CN111574197A - 一种用煤窑灰制备轻质陶瓷砂颗粒的方法及其应用 - Google Patents
一种用煤窑灰制备轻质陶瓷砂颗粒的方法及其应用 Download PDFInfo
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- CN111574197A CN111574197A CN202010436690.0A CN202010436690A CN111574197A CN 111574197 A CN111574197 A CN 111574197A CN 202010436690 A CN202010436690 A CN 202010436690A CN 111574197 A CN111574197 A CN 111574197A
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- lightweight ceramic
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- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims 1
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- 235000019832 sodium triphosphate Nutrition 0.000 claims 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种用煤窑灰制造作为建筑材料的轻质陶瓷砂颗粒的方法。更具体地说，本发明涉及一种直接以池灰和粉煤灰为二次原料制造烧结合成轻质陶瓷砂颗粒的新工艺。所述合成轻质陶瓷砂颗粒可用作建筑材料。本发明的新颖之处在于生产成本低，轻质砂产量高，可与快速耗竭的天然砂和碎石竞争。
Description
技术领域
本发明涉及轻质砂技术领域，尤其涉及一种用煤窑灰直接制备烧结合成轻质陶瓷砂颗粒的方法，所述轻质陶瓷砂颗粒可用作建筑材料。本发明的新颖之处在于以高产量生产成本低的轻质砂，以对抗快速耗竭的自然资源，如天然砂和碎石。
背景技术
煤燃烧产物（粉煤灰和底灰）是燃煤电站燃烧煤时产生的废弃副产品。目前，全世界每年生产约14亿吨煤燃烧产物（CCP）。CCP的平均利用率约55%左右，而其余45%中的大部分通过湿式处置系统倾倒进灰池（泻湖）。
发明内容
在湿式处理系统中，CCP通常以1:10的比例与水混合，通过管道输送，以泥浆形式排入人工建造的灰池或灰堤中。处理这种泥浆需要用大面积的土地来建设灰池，同时还需要大量的水，而水正成为越来越稀缺的资源。此外，这种湿法处理工艺降低了火山灰活性，而火山灰活性是粉煤灰用于水泥生产的一个重要特性。
全球建筑和其他行业对优质砂的需求给日益减少的天然砂源带来了越来越大的压力。每年的砂产量和消耗量超过自然界产砂量的两倍。砂子这样的微粒物质是一种大量消耗的建筑材料，也是建筑行业必不可少的组成部分。目前，在全世界消耗的400亿吨砂子中，300亿吨用于混凝土和砂浆生产。在大多数生态脆弱的环境中，快速的城市化给天然砂矿床的供应带来了越来越大的压力。天然砂需要数百万年才能形成，而且正在迅速枯竭。对砂子的极度高消耗已危及到东南亚海岸线，导致30个岛屿消失。
参考一篇公开号JPH09156998A的日本专利，其公开了一种通过模塑和烧结非常细的粉煤灰颗粒而获得的陶瓷，这种粉煤灰的颗粒直径为1～10微米。粉煤灰的极细颗粒相互粘结，粘结的极细颗粒之间形成大量的细小空隙。这些空隙具有从陶瓷颗粒表面通向内部的微观结构，其体积密度为1～1.9g/cm3，吸水率为10～50vol%，同时具有高透气性，高透水性以及适当的保水性。
