WO1996040696A1 - Preparation of ammonium glyphosate using aqueous ammonium hydroxide in a liquid-solid reaction system - Google Patents
Preparation of ammonium glyphosate using aqueous ammonium hydroxide in a liquid-solid reaction system Download PDFInfo
- Publication number
- WO1996040696A1 WO1996040696A1 PCT/US1996/003081 US9603081W WO9640696A1 WO 1996040696 A1 WO1996040696 A1 WO 1996040696A1 US 9603081 W US9603081 W US 9603081W WO 9640696 A1 WO9640696 A1 WO 9640696A1
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- WO
- WIPO (PCT)
- Prior art keywords
- ammonium hydroxide
- glyphosate
- moisture content
- reaction mass
- ammonium
- Prior art date
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000000908 ammonium hydroxide Substances 0.000 title claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 44
- PDYXIVPKOMYDOK-UHFFFAOYSA-N Glyphosate-monoammonium Chemical compound [NH4+].OC(=O)CNCP(O)([O-])=O PDYXIVPKOMYDOK-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000007787 solid Substances 0.000 title abstract description 21
- 238000002360 preparation method Methods 0.000 title description 3
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000005562 Glyphosate Substances 0.000 claims abstract description 44
- 229940097068 glyphosate Drugs 0.000 claims abstract description 44
- 239000002253 acid Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000002671 adjuvant Substances 0.000 claims abstract description 17
- 230000003247 decreasing effect Effects 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 63
- 239000000203 mixture Substances 0.000 claims description 52
- 239000000843 powder Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- -1 ammonia cation Chemical class 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 230000007423 decrease Effects 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- IEOOTHOCJCTZLK-UHFFFAOYSA-N azane 2-[methyl(phosphono)amino]acetic acid Chemical compound N.OP(=O)(O)N(C)CC(O)=O IEOOTHOCJCTZLK-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 230000002363 herbicidal effect Effects 0.000 abstract description 10
- 239000004009 herbicide Substances 0.000 abstract description 9
- 239000005648 plant growth regulator Substances 0.000 abstract description 5
- 238000000227 grinding Methods 0.000 abstract description 4
- 230000003134 recirculating effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 38
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 28
- 235000010265 sodium sulphite Nutrition 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000009472 formulation Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- YWICANUUQPYHOW-UHFFFAOYSA-M sodium;2-(phosphonomethylamino)acetate Chemical compound [Na+].OP(O)(=O)CNCC([O-])=O YWICANUUQPYHOW-UHFFFAOYSA-M 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000009877 rendering Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 235000008504 concentrate Nutrition 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- 150000004005 nitrosamines Chemical class 0.000 description 2
- 235000012149 noodles Nutrition 0.000 description 2
- 230000000361 pesticidal effect Effects 0.000 description 2
- 231100000208 phytotoxic Toxicity 0.000 description 2
- 230000000885 phytotoxic effect Effects 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KXYZDDCGTMTNFE-UHFFFAOYSA-N P(O)(O)=O.NC(CCC)C(=O)O Chemical compound P(O)(O)=O.NC(CCC)C(=O)O KXYZDDCGTMTNFE-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 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
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- ZOMSMJKLGFBRBS-UHFFFAOYSA-N bentazone Chemical compound C1=CC=C2NS(=O)(=O)N(C(C)C)C(=O)C2=C1 ZOMSMJKLGFBRBS-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008029 eradication Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- DXTIKTAIYCJTII-UHFFFAOYSA-N guanidine acetate Chemical compound CC([O-])=O.NC([NH3+])=N DXTIKTAIYCJTII-UHFFFAOYSA-N 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000007425 progressive decline Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
Definitions
- This invention relates to a dry, non-clumping herbicidal composition together with a method for making the composition. More particularly, the present invention relates to an ammonium glyphosate herbicide and an efficient method for making solid ammonium glyphosate products that readily dissolve in water and that can be used to prepare highly-loaded, adjuvant- containing dry/solid glyphosate compositions.
- N-phosphonomethylglycine [HOOCCH 2 NH CH 2 PO(OH) 2 ]
- glyphosate acid or simply glyphosate
- glyphosate an organic acid
- glyphosate is typically formulated as a water- soluble salt, particularly as the mono-isopropylamine (IPA) salt to kill or control weeds or plants.
