CN116253573B - 一种危废炉用刚玉-锆莫来石浇注料 - Google Patents

一种危废炉用刚玉-锆莫来石浇注料 Download PDF

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CN116253573B
CN116253573B CN202211676985.0A CN202211676985A CN116253573B CN 116253573 B CN116253573 B CN 116253573B CN 202211676985 A CN202211676985 A CN 202211676985A CN 116253573 B CN116253573 B CN 116253573B
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CN116253573A (zh
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陈松林
俞小平
王俊涛
胡建辉
邵开君
俞盛
杨力
魏瀚
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Ruitai Technology Co ltd
Yixing Jinhua Refractory Co ltd
Yixing Ruitai Refractory Material Engineering Co ltd
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Yixing Jinhua Refractory Co ltd
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Abstract

本专利涉及一种危废炉用刚玉‑锆莫来石浇注料，原料配方包括：废电瓷、电熔刚玉、电熔锆莫来石、高效增强剂、抗侵蚀配料、莫来石纤维、CA75水泥、水等，其中，所述的抗侵蚀配料为熔融石英和回收料的预混合物，高效增强剂是由双峰氧化铝微粉、硅微粉、碳酸锂预混而成。该浇注料在实际危废炉二燃室和回转窑窑头部位服役，使用寿命超过24个月，表现出优异的抗侵蚀性和抗热震性等综合使用效果。

