CN109843829A - 陶瓷组合物和作为热回收单元的一部分的包含所述陶瓷组合物的材料 - Google Patents

陶瓷组合物和作为热回收单元的一部分的包含所述陶瓷组合物的材料 Download PDF

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CN109843829A
CN109843829A CN201780046883.1A CN201780046883A CN109843829A CN 109843829 A CN109843829 A CN 109843829A CN 201780046883 A CN201780046883 A CN 201780046883A CN 109843829 A CN109843829 A CN 109843829A
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ceramic composition
pipe
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CN109843829B (zh
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R·埃拉纳·赫南多
M·普瑞萨·艾尔瑞
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Abstract

本发明涉及陶瓷组合物、和包含涂层形式的陶瓷组合物与钢基材的材料。另外，本发明涉及获得所述材料的方法及其作为热回收单元的一部分的用途。

Description

陶瓷组合物和作为热回收单元的一部分的包含所述陶瓷组合 物的材料
技术领域
本发明涉及陶瓷组合物、和包含涂层形式的陶瓷组合物与钢基材的材料。另外，本发明涉及获得所述材料的方法及其作为热回收单元的一部分的用途。
背景技术
热回收装置的目的是回收废热并重复使用。热回收锅炉，特别是其中所含的管子受到化学腐蚀的影响，所述化学腐蚀是由于暴露于烟雾、灰烬、烟灰和焦炭颗粒而粘附在管表面上并导致热回收单元的化学腐蚀和效率损失。对于许多工业设施而言，火侧污染是一个主要的操作问题。整个对流区域都会发生污垢。活性表面上的灰烬和烟灰沉积引起高温下的化学腐蚀和热传递损失，这降低了锅炉的操作效率。
目前使用几种不同的清洁方法来清洁灰沉积物的对流区，包括离线水力喷射、在线水力喷射、在线炸药清洁、吹灰器和声波喇叭。根据工作条件的严重程度，清洁方法的安排频率不同，但在所有情况下都是昂贵的方法。
由于上述原因，需要在严酷的腐蚀性和高温环境下开发更长寿命的热回收单元管，以避免烟雾、灰烬、烟灰和焦炭颗粒的粘附。
发明概述
本发明的第一方面涉及陶瓷组合物(本文是“本发明陶瓷组合物”)，其特征在于它包含相对于最终陶瓷组合物以下列等效氧化物表示的重量百分比：
·在54％至66％的SiO2,
·在10％至20％的Cr2O3,
·在3％至12％的Na2O和
·在3％至12％的ZrO2。
在优选的实施方案中，本发明的组合物包含至多10％的选自Al2O3、B2O3、BaO、CaO、CoO、K2O、Li2O、MnO2、TiO2或其任意组合的氧化物。
优选地，本发明的组合物包含相对于最终陶瓷组合物以下列等效氧化物表示的重量百分比：
·在54％至66％的SiO2,
·在12％至20％的Cr2O3,
·在5％至12％的Na2O和
·在5％至12％的ZrO2。
本发明的另一方面涉及材料(本文“本发明的材料”)，其特征在于它包含作为本发明的均匀涂层份上述陶瓷组合物和钢基材。
优选地，陶瓷涂层的厚度在50μm和300μm之间。更优选地，其厚度在100μm和160μm之间。
在烧结过程中，由于基材的脱气和涂层中的内部反应，在涂层中产生小气泡的无定形结构。因此，涂层中的孔隙率水平高于面积的10％；优选地，孔隙率在15％和35％之间。
气泡的存在不会影响本发明材料的耐化学性，但是它令人愉悦地提高了本发明材料的弹性、拉伸强度和耐刮擦性的机械性能。
在本发明的优选实施方案中，基材是管，并且上述陶瓷组合物沉积在其表面的至少一个上。陶瓷组合物可以沉积在管的内表面、管的外表面上或管的内表面和外表面上。优选地，陶瓷组合物沉积在管的外表面上。
本发明的另一方面涉及获得本发明材料的方法，该方法包括以下步骤：
a)制备如前所述的本发明的陶瓷组合物和溶剂的悬浮液，所述悬浮液的平均粒度为40μm至200μm，
b)预处理基材的至少一个表面，
c)将步骤(a)中获得的悬浮液沉积到步骤(b)的预处理表面上，
(d)干燥步骤(c)中获得的涂层，和
(e)将步骤(d)中获得的材料在700℃至1000℃的温度下烧结。
步骤(a)涉及制备前述陶瓷组合物和溶剂的悬浮液，所述悬浮液的平均粒度为40μm-200μm。
在优选的实施方案中，陶瓷组合物的重量百分比相对于最终悬浮液为65％至75％。
在另一个优选的实施方案中，溶剂的重量百分比相对于最终悬浮液为25％至35％。
步骤(a)的溶剂优选为水。悬浮液是平滑且均匀的糊状物，平均粒径为40μm至200μm。
优选地，通过研磨硼硅酸盐玻璃、粘土、硼砂、亚硝酸钠和水来获得悬浮液。
应该在沉积玻璃料之前对基材的表面进行预处理。非常重要的是保证清洁表面没有污染物、外部颗粒和/或化学残留物，以在陶瓷涂层和基材之间获得良好的粘合/粘附。表面预处理可以是喷丸、喷砂、酸洗和钝化。优选地，步骤(b)通过喷丸处理进行。
