CN114988853B - 一种耐氢氟酸和碱的致密蓄热蜂窝陶瓷填料 - Google Patents

一种耐氢氟酸和碱的致密蓄热蜂窝陶瓷填料 Download PDF

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CN114988853B
CN114988853B CN202210740006.7A CN202210740006A CN114988853B CN 114988853 B CN114988853 B CN 114988853B CN 202210740006 A CN202210740006 A CN 202210740006A CN 114988853 B CN114988853 B CN 114988853B
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吴汉阳
高洪跃
查昊燃
吴根洋
徐鹏
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Jiangxi Boxin Environmental Protection Technology Co ltd
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Abstract

本发明公开了一种新型耐氢氟酸和碱的致密蓄热蜂窝陶瓷填料，它的化学组成：Al2O3，CaF，CaO+MgO，其它，并按以下步骤制备工艺而成；a、选用刚玉或融熔刚玉为主料并按要求称量；b、根据步骤a称量球磨干混；c、出磨过筛后在，上述混合料中加入粘合剂、润滑剂和适量水充分混合，烧成得到致密蓄热蜂窝陶瓷填料，d、在步骤c中的致密蓄热蜂窝陶瓷填料蜂窝壁上浸涂耐酸碱合金复合涂层，所述耐酸碱合金复合涂层包括：耐酸碱合金粉末、乙基纤维素、松油醇或丙三醇、椰油酸异辛酯或月桂酸异丙酯。本发明解决RTO处理VOCs中遇到含HF气体迅速腐蚀蓄热蜂窝的难题，可大大延长致密蓄热陶瓷填料在RTO处理中的使用寿命。

