CN113831587A - 光热转换胶乳海绵及其制备方法和应用 - Google Patents
光热转换胶乳海绵及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开一种光热转化胶乳海绵及其制备方法和应用，制备方法包括以下步骤：将光热转换填料制备为水分散体；将光热转换填料水分散体加入胶乳中混合，制备具有孔隙的胶乳海绵；将所述胶乳海绵浸入水凝胶溶液中，使所述水凝胶溶液在所述孔隙中发生交联反应形成凝胶，即可得到光热转化胶乳海绵。光热转化胶乳海绵由所述方法制备而成，可应用于污水处理领域、海水淡化领域、光热发电领域和光热储能领域。本发明提供的光热转换胶乳海绵具有高效的水蒸发能力，其吸收范围宽、隔热性能优良，水运输通道畅通且亲水性高。
Description
技术领域
本发明涉及光热材料技术领域，尤其涉及一种光热转换胶乳海绵及其制备方法和应用。
背景技术
太阳能是一种取之不尽用之不竭的绿色清洁能源，采用光热材料将太阳能转换为热能进行水分蒸发是一种高效节能的方法，该方法被广泛应用于海水淡化、污水处理、光热发电、光热储能等众多领域。目前光热转换材料的研究主要集中在纳米流体光热转换材料和水气界面光热转换材料这两种。纳米流体光热转换材料的工作原理是指将光热颗粒材料分散在水中，通过光热转换对水体加热产生蒸汽，由于是对整个水体进行加热，因此，存在能量损耗大、转换效率较低的问题。水气界面光热转换材料是二维或三维的光热材料，其可以自漂浮在水气界面，通过光热转换使热量局域在空气-水界面驱动界面水蒸发，由于是对水体表层加热，因此光热转换效率高、热损耗小，是目前研究的重点。
其中影响水气界面材料光热转换效率的因素主要有以下四个方面：
第一，材料的光吸收范围和光热性能。若材料光吸收范围越大，光热性能越好，则光热转换效率越高。
第二，材料的隔热性能。若材料的导热系数越低，热损失越小，则水蒸发效率越高。
第三，水的运输通路是否畅通。
第四，材料的亲水性。若材料的亲水性越好，水的运输越快，则水蒸发效率越高。
其中，对于水气界面光热转换材料而言，光吸收范围和光热性能主要由光热转化填料来决定，而材料的隔热性能，水通路以及亲水性能则主要由基材来决定，目前主要限制水气界面光热转换材料发展的是基材的选择，国内外关于界面光热材料基体材料的研究主要有炭化木材、炭化萝卜、纱布、滤纸、双层膜等，但这些基体材料要么成本较高，要么耐久性差，转换效率低，难以大规模的生产应用。
发明内容
本发明的目的在于克服现有技术中所述的缺陷，从而提供一种光热转换胶乳海绵及其制备方法和应用，该光热转换胶乳海绵具有高效的水蒸发能力，其吸收范围宽、隔热性能优良，水运输通道畅通且亲水性高。其制备方法简单，适用于制胶废水等的污水处理或海水淡化领域。
为了实现上述目的，本发明提供如下技术方案：
一种制备光热转化胶乳海绵的方法，包括以下步骤：
将光热转换填料制备为水分散体；
将光热转换填料水分散体加入胶乳中混合，制备具有孔隙的胶乳海绵；
将所述胶乳海绵浸入水凝胶溶液中，使所述水凝胶溶液在所述孔隙中发生交联反应形成凝胶，即可得到光热转化胶乳海绵。
作为一种可实施的方式，所述光热转换填料为碳、半导体或具有共轭结构的高聚物中的一种或几种。
作为一种可实施的方式，所述碳为炭黑、石墨烯、碳纳米管中的一种或几种。
作为一种可实施的方式，所述半导体为三氧化二钛、二硫化钼、硫化铜或黑磷中的一种或几种。
作为一种可实施的方式，所述具有共轭结构的高聚物为聚多巴胺、聚吡咯、聚苯胺中的一种或几种。
作为一种可实施的方法，所述胶乳为配合胶乳，包括以下重量份的原料：
