CN111499319B - 一种利用固体废弃物制备树木涂白剂的方法 - Google Patents
一种利用固体废弃物制备树木涂白剂的方法 Download PDFInfo
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- CN111499319B CN111499319B CN202010392632.2A CN202010392632A CN111499319B CN 111499319 B CN111499319 B CN 111499319B CN 202010392632 A CN202010392632 A CN 202010392632A CN 111499319 B CN111499319 B CN 111499319B
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- Processing Of Solid Wastes (AREA)
Abstract
本申请公开了一种利用固体废弃物制备树木涂白剂的方法，以材料来源广泛，成本低的贝壳、蛋壳、碎玻璃、废弃陶瓷抛光粉、脱硫灰为原料，采用一锅烧工艺制备成膜物质和泡沫玻璃。涂白剂配方组成以石灰和生物胶为成膜物质,泡沫玻璃为保温隔热材料，水化产物固化CO2，吸附空气中颗粒物质并具有杀菌、杀虫性能。蛋壳负载MOFs光催化剂，利用自然光照条件下，降解空气中二氧化硫。为增加涂白剂硬化后强度，配以糖水拌和，糖水的制备方法是以煮地瓜的水，经高温熬制。具有保护树木，保障公共安全，净化空气的社会效益和环境效益。
Description
技术领域
本发明属于涂料制备领域，具体涉及一种利用固体废弃物制备树木涂白剂的方法。
背景技术
建设美丽家园，向往美好的生活是人类共同愿望。随着生活水平提高和经济的快速发展，生态环境造成人为破坏。海产品加工过程产生的贝壳，生活垃圾蛋壳、建筑垃圾碎玻璃、成分不稳定且复杂的半干法烟气脱硫灰 、陶瓷生产线上研磨抛光产生的粉体等，量大面广，难以有效利用。固体废弃物大量堆放占用土地，影响企业生产。腐烂物质，污染空气、土壤、水体，是影响公共安全的致病菌来源。为了治理环境，植树造林净化空气，涵养水土，防风固沙。森林是地球的肺，保护树木是人类的责任。
每年冬季树木涂白都是园林与果农的防护性工作。目的是减少树木死亡和提高果树产量。在冬季由于日光照射的原因会导致昼夜温差过大，从而使得树木冻伤。而涂白之后树干白色的部分能反射40%~70%的阳光，从而减少昼夜温差。由于大部分害虫都有趋暗性，所以涂白的树干可以防止害虫侵害树木。传统涂白剂成膜物质主要是天然石灰石煅烧产物石灰，为树木提供一定的碱性环境，PH值为12.5，害虫能够安全生存的PH值范围为6.5～9。树木涂白后，白度 83.6%，反光的效果更佳。在晚上可以让出行的人更加容易看清道路，并且给人一种整洁美观的感受。
根据地域和果树种类不同，涂白剂配方也不同。现在市场上的树木涂白剂配方都是以生石灰和石硫合剂为主，加上食盐，豆面，植物油等。盐能使生石灰跟硫磺渗入树木表皮，保持水分和防止石灰脱落；豆面可以增强涂白剂的附着力；硫磺和植物油会提高涂白剂的杀虫、杀菌效果，也会提高涂白剂的附着力，但是会降低涂白剂的白度和增加成本。改进的产品以低碱性或中性有机成膜物质为主，降低土壤的碱性化，并配以杀虫剂，增白剂，隔热材料，延长涂膜不脱落的增粘剂。这样配方设计都是以保持传统涂白剂功能不变，配方复杂，价格提高，影响大面积推广应用。并且有些涂白剂涂装过程有刺鼻的气味，危害工作人员，污染环境。