- IPA mono-isopropylamine
- Glyphosate is sold commercially as an aqueous concentrate in the form of its IPA salt by Monsanto Company of St. Louis, Missouri (U.S.A.) under the registered trademark Roundup®.
- Roundup® brand herbicide is sold as a water-soluble liquid concentrate.
- aqueous concentrates include a significant amount of solvent that adds to the size and weight of packaging containers and increases costs associated with post- manufacture delivery of the product to market.
- a less readily apparent benefit also resides in the advantage of making a water-soluble, dry glyphosate. Namely, a granular formulation is believed to provide superior handling characteristics (i.e. controlled spillage) and is expected to be substantially lighter and less awkward to transport (and often hand carry) thereby making the product better suited for use in remote geographic locations.
- a method for preparing a dry, water-soluble salt of bentazon or of a herbicide containing a carboxylic acid functionality which involves repeated treatments of the salt with a neutralizing base selected from the group consisting of ammonia, an alkyla ine, a hydroxyalkylamine, an alkaline salt of an alkali metal and combinations thereof.
- a phytotoxic preparation comprising the monoammonium salt of N- phosphonomethylglycine as a powder or granule in combination with a wetting agent, surfactant and/or a pulverulent additive.
- the monoammonium salt is derived from reacting glyphosate acid with ammonium bicarbonate.
- U.S. Patent No. 5,324,708 which issued on June 28, 1994 to Moreno, et. al. discloses a composition and related methods for preparing and using a non- hygroscopic monoammonium glyphosate salt such as the mono-isopropylammonium salt of N-(phosphono-methyl)- glycine and the mono-isopropylammonium salt of (3-amino- 3-carboxypropyl)-methane phosphonic acid in dry powder form [sic].
- a non- hygroscopic monoammonium glyphosate salt such as the mono-isopropylammonium salt of N-(phosphono-methyl)- glycine and the mono-isopropylammonium salt of (3-amino- 3-carboxypropyl)-methane phosphonic acid in dry powder form [sic].
- a dry glyphosate composition in which N-phosphono-methylglycine is admixed with, inter alia, an inorganic or organic, non- caustic base material such as diammonium phosphate or a basic guanidine salt such as guanidinium acetate.
- EPO application Publication No. 0 394 211 which was published on October 24, 1990, discloses an invention comprising a dry pesticidal composition and related methods for use and production. More particularly, the invention relates to the enhanced solubility of the pesticidal composition as achieved by the addition of an effective amount of an organosilicone block copolymer or a fluorocarbon wetting agent.
- PCT application Publication No. WO 90/07275 which was published on July 12, 1990, there is disclosed an invention by which granular, water-soluble glyphosate compositions are made as by admixing, pan granulation, drying, spraying and extrusion.
- WO 92/12637 which was published on August 6, 1992, there is disclosed an invention relating to a dry, water soluble glyphosate including a composition comprising substantially nonreacted glyphosate, an acid acceptor such as sodium acetate and a liquid or solid surfactant. All of the foregoing patents and publications are herein incorporated by reference.
- glyphosate acid is charged to, as for example, a suitable blender such as a ribbon blender where it is blended and then, if necessary, partially pre-dried by recirculation through a hot air grinding/drying system. While the acid is being continuously recirculated, a solution of cooled ammonium hydroxide is added, as by spraying, at a particular and critical rate to react with the acid. After a specified amount of ammonium hydroxide has been added, the reaction mass/product of the reaction, which is in the form of a powder, is suitable for end use as a herbicide or as a plant growth regulator.
- a suitable blender such as a ribbon blender
- a solution of cooled ammonium hydroxide is added, as by spraying, at a particular and critical rate to react with the acid.
- the reaction mass/product of the reaction which is in the form of a powder, is suitable for end use as a herbicide or as a plant growth regulator.
- the powdered reaction product due to its highly sorptive character is capable of being further formulated to absorb/adsorb an exceptionally high level of an adjuvant such as a wetting agent, an anti-foaming agent and particularly a surfactant composition.
- an adjuvant such as a wetting agent, an anti-foaming agent and particularly a surfactant composition.
- the powdered reaction product or the adjuvant-loaded product may be granulated to provide a free-flowing (i.e. non-caking), substantially dust-free and water soluble ammonium glyphosate herbicide and/or plant growth regulator.
- the powder may be further ground and/or dried prefatory to packaging.
