CN106966707A - 利用煤矸石制备轻质高强陶粒的方法 - Google Patents
利用煤矸石制备轻质高强陶粒的方法 Download PDFInfo
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- 239000000463 material Substances 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000292 calcium oxide Substances 0.000 claims abstract description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
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- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
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- 239000004411 aluminium Substances 0.000 claims description 6
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Abstract
本发明公开了一种利用煤矸石制备轻质高强陶粒的方法，包括如下步骤：将含碳量为5～15％的煤矸石通过破碎粉磨得到能全部通过325目的煤矸石粉料；按质量百分比，将40～80％的煤矸石粉料、0％～45％的铝矾土粉料、1％～9％的氧化钙，5％～15％的钾长石，混合均匀，得到原料；将原料球磨后在造粒机中造粒，再与球磨后原料混合，在陶粒成型机上成型，烘干、筛分，得到陶粒坯体；再经三次升温焙烧，随炉冷却，得到轻质高强陶粒。该方法使用煤矸石含量达40％～80％，制得陶粒的堆积密度在0.6～1.55g/cm3之间，相同密度下其强度比现有技术提高10～50％；满足建筑用轻集料和油气开采用陶粒支撑剂材料的要求。
Description
技术领域
本发明涉及陶瓷材料领域，特别是涉及一种利用煤矸石制备低密度高强度陶粒材料的技术。
背景技术
煤矸石是我国排放量最大的工业废渣，目前积存煤矸石达10亿吨以上。其堆放不仅占用土地、污染大气、农田和水体，还存在发生火灾，雨季崩塌，淤塞河流造成灾害的隐患。如何综合利用煤矸石也是目前迫在眉睫需要解决的问题。
陶粒一般以粘土、岩土等矿产资源，粉煤灰、污泥、底泥、垃圾等废渣以及废液为主要原料经过加工、制粒、烧制而成。陶粒具有密度小、质轻、综合强度高、保温隔热、耐火抗震性能好、耐腐蚀等其它材料无法比拟的优异性能，在全世界得到快速发展。陶粒最初主要作为一种人造轻集料在建筑行业被广泛使用，随着科学技术的发展和对陶粒认识的深入，陶粒已广泛应用于各行各业，并且应用领域还在继续扩大。
目前低密度高性能陶粒材料的研究开发主要还是建立在矿物原材料的基础上，而以煤矸石为主要原料制备轻质高性能陶粒材料的研究和技术开发较少，主要集中在建筑用轻集料方面：CN 201410376390.2公开了一种以煤矸石和废弃植物粉料为原料制造陶粒的方法；CN 201310508355.7公开了一种以煤矸石和千枚岩为原料制备陶粒的方法；CN201310196979.X公开了一种用于人造轻集料的陶粒，以煤矸石、煤泥、石英砂和长石混合焙烧制得。以煤矸石为主要原料制备陶粒用于油气开采方面已有一些公开技术，但普遍强度较低：CN 201610253752.8公开了一种以煤矸石作和砂土为原料，所制备的陶粒支撑剂主要用来代替天然石英砂于35MPa闭合压力下压裂作业使用；CN 201010136972.5公开了一种以铝矾土和煤矸石为内核，四氧化三锰为外壳的陶粒支撑剂，其体积密度为1.55g/cm3，52MPa下破碎率为5.5％。文献(陈平，刘凯，刘毅，等.低密高强压裂支撑剂的研究[J].陕西科技大学学报,2014,32(1)：63-67.)以煤矸石矿渣和粉煤灰矿渣为主料，TiO2、ZnO和白云石为添加剂，在1340℃左右制备了低密度高强度陶粒支撑剂。CN 201210201367.0以煤矸石、氧化铝粉、碳酸钡和氧化铝短切纤维为原料制备了高性能陶粒材料，但该技术中使用的氧化铝短切纤维成本较高且制备技术复杂；
