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厨余垃圾是指居民日常生活及食品加工、单位供餐、饮食服务等活动中产生的垃圾[1]。相比其他各类垃圾,厨余垃圾富含蛋白质、淀粉等有机物以及氮、磷、钾等各种营养元素,开发利用价值较大,但也因此易腐烂脏臭,致病菌、蚊虫等容易滋生繁殖[2]。随着城镇化发展和垃圾分类政策的实施,厨余垃圾的精细化、高值化利用成为研究热点。
目前,厨余垃圾资源化处理的主要技术有厌氧消化产能和好氧发酵制肥。其中,厌氧消化和好氧堆肥技术成熟,但处理工艺复杂、处理周期长达30~40 d、运维成本高、产品附加值低,难以实现厨余垃圾的全量资源化。厨余垃圾制备液态有机肥是好氧发酵制肥技术的新突破,它利用微生物、酶的作用,通过微环境调控可以在短时间实现厨余垃圾固相、液相的全降解,并转化为易于作物吸收利用的液态有机肥。利用厨余垃圾制备的液态有机肥富含可溶性糖、游离氨基酸等作物直接吸收利用的小分子物质[3],对作物生长具有良好的调节效果,能够提高作物产量和品质[4-5]。然而厨余垃圾中富含的纤维素、半纤维素、木质素相互缠绕交联,形成难降解的大分子物质,成为制约厨余垃圾快速液化的关键,也限制了腐殖质前体物的生成,使液态有机肥产品肥效差,市场化困难。有研究表明,通过热水解工艺可以打破木质纤维素的结构交联,不同热水解温度下有不同的热水解机制,在较低温度下 (<121 ℃) 胞外聚合物的溶解占主导地位,而在较高温度下 (>121 ℃) 下细胞破裂比例升高,胞内成分得到释放,因此较高的温度有利于大分子有机物的分解和营养物质的释放,同时促进腐殖质的生成。多数研究报告显示,厨余垃圾最佳热水解温度为160~180 ℃,处理时间是30~60 min,此时能产生最高的有机物和营养物质,但温度高于180 ℃可能会产生更多的难降解化合物并降低微生物的降解性能,同时较高的温度还会增加工艺能耗和运行成本。因此,本研究选取低温90 ℃和高温170 ℃的热水解温度进行比较。腐殖质是土壤矿质元素的活化剂和保肥剂,可以降低环境毒性,修复受损土壤,促进植物生长,调节土壤酸碱性[6-7]。ZHU等[8]发现热水解加速了木质纤维素的降解和腐殖质的产生,使堆肥过程中嗜热细菌的相对丰度增加。GAO等[9]通过评价水解前后营养物质的释放和腐殖质的合成,证明了厨余垃圾热水解产生的水解液的肥料潜力。但是在厨余垃圾制备液态有机肥的过程中,存在易降解有机物水解酸化与大分子物质 (蛋白质、淀粉、脂肪等) 降解转化不同步的问题,为此笔者团队前期开展了厨余垃圾降解功能菌剂的筛选与复配,发现抗酸化复合菌剂与米曲霉联用可实现易腐有机物与难降解有机物的同步转化[10-13]。在厨余垃圾高效降解转化的基础上,如何实现厨余垃圾定向腐殖化,提高厨余垃圾液态有机肥的产品附加值,成为研究难点。
近年来,学者们指出腐殖质前体物主要包括多酚、羧酸、氨基酸,多糖和还原糖,前体物的产生与细菌的活动密切相关,微生物通过降解有机物从而释放前体物,随着微生物的生长,它们开始通过次生代谢途径将前体物聚合,如莽草酸和丙二酸途径。最终前体物在酶的作用下聚合或自动形成腐殖质[14-15]。但值得注意的是,这些前体物也是微生物活动的能源,容易在微生物的作用下矿化成CO2,造成前体物的浪费[16]。因此,腐殖质形成和微生物生长繁殖之间存在底物竞争,影响腐殖质形成效率,难以实现厨余垃圾的定向腐殖化[17]。美拉德反应作为氨基酸和还原糖之间缩合的化学反应,这是氨基酸和还原糖合成腐殖质的主要途径,在非生物过程中,可以通过MnO2催化并促进腐殖质的合成,提高腐殖化效率[18]。其机理是,由于MnO2具有氧化性,其可以破坏酚类的物质的苯环结构,释放自由电子,增加反应体系内的活性基团,进而通过酚类和还原糖、氨基酸的缩合形成腐殖质[19]。此外,QI等[20]发现,在富含木质纤维素的材料中MnO2的存在加速了有机组分的降解,同时通过驱动官能团浓度的变化增加了腐殖质浓度,加速有机废弃物向高品质产品的转化。一方面,因为MnO2吸收电子变成Mn2+,这是各种代谢酶最重要的辅助因子之一,因此MnO2可以作为酶启动子刺激酶活性,刺激细菌分解并利用有机物;另一方面,引入 MnO2进入系统也可能改变微生物多样性,因为锰结核内部存在丰富多样的原核生物群落[21]。然而,关于MnO2在大分子有机物质的降解以及催化糖类物质和氨基酸缩合形成腐殖质的研究鲜有报道[17]。
为实现厨余垃圾定向腐殖化制备高品质液态有机肥,本研究在不同热水解温度下研究热水解对厨余垃圾中腐殖质前体物的影响,通过添加自主筛选的抗酸化复合菌剂和米曲霉,开展MnO2强化厨余垃圾快速定向腐殖化的研究;通过解析肥料化过程中腐殖质类、蛋白质类和糖类物质的转化规律,探究MnO2强化厨余垃圾定向腐殖化的作用机制,以期为厨余垃圾全量化和高值化利用提供参考。
二氧化锰对厨余垃圾制备液体肥中腐殖质形成的影响
Effect of manganese dioxide on humus formation in liquid fertilizers prepared from food waste
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摘要: 厨余垃圾全量化制备液态有机肥是其高值资源化利用的重要途径之一。厨余垃圾中腐殖质合成前体物的释放与定向腐殖化是制备高品质液态有机肥的技术难题。通过厨余垃圾热水解 (90和170 ℃) 破坏大分子木质纤维素结构,探究厨余垃圾中蛋白质、氨基酸、可溶性糖等腐殖质合成前体物的转化规律,通过添加二氧化锰 (MnO2) 与功能微生物 (抗酸化复合菌剂和米曲霉酶源产物) 协同定向腐殖化,阐明MnO2强化厨余垃圾定向腐殖化制备液态有机肥的作用机制。结果表明,厨余垃圾在170 ℃热水解1 h效果最佳,液相中可溶性蛋白质和还原糖质量分数与热水解前相比分别提高了22%和12%。添加MnO2后,发酵前期 (24 h) 还原糖质量分数提高了69%,96 h游离氨基酸的质量分数提高了27.3%,进一步提高了厨余垃圾中腐殖质合成前体物的释放。随着腐殖化反应的进行,发酵结束时 (168 h) 还原糖和游离氨基酸的质量分数分别降低了88%和22%,腐殖酸和富里酸质量分数分别提高了85%和33%。