- Significant advantages achieved by the present invention reside in its relative simplicity, comparative low cost and in the fact that no highly specialized equipment is required to practice the invention. Thus, where conventional blending and milling/grinding equipment already exist, the present invention can be carried out efficiently on a commercial scale to produce a very high quality dry ammonium glyphosate product.
- FIG. 1 is a schematic diagram illustrating the process for preparing dry ammonium glyphosate in accordance with the present invention.
- the present invention relates to a novel method for reacting N-phosphonomethylglycine (glyphosate acid) with ammonium hydroxide to produce ammonium glyphosate powder, a key raw material which may be used as is or in granulated form or as a starting material in the formulation of a granulated surfactant-loaded dry glyphosate composition.
- ammonium glyphosate as well as alkali metal glyphosates such as sodium glyphosate have been made in dry, powder form.
- sodium glyphosate has been produced by reacting glyphosate acid with sodium acetate or by extruding the acid with sodium hydroxide as described above in PCT application Publication No. WO 92/12637 and U.S. Patent No. 5,070,197 respectively.
- sodium glyphosate granules and powders have, until now, provided satisfactory dry glyphosate compositions.
- the sodium salt is much more hygroscopic meaning it is not as resistant against ambient humidity.
- the sodium glyphosate salt is considered more difficult and more expensive to process as a dry composition and, once formed as such, it has a greater tendency to agglomerate which results in undesirable "caking" of the finished material.
- sodium glyphosate salt compositions have a lower concentration of the active glyphosate than their counterpart ammonium glyphosate salt compositions.
- the per pound cost of sodium cation is much more expensive than the cost of obtaining the ammonium cation.
- the comparative disadvantages of sodium glyphosate compositions are, thus, apparent.
- solid and/or “dry” mean the physical state in which the formulation has a specific shape and volume and resists deformation.
- the solid may take the form of pellets, flakes, granules, powder or the like. Further, it will be understood that the solid formulation may subsequently be dissolved in a suitable diluent, usually and preferably water, and applied to the locus where plant regulation or eradication is desired as by spraying or other conventional means.
- adherence to the process of the present invention and the manner and extent to which the reaction between the glyphosate acid and the ammonium hydroxide is controlled in accordance with the process are critical in ensuring the creation of a solid, free-flowing (i.e.non-caking) and water soluble ammonium glyphosate salt which, importantly, is capable of being further formulated to absorb/adsorb an exceptionally high level of adjuvants such as surfactants.
- the reactant mixture is continuously dried and conditioned to maintain a suitable moisture content throughout the step of ammonium hydroxide addition such that a free-flowing, readily handleable, powder is generated.
- This not only allows processing in conventional equipment, but also produces an ammonium glyphosate powder that can be used to make dry glyphosate products highly-loaded with adjuvants.
- the inventors have determined that the moisture content in the reaction mass during the ammonium hydroxide addition to the glyphosate acid is a critical aspect of the invention.
- the amount of ammonium hydroxide which is required in order to practice the invention is equivalent to that amount which is required to achieve approximately 95- 105% neutralization of the acid which can be determined by conventional analytical methods known to those ordinarily skilled in the art such as by pH measurement.
- the wet cake is charged to an actuated and suitable conventional blender.
- a pre-determined quantity of sodium sulfite may be added to prevent the possible formation of nitrosamines.
- sodium sulfite is not necessary to practice the invention and does not affect the reaction between the glyphosate acid and ammonium hydroxide, certain governmental regulations require that nitrosamine levels in products of this nature be below 1 ppm.
- the effective range of sodium sulfite to be added as ensurance against the presence of unacceptable levels of nitrosamines is between 0.2 and 1.0 wt.% of the dried, finished product.
- a pre-drying step occurs next during which the wet cake and, if desired, sodium sulfite are continuously circulated through a hot air drying and milling system which is arranged in communication with the blender.
- a constant and elevated drying air temperature of about 170 to 300 degrees Fahrenheit, and preferably 250° to 270° F, is maintained and the mixture is continuously circulated until its total moisture content is below about 6 wt.%.
- a sample of the mixture is then recovered and assayed. If the moisture content of the wet cake starting material is already below about 6 wt.%, then the pre-drying step is unnecessary.
- the temperature of the drying air system is substantially reduced to a temperature of about 150 to 200 degrees Fahrenheit as the mixture continues to circulate.
- a cooled solution of ammonium hydroxide is then added to the mixture, as by spray application into the blender, to form an ammonium glyphosate reaction mass.
