CN109336437A - 一种石灰石微粉-钢渣粉-矿渣粉复合掺合料及其制备工艺 - Google Patents
一种石灰石微粉-钢渣粉-矿渣粉复合掺合料及其制备工艺 Download PDFInfo
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- CN109336437A CN109336437A CN201811249561.XA CN201811249561A CN109336437A CN 109336437 A CN109336437 A CN 109336437A CN 201811249561 A CN201811249561 A CN 201811249561A CN 109336437 A CN109336437 A CN 109336437A
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- steel
- slag powder
- slag
- powder
- making
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- 239000002893 slag Substances 0.000 title claims abstract description 148
- 239000000843 powder Substances 0.000 title claims abstract description 94
- 235000019738 Limestone Nutrition 0.000 title claims abstract description 67
- 239000006028 limestone Substances 0.000 title claims abstract description 67
- 238000009628 steelmaking Methods 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002156 mixing Methods 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004567 concrete Substances 0.000 claims abstract description 39
- 239000004568 cement Substances 0.000 claims abstract description 35
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 19
- 239000010959 steel Substances 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium monoxide Chemical compound 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[Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 21
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound 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[Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Tris Chemical compound 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OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003595 mist Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 15
- 239000003638 reducing agent Substances 0.000 abstract description 10
- 239000011083 cement mortar Substances 0.000 abstract description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound 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- 238000010348 incorporation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials 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- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0042—Powdery mixtures
