AU2005210449A1 - Fertilizer compositions - Google Patents
Fertilizer compositions Download PDFInfo
- Publication number
- AU2005210449A1 AU2005210449A1 AU2005210449A AU2005210449A AU2005210449A1 AU 2005210449 A1 AU2005210449 A1 AU 2005210449A1 AU 2005210449 A AU2005210449 A AU 2005210449A AU 2005210449 A AU2005210449 A AU 2005210449A AU 2005210449 A1 AU2005210449 A1 AU 2005210449A1
- Authority
- AU
- Australia
- Prior art keywords
- composition
- zeolite
- nitrification
- agent
- nitrification inhibitor
- 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.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims description 71
- 239000003337 fertilizer Substances 0.000 title claims description 24
- 239000003112 inhibitor Substances 0.000 claims description 61
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 55
- 239000010457 zeolite Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 52
- 229910021536 Zeolite Inorganic materials 0.000 claims description 51
- 239000003795 chemical substances by application Substances 0.000 claims description 41
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 38
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 37
- 239000002002 slurry Substances 0.000 claims description 19
- 239000004202 carbamide Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 15
- 239000002689 soil Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 230000002708 enhancing effect Effects 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 150000004676 glycans Chemical class 0.000 claims description 8
- 229920001282 polysaccharide Polymers 0.000 claims description 8
- 239000005017 polysaccharide Substances 0.000 claims description 8
- 229920001285 xanthan gum Polymers 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000000375 suspending agent Substances 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 239000000230 xanthan gum Substances 0.000 claims description 6
- 235000010493 xanthan gum Nutrition 0.000 claims description 6
- 229940082509 xanthan gum Drugs 0.000 claims description 6
- 229910052680 mordenite Inorganic materials 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 230000000813 microbial effect Effects 0.000 claims description 4
- 229920002907 Guar gum Polymers 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- 239000000665 guar gum Substances 0.000 claims description 3
- 235000010417 guar gum Nutrition 0.000 claims description 3
- 229960002154 guar gum Drugs 0.000 claims description 3
- 230000002401 inhibitory effect Effects 0.000 claims description 3
- 230000005764 inhibitory process Effects 0.000 claims description 3
- DCUJJWWUNKIJPH-UHFFFAOYSA-N nitrapyrin Chemical compound ClC1=CC=CC(C(Cl)(Cl)Cl)=N1 DCUJJWWUNKIJPH-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 230000003389 potentiating effect Effects 0.000 claims description 3
- 229910021647 smectite Inorganic materials 0.000 claims description 3
- 230000002195 synergetic effect Effects 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 244000007835 Cyamopsis tetragonoloba Species 0.000 claims description 2
- 229920002307 Dextran Polymers 0.000 claims description 2
- 229920002148 Gellan gum Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 2
- 229920000881 Modified starch Polymers 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 229940071826 hydroxyethyl cellulose Drugs 0.000 claims description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 2
- 239000011344 liquid material Substances 0.000 claims description 2
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 2
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 2
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 235000019426 modified starch Nutrition 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011236 particulate material Substances 0.000 claims description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 229920001059 synthetic polymer Polymers 0.000 claims description 2
- 239000011573 trace mineral Substances 0.000 claims description 2
- 235000013619 trace mineral Nutrition 0.000 claims description 2
- 230000003019 stabilising effect Effects 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 239000008187 granular material Substances 0.000 description 9
- 210000002700 urine Anatomy 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical group [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008202 granule composition Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 241000605122 Nitrosomonas Species 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000012813 breadcrumbs Nutrition 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- MKGIQRNAGSSHRV-UHFFFAOYSA-N 1,1-dimethyl-4-phenylpiperazin-1-ium Chemical compound C1C[N+](C)(C)CCN1C1=CC=CC=C1 MKGIQRNAGSSHRV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 241000605159 Nitrobacter Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
-
- 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
- C05G3/80—Soil conditioners
-
- 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
-
- 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
Description
WO 2005/075602 PCT/NZ2005/000013 -1 FERTILIZER COMPOSITIONS TECHNICAL FIELD The present invention relates to the treatment of the soil and/or pasture, 5 compositions for application to the soil and/or pasture, procedures for preparing such compositions, compositions thus formed, fertiliser compositions and related uses. BACKGROUND 10 Nitrification is the process of conversion of a relatively immobile form of nitrogen (N) from an ammonium (NH 4
+
) form into the more mobile nitrate (NO3-) form. During nitrification the NH4 is believed to be first oxidised to nitrite (NO2-) and that this conversion is largely brought about by Nitrosomonas bacteria. Thereafter the NO2- in turn, it is believed, is oxidised to NO3- by Nitrobacter 15 bacteria. Nitrates, produced from the nitrification process, is subject to losses by leaching from soils and can potentially contaminate surface and ground water. Nitrates can also undergo denitrification in the absence of oxygen by a taxonomically diverse group of microorganisms to gaseous oxides of N (e.g. N 2 0) 20 and nitrogen gas (N 2 ), which are commonly lost to the atmosphere. These losses of N account for inefficiencies in the use of applied N by plants, whether from N including fertilisers or urine, or both. N 2 0 is one of the greenhouse gases and also has a catalytic effect on the destruction of stratospheric ozone. An approach previously proposed to increase plant N use efficiency and 25 minimise potential adverse environmental effects by nitrogeneous compounds is the use of nitrification inhibitors. Since NH 4 + is less subject to loss from soils, delaying the microbial transformation (nitrification process) ofNH 4 + to NO3 through the use of nitrification inhibitors can result in an increase in potential N availability for plant growth and a decrease in NO3- and N 2 0 production.
