CN115368624B - 基于餐厨垃圾的多孔水凝胶保水材料及其制备方法和应用 - Google Patents
基于餐厨垃圾的多孔水凝胶保水材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开一种基于餐厨垃圾的多孔水凝胶保水材料及其制备方法和应用,制备方法包括:将餐厨垃圾加水打碎浆化;加入过硫酸盐和双氧水反应后加入尿素改性;惰性气体保护下加入丙烯酸盐、丙烯酸、N,N‑亚甲基双丙烯酰胺、过硫酸盐和多元醇,反应得到多孔水凝胶。与现有技术相比,本发明采用餐厨垃圾制备高性能多孔水凝胶保水材料,具有工艺简单、成本低廉,保水性能优越,可实现餐厨垃圾的高值化转化利用,具有较高的经济与社会环境效益。
Description
技术领域
本发明属于环境与材料技术领域,涉及一种基于餐厨垃圾的高性能多孔水凝胶保水材料及其制备方法和应用。
背景技术
餐厨垃圾是人类生活消费的必然产物,其资源化利用具有重要社会和环境效益。而当前餐厨垃圾资源化率仅为19.5%,大量的餐厨垃圾作为城市生活垃圾的主要组分被填埋或焚烧。
餐厨垃圾资源化技术主要有好氧堆肥、厌氧发酵、饲料化,而填埋和焚烧都不是对环境无害且经济有效的最终处理方式。其中,好氧堆肥和厌氧消化,已经成为餐厨垃圾资源化利用的主流技术。好氧堆肥将餐厨垃圾有机物的某些分解产物或微生物的某些合成产物进一步缩聚为复杂腐殖质,最终实现有机物的矿质化和腐殖化,腐殖化产品可作为肥料或土壤改良剂。堆肥处理方法简单,技术要求低,实用性强,可将废弃物减量40%以上。但是,由于餐厨垃圾具有高含水率、C/N不平衡、腐殖化过程营养元素流失严重等特点,严重制约其好氧堆肥的发展。另外,餐厨垃圾中的高盐和高氨氮含量可导致厌氧消化的微生物活性下降,最终导致生物气产量减少等问题。
高吸水性聚合物(水凝胶)是一种功能高分子材料,可吸收自身重量几百倍甚至上千倍的水,而且在压力下仍能保持大部分的水。它一般是由亲水性高分子链轻度交联而成的三维网状结构,其分子链上带有大量的亲水性基团如-OH、-COOH以及-CONH2等,主要应用于卫生用品、农业、医药、污染土壤及废水处理等领域。
中国专利《一种餐厨垃圾基复合凝胶缓释肥的制备方法》(公开号CN110577433A,公开日期2019年12月17日),公开了一种餐厨垃圾基复合凝胶缓释肥的制备方法,以餐厨垃圾中的剩余米饭作为底物,加入尿素,丙烯酸,N,N-亚甲基双丙烯酰胺,过硫酸盐,蒙脱土等生成复合凝胶缓释肥,具有一定的吸水性(最大溶胀率,为102.3g/g)。但是,目前餐厨垃圾大多数为混合物,单独分选出剩余米饭具有一定操作难度,且无法实现餐厨垃圾的近全量资源化利用。通过研发可将混合餐厨垃圾制备更高性能的水凝胶技术,是餐厨垃圾领域的研究热点和资源化利用新技术。
发明内容
本发明提出一种基于餐厨垃圾的高性能多孔水凝胶保水材料及其制备方法和应用,本发明创新地采取了:(1)添加过硫酸盐热预处理过程,实现了高含水率混合餐厨垃圾的绿色催化氧化,提高了餐厨垃圾的利用率和转换率;(2)利用自由基聚合交联聚合交联技术,将餐厨垃圾中含有的不饱和废油脂、淀粉、纤维素、蛋白质等四种典型组分,其间存在大量-OH、-COOH和C=C等特征官能团,进行诱导聚合,并通过冷冻干燥优化水凝胶赋存空间状态,合成了具有高性能多孔水凝胶保水材料。
为实现上述目的,本发明采用以下技术方案:
一种基于餐厨垃圾的多孔水凝胶保水材料的制备方法,包括以下步骤:
(1)将餐厨垃圾加水打碎浆化,得到餐厨垃圾浆液;
(2)向所述餐厨垃圾浆液中加入过硫酸盐和双氧水,70℃~90℃条件下反应后离心得到上清液;
(3)65℃~85℃条件下向所述上清液中加入尿素并充分混合得到改性浆液;
