous modifier; the siliceous modifier preferably includes one or both of fly ash and waste glass; in the present invention, the modifier The total addition amount of the quality agent is preferably 1 to 5 wt % of the molten blast furnace slag, and more preferably 3 to 4 wt %. The addition of the modifier in the present invention can promote the formation of more glass phases.
在本发明中，所述不锈钢酸洗污泥、熔融高炉渣和改质剂混合的时间优选为3～10min，更优选为4～6min。In the present invention, the mixing time of the stainless steel pickling sludge, the molten blast furnace slag and the modifier is preferably 3-10 minutes, more preferably 4-6 minutes.
在本发明中，优选将所述不锈钢酸洗污泥和改质剂分别分多次掷入所述熔融高炉渣中。In the present invention, preferably, the stainless steel pickling sludge and the modifier are respectively thrown into the molten blast furnace slag in multiple times.
本发明最大限度利用高炉渣的组成特点及物理显热，熔融状态下消纳处理不锈钢酸洗污泥，添加的含硅质改质剂可使粒化渣中玻璃相更多的形成，高炉渣中的MgO可使粒化渣中Cr元素形成MgCr2O4相。The invention makes maximum use of the compositional characteristics and physical sensible heat of blast furnace slag, and absorbs and treats stainless steel pickling sludge in a molten state. The MgO in the granulated slag can make the Cr element in the granulated slag form the MgCr 2 O 4 phase.
得到熔渣后，本发明将所述熔渣进行冷淬，得到粒化渣。在本发明中，所述冷淬的冷却速率优选为300～500℃/min，更优选为350～400℃。本发明控制较高的冷却速率，利用高压水淬，使粒化渣中99％以上为玻璃相，保证其活性和稳定性。After the slag is obtained, the present invention performs cold quenching on the slag to obtain granulated slag. In the present invention, the cooling rate of the quenching is preferably 300-500°C/min, more preferably 350-400°C. The invention controls a higher cooling rate and utilizes high-pressure water quenching, so that more than 99% of the granulated slag is a glass phase, thereby ensuring its activity and stability.
在本发明中，熔渣中的MgCr2O4相和极少量未与MgO结合的Cr元素在快速冷淬后，均匀存在水淬渣的玻璃相中。In the present invention, the MgCr 2 O 4 phase in the molten slag and a very small amount of Cr element that is not combined with MgO are uniformly present in the glass phase of the water-quenched slag after rapid quenching.
得到粒化渣后，本发明将所述粒化渣进行研磨，得到矿渣粉。在本发明中，所述矿渣粉的粒径优选为小于0.1mm；所述矿渣粉的比表面积优选为 500m2/kg以上，更优选为600m2/kg。本发明将粒化渣磨细成为矿渣粉的作用是激发更强的水化活性及作为填充料。After the granulated slag is obtained, the present invention grinds the granulated slag to obtain slag powder. In the present invention, the particle size of the slag powder is preferably less than 0.1 mm; the specific surface area of the slag powder is preferably 500 m 2 /kg or more, more preferably 600 m 2 /kg. The function of grinding the granulated slag into slag powder in the present invention is to stimulate stronger hydration activity and act as a filler.
得到矿渣粉后，本发明将所述矿渣粉和硅酸盐水泥熟料混合，得到矿渣水泥。在本发明中，所述矿渣粉和硅酸盐水泥熟料的质量比优选为40～50： 50～60。After the slag powder is obtained, the present invention mixes the slag powder and Portland cement clinker to obtain slag cement. In the present invention, the mass ratio of the slag powder and Portland cement clinker is preferably 40-50: 50-60.
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some, but not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
实施例1实验室试验Example 1 Laboratory test
将含水量较高的原始不锈钢酸洗污泥在400℃干燥2h，得到含水量为1％的不锈钢酸洗污泥，备用；The original stainless steel pickling sludge with high water content was dried at 400 °C for 2 hours to obtain stainless steel pickling sludge with a water content of 1%, which was used for later use;
改质剂为粉煤灰；The modifier is fly ash;
将10g所述不锈钢酸洗污泥、3g改质剂和100g高炉渣，混合均匀，置于瓷舟中；10g of the stainless steel pickling sludge, 3g of modifier and 100g of blast furnace slag were mixed uniformly and placed in a porcelain boat;
将所述瓷舟置于横式电阻炉中，按以5℃/min的速率升温至1450℃，保温5min，得到熔渣。The porcelain boat was placed in a horizontal resistance furnace, heated to 1450°C at a rate of 5°C/min, and kept for 5 minutes to obtain slag.