Description

一种耐氢氟酸和碱的致密蓄热蜂窝陶瓷填料
技术领域
本发明涉及蓄热蜂窝陶瓷填料领域，尤其涉及一种耐氢氟酸和碱的致密蓄热蜂窝陶瓷填料。
背景技术
目前在VOCs处理中使用最多最成熟最稳定的技术是蓄热燃烧技术，使用最多的装备是RTO设备，RTO设备中核心材料就是蓄换热材料。随着工业发展及环保要求的持续提高，RTO需处理VOCs气体成份越来越复杂，使用RTO处理VOCs废气的行业从以前的涂布、印刷、涂料等行业逐步发展到石化、煤化、塑化、防水、精细化工、垃圾处理等各行各业。目前RTO处理VOCs过程中遇到了一些工况含有HF气体，同时温度又高于700℃。当前正在使用的蓄换热材料（陶瓷蜂窝、致密蜂窝、MLM卡片组合蜂窝）均经不住HF的腐蚀，多孔陶质和致密高硅、致密堇青石使用寿命均不超过一个月，致密高铝（Al2O3:60-75）也超不过三个月，产品就会腐蚀粉化、垮塌，使系统崩溃，不能正常运转。
发明内容
针对上述现有技术中蓄热蜂窝陶瓷填料存在的问题，本发明提供一种能最大化的解决目前RTO处理VOCs中遇到含HF气体迅速腐蚀蓄热蜂窝的难题，可大大延长蓄热材料在RTO中遇到HF腐蚀后的使用寿命的耐氢氟酸和碱的致密蓄热蜂窝陶瓷填料。
本发明要解决的技术问题所采取的技术方案是：一种耐氢氟酸和碱的致密蓄热蜂窝陶瓷填料，它的化学组成范围：Al2O3≥96wt%，CaF2≤0.1-2.0wt%，CaO+MgO≤2wt%，其它≤0.5wt%，并按以下步骤制备工艺而成；
a、选用刚玉或融熔刚玉为主料并按要求称量, 刚玉或融熔刚玉：96-99.5wt%、CaF2：0.1-2.0wt%、CaO+MgO：0-2wt%；
b、根据步骤a选α-Al2O3转化率大于95%的刚玉粉，工业纯CaF2、白云石、CaO、CaCO3、MgO、MgCO3，通过计算调整各种原料的比例，称量球磨干混，确保混合料中Al2O3大于96wt%；
c、出磨过筛后在，上述混合料中加入混合料重量的3-5wt%粘合剂、2-3wt%润滑剂和适量水充分混合，经捏合、练泥、成型、干燥、切割、吹灰、装坯、烧成得到致密蓄热蜂窝陶瓷填料，吸水率<0.5wt%,体积密度在3.65g/cm3以上；
d、在步骤c中的致密蓄热蜂窝陶瓷填料蜂窝壁上浸涂耐酸碱合金复合涂层，厚度大于0.01mm，真空烧结温度1200℃-1500℃，所述耐酸碱合金复合涂层包括：耐酸碱合金粉末：5-20wt%、乙基纤维素：0.1-2wt%、松油醇或丙三醇：0.5-5wt%、椰油酸异辛酯或月桂酸异丙酯：80-95wt%；所述耐酸碱合金粉末化学组成包括：Ni:>63wt%，Cu：28-34wt%，Fe:<2.5wt%。
进一步地，所述致密蓄热蜂窝陶瓷填料胎体中主晶相为刚玉相，且含量大于95V%，玻璃相加气相小于5v%。
进一步地，所述致密蓄热蜂窝陶瓷填料在10%氢氟酸溶液中浸泡三天失重小于2.5wt%，也即抗10%氢氟酸溶液浸泡三天的抗酸能力大于97.5wt%。
进一步地，所述耐酸碱合金粉末粒度d50≤2.5um。
本发明采用的措施是：①制备Al2O3含量超过96%刚玉材质的蓄热蜂窝材料；②刚玉瓷蜂窝蓄热体必须完全致密，吸水率小于0.5wt%；③刚玉蓄热体蜂窝中刚玉相必须大于95v%；④在致密刚玉蜂窝蓄热体蜂窝壁上浸涂一层耐HF耐高温的复合耐酸碱合金，通过精确原料配比，使合金原料、有机原料复配呈复合耐酸碱合金浆体，利用高温烧结法制备出均匀薄薄的镍铜合金涂层，使Ni原子和Cu原子牢固结合形成耐酸碱溶体，利用浸涂烧结法在填料表面制备出的蒙乃尔合金层，与填料基体结合强度高，且比只使用合金的耐腐蚀性能更优越，采用浸涂方法涂敷在蓄热陶瓷填料蜂窝壁上，干燥后经1200℃-1500℃真空烧结。这种刚玉耐酸碱合金复合蜂窝材料将极大提高蜂窝蓄热体的抗HF腐蚀能力，可以使RTO设备稳定运行12月以上。
本发明与现有技术相比，有以下有益效果：本发明采用刚玉来制备吸水率接近零的致密蓄热蜂窝陶瓷填料；为最大程度提高填料耐氢氟酸腐蚀的能力，在致密刚玉蜂窝陶瓷所有蜂窝壁上再复合一层厚度大于0.01mm的耐酸碱合金层，形成一种层状复合蓄热材料，该复合蓄热材料能最大化的解决目前RTO处理VOCs中遇到含HF气体迅速腐蚀蓄热蜂窝的难题，可大大延长蓄热材料在RTO中遇到HF腐蚀致使蓄热陶瓷寿命极短的问题。
实施方式
为了使本领域技术人员更好地理解本发明的技术方案，下面进一步详细描述本发明。实施例1
所述一种耐氢氟酸和碱的致密蓄热蜂窝陶瓷填料，它的化学组成范围：Al2O396wt%，CaF2 2.0wt%，CaO+MgO 1.5wt%，其它 1.5wt%，并按以下步骤制备工艺而成；
a、选用刚玉或融熔刚玉为主料并按要求称量, 刚玉或融熔刚玉：96wt%、CaF2：2.0wt%、CaO+MgO：1.5wt%；
b、根据步骤a选α-Al2O3转化率大于95%的刚玉粉，工业纯CaF2、白云石、CaO、CaCO3、MgO、MgCO3，通过计算调整各种原料的比例，称量球磨干混，确保混合料中Al2O3大于96wt%；
c、出磨过筛后在，上述混合料中加入混合料重量的3wt%粘合剂、2wt%润滑剂和适量水充分混合，经捏合、练泥、成型、干燥、切割、吹灰、装坯、烧成得到致密蓄热蜂窝陶瓷填料，吸水率为0.4wt%,体积密度在3.92g/cm3；
d、在步骤c中的致密蓄热蜂窝陶瓷填料蜂窝壁上浸涂耐酸碱合金复合涂层，厚度为0.02mm，真空烧结温度1400℃，所述耐酸碱合金复合涂层包括：耐酸碱合金粉末（所述耐酸碱合金粉末粒度d50为2.5um；）：10wt%、乙基纤维素： 2wt%、松油醇或丙三醇：5wt%、椰油酸异辛酯或月桂酸异丙酯：83wt%；所述耐酸碱合金粉末化学组成包括：Ni: 65wt%，Cu：33wt%，Fe: 2.wt%。
将实施例1制得的致密蓄热蜂窝陶瓷填料在10%氢氟酸溶液中浸泡三天失重为2wt%，也即抗10%氢氟酸溶液浸泡三天的抗酸能力为98wt%。
实施例
所述一种耐氢氟酸和碱的致密蓄热蜂窝陶瓷填料，它的化学组成范围：Al2O397wt%，CaF2 1wt%，CaO+MgO 1.5wt%，其它 0.5wt%，并按以下步骤制备工艺而成；
a、选用刚玉或融熔刚玉为主料并按要求称量, 刚玉或融熔刚玉：97wt%、CaF：1wt%、CaO+MgO：1.5wt%；
b、根据步骤a选α-Al2O3转化率大于95%的刚玉粉，工业纯CaF2、白云石、CaO、CaCO3、MgO、MgCO3，通过计算调整各种原料的比例，称量球磨干混，确保混合料中Al2O3大于96wt%；
c、出磨过筛后在，上述混合料中加入混合料重量的5wt%粘合剂、3wt%润滑剂和适量水充分混合，经捏合、练泥、成型、干燥、切割、吹灰、装坯、烧成得到致密蓄热蜂窝陶瓷填料，吸水率 0.3wt%,体积密度为4.03g/cm3；
d、在步骤c中的致密蓄热蜂窝陶瓷填料蜂窝壁上浸涂耐酸碱合金复合涂层，厚度0.03mm，真空烧结温度1500℃，所述耐酸碱合金复合涂层包括：耐酸碱合金粉末（所述耐酸碱合金粉末粒度d50为2.2um；）：15wt%、乙基纤维素：1wt%、松油醇或丙三醇：2wt%、椰油酸异辛酯或月桂酸异丙酯：82wt%；所述耐酸碱合金粉末化学组成包括：Ni:64wt%，Cu：34wt%，Fe:2wt%。
将实施例2制得的致密蓄热蜂窝陶瓷填料在10%氢氟酸溶液中浸泡三天失重为1.3wt%，也即抗10%氢氟酸溶液浸泡三天的抗酸能力为98.7wt%。
以上实施方式仅用以说明本发明的技术方案而非限制，尽管参照具体实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，其均应涵盖在本发明的权利要求保护的范围中。