胶乳原料100份、硫磺2-4份、促进剂1-4份、防老剂1-2份、表面活性剂0.5-2份、氢氧化钾0-0.2份。
作为一种可实施的方法，所述配合胶乳的制备方法为：
将所述硫磺、促进剂、防老剂、发泡剂分别制备为20-60wt％的水分散体；
向所述胶乳原料中加入硫磺水分散体、促进剂水分散体、防老剂水分散体、表面活性剂和氢氧化钾进行搅拌，得配合胶乳。
作为一种可实施的方式，所述胶乳海绵的制备方法为：先将所述胶乳与所述光热转换填料水分散体进行混合，然后加入表面活性剂，并通过机械搅拌的方式混入空气打发，再加入氧化锌水分散体和硅氟化钠水分散体对泡沫胶乳进行胶凝制得泡沫凝胶，将所述泡沫凝胶经硫化、干燥而制得胶乳海绵；
其中，所述光热转换填料水分散体中光热转换填料的添加量为1-20份，所述表面活性剂的用量为0.5-2份，所述氧化锌水分散体中氧化锌的添加量为2-4重量份，所述硅氟化钠水分散体中硅氟化钠的添加量为1-3重量份。
作为一种可实施的方式，所述胶乳海绵的制备方法为：先将所述胶乳与所述光热转换填料水分散体进行混合，再加入有机发泡剂进行化学发泡制得泡沫凝胶，然后将所述泡沫凝胶经硫化、干燥制得胶乳海绵；其中，所述光热转换填料水分散体中光热转换填料的添加量为1-20份，所述有机发泡剂为过氧化氢和/或碳酸氢铵。
作为一种可实施的方式，所述水凝胶为聚丙烯酰胺和/或聚乙烯醇。
一种光热转换胶乳海绵，由上述方法制备而成。
一种光热转换胶乳海绵，包括具有多孔结构的海绵本体，所述海绵本体内分布有光热转换填料，所述多孔结构为水运输通道，所述水运输通道中填充有水凝胶。
一种光热转换胶乳海绵在污水处理领域、海水淡化领域、光热发电领域和光热储能领域的应用。
与现有技术相比，本发明具有以下有益效果：
本发明提供的光热转化胶乳海绵主要由胶乳、光热转换填料和水凝胶制备而成，其中在制备的过程中，将胶乳与光热转换填料混合制备成胶乳海绵，其中胶乳海绵具有泡孔结构且泡孔结构为全部连孔或绝大部分连孔少部份不连孔，这些多孔结构一方面为水的运输提供通道，另一方面可使封存在泡孔内的气体具有极低的热传导系数，阻止热量的耗散，从而提高水蒸发效率。另外胶乳海绵其自身具有良好自漂性、吸收震动性和耐压缩抗疲劳性，其可以以较大的表面积漂浮在水面，相应地，分布于胶乳中的光热转化填料为碳、半导体或者具有共轭结构的高聚物，它们具有较宽的光吸收范围和较强的吸光能力；胶乳海绵虽然具有丰富的孔隙结构，可以为水提供自下而上的运输通路，但由于其具有疏水性，水的传输较慢，影响水蒸发效率。因此，本申请在制备过程中，将胶乳海绵浸泡于水凝胶溶液中，使水凝胶溶液在孔隙中发生交联反应形成凝胶，从而大大提高水运输的速度，和水的蒸发效率。
具体实施方式
下面将对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例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。
此外，下面所描述的本发明不同实施方式中所涉及的重量份若未做特殊说明，则1份均代指1g。需要说明的是，胶乳原料由海南橡胶集团公司提供；防老剂为2，6-二叔丁基对甲酚。
胶乳发泡剂就是使对象物质成孔的物质，它可分为化学发泡剂和物理起泡剂两大类。化学发泡剂是那些经加热分解后能释放出二氧化碳和氮气等气体，并在胶料中形成泡沫的化合物；物理起泡剂是帮助胶乳在机械搅拌的作用下产生泡沫的物质。物理起泡剂是属于表面活性剂，能有效降低液体的表面张力，并在液膜表面双电子层排列而包围空气，形成气泡，再由单个气泡组成泡沫。在本申请既可以采用物理发泡也可以采用化学发泡制备胶乳海绵。
实施例1