树木对环境具有净化空气的功能，产生功能的器官主要以树叶为主，其次树皮。到了冬季，落叶树木基本失去树叶净化功能。树干涂上1.0m-1.2m高度涂白剂，减少树皮和空气的交换作用。冬季由于取暖原因，产生雾霾天气增多，因此更需要开发一种在自然光照条件下，吸附二氧化碳、滤除PM、又能杀菌并降解其他污染物的新型绿色环保多功能树木涂白剂。为了降低成本，拓宽材料来源，以固体废弃物为原料，替代天然材料。营造空气清新，天空更蓝的美好的生态环境。
发明内容
本发明的目的是利用固体废弃物制备树木涂白剂的方法，根据固体废弃物的化学成分，科学设计，工艺简单。以材料来源广泛，成本低的贝壳、蛋壳、碎玻璃、废弃陶瓷抛光粉、脱硫灰为原料，采用一锅烧工艺制备成膜物质和泡沫玻璃。涂白剂配方组成以石灰和生物胶为成膜物质,泡沫玻璃为保温隔热材料，水化产物固化CO2，吸附空气中颗粒物质并具有杀菌、杀虫性能。蛋壳负载MOFs光催化剂，利用自然光照条件下，降解空气中二氧化硫。为增加涂白剂硬化后强度，配以糖水拌和，糖水的制备方法是以煮地瓜的水，经高温熬制。
本发明的方案如下：一种利用固体废弃物制备树木涂白剂的方法，
一锅烧工艺制备复合材料：将废玻璃粉、脱硫灰、贝壳粉、陶瓷抛光粉，加水搅拌均匀成球，直径1-2cm，烘干预热煅烧，温度850℃，保温1.5h。 冷却后粉磨，细度0.08mm方孔筛筛余<1%。煅烧产物组成有石灰和生物胶成膜物质。除此之外还有轻质多孔泡沫玻璃。
贝壳主要成分95%碳酸钙和5%有机质。微观形成砖-泥纳米结构，宏观表现高的力学韧性。贝壳高温煅烧与石灰石相比，贝壳杂质少，白度91.4%，分解温度低，孔隙大，砖-泥破坏形成无机石灰和有机胶凝物质。因此不需要矿山开采，能耗少，并有更好的吸附空气中颗粒物质并具有杀菌、杀虫性能。
有机胶凝材料、石灰水化产物相互交织形成网状，起到柔性抗裂、增强、增粘，延长涂层不脱落。轻质多孔的泡沫玻璃，提高保温和隔热性能，避免昼夜温差过大，树木冻伤。同时增加了对空气中颗粒物质的吸附空间。
蛋壳负载MOFs光催化材料的制备工艺：将硝酸钴和二甲基咪唑溶解在100ml的去离子水中，在室温下搅拌8h得到溶液。再加入蛋壳粉，硝酸镍搅拌1h，离心干燥，鹅蛋壳颜色由白色变为粉色。
蛋壳负载有机金属骨架形成多孔性光催化材料，在太阳光照射下，产生更多活性自由基•O2 -、•OH和 • CO3 -，吸附分解空气中有毒有害污染物质，尤其对SO2净化效果更佳。光催化材料与复合材料协效作用增强了对树木的保护和空气净化功能。
糖水的熬制：将1斤块状地瓜放到1.5L水里煮熟，取出地瓜。
涂白剂涂装：将复合材料和蛋壳负载MOFs光催化材料，加水和糖水，比例1:1搅拌混合消化，防止产品灼伤树木。糖水增加涂白剂硬化后的强度。以1～1.2米为涂刷高度，先在涂刷一圈作为涂白最高线，再由下往上涂刷，使其均匀分布在树皮表面，刷至底部为止。产品粘稠度合适，在树木涂刷过程中，液体能很好地覆盖树木表面，只有少量产品流入地面，利用率高，同时产品的碱性较弱，不会造成土壤盐碱化。产品干燥后，白度好，能达到产品的预期效果。干燥后的产品附着强，不易脱落，持续时间长，能很好地保证树木过冬。
本发明的优势为：
以就地取材，来源广泛的固体废弃物为原料制备低成本的高性能树木涂白剂，具有保护树木，保障公共安全，净化空气的社会效益和环境效益。
附图说明
图1 为蛋壳负载MOFs光催化材料SEM照片；
图2 为成膜材料SEM照片；
图3 细菌培养皿，其中（1）为树皮表面无细菌的培养皿，（2）为树皮表面覆盖细菌的培养皿；