- a standard commercial ammonium hydroxide solution is employed; preferably one that contains approximately 29 wt.% ammonia.
- the solution is first cooled to about 40 to 50 degrees Fahrenheit because it is known that liquid ammonium hydroxide is volatile and that it boils at 86 degrees Fahrenheit. Thus, ammonium hydroxide loss is controlled and the " likelihood of atmospheric pollution by the evaporating solution is reduced.
- the solution is sprayed, as by one or more nozzles into the blender containing the wet cake and sodium sulfite, if present, using a coarse spray.
- the flow of the sprayed solution is metered such that the moisture content of the reaction mass consistently decreases from the initial concentration of circa 6 wt.% down to about 2 wt.% (i.e. loss of weight on drying or LOD) or less during the period in which the ammonium hydroxide is added and the exothermic reaction proceeds.
- the ammonium hydroxide spray rate is designed in such a way as to control the rate at which water is introduced with the ammonium hydroxide and formed as a product of the reaction between the glyphosate acid and the ammonium hydroxide.
- the object is to introduce the water at a rate slower than the rate at which moisture is being driven from the wet cake/sodium sulfite mixture due to the circulating dryer system.
- Other ammonium hydroxide addition rates were experimented with but did not yield the highly desirable product generated by the present invention.
- the ammonium glyphosate powder produced had less sorptive capacity rendering it unfit for further processing such as loading with adjuvants and particularly with surfactants.
- Addition rates in excess of the 40% higher rate have an immediate adverse effect on the physical characteristics of the reaction mass; the reaction mass becomes a very wet and "dough ⁇ like" cohesive mass rendering it unsuitable for completion of the process.
- the material in the blender again also becomes very wet and "dough-like" rendering it unsuitable for use in completing the process.
- the pre-drying step may be avoided or abbreviated such that the moisture content in the mixture of glyphosate acid and sodium sulfite may be initially greater than about 6 wt.%.
- the ammonium hydroxide addition rate under such circumstances would be so slow as to render the process economically unfeasible.
- samples should periodically be obtained and assayed to measure the moisture content to ensure that the rate of water removal from the reaction is greater than the rate at which water is being added. This can simply be determined by observing progressive decreases in the moisture content of the mixture.
- ammonium glyphosate is in the form of a powdered product which may be further processed.
- Such further processing may include: the addition of sodium sulfite, grinding, drying, granulating or formulating with adjuvants. The decision regarding which, if any, of these further processes is to be performed is dictated, largely, based upon the intended end-use of the product.
- a quantity of sodium sulfite may be again optionally added.
- the reaction mass may be further ground to make it more suitable for further processing. If further processing such as granulation or formulation with adjuvants is to be performed immediately, it is not necessary to further dry the product at this stage. However, if the product is to be shipped or stored for more than a few days, for example, then it should be further dried to less than 1 wt.% moisture at this time to prevent caking. Where it is desired to use the product without the addition of any adjuvants as a herbicide or plant growth regulator, then it is desirable to granulate or agglomerate it, such as by pan granulation and drying or by other methods known in the art.
- adjuvants such as surfactants, anti-foa ing agents, wetting agents and the like
- these may be added as by blending in suitable equipment and, preferably, by kneading, extruding and drying or as by other methods well-known to the ordinarily skilled artisan.
- EXAMPLE 1 In a plant-scale reactor system comprised of a stainless steel ribbon blender, a suitable hot air drying system such as an air-swept hammer mill supplied with hot air and an adapted dust collector, all of which were in communication with each other as by suitable connecting conduits, 2400 lbs. of standard grade N- phosphonomethylglycine "wet cake" having an assayed moisture content of about 10% LOD was charged to the ribbon blender where it was immediately mixed. Once all of the wet cake had been deposited in the ribbon blender, 4.8 lbs. of solid sodium sulfite was also charged to the blender and combined with the wet cake whereupon it was intimately mixed. The combination of wet cake and sodium sulfite was then circulated within the hot air-swept mill system using an air inlet temperature of about 250° F for one hour. A sample of the mixture was then recovered and assayed to determine its moisture content/LOD.
- a suitable hot air drying system such as an air-swept hammer mill supplied with hot air and an
- reaction mass was a free-flowing powdered product particularly well-suited for immediate and desirable further processing.
- reaction mass was, at this point, conditioned in such a way as to ensure that it would not cake during storage.