(4)惰性气体保护下,向所述改性浆液中加入丙烯酸盐、丙烯酸、N,N-亚甲基双丙烯酰胺、过硫酸盐和多元醇,反应得到所述多孔水凝胶。
优选的,步骤(1)中加入的水与所述餐厨垃圾的重量比为3~5:1。
优选的,步骤(2)中,过硫酸盐、双氧水和所述餐厨垃圾浆液的质量比为3~5:0.1~0.5:100。
优选的,步骤(3)中,尿素和所述餐厨垃圾浆液的质量比为4.8~16.7:100。
优选的,步骤(4)中,丙烯酸盐、丙烯酸、N,N-亚甲基双丙烯酰胺、过硫酸盐、多元醇和所述餐厨垃圾浆液的质量比为0.5~2:6.8~12:0.2~0.6:0.7~1.3:0.05~0.1:100。
优选的,步骤(4)中,所述多元醇为木糖醇或山梨醇中的一种或两种。
优选的,所述多元醇为木糖醇和山梨醇的混合物,更优选的,木糖醇和山梨醇的质量比为2~3:1。
优选的,步骤(4)中所述反应在搅拌条件下进行15~45min使体系到达所需粘度。
优选的,所述制备方法还包括将获得的多孔水凝胶真空冷冻干燥的步骤。更优选的,真空冷冻干燥的时间为5 d ~ 10d。
本发明还提供上述制备方法制得的多孔水凝胶。
得到的多孔水凝胶保水材料呈土黄色至棕褐色的凝胶状。
本发明还提供上述制备方法制得的多孔水凝胶的应用。
优选的,所述应用包括:将所述多孔水凝胶施用于碱性土壤中。
优选的,所述应用包括将所述多孔水凝胶研磨破碎后过100目筛网,按2-10 g/平方米的用量施加,即可实现高效保水。
本发明与现有技术相比,具有如下优点和有益效果:
本发明采用双氧水使餐厨垃圾形成了腐殖质类物质的官能团,使得餐厨垃圾絮体结构解体,结构被破坏,表面出现了许多微孔,使得易降解有机物质和大部分难降解有机物质转化为可溶性小分子物质,进而生成腐殖质类物质,导致多孔结构絮体出现。而这些多孔结构絮体的出现可以进一步促进自由基聚合交联反应,增加交联位点,进而提高水凝胶的吸水性。
本发明适用于混合餐厨垃圾,具有工艺简单、餐厨垃圾利用率高、高吸水性能、成本低廉等优点,可显著提升餐厨垃圾的利用途径,实现餐厨垃圾的高值化利用。
附图说明
图1是实施例1~5制得的多孔水凝胶的溶胀平衡曲线。
图2是实施例1制得的多孔水凝胶保水材料典型扫描电子显微镜图(SEM)。
图3是餐厨垃圾扫描电子显微镜图(SEM)。
具体实施方式
以下结合附图所示实施例对本发明作进一步的说明。
实施例中的餐厨垃圾是米饭,白菜,猪肉,豆腐分别按 35%,45%,16%,4%的重量比例配成。实施例中,丙烯酸钾、尿素、丙烯酸、过硫酸盐和N ,N-亚甲基双丙烯酰胺均为分析纯,购自上海Aladdin生化科技股份有限公司,使用前不经任何预处理。
吸水能力测定步骤为:选取干燥块状样品 0.2~0.5 g 于盛有 150 mL 去离子水中,室温下(25~30 ℃)静置吸水,直至吸水平衡,即用滤纸拭去吸水凝胶表面水分后连续称重测量之差≤0.05 g。水凝胶最大溶胀率Qm,也为最大吸水率,计算公式如下:
Qm=(W1-W0)/W0
其中,W0(g)和 W1(g)分别为干燥和吸水平衡后的凝胶质量。
实施例1
按照重量比1:5将餐厨垃圾和水混合打成浆液,每100 g浆液中加入3.0 g的过硫酸钾和0.5 g双氧水,80℃热处理4h后,离心,取上层清液备用。将上层清液加入反应容器中,放入磁力搅拌水浴锅中,N2氛围下,每100g浆液加入13 g的尿素,70℃搅拌预热10min。然后按照每100g浆液加入1.0 g丙烯酸钾,8.6g丙烯酸,1.0 g过硫酸钾,0.4 g N ,N-亚甲基双丙烯酰胺和0.05 g多元醇(木糖醇和山梨醇的质量比为2:1)的比例快速加入上述试剂,搅拌直至体系所达粘度,静置,得到水凝胶。将所得到的水凝胶乙醇冲洗三遍,纯水冲洗三遍,真空冷冻干燥后得到所述的基于餐厨垃圾的高性能多孔水凝胶。
