植物营养功能性材料制备及其应用研究
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摘要
21世纪,人口、资源、环境间的矛盾日见突出。化学肥料利用率低以及障碍性土壤地力贫瘠已成为制约我国农业生产和威胁国家粮食安全的关键因素。新型植物营养功能性材料研制并应用于大田作物专用缓/控释肥料和荒漠化土地改良剂的生产,成为农业领域资源高效利用、环境友好新型材料技术的主流。本研究从植物营养功能性材料制备入手,选用工农业废弃物为主要原料,采用现代化工工艺和纳米材料制备技术原创性的研制了2类植物营养功能性材料,通过综合分析方法对功能性材料性能进行了表征测试；将其应用于大田作物缓/控释肥料和荒漠化土地修复等农业和生态环境领域,同时对功能性材料的土壤生物学效应和生态环境安全评价进行了比较系统的探索研究。获得主要研究结果如下：
1、研发了植物营养功能性材料制备工艺,材料表征结果表明胶团粒径达到纳米-亚微米级。
选用农业废弃物、工业副产物及廉价、环保的化工原料,通过微乳化、高剪切和非均相混聚等技术,在液相条件下,研制了3种微乳化型和4种化学聚合(缩合)反应型纳米-亚微米级植物营养功能性材料,通过扫描电镜、透射电镜和激光粒度分析仪对植物营养功能性材料进行了表征测试,结果表明,供试材料90%以上胶团粒径在10-120nm范围,胶团粒径达到纳米-亚微米级。
2、植物营养功能性材料应用于包膜剂生产的作物专用缓/控释肥料,可有效提高氮肥利用率,改善土壤微生物种群结构
通过“异粒变速”养分缓/控释工艺,制备成养分释放速率与小麦、玉米和水稻生各育期对养分的需求基本吻合的专用缓/控释肥料。缓/控释肥料的应用有效促进不同作物的生长,不同区域较农民习惯施肥处理作物产量增加了2.07%-7.17%；缓/控释肥料可以提升土壤在关键生育期的供氮能力和土壤地力水平,较习惯施肥氮肥可提高利用率在10个百分点以上；在生育期可以降低土壤脲酶活性,土壤细菌shannon指数显著大于施尿素肥料处理(p<0.05),结果表明,用功能性材料作为包膜材料的缓/控释肥料对土壤微生物多样性存在促进作用,有利于土壤微生物活性提高,并能够促进种群数量增加。
3、植物营养功能性固沙保水剂材料能够改善荒漠化土地保肥持水性能,改善荒漠化土壤的物理结构
多功能固沙保水剂对土层具有很强的固结能力,与土壤矿物发生络合反应,形成蜂窝状结构,改善了荒漠化土地中的孔隙状况,增加了荒漠化土地中的团粒结构。同时,功能性材料胶团径达到纳米-亚微米级后增强了其比表面积,在土壤表面形成致密的网状结构,形成相对厚的吸附水层或水膜,从而增强荒漠化土地的吸水、持水能力,这是多功能固沙保水剂保水、保肥的根本原因。田间试验表明施用功能性材料能提高5-10cm土层温度0.6-2.6℃和0-20cm上层土壤含水量；种植黑麦草比对照增产2倍以上
4、植物营养功能性材料提高了土壤生物多样性,生态环境安全
在室内模拟条件下,选用混合菌剂,植物营养功能性材料在4-20周降解率均达98%以上,降解产物为稳定的小分子、CO2和H2O。功能性材料在降解释放过程中能够增加了土壤有益细菌数量,提高土壤肥力水平,抑制了反硝化细菌的数量,减少了氮素的损失,可以提高氮素肥料的利用率；施用功能性材料处理土壤动物的线虫动物门、蜱螨目的个体数均有所增加,提高了土壤生物多样性。
综上所述,自主研制的3种微乳化型和4种化学聚合(缩合)反应型纳米-亚微米级植物营养功能性材料具有环境友好性,应用结果表明,功能材料可以提高氮肥利用率,修复荒漠化土地,改善土壤理化性状,增强土壤保肥持水性能；植物营养功能性材料的应用对于维持农田可持续利用、保障国家粮食安全具有重要意义。
The inconsistency among the natural resources, environment and people is getting more and more serious in21th century. Low fertilizer use efficiency and low soil fertility of the cultivated land have turned into the key factors to restrict agricultural production, and threaten national food safety. New functional materials with the character of plant nutrition to be applied for the restoration of desertification and production of slow-release fertilizers become a mainstream in high efficient use of agricultural resources and environmental friendly new material technique. It is a creative technique to prepare functional materials with the character of plant nutrition through modern chemical technology and nano-material technology using industrial and agricultural waste as main raw material. After material preparation and characterization, the functional materials were applied in slow-release fertilizer production and restoration of desertification. The risk of the functional materials in soil and environment was also evaluated in this paper. Main results were as follow:
1. Preparation and characterization of plant nutrition functional material in nano and sub-nano grade
Three micro-emulsified and five chemically polymerized nano, sub-nano plant nutrition functional materials were prepared through micro-emulsification, high shear and heterogeneous polymerization techniques using waste, industrial by-product and cheap, environmental friendly chemical materials. Then the materials were characterized with scanning electron microscope (SEM), transmission electron microscope (TEM) and laser particle size analyzer. The results showed that90%colloid particles of the materials were in the size of10-120nm as nano and sub-nano grade.