WO 2005/075602 PCT/NZ2005/000013 -2 Nitrification inhibitors are compounds that delay the microbial oxidation of
NH
4 + to NO2- (the first step of the nitrification process) for a certain period by depressing the activity of Nitrosomonas bacteria in soils. The second step of nitrification it is believed normally is not influenced. 5 An ideal nitrification inhibitor should have the following characteristics: - Specificity. It should block the conversion of NH 4 + to NO3 and be non-toxic to other soil organisms, animals and humans. - Mobility. It should move with N fertilisers or nutrient solution. - Persistence. It should stay in soils for an adequate period. 10 - Economy. It should be cheap as it is frequently to be used as an additive to fertilisers. Examples of compositions that hitherto have been considered for application to soils or pasture include those disclosed by Sumitomo Chemical Co Ltd in its New Zealand Patent Specification No. 161791 where they disclose a 15 nitrophosphate fertiliser containing a nitrification inhibitor in the amount of from 1 to 20% by weight based on total nitrogen content and where the fertiliser contains nitrate nitrogen of from 20 to 80% by weight based on total nitrogen content. Examples of nitrification inhibitors given in New Zealand are as follows: - N-2,5-dichlorophenyl succinamic acid 20 - 2-chloro-6-trichloromethyl pyridine ("Nitrapyrin") - dicyandiamide ("DCD or "DCDIN"") which is HN=C(NH 2 )-NH-CN - zinc ethylene-bis-dithiocarbamate - 2,4,6-trichloroaniline - pentachlorophenol 25 - thio-urea. Other known nitrification inhibitors include ATS (ammonium thiosulphate) and water soluble DMPP (3,4-dimethypyrazole phosphate). Still other options are discussed in the prior art. The term "nitrification inhibitor" or its plural refers to any suitable 30 compound or compounds and is inclusive of those discussed above.
WO 2005/075602 PCT/NZ2005/000013 -3 It is an object of the present invention to provide advantageous compositions inclusive of nitrification inhibitor(s) capable of agricultural use. BRIEF DESCRIPTION OF THE INVENTION 5 In one aspect the invention is a method of producing a composition suitable (alone or in conjunction with at least one other material) to be applied to the soil and/or pasture, said method comprising or including formulating a slurry of at least one zeolite as a particulate carrier with a liquid (preferably at least water) after, as and/or prior to the inclusion of at least one 10 nitrification inhibitor therein, and drying the slurry to result in an at least substantially dry particulate material with the zeolite carrying the nitrification inhibitor(s). The nitrification inhibitor(s) may be soluble to some extent in the liquid but preferably is present as a particle prior to the drying step. 15 Preferred particle size ranges for the solid carrier or zeolite is from 1 to 3mm (typically 100% passing a 3mm screen and < 1% a 1mm screen). Chemically preferably the zeolite is 65 to 95% w/w mordenite and 5 to 20% smectite. The nitrification inhibitor is preferably (but optionally) able to pass through 20 a 200pm screen. The nitrification inhibitor(s) prior to drying is supported in the liquid by a suspension agent (preferably a gum). Preferably the slurry prior to drying (preferably to a dryness of less than 8 % w/w water/composition) includes as the suspension agent or otherwise a tackifier 25 (e.g. a gum). Examples of suitable gums for one or both purposes include microbial polysaccharides such as dextran, gellan, rhamsan, guar and xanthan gums; polysaccharide derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, microcrystalline cellulose and modified starches; and synthetic polymers such as 30 polyvinyl alcohols, polyvinyl acetates and cross-linked polyacrylates.