步骤(c)是指将步骤(a)中获得的悬浮液沉积到步骤(b)的预处理表面上。可以在步骤(c)中使用任何适用的沉积技术，即与制造工艺兼容的任何竞争性沉积技术；优选电泳沉积(EPD)、浸渍、瀑布玻璃和喷涂。更优选地，步骤(c)通过喷雾执行。
步骤(c)的沉积过程应沿着基材提供均匀的涂层，例如沿着管长度，确保适当的表面润湿和过量悬浮液的排出。
下一步，步骤(d)是指在50℃至150℃的受控温度下完全干燥步骤(c)中得到的涂层以通过常规的加热系统基于对流、传导、电阻、辐射或感应技术去除残留的湿度。优选地，步骤(d)在70℃至120℃的温度下进行。
本发明的方法在步骤(e)中获得的材料在700℃至1000℃的温度下烧结完成；将步骤(d)中获得的材料逐渐加热直至达到烧结温度。闭环系统在烧结过程中保持温度恒定。烧结温度范围在700℃到1000℃之间，与最终涂层材料的机械和化学性质密切相关；选择烧结温度以提供最终材料，以在热回收单元的工作条件下获得最佳性能。优选地，烧结温度范围为850℃至950℃。请注意，烧结温度公差在指定设定点附近±30℃，最好为±10℃。此外，可以应用自然或强制冷却程序，优选在室温下自然冷却。
本发明的材料由钢基材和陶瓷组合物形成，以下列等效氧化物表示：
·在54％至66％的SiO2,
·在10％至20％的Cr2O3,
·在3％至12％的Na2O和
·在3％至12％的ZrO2。
如前所述，优选地，本发明的材料包含涂层形式的陶瓷组合物，所述陶瓷组合物包含至多10％的选自Al2O3、B2O3、BaO、CaO、CoO、K2O、Li2O、MnO2、TiO2或其任意组合的氧化物
更优选地，本发明的材料包含涂层形式的陶瓷组合物，具有相对于最终陶瓷涂层以下列等效氧化物表示的重量百分比：
·在54％至66％的SiO2,
·在12％至20％的Cr2O3,
·在5％至12％的Na2O和
·在5％至12％的ZrO2
本发明的最后一个方面涉及使用本发明的材料作为热回收单元的一部分，在400℃至750℃的金属温度下工作。优选地，热回收单元是从锅炉或焚烧炉中选择的。热回收单元可以是城市垃圾焚烧炉、废物回收锅炉和生物质锅炉。
本发明的管具有以下优点：
管易于清洁，从而降低了清洁和维护成本。
管具有防污性能、高耐腐蚀性、高侵蚀性、耐磨性。
管的寿命期望更长。
灰烬不会粘在管子上，因此热转移不会随着时间的推移而显着受到影响，可以显着或几乎避免清洁，并且可以实现由于管清洁而显着降低成本。
通过使用本发明的管获得了热回收热效率的提高。
除非另外定义，否则本文使用的所有技术和科学术语具有与本发明所属领域的普通技术人员通常理解的含义相同的含义。与本文描述的那些类似或等同的方法和材料可用于实施本发明。在整个说明书和权利要求书中，词语“包括”及其变体并不旨在排除其他技术特征、添加剂、组分或步骤。通过阅读说明书，本发明的其它目的，优点和特征对于本领域技术人员来说将变得显而易见，或者可以通过本发明的实践来学习。以下实施例，附图是以说明的方式提供的，并不意图限制本发明。
附图简述
图1.基材和陶瓷涂层的光学显微镜图。.
图2.通过SEM-EDX技术分析陶瓷涂层的化学组成的映射结果。
图3.在480℃下进行六次热循环后样品的目视检查。
图4.陶瓷涂层管与非陶瓷涂层管在城市垃圾焚烧炉中使用两年后的比较。
实施例
实施例1
通过研磨Keracoat SL RT100(64％-66％)的市售硅酸盐、粘土(3％-3.7％)、硼砂(0.15％)、亚硝酸钠(0.15％)和水(30％-31.7％)的混合物获得悬浮液。形成光滑均匀的糊状物并将其筛分以获得40μm和200μm之间的平均粒度。
陶瓷组合物特此以下列等效氧化物表示：
61％的SiO2,
16％的Cr2O3,
6％的Na2O,
7％的ZrO2
2％B2O3,
2％Al2O3和
3％TiO2。
将该悬浮液沉积在不锈钢管的外表面上。通过喷丸预处理管的外表面以保证清洁表面以使陶瓷涂层与钢基材良好粘合。将悬浮液喷雾到预处理的表面上，并在85℃的控制温度下通过对流完全干燥。最后，烧结在900℃下进行。
图1显示了涂层厚度测量的结果。通过光学显微镜可以观察到111.0μm、114.4μm和119.7μm的厚度值，如图1所示。
陶瓷涂层使管的硬度大大增加，涂层中的维氏硬度(HV)为724，基材中为155。
使用SEM-EDX技术分析陶瓷组合物的化学组成。显示涂层中存在的主要化学元素的映射结果如图2所示。
SEM定性分析：Na、Mg、Ca、Al、Cr、Si、Zn和Zr氧化物。
沉积在钢基材上的陶瓷涂层的耐热性已经在480℃下在1小时内进行了六次热循环检查，目视检查后涂层上没有缺陷或变质的迹象(见图3)。
在基板上和涂层上在480℃下进行6个热循环1小时后测量粗糙度。涂层区域的粗糙度为0.9μmm RA，基板上的粗糙度为6.13μm RA。
此外，涂有上述陶瓷涂层的一系列不锈钢管已暴露于真实条件下，作为城市垃圾焚烧炉的加热器的一部分2年。这座城市垃圾焚烧炉的工作条件是：
蒸汽温度:300℃
压力:170bar
烟气温度:850℃
管的内部流体介质:蒸汽
管的外部流体介质:废物到能源烟雾
其他说明:碱性灰烬
化学分析表明，灰分的主要成分是：二氧化硅、铝、铁和钙；次要成分是钛、镁、钠、钾或磷酸盐；极少量的钡、锶、铷；和重金属，如锌、铜、铅、铬、镍或镉。
图4显示(从左到右)：
两年前安装的本发明的涂层管，然后用手洗，
刚安装的本发明的涂层管，和
两年前安装了两个管子(没有涂层)，并进行了喷丸处理。
如图4所示，灰分很容易从本发明的涂覆管中除去，此外，可以注意到涂层没有变质。

