CN102584471B - 有机硅水溶长效复合肥及制备方法 - Google Patents
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Abstract
本发明属于包膜型缓控释长效复合肥料技术领域，涉及采用有机硅包覆复合肥颗粒，构成环保型缓控释复合肥料及其制备方法。有机硅水溶长效复合肥由水溶性颗粒状内核与疏水性聚合物外包膜层构成。制备方法：①制备水溶性颗粒状内核：以尿素、重过磷酸钙、氯化钾为主要营养元素，经粉碎、混合、造粒、干燥得颗粒状复合肥，作为包膜肥料内核；②制备包膜剂：以一甲基三氯硅烷为主体原料，共水解、缩合，水洗除酸后，制得改性有机硅甲基硅树脂聚合物；③包膜：将水溶性颗粒状内核投入包膜机中，预热，间歇喷入包膜剂，加热保温，脱水缩聚交联固化，在肥料颗粒表面形成疏水性的甲基硅树脂包膜。制造、使用全程无三废、无毒副作用及环境污染，属环保产品。
Description
技术领域
本发明属于包膜型缓控释长效复合肥料技术领域，涉及采用有机硅包覆复合肥颗粒，构成环保型缓控释复合肥料及其制备方法。
背景技术
在现代农业生产中，施用化肥是获得作物增产高产的重要手段之一。但是，化肥大都是无机盐类，具有可溶易溶于水的特性，这种“速溶”速效的特点，与农作物生育过程中对养分的需求并不协调，造成化肥的多施、流失、浪费与污染环境。特别是用量最大，通常实际利用率仅有30％～40％的氮肥，它大约仅利用了1/3，而2/3损失了。这种肥料的高耗低效，不仅导致资源、能源的巨大浪费，而且恶化了生态环境，危及人类的生存与健康。
发明内容
为了克服现有技术的缺点，本发明提供一种有机硅水溶长效复合肥及制备方法，具有包覆材料新颖首创，工艺合理，制造、使用全程无三废、无毒副作用及无环境污染，属环保产品。
有机硅水溶长效复合肥由水溶性颗粒状内核与疏水性聚合物外包膜层构成。
所述的颗粒状内核是由含有氮、磷、钾、钙、镁、硫及必要的微量元素的化合物，粒径为2-4mm。
所述的疏水性聚合物外包膜层为疏水透气的改性有机硅甲基硅树脂。
所述疏水性聚合物外包膜层的厚度为15-50μm。
所述的改性有机硅甲基硅树脂为一甲基三氯硅烷(CH3SiCl3)、二甲基二氯硅烷[(CH3)2SiCl2]和长碳链烷基(甲基)二甲氧基硅烷[CnH2n+1(CH3)Si(OCH3)2]的共水解、缩合聚合物，mol比为CH3SiCl3∶(CH3)2SiCl2∶CnH2n+1(CH3)Si(OCH3)2＝75-85∶10-20∶3-5。
有机硅水溶长效复合肥制备方法，包括下列步骤：①制备水溶性颗粒状内核：以尿素或/和碳铵、重过磷酸钙或/和钙镁磷肥、氯化钾或/和硫酸钾为主要营养元素(N.P.K)，并根据作物品种类别与测土数据，科学合理设计(N.P.K)配比，适量添加铁、锌、铜、锰的硫酸盐及硼砂等微量元素，并添加尿氮抑制稳定剂和聚乙烯醇(PVA)粘合剂，经粉碎、混合、造粒、干燥得颗粒状复合肥，作为包膜肥料内核；②制备包膜剂：以一甲基三氯硅烷(CH3SiCl3)为主体原料，添加少量改性剂二甲基二氯硅烷[(CH3)2SiCl2]和长碳链烷基(甲基)二甲氧基硅烷(CnH2n+1(CH3)Si(OCH3)2)共水解、缩合，水洗除酸后，制得改性有机硅甲基硅树脂聚合物；改性有机硅甲基硅树脂聚合物加KOH水溶液在70℃～90℃碱解处理2～4h，制得低聚甲基硅醇钾水溶液即包膜剂，固含量在30％～40％；③包膜：将水溶性颗粒状内核投入包膜机中，预热至110～120℃，间歇喷入包膜剂，加热保温，包膜剂加完后，升温至145～155℃，低聚甲基硅醇在酸催化作用下，脱水缩聚交联固化，在肥料颗粒表面形成疏水性的甲基硅树脂包膜。