WO 2005/075602 PCT/NZ2005/000013 -4 In another aspect the invention is a method of producing a composition suitable (alone or in conjunction with at least one other material) to be applied to the soil and/or pasture, said method comprising or including the steps of formulating an aqueous slurry of a particulate nitrification agent or agents 5 together with one or both of a suitable suspension stabilising agent and a zeolite carrier or carriers in a particulate form, and drying the slurry to at least a substantially dried particulate form which has the nitrification inhibitor(s) adhered to or otherwise carried by the zeolite(s) carrier. Preferably the formation of said slurry is a stage wise process. 10 Preferably said stage wise process involves optionally milling in water the nitrification inhibitor(s). Preferably the suspension stabilising agent and/or tack providing agent is added to the initial slurry and thereafter the zeolite(s) carrier is added. In preferred forms of the present invention the nitrification agent is selected from the range of 15 particulate nitrification agents including DCD and ATS. Preferably said suspension stabilising agent and/or tack providing agent is a gum. Preferably said gum is a polysaccharide gum such as, by way of example, one or more of xanthan gum, guar gum, etc. [e.g. as earlier exemplified]. Preferably the composition produced by the process is any of the 20 compositions hereinafter described. In yet a further aspect the present invention consists in the aforementioned process(es) and the optional additional step of adding a flow enhancing agent such as a particulate agent such as talc to the dried product. In still a further aspect the present invention consists in the aforementioned 25 process(es) and the additional optional step (irrespective of whether or not a flow enhancing agent has been utilised) of admixing or otherwise associating the zeolite carried nitrification inhibitor(s) with a fertilising agent, compound or composition irrespective of whether or not it includes nitrogen. Preferably however it includes nitrogen and may be, by way of example, urea.
WO 2005/075602 PCT/NZ2005/000013 -5 In another aspect the present invention consists in a composition for pasture application in the form of particulate zeolite or zeolites carrying at least one nitrification inhibitor. Preferably said composition has a tack providing agent and/or adhesive at 5 least in part binding the at least one nitrification inhibitor to the particulate zeolite(s). Preferably but not necessarily the nitrification inhibitor(s) is (are) low water solubility. Preferably said tack providing agent and/or adhesive is a gum. 10 Preferably said gum is a polysaccharide gum (e.g. at least one or both of xanthan gum and/or guar gum). Preferably the composition has a composition of 30 to 70% w/w zeolite(s), 1 to 50% w/w nitrification inhibitor(s), and 15 0.1 to 5% w/w tack providing agent/adhesive, and optionally 0 to 5% w/w flow enhancing agent. In a further aspect the present invention consists in a composition of any of the preceding kinds in admixture with a fertiliser. Preferably said fertiliser is a nitrogen containing fertiliser. In other forms it 20 is or can include trace elements or other fertilising elements. In another aspect the present invention consists in a fertiliser composition comprising 10 to 80% w/w fertiliser(s), 10 to 70% w/w zeolite(s), 25 1 to 45% w/w nitrification inhibitor(s), 0.05 to 5% w/w tackifying and/or suspension agent(s) and optionally other inclusion(s) (e.g. flow enhancing agents, etc.). Preferably the fertiliser is from 50 to 80% w/w of the composition. The fertiliser may be urea. The urea may be about 60% of the composition. 30 Preferably the nitrification inhibitor is one or both of DCD and ATS.
WO 2005/075602 PCT/NZ2005/000013 -6 Preferably said the composition is formed by any of the methods hereinbefore described and/or hereinafter described with or without reference to any example thereof and/or any of the accompanying drawings. In still a further aspect the present invention consists in a method of 5 potentiating the nitrification inhibition of a nitrification inhibitor (preferably but optionally selected from one or both of DCD and ATS) which comprises or includes coupling the nitrification inhibitor with a zeolite. In yet a further aspect the present invention consists in a synergistic nitrification inhibiting composition comprising or including an effective amount 10 of a particulate zeolite carrying an effective amount of at least one nitrification inhibitor. Preferably the w/w ratio of zeolite(s) to nitrification inhibitor(s) is from 95% / 5% to 35% / 65% (i.e. 9:1 to7:13). Preferably the nitrification inhibitor is one or both of DCD and ATS. 15 In still a further aspect the present invention consists in, in a fertiliser delivery system, particulate zeolite(s) carrying (optionally adhered) nitrification