参考一篇专利号为US8257486B2的美国专利，其公开了一种用于制备化学活化冷凝粉煤灰建筑材料的组成及制备方法。该化学活化剂是一种pH值为11.2～13.6，密度为1.25～1.40gm/cc的碱性水溶液，在水介质中含有不同浓度的羟基、硫酸盐、醋酸盐和含有钙、镁、钠、钾和铝的氯化物。化学活化剂溶液与粉煤灰或池灰混合料中的矿物成分反应，形成粘合性。化学活化粉煤灰混合料或池灰的粘结材料主要是含水二氧化硅和硅酸盐组相，在大气条件下凝结时达到适合建筑施工用途的强度。在该发明的一个实施例中，粉煤灰、池灰及其混合物在重量为80%至99%的范围内使用。
参考一篇公开号为CN107827435A的中国专利，其公开了一种轻质陶瓷大板。该轻质陶瓷大板由以下重量百分比的原料组成：粉煤灰35～60%，废玻璃5～10%，高岭土5～12%，发泡剂0.1～0.5%，钾长石10～20%，钠长石10～20%，瓷砖抛光废渣5～30%，电解液0.1～0.2%；还公开了一种轻质陶瓷大板的制备方法，包括以下步骤:（1）配料，（2）球磨，（3）成浆，（4）陈化，（5）均质，（6）铺放处理，（7）筛分，（8）铺放处理，（9）喷雾干燥，（10）陈化，（11）铺放处理，（12）烧成，（13）冷却。该发明的优点是：轻质陶瓷大板表面可随意装饰各种效果的涂料，改性树脂，墙布，壁纸，安装钉并进行钻孔，市场前景广阔，进一步响应了国家支持的固废利用政策和世界建筑行业节能环保的趋势。
参阅一篇名称为《粉煤灰制成的陶瓷砖：制备与力学特性》的文献，该文献载于《陶瓷国际》期刊43(15)•2017年6月；该文献公开了粉煤灰（CFA）的用途，例如作为陶瓷生产的原料。该研究采用碱活化预处理粉煤灰制备的粘土类和长石类材料与未处理的粉煤灰（视为类石英材料）混合，烧结制备全灰基瓷砖。所得瓷砖具有良好的烧结性能，如烧成温度低，烧结范围宽；此外，与完全由未经处理的粉煤灰生产的瓷砖相比，这种瓷砖显示出更好的生坯强度（由于氢键作用）和烧结后性能（由于造渣和莫来石骨架效应）。在1100℃下烧结的全灰基瓷砖具有最佳的烧结后性能（体积密度2.5g/cm³，断裂模量50.1MPa，吸水率0%）。因此，该方法适用于制备完全由粉煤灰制成的新型陶瓷砖，突出了其在粉煤灰陶瓷领域中的重要性。
参考一篇公开号为WO2016202484的国际专利，其公开了直接由粉煤灰获得的轻质细陶瓷颗粒，及其在不同技术领域中的用途以及包含这种轻质陶瓷颗粒的建筑材料成分。进一步公开了该发明提供的轻质细陶瓷颗粒作为用于建筑目的的集料的用途，特别是与粉煤灰组合的用途。该发明提供的轻质细陶瓷颗粒还用作涂料或涂料配方中的添加剂，铸造砂，废水处理的添加剂，园艺用基质，水培园艺用基质，绿色屋顶用基质或土工技术用基质。还公开了包含该发明的轻质细陶瓷颗粒的灰浆或混凝土形式的建筑材料成分。该发明提供的轻质细陶瓷颗粒，特别是由它们制成的建筑材料成分物，具有卓越的质量和可加工性，隔音和内部固化的可持续性。
参考印度专利申请3099/MUM/2011，其公开了用工业废物制造烧结砂等轻质细颗粒建筑材料。更具体地说，该发明涉及一种利用粉煤灰制造烧结合成砂的新方法。该发明涉及以高产量和相对较低的成本生产烧结砂等轻质细颗粒，从而与快速耗竭的天然砂竞争。作为最接近的现有技术，3099/MUM/2011公开了用粉煤灰制造轻质陶瓷材料。
然而，由于池灰的特性明显不同于干式的粉煤灰、底灰或两者的组合，因此现有技术中没有一种方法可以处理池灰。所有对其进行简单改造的工艺，包括3099/MUM/2011中的工艺，均被发现无法用于处理池灰。
上述现有技术中并没有提到由煤窑灰生产的轻质砂颗粒，这是本发明的一个关键特征。
目前迫切需要解决由粉煤灰，底灰和水混合而成的池灰问题。与此同时，由于日益增长的建筑活动对天然砂的需求极大，我们正面临天然砂的巨大短缺，这迫使我们必须研究和开发寻找合适的替代品。