Claims (4)

1.一种耐氢氟酸和碱的致密蓄热蜂窝陶瓷填料，其特征在于：它的化学组成范围：Al2O3≥96wt%，CaF2≤0.1-2.0wt%，CaO+MgO≤2wt%，其它≤0.5wt%，并按以下步骤制备工艺而成；
a、选用融熔刚玉为主料并按要求称量, 融熔刚玉：96-99.5wt%、CaF2：0.1-2.0wt%、CaO+MgO：0-2wt%；
b、根据步骤a选α-Al2O3转化率大于95%的融熔刚玉，工业纯CaF2、白云石、CaO、CaCO3、MgO、MgCO3，通过计算调整各种原料的比例，称量球磨干混，确保混合料中Al2O3大于96wt%；
c、出磨过筛后在，上述混合料中加入混合料重量的3-5wt%粘合剂、2-3wt%润滑剂和适量水充分混合，经捏合、练泥、成型、干燥、切割、吹灰、装坯、烧成得到致密蓄热蜂窝陶瓷填料，吸水率<0.5wt%,体积密度在3.65g/cm3以上；
d、在步骤c中的致密蓄热蜂窝陶瓷填料蜂窝壁上浸涂耐酸碱合金复合涂层，厚度大于0.01mm，真空烧结温度1200℃-1500℃，所述耐酸碱合金复合涂层包括：耐酸碱合金粉末：5-20wt%、乙基纤维素：0.1-2wt%、松油醇或丙三醇：0.5-5wt%、椰油酸异辛酯或月桂酸异丙酯：80-95wt%；所述耐酸碱合金粉末化学组成包括：Ni:>63wt%，Cu：28-34wt%，Fe:<2.5wt%。
2.根据权利要求1所述的一种耐氢氟酸和碱的致密蓄热蜂窝陶瓷填料，其特征在于：所述致密蓄热蜂窝陶瓷填料胎体中主晶相为刚玉相，且含量大于95V%。
3.根据权利要求1或2所述的一种耐氢氟酸和碱的致密蓄热蜂窝陶瓷填料，其特征在于：所述致密蓄热蜂窝陶瓷填料在10%氢氟酸溶液中浸泡三天失重小于2.5wt%，也即抗10%氢氟酸溶液浸泡三天的抗酸能力大于97.5wt%。
4.根据权利要求1或2所述的一种耐氢氟酸和碱的致密蓄热蜂窝陶瓷填料，其特征在于：所述耐酸碱合金粉末粒度d50≤2.5um。
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