inhibitor(s). In another aspect, as a broadcastable or selectively applicable fertilising composition, (I) liquid and/or solid material(s) having an N and/or other fertilising 20 elemental content together with (II) particulate zeolite(s) carrying a nitrification inhibitor or nitrification inhibitors. In still another aspect the invention is the use of any composition, fertiliser or product of the present invention on soil and/or pasture. As used herein the term "zeolite" includes a zeolite of a kind (see 25 attachment) As used herein the term "slurry" is not restrictive to water carried particle mixtures but preferably includes water in the liquid or has water as the sole liquid. As used herein "nitrification inhibitor(s)" includes one or more inhibitor and preferably, but not only, one of those previously referred to. Examples include 30 - N-2,5-dichlorophenyl succinamic acid, WO 2005/075602 PCT/NZ2005/000013 -7 - 2-chloro-6-trichloromethyl pyridine ("Nitrapyrin"), - dicyandiamide ("DCD or "DCDIN""), - zinc ethylene-bis-dithiocarbamate, - 2,4,6-trichloroaniline, 5 - pentachlorophenol, - thio-urea, - ATS (ammonium thiosulphate), and - DMPP (3,4-dimethypyrazole phosphate). As used herein the term "and/or" means "and" and "or", or both. 10 As used herein the term "s" following a noun means the singular and plural forms of that noun. Nothing herein precludes other agents in addition to the nitrification agent(s) also being carried by the zeolite(s). 15 BRIEF DESCRIPTION OF THE DRAWINGS A preferred form of the present invention will now be described with reference to the accompanying drawings in which Figure 1 shows a flow diagram of one form of preparative method in accordance with the present invention leading either to a particulate form having a 20 nitrification inhibitor or inhibitors carried by a particulate carrier or carriers or to a resultant mix thereof with a fertiliser, Figure 2 shows a more specific procedure of which the procedure of Figure 1 is generic, and Figure 3 demonstrates efficacy as explained hereinafter. 25 WO 2005/075602 PCT/NZ2005/000013 -8 DETAILED DESCRIPTION OF THE INVENTION In the preferred form of the present invention the zeolite is of a kind that is preferably with a substantially w/w Mordinite presence (preferably at least 20%, more preferably greater than 40% and most preferably at least 50% e.g. 55 to 95%). 5 Various aspects of the present invention will now be demonstrated by the following examples which are not limiting of the invention. Example 1 shows one suitable zeolite form. Example 1 10 Composition: Clinoptilolite 25-65% Mordenite 25-65% Smeetite <5% Opal C 5-20% K Feldspar 5-20% 15 Density 1.2 g.cm 3 Porosity 60% Slurry pH 5.6 CEC 80 meq/100g 20 Internal surface area 35 m 2 /g Colour Opaque Absorbencies Water 55% Oil 45% 25 Example 2 shows a more preferred higher mordenite containing zeolite form. Example 2 Composition: Mordenite 65-95% WO 2005/075602 PCT/NZ2005/000013 -9 Smectite 5-20% Opal C <5% K Feldspar 5-20% 5 Density 0.89g.cm 3 Porosity 60% Slurry pH 5 to 6 for 20%w/v CEC 120 meq/100g Internal surface area 48m2/g 10 Pore size 7 Angstroms Colour Off white Absorbencies Water 55% Oil 45% 15 Examples 3 and 4 show two composition forms where the nitrification agent is DCD alone. Analogous examples can be formed with other nitrification agents disclosed herein or blends of any such agents disclosed herein. The more soluble nitrification agents will be more adsorbed into the zeolite rather than to adhere to 20 the zeolite as is the case with the less soluble nitrification agents. Example 3 - A DCD/Zeolite composition 250 gram DCD (ground until 100% passing 200pm screen) 25 250 gram Water WO 2005/075602 PCT/NZ2005/000013 -10 Water and DCD were blended until a smooth slurry was formed. To this slurry 5 grams of xanthan gum was added and stirred until fully hydrated (approx 15 min). The suspension was then added to 500 gram of zeolite (1-3mm) and mixed until the 5 zeolite grains were evenly coated and the mix was the consistency of bread crumbs. 50 grams of talc was then added to form a free flowing, granular DCD product. Final product contains 23.7% DCD and 0.47% xanthan gum. 10 The product of Example 3 is a heterogeneous mix of granules typically 1-3mm particle size range. This material is relatively free flowing and is stable in blends with fertilisers. 15 Example 4 - A DCD/Zeolite composition 165 grams of DCD 300 grams of 55% w/w ATS solution 20 DCD and ATS were mixed and blended for 5 minutes with a Silverstone type blender. 4.65 grams of xanthan gum was added and allowed to fully hydrate. The above mix was added to 470 grams of zeolite (1-3mm) and stirred until bread crumb like granules were formed. The wet granules were dried to yield 800 grams 25 of product. The product of Example 4 is a heterogeneous mix of granules typically 1-3mm particle size range. This material is relatively free flowing and is stable in blends with fertilisers. 