CN1147451C - 用于抑制或调节硝化作用的活性物质组合物 - Google Patents

用于抑制或调节硝化作用的活性物质组合物

Info

Publication number
CN1147451C
CN1147451C CNB951917048A CN95191704A CN1147451C CN 1147451 C CN1147451 C CN 1147451C CN B951917048 A CNB951917048 A CN B951917048A CN 95191704 A CN95191704 A CN 95191704A CN 1147451 C CN1147451 C CN 1147451C
Authority
CN
China
Prior art keywords
ppm
triazole
composition
effect
dcd
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
CNB951917048A
Other languages
English (en)
Other versions
CN1149285A (zh
Inventor
M
M·格拉巴斯
S·兰格
Ъ
H·-J·米歇尔
���Ǿ�
H·沃茨尼亚克
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SKW Stickstoffwerke Piesteritz GmbH
Original Assignee
SKW Stickstoffwerke Piesteritz GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SKW Stickstoffwerke Piesteritz GmbH filed Critical SKW Stickstoffwerke Piesteritz GmbH
Publication of CN1149285A publication Critical patent/CN1149285A/zh
Application granted granted Critical
Publication of CN1147451C publication Critical patent/CN1147451C/zh
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES 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
    • C05G3/00Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/90Mixtures 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
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/20Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
    • Y02P60/21Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S71/00Chemistry: fertilizers
    • Y10S71/902Nitrification inhibition

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Fertilizers (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Peptides Or Proteins (AREA)
  • Treatment Of Sludge (AREA)
  • Processing Of Solid Wastes (AREA)
  • Activated Sludge Processes (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Medicines Containing Plant Substances (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

本文描述了抑制硝化作用的制剂,其特征是作为活性组分含有1H-1,2,4-三唑或一种取代的1H-1,2,4-三唑或者它们的盐类或金属络合物和至少一种其它的化合物如一种取代的吡唑、其盐类或者金属络合物、双氰胺、脒基硫脲、硫脲、硫氰酸铵、硫代硫酸铵,本发明的制剂相对于单一的化合物具有明显的协同效果,因此提高了效率,减少了用量,在经济上更为有利。

