CN104310961A - 复合陶瓷太阳能集热板及其制备方法 - Google Patents
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Abstract
本发明涉及复合陶瓷太阳能集热板及其制备方法,属于废弃物综合利用技术领域。本发明要解决的第一个技术问题是提供一种复合陶瓷太阳能集热板及其制备方法。本发明复合陶瓷太阳能集热板的制备方法,包括如下步骤:a、浆料的制备:将钒钛磁铁矿选钛矿尾矿、昔格达土和添加剂混合,得混合物料,然后将混合物料加水、球磨,得浆料;b、陈腐:将浆料陈腐24~48h;c、陶瓷生坯的制备:将陈腐后的浆料浇筑成型,得陶瓷生坯;d、一次干燥;e、复合坯的制备:将黑色陶瓷材料喷涂于干燥后的陶瓷生坯上,形成0.5~4mm的表层,得复合坯;f、二次干燥;g、烧结,即得复合陶瓷太阳能集热板。本发明复合陶瓷太阳能集热板成本低廉、工艺简单。
Description
技术领域
本发明涉及复合陶瓷太阳能集热板及其制备方法,属于废弃物综合利用技术领域。
背景技术
当电力、煤炭、石油等不可再生资源频频告急,如何开发太阳能资源,成为当今科研领域的重要课题。
常用的太阳能集热材料有以下三种:
(1)、铜质太阳能集热管:是采用焊接工艺将铜板经弯曲、焊接成集热管,然后在表面采用化学电镀或者直接喷涂太阳能吸收涂层。该集热器主要缺点是:铜是一种昂贵的金属,在焊缝处容易腐蚀;涂层在长期使用后,出现阳光吸收率衰减,使用寿命缩短。
(2)、真空玻璃管:真空玻璃管是由同轴内外玻璃管组成,一端封闭,内外管间为真空。内部玻璃管表面采用镀膜或者喷涂工艺覆盖太阳能吸收涂层。其内部结构为真空层、密封圈、防尘圈、尾托,该结构存在着阳光吸收面积只占采光投影面积的60%左右,在阳光直射时有大约40%阳光没有充分利用,故集热效率低。同时长期在高温条件下使用会导致密封圈氧化,真空度下降,保温效果降低。一头封闭的盲管结构由于水温高容易产生水垢使得热量交换能力下降。玻璃管通常采用硼硅玻璃制成,硼硅玻璃在1650℃生产,能耗较高,氧化硼的价格昂贵,因此,真空玻璃管集热器存在着生产成本高、能耗大、工艺复杂。吸收光面积减小等缺点。
(3)、公开号为CN101551172A的中国专利申请公开了一种复合陶瓷太阳能板。基体是普通陶瓷,表面是由提钒尾渣在1200℃烧结而成的中空陶瓷板,然而提钒尾渣中铁、镓等有价元素未加以利用,同时烧成温度高,对其大规模生产产生了制约。
因此,寻找一种成本较低、能耗小、工艺简单的太阳能板显得十分重要。
发明内容
本发明要解决的第一个技术问题是提供一种复合陶瓷太阳能集热板的制备方法。
本发明复合陶瓷太阳能集热板的制备方法,包括如下步骤:
a、浆料的制备:将钒钛磁铁矿选钛矿尾矿、昔格达土和添加剂混合,得混合物料,然后将混合物料加水、球磨,得浆料;
其中,混合物料中按质量比,钒钛磁铁矿选钛矿尾矿:昔格达土:添加剂=0~50:50~100:0.1~0.3,所述添加剂为碳酸钠或硅酸钠;按质量比,混合物料:水=40~60:40~10;
b、陈腐:将浆料陈腐24~48h;
c、陶瓷生坯的制备:将陈腐后的浆料浇筑成型,得陶瓷生坯;
d、一次干燥:干燥陶瓷生坯,至含水量<1%;
e、复合坯的制备:将黑色陶瓷材料喷涂于干燥后的陶瓷生坯上,形成0.5~4mm的表层,得复合坯;
f、二次干燥:将复合坯干燥,至含水量<1%;
g、将干燥的复合坯体烧结,即得复合陶瓷太阳能集热板。
进一步的,所述昔格达土的组成成分及含量优选为:SiO2 54.71~64.06%、Al2O3 11.10~19.03%、CaO 3.82~8.08%、MgO 1.20~2.85%、Na2O 0.58~1.21%、Fe2O3 2.82~3.65%、K2O2.82~3.65%;昔格达土粒径<0.355mm。