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
本发明提供一种石灰石微粉‑钢渣粉‑矿渣粉复合掺合料及其制备工艺，该复合掺合料按重量比包括石灰石微粉10％～30％、钢渣粉20％～50％、矿渣粉30％～60％，其制备方法为分别将石灰石和钢渣烘干、破碎、粉磨、分级或筛分得到石灰石微粉和钢渣粉；然后将所述石灰石微粉、钢渣粉和矿渣粉按照配比混合均匀得到石灰石微粉‑钢渣粉‑矿渣粉复合掺合料，其中所述矿渣粉性能满足GB/T18046‑2017《用于水泥、砂浆和混凝土中的粒化高炉矿渣粉》标准中S95级技术要求。本发明选用高活性S95级矿渣粉，通过石灰石微粉与钢渣粉、矿渣粉相互激发，产生微集料效应，提高掺合料对水泥和减水剂的相容性、降低水泥砂浆干缩率、提高混凝土强度。
Description
技术领域
本发明属于建筑材料技术领域，尤其涉及一种石灰石微粉-钢渣粉-矿渣粉复合掺合料及其制备工艺。
背景技术
保护环境、降低自然资源的消耗和提高水泥混凝土性能是目前水泥与混凝土领域面临的两个最为重要的问题。混凝土掺合料的应用，一方面可以有效控制硅酸盐水泥的生产总量，使现有的工业废渣得以回收再利用，从而降低建材工业自身和其它工业产业对资源和环境的负荷；另一方面，混凝土掺合料对混凝土的力学性能、工作性能、抗侵蚀性能和耐久性能等诸多性能有显著的改善作用，是当代高性能混凝土不可或缺的结构组分。因此，如何利用工业废渣、天然矿物以及低品位矿物掺合料制备高强高性能混凝土是目前研究热点之一。
在开采加工骨料过程中会产生石灰石粉和石灰石屑，如果不将其利用起来，会对生态环境造成污染。石灰石粉的主要成分是方解石(CaCO3)，在掺有石灰石粉的混凝土中，由水泥水化生成的Ca(OH)2晶体团聚在CaCO3周围，并与其反应生成碱式碳酸钙，使得界面过渡区强度增强，从而提高了混凝土强度。但单独使用石灰石粉时混凝土强度低，所以一般不单独使用。
钢渣是炼钢过程中排出的固体废弃物，钢渣的排放量一般约为钢产量的15～20％。2017年我国粗钢产量达到8.32亿吨，占全球总产量的49.18％。按照渣钢比16％估算，我国钢渣的年排放量约为1.33亿吨。大量钢渣闲置堆弃，既严重污染环境又占用土地，因此，迫切需要对钢渣进行减量化、二次资源化和高效利用。近年来的研究结果表明，将钢渣开发用作水泥混合材或混凝土掺合料很有可能成为其高效、高附加值利用的重要途径。钢渣中富含C3S和C2S等矿物，是一种类似于劣质硅酸盐水泥熟料的工业废渣，具有开发作为水泥和混凝土生产原料的潜能。钢渣微粉用作辅助性胶凝材料可以改善水泥混凝土的耐磨、抗冲击和抗碳化等性能。钢渣作为辅助性胶凝材料而减少水泥熟料的使用量，既可减轻水泥工业对资源、能源和环境的压力，也可解决钢铁工业废弃物产生的环境问题，对于促进我国钢铁工业和建材工业的可持续发展具有不可替代的双赢效果。
高炉矿渣是高炉炼铁生产过程中排放的工业废渣，其化学成份主要是SiO2、CaO、A12O3、Fe2O3等，与水泥熟料一样，具有潜在的水化活性。将矿渣微粉掺入混凝土后，可以改善混凝土的泵送、坍落度损失等工作性，提高混凝土的后期强度，具有良好的耐久性、耐蚀性和耐磨性。但单独使用时混凝土收缩较大，易产生开裂。
考虑到石灰石粉和钢渣粉在单独使用时早期强度低，而高炉矿渣粉活性较高，若将三者复配石灰石粉、钢渣粉与矿渣粉相互激发，则有望填充水泥颗粒的空隙，产生微集料效应，从而制备出早期强度高、后期强度持续增长、兼具补偿收缩效应的复合掺合料。目前，已有将钢渣粉、矿渣粉和石灰石粉混合制备混凝土掺合料的研究，如申请号为201611132042.6的专利申请公开了将1-5份热闷炉砖钢渣粉、4-10份粒化高炉矿渣粉和0-1.6份石灰石粉混合得到混凝土矿物掺合料，不过该混凝土矿物掺合料所用原料粒径较大、活性不高，使用其制备的混凝土抗压强度较差，7d抗压强度仅为25.1～30.3MPa，28d抗压强度仅为44.6～50.2MPa，远远不能满足需求。
发明内容
基于此，本发明提供一种石灰石微粉-钢渣粉-矿渣粉复合掺合料及其制备工艺，掺入该复合掺合料的混凝土具有很高的抗压强度；该制备工艺工序简单、容易操作，可制备出早期强度高、后期强度持续增长、兼具补偿收缩效应的复合掺合料。
本发明所述石灰石微粉-钢渣粉-矿渣粉复合掺合料按重量比包括以下组分：石灰石微粉10％～30％、钢渣粉20％～50％、矿渣粉30％～60％，其中矿渣粉性能满足GB/T18046-2017《用于水泥、砂浆和混凝土中的粒化高炉矿渣粉》标准中S95级技术要求。
相对于现有技术，本发明选用S95级矿渣粉，通过石灰石微粉、钢渣粉与高活性矿渣粉相互激发，产生微集料效应，提高掺合料对水泥和减水剂的相容性、降低水泥砂浆干缩率、提高混凝土强度。
进一步，所述石灰石微粉中位径D(50)≤6μm。
