CN111110899A - 类石墨烯与藻钙的复合空气净化材料及其制备方法和应用 - Google Patents
类石墨烯与藻钙的复合空气净化材料及其制备方法和应用 Download PDFInfo
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- CN111110899A CN111110899A CN201911344093.9A CN201911344093A CN111110899A CN 111110899 A CN111110899 A CN 111110899A CN 201911344093 A CN201911344093 A CN 201911344093A CN 111110899 A CN111110899 A CN 111110899A
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Abstract
本发明属于空气净化技术领域，具体涉及一种类石墨烯与藻钙的复合空气净化材料及其制备方法和应用。该方法包括步骤：1)将类石墨烯、藻钙材料和催化材料混合均匀，得到预混粉体；2)向预混粉体中加入液相介质并制浆，得到混合浆料；3)将混合浆料进行成型，得到材料颗粒；4)对材料颗粒依次进行筛分、抛光和抛光养护，并在抛光养护过程中将材料颗粒与改性功能助剂混合，得到表面覆盖有改性功能助剂的材料颗粒；5)对材料颗粒进行加热干燥，即得类石墨烯与藻钙的复合空气净化材料。本发明所提供的类石墨烯与藻钙的复合空气净化材料具有净味、除臭、除味、空气净化、除醛、抗菌防霉的全面净化效果。
Description
技术领域
本发明属于空气净化技术领域，具体涉及一种类石墨烯与藻钙的复合空气净化材料及其制备方法和应用。
背景技术
2004年，英国曼彻斯特大学的海姆和诺沃肖洛夫，用透明胶将一块石墨片反复粘贴与撕开，石墨片的厚度逐渐减小，最终形成了厚度只有0.335纳米的石墨烯，也就是只有一个原子厚度的石墨烯，这是世界上第一次得到单层的石墨烯，也将石墨烯的概念带给了世界。
在我国，石墨烯行业仍在量产摸索阶段，主要的制备方法有微机械剥离法、外延生长法、氧化石墨还原法和气相沉积法。其中氧化石墨还原法优点在于制备成本相对较低，是主要的制备方法。但在已经产业化的制造方式中，低成本的得到优秀的单层石墨烯还存在很多技术阻碍，这也使得在石墨烯的制造过程中，会产出大量碳层数多于10层、厚度在5-100纳米范围内的超薄的石墨烯层状堆积体，称之为石墨烯微片，它保持了石墨原有的平面型碳六元环共轭晶体结构，相对于普通石墨，石墨烯微片的厚度处在纳米尺度范围内，虽未达到单层石墨烯的各项优异性能，但在各方面也表现出色。这种具有功能性的材料，带给了我们在空气净化领域发展上的新思路，类似的材料还有过渡金属硫族化物、过渡金属氧化物及硅烯类等具有二维尺度片状或类片状夹层材料，我们将其统称为类石墨烯材料。
空气净化技术领域方面，现有针对室内污染的主要解决技术有活性炭、空气净化器、光触媒等类型。其中，活性炭以物理吸附为主，存在问题是吸附饱和后易将吸附的有害气体释放出来形成二次污染，对人体造成伤害；至于空气净化器，滤网式以空气循环过滤吸附，对有害气体分子无净化能力，而且滤网要定期更换，离子式净化器因强电场电晕容易产生臭氧浓度超标引起副作用；光触媒以液体喷涂于污染释放面，通过光照与液体表面甲醛发生反应消除甲醛，对家具有一定的腐蚀作用，且净化效果根据光照、通风条件变化，难以将空气中游离的有害气体分子捕获，时效性较短。
