石蜡改性一步法制备蓖麻油基聚氨酯包膜尿素及其应用

    One-step preparation of castor oil based polyurethane coated urea by paraffin modification and its application

    • 摘要: 为了简化聚氨酯包膜尿素传统合成工艺的复杂性,该研究以蓖麻油和多亚甲基多苯基异氰酸酯(polymethylene polyphenylene isocyanate,PAPI)为原料,液体石蜡为改性剂,一步法制备蓖麻油基聚氨酯包膜尿素(polyurethane coated urea,PCU),系统分析了其缓释和控失性能,并通过单因素试验探讨了关键工艺参数对其性能的影响。结果表明:在液体石蜡添加量为0.5%、蓖麻油含量为60%、包膜温度为60 ℃、转速为20 r/min的条件下,制备出的5%聚氨酯包膜尿素,缓释期长达66 d,与未改性体系相比延长了34.7%;液体石蜡的引入明显改善了PCU的均匀性和致密性,5%~9%包膜量的聚氨酯包膜尿素使氨挥发量降至170~340 mg/L,降幅达71.67%~85.83%,对比纯尿素处理组,30 d累计总氮流失率降低60.05%~91.01%;经田间试验验证,减施20%的条件下,PCU5处理组(5%包膜量的PCU)玉米作物产量提高到11 914.35 kg/hm2,对比纯尿素增产22.1%。该工艺通过原料配比优化和液体石蜡疏水改性的协同效应,实现了PCU的高效利用,研究结果将为中国农业的绿色发展和肥料的综合利用提供一定的理论支撑和技术指导。

       

      Abstract: Food security has been threatened by the increase in industrialization, urbanization, and desertification. The fertilizer can be applied to grow, while the fertilizer utilization rate is only 40% in China. The annual loss of nitrogen has reached up to 120 Tg, due to the ammonia evaporation volume and nitrogen oxide emissions. The unabsorbed nutrients are lost during leaching and runoff pathways, leading to soil acidification, the eutrophication of the water bodies, and greenhouse gas environmental issues. Therefore, it is an urgent need to improve the utilization rate of the fertilizer, in order to alleviate the agricultural surface pollution due to the high production in the food industry. In this study, a one-step coating was proposed to prepare the castor oil-based polyurethane-coated urea (PCU), in order to solve the complex procedure and the unfriendly environment of the conventional petroleum-based polyurethane-coated urea. The castor oil (CO) and Polymethylene polyphenyl isocyanate (PM-200) were used as the raw materials, while the paraffin was introduced as a modifier. A systematic investigation was then implemented to determine the water absorption, porosity, swelling capacity, and water contact angle of the liquid paraffin-modified polyurethane membranes before and after 7 days of immersion. The membrane with the 0.5% liquid paraffin also exhibited the lowest porosity (1.01%) and swelling capacity (1.67). Notably, the water contact angle of the 0.5% liquid paraffin-modified membrane reached 102.8°, indicating a 4.35° increase, compared with the unmodified polyurethane membrane. The optimal slow-release ratios were explored using a UV spectrophotometer, Kjeldahl nitrogen tester, and scanning electron microscope. The slow-release performance, nitrogen loss, and microstructure were determined to be the influencing factors on the castor oil content, paraffin wax addition, coating temperature, and rotational speed. The soil column drenching and field tests were carried out to validate the application. Paraffin tests showed that the slow-release period of PCU with 5% coating reached 66 days, which was 34.7% longer than that of the unmodified system, under the optimal conditions of 60% castor oil, 0.5% paraffin addition, 60 ℃ coating temperature, and 20 r/min rotational speed; Paraffin was significantly improved the hydrophobicity, where the pores of the film layer were filled to reduce the surface energy. As a result, the cumulative ammonia evaporation volume of PCU with 5%-9% coating decreased from 1 200 mg/kg (normal urea) to 170-340 mg/kg within 30 days, indicating a reduction of 71.67%-85.83%. Additionally, the 30-day leaching loss rate of the total cumulative nitrogen decreased by 77.94%-91.01%, and the losses of ammonium nitrogen, nitrate nitrogen, and amide nitrogen dropped to 119.6, 151.4, and 50.2 mg/L, respectively, indicating a decrease of 82%-93%. A field experiment was conducted in Xinxiang City, Henan Province, China. Furthermore, the maize plant height, stem thickness, chlorophyll content (SPAD value) and dry matter accumulation of the homemade film-wrapped urea-treated group were 73.13 cm, 1.883 cm, 61.20, and 322 g, respectively, under the condition of 20% yield reduction, compared with the ordinary urea-treated group, which were 11.07%, 2.3%, 9.76%, and 10.30% higher, respectively. The yield reached 11 914.35 kg/hm², which was 22.1% higher than the normal urea treatment group. The optimal raw material ratio and paraffin hydrophobic modification can be expected to overcome the technical limitations of the conventional multi-step modification of the vegetable oil-based polyols, which was 22.1% higher than that of the control. The finding can provide a promising potential approach for high-efficiency slow-release fertilizers, in order to prevent and control agricultural surface pollution.

       

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