Description

用于抑制或调节硝化作用的活性物质组合物
本发明涉及由两种或多种活性物质组成,用于抑制或控制栽培土壤或底物中铵氮(ammonium stickstoff)的硝化作用的组合物。
象铵氮或酰胺氮这种还原氮在相对较短的时间内在土壤中经过微生物转化经亚硝酸氮的中间过程转化为硝酸氮。这种硝化过程主要受下列因素的影响:温度,土壤湿度,土壤中的pH值及微生物的活性。这种情况的缺点是,与铵氮相反,硝酸氮不能通过土壤中的吸着载体被吸着,而是通过沉淀与地表水一起流失到更深层的土壤层中,超出植物的吸收范围,并储存在地下水中。在不利的气候和土壤情况下,这种洗涤损失规模可达到在土地中可用还原氮的20%以上。再加上脱氮作用的损失,即在绝氧情况下,通过硝化作用形成的硝酸氮还原成气体而消失,这在不利的情况下也达到类似的数量级。
通过利用合适的化学物质进行抑制或调节硝化作用,植物可以明显更好地吸收化肥中的氮。另一方面这种方法还提供了以下的优点,即减少地下水和地表水中的硝酸负载,但也抑制了人工培植植物中,特别是饲料农作物中的硝酸盐富集。
除了取代的吡唑(US3494757,DD133088)以外,已知的解决方案是如下化合物,双氰胺(DE 2702284,DE 2714601)、脒基硫脲(JP 7301138)、硫脲(DE 2051935)和1,2,4-三唑或4-氨基-1,2,4-三唑(JP 7104135),以及其它的三唑衍生物(US 3697244,US 3701645)。
此外还推荐了以上的物质结合而形成的活性组合物。例如在此应提到的吡唑与DCD(DD222471),或与脒基硫脲(DD 247894)的混合,还有4-氨基-1,2,4-三唑(ATC)与DCD(SU 1137096)的组合物,此外还有ATC在脲/硫脲或脲/DCD混合物中的熔融组合物(DD 227957)。同样也推荐由双氰胺与硫代硫酸铵组成的组合物(DE 3714729)。
这些已知的硝化抑制剂的缺点在于,一是部分添加剂效率低,因此用量高,二是由于挥发性强或不稳定性,给实际使用带来了不便,三是分解过程太快达不到使用目的。
除此之外一些抑制剂的部分有效硝化抑制作用因为与几种化肥种类的″不相容性反应″而大大减低。
本发明的目的是,找出适合运用到无机和有机的氮肥中的活性组合物,这些活性组合物对于抑制硝化作用起协同作用,并显示出相对于单一活性物质或者以上提到的组合物的使用优越性。
使人惊奇地发现,含有1H-1,2,4-三唑或者取代的1H-1,2,4-三唑及其盐类或者金属络合物和至少一种另外的化合物如取代的吡唑、其盐类或配位化合物,双氰胺、脒基硫脲、硫脲、硫氰酸铵、硫代硫酸铵作为活性成分的活性组合物,在抑制或控制栽培土壤和底物中铵氮的硝化作用中显示出明显的协同效应,从而突出地提高了相对于单一化合物的作用程度。
本发明的活性组合物可以以混合比0.5∶99.5-99.5∶0.5进行使用。在含有多于两种组分的组合物情况中,可以以任意的混合比将单一组分混合。
本发明的活性组合物有提高作用时间的优点,这样硝化过程在更长的时间内被抑制,有利于充分利用化肥中的氮,这种得到改善的作用甚至减低了用量。因而提高了农作物的生物物质生长量。
本发明的组合物可以和含有酰胺氮和铵氮的无机和有机固体或液体肥料一起混合使用。
这些活性组合物优先使用量为0.5-20kg/ha。
以下的例子用于解释本发明,而不是对此加以限制。在表格1中列举了在试验中涉及的基本组分1H-1,2,4-三唑  及其盐类和金属络合物的各种选择。在表格2中列举了添加到三唑中的几个混合成分。表1:
    名称     名称/化学式
    TrTr×HClHMTNa-TrFe-TrGTrCTSMT     1H-1,2,4-三唑1H-1,2,4-三唑×HCl1-羟甲基-1,2,4-三唑×HCl1-钠-1,2,4-三唑盐Fe(Tr)6]Cl31-脒基-1,2,4-三唑×HCl[Cu(Tr)2]SO4×2H2O[Mn(Tr)4]Cl2
表2:
    符号     名称/化学式
    GTHTHARDCDATSMPCMPGMPMg-MPZn-MPGZCGM     脒基脲硫脲硫氰酸铵双氰胺硫代硫酸铵3-甲基吡唑1-氨基甲酰基-3-甲基吡唑1-脒基-3-甲基吡唑×HCl镁-3-甲基吡唑盐[Zn(MP)2]SO4[(GMPH)2]ZnCl4]Mg(GMP)2Cl2×H2O
以下所举的例子的组合效应都是一按同样的方法确定的。
实施例
本发明的组合物按下列表格中所列出的具体物质和组合物浓度顺序(以土地质量的ppm表示),与作氮源的尿素一起加入类似黑土的沙质粘性土壤中,加水至最大容量的50%,而后均匀混合。氮的剂量为10毫克/100克土壤。如此制成的土样被装进塑料瓶中,关紧盖子,在20℃培养,然后观察硝酸盐形成的时间过程以及铵氮的减少。
抑制的百分比按以下公式计算:
Figure C9519170400061
K=没有活性物质的氮肥土壤试样中的硝酸盐含量
W=有活性物质的氮肥土壤试样中的硝酸盐含量
B=没有活性物质,没有氮肥的土壤试样中的硝酸盐含量
对于以百分比计算的抑制作用与硝化动力学时间过程的依赖关系,借助于非直线性回归得出了作为标准的t50值,t50值在时间上以天数表现,在此时的抑制作用仅为50%。
为了按照GROEGER以及其它的(Pharmazie 36(1981),81~87页)的不相关模型计算出组合效应,如此所算出的t50值将进行Logit-Probit-转换(剂量-作用-曲线的线性化),不相关模型体现了GOWING(Weeds 8(1960),379~391页)或COLBY(Weeds15(1967),20~22页)观点的普遍性。
例1:组合物1H-1,2,4-三唑/DCD
按照上面描述的实验方法测出和算出三唑(Tr)和DCD以及它们的组合物的t50值。
表3a:1H-1,2,4-三唑、DCD和它们的组合物的t50
1H-1,2,4-三唑(ppm)     DCD(ppm)     混合比三唑∶DCD     t50值(天数)
    0.0960.2270.5450.9091.252.03.05.0     5.514.030.041.546.050.052.357.0
    1.252.03.03.8465.05.8828.3339.09110.0     10.014.317.619.722.023.627.328.429.6
    5.03.02.01.25     5.03.02.01.25     50∶50     73.858.257.152.5
    1.6671.00.6670.417     8.3335.03.3332.083     17∶83     106.671.553.737.1
    0.9090.5450.3640.227     9.0915.4453.6362.273     9∶91     111.869.445.528.7
    0.250.156     3.752.344     6∶94     37.323.9
表3a:(续)
1H-1,2,4-三唑(ppm)     DCD(ppm)     混合比三唑∶DCD     t50值(天数)
    0.190.119     3.812.38     5∶95     32.122.2
    0.3850.2310.1540.096     9.6155.7693.8462.404     4∶96     73.541.529.621.3
    0.1960.118     9.8045.882     2∶98     48.131.2
表3b:根据不相关模型(UAM)计算出来的活性物质节约率及效
      果改善情况
  混合比Tr∶DCD 组合物浓度(ppm)   实验效果   UAM效应   效果改善情况   节约剂量(%)
    50∶50     10642.5     74585752     82726148     -8-14-44     -53-68-1714
    17∶83     10642.5     100715437     64503929     3621148     -554231
    9∶91     10642.5     100694529     53403123     4729146     -694729
    6∶94     42.5     4730     3728     102     3612
    5∶95     42.5     4028     3426     62     2511
    4∶96     10642.5     92523727     52613325     40942     -402111
    2∶98     106     6039     4636     143     4817
例2:组合物1H-1,2,4,-三唑/GTH
  与例1相似的实验方法和以电子数据处理为依据的求值
表4a:三唑与脒基硫脲(GTH)的单一化合物及各种混合物的t50
  1H-1,2,4-三唑(ppm)     GTH(ppm)     混合比三唑∶GTH     t50值(天数)
    0.0960.2270.5450.9091.252.03.05.0     5.514.030.041.546.050.052.357.0
    2.04.06.08.010.012.0     1.09.318.428.037.447.2
    5.02.51.25     5.02.51.25     50∶50     63.453.840.3
    0.9090.5450.227     9.0915.4452.273     9∶91     81.870.319.2