优选地,所述钒钛磁铁矿选钛矿尾矿的组分及含量为:TiO2 4.12~7.00%、Fe 10.50~13.10%、S 0.1~0.2%、SiO2 40.59~41.80%、CaO 11.59~13.14%、MgO 7.10~10.80%,其余为不可避免杂质;所述钒钛磁铁矿选钛矿尾矿粒度<0.18mm;钒钛磁铁矿选钛矿尾矿优选在使用先于1100℃煅烧5~10min。
进一步的,作为优选方案,所述a步骤混合物料中按质量比,钒钛磁铁矿选钛矿尾矿:昔格达土:添加剂=10~50:50~90:0.1~0.3;球磨时,球料比=2:1,球磨时间为18~24h。
进一步的,所述e步骤中黑色陶瓷材料在使用前,优选先加入水,球磨22~24h,再用于制备复合坯。进一步优选,按质量比,黑色陶瓷材料:水=10:6~7;球磨时,球料比为2:1。
优选地,所述e步骤中,喷涂压强为0.4~0.8MP。
进一步的,所述d步骤一次干燥和g步骤二次干燥的干燥温度优选小于40℃。
进一步的,作为优选方案,所述g步骤中烧结温度为1106~1140℃,烧结时间为6~40min;更优选为30~40min。
本发明要解决的第二个技术问题是提供一种复合陶瓷太阳能集热板,所述复合陶瓷太阳能集热板通过上述方法制备得到。
本发明有益效果:
1、本发明复合陶瓷太阳能集热板的烧结温度低,能耗低。
2、本发明复合陶瓷太阳能集热板成本低廉、工艺简单。
3、本发明复合陶瓷太阳能集热板吸光率高。
4、本发明用钒钛磁铁矿选钛矿尾矿为主要原料之一,属工业废渣综合利用,为难以处理的钒钛磁铁矿选钛矿尾矿找到了一条回收利用途径。
附图说明
图1 陶瓷生坯示意图;
图2 A-A剖视图;
图3 B-B剖视图;
图中标记:1—实心扁底边,2—扁底边陶瓷太阳板,3—黑瓷层或者太阳能吸收涂料。
具体实施方式
本发明复合陶瓷太阳能集热板的制备方法,包括如下步骤:
a、浆料的制备:将钒钛磁铁矿选钛矿尾矿、昔格达土和添加剂混合,得混合物料,然后将混合物料加水、球磨,得浆料;
其中,混合物料中按质量比,钒钛磁铁矿选钛矿尾矿:昔格达土:添加剂=0~50:50~100:0.1~0.3,所述添加剂为碳酸钠或硅酸钠;按质量比,混合物料:水=40~60:40~10;球磨时,球料比=2:1,球磨时间为18~24h;
b、陈腐:将浆料陈腐24~48h;
c、陶瓷生坯的制备:将陈腐后的浆料浇筑成型,得陶瓷生坯;
d、一次干燥:干燥陶瓷生坯,至含水量<1%;
e、复合坯的制备:将黑色陶瓷材料喷涂于干燥后的陶瓷生坯上,形成0.5~4mm的表层,得复合坯;
f、二次干燥:将复合坯干燥,至含水量<1%;
g、将干燥的复合坯体于1106~1140℃下保温烧结6~40min,即得复合陶瓷太阳能集热板。
其中,所述钒钛磁铁矿选钛矿尾矿是钒钛磁铁矿经采选,分离出铁精矿、钛精矿后剩余的选矿尾矿。昔格达土主要分布于四川南部金沙江、雅砻江、大渡河等河谷中,岩性下部以砾岩为主,岩性下部以砾岩为主,泥钙质胶结,成分复杂;中部为灰色、杂色条带状粘土岩与黄色细砂岩互层,其顶部为***厚层状钙质粘土岩,含介形虫、硅藻及孢粉等化石;上部以黄色厚,巨厚层细砂岩为主,夹杂色条带状粘土岩,含钙质结核。
优选地,所述钒钛磁铁矿选钛矿尾矿的组分及含量为:TiO2 4.12~7.00%、Fe 10.50~13.10%、S 0.1~0.2%、SiO2 40.59~41.80%、CaO 11.59~13.14%、MgO 7.10~10.80%,其余为不可避免杂质;;所述钒钛磁铁矿选钛矿尾矿粒度<0.18mm。所述昔格达土的组成成分及含量为:SiO2 54.71~64.06%、Al2O3 11.10~19.03%、CaO 3.82~8.08%、MgO 1.20~2.85%、Na2O 0.58~1.21%、Fe2O3 2.82~3.65%、K2O 2.82~3.65%。