我们现有技术CN102633450A“一种具有负离子仿生功能的复合材料及其生产方法”、CN102633482A“一种具有净化甲醛功能的复合材料及其生产方法”、CN102633483A“一种具有自调湿功能的复合材料及其生产方法”可以制备得到一种藻钙生态无机材料，其具有三大特点，其一，晶体结构大量含有呈类似于上、下壳层蘑菇状的圆盘筛，筛面自中心部位向圆盘边缘辐射状分布圆柱形通孔；其二，组成中含有二氧化钛催化酶及中价氧化物，能自向发生催化氧化及微电场；其三，宏观性能表现出显着的吸附性能、分解净化性能、负离子诱生性、抗菌防霉祛味性及环境友好性。为了突破现有技术，我们将藻钙与类石墨烯材料进行创新结合，制得一种新型空气净化材料，解决了空气净化材料领域现有的时效短、过饱和以及吸附不分解的难题。
发明内容
为解决现有技术的不足，本发明提供了一种类石墨烯与藻钙的复合空气净化材料及其制备方法和应用。本发明所提供的净化材料拥有更高的比表面积，催化分解速度更快，空气净化效果迅速及持久的效果。
本发明所提供的技术方案如下：
一种类石墨烯与藻钙的复合空气净化材料的制备方法，包括以下步骤：
1)按照重量份计，将1～100份的类石墨烯、10～75份的藻钙材料和0.5～2.2份的催化材料混合均匀，得到预混粉体；
2)向步骤1)得到的所述预混粉体中加入1～67重量份的液相介质并制浆，得到混合浆料；
3)将步骤2)得到的混合浆料进行成型，得到材料颗粒；
4)对步骤3)得到的所述材料颗粒依次进行筛分、抛光和抛光养护，并在抛光养护过程中将步骤3)得到的所述材料颗粒与0.8～1.5份的所述改性功能助剂混合，得到表面覆盖有所述改性功能助剂的材料颗粒；
5)对步骤4)得到的所述材料颗粒进行加热干燥，即得所述类石墨烯与藻钙的复合空气净化材料。
基于上述技术方案，在造粒工艺中引入物理发泡剂及稳泡剂进行物理方法致孔，优化了类石墨烯与藻钙的复合空气净化材料介质的孔结构大小和分布；然后在养护工艺当中表面搭载功能助剂，使类石墨烯与藻钙的复合空气净化材料介质具有净味、除臭、除味、空气净化、除醛、抗菌防霉的全面净化效果。
上述技术方案所制备得到的类石墨烯与藻钙的复合空气净化材料以类石墨烯、藻钙材料、催化材料为主体。其中：
类石墨烯其理论比表面积为2630m2/g，而最好的椰壳活性炭比表面积为1000-1600m2/g，类石墨烯材料是其1.6～2.6倍，大幅提高了天然吸附能力；类石墨烯材料电子迁移率超过15000cm2/V·s，从而能量损失率极小，为有效催化提供能量；
藻钙材料为具有晶体结构大量含有呈类似于上、下壳层蘑菇状的圆盘筛，筛面自中心部位向圆盘边缘辐射状分布圆柱形通孔；组成中含有二氧化钛催化酶及中价氧化物，能自向发生催化氧化及微电场的特征材料。例如CN102633450A“一种具有负离子仿生功能的复合材料及其生产方法”所提供的具有负离子仿生功能的复合材料、CN102633482A“一种具有净化甲醛功能的复合材料及其生产方法”所提供的具有净化甲醛功能的复合材料、CN102633483A“一种具有自调湿功能的复合材料及其生产方法”所提供的具有自调湿功能的复合材料。该类材料拥有良好的成型微孔骨架，能自调湿，净化甲醛及生态友好性；
催化材料能在类石墨烯结构层催化所吸附的有害气体，激发原子层内的电流变化，稳固有害气体分解后产生的极性分子，加快分解进行，同时牢固吸附，不产生二次污染。
基于上述各材料的组合，上述技术方案所提供的类石墨烯与藻钙的复合空气净化材料具有净味、除臭、除味、空气净化、除醛、抗菌防霉的全面净化效果。