进一步，所述石灰石微粉CaO含量≥40％，MgO含量≤3％。
进一步，所述钢渣粉的比表面积为350～500m2/kg。
进一步，所述矿渣粉的比表面积为400～500m2/kg。
本发明所述石灰石微粉-钢渣粉-矿渣粉复合掺合料的制备工艺包括以下步骤：
1)分别将石灰石和钢渣烘干、破碎、粉磨、分级或筛分得到石灰石微粉和钢渣粉；
2)将所述石灰石微粉、钢渣粉和矿渣粉按照10％～30％、20％～50％和30％～60％的重量比混合均匀得到石灰石微粉-钢渣粉-矿渣粉复合掺合料，其中所述矿渣粉性能满足GB/T18046-2017《用于水泥、砂浆和混凝土中的粒化高炉矿渣粉》标准中S95级技术要求。
进一步，所述钢渣粉和矿渣粉的比表面积分别为350～500m2/kg和400～500m2/kg。
进一步，所述石灰石经粉磨后得到石灰石粉，所述石灰石粉的比表面积为500～700m2/kg；所述石灰石粉筛分后得到石灰石微粉，所述石灰石微粉中位径D(50)≤6μm。
进一步，所述石灰石微粉CaO含量≥40％，MgO含量≤3％。
进一步，步骤1)中所述粉磨过程掺入三乙醇胺助磨剂，所述三乙醇胺的掺量为0.02％～0.05％。
附图说明
图1为水泥净浆流动度对比图。
具体实施方式
本发明通过将S95级矿渣粉与石灰石微粉、钢渣粉混合，利用三者之间的相互激发、协同作用，制备出早期强度高、后期强度持续增长、兼具补偿收缩效应的复合掺合料，改善水泥与减水剂的相容性，提高混凝土强度。以下通过具体实施例来详细说明本发明的技术方案。
本发明所述石灰石微粉-钢渣粉-矿渣粉复合掺合料通过以下工艺制备而得：
1)分别将石灰石和钢渣烘干、破碎、粉磨、分级或筛分得到石灰石微粉和钢渣粉；
具体地，将石灰石烘干至水分小于1％，然后使用鄂式破碎机将其破碎至粒径小于4.75mm，接着使用5kg规格球磨机粉磨并在粉磨过程中掺入0.03％的三乙醇胺助磨剂，得到勃氏比表面积为620m2/kg、中位径为D(50)为10.804μm、密度为2.68g/cm3的石灰石粉。最后通过螺旋给料机将石灰石粉送入转速为2500r/min的气流分级机中进行分级，得到中位径D(50)为5.1μm的石灰石微粉。
将钢渣烘干至水分小于1％，然后使用鄂式破碎机将其破碎至粒径小于4.75mm，接着使用5kg规格球磨机粉磨并在粉磨过程中掺入0.03％的三乙醇胺助磨剂，最后过0.9mm筛得到勃氏比表面积为440m2/kg、密度为3.29g/cm3，中位径为D(50)为17.819μm的钢渣粉。
2)将所述石灰石微粉、钢渣粉和矿渣粉按照一定配比混合均匀得到石灰石微粉-钢渣粉-矿渣粉复合掺合料。
通过立磨制备出勃氏比表面积为460m2/kg、密度为2.89g/cm3、中位径为D(50)为11.003μm的矿渣粉，其性能满足GB/T18046-2017《用于水泥、砂浆和混凝土中的粒化高炉矿渣粉》标准中S95级技术要求，活性指数7d不小于70％、28d不小于95％，流动度比不小于95％，含水量不大于1.0％。然后将该矿渣粉与上述的石灰石微粉、钢渣粉按照表1的重量配比混合均匀，得到石灰石微粉-钢渣粉-矿渣粉复合掺合料。
<表1>石灰石微粉-钢渣粉-矿渣粉复合掺合料组分配比
请参看表2，该表反映了复合掺合料中石灰石微粉、钢渣粉和矿渣粉的化学成分。本发明的复合掺合料中钢渣粉含有较多的CaO、Fe2O3和SiO2，而矿渣粉则主要含CaO、SiO2和Al2O3，石灰石粉主要成分是CaO。石灰石微粉、钢渣粉和矿渣粉中游离CaO含量极低，具有较高的质量。
<表2>石灰石微粉、钢渣粉和矿渣粉化学成分
| 化学成分 | SiO<sub>2</sub> | TFe<sub>2</sub>O<sub>3</sub> | Al<sub>2</sub>O<sub>3</sub> | CaO | MgO | SO<sub>3</sub> | f-CaO | 烧失量 |
| 钢渣粉/％ | 14.76 | 31.46 | 2.98 | 34.75 | 6.49 | 0.33 | 1.59 | 2.19 |
| 矿渣粉/％ | 33.72 | 0.37 | 14.01 | 37.75 | 6.81 | 1.36 | 0.045 | 0.57 |
| 石灰石微粉/％ | 14.69 | 1.25 | 3.41 | 42.87 | 1.63 | 0.42 | 0.076 | 34.8 |
请参看表3，该表是将各种配比的石灰石微粉-钢渣粉-矿渣粉复合掺合料与水泥按照1:1的重量配比混合，再加入适量水和减水剂，得到水泥净浆，然后依据JC/T1083-2008《水泥与减水剂相容性试验方法》标准进行相容性试验的试验结果。作为比较，同时配制了不掺合本发明的复合掺合料的水泥净浆作为空白样。表3反映，与单纯使用水泥的水泥净浆(空白样)相比，掺合50％石灰石微粉-钢渣粉-矿渣粉复合掺合料后的水泥净浆(实施例1～实施例6)的初始5min流动度为空白样的123％～134％，60min流动度为空白样的107％～122％；同时掺合50％石灰石微粉-钢渣粉-矿渣粉复合掺合料后初始5min Marsh时间可缩短至空白样的0.87，60min Marsh时间可缩短至空白样的0.85。说明掺合石灰石微粉-钢渣粉-矿渣粉复合掺合料可明显改善水泥与减水剂的相容性。此外，与只掺合矿渣粉的水泥净浆(对比例)相比，掺合石灰石微粉-钢渣粉-矿渣粉复合掺合料后的水泥与减水剂的相容性也更好。