    0.3850.2310.154     9.6155.7693.846     4∶96     60.535.425.1
    0.1960.118     9.8045.882     2∶98     49.428.9
表4b:根据不相关模型(UAM)计算出来的活性物质节约率及效
      果改善情况
  混合比Tr∶GTH 组合物浓度(ppm)   实验效果   UAM效应 效果改善情况   节约剂量(%)
    50∶50     1052.5     958168     958668     0-60     -4-291
    9∶91     1062.5     10010029     745321     26478     899323
    4∶96     1064     915438     593824     321614     623234
    2∶98     106     7443     5132     2311     4427
例3:组合物1H-1,2,4-三唑/硫脲
与例1相似的实验方法和以电子数据处理为依据的求值
表5a:三唑与硫脲(TH)的单一化合物及各种混合物的t50
  1H-1,2,4-三唑(ppm)     TH(ppm)     混合比三唑∶TH     t50值(天数)
    0.10.250.51.02.03.05.0     5.814.329.042.149.151.956.2
    2.04.08.010.016.0     6.58.510.512.617.3
    3.02.0     3.02.0     50∶50     58.254.8
    0.9090.5450.227     9.0915.4452.273     9∶91     49.942.227.1
    0.3850.1540.096     9.6153.8462.404     4∶96     37.124.714.9
    0.1960.118     9.8045.882     2∶98     26.418.0
表5b:根据不相关模型(UAM)计算出来的活性物质节约率及效
      果改善情况
  混合比Tr∶TH 组合物浓度(ppm)   实验效果   UAM效应 效果改善情况   节约剂量(%)
    50∶50     64     8782     8072     710     4042
    9∶91     1062.5     756340     634928     121412     394142
    4∶96     1042.5     553722     482618     8115     244025
    2∶98     106     4027     3827     10     52
例4:组合物1H-1,2,4,-三唑/硫氰酸铵
与例1相似的实验方法和以电子数据处理为依据的求值
表6a:三唑与硫氰酸铵(AR)的单一化合物及各种混合物的t50
  1H-1,2,4-三唑(ppm)     AR(ppm)     混合比三唑∶AR     t50值(天数)
    0.0960.2270.5450.9091.252.03.05.0     5.514.030.041.546.050.052.357.0
    2.04.08.010.016.0     3.16.38.59.311.9
    3.02.01.25     3.02.01.25     50∶50     56.952.546.3
    0.5450.3640.227     5.4453.6362.273     9∶91     61.640.835.1
    0.190.119     3.812.38     5∶95     33.725.7
    0.1960.118     9.8045.882     2∶98     29.122.4
表6b:根据不相关模型(UAM)计算出来的活性物质节约率及效果改善情况
  混合比Tr∶AR 组合物浓度(ppm)   实验效果   UAM效应 效果改善情况   节约剂量(%)
    50∶50     642.5     575246     574939     037     -21529
    9∶91     642.5     624135     302417     321718     796268
    5∶95     42.5     3426     1812     1614     6666
    2∶98     106     2922     2216     76     3641
例5:组合物1-羟甲基-1,2,4-三唑×HCl/GTH
与例1相似的实验方法和以电子数据处理为依据的求值
表7a:单一化合物及其混合物的t50
    HMT(ppm)     GTH(ppm)     混合比HMT∶GTH     t50值(天数)
    0.250.50.751.02.05.07.5     14.822.929.737.444.150.057.1
    1.02.04.08.010.0     1.13.410.229.138.2
    5.02.51.25     1.00.50.25     83∶17     53.144.238.7
    3.01.5     3.01.5     50∶50     52.143.1
    1.00.5     5.02.5     17∶83     56.929.1
    0.5450.273     5.4552.727     9∶91     64.928.3
    0.2860.143     5.7142.857     5∶95     61.723.9
    0.118     5.882     2∶98     39.4
表7b:根据不相关模型(UAM)计算出来的活性物质节约率及效
      果改善情况
  混合比HMT∶GTH 组合物浓度(ppm)   实验效果   UAM效应 效果改善情况   节约剂量(%)
    83∶17     632.5     806658     877354     -7-74     -50-3211
    50∶50     63     7865     8062     -23     -108
    17∶83     63     8544     5936     268     5921
    9∶91     63     9742     4726     5016     8842
    5∶95     63     9236     3820     5616     8547
    2∶98     6     59     31     28     59
例6:组合物1-钠-1,2,4-三唑盐/DCD与例1相似的实验方法和以电子数据处理为依据的求值
表8a:单一化合物及其混合物的t50
    Na-Tr(ppm)     DCD(ppm)     混合比Na-Tr∶DCD     t50值(天数)
    0.250.50.751.01.52.05.0     9.721.426.131.933.738.441.8
    1.02.04.06.010.0     12.422.126.129.638.1
    5.02.5     1.00.5     83∶17     52.146.7
3.01.5 3.01.5 50∶50 60.151.9
    1.00.5     5.02.5     17∶83     73.251.4
    0.5450.273     5.4552.727     9∶91     64.242.9
    0.2310.115     5.7692.885     4∶96     47.935.1
表8b:根据不相关模型(UAM)计算出来的活性物质节约率及效
      果改善情况
  混合比Na-Tr∶DCD 组合物浓度(ppm)   实验效果   UAM效应 效果改善情况   节约剂量(%)
    83∶17     63     7870     7965     -15     -520
    50∶50     63     9078     7761     1317     5551
    17∶83     63     10077     6850     3227     -66
    9∶91     63     9664     6345     3319     -53
    4∶96     63     7253     5740     1513     4741
例7:1H-1,2,4-三唑/MP
与例1相似的实验方法和以电子数据处理为依据的求值
表9a:单一化合物及其混合物的t50
    Tr(ppm)     MP(ppm)     混合比Tr∶MP     t50值(天数)
    0.10.250.50.751.01.53.0     5.314.927.836.841.948.756.9
    0.10.250.50.6561.02.0     9.124.543.646.348.752.3
    1.00.5     1.00.5     50∶50     95.672.7
    1.8180.909     0.1820.091     91∶9     69.851.7