可见,热水解联合MnO2催化,可明显促进腐殖质合成前体物的生成和发酵后期的定向腐殖化。该研究结果可为厨余垃圾全量化制备液态有机肥提供参考。Abstract: The preparation of liquid organic fertilizers from food waste in full quantification is one of the most important ways of its high-value resource utilization. The release and directed humification of humus synthetic precursors in food waste is a technical challenge for the preparation of high quality liquid organic fertilizers. In this study, in order to achieve targeted humification of food waste thermal hydrolysis, functional microbial enhancement, and the addition of manganese dioxide (MnO2) catalysis were performed, The thermal hydrolysis under different conditions (90 and 170 ℃) was first performed, and then the anti-acidification compound bacterial agents, enzyme-derived products of Aspergillus oryzae and MnO2 was added. The mechanism of MnO2-enhanced targeted humification of food waste to produce liquid organic fertilizers was investigated. The results showed that food waste was subjected to the targeted humification at 170 ℃. The results showed that the highest efficiency was achieved by thermal hydrolysis of food waste at 170 ℃ for 1 h. The mass of soluble protein and reducing sugar in the liquid phase increased by 22% and 12% than that before thermal hydrolysis, respectively. The addition of MnO2 increased the mass of reducing sugars by 69% at the first stage of fermentation (24 h) and the mass of free amino acids by 27.3% at 96 h. This further enhanced the release of precursors for humus synthesis from food waste. As the humification reaction proceeded, the mass of reducing sugars and free amino acids decreased by 88% and 22% at the end of fermentation (168 h), and the contents of humic and fulvic acids increased by 85% and 33%, respectively. Thermal hydrolysis in combination with MnO2 catalysis significantly promoted the production of precursors for humus synthesis and targeted humification in the later stages of fermentation. This study may provide technical support for the preparation of liquid organic fertiliser from food waste in a fully quantified form.
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Key words:
- food waste /
- manganese dioxide /
- humification /
- thermal hydrolysis /
- liquid organic fertilizer
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表 1 不同热水解温度下理化指标变化情况
Table 1. Changes of physical and chemical indexes under different thermal hydrolysis temperatures
处理组 TS/% 含水率/% 有机质/% pH SCOD/(mg·L−1) 总碳/% 总氮/% CK 13.95 86.05 93.75 5.9 18 048 45.93 0.568 90 ℃ 12.75 87.25 94.12 5.5 24 308 46.77 0.614 170 ℃ 11.95 88.05 95.08 5.2 28 780 46.2 0.567 -
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