将瓷舟快速拉出高温区，以400℃/min的冷却速率进行水淬，得到粒化渣；The porcelain boat was quickly pulled out of the high temperature zone, and water quenched at a cooling rate of 400°C/min to obtain granulated slag;
将所述粒化渣磨细后的矿渣粉(比表面积为689m2/kg)和硅酸盐水泥熟料按照1:1的质量比混合，得到矿渣水泥。The slag powder (with a specific surface area of 689 m 2 /kg) after the granulated slag was ground and the Portland cement clinker were mixed in a mass ratio of 1:1 to obtain slag cement.
实施例2Example 2
与实施例1的制备方法基本相同，不同之处仅在于，将所述不锈钢酸洗污泥的添加量由“10g”调整为“5g”。The preparation method is basically the same as that of Example 1, except that the addition amount of the stainless steel pickling sludge is adjusted from "10 g" to "5 g".
测试例1Test Example 1
实施例1制备的粒化渣的SEM图如图1所示，图1中，白色细小颗粒为镁铬尖晶石相，周围其他相为玻璃相。The SEM image of the granulated slag prepared in Example 1 is shown in FIG. 1 . In FIG. 1 , the white fine particles are magnesia-chromium spinel phase, and other surrounding phases are glass phases.
实施例1制备的粒化渣在高倍率下镁铬尖晶石相SEM-EDS照片如图2 所示。图2中5K×高倍率下白色颗粒为镁铬尖晶石相。Figure 2 shows the SEM-EDS photograph of the magnesia-chromium spinel phase of the granulated slag prepared in Example 1 at high magnification. In Figure 2, the white particles at 5K × high magnification are magnesia-chromium spinel phases.
图3为图2的EDS面扫描图谱，图3中颗粒状物质主要是镁铬尖晶石相，颗粒平均尺寸为5μm。Fig. 3 is the EDS surface scanning pattern of Fig. 2. The granular material in Fig. 3 is mainly a magnesia-chromium spinel phase, and the average particle size is 5 μm.
实施例1和实施例2制备的粒化渣的XRD图如图4所示。由图4可以看出，高炉渣中添加5％、10％的不锈钢酸洗污泥主要物相为玻璃相，占比分别为99％和99.5％，仅有极少的钙铝黄长石相生成。矿渣粉具有较高的潜在活性，与硅酸盐水泥熟料掺混制备成矿渣水泥后，可发生水化硬性胶凝反应。The XRD patterns of the granulated slag prepared in Example 1 and Example 2 are shown in FIG. 4 . It can be seen from Figure 4 that the main phase of stainless steel pickling sludge added 5% and 10% in blast furnace slag is glass phase, accounting for 99% and 99.5%, respectively, and only a very small amount of mayorite phase is formed. The slag powder has high potential activity. After being mixed with Portland cement clinker to prepare slag cement, hydration and hardening gelation reaction can occur.
测试例2
将实施例1制备的矿渣水泥与标准砂按1：3，水灰比为0.5充分搅拌混合，填入40×40×160mm钢磨具静置24h后，脱模，将制备的水泥块在标准养护箱中固化28天，得到水泥试样。The slag cement prepared in Example 1 and the standard sand were fully stirred and mixed at a ratio of 1:3 and a water-cement ratio of 0.5, filled with a 40×40×160mm steel abrasive tool and allowed to stand for 24 hours. After curing in a curing box for 28 days, a cement sample was obtained.
普通高炉水渣与污泥添加的粒化渣水化28天的抗压强度对比图如图5 所示。由图5可以看出，采用两种不同的高炉水渣制备的矿渣水泥：工业高炉渣制备的高炉水渣矿渣水泥和本发明粒化渣制备的矿渣水泥，水化28天后的抗压强度对比，均高于42.5MPa水泥强度测试标准。Figure 5 shows the comparison of the compressive strength of ordinary blast furnace water slag and granulated slag added with sludge after hydration for 28 days. As can be seen from Figure 5, the slag cement prepared by two different blast furnace slag: the blast furnace slag slag cement prepared by industrial blast furnace slag and the slag cement prepared by granulated slag of the present invention, the compressive strength comparison after hydration for 28 days , all higher than the 42.5MPa cement strength test standard.
测试例3Test case 3
将实施例1～2按照测试例2的方法制备得到水泥试样，然后将水泥试样磨细至0.074mm以下，按国标固体废物浸出毒性浸出方法(HJ 557-2010) 测试Cr元素浸出浓度。本发明制备的矿渣水泥水化28天的水泥浆体中Cr 浸出浓度为0.014mg/L，远低于GB 30760-2014规定的烧成熟料中Cr浸出 0.2mg/L标准值。Cement samples were prepared in Examples 1-2 according to the method of Test Example 2, and then the cement samples were ground down to less than 0.074 mm, and the leaching concentration of Cr was tested according to the national standard solid waste leaching toxicity leaching method (HJ 557-2010). The Cr leaching concentration in the slag cement hydrated for 28 days prepared by the present invention is 0.014 mg/L, which is far lower than the standard value of 0.2 mg/L Cr leaching in burnt clinker specified in GB 30760-2014.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.
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