如图1所示,所制得的高性能多孔水凝胶的吸水率可达到291.1g/g。其扫描电子显微镜图可以看到明显且丰富的微孔结构。和餐厨垃圾相比(图3)相比,本实施例制得的多孔水凝胶的扫描电子显微镜图(附图2)可以看到明显且丰富的微孔结构。
实施例2
按照重量比1:5将餐厨垃圾和水混合打成浆液,每100 g浆液中加入3.0 g的过硫酸钾和0.1 g双氧水,80℃热处理4h后,离心,取上层清液备用。将上层清液加入反应容器中,放入磁力搅拌水浴锅中,N2氛围下,每100g浆液加入13 g的尿素,70℃搅拌预热10min。然后按照每100g浆液加入1.0 g丙烯酸钾,8.6g丙烯酸,1.3 g过硫酸钾,0.4 g N ,N-亚甲基双丙烯酰胺和0.07 g多元醇(木糖醇和山梨醇的质量比为2:1)的比例快速加入上述试剂,搅拌直至体系所达粘度,静置,得到水凝胶。将所得到的水凝胶乙醇冲洗三遍,纯水冲洗三遍,真空冷冻干燥后得到所述的基于餐厨垃圾的高性能多孔水凝胶。
如图1所示,所制得的高性能多孔水凝胶的吸水率可达到491.9 g/g。
实施例3
按照重量比1:3将餐厨垃圾和水混合打成浆液,每100 g浆液中加入5.0 g的过硫酸钾和0.2 g双氧水,80℃热处理4h后,离心,取上层清液备用。将上层清液加入反应容器中,放入磁力搅拌水浴锅中,N2氛围下,每100g浆液加入4.8 g的尿素,70℃搅拌预热10min。然后按照每100g浆液加入2.0 g丙烯酸钾,8.6g丙烯酸,1.3 g过硫酸钾,0.6 g N ,N-亚甲基双丙烯酰胺和0.05 g多元醇(木糖醇和山梨醇的质量比为3:1)的比例快速加入上述试剂,搅拌直至体系所达粘度,静置,得到水凝胶。将所得到的水凝胶乙醇冲洗三遍,纯水冲洗三遍,真空冷冻干燥后得到所述的基于餐厨垃圾的高性能多孔水凝胶。
如图1所示,所制得的高性能多孔水凝胶的吸水率可达到342.9 g/g。
实施例4
按照重量比1:4将餐厨垃圾和水混合打成浆液,每100 g浆液中加入4.0 g的过硫酸钾和0.3 g双氧水,70℃热处理4h后,离心,取上层清液备用。将上层清液加入反应容器中,放入磁力搅拌水浴锅中,N2氛围下,每100g浆液加入16.7 g的尿素,75℃搅拌预热10min。然后按照每100g浆液加入0.5 g丙烯酸钾,12.0g丙烯酸,0.7 g过硫酸钾,0.2 g N ,N-亚甲基双丙烯酰胺和0.1 g多元醇(木糖醇和山梨醇的质量比为2:1)的比例快速加入上述试剂,搅拌直至体系所达粘度,静置,得到水凝胶。将所得到的水凝胶乙醇冲洗三遍,纯水冲洗三遍,真空冷冻干燥后得到所述的基于餐厨垃圾的高性能多孔水凝胶。
如图1所示,所制得的高性能多孔水凝胶的吸水率可达到370.0 g/g。
实施例5
按照重量比1:5将餐厨垃圾和水混合打成浆液,每100 g浆液中加入3.0 g的过硫酸钾和0.5 g双氧水,90℃热处理4h后,离心,取上层清液备用。将上层清液加入反应容器中,放入磁力搅拌水浴锅中,N2氛围下,每100g浆液加入13.0 g的尿素,65℃搅拌预热10min。然后按照每100g浆液加入0.5 g丙烯酸钾,6.8g丙烯酸,0.7 g过硫酸钾,0.2 g N ,N-亚甲基双丙烯酰胺和0.05 g多元醇(木糖醇和山梨醇的质量比为2:1)的比例快速加入上述试剂。搅拌直至体系所达粘度,静置,得到水凝胶。将所得到的水凝胶乙醇冲洗三遍,纯水冲洗三遍,真空冷冻干燥后得到所述的基于餐厨垃圾的高性能多孔水凝胶。
如图1所示,所制得的高性能多孔水凝胶的吸水率可达到323.6 g/g。
对比例1