该材料可真空保存。
具体的，所述类石墨烯材料选自石墨烯微片、二维过渡金属硫族化物、二维过渡金属氧化物、二维过渡金属碳化物、二维过渡金属碳氮化物或磷烯类单层黑磷中的任意一种或多种的混合。
具体的，所述石墨烯微片为碳层数10至100层的纳米尺度的石墨烯微片；
所述二维过渡金属硫族化物为MoS2、WS2或WSe2；
所述二维过渡金属氧化物为MnO2、MnO、Mn2O3或NiO；
所述二维过渡金属碳化物为Ti3C2、TiC或Ti3AlC2；
所述二维过渡金属碳氮化物为Ti3CN、
所述磷烯类单层黑磷为黑磷层数2层以上纳米尺度二维结构层。
具体的，所述藻钙材料为：具有自调湿功能的粉料(CN102633483A)、具有甲醛净化功能的复合材料(CN102633482B)或者具有负离子仿生功能的复合材料(CN102633450A)。
具体的，所述催化材料为过渡金属氧化物催化剂、过渡金属氧化物催化剂的盐、碱土金属氧化物催化剂、碱土金属氧化物催化剂的盐、钙钛矿粉或稀土金属氧化物纳米粉体中的任意一种或多种的混合。
具体的，所述过渡金属氧化物催化剂为CoO、CuO、WO、NiO、MoO或ZnO；
所述稀土金属氧化物为La2O3或LaNiO3。
具体的，所述改性功能助剂为十二烷基苯磺酸钠、植物精油、热敏性微生物缓释颗粒、生物酶中的任意一种或多种的混合。热敏性微生物缓释颗粒即为用微生物萃取液浸渍聚合物树脂得到的微粒，随温度的提高，微生物的芳香物质会缓慢释放。
具体的，步骤4)中：
在抛光过程中将植物精油后生物酶雾化喷洒在颗粒物表面；
或者，再抛光过程中将热敏性微生物缓释颗粒采用筛机均匀附加在颗粒物表面。
具体的，所述液相介质包括重量比为97:1～2:1～2的水、十二烷基硫酸钠和淀粉。
具体的，类石墨烯与藻钙的复合空气净化材料的制备方法包括以下步骤：
1)原材料预混：将类石墨烯材料、藻钙材料、催化材料计量，借助粉料搅拌机搅拌均匀后待用。
2)制浆：将预混粉体与液相介质混合，采用搅拌机进行搅拌，搅拌转速800-1000转/min，搅拌时间1分钟，制成均匀糊状粘稠样。
3)成型：将制得的混合浆注入造粒机造粒或注入各类板型、片形模具，制得圆形或不规则颗粒，粒径大小φ＝0.3～3.5mm，板型、片形尺寸依模具而定。
4)养护改性：将以上工艺制备得到的材料用筛分机筛除破碎、粉粒状的物质后，进行抛光，抛光养护过程中借助振动筛及雾化喷淋设备将功能粉体与改性功能助剂连续均匀加入混合，使成型后的材料外层均匀涂覆有改性功能助剂材料。
5)干燥：采用电热恒温干燥炉干燥，时间为45min，干燥温度40～45℃，干燥后含水率≤3.5％。
进一步的，可进行抽真空保存：采用塑料薄膜袋抽真空保存所制备类石墨烯与藻钙的复合空气净化材料。
本发明还提供的上述制备方法制备得到的类石墨烯与藻钙的复合空气净化材料。
具体的，类石墨烯与藻钙的复合空气净化材料包括以下重量份的各组分：1～100份类石墨烯，10～75份藻钙材料，0.5～2.2份催化材料，0.8～1.5份改性功能助剂，0.03～2.01份的液相介质。
本发明还提供了类石墨烯与藻钙的复合空气净化材料的应用，作为空气净化材料。
本发明所提供的类石墨烯与藻钙的复合空气净化材料具有净味、除臭、除味、空气净化、除醛、抗菌防霉的全面净化效果。
附图说明
图1是本发明所提供的类石墨烯与藻钙的复合空气净化材料的制备方法的流程图。
具体实施方式
以下对本发明的原理和特征进行描述，所举实施例只用于解释本发明，并非用于限定本发明的范围。