2. Application of the materials as coating agent for slow-release fertilizer, the use efficiency of nitrogen increased and the soil microbial diversity improved
Specific slow-release fertilizers for wheat, maize and rice were prepared to release nitrogen to meet the demand of crops at different stage. The crop yield enhanced by2.07%to7.17%by use of the functional materials coated slow-release fertilizers in different area comparied with regular fertilizer, soil fertility improved and nitrogen use efficiency increased by more than10%. During crop growth stage, the urease activity decreased. The bacterial Shannon index enhanced significantly comparing with the urea treatment. In all, the soil microbial diversity could be promoted, enzyme activity and microbial population enhanced by the use of slow-release fertilizers.
3. Application of the materials in desert as sand-fixing and water retaining polymer, the soil characters of sand-fixing, water retaining and physical struncture improved
Using the materials as sand-fixing and water retaining agent, the soil pore status, aggregate structure improved as its high fixing and complexing reaction with soil minerals. In addition, nano and sub-nano composite materials had huge specific surface area. They formed tight net structure on soil surface, and formed relatively thick adsorption water or water film to enhance the ability of water absorbing and retaining. It is the main reason of the materials for sand-fixing and water retaining. Field experiment with the use of the materials also showed that the soil temperature at5-10cm layer could increase0.6～2.6℃and the soil water content at0-20cm almost two times of the control. The biomass of ryegrass was two times higher than that of the control.
4. In laboratory conditions, the selected five water-soluble functional materials could be degraded more than98%within4-20weeks when they mixed with microorganisms. The degradated products are small stable molecules, CO2and H2O. The number of beneficial bacteria increased while denitrifying bacteria decreased, which means decrease of nitrogen loss and increase of nitrogen use efficiency. Application of the fertilizers also enhanced the number of nematoda phylum, acari, and improved soil biodiversity.
In summary, the functional materials with the character of plant nutrition performed environmental friendly characters. They could not only increase nitrogen use efficiency but also control desertification of soil. These materials are very important for cultivited land sustainable use and national food security.
1、研发了植物营养功能性材料制备工艺,材料表征结果表明胶团粒径达到纳米-亚微米级。
选用农业废弃物、工业副产物及廉价、环保的化工原料,通过微乳化、高剪切和非均相混聚等技术,在液相条件下,研制了3种微乳化型和4种化学聚合(缩合)反应型纳米-亚微米级植物营养功能性材料,通过扫描电镜、透射电镜和激光粒度分析仪对植物营养功能性材料进行了表征测试,结果表明,供试材料90%以上胶团粒径在10-120nm范围,胶团粒径达到纳米-亚微米级。
2、植物营养功能性材料应用于包膜剂生产的作物专用缓/控释肥料,可有效提高氮肥利用率,改善土壤微生物种群结构
通过“异粒变速”养分缓/控释工艺,制备成养分释放速率与小麦、玉米和水稻生各育期对养分的需求基本吻合的专用缓/控释肥料。缓/控释肥料的应用有效促进不同作物的生长,不同区域较农民习惯施肥处理作物产量增加了2.07%-7.17%；缓/控释肥料可以提升土壤在关键生育期的供氮能力和土壤地力水平,较习惯施肥氮肥可提高利用率在10个百分点以上；在生育期可以降低土壤脲酶活性,土壤细菌shannon指数显著大于施尿素肥料处理(p<0.05),结果表明,用功能性材料作为包膜材料的缓/控释肥料对土壤微生物多样性存在促进作用,有利于土壤微生物活性提高,并能够促进种群数量增加。
3、植物营养功能性固沙保水剂材料能够改善荒漠化土地保肥持水性能,改善荒漠化土壤的物理结构
多功能固沙保水剂对土层具有很强的固结能力,与土壤矿物发生络合反应,形成蜂窝状结构,改善了荒漠化土地中的孔隙状况,增加了荒漠化土地中的团粒结构。同时,功能性材料胶团径达到纳米-亚微米级后增强了其比表面积,在土壤表面形成致密的网状结构,形成相对厚的吸附水层或水膜,从而增强荒漠化土地的吸水、持水能力,这是多功能固沙保水剂保水、保肥的根本原因。田间试验表明施用功能性材料能提高5-10cm土层温度0.6-2.6℃和0-20cm上层土壤含水量；种植黑麦草比对照增产2倍以上
4、植物营养功能性材料提高了土壤生物多样性,生态环境安全
在室内模拟条件下,选用混合菌剂,植物营养功能性材料在4-20周降解率均达98%以上,降解产物为稳定的小分子、CO2和H2O。功能性材料在降解释放过程中能够增加了土壤有益细菌数量,提高土壤肥力水平,抑制了反硝化细菌的数量,减少了氮素的损失,可以提高氮素肥料的利用率；施用功能性材料处理土壤动物的线虫动物门、蜱螨目的个体数均有所增加,提高了土壤生物多样性。
综上所述,自主研制的3种微乳化型和4种化学聚合(缩合)反应型纳米-亚微米级植物营养功能性材料具有环境友好性,应用结果表明,功能材料可以提高氮肥利用率,修复荒漠化土地,改善土壤理化性状,增强土壤保肥持水性能；植物营养功能性材料的应用对于维持农田可持续利用、保障国家粮食安全具有重要意义。