以煤矸石为原料制备用途广泛的陶粒材料，不仅可以降低生产成本，也可降低资源消耗和环境污染，具有显著的经济和社会效益。
发明内容
本发明提供了一种利用煤矸石制备轻质高强度陶粒的方法，该方法使用煤矸石含量达40％～80％，制得陶粒的堆积密度在0.6～1.55g/cm3之间，相同密度下其强度比现有技术提高10～50％；满足建筑用轻集料和油气开采用陶粒支撑剂材料的要求。
为此，本发明的技术方案如下：
一种利用煤矸石制备轻质高强陶粒的方法，包括如下步骤：
1)将含碳量为5～15％的煤矸石通过破碎粉磨获得的煤矸石粉料能全部通过325目标准筛；
2)按质量百分比，将40～80％的煤矸石粉料、0％～45％的铝矾土粉料、1％～9％的氧化钙，5％～15％的钾长石，混合均匀，得到原料；
3)将所述原料置于球磨机中球磨至粉料能全部通过540目标准筛，得到混合粉料；
4)将所述混合粉料置于高速搅拌混合造粒机中，得到平均粒径为10～0.1mm的颗粒；
5)将所述颗粒在陶粒成型机上添加10～20％混合粉料进行成型、烘干、筛分，得到陶粒坯体；
6)将所述陶粒坯体置于窑炉中，先以3～5℃/min的速率升温到500～700℃，保温10～30min，再以10～15℃/min的速率升温到900～1100℃，保温20～30min，最后以5～10℃/min的速率升温到1200～1500℃，保温40～90min；随炉冷却，即得到所述轻质高强陶粒。
进一步，原料中铝矾土粉料的含量为0％～40％，还可以为2％～30％。
进一步，步骤2)所述原料的含量为50～80％的煤矸石粉料、2％～30％的铝矾土粉料、2％～6％的氧化钙，6％～12％的钾长石。
进一步，步骤1)所述煤矸石中三氧化二铝的含量为30～50％。
进一步，含碳量高于15％的煤矸石经700～1000℃煅烧，使含碳量介于5～15％后，能作为步骤1)中的煤矸石使用。
进一步，步骤4)中所述混合粉料在高速搅拌混合造粒机中形成颗粒的条件为：一次性喷入占粉料总质量10～22％的水，高速搅拌5～20min。
进一步，步骤2)所述铝矾土为三氧化二铝含量为55～70％的铝矾土。
进一步，步骤2)所述所述氧化钙可通过方解石，碳酸钙或石膏等矿物原料经煅烧后得到。
进一步，步骤5)中所述陶粒成型机为挤出、旋转或碾压式成型机中的任意一种。
本专利以煤矸石为主要原材料，引入新型添加剂对原理材料配方进行重新设计、改进了现有的原材料处理和陶粒成型工艺，并采用新的热处理工艺对陶粒进行煅烧。所获得的陶粒材料具有密度低、强度高的特点，能够满足建筑用轻集料和油气开采用陶粒支撑剂材料的要求。该项技术解决了现有技术中煤矸石添加量比较低，制备工艺复杂和材料性能较低的问题，能显著提高煤矸石固体废弃物的用量，生产的轻质高性能材料具有更广阔的应用前景，为煤矸石的资源化利用开拓了新的途径。
采用本发明所制备的陶粒支撑剂材料，其堆积密度在0.6～1.55g/cm3之间，材料视密度在2.20～2.70g/cm3之间，相同密度下其强度比现有技术提高10～50％。采用本发明所制备的建筑用轻集料陶粒，其容重在700～1000kg/m3，相同密度条件下，筒压强度提高30～50％。
附图说明
图1为实施例1得到的产品的剖面图；
图2为实施例2得到的产品的微观形貌图；
图3为实施例3得到的产品的微观形貌图；
图4为实施例4得到的产品的微观形貌图。
具体实施方式
以下结合实施例对本发明高掺量粉煤灰陶粒支撑剂的制备方法进行详细描述。
实施例1
一种利用煤矸石制备轻质高强陶粒的方法，包括如下步骤：