实施例1
类石墨烯与藻钙的复合空气净化材料的原料配方组成(物质计量单位均为重量份)：
1)类石墨烯材料，采用石墨烯微片80份；
2)藻钙材料，20份；
3)催化材料，采用La2O3微粉1.5份；
4)功能助剂，采用玫瑰植物精油0.8份；
5)液相介质12份，按清水:十二烷基硫酸钠:淀粉＝97:1.5:1.5复配而得；
如图1所示，采用上述原料生产制备类石墨烯与藻钙的复合空气净化材料的工艺如下：
1)原材料预混：将类石墨烯材料、藻钙材料、催化材料精确计量，借助粉料搅拌机搅拌均匀后待用。
2)制浆：将预混粉体与液相介质混合，采用搅拌机进行搅拌，搅拌转速1000转/min，搅拌时间1分钟，制成均匀糊状粘稠样。
3)造粒：将制得的混合浆注入造粒机造粒，制得圆形颗粒。
4)养护：将造粒颗粒直接送入抛光机抛光，在抛光过程中将玫瑰植物精油雾化喷洒在颗粒物表面。
5)干燥：采用电热恒温干燥炉干燥，时间为75min，干燥温度45℃。
6)抽真空保存：采用塑料薄膜袋抽真空保存所制备类石墨烯与藻钙的复合空气净化材料。
采用上述原料和工艺制成的类石墨烯与藻钙的复合空气净化材料的性能测试结果见下表1，同时表1中采用活性炭净化介质作为性能对比组。
实施例2
类石墨烯与藻钙的复合空气净化材料的原料配方组成(物质计量单位均为重量份)：
1)类石墨烯材料，采用MoS2粉体50份；
2)藻钙材料，50份；
3)催化材料，采用LaNiO3微粉1.5份；
4)功能助剂，采用热敏性微生物缓释颗粒1份；
5)液相介质30份，按清水:十二烷基硫酸钠:淀粉＝97:1.5:1.5复配而得；
如图1所示，采用上述原料生产制备类石墨烯与藻钙的复合空气净化材料的工艺如下：
1)原材料预混：将类石墨烯材料、藻钙材料、催化材料精确计量，借助粉料搅拌机搅拌均匀后待用。
2)制浆：将预混粉体与液相介质混合，采用搅拌机进行搅拌，搅拌转速1000转/min，搅拌时间1分钟，制成均匀糊状粘稠样。
3)造粒：将制得的混合浆注入造粒机造粒，制得圆形颗粒。
4)养护：将造粒颗粒直接送入抛光机抛光，在抛光过程中将热敏性微生物缓释颗粒采用筛机均匀附加在颗粒物表面。
5)干燥：采用电热恒温干燥炉干燥，时间为75min，干燥温度45℃。
6)抽真空保存：采用塑料薄膜袋抽真空保存所制备类石墨烯与藻钙的复合空气净化材料。
采用上述原料和工艺制成的类石墨烯与藻钙的复合空气净化材料的性能测试结果见下表1，同时表1中采用活性炭净化介质作为性能对比组。
实施例3
类石墨烯与藻钙的复合空气净化材料的原料配方组成(物质计量单位均为重量份)：
1)类石墨烯材料，采用MnO2粉体40份；
2)藻钙材料，60份；
3)催化材料，采用硝酸镍微粉2份；
4)功能助剂，采用生物酶1.5份；
5)液相介质36份，按清水:十二烷基硫酸钠:淀粉＝97:1.5:1.5复配而得；
如图1所示，采用上述原料生产制备类石墨烯与藻钙的复合空气净化材料的工艺如下：
1)原材料预混：将类石墨烯材料、藻钙材料、催化材料精确计量，借助粉料搅拌机搅拌均匀后待用。
2)制浆：将预混粉体与液相介质混合，采用搅拌机进行搅拌，搅拌转速1000转/min，搅拌时间1分钟，制成均匀糊状粘稠样。
3)造粒：将制得的混合浆注入造粒机造粒，制得圆形颗粒。
4)养护：将造粒颗粒直接送入抛光机抛光，在抛光过程中将生物酶雾化喷洒在颗粒物表面。
5)干燥：采用电热恒温干燥炉干燥，时间为75min，干燥温度45℃。
6)抽真空保存：采用塑料薄膜袋抽真空保存所制备类石墨烯与藻钙的复合空气净化材料。