进一步的,为了减小陶瓷烧结收缩率,以及减小球磨时间,所述钒钛磁铁矿选钛矿尾矿在使用先于1100℃煅烧5~10min,钒钛磁铁矿选钛矿尾矿粒度<0.18mm,昔格达土粒径<0.355mm。泥浆细度过粗,抗折强度低,造成较多的半成品破损,加工性能差。待别是双面吃浆产品及立浇座便器等在双面吃浆部位,易造成接触不实,分层而在烧成中出现分层或凸起等现象,同时在烧成过程中,颗粒间接触面少,瓷化不完全,产品吸水率大,易出现风惊、炸裂。
进一步的,作为优选方案,所述a步骤混合物料中按质量比,钒钛磁铁矿选钛矿尾矿:昔格达土:添加剂=10~50:50~90:0.1~0.3;
b步骤所述陈腐是指浆料放置在不透日光,不通空气的室内,储存一段时间,以利浆料的氧化和水解反应的进行,从而改善浆料的性能。
优选地,c步骤可以采用注浆成型法,包括常压注浆成型、高压注浆成型、真空注浆成型或者离心注浆成型的方法制备陶瓷生坯,陶瓷生坯如图1所示。
进一步的,e步骤黑色陶瓷材料的组成和制备方法见申请号为201410309800.1,发明名称为“黑色陶瓷材料及其制备方法”的中国专利申请。
进一步的,为了使得黑丝陶瓷材料分布更均匀,同时提高浆料的细度,所述黑色陶瓷材料在使用前,先加入水,球磨22~24h,再用于制备复合坯,其中,按质量比,黑色陶瓷材料:水=10:6~7;球磨时,球料比为2:1。为了使得复合坯的制备更加方便,可以采用压强为0.4~0.8MP的压枪喷涂。
d步骤一次干燥和g步骤二次干燥的干燥温度小于40℃。g步骤中保温烧结时间优选为30~40min。
下面结合实施例对本发明的具体实施方式做进一步的描述,并不因此将本发明限制在所述的实施例范围之中。
本发明实施例中所用所述昔格达土的组成成分及含量为:SiO2 54.71%、Al2O3 17.99%、CaO 4.36%、MgO 2.11%、Na2O 0.69%、Fe2O3 7.05%、K2O 3.65%,其余为不可避免杂质。钒钛磁铁矿选钛矿尾矿各组分及重量百分比为:TiO2 4.16%、Fe 7.89%、S 0.6%、SiO2 45.61%、CaO 10.89%、MgO 8.12%,其余为不可避免杂质。
实施例1
将昔格达土粉碎至粒度小于0.355mm,取粉碎后的昔格达土100克、0.3克工业纯碳酸钠和53毫升的水在球磨机内球磨20h。通过0.061mm的网筛过滤后,陈腐24小时。将泥浆通过注浆成型法制备中空太阳能板坯体,在25~28℃下自然干燥至含水量0.8%。取100克黑色陶瓷材料,60毫升水,放在球磨机内,按球料比2:1的比例球磨24h,取出球磨好的浆料,置于喷枪内,在干燥的中空太阳能板坯体表面上喷涂2mm。在室温下干燥喷涂后的中空太阳能陶瓷板24小时,得到含水量小于1%的中空太阳能陶瓷板。将此中空太阳能陶瓷板置于窑炉内1106℃烧结30min后随炉冷却,即得复合陶瓷太阳能集热板。
经测定,其阳光吸收率为0.9,壁厚2mm,耐压为0.2MP。
实施例2
将昔格达土粉碎至粒度小于0.355mm,将一定量的钒钛磁铁矿选钛矿尾矿在温度为1100℃煅烧10min,冷却至室温,再粉碎到粒度小于0.18mm,取粉碎后的昔格达土90克、取上述高温处理后的选钛矿尾矿10克,工业纯硅酸钠0.3克和49毫升的水,按球料比2:1的比例在球磨机内球磨24h。通过0.061mm的网筛过滤后,陈腐24小时。将泥浆通过注浆成型法制备中空太阳能板坯体,在25~28℃下自然干燥至含水量0.8%。取100克黑色陶瓷材料,加65毫升水,放在球磨机内,按球料比2:1的比例球磨24h,取出球磨好的浆料,置于喷枪内,在干燥的中空太阳能板坯体表面上喷涂2.5mm。在30℃下干燥喷涂后的中空太阳能陶瓷板24小时,得到含水量为0.7%的中空太阳能陶瓷板。于窑炉内1126℃烧结,在烧成温度保温38min后停止,随炉冷却至室温,即得复合陶瓷太阳能集热板。
经测定,其阳光吸收率为0.90,壁厚2.5mm,耐压为0.3MP。
实施例3