本发明提供了一种光热转化胶乳海绵，包括以下重量份的原料：
胶乳原料100份、硫磺2份、促进剂4份、防老剂1份、发泡剂0.5份；光热转换填料1份、氧化锌2份、硅氟化钠1份。其中，本实施例中的光转换填料为半导体，例如三氧化二钛、二硫化钼、硫化铜或黑磷；水凝胶为聚丙烯酰胺和/或聚乙烯醇。
S1、按上述重量份将硫磺、促进剂、防老剂、硅氟化钠、氧化锌和光热转换剂分别用去离子水配制成50wt％的水分散体；
S2、向胶乳原料中加入硫磺水分散体、促进剂水分散体、防老剂水分散体，制备成配合胶乳；
S3、将配合胶乳与光热转换填料水分散体混合均匀，然后加入表面活性剂，并通过起泡机进行机械起泡，起泡过程再加入氧化锌水分散体、硅氟化钠水分散体，得到泡沫胶乳；
S4、将泡沫胶乳经过注模、胶凝、硫化、脱模、水洗、干燥，制得黑色的具有孔隙的胶乳海绵；
S5、将黑色的胶乳海绵浸泡于水凝胶溶液中，使水凝胶溶液渗入胶乳孔隙中，并在海绵的孔隙中交联反应形成凝胶，放入烘箱干燥，得到具有高效水蒸发效率的光热转化胶乳海绵。
由该方法制备而成的光热转化胶乳海绵包括具有多孔结构的海绵本体，所述海绵本体内分布有光热转换填料，多孔结构形成水运输通道，水运输通道中填充水凝胶。
本发明将具有优异隔热性能的多孔胶乳海绵与光热转换填料和水凝胶复合，制备的光热转化胶乳海绵具有高效水蒸发效率，可应用于制胶废水等污水处理、海水淡化等领域。
实施例2
与实施例1不同的是，本实施例的光热转化胶乳海绵，包括以下重量份的原料：
胶乳原料100份、硫磺4份、促进剂1份、防老剂2份、有机发泡剂2份、氢氧化钾0.2份；光热转换填料20份、氧化锌4份、硅氟化钠3份。其中，本实施例中的光转换填料为具有共轭结构的高聚物，例如聚多巴胺、聚吡咯、聚苯胺；水凝胶为聚丙烯酰胺。
本实施例胶乳海绵的制备方法为先将配合胶乳与光热转换填料水分散体进行混合，再加入等比例混合的过氧化氢和碳酸氢铵进行化学发泡制得泡沫凝胶，然后将泡沫凝胶经硫化、干燥制得胶乳海绵。
实施例3
与实施例1不同的是，本实施例的光热转化胶乳海绵，包括以下重量份的原料：
胶乳原料100份、硫磺3份、促进剂2.5份、防老剂1.5份、表面活性剂1份、氢氧化钾0.1份；光热转换填料10份、氧化锌3份、硅氟化钠2份。其中，本实施例中的光转换填料为炭黑；水凝胶为聚丙烯酰胺。
实施例4
与实施例3不同的是，本实施例的光热转化胶乳海绵中光转换填料为多壁碳纳米管。
实施例5
与实施例3不同的是，本实施例的光热转化胶乳海绵中光转换填料为石墨烯。
对比例
与实施例3不同的是，所制得的黑色胶乳海绵没有浸泡于水凝胶中，而是直接使用。
下面将分别对实施例3-5以及对比例进行检测，检测指标包括导热系数、吸水性能和光热转换效率，其中导热系数越大，则保温性能差，散热越大，光热转化胶乳海绵的转换越低；亲水性能由接触角来表征，接触角越小，说明被测部位的亲水性越好，运用于本申请中，则代指水自下而上的运输速度越快，吸水性能好。检测结果如下表所示：
由上表可以看出，对比例中没有复合水凝胶，其光热转换效率仅达到81％，而实施例3-5中复合有水凝胶的光热转化胶乳海绵的光热转换效率均达到90％以上，其中以实施例5的光热转换效率为最高，这说明光热转换填料自身的性能也会影响光热转换效率，与石墨烯复合的胶乳海绵的光热转换效率高于与多壁碳纳米管复合的胶乳海绵的光热转换效率，高于与炭黑复合的胶乳海绵的光热转换效率。
以上所述仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。
Claims (10)
1.一种制备光热转化胶乳海绵的方法，其特征在于，包括以下步骤：