    1.9230.962     0.0770.038     96∶4     59.842.8
    0.0770.038     1.9230.962     4∶96     61.052.4
表9b:根据不相关模型(UAM)计算出来的活性物质节约率及效
      果改善情况
  混合比Tr∶MP 组合物浓度(ppm)   实验效果   UAM效应 效果改善情况   节约剂量(%)
    50∶50     21     100100     9074     1026     8693
    91∶9     21     10077     8364     1713     8836
    96∶4     21     9064     8163     91     405
    4∶96     21     9179     8874     35     2718
例8:组合物铜-三唑络合物/1-脒基-3-甲基吡唑鎓-锌酸
     盐-络合物
与例1相似的实验方法和以电子数据处理为依据的求值
表10a:单一化合物及其混合物的t50
    CTS(ppm)     GZC(ppm)     混合比CTS∶GZC     t50值(天数)
    0.10.250.51.21.82.5     1.94.911.627.036.143.1
    0.250.50.751.53.0     9.519.126.843.359.1
    1.00.50.25     1.00.50.25     50∶50     77.253.621.9
    1.8180.909     0.1820.091     91∶9     45.927.8
    0.1820.091     1.8180.909     9∶91     53.630.0
表10b:根据不相关模型(UAM)计算出来的活性物质节约率及效
       果改善情况
  混合比CTS∶GZC  组合物浓度(ppm)   实验效果   UAM效应 效果改善情况   节约剂量(%)
    50∶50     210.5     1008033     724219     283814     846137
    91∶9     21     6942     6436     56     1413
    9∶91     21     8045     7451     5-5     16-15
例9:组合物1H-1,2,4-三唑/双氰胺/硫氰酸铵
与例1相似的实验方法和以电子数据处理为依据的求值
表11a:单一化合物及其混合物的t50
      Tr(ppm)     DCD(ppm)     AR(ppm)     混合比Tr∶DCD∶AR   t50值(天数)
    0.0960.2270.5450.9091.252.03.05.0     5.513.830.241.546.050.152.357.0
    1.252.03.03.8645.05.8828.33310.0     10.114.317.619.722.123.627.429.6
    2.04.08.010.016.0     2.86.38.59.311.9
    0.8330.5     4.1672.5     0.8330.5     14.3∶71.4∶14.3     67.152.4
    0.3850.231     3.8462.308     0.7690.462     7.7∶76.9∶15.4     58.937.7
    0.1920.115     3.8462.308     0.9620.575     3.8∶77∶19.2     45.734.7
表11b:根据不相关模型(UAM)计算出来的活性物质节约率及效
       果改善情况
  混合比Tr∶DCD∶AR 组合物浓度(ppm)   实验效果   UAM效应 效果改善情况 节约剂量(%)
 14.3∶71.4∶14.3     5.833.5     10079     6753     3326     -61
 7.7∶76.9∶15.4     5.03.0     8957     5339     3618     7546
 3.8∶77∶19.2     5.03.0     6952     4431     2521     5654
例10:组合物1H-1,2,4-三唑氢氯化物/脒基硫脲/硫脲
与例1相似的实验方法和以电子数据处理为依据的求值
表12a:单一化合物及其混合物的t50
    Tr×HCl(ppm)     GTH(ppm)     TH(ppm)     混合比Tr×HCl∶GTH∶TH    t50值(天数)
    0.150.30.751.53.04.5     5.011.528.441.348.952.1
    2.04.08.010.016.0     1.99.528.137.060.1
    2.04.08.010.016.0     6.38.710.913.018.1
    0.1150.231     2.3084.615     0.5571.155     3.8∶77∶19.2     17.944.8
    0.1150.231     1.4222.885     1.4222.885     3.8∶48.1∶48.1     11.937.9
    0.231     1.155     4.615     3.8∶19.2∶77     27.8
    0.5     2.0     0.5     17∶66∶17     53.1
    0.5     1.25     1.25     16.6∶41.7∶41.7     39.9
    0.1880.375     1.8753.75     0.9371.875     6.3∶62.5∶31.2     21.347.1
表12b:根据不相关模型(UAM)计算出来的活性物质节约率及效
       果改善情况
    混合比Tr×HCl∶GTH∶TH 组合物浓度(ppm)   实验效果 UAM效应   效果改善情况 节约剂量(%)
    3.8∶77∶19.2     3.06.0     2767     1635     1132     3657
    3.8∶48.1∶48.1     3.06.0     1957     1230     727     2851
    3.8∶19.2∶77     6.0     42     25     17     40
    17∶66∶17     3.0     81     33     48     74
    16.6∶41.7∶41.7     3.0     60     30     30     55
    6.3∶62.5∶31.2     3.06.0     3371     1738     1633     4356
例11:组合物1-脒基-1,2,4-三唑×HCl/DCD/硫脲
与例1相似的实验方法和以电子数据处理为依据的求值
表13a:单一化合物及其混合物的t50
    GTr(ppm)     DCD(ppm)     TH(ppm)     混合比GTr∶DCD∶TH    t50值(天数)
    1.42.144.38.510.0     27.537.547.349.255.2
    1.02.03.05.08.010.0     8.914.217.122.326.830.1
    2.04.08.010.016.0     6.38.710.913.018.1
    0.1920.308     3.8406.160     0.9681.54   3.8∶76.8∶19.4     43.861.7
    0.1920.308     2.4043.846     2.4043.846   3.8∶48.1∶48.1     37.457.8
    0.1920.308     0.9681.540     3.8466.160   3.8∶19.4∶76.8     27.932.7
表13b:根据不相关模型(UAM)计算出来的活性物质节约率及效果改善情况
  混合比GTr∶DCD∶TH 组合物浓度(ppm)   实验效果   UAM效应   效果改善情况 节约剂量(%)
  3.8∶76.8∶19.4     5.08.0     6693     4832     1861     6098
  3.8∶48.1∶48.1     5.08.0     5687     4655     1031     4084
  3.8∶19.4∶76.8     5.08.0     4249     4251     0-2     -1-10
例12:组合物1H-1,2,4-三唑/DCD/硫代硫酸铵
与例1相似的实验方法和以电子数据处理为依据的求值
表14a:单一化合物及其混合物的t50
    Tr(ppm)     DCD(ppm)    ATS(ppm)   混合比Tr∶DCD∶ATS    t50值(天数)
    0.0960.2270.5450.9091.252.03.05.0     5.514.030.041.546.050.052.357.0
    1.252.03.03.8465.05.8828.3339.09110.0     10.014.317.619.722.023.627.328.429.0
    2.04.08.010.016.0     00000