1)将含碳量为20％的煤矸石在800℃煅烧后获得含碳量为7％左右的煤矸石，其三氧化二铝含量为40％，该煤矸石块体通过破碎粉磨后获得粒径为400目的粉料；
2)按质量百分数将69％的煤矸石粉，14％的铝矾土(三氧化二铝含量为65％)，5％的碳酸钙(煅烧后形成2％氧化钙)，12％的钾长混合均匀，得到原料；
3)将所述原料置于球磨机中，按照球料比1:1加入高铝球，球磨1小时后，取出过600目标准筛得到混合粉料；
4)将所述混合粉料置于高速搅拌混合造粒机中，在粉料高速搅拌旋转的过程中一次性喷入占粉料总质量15％的水，高速搅拌10min，形成细小致密的颗粒；
5)将颗粒在盘式成型机上添加10％混合粉料旋转20min后形成圆球状颗粒，烘干后过20～50目筛获得陶粒坯体；
6)将所述陶粒坯体置于窑炉中，先以3℃/min的速率升温到550℃，并保温20min，再以10℃/min的速率升温到1100℃，保温20min，最后以10℃/min的速率升温到1300℃，保温60min后随炉冷却，即得到所述轻质高强陶粒。
按照中华人民共和国石油天然气行业标准SY/T5108-2014和SY/T5108-2006测试，陶粒性能为：堆积密度1.45g/cm3，52MPa压力下破碎率5％，圆度＞0.9，球度＞0.9，酸溶解度3.12％，视密度2.50g/cm3。对比现有技术(CN101787270A：堆积密度1.509/cm3，视密度2.659/cm3，52MPa条件下破碎率6.5％)，其密度要低、性能有较大提高。
附图一中对应实施例1陶粒剖面图片显示，陶粒材料内部致密气孔较少，表明用这种技术获得的材料性能较好。
实施例2
一种利用煤矸石制备轻质高强陶粒的方法，包括如下步骤：
1)将含碳量为15％，三氧化二铝含量为30％的煤矸石通过破碎粉磨后获得粒径为400目的粉料；
2)按质量百分数将80％的煤矸石粉，10％的方解石(煅烧后形成5％氧化钙)，10％的钾长混合均匀，得到原料；
3)将所述原料置于球磨机中，按照球料比1:1加入高铝球，球磨1小时后，取出过500目标准筛得到混合粉料；
4)将混合粉料置于高速搅拌混合造粒机中，在粉料高速搅拌旋转的过程中喷入占粉料总质量10％的水，高速搅拌15min，形成细小致密的颗粒；
5)将颗粒在碾压式成型机上添加15％混合粉料形成直径12～25mm短柱状陶粒，烘干后得到陶粒坯体；
6)将所述陶粒坯体置于窑炉中，先以5℃/min的速率升温到600℃，并保温30min，再以15℃/min的速率升温到1000℃，保温25min，最后以8℃/min的速率升温到1200℃，保温60min后随炉冷却，即得到所述轻质高强陶粒。
按照中华人民共和国国家标准GBT17431.2-2010轻集料及其试验方法测定陶粒性能为：容重812kg/m3，筒压强度12MPa，吸水率8％。对比现有技术(CN103553553A：陶粒筒压强度5.0MPa，容重598kg/m3，吸水率7.2％)，其性能有较大提高。
图2所示本实施例产品的微观形貌图中可以看出，材料内部形成了由针状结晶体构成的三维交织的空间网状结构有利于在控制材料低密度的同时提高材料的力学性能。
实施例3
一种利用煤矸石制备轻质高强陶粒的方法，包括如下步骤：
1)将含碳量为5％，三氧化二铝含量为50％的煤矸石通过破碎粉磨后获得粒径为600目的粉料；
2)按质量百分数将50％的煤矸石粉，40％的铝矾土(三氧化二铝含量为70％)4％的氧化钙，6％的钾长混合均匀，得到原料；
3)将所述原料置于球磨机中，按照球料比1:1加入高铝球，球磨2小时后，取出过500目标准筛得到混合粉料；
4)将所述混合粉料置于高速搅拌混合造粒机中，在粉料高速搅拌旋转的过程中喷入占粉料总质量18％的水，高速搅拌10min，形成细小致密的颗粒；
5)将颗粒在盘式成型机上添加10％混合粉料旋转30min后形成圆球状颗粒，烘干后过20～50目筛获得陶粒坯体；
6)将所述陶粒坯体置于窑炉中，先以3℃/min的速率升温到700℃，并保温25min，再以12℃/min的速率升温到1150℃，保温20min，最后以10℃/min的速率升温到1450℃，保温40min后随炉冷却，即得到所述轻质高强陶粒。