将光热转换填料制备为水分散体；
将光热转换填料水分散体加入胶乳中混合，制备具有孔隙的胶乳海绵；
将所述胶乳海绵浸入水凝胶溶液中，使所述水凝胶溶液在所述孔隙中发生交联反应形成凝胶，即可得到光热转化胶乳海绵。
2.根据权利要求1所述的方法，其特征在于，所述光热转换填料为碳、半导体或具有共轭结构的高聚物中的一种或几种。
3.根据权利要求2所述的方法，其特征在于，所述碳为炭黑、石墨烯、碳纳米管中的一种或几种；所述半导体为三氧化二钛、二硫化钼、硫化铜或黑磷中的一种或几种；所述具有共轭结构的高聚物为聚多巴胺、聚吡咯、聚苯胺中的一种或几种。
4.根据权利要求1所述的方法，其特征在于，所述胶乳为配合胶乳，包括以下重量份的原料：
胶乳原料100份、硫磺2-4份、促进剂1-4份、防老剂1-2份、氢氧化钾0-0.2份。
5.根据权利要求4所述的方法，其特征在于，所述配合胶乳的制备方法为：
将所述硫磺、促进剂、防老剂分别制备为20-60wt％的水分散体；
向所述胶乳原料中加入硫磺水分散体、促进剂水分散体、防老剂水分散体和氢氧化钾进行搅拌，得配合胶乳。
6.根据权利要求1-5中任一项所述的方法，其特征在于，所述胶乳海绵的制备方法为：先将所述胶乳与所述光热转换填料水分散体进行混合，然后加入表面活性剂，并通过机械搅拌的方式混入空气打发，再加入氧化锌水分散体和硅氟化钠水分散体对泡沫胶乳进行胶凝制得泡沫凝胶，将所述泡沫凝胶经硫化、干燥而制得胶乳海绵；
其中，所述光热转换填料水分散体中光热转换填料的添加量为1-20份，所述表面活性剂的用量为0.5-2份，所述氧化锌水分散体中氧化锌的添加量为2-4重量份，所述硅氟化钠水分散体中硅氟化钠的添加量为1-3重量份。
7.根据权利要求1-5中任一项所述的方法，其特征在于，所述胶乳海绵的制备方法为：先将所述胶乳与所述光热转换填料水分散体进行混合，再加入有机发泡剂进行化学发泡制得泡沫凝胶，然后将所述泡沫凝胶经硫化、干燥制得胶乳海绵；其中，所述光热转换填料水分散体中光热转换填料的添加量为1-20份，所述有机发泡剂为过氧化氢和/或碳酸氢铵。
8.根据权利要求1所述的方法，其特征在于，所述水凝胶为聚丙烯酰胺和/或聚乙烯醇。
9.一种光热转换胶乳海绵，其特征在于，包括具有多孔结构的海绵本体，所述海绵本体内分布有光热转换填料，所述多孔结构为水运输通道，所述水运输通道中填充有水凝胶。
10.一种如权利要求1-9中任一项所述的热转换胶乳海绵在污水处理领域、海水淡化领域、光热发电领域和光热储能领域的应用。
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| CN114752075A (zh) * | 2022-03-08 | 2022-07-15 | 武汉工程大学 | 一种硫化铜-石墨烯-聚苯胺复合水凝胶的制备方法 |
| CN114752075B (zh) * | 2022-03-08 | 2024-03-22 | 武汉工程大学 | 一种硫化铜-石墨烯-聚苯胺复合水凝胶的制备方法 |
| CN115260612A (zh) * | 2022-06-17 | 2022-11-01 | 中国科学院青岛生物能源与过程研究所 | 一种高光热转化效率的木质纤维基泡沫材料及制备和应用 |
| CN115260611A (zh) * | 2022-06-17 | 2022-11-01 | 中国科学院青岛生物能源与过程研究所 | 一种高光热转化效率的可降解生物基泡沫材料及制备和应用 |
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