    0.115     2.308     0.557     4∶77∶19     35.7
    0.115     1.422     1.422     4∶48∶48     27.8
    0.115     0.577     2.308     4∶19∶77     14.1
表14b:根据不相关模型(UAM)计算出来的活性物质节约率及效
       果改善情况
  混合比Tr∶DCD∶ATS 组合物浓度(ppm)   实验效果   UAM效应   效果改善情况 节约剂量(%)
  4∶77∶19     3.0     53     35     18     55
  4∶48∶48     3.0     42     30     12     42
  4∶19∶77     3.0     21     24     -3     -20
例13:组合物铁-三唑络合物/DCD/硫代硫酸铵
与例1相似的实验方法和以电子数据处理为依据的求值
表15a:单一化合物及其混合物的t50
    Fe-TR(ppm)    DCD(ppm)     ATS(ppm)     混合比Fe-Tr∶DCD∶ATS   t50值(天数)
    0.0270.1630.390.650.91.442.154.06.0     3.910.321.229.433.335.739.442.949.9
    0.51.02.55.07.510.0     4.89.315.422.627.332.8
    2.04.06.08.010.0     0.090.090.10.10.1
    2.01.0     2.01.0     2.01.0     33.3∶33.3∶33.3     54.645.8
    0.2310.115     4.6152.308     1.1540.577     3.8∶77∶19.2     51.235.8
    0.2310.115     2.8851.422     2.8851.422     3.8∶48.1∶48.1     44.928.8
    0.2310.115     1.1540.577     4.6152.308     3.8∶19.2∶77     29.516.7
    0.5450.273     4.3642.182     1.0910.545     9.1∶72.7∶18.2     57.939.7
表15b:根据不相关模型(UAM)计算出来的活性物质节约率及效
       果改善情况
    混合比Fe-Tr∶DCD∶ATS 组合物浓度(ppm)   实验效果   UAM效应   效果改善情况 节约剂量(%)
  33.3∶33.3∶33.3     6.03.0     8268     6652     1616     5855
    3.8∶77∶19.2     6.03.0     7753     4632     2921     7663
    3.8∶48.1∶48.1     6.03.0     6743     4027     2716     6956
    3.8∶19.2∶77     6.33.0     4425     3221     124     4426
    9.1∶72.7∶18.2     6.03.0     8760     5539     3221     8160
例14:组合物锰-三唑络合物/1-脒基-3-甲基吡唑-镁-
      络合物/DCD
与例1相似的实验方法和以电子数据处理为依据的求值
表16a:单一化合物及其混合物的t50
    MT(ppm)     GM(ppm)     DCD(ppm)     混合比MT∶GM∶DCD    t50值(天数)
    0.20.51.01.52.03.0     5.615.528.435.442.149.7
    0.20.61.01.52.0     8.525.642.946.848.4
    2.04.08.010.016.0     20.725.931.535.452.5
    1.6671.00.667     1.6671.00.667     1.6671.00.667   33.3∶33.3∶33.3     106.985.761.8
    0.4170.250.167     0.4170.250.167     4.1662.51.666   8.3∶8.3∶83.4     64.144.834.1
    0.1850.111     0.1850.111     4.6302.778   3.7∶3.7∶92.6     60.740.1
    0.543     0.109     4.348   10.9∶2.1∶87     54.6
    0.109     0.543     4.348   2.1∶10.9∶87     61.4
表16b:根据不相关模型(UAM)计算出来的活性物质节约率及效
       果改善情况
  混合比MT∶GM∶DCD 组合物浓度(ppm)   实验效果 UAM效应   效果改善情况 节约剂量(%)
  33.3∶33.3∶33.3     5.03.02.0     10010093     897662     112431     849168
  8.3∶8.3∶83.4     5.03.02.0     966751     644531     322220     734444
  3.7∶3.7∶92.6     5.03.0     9160     5437     3723     7350
  10.9∶2.1∶87     5.0     82     59     23     52
  2.1∶10.9∶87     5.0     92     63     29     67
例15:组合物1H-1,2,4-三唑/MP/GTH
与例1相似的实验方法和以电子数据处理为依据的求值
表17a:单一化合物及其混合物的t50
    Tr(ppm)     MP(ppm)     GTH(ppm)     混合比Tr∶MP∶GTH   t50值(天数)
    0.10.250.50.751.01.53.0     5.814.329.042.149.151.956.2
    0.10.250.50.6561.02.0     9.124.543.646.348.752.3
    2.04.06.08.010.012.0     1.09.318.428.037.447.2
    1.6671.0     1.6671.0     1.6671.0   33.3∶33.3∶33.3     112.1105.7
    0.2270.136     0.2270.136     4.5462.727   4.5∶4.5∶91     73.447.8
    0.1190.071     0.1190.071     4.7622.857   2.4∶2.4∶95.2     44.929.3
表17b:根据不相关模型(UAM)计算出来的活性物质节约率及效
       果改善情况
  混合比Tr∶MP∶GTH 组合物浓度(ppm)   实验效果   UAM效应   效果改善情况   节约剂量(%)
  33.3∶33.3∶33.3     5.03.0     100100     9892     28     6569
  4.5∶4.5∶91     5.03.0     10072     5635     4437     9159
  2.4∶2.4∶95.2     5.03.0     6744     4023     2721     4846
例16:组合物1H-1,2,4-三唑/MP/DCD
与例1相似的实验方法和以电子数据处理为依据的求值
表18a:单一化合物及其混合物的t50
    Tr(ppm)     MP(ppm)     DCD(ppm)   混合比Tr∶MP∶DCD   t50值(天数)
  0.10.250.50.751.01.53.0     5.213.428.140.746.949.852.1
    0.10.250.50.6561.02.0     7.619.435.740.146.149.7
    0.51.02.55.010.013.0     4.19.114.222.330.741.8
    1.6671.0     1.6671.0     1.6671.0  33.3∶33.3∶33.3     112.9102.3
    0.2270.136     0.2270.136     4.5462.727  4.5∶4.5∶91     79.452.9
    0.1190.071     0.1190.071     4.7622.857  2.4∶2.4∶95.2     57.141.8
表18b:根据不相关模型(UAM)计算出来的活性物质节约率及效
       果改善情况
  混合比Tr∶MP∶DCD 组合物浓度(ppm)   实验效果    UAM效应   效果改善情况   节约剂量(%)
 33.3∶33.3∶33.3     5.03.0     100100     9588     512     8289
 4.5∶4.5∶91     5.03.0     10079     6447     3632     9463
 2.4∶2.4∶95.2     5.03.0     8663     5438     3225     6654