Description

一种危废炉用刚玉-锆莫来石浇注料
技术领域
本发明属于无机非金属材料的耐火材料技术领域，具体涉及一种危废炉用刚玉-锆莫来石浇注料。
背景技术
高温焚烧法是危险废物处理的重要方法，高温焚烧技术较其它技术在有害成份处理的彻底性、排除物的减量化(80wt％/95vol％)，以及对多种复杂有机物的适应性等方面具有显著的优势。危废焚烧设备包括一燃室和二燃室两个燃烧室，一燃室对大部分有机物进行汽化、分解和燃烧，二燃室对所有的有机物质和可燃气体进行氧化焚烧，一燃室中的温度要高于850℃，二燃室中的温度要高于1200℃，在一燃室热解和初步燃烧，在二燃室深度燃烧达到焚烬效果。焚烧炉炉衬热面长期与液态熔渣接触，不但熔渣中的Na2O、K2O、CaO、Fe2O3、SiO2和Cl等成分极易与材料反应形成液相或膨胀相，导致材料过早损毁，而且物料和熔渣的冲刷也加速了材料消耗，导致材料服役寿命较低。同时，熔渣中的钠和钾成分也极易与HCl和HF反应生成大量侵蚀性的气相NaCl、KCl、NaF和KF，在冷却过程中沉积并附着在炉衬表面，加速了材料的损毁。中国专利CN106747523A低铁莫来石砖及其制造方法公开了解决铁含量高导致致密性差、气孔率高、抗侵蚀性差的问题。专利CN109970437A一种危废焚烧炉用Al2O3-Cr2O3-ZrO2砖及其制备方法和CN113979760A一种用于危废气化熔融炉的高热震铬刚玉砖的制备方法公开了引入Cr2O3提高耐火砖抗渣侵蚀性和渗透性的方法。专利CN111995379A一种危废处置设备用含锆刚玉尖晶石砖及其制备方法、CN112110736A一种危废处置设备用刚玉尖晶石砖及其制备方法通过引入氧化铬或氧化锆或尖晶石来解决抗侵蚀性差或抗热震性低问题。专利CN107117948A化工危废焚烧炉用刚玉莫来石复合砖及其制备方法、CN112194470A一种危废焚烧炉回转窑用铬刚玉复合砖及其制备方法、CN114315329A一种危废回转窑用刚玉碳化硅复合砖及其制备方法，采用复合整体结构客服原来的两层结构的磨损问题。由于危废焚烧炉内的危废物种类复杂多变，在氧化性气氛下，危废焚烧炉使用MgO、MgO-Cr2O3、Al2O3-Cr2O3、Al2O3-SiO2质耐火材料，高温下液态熔渣几乎全部渗透到耐火材料内部，导致材料强度显著降低和大面积剥落；在还原性气氛下，危废焚烧炉可以使用SiC质耐火材料，SiC耐火材料不可避免的会面临氧化而被侵蚀的难题。另外，以上公开的专利都是采用耐火砖的方法，在砌筑窑炉时的砖缝依然是最薄弱的最易被渗透侵蚀损毁的起始。为了克服砖缝问题，中国专利CN 111439993 A一种危废回转窑用铬刚玉浇注料、CN114213112A一种环保型铬刚玉浇注料、CN115368151A一种抗剥落和抗水蒸气侵蚀的耐火浇注料及其制备方法，采用整体性好的浇注料方案，但这些浇注料或存在气孔率大、或环保、或价格高等问题。如何在成本可控的前提下，尽可能提高危废炉耐火材料的抗侵蚀性、抗热震性成为提高耐火材料使用性能的关键的技术难题。
本发明从危废炉实际工况需求出发，综合了各材料体系的优劣势，制备适用性广、性能良好、性价比高的一种危废炉用刚玉-锆莫来石浇注料，满足其长寿命服役的要求。
发明内容
一种危废炉用刚玉-锆莫来石浇注料，其特征技术在于原料配方，按重量份数计，配方为：
所述的抗侵蚀配料为熔融石英和回收料按1：(0.5～1)的预混合物，回收料为氮化硅结合碳化硅耐火材料回收料、自烧结碳化硅耐火材料回收料、氮化硅铁耐火材料回收料中的两种或多种混合物，抗侵蚀配料经球磨后控制粒度为0.088～0.044mm；
所述的高效增强剂是由双峰氧化铝微粉、硅微粉、碳酸锂预混而成，三者的重量比为(2.4～2.6)：1：(0.05～0.1)；
所述的双峰氧化铝微粉是指微粉粒度呈现双峰分布的双峰活性氧化铝微粉，粒度为D50≤3μm、D90≤5μm，Al2O3≥99％；
所述的硅微粉的粒度D90≤1μm，平均粒径都在0.1～0.3μm；
进一步，所述的碳酸锂可以替换为氢氧化锂、锂辉石中的一种或两种混合物。
本发明的一种危废炉用刚玉-锆莫来石浇注料的制备方法和施工养护：将上述原料按照重量份数要求称重后放入混料机中，强力混碾搅拌5～20min，作为浇注料，浇注施工；施工完毕湿养护72h之后拆模，自然干燥48～72h，之后在120℃烘烤48h，然后以≤20℃/h缓慢升温至工作温度服役。
本发明的用于危废焚烧炉的刚玉-锆莫来石耐火浇注料独特设计表现在：
本发明以刚玉和锆莫来石等主体浇注料配伍的基础上满足抗侵蚀性能要求，引入高效增强剂，对于进一步填充骨料和细粉之间的空隙，克服一般浇注料气孔率大导致抗渗透性差的缺点，也能改善耐火浇注料的流动性和施工性，增加了体密，使得浇注料的致密性增强，又增加浇注料的流动性、施工性和烧结性能，达到既减少了水泥的加入量，又提高了中温强度的效果。
把熔融石英和碳化硅耐或氮化硅回收料作为抗侵蚀配料加入配方体系，碳化硅、氮化硅复合耐火材料的高温性能优异，但由于烧结温度极高，一般采用原位反应烧结，当这种耐火材料使用后，进行二次利用变得更加困难，进而二次烧结制成耐火材料需要更高的温度，但本发明回收料进行破碎，辅以高效增强剂促进烧结，既克服了单纯使用碳化硅或氮化硅二次回收料难以烧结的难题，又是其在刚玉-锆莫来石浇注料体系中发挥其高抗侵蚀、高强度的特性，提高浇注料的抗侵蚀性和力学性能。
