CN110763066B - 余热锅炉换热管 - Google Patents

余热锅炉换热管 Download PDF

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CN110763066B
CN110763066B CN201910993860.2A CN201910993860A CN110763066B CN 110763066 B CN110763066 B CN 110763066B CN 201910993860 A CN201910993860 A CN 201910993860A CN 110763066 B CN110763066 B CN 110763066B
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heat exchange
exchange tube
anticorrosive coating
waste heat
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CN110763066A (zh
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马增益
李文瀚
张艺颗
严建华
高若峰
陈哲
蔡亚明
钟浦城
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Zhejiang University ZJU
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Abstract

本发明公开了一种余热锅炉换热管，包括管体，所述管体的外表面喷涂有一层防腐涂层；所述防腐层的成分为Al2O3、CaAl2O4和Ca3(PO4)2。在纳米防腐涂层表面，HF与Al2O3，CaAl2O4和Ca3(PO4)2反应生成AlF3和Ca5(PO4)3F，紧密地包裹在涂层表面，从而有效阻止HF对涂层内部及换热管的腐蚀。同时，由于采用本发明特定组成的防腐涂层，从而使得本发明换热管可在600℃以上高温下耐氟腐蚀，最高可在1000℃以上高温下使用。

Description

余热锅炉换热管
技术领域
本发明涉及余热锅炉防腐蚀技术领域，特别是针对一种耐高氟烟气腐蚀的余热锅炉换热管。
背景技术
我国氟化工行业自上世纪五六十年代起步，经过60多年的快速发展，我国已成为世界最大的基础氟化工产品生产国和出口国。氟化工生产过程中，如产品脱氢、精炼等工序均会产生含氟有机高沸物等有机废液和废渣。这些废物中含氟量达到1％以上，最高的超过50％。含氟有机废弃物因为氟的存在而化学性质稳定，其中相当一部分属于不易降解的持久性生物累积毒性物质。这些废弃物具有高毒性、腐蚀性、持久性、生物积累性和远距离迁移性，引起生物体“三致”即致残、致畸、致突变，对生态环境和人体健康的危害具有长期性、潜伏性和难逆转性。因此，我国把这些氟化工产生的固体废物列入《国家危险废物名录》。
焚烧法作为一种高温下的氧化燃烧反应，可以用高温将可燃性有机物进行分解，具有减量大的优点。但是高含氟危险废物焚烧过程中，产生的高温烟气含有高浓度HF，会对余热锅炉换热面造成严重腐蚀，影响余热锅炉的安全运行。在《危险废物集中焚烧处置工程建设技术规范》(HJ/T176－2005)中危险废物处置系统一般要求6.1.3规定，“对于用来处理含氟较高或含氯大于5％的危险废物焚烧系统，不得采用余热锅炉降温…”。这与国家持续深化节能减排的国策是违背的，因此，如何突破高含氟固废焚烧余热利用过程中氟腐蚀的技术难题，回收烟气热量，产生蒸汽实现能源回收利用的同时，降低烟气温度，减少急冷塔用水，对氟化工行业的长远发展具有重要意义。
目前，耐氟腐蚀换热管一般采用在换热管表面涂覆一层氟塑料薄膜的方法。但由于氟塑料薄膜在高温下不稳定，一般只能在300℃工况下使用，从而限制了换热管的使用范围。
发明内容
本发明提供一种余热锅炉换热管，耐高氟烟气腐蚀，且可在600℃以上高温下耐氟腐蚀，最高可在1000℃以上高温下使用。
一种余热锅炉换热管，包括管体，所述管体的外表面喷涂有一层防腐涂层；所述防腐层的成分为Al2O3、CaAl2O4和Ca3(PO4)2。
管体为普通的换热管管体，比如3087碳钢管。
可选的，所述防腐层中Al2O3、CaAl2O4和Ca3(PO4)2各自的占比分别为80-90％，5-10％和5-10％。
可选的，所述防腐涂层的厚度为1-2mm。
可选的，所述防腐涂层的原料包括纳米氧化铝、铝酸钙和磷酸钙、纳米铝粉和纳米氧化铝溶胶。
所述的纳米氧化铝的粒径范围为10～30nm；所述的纳米铝粉的粒径范围为20～100nm；纳米氧化铝溶胶固含量为20～25％，粒度为10～15nm，pH值4～5；铝酸钙和磷酸钙纯度≥99％；五种原料可市购获得。
可选的，以质量份计，所述原料的配比为：40-50份纳米氧化铝，5-10份铝酸钙，5-10份磷酸钙，20-30份纳米铝粉；向上述原料混合物中加入10-20纳米氧化铝溶胶，使其分散均匀。
氧化铝、铝酸钙和磷酸钙与HF反应后生成物抱覆涂层表面，从而防止HF的进一步腐蚀；纳米铝粉起到增强涂层强度与韧性的作用；纳米氧化铝溶胶主要起到分散均匀的效果；
可选的，所述防腐涂层的喷涂方法包括：