Claims (2)

1.活性成分的协同组合物在抑制或调节裁培土壤和底物中铵氮的硝化作用中的应用,所述组合物包含下列成分:
a)1H-1,2,4-三唑、1-羟甲基-1,2,4-三唑、1-脒基-1,2,4-三唑,或其盐或其金属配合物,及
选自如下的成分:
b)3-甲基吡唑、1-氨基甲酰基-3-甲基吡唑、1-脒基-3-甲基吡唑、或它们的盐或金属配合物、双氰胺、脒基硫脲、硫脲、硫氰酸铵和硫代硫酸铵,
其中,成分a)和b)的混合比为24∶1至1∶49重量份。
2.权利要求1的应用,其中当选自b)的活性成分为两种时,两种成分的重量比为1∶1至2.1∶87。
CNB951917048A 1994-02-21 1995-02-20 用于抑制或调节硝化作用的活性物质组合物 Expired - Lifetime CN1147451C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4405392.4 1994-02-21
DE4405392A DE4405392C1 (de) 1994-02-21 1994-02-21 Wirkstoffkombinationen zur Hemmung bzw. Regelung der Nitrifikation

Publications (2)

Publication Number Publication Date
CN1149285A CN1149285A (zh) 1997-05-07
CN1147451C true CN1147451C (zh) 2004-04-28

Family

ID=6510700

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB951917048A Expired - Lifetime CN1147451C (zh) 1994-02-21 1995-02-20 用于抑制或调节硝化作用的活性物质组合物

Country Status (25)