发明内容
针对现有技术中存在的问题，其中一种可取的方法是将池灰转化为陶瓷砂，作为天然砂，人工砂，细骨料和轻质细骨料的替代品，用于生产混凝土、灰浆、石膏、砖块和瓷砖。
本发明通过池灰和粉煤灰直接造粒的一步生产工艺克服了上述问题，无需用到干燥灰池。干燥灰池不仅是一个复杂的过程，而且成本较高，能耗较大。
赞成这种方法的理由有：（1）池灰占合成颗粒总重量的50-95%，粉煤灰占50-5%；（2）自然资源（如沙子和细集料）正在快速耗竭；（3）对生态和绿色产品的需求正在持续增加；（4）满足自然资源可持续管理和循环经济的需要。
基于本发明中的主要成分是废弃副产物，即池灰和粉煤灰（干）的事实，原料便宜，使得人造陶瓷砂具有竞争力，从而有助于缓解废物处理问题。因此，利用池灰和粉煤灰的混合物成功经济地生产颗粒物，不仅可以减少环境污染，而且可以产生巨大的经济效益。
本发明涉及用工业废料的混合物制造轻质陶瓷砂。上述制造工艺是一种制造合成轻质陶瓷砂的新工艺。是由两种不同的工业废料（即煤窑灰和干粉煤灰）生产轻质陶瓷砂以代替天然砂，尽管这两种工业废料都来自燃煤发电厂，但这有助于保护天然砂来源地所在的生态环境。
本发明提供的轻质陶瓷砂颗粒是天然砂、碎石和轻质细集料的最佳替代品。
本发明的主要目的是提供一种新颖、简单和经济的方法，从不同的工业废料组合中制造出具有定义明确的陶瓷轻质砂。
本发明的另一个目的是提供一种替代天然砂、人工砂（也称为碎石）、轻质细集料以生产混凝土、石膏、灰浆、底灰和屋顶瓦片的方法。
本发明的另一个目的是使用池灰和粉煤灰的混合物制造所述轻质陶瓷砂颗粒，池灰和粉煤灰是不受欢迎的副产物和/或损耗。
本发明的另一个目的是以高产量和最低的制造成本生产粒度分级的细颗粒，而不需要耗费能源干燥煤窑灰。
本发明的另一个目的是制造轻质陶瓷砂，作为天然砂或来自自然资源的碎石的替代品。
在一个方面，本发明公开了一种制造轻质陶瓷砂的新颖、简单和经济的方法。
另一方面，上述产品由工业废物生产，其中的主要原料是池灰和粉煤灰。
在又一方面，本发明涉及以高产量和非常低的制造成本制造细颗粒，以与快速耗尽的天然砂竞争，所述天然砂包括由膨胀粘土，膨胀玻璃和火山活动产生的碎石和轻质细集料。
在又一方面，本发明提供一种制造轻质陶瓷砂颗粒的新方法，包括以下步骤：
1、利用压滤机形成池灰饼；
2、将池灰，粉煤灰及外加剂放入高强度剪切搅拌机中；
3、原料均匀混合，随后形成颗粒；
4、制备出颗粒级配为亚圆形细颗粒的颗粒；
5、使用流化床干燥工艺干燥颗粒；
6、在高温（975～1300℃）下烧结具有所需颗粒级配、形状和强度的颗粒。
具体实施方式
通过参考以下对本发明的详细描述并结合表格，可以更容易地理解本发明，表格为本发明披露的一部分。应当理解，本发明不限于在此描述和/或示出的特定装置、方法、条件或参数，并且在此使用的术语仅用于实施例而不旨在限制所要求保护的发明范围。此外，如在包括所附权利要求书的说明书中所使用的，单数形式“a”，“an”和“the”包括复数，并且对特定数值的引用至少包括该特定值，除非内容另有明确指示。范围可以在本文中表示来自于“大约”或“近似”的另一个特定值。当表示这样一个范围时，另一个实施例包括从一个特定值和/或到另一个特定值。此外，应当理解，除非另有说明，本文所述的尺寸和材料特性是示例性的而不是限制性的，并且是为了更好地理解合适用途的示例性实施例，并且取决于特定应用，所述值之外的变化也可以在本发明的范围内。
现参考表格对实施例进行详细描述。为了避免不必要地混淆本发明，例如可以不描述众所周知的特征或者可以不冗余地描述基本上相同的元件。这样做是为了便于理解。
提供的表格和以下描述是为了使本领域技术人员能够完全理解本发明，并且不能理解为限制如所附权利要求中所阐述的本发明的范围。