30 WO 2005/075602 PCT/NZ2005/000013 -11 These Example's 3 and 4 products are mixable in all proportions with urea which is the preferred product for delivery to enhance the nitrogen use efficacy of the urea. Trial Performance 5 The uniform placement of a fertiliser or nitrification inhibitor is most uniform and efficacious if applied as a liquid or suspension. When applied as a DCD zeolite granule of the present invention (e.g. a composition of Example 3), we have found the granule application surprisingly gave equal or superior efficacy to such liquid or suspension applications as either 10 measured as nitrate or ammonia reduction or expressed as dry matter production. See Figure 3 in respect of nitrogen losses and Table 1. This is illustrated from field trial data showing statistically the same efficacy in terms of soil N fractions but a statistically significant advantage in terms of dry matter production. 15 This may be due to a release characteristic from the zeolite core or an absorption property of the material. In any event, the association with the zeolite in such scenarios of application provide advantages. Field trials show, almost without exception, at least equality of performance from the particulate (zeolite) application to that of a liquid vehicle application. 20 The following data presents some results from a range of field trials evaluating the DCD carried in/on zeolite particles when applied dry versus dissolved DCD formulations when applied as a spray, where high nitrogen application rates of order of 600 kg/ha of N have been applied to all treatments. Pasture measurements were assessed by mowing cuts. 25 WO 2005/075602 PCT/NZ2005/000013 -12 DCD N Care trial 1 Woodlands. The granule composition was as in Example 3 Table 1 Form Total yield (kg/ha) Control 1715 LiquidDCD (15kgDCD/ha) 3194 Zeolite DCD granule (15 kg DCD /ha) 3957 Lsd 294 5 DCD N Care trial 2 Rotorua. The granule composition was as in Example 3 Table 2 Form Total yield (kg/ha) Control 4254 Zeolite DCD granule (30 kg/ha DCD) 5202 Lsd (5%) 493 DCD N Care trial 3 Ruakura. The granule composition was as in Example 3 10 Table 3 Form Total leaching (kg N/ha) Control (no urine) 11 Urine 210 Urine plus Zeolite DCD granule (12 kg 145 DCD /ha) Lsd WO 2005/075602 PCT/NZ2005/000013 - 13 Table 4 is that table identified as Table 1 in our priority specification (the provisional specification of NZ Patent Application No. 531078). This table shows a range of DCD inhibitor rates and formulations including liquid (DCD L) and their impact on pasture production parameters. Urine was applied at 600 kg N/ha. 5 Table 4 Treat Form Urine 15.12.03 15.01.04 Total Kg/ha Grass Clover Kg/ha Grass Clover Yield (kg/ha) DM % % DM % % 1 Control 0 641 66.1 30.1 392 52.0 40.3 1715 2 Urea 0 1099 63.3 31.1 508 52.5 38.8 2795 3 Urea + 1771 75.3 20.8 503 67.4 22.3 3301 4 Super U 0 1243 66.8 28.3 384 53.6 39.2 2952 5 Super U + 2104 72.4 17.4 479 65.2 29.2 3852 6 Coated N 0 1168 67.2 29.4 394 58.6 35.0 2877 7 Coated N + 1933 80.3 11.2 637 71.6 21.8 3565 8 DCD (L) 15 + 1827 77.4 18.5 443 73.2 19.7 3194 9 DCD (L) 30 + 1881 76.2 17.0 611 74.9 19.4 3636 10 Zeolite 15 + 2104 77.0 18.7 636 74.7 19.9 3957 11 Zeolite 30 + 2020 75.3 21.1 618 71.8 16.8 3792 12 Urea 0 988 67.9 27.9 380 54.7 33.9 2356 13 Urea + 2065 76.2 18.4 662 80.7 15.0 3780 us* *** ***** SED 182 6.9 5.9 124 7.3 5.7 294 Contra + - Urine *** ** *** * *** *** ** sts Urea v SuperU NS NS NS NS NS t t Super U v Coated N NS NS NS NS NS NS NS Urea v Coated N NS NS NS NS NS NS NS Urine v Super U v Coated N NS NS NS NS NS NS NS Urea v Coated N & Super U NS NS NS N S NS NS NS 2 Urea v DCD (all) N S NS NS N S NS NS NS All Super U v Coated N NS NS NS NS NS NS NS with Urine Urea v DCD (Zeolite & Liq DCD) NS N S NS NS NS f NS 30kg/ha v 15 kg/ha NS NS NS NS NS NS NS Zeolite v Liquid DCD NS N S NS N S NS NS * Interaction NS NS NS NS NS NS NS 10
Claims (50)
1. A method of producing a composition suitable (alone or in conjunction with at least one other material) to be applied to the soil and/or pasture, said method comprising or including 5 formulating a slurry of at least one zeolite as a particulate carrier with a liquid after, as and/or prior to the inclusion of at least one nitrification inhibitor therein, and drying the slurry to result in an at least substantially dry particulate material with the zeolite carrying the nitrification inhibitor(s). 10
2. A method of claim 1 wherein the liquid is at least water.
3. A method of claim 1 or 2 wherein the nitrification inhibitor(s) is soluble to some extent in the liquid.
4. A method of claim 1 or 2 wherein the nitrification inhibitor(s) is present as a particle prior to the drying step. 15
5. A method of any one of the preceding claims wherein particle size ranges for the particulate carrier or zeolite is from 1 to 3mm (typically 100% passing a 3mm screen and < 1% a 1mm screen).