所述管体的外表面经喷砂预处理；
所述原料混匀后的氧化铝溶胶混合物喷涂于经过喷砂预处理的换热管外表面；
经流平和低温烘烤后在所述管体外表面形成所述防腐涂层。
可选的，所述烘烤温度为200～300。
可选的，所述管体的内壁上设置环形肋片。
可选的，所述环形肋片由支撑柱安装于所述管体的内表面处，所述支撑柱依次贯穿所有环形肋片。
与现有技术相比，本发明至少具有如下有益效果：
(1)纳米氧化铝防腐涂层其化学组分包括Al2O3，CaAl2O4和Ca3(PO4)2。在纳米防腐涂层表面，HF与Al2O3，CaAl2O4和Ca3(PO4)2反应生成AlF3和Ca5(PO4)3F，紧密地包裹在涂层表面，从而有效阻止HF对涂层内部及换热管的腐蚀。
(2)同时，由于采用本发明特定组成的防腐涂层，从而使得本发明换热管可在600℃以上高温下耐氟腐蚀，最高可在1000℃以上高温下使用。
(3)该耐高氟烟气腐蚀的余热锅炉换热管内部采用环肋结构，增强了管内流体扰动换热。
附图说明
图1是本发明的换热管结果示意图。
图2是本发明换热管的换肋片示意图。
图3是本发明换热管的管壁结构图。
图4是防腐涂层成分的XRD定性成分分析结果图。
图5是HF烟气腐蚀后防腐层成分分析结果图(XRD)。
图中所示附图标记如下：
1-余热锅炉换热管 2-环形肋片 3-支撑柱
11-管体 12-防腐涂层
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
需要说明的是，当组件被称为与另一个组件“连接”时，它可以直接与另一个组件连接或者也可以存在居中的组件。当一个组件被认为是“设置于”另一个组件，它可以是直接设置在另一个组件上或者可能同时存在居中组件。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
如图1所示，一种实施方式中，余热锅炉换热管1包括管体12和管体表面的防腐涂层11，防腐涂层成分分析(定性)结果如图4所示，防腐层的化学组分包括Al2O3，CaAl2O4和Ca3(PO4)2。经计算，Al2O3，CaAl2O4和Ca3(PO4)2的占比(质量比)分别为80-90％，5-10％和5-10％。防腐涂层的厚度为1～2mm。
管体12可采用常规换热管管体的任意一种。比如3087碳钢管。
另一种实施方式中，管体内壁上设置环肋结构，环肋结构包括环形肋片2和支撑条3，环形肋片与管体同轴布置，环形肋片的环边宽度为4～6mm(即内环与外环之间的垂直间距)。
实施例1
纳米氧化铝防腐涂层3包括以下五种配料：纳米氧化铝、铝酸钙、磷酸钙、纳米铝粉和纳米氧化铝溶胶；所述纳米氧化铝的平均粒径为20nm，纯度≥99.9％；所述的纳米铝粉的平均粒径为50nm；纳米氧化铝溶胶平均粒度10～15nm，固含量为25％，pH值4；；所述铝酸钙和磷酸钙纯度≥99％。原料市购获得。
纳米氧化铝防腐涂层由以下质量份数的成分组成：纳米氧化铝50份，铝酸钙5份，磷酸钙5份，纳米铝粉20份。按比例混合的涂层配料加入20份纳米氧化铝溶胶，在球磨机中研磨2h得到均质相混合物。均质相混合物喷涂于经过喷砂预处理的换热管外表面，经过流平和低温(300℃)烘烤，在换热管1外表面形成2mm纳米防腐涂层3。
经计算，该实施例制备得到的换热管的防腐涂层中Al2O3，CaAl2O4和Ca3(PO4)2的占比(质量比)分别为90％，5％和5％。
实施例2
纳米氧化铝防腐涂层3包括以下五种配料：纳米氧化铝、铝酸钙、磷酸钙、纳米铝粉和纳米氧化铝溶胶；所述纳米氧化铝的平均粒径为20nm，纯度≥99.9％；所述的纳米铝粉的平均粒径为50nm；纳米氧化铝溶胶粒度10～15nm，固含量为25％，pH值4；；所述铝酸钙和磷酸钙纯度≥99％。
纳米氧化铝防腐涂层由以下质量份数的成分组成：纳米氧化铝40份，铝酸钙10份，磷酸钙10份，纳米铝粉30份。按比例混合的涂层配料加入10份纳米氧化铝溶胶，在球磨机中研磨2h得到均质相混合物。均质相混合物喷涂于经过喷砂预处理的换热管1外表面，经过流平和低温(300℃)烘烤，在换热管1外表面形成2mm纳米防腐涂层3。
经计算，该实施例制备得到的换热管的防腐涂层中Al2O3，CaAl2O4和Ca3(PO4)2的占比(质量比)分别为83.2％，8.4％和8.4％。
应用例
根据上述实施例1和2中方法制备得到的纳米防腐涂层，由于原料中使用了纳米氧化铝颗粒、纳米铝粉及纳米氧化铝溶胶，大幅增强了防腐涂层的强度与韧性。将涂有纳米防腐涂层的换热管放置于温度为600℃、HF含量为3000mg/L的烟气中，维持2个月后，换热管未被腐蚀。检测纳米防腐涂层成分如下图，HF与Al2O3，CaAl2O4和Ca3(PO4)2反应生成AlF3和Ca5(PO4)3F，紧密地包裹在涂层表面，从而有效阻止HF对涂层内部及换热管的腐蚀。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。不同实施例中的技术特征体现在同一附图中时，可视为该附图也同时披露了所涉及的各个实施例的组合例。
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。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (8)