为了更好得理解本发明的本质，现将对制备轻质陶瓷砂的方法的优选实施例进行描述。
实施例一。
一种由池灰和粉煤灰制备轻质陶瓷砂颗粒的方法。所述方法混合了50～95wt%的池灰和50～5wt%的粉煤灰。使用高强度剪切搅拌机将池灰和粉煤灰转化为颗粒并在150～300℃下干燥所述颗粒。干燥后颗粒在975～1300℃的温度范围内的高温烧结。最终产品符合统一的DIN13139（砂浆用砂）和DIN12620（混凝土用细集料）的粒度级配标准。同时，该产品还符合DIN 13055（混凝土和砂浆用轻质骨料）的要求。
实施例二。
一种如实施例一所述的轻质陶瓷砂颗粒的制备方法，包括以下步骤：
（a）将池灰和粉煤灰混合物转化为颗粒；
（b）干燥所述颗粒以获得干燥颗粒；
（c）高温烧结所述干燥颗粒，从而获得所述轻质陶瓷砂颗粒。
实施例三。
实施例一的制备方法优选使用50～95wt%的池灰和50～5wt%的粉煤灰。与实施例一的不同之处在于，在本实施例中，在形成颗粒之前，将硼润土添加到粉煤灰或池灰中，池灰的质量百分比可在50～95wt%之间，粉煤灰的质量百分比为45～5wt%，膨润土的质量百分比为5～0 wt%。
实施例四。
与实施例一的不同之处在于，在本实施例中，在形成颗粒之前向粉煤灰或池灰中添加细二氧化硅，所述池灰的质量百分比范围为50～95wt%，粉煤灰的质量百分比为40～5wt%，细二氧化硅的质量百分比为10～0wt%。
实施例五。
在实施例二的制备方法中包括干燥步骤，其中，所述干燥为使用流化床干燥，干燥温度在150～300°C之间。
实施例六。
实施例二的制备方法中涉及高温烧结步骤，其中，高温烧结的温度范围为975～1300°C。
实施例七。
前述的制备方法所制备的轻质陶瓷砂颗粒，其中，所述轻质陶瓷砂颗粒的尺寸不限于在0.063毫米至4毫米的范围内。此外，所述轻质陶瓷砂的级配符合DIN 13139（石膏用砂）的标准。此外，所述轻质陶瓷砂的级配符合DIN 12620（混凝土用细集料）的粒度级配。此外，所述轻质陶瓷砂的级配符合DIN 13055:2016的轻质骨料定义。
实施例八。
前述的制备方法所制备的轻质陶瓷砂颗粒的体积密度不限于在750kg/m3至1180kg/m3的范围之间。
下面结合实验细节，对本发明的具体实施方式作进一步的描述，使本发明的技术方案更加清楚、明确。下面描述的实验细节是示例性的，旨在解释本发明，而不能理解为对本发明的限制。
从燃煤电厂采集了池灰和粉煤灰样品。在造粒过程之前，测定池灰的含水量，其通常范围为25～35wt%。然后将所得的滤饼转移到高强度剪切混合料中。在混合料中还加入了粉煤灰（干态）和外加剂。
所述轻质陶瓷砂颗粒的配方如表1所示。制备所述轻质陶瓷砂颗粒的组合物的配比为：池灰饼50～95wt%，粉煤灰50～5wt%，细二氧化硅10～0wt%，膨润土5～0wt%，该组合物提高了生坯的强度。
表1：轻质陶瓷砂颗粒的配方表。
池灰饼置于高强度剪切搅拌机中。粉煤灰，膨润土，外加剂和/或添加到滤饼中的细二氧化硅都在转子和锅中旋转。混合和搅拌60秒以确保混合均匀。如果混合料因粉煤灰含量高而干燥，则向混合料中加水。这种加水操作是在转子和锅都在旋转的条件下进行的。旋转进行3～6分钟。在旋转过程中形成多个颗粒/球体。由此获得的颗粒，在本文中称为砂前体。
然后用流化床干燥机干燥湿润的砂前体。细颗粒在干燥机中的停留时间取决于干燥机的长度，干燥温度，干燥时间和空气流量等因素。实验条件下，干燥机温度为150～300℃，供气量为750～1500m3/h，干燥时间为4～8分钟。
在回转窑中烧制水分在1～5wt%之间的干燥砂前体。砂前体在窑炉中的停留时间取决于几个因素，如窑炉长度，窑炉温度（约为975～1300°C)，化学成分，颗粒大小，砂前体的吞吐量和温度。所产生的轻质陶瓷砂颗粒的大小通常在0.063毫米至4毫米之间。根据煤的来源，这些轻质陶瓷砂颗粒的体积密度在750kg/m3至1180kg/m3之间。