6. A method of any one of the preceding claims wherein the zeolite is 65 to 95% w/w mordenite and 5 to 20% smectite. 20
7. A method of any one of the preceding claims wherein the nitrification inhibitor is able to pass through a 200 im screen.
8. A method of any one of the preceding claims wherein the nitrification inhibitor(s) prior to drying is supported in the liquid by a suspension agent.
9. A method of claim 8 wherein the suspension agent is a gum. 25
10. A method of any one of the preceding claims wherein the drying is to a dryness of less than 8 % w/w water/composition).
11. A method of any one of the preceding claims wherein the slurry prior to drying has, as the suspension agent or otherwise, a tackifier.
12. A method of claim 11 wherein the trackifier is a gum. WO 2005/075602 PCT/NZ2005/000013 - 15
13. A method of claim 9 or 12 wherein the gum(s) is (are) selected from microbial polysaccharides such as dextran, gellan, rhamsan, guar and xanthan gums; polysaccharide derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, microcrystalline cellulose and modified starches; and 5 synthetic polymers such as polyvinyl alcohols, polyvinyl acetates and cross linked polyacrylates.
14. A method of producing a composition suitable (alone or in conjunction with at least one other material) to be applied to the soil and/or pasture, said method comprising or including the steps of 10 formulating an aqueous slurry of a particulate nitrification agent or agents together with one or both of a suitable suspension stabilising agent and a zeolite carrier or carriers in a particulate form, and drying the slurry to at least a substantially dried particulate form which has the nitrification inhibitor(s) adhered to or otherwise carried by the zeolite(s) carrier.
15 15. A method of claim 15 wherein the formation of said slurry is a stage wise process.
16. A method of claim 15 wherein said stage wise process involves optionally milling in water the nitrification inhibitor(s).
17. A method of any one of claims 14 to 16 wherein a suspension stabilising 20 agent and/or tack providing agent is added to the initial slurry and thereafter the zeolite(s) carrier is added.
18. A method of claim 17 wherein said suspension stabilising agent and/or tack providing agent is a gum.
19. A method of claim 18 wherein said gum is a polysaccharide gum. 25
20. A method of any one of the preceding claims wherein the nitrification agent(s) is(are) selected from the range of particulate nitrification agents - N-2,5-dichlorophenyl succinamic acid, - 2-chloro-6-trichloromethyl pyridine ("Nitrapyrin"), - dicyandiamide ("DCD or "DCDIN""), 30 - zinc ethylene-bis-dithiocarbamate, WO 2005/075602 PCT/NZ2005/000013 -16 - 2,4,6-trichloroaniline, - pentachlorophenol, - thio-urea, - ATS (ammonium thiosulphate), and 5 - DMPP (3,4-dimethypyrazole phosphate).
21. A method of claim 20 wherein the nitrification agent is DCD and/or ATS.
22. A method of claim 21 wherein DCD and no ATS is present.
23. A method of any one of the preceding claims with the optional additional step of adding a flow enhancing agent such as a particulate agent to the dried 10 product.
24. A method of claim 23 wherein the flow enhancing agent is a particulate agent and/or talc.
25. A method of any one of the preceding claims with the additional optional step (irrespective of whether or not a flow enhancing agent has been utilised) of 15 admixing or otherwise associating the zeolite carried nitrification inhibitor(s) with a fertilising agent, compound or composition.
26. A method of claim 25 wherein the fertilising compound is urea.
27. A composition produced by a method of any one of the preceding claims.
28. A composition for pasture application in the form of particulate zeolite or 20 zeolites carrying at least one nitrification inhibitor.
29. A composition of claim 28 wherein the nitrification inhibitor(s) is (are) low water solubility.
30. A composition of claim 28 or 29 wherein said composition has a tack providing agent and/or adhesive at least in part binding the at least one nitrification 25 inhibitor to the particulate zeolite(s).
31. A composition of claim 30 wherein said tack providing agent and/or adhesive is a gum.
32. A composition of claim 30 wherein said gum is a polysaccharide gum.
33. A composition of claim 32 with at least one or both of xanthan gum and/or 30 guar gum. WO 2005/075602 PCT/NZ2005/000013 -17
34. A composition of any one of claim 27 to 32 of 30 to 70% w/w zeolite(s), 1 to 50% w/w nitrification inhibitor(s), and 0.1 to 5% w/w tack providing agent/adhesive, and optionally 5 0 to 5% w/w flow enhancing agent.
35. A composition of any one of claims 28 to 34 in admixture with a fertiliser.
36. A composition of claim 35 wherein said fertiliser is a nitrogen containing fertiliser, trace element(s) and/or other fertilising element(s).