- an additional and equal quantity of sodium sulfite was charged to the blender and mixed for approximately ten minutes to ensure uniform dispersion with the powdered reaction mass.
- This combination was next physically comminuted by passing the dry powdered composition through an air classifying mill to reduce the discrete particles of the composition to a substantially small and uniform size.
- an air classifying mill was used because it happened to be a part of the equipment train used for this Example 1, this milling procedure is not required to practice the invention.
- the product was subjected to conventional fluid bed drying to ensure that the resulting finished product exhibited a residual moisture content of no greater than 1.0% LOD.
- the powdered reaction mass/product produced in accordance with the novel process of this invention is particularly well adapted to be further formulated to absorb/adsorb high levels of adjuvants.
- the relative simplicity of the present invention its ability to be practiced using conventional equipment and the comparative low cost of the ammonium cation furnished by ammonium hydroxide deem very significant the capacity of the powdered reaction mass/product to absorb/adsorb high levels of adjuvants.
- Example 2 presented below illustrates the exceptional sorptive capacity of the powdered reaction mass/product when loaded with surfactant.
- the powdered reaction mass/product formed by the process described in Example 1 can be used to make a dry formulation of ammonium glyphosate containing a high level of surfactant of at least about 20 wt.%.
- 16 kilograms of the powdered reaction mass/product is blended with 4 kilograms of a polyoxyethylene alkylamine surfactant and 1.4 kilograms of water in a jacketed batch kneader, such as a Fuji Paudal, for approximately 10 minutes with water at a temperature of about 80° C circulating in the jacket.
- the dough that is formed is then extruded, as for example in a Fuji Paudal twin screw extruder, fitted with screens having approximately 1 mm. diameter borings.
- the extrudate obtained consisted of discrete, "spaghetti-like" short noodles which did not stick together and which were easily and conveniently dried, such as for example in a Fitz-Aire fluid bed dryer, without "formation of undesirable lumping.
- a product made in accordance with all of the process variables of the invention but, wherein the addition rate of ammonium hydroxide solution was 40% higher a doughy product was produced that was undesirably wet and sticky to touch.
- the extrudate produced therefrom consisted of undesirably long "spaghetti-like” noodles that stuck together and formed large agglomerates. This extrudate was very difficult to fluidize in the fluid bed dryer and resulted in the formation of a large quantity of dried agglomerates which, in order to be usable, would then have to be ground and recycled back through the extrusion process.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
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Abstract
Description
Claims
Priority Applications (12)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
HU9802333A HUP9802333A3 (en) | 1995-06-07 | 1996-03-05 | Preparation of ammonium glyphosate using aqueous ammonium hydroxide in a liquid-solid reaction system |
AT96913769T ATE201210T1 (en) | 1995-06-07 | 1996-03-05 | PRODUCTION OF AMMONIUM GLYPHOSATE USING AQUEOUS AMMONIUM HYDROXIDE IN A LIQUID-SOLID REACTION SYSTEM |
EP96913769A EP0845000B1 (en) | 1995-06-07 | 1996-03-05 | Preparation of ammonium glyphosate using aqueous ammonium hydroxiye in a liquid-solid reaction system |
JP9500436A JP2963543B2 (en) | 1995-06-07 | 1996-03-05 | Production of ammonium glyphosate using aqueous ammonium hydroxide in a liquid-solid reaction system |