Claims (16)

1.乙酰基组合物，其特征在于，它包含相对于最终陶瓷组合物以下列等效氧化物表示的重量百分比：
·在54％至66％的SiO2,
·在10％至20％的Cr2O3,
·在3％至12％的Na2O和
·在3％至12％的ZrO2。
2.根据权利要求1所述的陶瓷组合物，其包含至多10％的选自Al2O3、B2O3、BaO、CaO、CoO、K2O、Li2O、MnO2、TiO2或其任意组合的氧化物。
3.根据权利要求1或2中任一项所述的陶瓷组合物，其特征在于，其包含相对于最终陶瓷涂层以下列等效氧化物表示的重量百分比：
·在54％至66％的SiO2,
·在12％至20％的Cr2O3,
·在5％至12％的Na2O和
·在5％至12％的ZrO2。
4.材料，其特征在于，它包含根据权利要求1至3中任一项所述的陶瓷组合物和钢基材。
5.根据权利要求4所述的材料，其中所述陶瓷组合物的厚度为100μm至160μm。
6.根据权利要求4或5中任一项所述的材料，其中所述陶瓷组合物的孔隙率高于面积的10％，优选孔隙率为15％至35％。
7.根据权利要求4至6中任一项所述的材料，其中所述基材是管，并且其中所述陶瓷组合物沉积在选自所述管的内表面或所述管的外表面的以下表面中的至少一个上。
8.根据权利要求7所述的材料，其中所述基材是管，并且其中所述陶瓷组合物沉积在所述管的外表面上。
9.一种获得根据权利要求4至8中任一项所述材料的方法，其特征在于包括以下步骤：
a)制备相对于最终悬浮液的重量百分比为65％至75％的根据权利要求1至3中任一项所述的陶瓷组合物的悬浮液，并且溶剂相对于最终悬浮液的重量百分比为25％至35％，所述悬浮液的平均粒径为40μm至200μm，
b)预处理所述基材的至少一个表面，
c)将步骤(a)中获得的悬浮液沉积到步骤(b)的预处理的表面上，
(d)干燥步骤(c)中获得的涂层，和
(e)将步骤(d)中获得的材料在700℃至1000℃的温度下烧结。
10.根据权利要求9所述的方法，其中步骤(a)的溶剂是水。
11.根据权利要求9和10中任一项所述的方法，其中步骤(b)通过喷丸处理执行。
12.根据权利要求9-11中任一项所述的方法，其中步骤(c)通过电泳沉积(EPD)、浸渍、瀑布玻璃或喷涂执行。
13.根据权利要求12所述的方法，其中步骤(c)通过喷雾执行。
14.根据权利要求9-13中任一项所述的方法，其中步骤(e)在850℃至950℃的温度下执行。
15.根据权利要求4至8中任一项所述的材料作为在400℃至750℃的金属温度下工作的热回收单元的一部分的用途。
16.根据权利要求15所述的材料的用途，其中所述热回收单元选自锅炉或焚烧炉。
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