按照中华人民共和国石油天然气行业标准SY/T5108-2014和SY/T5108-2006测试，陶粒性能为：堆积密度1.55g/cm3，69MPa压力下破碎率＜6％，圆度＞0.9，球度＞0.9，酸溶解度3.12％，视密度2.70g/cm3，对比现有技术(CN102757780A：:采用铝矿石52％、废旧耐火材料15％、煤矸石25％、赤泥4％、采矿选矿废渣4％为原料制备的陶粒支撑剂堆积密度1.55/cm3，视密度2.85/cm3，69MPa条件下破碎率6.8％)，本发明技术所用煤矸石用量大，且性能有较大提高。
图3中本实施例产品的微观形貌显示，陶粒烧结致密内部缺陷较少，在材料内部形成了晶须网络结构，使得材料获得了较好的性能。
实施例4
一种利用煤矸石制备轻质高强陶粒的方法，包括如下步骤：
1)将含碳量为12％，三氧化二铝含量为30％的煤矸石通过破碎粉磨后获得粒径为400目的粉料。
2)按质量百分数将70％的煤矸石粉，15％铝矾土(三氧化二铝含量为55％)3％氧化钙，12％的钾长混合均匀，得到原料；
3)将所述原料置于球磨机中，按照球料比1:1加入高铝球，球磨1小时后，取出过500目标准筛得到混合粉料；
4)将所述混合粉料置于高速搅拌混合造粒机中，在粉料高速搅拌旋转的过程中喷入占粉料总质量20％的水，高速搅拌10min，形成细小致密的颗粒；
5)将颗粒在碾压式成型机上添加15％混合粉料形成粒径为12～25mm椭圆形陶粒，烘干后得到陶粒坯体；
6)将所述陶粒坯体置于窑炉中，先以5℃/min的速率升温到600℃，并保温10min，再以15℃/min的速率升温到1000℃，保温20min，最后以10℃/min的速率升温到1300℃，保温40min后随炉冷却，即得到所述轻质高强陶粒。
按照中华人民共和国国家标准GBT17431.2-2010轻集料及其试验方法测定陶粒性能为：容重900kg/m3，筒压强度15MPa，吸水率7.3％。对比现有技术(CN103553553A：陶粒筒压强度5.0MPa，容重598kg/m3，吸水率7.2％)，其性能有较大提高。
图4中本实施例得到陶粒的微观形貌显示，陶粒烧结致密内部缺陷较少，在材料内部形成由柱状晶交织而成的三维网络结构，使得陶粒材料获得了较好的性能。
Claims (10)
1.一种利用煤矸石制备轻质高强陶粒的方法，其特征在于包括如下步骤：
1)将含碳量为5～15％的煤矸石通过破碎粉磨获得的煤矸石粉料能全部通过325目标准筛；
2)按质量百分比，将40～80％的煤矸石粉料、0％～45％的铝矾土粉料、1％～9％的氧化钙，5％～15％的钾长石，混合均匀，得到原料；
3)将所述原料置于球磨机中球磨至粉料能全部通过540目标准筛，得到混合粉料；
4)将所述混合粉料置于高速搅拌混合造粒机中，得到平均粒径10～0.1mm的颗粒；
5)将所述颗粒在陶粒成型机上添加10～20％混合粉料进行成型、烘干、筛分，得到陶粒坯体；
6)将所述陶粒坯体置于窑炉中，先以3～5℃/min的速率升温到500～700℃，保温10～30min，再以10～15℃/min的速率升温到900～1100℃，保温20～30min，最后以5～10℃/min的速率升温到1200～1500℃，保温40～90min；随炉冷却，即得到所述轻质高强陶粒。
2.如权利要求1所述利用煤矸石制备轻质高强陶粒的方法，其特征在于：原料中铝矾土粉料的含量为0％～40％。
3.如权利要求1所述利用煤矸石制备轻质高强陶粒的方法，其特征在于：原料中铝矾土粉料的含量为2％～30％。
4.如权利要求1所述利用煤矸石制备轻质高强陶粒的方法，其特征在于：步骤2)所述原料的含量为50～80％的煤矸石粉料、2％～30％的铝矾土粉料、2％～6％的氧化钙，6％～12％的钾长石。
5.如权利要求1所述利用煤矸石制备轻质高强陶粒的方法，其特征在于：步骤1)所述煤矸石中三氧化二铝的含量为30～50％。