CA002221298A CA2221298C (en) | 1995-06-07 | 1996-03-05 | Preparation of ammonium glyphosate using aqueous ammonium hydroxide in a solid reaction system |
DE69612857T DE69612857T2 (en) | 1995-06-07 | 1996-03-05 | Production of ammonium glyphosate using aqueous ammonium hydroxide in a liquid-solid reaction system |
BR9608562A BR9608562A (en) | 1995-06-07 | 1996-03-05 | Preparation of ammonium glyphosate using aqueous ammonium hydroxide in a solid-liquid reaction system |
DK96913769T DK0845000T3 (en) | 1995-06-07 | 1996-03-05 | Preparation of ammonium glyphosate using aqueous ammonium hydroxide in a liquid-solid reaction system |
UA98010006A UA48971C2 (en) | 1995-06-07 | 1996-03-05 | Method for production of dry phytoactive composition of ammonium glyphosate |
NZ307310A NZ307310A (en) | 1995-06-07 | 1996-03-05 | Preparation of ammonium glyphosate using aqueous ammonium hydroxide in liquid-solid reaction system |
AU56620/96A AU694877B2 (en) | 1995-06-07 | 1996-03-05 | Preparation of ammonium glyphosate using aqueous ammonium hydroxide in a liquid-solid reaction system |
GR20010401207T GR3036355T3 (en) | 1995-06-07 | 2001-08-08 | Preparation of ammonium glyphosate using aqueous ammonium hydroxide in a liquid-solid reaction system |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US472,152 | 1995-06-07 | ||
US08/472,152 US5614468A (en) | 1995-06-07 | 1995-06-07 | Preparation of ammonium glyphosate using aqueous ammonium hydroxide in a liquid-solid reaction system |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996040696A1 true WO1996040696A1 (en) | 1996-12-19 |
Family
ID=23874396
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1996/003081 WO1996040696A1 (en) | 1995-06-07 | 1996-03-05 | Preparation of ammonium glyphosate using aqueous ammonium hydroxide in a liquid-solid reaction system |
Country Status (23)
Country | Link |
---|---|
US (2) | US5614468A (en) |
EP (1) | EP0845000B1 (en) |
JP (1) | JP2963543B2 (en) |
KR (1) | KR100266126B1 (en) |
CN (1) | CN1068601C (en) |
AR (1) | AR004487A1 (en) |
AT (1) | ATE201210T1 (en) |
AU (1) | AU694877B2 (en) |
BR (1) | BR9608562A (en) |
CA (1) | CA2221298C (en) |
DE (1) | DE69612857T2 (en) |
DK (1) | DK0845000T3 (en) |
ES (1) | ES2157441T3 (en) |
GR (1) | GR3036355T3 (en) |
HU (1) | HUP9802333A3 (en) |
IL (1) | IL118577A (en) |
NZ (1) | NZ307310A (en) |
PT (1) | PT845000E (en) |
RU (1) | RU2164519C2 (en) |
TW (1) | TW306867B (en) |
UA (1) | UA48971C2 (en) |
WO (1) | WO1996040696A1 (en) |
ZA (1) | ZA964775B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001008491A1 (en) * | 1999-07-29 | 2001-02-08 | Monsanto Technology Llc | Process for making ammonium glyphosate flakes |
WO2001008492A1 (en) * | 1999-07-28 | 2001-02-08 | Monsanto Technology Llc | Process for making a downstream processable ammonium glyphosate paste |
WO2001008480A1 (en) * | 1999-07-29 | 2001-02-08 | Monsanto Technology Llc | Process for making ammonium glyphosate powder |
US6734142B2 (en) | 2001-04-23 | 2004-05-11 | Monsanto Technology Llc | Ammonium glyphosate compositions and process for their preparation |
US7141532B2 (en) | 2002-08-31 | 2006-11-28 | Monsanto Technology Llc | Process for the preparation of a dry pesticidal composition containing a dicarboxylate component |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5633397A (en) * | 1995-06-07 | 1997-05-27 | Monsanto Company | Preparation of ammonium glyphosate via a gas-solid reaction system |
CN1072672C (en) * | 1999-11-08 | 2001-10-10 | 浙江新安化工集团股份有限公司 | Preparation method for ammonium glyphosphonate |
US20050037924A1 (en) * | 2002-08-31 | 2005-02-17 | Monsanto Technology Llc | Sodium glyphosate compositions and process for their preparation |
EP2292095A2 (en) | 2002-08-31 | 2011-03-09 | Monsanto Technology LLC | Pesticide compositions containing a dicarboxylic acid or derivative thereof |