本发明的有益效果：(1)本发明的刚玉-锆莫来石浇注料在危废焚烧炉中使用后，具有较高的抗侵蚀性、抗热震性和抗剥落性。(2)材料的耐压强度对温度的敏感性低，在常温、中温、高温强度相对保持稳定。实验数据证实，本发明的刚玉-锆莫来石浇注料致密度高，体积密度≥2.8g/cm3，显气孔率≤18％，110℃烘干耐压强度≥80MPa，900℃×5h中温处理后耐压强度≥70MPa，明显由于现有常规耐火浇注料的耐压强度。经1500℃×3h高温烧结后，本发明的耐火浇注料的抗折强度达到15MPa以上，比现有同类浇注料的抗折性能提高了30％以上，1100℃×0.5h水循环的抗热震性检测超过15次。在某宁危废炉二燃室和回转窑窑头部位服役，使用寿命超过24个月，表现出优异的抗侵蚀性和抗热震性等综合使用效果。表1列出了本发明的刚玉-锆莫来石浇注料性能指标。
表1本发明的一种危废炉用刚玉-锆莫来石浇注料性能
附图说明
图1为实施例1的微观形貌见说明书附图SEM照片
具体实施方式
实施例1
一种危废炉用刚玉-锆莫来石浇注料，按重量份数计配方为：
所述的抗侵蚀配料为熔融石英和回收料按1：1的混合物。回收料为氮化硅结合碳化硅耐火材料回收料、自烧结碳化硅耐火材料回收料、氮化硅铁耐火材料回收料中的两种或多种混合物，抗侵蚀配料经球磨后控制粒度为0.088～0.044mm；所述的高效增强剂是由双峰氧化铝微粉、硅微粉、碳酸锂预混而成，三者的重量比为2.4：1：0.05；所述的双峰氧化铝微粉是指微粉粒度呈现双峰分布的双峰活性氧化铝微粉，粒度为D50≤3μm、D90≤5μm，Al2O3≥99％；所述的硅微粉的粒度D90≤1μm，平均粒径都在0.1～0.3μm。
施工养护：将上述原料按照重量份数要求称重后放入混料机中，强力混碾搅拌20min，作为浇注料，浇注施工；施工完毕湿养护72h之后拆模，自然干燥48h，之后在120℃烘烤48h，然后以20℃/h缓慢升温至工作温度服役。
实施例1的致密度高，显气孔率17.5％，体积密度2.90g/cm3，110℃烘干耐压强度88MPa，900℃×5h中温处理后耐压强度71MPa，明显由于现有常规耐火浇注料的耐压强度。经1500℃×3h高温烧结后，本发明的耐火浇注料的抗折强度15.6MPa，比现有同类浇注料的抗折性能提高了30％以上，1100℃×0.5h水循环的抗热震性检测超过15次。在某宁危废炉二燃室服役，使用寿命超过24个月，表现出优异的抗侵蚀性和抗热震性等综合使用效果。表2列出了实施例1的性能。实施例1的微观形貌见说明书附图SEM照片(见附图1)，可看出在大颗粒间隙中形成了相对致密的细晶粒相，且还有少量增韧作用的短纤维；从整个微观形貌来看，一方面致密程度得到了显著改善，另一方面增韧效果得到了显著改善，说明对于配方的调整发挥了决定性作用。
实施例2
一种危废炉用刚玉-锆莫来石浇注料，按重量份数计配方为：
所述的抗侵蚀配料为熔融石英和回收料按1：1的混合物，回收料为氮化硅结合碳化硅耐火材料回收料、自烧结碳化硅耐火材料回收料、氮化硅铁耐火材料回收料中的两种或多种混合物，抗侵蚀配料经球磨后控制粒度为0.088～0.044mm；所述的高效增强剂是由双峰氧化铝微粉、硅微粉、碳酸锂预混而成，三者的重量比为2.5：1：0.05；所述的双峰氧化铝微粉是指微粉粒度呈现双峰分布的双峰活性氧化铝微粉，粒度为D50≤3μm、D90≤5μm，Al2O3≥99％；所述的硅微粉的粒度D90≤1μm，平均粒径都在0.1～0.3μm。
施工养护：将上述原料按照重量份数要求称重后放入混料机中，强力混碾搅拌5min，作为浇注料，浇注施工；施工完毕湿养护72h之后拆模，自然干燥72h，之后在120℃烘烤48h，然后以15℃/h缓慢升温至工作温度服役
实施例2的致密度高，显气孔率17.8％，体积密度2.82g/cm3，110℃烘干耐压强度82MPa，900℃×5h中温处理后耐压强度71MPa，明显由于现有常规耐火浇注料的耐压强度。经1500℃×3h高温烧结后，本发明的耐火浇注料的抗折强度15.3MPa，比现有同类浇注料的抗折性能提高了30％以上，1100℃×0.5h水循环的抗热震性检测超过15次。在某宁危废回转窑窑头部位服役，使用寿命超过24个月，表现出优异的抗侵蚀性和抗热震性等综合使用效果。表2列出了实施例2的性能。
实施例3
一种危废炉用刚玉-锆莫来石浇注料，按重量份数计配方为：
所述的抗侵蚀配料为熔融石英和回收料按1：1的混合物，回收料为氮化硅结合碳化硅耐火材料回收料、自烧结碳化硅耐火材料回收料、氮化硅铁耐火材料回收料中的两种或多种混合物，抗侵蚀配料经球磨后控制粒度为0.088～0.044mm；
所述的高效增强剂是由双峰氧化铝微粉、硅微粉、碳酸锂预混而成，三者的重量比为2.6：1：0.1；所述的双峰氧化铝微粉是指微粉粒度呈现双峰分布的双峰活性氧化铝微粉，粒度为D50≤3μm、D90≤5μm，Al2O3≥99％；所述的硅微粉的粒度D90≤1μm，平均粒径都在0.1～0.3μm。
施工养护：将上述原料按照重量份数要求称重后放入混料机中，强力混碾搅拌15min，作为浇注料，浇注施工；施工完毕湿养护72h之后拆模，自然干燥72h，之后在120℃烘烤48h，然后以20℃/h缓慢升温至工作温度服役。
实施例3的致密度高，显气孔率17.7％，体积密度2.91g/cm3，110℃烘干耐压强度89MPa，900℃×5h中温处理后耐压强度73MPa，明显由于现有常规耐火浇注料的耐压强度。经1500℃×3h高温烧结后，本发明的耐火浇注料的抗折强度15.9MPa，比现有的同类浇注料的抗折性能提高了30％以上，1100℃×0.5h水循环的抗热震性检测超过15次。在某宁危废炉二燃室服役，使用寿命超过24个月，表现出优异的抗侵蚀性和抗热震性等综合使用效果。表2列出了实施例3的性能。
表2本发明的一种危废炉用刚玉-锆莫来石浇注料实施例性能列表