采用上述原料和工艺制成的类石墨烯与藻钙的复合空气净化材料的性能测试结果见下表1，同时表1中采用活性炭净化介质作为性能对比组。
对比例1
采用上述原料和工艺制成的类石墨烯与藻钙的复合空气净化材料的性能测试结果见下表1，同时表中采用活性炭净化介质作为性能对比组。
测试结果对照表1
从上表1可知，本发明的各项性能显著优于活性炭净化介质。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (10)
1.一种类石墨烯与藻钙的复合空气净化材料的制备方法，其特征在于，包括以下步骤：
1)按照重量份计，将1～100份的类石墨烯、10～75份的藻钙材料和0.5～2.2份的催化材料混合均匀，得到预混粉体；
2)向步骤1)得到的所述预混粉体中加入1～67重量份的液相介质并制浆，得到混合浆料；
3)将步骤2)得到的混合浆料进行成型，得到材料颗粒；
4)对步骤3)得到的所述材料颗粒依次进行筛分、抛光和抛光养护，并在抛光养护过程中将步骤3)得到的所述材料颗粒与0.8～1.5重量份的改性功能助剂混合，得到表面覆盖有所述改性功能助剂的材料颗粒；
5)对步骤4)得到的所述表面覆盖有所述改性功能助剂的材料颗粒进行加热干燥，即得所述类石墨烯与藻钙的复合空气净化材料。
2.根据权利要求1所述的类石墨烯与藻钙的复合空气净化材料的制备方法，其特征在于：所述类石墨烯材料选自石墨烯微片、二维过渡金属硫族化物、二维过渡金属氧化物、二维过渡金属碳化物、二维过渡金属碳氮化物或磷烯类单层黑磷中的任意一种或多种的混合。
3.根据权利要求2所述的类石墨烯与藻钙的复合空气净化材料的制备方法，其特征在于：
所述石墨烯微片为碳层数10至100层的纳米尺度的石墨烯微片；
所述二维过渡金属硫族化物为MoS2、WS2或WSe2；
所述二维过渡金属氧化物为MnO2、MnO、Mn2O3或NiO；
所述二维过渡金属碳化物为Ti3C2、TiC或Ti3AlC2；
所述二维过渡金属碳氮化物为Ti3CN；
所述磷烯类单层黑磷为黑磷层数2层以上纳米尺度二维结构层。
4.根据权利要求1所述的类石墨烯与藻钙的复合空气净化材料的制备方法，其特征在于，所述藻钙材料为：具有自调湿功能的粉料、具有甲醛净化功能的复合材料或者具有负离子仿生功能的复合材料。
5.根据权利要求1所述的类石墨烯与藻钙的复合空气净化材料的制备方法，其特征在于，所述催化材料为过渡金属氧化物催化剂、钙钛矿粉或稀土金属氧化物纳米粉体中的任意一种或多种的混合。
6.根据权利要求5所述的类石墨烯与藻钙的复合空气净化材料的制备方法，其特征在于：
所述过渡金属氧化物催化剂为CoO、CuO、WO、NiO、MoO或ZnO；
所述稀土金属氧化物为La2O3或LaNiO3。
7.根据权利要求1所述的类石墨烯与藻钙的复合空气净化材料的制备方法，其特征在于：所述改性功能助剂为十二烷基苯磺酸钠、植物精油、热敏性微生物缓释颗粒或生物酶中的任意一种或多种的混合。
8.根据权利要求1至7任一所述的类石墨烯与藻钙的复合空气净化材料的制备方法，其特征在于，所述液相介质包括重量比为97:1～2:1～2的水、十二烷基硫酸钠和淀粉。
9.一种根据权利要求1至8任一所述的制备方法制备得到的类石墨烯与藻钙的复合空气净化材料。
10.一种根据权利要求9所述的类石墨烯与藻钙的复合空气净化材料的应用，其特征在于：作为空气净化材料。
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