37. A fertiliser composition comprising 10 10 to 80% w/w fertiliser(s), 10 to 70% w/w zeolite(s), 1 to 45% w/w nitrification inhibitor(s), and 0.05 to 5% w/w tackifying and/or suspension agent(s), and optionally, other inclusion(s) (e.g. flow enhancing agents, etc.). 15
38. A composition of claim 37 wherein the fertiliser is from 50 to 80% w/w of the composition.
39. A composition of claim 37 or 38 wherein the fertiliser is urea.
40. A composition of claim 39 wherein the urea is about 60% w/w of the composition. 20
41. A composition of any one of claims 37 to 40 wherein the nitrification inhibitor(s) is(are) one (or both) of DCD and ATS.
42. A composition of any one of claims 37 to 41 is formed by any of the methods hereinbefore described and/or hereinbefore described with or without reference to any example thereof and/or any of the accompanying drawings. 25
43. A method of potentiating the nitrification inhibition of a nitrification inhibitor which comprises or includes coupling the nitrification inhibitor with a zeolite.
44. A method of potentiating the nitrification inhibition of a nitrification inhibitor selected from one or both of DCD and ATS. WO 2005/075602 PCT/NZ2005/000013 - 18
45. A synergistic nitrification inhibiting composition comprising or including an effective amount of a particulate zeolite carrying an effective amount of at least one nitrification inhibitor.
46. A synergistic nitrification inhibiting composition comprising the w/w 5 ratio of zeolite(s) to nitrification inhibitor(s) is from 9:1 to 7:13.
47. A composition of claim 45 or 46 wherein the nitrification inhibitor is one or both of DCD and ATS.
48. In a fertiliser delivery system, particulate zeolite(s) carrying (optionally adhered) nitrification inhibitor(s). 10
49. As a broadcastable or selectively applicable fertilising composition, (I) liquid and/or solid material(s) having an N and/or other fertilising elemental content together with (II) particulate zeolite(s) carrying a nitrification inhibitor or nitrification inhibitors. 15
50. The use of any composition, of any one of claims 27 to 47 and 49 on soil and/or pasture.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2011265401A AU2011265401B2 (en) | 2004-02-09 | 2011-12-21 | Fertilizer Compositions |
| AU2011265399A AU2011265399B2 (en) | 2004-02-09 | 2011-12-21 | Fertilizer Compositions |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NZ531078 | 2004-02-09 | ||
| NZ531078A NZ531078A (en) | 2004-02-09 | 2004-02-09 | Fertiliser compositions for reducing the progress of the production of nitrates in the soil |
| PCT/NZ2005/000013 WO2005075602A1 (en) | 2004-02-09 | 2005-02-07 | Fertilizer compositions |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2011265399A Division AU2011265399B2 (en) | 2004-02-09 | 2011-12-21 | Fertilizer Compositions |
| AU2011265401A Division AU2011265401B2 (en) | 2004-02-09 | 2011-12-21 | Fertilizer Compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU2005210449A1 true AU2005210449A1 (en) | 2005-08-18 |
| AU2005210449A8 AU2005210449A8 (en) | 2010-04-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2005210449A Abandoned AU2005210449A1 (en) | 2004-02-09 | 2005-02-07 | Fertilizer compositions |
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| EP (1) | EP1720957A4 (en) |
| AU (1) | AU2005210449A1 (en) |
| WO (1) | WO2005075602A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2925826B1 (en) * | 2007-12-31 | 2010-01-29 | Agrofinance Internationale | UREASE AND NITRIFICATION INHIBITOR COMPOSITION |
| WO2012154018A1 (en) * | 2011-05-11 | 2012-11-15 | Alanis Ortega Javier Isaias | Activated, micronized zeolite, method for activating and micronizing same and use thereof as a carrier in pharmaceutical preparations and dietary supplements |
| NL2008236C2 (en) | 2012-02-06 | 2013-08-08 | Holding Company Belgie Nv | Water and nutrient management in crops production. |
| CN102775249B (en) * | 2012-07-20 | 2014-03-12 | 昆明环资农业科技有限公司 | Soil conditioner for facility agriculture planting |
| MX368841B (en) | 2012-10-01 | 2019-10-18 | Gary David Mcknight | Improved liquid formulations of urease inhibitors for fertilizers. |
| US20150052960A1 (en) * | 2013-08-23 | 2015-02-26 | Koch Agronomic Services, Llc | Urease inhibitor and non-ufp solid carrier composition |