调节包膜剂用量，制得包膜厚度在15-50μm，控释时间分别为30天、60天、90天、120天等不同规格的控释复合肥包膜颗粒。
本发明有下列有点：(1)、有机硅材料应用于农业已有几十年历史，但用作固态复合肥包膜材料为本发明首创和亮点所在。(2)、采用水溶性改性甲基硅树脂低聚物作包膜材料，避免了有毒有害溶剂的使用，既有利于包膜操作，又避免了对环境的危害。(3)、采用硫酸作离子交换剂，同时也是甲基硅醇树脂缩合交联固化的催化剂，而且离子交换生成的硫酸钾(K2SO4)也是复合肥的有效成分，一剂多用。(4)、有机硅聚合物膜具有很好的疏水透气性，包复于复合肥表面就形成了疏水透气膜，当肥料颗粒浸泡于水中时，疏水膜阻止大量水直接进入肥料颗粒内部，防止养分的速溶释放；同时膜又具良好的透气性，施入土壤后，土壤中的水汽可以缓慢地透过膜层进入颗粒内部，使肥料缓慢溶胀溶解，在溶胀溶解过程中，膜内压力逐步升高，导致膜的破裂，直至崩溃，养分从逐步释放到全部释放会是一个缓慢的过程。包膜厚度控制释放速度，以此，完成肥料的长效缓释过程。(5)、肥料养分释放后，残留的有机硅树脂包膜及粘合剂PVA，在土壤中酸、碱、微生物作用下逐渐降解，PVA降解较快约在6～8月内降解成水和CO2；有机硅聚合物降解过程相对要慢一些，但在降解过程中形成的低聚硅氧烷中小分子，含有较多的硅羟基(Si-OH)可以同土壤中固有的硅羟基和铝羟基活性基团相结合，有利于改善土壤的团粒结构，提高土壤保温保水与透气性，优化土质。降解中有机成分可以增加土壤的有机质，为土壤中微生物提供碳源和能量，激活土壤中微生物的活性，促进作物生长。(6)、有机硅树脂降解的最终产物是水(H2O)、二氧化碳(CO2)和硅酸(H2SiO3)。硅酸是可以被作物吸收利用的硅肥，硅肥是农作物生长的重要营养元素之一，特别是水稻、小麦、玉米、高粱等作物生长的必要营养元素，硅在作物生长过程中具有极其重要的作用，可以增强作物耐旱、抗病、抗伏能力，促进作物对氮、磷的吸收利用，有利于作物籽粒的形成与增重。硅酸是不可忽缺的肥料元素之一，也可以说有机硅本身也是一种肥料。(7)、有机硅材料本身生理惰性，生物相容性好，无毒副作用。本发明包膜复合肥生产过程无三废，施用过程乃至残留物对生物环境均无害，是绿色的环保型产品。(8)、以不同(NPK)配比的颗粒为内核，配合不同包膜厚度(即不同控释时间)，制得各种规格的粒料，再以适当比例复配，可制得适合不同作物要求及相应控释特性的有机硅材料水溶长效复合肥，从而大大延长肥料的有效期，做到一次施肥，作物整个生育期有肥效，均衡供给作物养分，将肥料的利用率提高到70％-80％。
具体实施方式
以适用于夏玉米的控释复合肥为例。
夏玉米对氮(N)、磷(P)、钾(K)营养元素总的需求比例大致为(21-8-11)，一般在6月初播种，9月底或10月初收获，生长期在110天左右。
玉米在不同的生育阶段，吸收养分的数量和比例差异很大，苗期植株小，生长慢，吸收营养少；进入拔节、孕穗到抽穗扬花期是玉米营养生长与生殖生长并进的最旺盛阶段，生长速度快，需要大量养分供给；后期即成熟期对养分的需求又有所减少。在各个生育阶段对N.P.K养分的吸收比例也是不同的，如苗期吸氮量仅占总需氮量的9.6％，中期(拔节至抽穗扬花)，吸氮量占到78.5％，后期吸氮也只占11.9％，而对磷的吸收各生育阶段比较平稳，累积吸磷量逐步上升；对钾的吸收则是苗期相对较大，以后则逐渐减少，花期以后则明显减少。
为此，本发明设计了三种不同N.P.K组成比例的配方，并分别通过包膜控制释放时间，最后按一定比例复配，制得与玉米不同生育期对养分需求相适应的控释长效复合肥。具体操作为：
实施例1：配制N-P-K为15-6-15包膜复合肥，控释时间为30天。