按照重量比1:5将餐厨垃圾和水混合打成浆液,于80℃热处理4h后,离心,取上层清液备用。将上层清液加入反应容器中,放入磁力搅拌水浴锅中,按照每100g浆液加入1.0g丙烯酸钾,8.6g丙烯酸,1.0 g过硫酸钾,0.4 g N ,N-亚甲基双丙烯酰胺的比例快速加入上述试剂,搅拌直至体系所达粘度,静置,得到水凝胶。将所得到的水凝胶乙醇冲洗三遍,纯水冲洗三遍,真空冷冻干燥后得到所餐厨垃圾的吸水材料,其吸水率为56.4 g/g。
对比例2
按照重量比1:5将餐厨垃圾和水混合打成浆液,每100 g浆液中加入3.0 g的过硫酸钾和0.5 g双氧水,80℃热处理4h后,离心,取上层清液备用。将上层清液加入反应容器中,放入磁力搅拌水浴锅中,按照每100g浆液加入1.0 g丙烯酸钾,8.6g丙烯酸,1.0 g过硫酸钾,0.4 g N ,N-亚甲基双丙烯酰胺的比例快速加入上述试剂,搅拌直至体系所达粘度,静置,得到水凝胶。将所得到的水凝胶乙醇冲洗三遍,纯水冲洗三遍,真空冷冻干燥后得到所述的基于餐厨垃圾的吸水材料,其吸水率为102.5 g/g。
与实施例1相比可以看出,将垃圾浆液预氧化,可以加强所得水凝胶的吸水性。
对比例3
按照重量比1:5将餐厨垃圾和水混合打成浆液,每100 g浆液中加入3.0 g的过硫酸钾和0.5 g双氧水,80℃热处理4h后,离心,取上层清液备用。将上层清液加入反应容器中,放入磁力搅拌水浴锅中,N2氛围下,每100g浆液加入13 g的尿素,70℃搅拌预热10min。然后按照每100g浆液加入1.0 g丙烯酸钾,8.6g丙烯酸,1.0 g过硫酸钾,0.4 g N ,N-亚甲基双丙烯酰胺的比例快速加入上述试剂,搅拌直至体系所达粘度,静置,得到水凝胶。将所得到的水凝胶乙醇冲洗三遍,纯水冲洗三遍,真空冷冻干燥后得到所述的基于餐厨垃圾的吸水材料,其吸水率为172.5g/g。
与实施例1相比可以看出,多元醇的加入可以大大加强吸水凝胶的吸水性。
与对比例2相比可以看出,尿素的改性也对于凝胶的吸水性也有很大的影响。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和应用本发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于这里的实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (4)
1.一种基于餐厨垃圾的多孔水凝胶保水材料的制备方法,其特征在于,包括以下步骤:
(1)将餐厨垃圾加水打碎浆化,得到餐厨垃圾浆液;
(2)向所述餐厨垃圾浆液中加入过硫酸盐和双氧水,70℃~90℃条件下反应后离心得到上清液;过硫酸盐、双氧水和所述餐厨垃圾浆液的质量比为3~5:0.1~0.5:100;
(3)65℃~85℃条件下向所述上清液中加入尿素并充分混合得到改性浆液,尿素和所述餐厨垃圾浆液的质量比为4.8~16.7:100;
(4)惰性气体保护下,向所述改性浆液中加入丙烯酸盐、丙烯酸、N,N-亚甲基双丙烯酰胺、过硫酸盐和多元醇,反应得到所述多孔水凝胶;所述多元醇为木糖醇和山梨醇的混合物,木糖醇和山梨醇的质量比为2~3:1;
丙烯酸盐、丙烯酸、N,N-亚甲基双丙烯酰胺、过硫酸盐、多元醇和所述餐厨垃圾浆液的质量比为0.5~2:6.8~12:0.2~0.6:0.7~1.3:0.05~0.1:100。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中加入的水与所述餐厨垃圾的重量比为3~5:1。
3.权利要求1-2任一所述的制备方法制得的多孔水凝胶。
4. 权利要求1-2任一所述的制备方法制得的多孔水凝胶的应用,其特征在于,所述应用包括:将所述多孔水凝胶施用于碱性土壤中;所述应用包括将所述多孔水凝胶研磨破碎后过100目筛网,按2-10 g/平方米的用量施加。
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