将昔格达土粉碎至粒度小于0.355mm,将一定量的钒钛磁铁矿选钛矿尾矿在温度为1100℃煅烧10min,冷却至室温,再粉碎到粒度小于0.18mm,取粉碎后的昔格达土50克、取上述高温处理后的选钛矿尾矿50克,工业纯碳酸钠0.2克和42毫升的水,按球料比2:1的比例在球磨机内球磨18h。通过0.061mm的网筛过滤后,陈腐24小时。将泥浆通过注浆成型法制备中空太阳能板坯体,在25~28℃下自然干燥至含水量0.75%。取100克黑色陶瓷材料,加70毫升水,放在球磨机内,按球料比2:1的比例球磨24h,取出球磨好的浆料,置于喷枪内,在干燥的中空太阳能板坯体表面上喷涂3.0mm。在28℃下干燥喷涂后的中空太阳能陶瓷板24小时,得到含水量为0.75%的中空太阳能陶瓷板。置于窑炉内1140℃烧结,在烧成温度保温30min后停止,随炉冷却至室温,即得复合陶瓷太阳能集热板。
经测定,其阳光吸收率为0.90,壁厚3mm,耐压为0.4MP。
Claims (10)
1.复合陶瓷太阳能集热板的制备方法,其特征在于,包括如下步骤:
a、浆料的制备:将钒钛磁铁矿选钛矿尾矿、昔格达土和添加剂混合,得混合物料,然后将混合物料加水、球磨,得浆料;
其中,所述混合物料中,按质量比,钒钛磁铁矿选钛矿尾矿:昔格达土:添加剂=0~50:50~100:0.1~0.3;所述添加剂为碳酸钠或硅酸钠;按质量比,混合物料:水=40~60:40~10;
b、陈腐:将浆料陈腐24~48h;
c、陶瓷生坯的制备:将陈腐后的浆料浇筑成型,得陶瓷生坯;
d、一次干燥:干燥陶瓷生坯,至含水量<1%;
e、复合坯的制备:将黑色陶瓷材料喷涂于干燥后的陶瓷生坯上,形成0.5~4mm的表层,得复合坯;
f、二次干燥:将复合坯干燥,至含水量<1%;
g、将干燥的复合坯体烧结,即得复合陶瓷太阳能集热板。
2.根据权利要求1所述的复合陶瓷太阳能集热板的制备方法,其特征在于,所述昔格达土的组分及含量为:SiO254.71~64.06%、Al2O311.10~19.03%、CaO 3.82~8.08%、MgO 1.20~2.85%、Na2O 0.58~1.21%、Fe2O32.82~3.65%、K2O 2.82~3.65%;昔格达土粒径<0.355mm。
3.根据权利要求1或2所述的复合陶瓷太阳能集热板的制备方法,其特征在于:所述钒钛磁铁矿选钛矿尾矿的组分及含量为:TiO24.12~7.00%、Fe 10.50~13.10%、S 0.1~0.2%、SiO240.59~41.80%、CaO 11.59~13.14%、MgO 7.10~10.80%,其余为不可避免杂质;所述钒钛磁铁矿选钛矿尾矿粒度<0.18mm;钒钛磁铁矿选钛矿尾矿在使用先于1100℃煅烧5~10min。
4.根据权利要求1~3任一项所述的复合陶瓷太阳能集热板的制备方法,其特征在于:所述a步骤混合物料中按质量比,钒钛磁铁矿选钛矿尾矿:昔格达土:添加剂=10~50:50~90:0.1~0.3;球磨时,球料比=2:1,球磨时间为18~24h。
5.根据权利要求1~4任一项所述的复合陶瓷太阳能集热板的制备方法,其特征在于:所述e步骤中黑色陶瓷材料在使用前,先加入水,球磨22~24h,再用于制备复合坯;其中,按质量比,黑色陶瓷材料:水=10:6~7;球磨时,球料比为2:1。
6.根据权利要求1~5任一项所述的复合陶瓷太阳能集热板的制备方法,其特征在于:所述e步骤中,喷涂压强为0.4~0.8MP。
7.根据权利要求1~6任一项所述的复合陶瓷太阳能集热板的制备方法,其特征在于:所述d步骤一次干燥和g步骤二次干燥的干燥温度均小于40℃。
8.根据权利要求1~7任一项所述的复合陶瓷太阳能集热板的制备方法,其特征在于:所述g步骤中烧结温度为1106~1140℃,烧结时间为6~40min。
9.根据权利要求8所述的复合陶瓷太阳能集热板的制备方法,其特征在于:烧结时间为30~40min。
10.权利要求1~7任一项所述方法制备得到的复合陶瓷太阳能集热板。
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