①制备水溶性颗粒状内核：将尿素28kg，碳铵12.5kg，重过磷酸钙8kg，钙镁磷肥15kg，氯化钾23.5kg，微量元素(包括硫酸亚铁、硫酸锌、硫酸铜、硫酸锰和硼砂等)4kg，尿氮抑制稳定剂(HQ、DCD)0.03kg，计量后加入破碎混合器中，高速粉碎混合15～30分钟，再加入10％的PVA水溶液5kg(粘合剂)，搅拌5～10分钟，混合均匀后，送入转鼓式造粒机，制得粒径2-3mm的圆形复合(混)肥颗粒，经干燥后过筛，碎末返回混合造粒。
②制备包膜剂：取16.4kgCH3SiCl3、3kg(CH3)2SiCl2、0.6kgC8H17(CH3)Si(OCH3)2，混合均匀后加入高位槽内。在100立升水解反应釜中加入60升水，在搅拌下，将高位槽中的混合单体缓慢滴入水解釜，釜的夹套内通入冷却水，控制水解、缩合反应温度在20-40℃，约在0.5-1h内滴完，滴完后继续搅拌反应1h，得改性甲基硅树脂缩聚物，停止搅拌，静置15分钟，放掉下部酸水，加水洗涤3-4次，洗至PH＝5-6，可得产物(折干基)约9.5kg，含水率在10～20％。
取改性甲基硅树脂缩聚物11.3kg(折干基约9.5kg，含水约1.8kg)加入碱解反应釜中，加30％KOH水溶液70kg，并补加2.6升水，搅拌下加热至70℃～90℃，碱解处理2h左右，得固含量为36％左右的改性低聚甲基硅醇钾水溶液。低聚甲基硅醇钾溶液在投入包膜使用前，每5份(体积份)低聚甲基硅醇钾溶液加入1份(体积份)96％的浓硫酸，配成固含量45％的酸性包膜剂。
所述的共水解反应式为：
m CH3SiCl3+3mH2O→mCH3Si(OH)3+3mHCl
n (CH3)2SiCl2+2nH2O→n(CH3)2Si(OH)2+2nHCl
j CnH2n+1(CH3)Si(OCH3)2+2jH2O→jCnH2n+1(CH3)Si(OH)2+2jCH3OH
所述的缩合反应式为：
m CH3Si(OH)3+n(CH3)2Si(OH)2+jCnH2n+1(CH3)Si(OH)2→(CH3SiO3/2)m[(CH3)2SiO]n[CmH2n+1(CH3)SiO]j+XH2O
③包膜：取水溶性颗粒状内核94kg，投入转鼓式包膜机内，预热至110℃，间歇喷入包膜剂约8kg，期间维持温度在110℃，蒸发的水份由抽风机排出，喷完后升温至145℃左右，附着于肥料颗粒表面的低聚甲基硅醇在酸催化和高温下，迅速原位脱水缩聚交联固化，在肥料颗料表面形成改性甲基硅树脂包膜。最后加入1.5kg隔离剂如滑石粉，混合均匀降温出料。
实施例2：配制N-P-K为24-10-11包膜复合肥，控释时间60天。
①制备水溶性颗粒状内核：将尿素52.5kg，重过磷酸钙23.5kg，氯化钾15kg，尿氮抑制稳定剂0.01kg，计量后加入破碎混合器中，高速粉碎混合15-30分钟，再加入10％PVA水溶液5kg，搅拌5-10分钟，混均匀后，送入转鼓式造粒机，得到粒径2-3mm的圆形复合肥颗粒，经干燥后过筛，碎粉返回混合造粒。
②制备包膜剂：同实施例1第②步。
③包膜：将水溶性颗粒状内核92.5kg加入转鼓式包膜机内，预热至120℃，间歇喷入包膜剂约12kg，喷浆过程中维持温度在120℃，蒸发的水汽由抽风机排出，喷完后升温至150℃，缩聚交联固化反应，在肥料颗粒表面形成改性甲基硅树脂包膜。最后加入1.5kg隔离剂如滑石粉，混均匀降温出料。
实施例3：配制N-P-K为19-7-9包膜复合肥，控释时间90天。
①制备水溶性颗粒状内核：将尿素42.5kg，重过磷酸钙8kg，钙镁磷肥24kg，氯化钾12.5kg，计量后加入破碎混合器内，高速粉碎混合15-30分钟，再加10％PVA水溶液5kg，搅拌5-10分钟，混匀后送入转鼓式造粒机，得到粒径2-3mm的圆形复合肥颗粒，经干燥后过筛，碎粉返回混合造粒。
②制备包膜剂：同实施例1第②步。