图4为树木涂装效果图，其中（1）为树木涂白剂涂装效果图，（2）为市场出售涂白剂涂装效果图，（3）为紫叶李涂树木涂白剂效果图，（4）为紫叶李没有涂树木涂白剂效果图。
具体实施方式
下面结合实施例详细说明本发明的方案。
实施例1一种利用固体废弃物制备树木涂白剂的方法，包括如下步骤：
步骤1：一锅烧工艺制备复合材料：将7%废玻璃粉、10%脱硫灰、80%贝壳粉、3%陶瓷抛光粉，加水搅拌均匀成球，直径1-2cm。烘干预热煅烧，温度850℃，保温1.5h。 冷却后粉磨，细度0.08mm方孔筛筛余<1%。
步骤2：鹅蛋壳负载MOFs光催化材料的制备：将0.4g硝酸钴和0.8g二甲基咪唑溶解在100ml的去离子水中，在室温下搅拌8h得到溶液。再加入2g蛋壳粉，0.4g硝酸镍搅拌1h，离心干燥，鹅蛋壳颜色由白色变为粉色。
步骤3：糖水的熬制：将1斤块状地瓜放到1.5L水里煮熟，取出地瓜。
步骤4：涂白剂涂装：将99%复合材料和1%MOFs光催化材料，加水和糖水，比例1:1搅拌混合消化2h，防止产品灼伤树木。以1～1.2米为涂刷高度，先在涂刷一圈作为涂白最高线，再由下往上涂刷，使其均匀分布在树皮表面，刷至底部为止。
特点：大量利用固体废弃物，具有保护树木，降解污染物和消融病菌的功能。
实施例2一种利用固体废弃物制备树木涂白剂的方法，包括如下步骤：
步骤1：一锅烧工艺制备复合材料：将5%废玻璃粉、7%脱硫灰、85%贝壳粉、3%陶瓷抛光粉，加水搅拌均匀成球，直径1-2cm。烘干预热煅烧，温度1050℃，保温0.5h。 冷却后粉磨，细度0.08mm方孔筛筛余<1%。 ；
步骤2：鹅蛋壳负载MOFs光催化材料的制备：将0.58g硝酸钴和0.65g二甲基咪唑溶解在100ml的去离子水中，在室温下搅拌8h得到溶液。再加入3g蛋壳粉，0.4g硝酸镍搅拌1h，离心干燥，鹅蛋壳颜色由白色变为粉色。
步骤3：糖水的熬制：将1斤块状地瓜放到1.5L水里煮熟，取出地瓜。
步骤4：涂白剂涂装：将98%复合材料和2%MOFs光催化材料，加水和糖水，比例1:1搅拌混合消化2h，防止产品灼伤树木。以1～1.2米为涂刷高度，先在涂刷一圈作为涂白最高线，再由下往上涂刷，使其均匀分布在树皮表面，刷至底部为止。
特点：大量利用固体废弃物，具有保护树木，降解污染物和消融病菌的功能。
实施例3一种利用固体废弃物制备树木涂白剂的方法，包括如下步骤：
步骤1：贝壳基石灰粉制备：将贝壳放到高温炉煅烧，温度950℃，保温1.0h。冷却后取出，密封，自动粉化形成石灰粉体材料；
步骤2：糖水的熬制：将1斤块状地瓜放到1.5L水里煮熟，取出地瓜。
步骤3：涂白剂涂装：将贝壳基石灰粉加水和地瓜糖水，搅拌混合消化2h，防止产品灼伤树木。以1～1.2米为涂刷高度，先在涂刷一圈作为涂白最高线，再由下往上涂刷，使其均匀分布在树皮表面，刷至底部为止。
特点：制备工艺简单，具有固化二氧化碳，调节环境温度、湿度、杀虫、防止灼伤、装饰和保护树木的功能。
试验例
1、原材料：
贝壳：贝壳取自菜市场海产品加工店，为牡蛎壳和扇贝壳混合物。
二甲基咪唑：广东翁江化学试剂有限公司。
六水硝酸钴：分析纯，上海麦克林。
六水硝酸镍：分析纯，上海麦克林。
啤酒瓶：使用到期后的废旧啤酒瓶。
培养基：营养琼脂来自青岛海博生物公司。
菌种：大肠杆菌和金黄色葡萄球菌，实验室冷冻保存。
地瓜：菜市场购买。
表1 原材料的化学成分 /%
| 组成 | SiO<sub>2</sub> | Al<sub>2</sub>O<sub>3</sub> | Fe<sub>2</sub>O<sub>3</sub> | CaO | MgO | Na<sub>2</sub>O | SO<sub>3</sub> |