为了说明和描述的目的，已经给出了对本发明的特定实施例的上述描述。其不旨在穷举或将本发明限于所公开的精确形式，并且根据上述描述，显然可能进行许多修改和变更。选择和描述实施例是为了最好地解释本发明的原理及其实际应用，从而使本领域的其他技术人员能够最好地利用本发明和具有适合于所设想的特定用途的各种修改的各种实施例。应当理解的是，视情况而定，可考虑对等价物进行省略和替换，但这样做的目的是在不背离本发明的精神或范围的情况下涵盖其应用或实现。
Claims (13)
1.一种用煤窑灰制备轻质陶瓷砂颗粒的方法，其特征在于，包括以下步骤：
（a）混合50～95wt%的池灰，40～5wt%的粉煤灰，5～0wt%的膨润土，10～0wt%的细二氧化硅和0～1wt%的天然外加剂形成混合物，将上述混合物转化为颗粒；
（b）干燥所述颗粒以获得干燥颗粒；
（c）高温烧结所述干燥颗粒，从而获得所述轻质陶瓷砂颗粒；
其中，所述轻质陶瓷砂颗粒的粒度级配符合DIN 13139（砂浆用砂），DIN 12620（混凝土用细集料）和DIN 13055（混凝土和砂浆用轻集料）标准，所述轻质陶瓷砂颗粒的体积密度在750kg/m3至1180kg/m3之间，并且使用符合ISO标准（22007-2）的热盘装置硬化所述颗粒使得其导热系数小于0.70W/(m*K)。
2.根据权利要求1所述的一种用煤窑灰制备轻质陶瓷砂颗粒的方法，其特征在于，所述池灰由50wt%～70wt%的SiO2、Al2O3和Fe2O3组成。
3.根据权利要求1所述的一种用煤窑灰制备轻质陶瓷砂颗粒的方法，其特征在于，所述天然外加剂为三磷酸五钠和三聚氰胺甲醛的磺化盐，所述天然外加剂的质量百分比优选在0～1wt%之间。
4.根据权利要求1所述的一种用煤窑灰制备轻质陶瓷砂颗粒的方法，其特征在于，在步骤（a）中，使用高强度剪切搅拌机将所述混合物转化为颗粒。
5.根据权利要求1所述的一种用煤窑灰制备轻质陶瓷砂颗粒的方法，其特征在于，在步骤（b）中，使用干燥机干燥所述颗粒，所述干燥机的干燥温度为150～300℃，干燥时间为4～8分钟；所述干燥机的供气量为750～1500m3/h。
6.根据权利要求1所述的一种用煤窑灰制备轻质陶瓷砂颗粒的方法，其特征在于，在步骤（c）中，所述干燥颗粒在975～1300℃的温度下高温烧结。
7.根据权利要求1所述的一种用煤窑灰制备轻质陶瓷砂颗粒的方法，其特征在于，根据煤的来源不同，所述轻质陶瓷砂颗粒的体积密度为780kg/m3～1175kg/m3。
8.根据权利要求1所述的一种用煤窑灰制备轻质陶瓷砂颗粒的方法，其特征在于，所述轻质陶瓷砂颗粒的尺寸范围为0.063毫米至4毫米。
9.根据权利要求1所述的一种用煤窑灰制备轻质陶瓷砂颗粒的方法，其特征在于，所述池灰和所述粉煤灰是从燃煤电厂接收得到的。
10.根据权利要求1所述的一种用煤窑灰制备轻质陶瓷砂颗粒的方法，其特征在于，所述轻质陶瓷砂颗粒由工业废物制备而成，所述工业废物的主要原料为池灰和粉煤灰。
11.根据权利要求1所述的一种用煤窑灰制备轻质陶瓷砂颗粒的方法，其特征在于，以高产量和最低制造成本制造粒度分级的轻质陶瓷砂细颗粒，而不需要耗费能源对所述池灰进行干燥。
12.一种采用权利要求1所述的方法获得的轻质陶瓷砂颗粒，其特征在于，所述轻质陶瓷砂颗粒包括以下组分：
池灰，50～95wt%；
粉煤灰，40～5wt%；
膨润土，5～0wt%；
二氧化硅，10～0wt%；
以及，天然外加剂，0～1wt%。
13.根据权利要求12所述的一种轻质陶瓷砂颗粒，其特征在于，所述轻质陶瓷砂颗作为天然砂或来自自然资源的碎石的替代品。
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