Country Link
US (2) US5951736A (zh)
EP (1) EP0746537B1 (zh)
JP (1) JP3977415B2 (zh)
KR (1) KR100350294B1 (zh)
CN (1) CN1147451C (zh)
AT (1) ATE195114T1 (zh)
AU (1) AU686344B2 (zh)
BG (1) BG61721B1 (zh)
BR (1) BR9506810A (zh)
CZ (1) CZ291383B6 (zh)
DE (1) DE4405392C1 (zh)
DK (1) DK0746537T3 (zh)
ES (1) ES2148496T3 (zh)
FI (1) FI963255A (zh)
GR (1) GR3034156T3 (zh)
HU (1) HU214831B (zh)
MX (1) MX9603491A (zh)
NO (1) NO963400L (zh)
NZ (1) NZ281915A (zh)
PL (1) PL177162B1 (zh)
PT (1) PT746537E (zh)
RU (1) RU2158721C2 (zh)
SK (1) SK282771B6 (zh)
UA (1) UA32588C2 (zh)
WO (1) WO1995022515A1 (zh)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6331198B1 (en) * 1999-02-12 2001-12-18 Council Of Scientific & Industrial Research Composition useful as nitrification inhibiting additive for ammonia producing fertilizers
AU4397400A (en) * 1999-04-08 2000-11-14 Skw Stickstoffwerke Piesteritz Gmbh Agents for improving the n-utilization of mineral and/or organic fertilizers that contain urea
KR20020060680A (ko) * 2000-05-15 2002-07-18 구마가야 나오히꼬 티오황산암모늄 함유 비료
JP4585686B2 (ja) * 2000-12-22 2010-11-24 エムシー・ファーティコム株式会社 有機物入り化成肥料及びその製造方法
DE10118322A1 (de) * 2001-04-12 2002-10-17 Piesteritz Stickstoff Heterozyklisch-substituierte (Thio)Phosphorsäuretriamide, Verfahren zu ihrer Herstellung und deren Verwendung als Mittel zur Regulierung bzw.Hemmung der enzymatischen Harnstoff-Hydrolyse
DE10216751A1 (de) * 2002-04-16 2003-11-06 Piesteritz Stickstoff Verwendung von 1,1,1,3,3,3-Hexaaminodiphosphazenium-Salzen als Mittel zur Regulierung bzw. Hemmung der enzymatischen Harnstoff-Hydrolyse
DE10342551B4 (de) * 2003-09-15 2016-08-11 Skw Stickstoffwerke Piesteritz Gmbh Verfahren zur Herstellung von Dicyandiamid und 1,2,4-Triazol als Nitrifikationshemmer enthaltenden Düngemittelgranulaten auf Harnstoffbasis und Verwendung von Sublimationshemmern für 1,2,4-Triazol
US7125829B2 (en) * 2004-08-09 2006-10-24 Dale Benincasa Solution for removing magnesium chloride compound from a surface contaminated therewith
DE102006015362B4 (de) 2006-04-03 2018-07-19 Skw Stickstoffwerke Piesteritz Gmbh N-(Pyrazolyalkyl)(thio)phosphorsäuretriamide, Verfahren zu ihrer Herstellung und deren Verwendung als Mittel zur Regulierung bzw. Hemmung der enzymatischen Harnstoff-Hydrolyse sowie der Nitrifikation
DE102009036229B4 (de) * 2009-08-05 2015-02-12 Skw Stickstoffwerke Piesteritz Gmbh Antibackmittel für harnstoffbasierte Düngemittel, Düngemittelformulierungen mit diesem Antibackmittel und Verfahren zu deren Herstellung
DE102010022943A1 (de) 2010-06-08 2011-12-08 Skw Stickstoffwerke Piesteritz Gmbh Mischung zur Behandlung von Düngemitteln
CN101913967A (zh) * 2010-08-11 2010-12-15 中国科学院沈阳应用生态研究所 一种旱地农田土壤的n2o减排方法
SI3623362T1 (sl) 2013-12-13 2023-03-31 Eurochem Agro Gmbh Gnojilna zmes, ki vsebuje nitrifikacijski inhibitor
EP3137435A1 (en) * 2014-05-02 2017-03-08 Mcknight, Gary, David Increased longevity of nitrogen content of soil through improved liquid delivery formulations of nitrification inhibitors to fertilizers
TR201815697T4 (tr) 2015-06-22 2018-11-21 Eurochem Agro Gmbh Üre ihtiva eden gübrelerin işlenmesi için karışım.
DE102017201608A1 (de) 2017-02-01 2018-08-02 Eurochem Agro Gmbh 3,4-Dimethylpyrazol enthaltende Mischung und ihre Verwendung
DE102017005463A1 (de) 2017-06-08 2018-12-13 Skw Stickstoffwerke Piesteritz Gmbh Zusammensetzungen mit N-((3(5)-Methyl-1H-pyrazol-1-yl)methyl)acetamid und deren Vewendung zur Herstellung von lagerfähigen Fertigdüngemitteln mit dualer Stickstoffstabilisierung
CN114980741A (zh) * 2020-01-16 2022-08-30 巴斯夫欧洲公司 包含硝化抑制剂和载体的混合物
EP4321498A1 (en) * 2022-08-10 2024-02-14 SABIC Global Technologies B.V. Triazole methanol as nitrification inhibitor for fertilizer application