The inconsistency among the natural resources, environment and people is getting more and more serious in21th century. Low fertilizer use efficiency and low soil fertility of the cultivated land have turned into the key factors to restrict agricultural production, and threaten national food safety. New functional materials with the character of plant nutrition to be applied for the restoration of desertification and production of slow-release fertilizers become a mainstream in high efficient use of agricultural resources and environmental friendly new material technique. It is a creative technique to prepare functional materials with the character of plant nutrition through modern chemical technology and nano-material technology using industrial and agricultural waste as main raw material. After material preparation and characterization, the functional materials were applied in slow-release fertilizer production and restoration of desertification. The risk of the functional materials in soil and environment was also evaluated in this paper. Main results were as follow:
1. Preparation and characterization of plant nutrition functional material in nano and sub-nano grade
Three micro-emulsified and five chemically polymerized nano, sub-nano plant nutrition functional materials were prepared through micro-emulsification, high shear and heterogeneous polymerization techniques using waste, industrial by-product and cheap, environmental friendly chemical materials. Then the materials were characterized with scanning electron microscope (SEM), transmission electron microscope (TEM) and laser particle size analyzer. The results showed that90%colloid particles of the materials were in the size of10-120nm as nano and sub-nano grade.
2. Application of the materials as coating agent for slow-release fertilizer, the use efficiency of nitrogen increased and the soil microbial diversity improved
Specific slow-release fertilizers for wheat, maize and rice were prepared to release nitrogen to meet the demand of crops at different stage. The crop yield enhanced by2.07%to7.17%by use of the functional materials coated slow-release fertilizers in different area comparied with regular fertilizer, soil fertility improved and nitrogen use efficiency increased by more than10%. During crop growth stage, the urease activity decreased. The bacterial Shannon index enhanced significantly comparing with the urea treatment. In all, the soil microbial diversity could be promoted, enzyme activity and microbial population enhanced by the use of slow-release fertilizers.
3. Application of the materials in desert as sand-fixing and water retaining polymer, the soil characters of sand-fixing, water retaining and physical struncture improved
Using the materials as sand-fixing and water retaining agent, the soil pore status, aggregate structure improved as its high fixing and complexing reaction with soil minerals. In addition, nano and sub-nano composite materials had huge specific surface area. They formed tight net structure on soil surface, and formed relatively thick adsorption water or water film to enhance the ability of water absorbing and retaining. It is the main reason of the materials for sand-fixing and water retaining. Field experiment with the use of the materials also showed that the soil temperature at5-10cm layer could increase0.6～2.6℃and the soil water content at0-20cm almost two times of the control. The biomass of ryegrass was two times higher than that of the control.
4. In laboratory conditions, the selected five water-soluble functional materials could be degraded more than98%within4-20weeks when they mixed with microorganisms. The degradated products are small stable molecules, CO2and H2O. The number of beneficial bacteria increased while denitrifying bacteria decreased, which means decrease of nitrogen loss and increase of nitrogen use efficiency. Application of the fertilizers also enhanced the number of nematoda phylum, acari, and improved soil biodiversity.
In summary, the functional materials with the character of plant nutrition performed environmental friendly characters. They could not only increase nitrogen use efficiency but also control desertification of soil. These materials are very important for cultivited land sustainable use and national food security.
引文
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