| 贝壳 | 0.46 | 0.43 | 0.23 | 49.13 | 0.54 | / | / |
| 抛光粉 | 70.62 | 17.44 | 0.47 | 0.83 | 3.19 | / | / |
| 脱硫灰 | 3.45 | 0.39 | 2.29 | 48.92 | 2.84 | / | 9.96 |
| 玻璃粉 | 68.32 | 6.68 | 1.92 | 7.76 | 2.45 | 9.21 | 0.78 |
2、试验方法：
2.1 废玻璃粉的制备工艺：
以废啤酒瓶为原料，用锤子破碎，球磨机粉磨15min，制备细粉。细度控制0.08mm方孔筛筛余<10%。
2.2 贝壳粉制备工艺：
将扇贝和牡蛎壳清洁干净，装到陶瓷罐，在行星磨上粉磨。细度控制0.08mm方孔筛筛余<10%。
2.3 一锅烧工艺制备复合材料：将7%废玻璃粉、10%脱硫灰、3%废抛光粉、80%贝壳粉，加水搅拌成球，直径1-2cm。烘干煅烧，温度850℃，保温1.5h。冷却后形成疏松多孔材料，装到陶瓷罐，在行星磨上粉磨30min，细度0.08mm方孔筛筛余<10%。
2.4 蛋壳负载MOFs光催化材料的制备：将0.4硝酸钴和0.8g二甲基咪唑溶解在100ml的去离子水中，在室温下搅拌8h得到溶液。再加入2g蛋壳粉，0.4g硝酸镍搅拌1h，离心干燥，鹅蛋壳颜色由白色变为粉色。
2.5 贝壳石灰粉制备工艺
将贝壳放到高温炉煅烧，温度950℃，保温1.0h。冷却后取出，密封，自动粉化形成石灰粉体材料 ；
2.6 糖水的熬制
将1斤块状地瓜放到1.5L水里煮熟，取出地瓜，剩余的水即为糖水。
2.7 涂白剂
2.8 涂白剂配方设计
基本配方以贝壳石灰粉加水搅拌混合消化2h。特点是工艺简单，保护树木，防止灼伤的功能。
净化空气的树木涂白剂配方将99%复合材料和1%MOFs光催化材料，加水和糖水，比例1:1搅拌混合消化2h。特点是大量利用固体废弃物，具有保护树木，降解污染物和消融病菌的功能。
2.9 涂白剂涂装
以1～1.2米为涂刷高度，先在涂刷一圈作为涂白最高线，再由下往上涂刷，使其均匀分布在树皮表面，刷至底部为止。产品粘稠度合适，在树木涂刷过程中，液体能很好地覆盖树木表面，只有少量产品流入地面，利用率高，同时产品的碱性较弱，不会造成土壤盐碱化。产品干燥后，白度好，能达到产品的预期效果。干燥后的产品附着强，不易脱落，持续时间长，很好地保证树木过冬。
3、试验及结果分析
3.1 涂白剂中午和夜晚温差检测结果
以2017.12.1-12.6为时间段，选择6课树为测试目标, 以石灰石煅烧石灰配制涂白剂为对比。把温度计固定在涂层上，观察中午和夜晚涂层温度。结果见表2。
表2 中午和夜晚温差检测结果
| 编号 | 1号/℃ | 2号/℃ | 3号/℃ | 4号℃/ | 5号/℃ | 6号/℃ |
| 1 | 6 | 4 | 6 | 2 | 4 | 7 |
| 2 | 5 | 4 | 6 | 2 | 3 | 6 |
| 3 | 6 | 4 | 5 | 2 | 4 | 7 |
| 对比1 | 8 | 5 | 7 | 3 | 5 | 9 |
| 对比2 | 7 | 6 | 7 | 3 | 5 | 8 |
| 对比3 | 8 | 6 | 8 | 4 | 6 | 8 |
表2说明，以固体废弃物为原料制备的树木涂白剂，温差小。通过白度和涂白剂中的多孔材料起到隔热保温的效果，减少太阳灼烧和冻害发生。
