CN108409509B - 农业组合物及其制备方法 - Google Patents
农业组合物及其制备方法 Download PDFInfo
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- CN108409509B CN108409509B CN201810427224.9A CN201810427224A CN108409509B CN 108409509 B CN108409509 B CN 108409509B CN 201810427224 A CN201810427224 A CN 201810427224A CN 108409509 B CN108409509 B CN 108409509B
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- methyl cinnamate
- nitrification
- agricultural composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims description 11
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- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical compound COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-N 0.000 claims abstract description 40
- 239000003112 inhibitor Substances 0.000 claims abstract description 36
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Classifications
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C7/00—Fertilisers containing calcium or other cyanamides
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
- Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Soil Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Fertilizers (AREA)
Abstract
本发明涉及硝化抑制剂领域，具体而言，涉及肉桂酸甲酯作为硝化抑制剂的应用。本发明通过纯菌培养和土壤添加试验，证明了肉桂酸甲酯具有良好的硝化抑制效果，可作为生物硝化抑制剂进行应用，且具有很好的硝化抑制效果。本发明还涉及一种农业组合物，其包括含肉桂酸甲酯在内的至少一种硝化抑制剂。该农业组合物施入土壤后，N素转化可得到有效调控。
Description
本申请是申请号为201711091302.4，申请日为2017年11月08日，发明创造名称为“肉桂酸甲酯作为硝化抑制剂的应用”的分案申请。
技术领域
本发明涉及硝化抑制剂领域，具体而言，涉及肉桂酸甲酯作为硝化抑制剂的应用，农业组合物。
背景技术
氮素是植物必需营养元素，也是作物产量的最重要的养分限制因子，施用氮肥已成为农业生产者获得高产的必要途径。据联合国粮农组织估计，发展中国家粮食增产作用的55％以上归功于化肥，其中氮肥又起了至关重要的作用。然而，肥料氮的超量和不合理施用及其在土壤中的迅速水解和硝化，导致氮肥利用率普遍较低。目前我国农业生产中氮肥利用率平均仅为20％-30％左右，单位使用量的增产效益自90年代逐渐下降。因此，如何合理施用氮肥以及提高氮肥利用率一直以来备受关注，成为农业生产中迫切需要解决的问题和研究热点。