③包膜：将水溶性颗粒状内核90.5kg加入转鼓式包膜机内，预热至120℃，间歇喷入包膜剂约16kg，喷浆过程中维持在120℃，蒸发出的水汽由抽风机排出。喷完后，升温至150℃，缩合交联固化反应，在复肥颗粒表面形成改性甲基硅树脂包膜。最后加入1.5kg隔离剂如滑石粉，混均匀降温出料。
将N-P-K含量分别为15-6-15、24-10-11、19-7-9的三种不同组分比例与不同控释时间的包膜复合肥按20％、50％、30％的质量比例进行复配，获得综合养分含量为21-8-11的水溶长效复合肥料。
主要质量指标：
1、总养分(N+P2O5+K2O)含量≥40％。
2、初期养分释放率≤15％。
3、90天内养分总释放率≥80％。
4、粒度(2-4mm颗粒含量)≥90％。
5、水分含量≤2～3％。
Claims (7)
1.一种有机硅水溶长效复合肥的制备方法，包括下列步骤：①制备水溶性颗粒状内核：以尿素或/和碳铵、重过磷酸钙或/和钙镁磷肥、氯化钾或/和硫酸钾为主要营养元素，并根据作物品种类别与测土数据，科学合理设计N、P、K配比，适量添加铁、锌、铜、锰的硫酸盐及硼砂微量元素，并添加尿氮抑制稳定剂和聚乙烯醇粘合剂，经粉碎、混合、造粒、干燥得颗粒状复合肥，作为包膜肥料内核；②制备包膜剂：以一甲基三氯硅烷（CH3SiCl3）为主体原料，添加改性剂二甲基二氯硅烷[（CH3）2SiCl2]和长碳链烷基（甲基）二甲氧基硅烷（CnH2n+1(CH3)Si(OCH3)2）共水解、缩合，水洗除酸后，制得改性有机硅甲基硅树脂聚合物；改性有机硅甲基硅树脂聚合物加KOH水溶液在70℃～90℃碱解处理2-4h，制得低聚甲基硅醇钾水溶液即包膜剂，固含量在30-40%；③包膜：将水溶性颗粒状内核投入包膜机中，预热至110-120℃，间歇喷入包膜剂，加热保温，包膜剂加完后，升温至145-155℃，脱水缩聚交联固化，在肥料颗粒表面形成所述厚度的疏水性甲基硅树脂包膜，得有机硅水溶长效复合肥颗粒。
2.根据权利要求1所述的制备方法，其特征在于：所述步骤①的尿素、碳铵、重过磷酸钙、钙镁磷肥、氯化钾、微量元素的质量比为28：12.5：8：15：23.5：4。
3.根据权利要求1所述的制备方法，其特征在于：所述步骤①的尿素、重过磷酸钙、氯化钾的质量比为52.5kg：23.5kg：15kg。
4.根据权利要求1所述的制备方法，其特征在于：所述步骤①的尿素、重过磷酸钙、钙镁磷肥、氯化钾的质量比为42.5：8：24：12.5。
5.根据权利要求1所述的制备方法，其特征在于：进行第③步前，在第②步所得的包膜剂中加入硫酸，混合配成酸性包膜剂，固含量为45%。
6.根据权利要求5所述的制备方法，其特征在于：所述硫酸的加入量为每5体积份的低聚甲基硅醇钾溶液加入1体积份96%的浓硫酸。
7.根据权利要求1所述的制备方法，其特征在于：所述第③步包膜后，添加所得有机硅水溶长效复合肥颗粒1-2%重量份的滑石粉，在转鼓中混合均匀。
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| CN1513915A (zh) * | 2002-05-14 | 2004-07-21 | 阎新育 | 一种纳米级防水微粉产品及其制备方法 |
| CN1903804A (zh) * | 2006-07-28 | 2007-01-31 | 浙江工业大学 | 一种膨润土片层桥联包覆型缓释复合肥料及其制备方法 |
| CN100999427A (zh) * | 2006-12-31 | 2007-07-18 | 沈阳农业大学 | 一种包膜控释蔬菜专用复合肥及其制法 |
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