1.余热锅炉换热管，包括管体，其特征在于，所述管体的外表面喷涂有一层防腐涂层；所述防腐涂层的成分为Al2O3、CaAl2O4和Ca3(PO4)2；所述防腐涂层中Al2O3、CaAl2O4和Ca3(PO4)2各自的占比分别为80-90％，5-10％和5-10％。
2.根据权利要求1所述余热锅炉换热管，其特征在于，所述防腐涂层的厚度为1-2mm。
3.根据权利要求1所述余热锅炉换热管，其特征在于，所述防腐涂层的原料包括纳米氧化铝、铝酸钙、磷酸钙、纳米铝粉和纳米氧化铝溶胶。
4.根据权利要求3所述余热锅炉换热管，其特征在于，以质量份计，所述原料的配比为：40-50份纳米氧化铝，5-10份铝酸钙，5-10份磷酸钙，20-30份纳米铝粉；向上述原料混合物中加入10-20份纳米氧化铝溶胶，使其分散均匀。
5.根据权利要求3或4所述余热锅炉换热管，其特征在于，所述防腐涂层的喷涂方法包括：
所述管体的外表面经喷砂预处理；
所述原料混匀后的氧化铝溶胶混合物喷涂于经过喷砂预处理的换热管外表面；
经流平和低温烘烤后在所述管体外表面形成所述防腐涂层。
6.根据权利要求5所述余热锅炉换热管，其特征在于，所述低温烘烤的温度为200～300℃。
7.根据权利要求1所述余热锅炉换热管，其特征在于，所述管体的内壁上设置环形肋片。
8.根据权利要求7所述余热锅炉换热管，其特征在于，所述环形肋片由支撑柱安装于所述管体的内表面处，所述支撑柱依次贯穿所有环形肋片。
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