有研究表明，通过硝化-反硝化作用损失的氮肥能够占到氮素损失量的34％左右。硝化抑制剂是一类能够抑制土壤中亚硝化细菌等微生物活性的一类物质的总称，其技术原理如下：它进入土壤后能抑制土壤中亚硝化、硝化、反硝化过程，从而阻碍NH4 +向NO2 -、NO3 -转化的过程。硝化抑制剂与氮肥配合施用，通过抑制硝化细菌的活性，抑制硝化作用，使施入氮源能够较长时间的以NH4 +-N的形态存在，供作物利用，而且其理化性质稳定对人畜及环境没有危害。因此，可通过在耕地中施入硝化抑制剂人为的控制氮肥施用时的铵硝比，调控作物根系的NH4 +-N浓度，优化作物根系的氮素营养供应状况，减少硝酸盐累积、淋失和氧化氮气体排放，可能是提高氮素养分资源高效利用，促进作物生长发育及提高产量的重要途径，具有广阔的生产应用前景。
硝化抑制剂在国外的研究起步很早且成效显著，用于大田应用中的试验及推广很多，据统计，我国单位面积化肥用量比世界平均水平高出2.7倍，由此造成的生态和环境压力与日倍增，但我国在这方面的研究较之落后。因此，发展新型硝化抑制剂成为一种必然趋势。
有鉴于此，特提出本发明。
发明内容
本发明的目的在于提供肉桂酸甲酯作为硝化抑制剂的应用，并提供一种农业组合物，以促进通过生化途径实现N肥高效利用技术的发展。
为了实现本发明的上述目的，特采用以下技术方案：
本发明涉及肉桂酸甲酯作为硝化抑制剂的应用。
肉桂酸甲酯是一种常见的根系分泌物，之前常被当作化感物质或其他功效物质对待，关于它在土壤中生态功能等方面的研究十分欠缺。本发明通过纯菌培养和土壤添加试验，证明了肉桂酸甲酯具有良好的硝化抑制效果，可作为生物硝化抑制剂进行应用，且具有很好的硝化抑制效果。
其分子结构式为：
根据本发明的一方面，本发明还涉及一种农业组合物，其包括含肉桂酸甲酯在内的至少一种硝化抑制剂。
硝化抑制剂的使用能减缓土壤硝化作用的进程，提供作物所需养分的同时最大限度的保证了环境安全。本发明提供的农业组合物主要能够更方便的施用硝化抑制剂。
根据本发明的一方面，本发明还涉及如上所述的农业组合物的制备方法，将各成分混合在一起，可选的，还包括压实、干燥、制粒。
与现有技术相比，本发明的有益效果为：
(1)成本较低。本发明将肉桂酸甲酯作为调控土壤N素转化的硝化抑制剂，并用于稳定肥料的农业组合物中；其制备的农业组合物生产投资较少，产品质量稳定，便于管理。
(2)与已有的硝化抑制剂DMPP等相比较，本发明具有合成方法简单，原料来源广泛，成本较低等优点。
(3)应用效果好。本发明所提供的硝化抑制剂可用于稳定肥料，施入土壤后，N素转化可得到有效调控。
具体实施方式
本发明涉及肉桂酸甲酯作为硝化抑制剂的应用。
优选的，如上所述的应用，在含N肥料中添加有纯N重量0.1％～10％的肉桂酸甲酯；
更优选的，在含N肥料中添加有纯N重量0.5％～10％的肉桂酸甲酯，或0.7％～7％，或0.9％～5％，或1％～3％，或1.2％～2％，或1.5％～1.8％。
优选的，如上所述的应用，所述含N肥料包括碳酸氢铵、硫酸铵、氯化铵以及尿素中的一种或多种。
根据本发明的一方面，本发明还设计一种农业组合物，其包括含肉桂酸甲酯在内的至少一种硝化抑制剂；
优选的，所述农业组合物还包括尿素、吸湿性粒子、粘结剂中的一种或多种。
优选的，所述农业组合物还包括至少一种肥料；
更优选的，所述肥料为无机肥或有机肥。
更优选的，所述肥料选自：基于氮的肥料，基于钾的肥料，基于磷的肥料，含锌微量营养元素肥料，含铜微量营养元素肥料，含硼微量营养元素肥料，含铁微量营养元素肥料，含锰微量营养元素肥料，含硫微量营养元素肥料，以及其混合物。
优选的，所述农业组合物还包括农业杀虫剂或农业杀菌剂；
更优选的，其包括但不限于，杀真菌剂，除草剂，杀螨剂，硝化抑制剂，杀虫剂，安全剂，杀节肢动物剂(arthropocides)，以及其混合物。