| CN106455576B (en) * | 2013-11-26 | 2020-01-14 | 加里·戴维·麦克奈特 | Nitrification inhibitors designed for urea-based and manure-based fertilizers |
| BR112016017083B1 (en) | 2014-01-31 | 2022-02-15 | Saudi Basic Industries Corporation | FERTILIZER CAPSULE, AND, METHOD OF PREPARATION OF A FERTILIZER CAPSULE CORE |
| US9650306B2 (en) | 2014-04-17 | 2017-05-16 | Gary David McKnight | Compositions and methods comprising nitrification inhibitors containing a mixture of protic and aprotic solvent systems |
| CN106458780B (en) | 2014-05-05 | 2019-11-12 | 赛贝克环球科技公司 | The granular fertilizer of coating, its manufacturing method and use |
| RU2675935C1 (en) * | 2015-02-24 | 2018-12-25 | КОХ АГРОНОМИК СЕРВИСИЗ, ЭлЭлСи | Granular fertilizer based on urea with nitrogen stabilizer additives |
| WO2017013573A1 (en) | 2015-07-20 | 2017-01-26 | Sabic Global Technologies B.V. | Fertilizer composition and methods of making and using same |
| US11104618B2 (en) | 2015-07-20 | 2021-08-31 | Sabic Global Technologies B.V. | Fertilizer composition and methods of making and using same |
| CN108349828A (en) | 2015-11-16 | 2018-07-31 | 沙特基础工业全球技术有限公司 | Coated granular fertilizer, its manufacturing method and application thereof |
| BR112018009872B1 (en) | 2015-11-16 | 2022-11-16 | Sabic Global Technologies B.V. | MANUFACTURING PROCESS OF A COATED FERTILIZER |
| EP3202753A1 (en) * | 2016-02-08 | 2017-08-09 | Lithos Industrial Minerals GmbH | Composition comprising zeolite |
| US11806689B2 (en) | 2016-02-08 | 2023-11-07 | Sabic Global Technologies B.V. | Method of making a fertilizer seed core |
| EP3612508A1 (en) | 2017-04-19 | 2020-02-26 | SABIC Global Technologies B.V. | Enhanced efficiency fertilizer with urease inhibitor and nitrification inhibitor in separate particles |
| CN110809569B (en) | 2017-04-19 | 2022-07-12 | 沙特基础工业全球技术公司 | Synergistic fertilizer with urease inhibitor and nitrification inhibitor separated in the same granule |
| AU2018255908B2 (en) | 2017-04-20 | 2023-06-29 | SABIC Agri-Nutrients Company | Enhanced efficiency fertilizer with embedded powder composition |
| WO2019030671A1 (en) | 2017-08-09 | 2019-02-14 | Sabic Global Technologies B.V. | Extruded fertilizer granules with urease and/or nitrification inhibitors |
| US11866383B1 (en) | 2018-04-04 | 2024-01-09 | Synsus Private Label Partners, Llc | Nitrification inhibiting compositions and their use in agricultural applications |
| WO2020033575A1 (en) * | 2018-08-08 | 2020-02-13 | Tessenderlo Kerley, Inc. | Compositions comprising solid thiosulfates, polysulfides and/or (bi)sulfites with an urea compound and methods for preparing same |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD291912A5 (en) * | 1990-02-15 | 1991-07-18 | Forschzent Bodenfruchtbarkeit | PROCESS FOR MODIFYING THE NITRIFICATIN INHIBITOR 2-CHLORO-6-TRICHLOROMETHYL-PYRIDINE |
| US5695542A (en) * | 1995-11-14 | 1997-12-09 | Chang; Hsin-Jen | Method of preparing a slow release fertilizer |
| CN1204631A (en) * | 1998-07-10 | 1999-01-13 | 寇庆德 | Nitrogenous fertilizer long-acting synergist |
| US6231632B1 (en) * | 1999-05-25 | 2001-05-15 | Engelhard Corporation | Urea processing agent |
| CN1163449C (en) * | 1999-10-29 | 2004-08-25 | 中国科学院沈阳应用生态研究所 | Long-acting complex fertilizer additive |
| CN1137872C (en) * | 2000-03-09 | 2004-02-11 | 刘芳 | Long-acting agent for nitrogen fertilizer |
| KR20020060680A (en) * | 2000-05-15 | 2002-07-18 | 구마가야 나오히꼬 | Fertilizers containing ammonium thiosulfate |
| KR100420573B1 (en) * | 2001-12-04 | 2004-03-02 | 바이오메디아 주식회사 | A method for producing a solid fertilizer for plant growth, the solid fertilizer chip and a pot for plant growth containing the solid fertilizer chip |
| CN1216016C (en) * | 2003-04-08 | 2005-08-24 | 西南农业大学 | Natural plant-carrying compound nitrogen fertilizer synergistic agent |
-
2005
- 2005-02-07 EP EP05710964A patent/EP1720957A4/en not_active Withdrawn
- 2005-02-07 AU AU2005210449A patent/AU2005210449A1/en not_active Abandoned
- 2005-02-07 WO PCT/NZ2005/000013 patent/WO2005075602A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| AU2005210449A8 (en) | 2010-04-08 |
| WO2005075602A1 (en) | 2005-08-18 |
| EP1720957A1 (en) | 2006-11-15 |
| EP1720957A4 (en) | 2011-07-06 |
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