3.2 涂白剂耐气候性观察
对比以石灰石煅烧石灰的树木涂白剂和以固体废弃物为原料制备的树木涂白剂使用效果，经过2017年11月份到2018年4月份柳树观察，见图4。以石灰石煅烧石灰的树木涂白剂涂膜经过雨雪天洗刷、大气侵蚀和冻融已经脱落。以固体废弃物为原料制备的树木涂白剂，粘附性好，脱落少，脱模保持时间长，耐久性好。经过3年使用，对比紫叶李与不涂树木涂白剂比较，树木虫害少。
3.3 粉尘颗粒检测
在路沿石和涂白剂树干上放置载玻片，24h后在显微镜下观察粉尘数量，数据表明，道路上的粉尘颗粒物质数量高于树木周围环境。因此人行道两边种植树木，吸附净化空气中粉尘。
鹅蛋壳负载有机金属骨架形成多孔性光催化材料，见图1。蛋壳是多孔性的，微观清晰表现出网状多孔结构，光催化剂吸附在骨架表面。通过对涂白剂的扫描电镜分析，见图2。涂膜呈对孔性，吸附空气颗粒物质和有毒有害物质。在太阳光照射下，光催化剂产生•O2 -、•OH和 • CO3 -自由基，降解有毒有害物质，尤其是对空气中SO2具有很强降解能力。
3.5 抗菌性能检测
从紫叶李树上取下1×0.5cm树皮涂敷树木涂白剂，放到杀菌的培养皿中，滴入牛奶营养液，放到养护箱观察。见图3经过3d，涂敷以固体废弃物为原料的涂白剂树皮，轮廓清晰，没有细菌生长。 涂敷以石灰石煅烧石灰制备的树木涂白剂的树皮，轮廓不清晰，表面布满细菌菌丝。
虽然以上描述了本发明的具体实施方式，但是熟悉本技术领域的技术人员应当理解，本发明所描述的具体实施例只是说明性的，而不是用于对本发明的范围的限定，熟悉本领域的技术人员在依照本发明的精神所作的等效的修饰以及变化，都应当涵盖在本发明的权利要求所保护的范围内。
Claims (7)
1.一种利用固体废弃物制备树木涂白剂的方法，其特征在于，包括步骤如下：
步骤1：一锅烧工艺制备复合材料：将废玻璃粉、脱硫灰、贝壳粉、陶瓷抛光粉，加水搅拌均匀成球，直径1-2cm；烘干预热煅烧，温度850℃，保温1.5h；冷却后粉磨，细度0.08mm方孔筛筛余<1%；所述材料的质量占比为废玻璃粉5-7%、脱硫灰7-10%、贝壳粉80-85%、陶瓷抛光粉3%；
步骤2：蛋壳负载MOFs光催化材料的制备：将硝酸钴和二甲基咪唑溶解在去离子水中，在室温下搅拌8h得到溶液；再加入蛋壳粉、硝酸镍搅拌1h，离心干燥；
步骤3：糖水的熬制：将块状地瓜放入水中煮熟，取出地瓜，剩余的水即为糖水；
步骤4：涂白剂涂装：将复合材料和蛋壳负载MOFs光催化材料，加水和糖水，比例1:1搅拌混合消化。
2.如权利要求1所述的一种利用固体废弃物制备树木涂白剂的方法，其特征在于，步骤2中所述干燥条件为真空干燥箱中加热至60℃，保温时间8h。
3.如权利要求1所述的一种利用固体废弃物制备树木涂白剂的方法，其特征在于，步骤2中，所述硝酸钴和二甲基咪唑的质量比为1:2，所述蛋壳粉与硝酸镍的质量比为5:1。
4.如权利要求1所述的一种利用固体废弃物制备树木涂白剂的方法，其特征在于，步骤3所述水的用量为地瓜用量的1.5倍。
5.如权利要求1所述的一种利用固体废弃物制备树木涂白剂的方法，其特征在于，步骤4所述复合材料和蛋壳负载MOFs光催化材料的质量比为98-99%：1-2%。
6.如权利要求1-5任一方法所获得涂白剂在树木涂白方面的应用。
7.如权利要求6所述的应用，具体步骤为：以1～1.2米为涂刷高度，先在涂刷一圈作为涂白最高线，再由下往上涂刷，使其均匀分布在树皮表面，刷至底部为止。
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