示例性除草剂包括但不限于，乙草胺(acetochlor)，甲草胺(alachlor)，氯氨基吡啶酸(aminopyralid)，莠去津(atrazine)，解草嗪(benoxacor)，溴苯腈(bromoxynil)，氟酮唑草(carfentrazone)，氯横隆(chlorsulfuron)，块草酯(clodinafop)，二氯吡啶酸(clopyralid)，麦草畏(dicamba)，氯甲草-甲基(diclofop-methyl)，二甲吩草胺(dimethenamid)，恶唑禾草灵(fenoxaprop)，氟酮磺隆(flucarbazone)，氟噻草胺(flufenacet)，唑嘧磺草胺(flumetsulam)，氟稀草酸(flumiclorac)，氯氟吡氧乙酸(fluroxypyr)，草铵膦(glufosinate-ammonium)，草甘麟(glyphosate)，氯吡嘧磺隆(halosulfuron-methyl)，咪草酯(imazamethabenz)，咪草啶酸(imazamox)，灭草烟(imazapyr)，灭草喹(imazaquin)，咪唑乙烟酸(imazethapyr)，异恶氟草酮(isoxaflutole)，二氯喹啉酸(quinclorac)，MCPA，MCP胺(MCP amines)，MCP酯(MCPAesters)，mefenoxam，甲基磺草酮(mesotrione)，异丙甲草胺(metolachlor)，s-异丙甲草胺(s-metolachlor)，嗪草酮(metribuzin)，甲横隆-甲基(metsulfuron methyl)，烟嘧磺隆(nicosulfuron)，百草枯(paraquat)，胺硝草(pendimethalin)，氨氯吡啶酸(picloram)，氟甲嘧磺隆(primisulfuron)，丙苯磺隆(propoxycarbazone)，氟丙磺隆(prosulfuron)，吡草醚-乙基(pyraflufen ethyl)，玉嘧磺隆(rimsulfuron)，西玛津(simazine)，磺酰磺隆(sulfosulfuron)，噻吩磺隆(thifensulfuron)，topramezone，苯草酮(tralkoxydim)，野麦畏(triallate)，醚苯磺隆(triasulfuron)，苯磺隆(tribenuron)，三氯吡氧乙酸(triclopyr)，氟乐灵(trifluralin)，2,4-滴(2,4-D)，2,4-滴胺(2,4-D amine)，2,4-滴酯(2,4-Dester)等。
优选的，如上所述的组合物，所述尿素占所述农业组合物的20wt％～100wt％；更优选为25wt％～70wt％，或30wt％～50wt％。
优选的，如上所述的组合物，所述肉桂酸甲酯的添加量为所述尿素重量的0.04％～10％；更优选为0.08％～7％，或0.1％～5％，或0.3％～3％，或0.5％～1％。
优选的，如上所述的组合物，所述农业组合物中的硝化抑制剂还包括双氰胺。
优选的，如上所述的组合物，所述肉桂酸甲酯与所述双氰胺的摩尔比为3～5:1；更优选为4:1。
优选的，如上所述的组合物，所述吸湿性粒子选自以下物质中的一种或多种：凹凸棒土，滑石，硅藻土，高岭土，二氧化硅，粘土，云母，膨润土，蒙脱石，白炭黑，炭黑，煤灰，草木灰，硅灰石，沸石，海泡石，蛭石珍珠岩，淀粉，蜡；
所述吸湿性粒子的添加量为工业上可接受的量，优选为占所述组合物质量的1％～20％，或1.5％～15％，或2％～7％，或5％。
优选的，如上所述的组合物，所述粘结剂选自以下物质中的一种或多种：羟丙基甲基纤维素，乙基纤维素，甲基纤维素，羧甲基纤维素，聚乙烯醇，聚乙烯吡咯烷酮，聚氧乙烯及其共聚物，胶乳，聚酰胺，糖，葡萄糖，麦芽糖，淀粉，木质素磺酸盐，瓜尔胶，尿素，海藻酸盐，多糖，水性聚酯，聚醚，环氧树脂，异氰酸酯，乙烯-乙酸乙烯酯共聚物，聚丙烯酸酯胶乳及其共聚物胶乳；
所述粘结剂的添加量为工业上可接受的量，优选为占所述组合物质量的1％～20％，或1.5％～15％，或2％～7％，或5％。