CN1244587C (en) * | 2002-09-05 | 2006-03-08 | 浙江新安化工集团股份有限公司 | Gas-liquid-solid three phase reactions and solvent exraction for preparing ammonia glyphosate acid |
AR037559A1 (en) * | 2002-11-19 | 2004-11-17 | Atanor S A | A SOLID HERBICIDE FORMULATION OF N-PHOSPHONOMETILGLYCIN, UNDER THE FORM OF DUST, GRANULES OR SCALES, SOLUBLE OR DISPERSABLE IN WATER, AND THE PROCEDURE TO PREPARE SUCH COMPOSITION |
CN1328283C (en) * | 2004-07-19 | 2007-07-25 | 中国科学院植物研究所 | Method of producing ammonium glyphosate |
ITMI20051138A1 (en) * | 2005-06-17 | 2006-12-18 | Sipcam Spa | PROCESS TO PREPARE AMMONIC GLYPHOSATE GRANULES |
US20110071027A1 (en) * | 2009-09-18 | 2011-03-24 | Volker Heide | High strength aqueous glyphosate salt concentrates and methods |
CN103109801B (en) * | 2013-03-06 | 2014-08-27 | 段凤羽 | Glyphosate assistant and preparation method thereof |
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- 1996-03-05 DK DK96913769T patent/DK0845000T3/en active
- 1996-03-05 WO PCT/US1996/003081 patent/WO1996040696A1/en active IP Right Grant
- 1996-03-05 NZ NZ307310A patent/NZ307310A/en unknown
- 1996-03-05 UA UA98010006A patent/UA48971C2/en unknown
- 1996-03-05 CN CN96196134A patent/CN1068601C/en not_active Expired - Lifetime
- 1996-03-05 DE DE69612857T patent/DE69612857T2/en not_active Expired - Lifetime
- 1996-03-05 EP EP96913769A patent/EP0845000B1/en not_active Expired - Lifetime
- 1996-03-05 ES ES96913769T patent/ES2157441T3/en not_active Expired - Lifetime
- 1996-03-05 PT PT96913769T patent/PT845000E/en unknown
- 1996-03-05 RU RU98100223/04A patent/RU2164519C2/en active
- 1996-03-05 BR BR9608562A patent/BR9608562A/en not_active IP Right Cessation
- 1996-03-05 AT AT96913769T patent/ATE201210T1/en not_active IP Right Cessation
- 1996-03-05 CA CA002221298A patent/CA2221298C/en not_active Expired - Lifetime
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- 1996-03-05 HU HU9802333A patent/HUP9802333A3/en unknown
- 1996-03-05 KR KR1019970709040A patent/KR100266126B1/en not_active IP Right Cessation
- 1996-03-14 TW TW085103069A patent/TW306867B/zh active
- 1996-05-23 AR ARP960102690A patent/AR004487A1/en active IP Right Grant
- 1996-06-05 IL IL11857796A patent/IL118577A/en not_active IP Right Cessation
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WO2001008492A1 (en) * | 1999-07-28 | 2001-02-08 | Monsanto Technology Llc | Process for making a downstream processable ammonium glyphosate paste |
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US6734142B2 (en) | 2001-04-23 | 2004-05-11 | Monsanto Technology Llc | Ammonium glyphosate compositions and process for their preparation |
US7141532B2 (en) | 2002-08-31 | 2006-11-28 | Monsanto Technology Llc | Process for the preparation of a dry pesticidal composition containing a dicarboxylate component |
Also Published As
Publication number | Publication date |
---|---|
PT845000E (en) | 2001-09-28 |
RU2164519C2 (en) | 2001-03-27 |
CA2221298A1 (en) | 1996-12-19 |
US5716903A (en) | 1998-02-10 |
CN1068601C (en) | 2001-07-18 |
JP2963543B2 (en) | 1999-10-18 |
KR19990022559A (en) | 1999-03-25 |
ES2157441T3 (en) | 2001-08-16 |
UA48971C2 (en) | 2002-09-16 |
CA2221298C (en) | 2001-06-05 |
KR100266126B1 (en) | 2000-09-15 |
CN1192743A (en) | 1998-09-09 |
GR3036355T3 (en) | 2001-11-30 |
DE69612857D1 (en) | 2001-06-21 |
HUP9802333A2 (en) | 1999-02-01 |
AR004487A1 (en) | 1998-12-16 |
AU694877B2 (en) | 1998-07-30 |
EP0845000B1 (en) | 2001-05-16 |
IL118577A0 (en) | 1996-10-16 |
HUP9802333A3 (en) | 1999-03-29 |
US5614468A (en) | 1997-03-25 |
DE69612857T2 (en) | 2002-03-28 |
TW306867B (en) | 1997-06-01 |
DK0845000T3 (en) | 2001-06-18 |
JPH10507467A (en) | 1998-07-21 |
AU5662096A (en) | 1996-12-30 |
IL118577A (en) | 2001-05-20 |
BR9608562A (en) | 1999-07-06 |
ZA964775B (en) | 1997-01-08 |
ATE201210T1 (en) | 2001-06-15 |
EP0845000A1 (en) | 1998-06-03 |
NZ307310A (en) | 1999-01-28 |
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