6.如权利要求1所述利用煤矸石制备轻质高强陶粒的方法，其特征在于：含碳量高于15％的煤矸石经700～1000℃煅烧，使含碳量介于5～15％后，能作为步骤1)中的煤矸石使用。
7.如权利要求1所述利用煤矸石制备轻质高强陶粒的方法，其特征在于：步骤4)中所述混合粉料在高速搅拌混合造粒机中形成颗粒的条件为：一次性喷入占粉料总质量10～22％的水，高速搅拌5～20min。
8.如权利要求1所述利用煤矸石制备轻质高强陶粒的方法，其特征在于：步骤2)所述铝矾土为三氧化二铝含量为55～70％的铝矾土。
9.如权利要求1所述利用煤矸石制备轻质高强陶粒的方法，其特征在于：步骤2)所述所述氧化钙可通过方解石，碳酸钙或石膏经煅烧后得到。
10.如权利要求1所述利用煤矸石制备轻质高强陶粒的方法，其特征在于：步骤5)中所述陶粒成型机为挤出、旋转或碾压式成型机中的任意一种。
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| CN111825430A (zh) * | 2019-04-15 | 2020-10-27 | 淮南东辰集团有限责任公司 | 一种高强煤矸石陶粒及其制备方法 |
| CN111825474A (zh) * | 2019-04-15 | 2020-10-27 | 淮南东辰集团有限责任公司 | 一种煤矸石陶粒及其制备方法 |
| CN109970434B (zh) * | 2019-04-17 | 2021-09-24 | 郑州市新郑梅久实业有限公司 | 一种陶粒砂及其生产工艺 |
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| CN110028947A (zh) * | 2019-05-15 | 2019-07-19 | 山西金宇科林科技有限公司 | 利用煤系高岭土制备高强低密石油压裂支撑剂及制备方法 |
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| CN111470790A (zh) * | 2020-04-03 | 2020-07-31 | 桂林理工大学 | 一种吸音陶粒及其制备方法和应用 |
| CN112646565A (zh) * | 2021-01-25 | 2021-04-13 | 河南郑矿机器有限公司 | 一种煤矸石低密度石油陶粒支撑剂的制备工艺 |
| CN113387605A (zh) * | 2021-06-18 | 2021-09-14 | 中南大学 | 一种多种类煤矸石低温自供热烧结制备轻骨料的方法 |
| CN113387605B (zh) * | 2021-06-18 | 2022-07-26 | 中南大学 | 一种多种类煤矸石低温自供热烧结制备轻骨料的方法 |
| CN114214056A (zh) * | 2021-12-30 | 2022-03-22 | 郑州鑫源防磨耐材有限公司 | 页岩气开采用压裂支撑剂及其制备方法 |
| RU2788201C1 (ru) * | 2022-05-17 | 2023-01-17 | Общество с ограниченной ответственностью "Лайк Филл" (ООО "Лайк Филл") | Шихта для стеклокерамического пропанта и способ его получения |
| CN114956631A (zh) * | 2022-06-30 | 2022-08-30 | 安徽建工建材科技集团有限公司 | 一种防辐射功能集料及其制备方法 |
| CN116003052A (zh) * | 2022-12-16 | 2023-04-25 | 中交一公局重庆万州高速公路有限公司 | 基于人造高强集料的高模量超高性能混凝土及其制备方法 |
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