如上所述的农业组合物的制备方法，将各成分混合在一起，可选的，还包括压实、干燥、制粒。
在一些实施方式中，所述农业组合物的粒径可类似于商购可得干肥产品的大小，例如0.1cm～3cm，或0.3cm～2cm，或0.5cm～1cm。
下面将结合实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限制本发明的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购买获得的常规产品。
实施例1
本实施例提供了一种农业组合物，所述农业组合物的原料组份为尿素40g、肉桂酸甲酯2g、吸湿性粒子10g、粘结剂10g；
将各成分混合在一起，压实、干燥、制粒。
实施例2
本实施例提供了一种农业组合物，所述农业组合物的原料组份为尿素40g、肉桂酸甲酯2g、双氰胺0.25g、吸湿性粒子10g、粘结剂10g；
将各成分混合在一起，压实、干燥、制粒。
实施例3
本实施例提供了一种农业组合物，所述农业组合物的原料组份为尿素40g、肉桂酸甲酯4g、吸湿性粒子5g、粘结剂5g、用复合有机肥(主要由菌菇废渣和牛粪发酵而成)补充至100g；
将各成分混合在一起，压实、干燥、制粒。
实施例4
本实施例提供了一种农业组合物，所述农业组合物的原料组份为尿素40g、肉桂酸甲酯4g、双氰胺0.42g、吸湿性粒子5g、粘结剂5g、用复合有机肥(主要由菌菇废渣和牛粪发酵而成)补充至100g；
将各成分混合在一起，压实、干燥、制粒。
实验例
(一)对纯的氨氧化细菌Nitrosomonas europaea(ATCC 19718)的抑制试验：在Nitrosomonas europaea的纯培养基(1L无菌水中含有2.5g(NH4)2SO4,0.5g KH2PO4,5mgCaCl2·2H2O,0.1g MgSO4·7H2O,0.5g NaHCO3,1g NaCl,1mL 75mg FeNaEDTA,11.92gHEPES)中加入不同浓度的肉桂酸甲酯、对硝基-肉桂酸甲酯、DMPP及双氰胺(简称DCD)计算产生的NO2 --N浓度，以NPI来反应硝化抑制效果：
亚硝酸盐生产抑制率Nitrite production inhibition(NPI％)＝(1-(NO2 - sample-NO2 - initial)/(NO2 - control-NO2 - initial))×100％
试验结果：NPI％
对上面结果简单说明：可以看出，当肉桂酸甲酯的添加浓度达到1mM(1毫摩尔每升)时，其对Nitrosomonas europaea的亚硝化过程抑制率达到100％，0.1mM也具有非常可观的抑制效果(达到98.8％)，随着添加浓度的降低，抑制效果逐渐减弱。DMPP是目前最普遍、也是公认效果最好的硝化抑制剂，因此本申请采用DMPP产品作为对照，可以看出在较高浓度添加时，肉桂酸甲酯抑制硝化的效果与DMPP相近，较低浓度添加时略微低于DMPP。同为肉桂酸衍生物的对硝基-肉桂酸甲酯硝化抑制效果很差。
同时申请人发现，将肉桂酸甲酯与DCD复配可显著提升其亚硝酸盐生产抑制率，以总摩尔数为0.01mM，设定不同摩尔比的肉桂酸甲酯：DCD的实验组进行实验验证；同时与总摩尔数为0.01mM不同摩尔比的肉桂酸甲酯：DMPP的对照组进行比较，重复对Nitrosomonaseuropaea的抑制试验，结果如下表所示：
从上表可知，将肉桂酸甲酯与DCD复配具有显著的增效作用，特别在肉桂酸甲酯与DCD的摩尔比为4:1时增效作用尤其显著，甚至比单独使用DMPP具有更佳的抑制效果。但肉桂酸甲酯与DMPP并没有表现出增效作用。
为进一步验证肉桂酸甲酯与DCD的复配效果，申请人采用Nitrosospiramultiformis ATCC 25196(N1)、Nitrosococcus oceani ATCC 19707(N2)两种常见的氨氧化细菌进一步进行亚硝酸盐生产抑制实验进行验证，其中各种抑制剂的总添加量均为0.01mM，肉桂酸甲酯-DCD复配组中肉桂酸甲酯和DCD的摩尔比为4:1；对硝基-肉桂酸甲酯-DCD复配组中对硝基-肉桂酸甲酯和DCD的摩尔比同样为4:1。结果如下表所示。