Claims (9)

1.一种危废炉用刚玉-锆莫来石浇注料，其技术特征在于，原料配方按重量份数计：
（1）废电瓷8~5mm5~8份；
（2）废电瓷5~3mm5~10份；
（3）电熔刚玉3~1mm15~40份；
（4）板状刚玉0.088~0.044mm8~22份；
（5）电熔锆莫来石1~0.010mm15~30份；
（6）电熔锆莫来石0.088~0.044mm5~20份；
（7）高效增强剂8~15份；
（8）抗侵蚀配料3~5份；
（9）莫来石纤维1~1.5份；
（10）CA75水泥3~5份；
（11）水3~5份；
所述的抗侵蚀配料为熔融石英和回收料按重量比1：（0.5~1）的预混合物，所述的高效增强剂是由双峰氧化铝微粉、硅微粉、碳酸锂预混而成。
2.根据权利要求1所述的浇注料，其技术特征在于，所述的回收料为氮化硅结合碳化硅耐火材料回收料、自烧结碳化硅耐火材料回收料、氮化硅铁耐火材料回收料中的两种或多种混合物。
3.根据权利要求1所述的浇注料，其技术特征在于，所述的抗侵蚀配料经球磨后控制粒度为0.088~0.044mm。
4.根据权利要求1所述的浇注料，其技术特征在于，所述的高效增强剂是由双峰氧化铝微粉、硅微粉、碳酸锂三者的重量比为（2.4~2.6）：1：（0.05~0.1）预混而成。
5.根据权利要求1所述的浇注料，其技术特征在于，所述的双峰氧化铝微粉是指微粉粒度呈现双峰分布的双峰活性氧化铝微粉，粒度为D50≤3μm、D90≤5μm，Al2O3 ≥99%。
6.根据权利要求1所述的浇注料，其技术特征在于，所述的硅微粉的粒度D90≤ 1μm，平均粒径都在0.1~0.3μm。
7.根据权利要求1所述的浇注料，其技术特征在于，所述的碳酸锂可以替换为氢氧化锂、锂辉石中的一种或两种混合物。
8.权利要求1-7任一项所述危废炉用刚玉-锆莫来石浇注料的制备方法，其特征在于：将上述原料按照重量份数要求称重后放入混料机中，强力混碾搅拌5~20min，作为浇注料。
9.权利要求1-7任一项所述危废炉用刚玉-锆莫来石浇注料的施工方法，其特征在于：进行浇注施工，施工完毕湿养护72h之后拆模，自然干燥48~72h，之后在120℃烘烤48h，然后以≤20℃/h缓慢升温至工作温度服役。
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