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3701645A (en) * 1970-09-25 1972-10-31 Henry H Scott Crop culture with 1h-1,2,4-triazoles
SU1137096A1 (ru) * 1983-05-27 1985-01-30 Предприятие П/Я Г-4302 Ингибитор нитрификации азотных удобрений
DD227957B5 (de) * 1984-08-08 1994-06-01 Wittenberg Stickstoff Ag Wirkstoffkombinationen zur Hemmung bzw. Regelung der Nitrifikation von Ammoniumstickstoff in Kulturboeden
DE4211808A1 (de) * 1992-04-08 1993-10-14 Wittenberg Stickstoff Ag Wirkstoffkombination zur Hemmung bzw. Regelung der Nitrifikation in Kulturböden bzw. Substraten

Also Published As

Publication number Publication date
US6066190A (en) 2000-05-23
UA32588C2 (uk) 2001-02-15
KR100350294B1 (ko) 2002-11-23
HUT75045A (en) 1997-03-28
DK0746537T3 (da) 2000-09-04
NO963400D0 (no) 1996-08-15
JP3977415B2 (ja) 2007-09-19
SK282771B6 (sk) 2002-12-03
PL316028A1 (en) 1996-12-23
GR3034156T3 (en) 2000-11-30
BG61721B1 (bg) 1998-04-30
PT746537E (pt) 2000-11-30
CZ291383B6 (cs) 2003-02-12
US5951736A (en) 1999-09-14
EP0746537A1 (de) 1996-12-11
DE4405392C1 (de) 1995-10-19
BR9506810A (pt) 1997-09-30
WO1995022515A1 (de) 1995-08-24
EP0746537B1 (de) 2000-08-02
ATE195114T1 (de) 2000-08-15
FI963255A0 (fi) 1996-08-20
ES2148496T3 (es) 2000-10-16
NO963400L (no) 1996-08-16
BG100762A (bg) 1997-03-31
HU214831B (hu) 1998-06-29
KR970701163A (ko) 1997-03-17
HU9602282D0 (en) 1996-10-28
AU686344B2 (en) 1998-02-05
AU1888695A (en) 1995-09-04
CZ236296A3 (en) 1997-04-16
JPH09509134A (ja) 1997-09-16
MX9603491A (es) 1998-01-31
NZ281915A (en) 1998-05-27
RU2158721C2 (ru) 2000-11-10
FI963255A (fi) 1996-08-20
SK103996A3 (en) 1997-06-04
CN1149285A (zh) 1997-05-07
PL177162B1 (pl) 1999-09-30

Similar Documents

Publication Publication Date Title
CN1147451C (zh) 用于抑制或调节硝化作用的活性物质组合物
CN1232441A (zh) 新的硝化抑制剂和多元酸在处理含有硝化抑制剂的无机肥料中的应用
EP1851183B1 (en) use of CALCIUM POLYSULFIDE, POTASSIUM POLYSULFIDE, CALCIUM THIOSULFATE, AND MAGNESIUM THIOSULFATE AS UREASE INHIBITORS
CN101362659B (zh) 纳米碳长效环保复合肥料
EP1183220B1 (de) Mittel zur verbesserung der n-ausnutzung mineralischer und/oder organischer harnstoffhaltiger düngemittel
DE212020000753U1 (de) Synergistischer und stabiler Stickstoffdünger
Schoenau Benefits of long-term application of manure
KR101317889B1 (ko) 일라이트를 이용한 염해지용 토양개량제 조성물 및 상기 토양개량제 조성물을 이용한 식목방법
CN1031071A (zh) 硝酸化作用抑制剂
EP4015489A1 (en) Improved ammonium-based composition and method for the manufacture thereof
CN107141136A (zh) 一种双核固能肥及其制备方法
EP4015488A1 (en) Method for producing an ammonium-based solid, particulate composition comprising an additive
KR101436611B1 (ko) 다공성 소결광물을 이용한 토양 내 염류집적 개선을 위한 토양개량제
EP4015490A1 (en) Method for the manufacture of an ammonium-based composition comprising an ammonium salt and an additive
EA012339B1 (ru) Азотное удобрение с биологически активной добавкой, снижающее уровень загрязнения сельскохозяйственной продукции радионуклидами и тяжелыми металлами, и способ его получения
CA2182011C (en) Combination of active substances for inhibiting or regulating nitrification
Soares et al. A Efficiency of neem (Azadirachta indica) as a nitrification inhibitor under laboratory conditions
CN117256242A (zh) 一种缓解冷浸烂泥田硫化氢中毒的方法
DD227957B5 (de) Wirkstoffkombinationen zur Hemmung bzw. Regelung der Nitrifikation von Ammoniumstickstoff in Kulturboeden
DE10252382A1 (de) Verwendung von Tetraaminophosphoniumsalzen als Mittel zur Regulierung bzw. Hemmung der enzymatischen Harnstoff-Hydrolyse
CN112125760A (zh) 一种环境友好型降低土壤中氨氮硝化作用的方法
Hussein Improving Nitrogen Fertilizers Efficiency in Soil by Using Nitrification Inhibitor (DMPP)
Tekle et al. Nitrogen Fertilizer Management to Mitigate Nitrous Oxide (N2O) Emission in Maize Production

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CX01 Expiry of patent term

Expiration termination date: 20150220

Granted publication date: 20040428