从上表可知，肉桂酸甲酯对N1、N2也具有很好的抑制效果，且肉桂酸甲酯-DCD复配组效果最佳。
(二)将土壤样品(15g，烘干重量)加入到100mL锥形烧瓶中，用蒸馏水处理以达到40％保水量(water holding capacity)。将样品在25℃下在黑暗中孵育7天以稳定微生物活性。然后进行28天的有氧培养实验，以研究土壤硝化对不同硝化抑制剂添加的反应。将NH4Cl溶液加入到每个锥形烧瓶中以提供400mg N kg-1土(干土计算)的NH4Cl溶液。以下各组硝化抑制剂的用量均为100μmol kg-1干土，其中肉桂酸甲酯-DCD复配组中肉桂酸甲酯和DCD的摩尔比为4:1；对硝基-肉桂酸甲酯-DCD复配组中对硝基-肉桂酸甲酯和DCD的摩尔比同样为4:1。在培养过程中第3，7，14和28天测定NH4 +-N和NO3 --N的浓度，通过以下公式计算硝化抑制率(NI)：
Nitrification inhibition硝化抑制率(NI％)＝(对照的硝化率nitrificationrate in control-样品的硝化率nitrification rate in sample)/对照的硝化率nitrification rate in control×100％
说明：对照指未添加硝化抑制剂的实验组，样品指添加硝化抑制剂的实验组。
上式中的硝化率nitrification rate(％)＝NO3 --N/(NH4 +-N+NO3 --N)×100％
对上面结果简单说明：可以看出，肉桂酸甲酯在土壤培养28天内都可以保持较稳定的硝化抑制率(＞25％)，但其在土壤中的效果比商品化的硝化抑制剂DMPP差。然而肉桂酸甲酯-DCD复配组效果与DMPP比却有显著提升。对硝基-肉桂酸甲酯硝化抑制效果较差，与DCD复配不存在增效作用。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，但本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (10)
1.一种农业组合物，其包括含肉桂酸甲酯在内的至少一种硝化抑制剂；
所述农业组合物中的硝化抑制剂还包括双氰胺，所述肉桂酸甲酯与所述双氰胺的摩尔比为3~5:1。
2.根据权利要求1所述的组合物，其特征在于，所述农业组合物还包括吸湿性粒子、粘结剂中的一种或多种。
3.根据权利要求1所述的组合物，其特征在于，所述农业组合物还包括至少一种肥料。
4.根据权利要求3所述的组合物，其特征在于，所述肥料包括尿素。
5.根据权利要求1所述的组合物，其特征在于，所述农业组合物还包括农业杀虫剂或农业杀菌剂。
6.根据权利要求4所述的组合物，其特征在于，所述尿素占所述农业组合物的25wt%~70wt%。
7.根据权利要求4所述的组合物，其特征在于，所述肉桂酸甲酯的添加量为所述尿素重量的0.04%~10%。
8.根据权利要求2所述的组合物，其特征在于，所述吸湿性粒子选自以下物质中的一种或多种：凹凸棒土，滑石，硅藻土，高岭土，二氧化硅，云母，膨润土，蒙脱石，白炭黑，炭黑，煤灰，草木灰，硅灰石，沸石，海泡石，蛭石珍珠岩，淀粉，蜡。
9.根据权利要求2所述的组合物，其特征在于，所述粘结剂选自以下物质中的一种或多种：羟丙基甲基纤维素，乙基纤维素，甲基纤维素，羧甲基纤维素，聚乙烯醇，聚乙烯吡咯烷酮，聚氧乙烯及其共聚物，聚酰胺，葡萄糖，麦芽糖，淀粉，木质素磺酸盐，瓜尔胶，尿素，海藻酸盐，多糖，水性聚酯，聚醚，环氧树脂，异氰酸酯，乙烯-乙酸乙烯酯共聚物，聚丙烯酸酯胶乳及其共聚物胶乳。
10.权利要求1~9任一项所述的农业组合物的制备方法，其特征在于，将各成分混合在一起，压实、干燥、制粒。
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