请同时参看图1，其中左图反映了只掺合矿渣粉的水泥净浆(对比例)的流动度，右图反映了掺合石灰石微粉-钢渣粉-矿渣粉复合掺合料后的水泥净浆的流动度。通过比较可知，本发明掺合石灰石微粉-钢渣粉-矿渣粉复合掺合料在一定程度上减小甚至消除了使用纯矿渣粉时新拌水泥混凝土表现出来的泌水、离析现象。
<表3>水泥与减水剂相容性试验配合比及试验结果
请参看表4，该表为将各种配比的石灰石微粉-钢渣粉-矿渣粉复合掺合料与水泥按照1:1的重量配比混合后制成水泥砂浆，然后依据JC/T603-2004《水泥胶砂干缩试验方法》标准进行干缩试验的测试结果。表4反映，与对比例相比，掺合石灰石微粉-钢渣粉-矿渣粉复合掺合料后的水泥砂浆在3～21d龄期干燥率均变小，有利于提高水泥基材料的早期抗裂性能。
<表4>水泥砂浆干缩试验结果
采用PO42.5R型水泥，采用细度模数为3.4的河砂作为细集料，由粒径为4.75～9.5mm和9.5～26.5mm连续级配石灰岩碎石按照20％：80％组成的粗集料以及减水率为30％、抗压强度比120％的增强型聚羧酸盐高效减水剂按照表5的配比制作混凝土，然后依据GB/T50081-2002《普通混凝土力学性能试验方法》标准进行力学性能试验以及依据GB/T50082-2009《普通混凝土长期性能和耐久性能试验方法》进行碳化试验，结果如表6所示。
表6反映，使用本发明所述石灰石微粉-钢渣粉-矿渣粉复合掺合料可制备出C60级高强混凝土，该混凝土的7d抗压强度达到设计强度(对比例)的84％以上，甚至高达90％，后期抗压强度持续增长；与对比例相比，28d抗压强度接近甚至超过对比例抗压强度；碳化深度值与对比例相差不大，甚至有所减小，碳化深度值在4～5mm之间变化，抗碳化性能优异；56d劈裂抗拉强度较对比例显著提高，有利于提高混凝土的抗裂性能。
<表5>混凝土配合比
<表6>混凝土碳化试验与力学性能试验结果
相对于现有技术，本发明通过将S95级矿渣粉与石灰石微粉、钢渣粉混合，利用三者之间的相互激发、协同作用，制备出早期强度高、后期强度持续增长、兼具补偿收缩效应的复合掺合料。该复合掺合料可明显改善水泥与减水剂的相容性，并且不会产生泌水、离析等问题。掺合该复合掺合料后的水泥砂浆具有较小的干燥率，可提高水泥基材料的早期抗裂性能。此外，将本发明的复合掺合料于等质量的水泥可制作出C60级高强混凝土，具有很好的抗压强度、抗裂性能与抗碳化性能。本发明的复合掺合料可等质量地与水泥混合，掺量极大，显著提高了固体废弃物的利用率和资源化利用水平，降低混凝土材料的生产成本。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。
Claims (10)
1.一种石灰石微粉-钢渣粉-矿渣粉复合掺合料，其特征在于按重量比包括以下组分：石灰石微粉10％～30％、钢渣粉20％～50％、矿渣粉30％～60％，其中矿渣粉性能满足GB/T18046-2017《用于水泥、砂浆和混凝土中的粒化高炉矿渣粉》标准中S95级技术要求。
2.根据权利要求1所述石灰石微粉-钢渣粉-矿渣粉复合掺合料，其特征在于：所述石灰石微粉中位径D(50)≤6μm。
3.根据权利要求2所述石灰石微粉-钢渣粉-矿渣粉复合掺合料，其特征在于：所述石灰石微粉CaO含量≥40％，MgO含量≤3％。
4.根据权利要求1所述石灰石微粉-钢渣粉-矿渣粉复合掺合料，其特征在于：所述钢渣粉的比表面积为350～500m2/kg。
5.根据权利要求1所述石灰石微粉-钢渣粉-矿渣粉复合掺合料，其特征在于：所述矿渣粉的比表面积为400～500m2/kg。
6.一种石灰石微粉-钢渣粉-矿渣粉复合掺合料的制备工艺，其特征在于包括以下步骤：
1)分别将石灰石和钢渣烘干、破碎、粉磨、分级或筛分得到石灰石微粉和钢渣粉；
2)将所述石灰石微粉、钢渣粉和矿渣粉按照10％～30％、20％～50％和30％～60％的重量比混合均匀得到石灰石微粉-钢渣粉-矿渣粉复合掺合料，其中所述矿渣粉性能满足GB/T18046-2017《用于水泥、砂浆和混凝土中的粒化高炉矿渣粉》标准中S95级技术要求。
7.根据权利要求6所述制备工艺，其特征在于：所述钢渣粉和矿渣粉的比表面积分别为350～500m2/kg和400～500m2/kg。
8.根据权利要求6所述制备工艺，其特征在于：所述石灰石微粉中位径D(50)≤6μm。
9.根据权利要求6所述制备工艺，其特征在于：所述石灰石微粉CaO含量≥40％，MgO含量≤3％。
10.根据权利要求6所述制备工艺，其特征在于：步骤1)中所述粉磨过程掺入三乙醇胺助磨剂，所述三乙醇胺的掺量为0.02％～0.05％。
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