WO2016127890A1 - 一种草甘膦农药活性组合物及其制备方法 - Google Patents

一种草甘膦农药活性组合物及其制备方法 Download PDF

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WO2016127890A1
WO2016127890A1 PCT/CN2016/073291 CN2016073291W WO2016127890A1 WO 2016127890 A1 WO2016127890 A1 WO 2016127890A1 CN 2016073291 W CN2016073291 W CN 2016073291W WO 2016127890 A1 WO2016127890 A1 WO 2016127890A1
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glyphosate
salt
activated carbon
solution
active composition
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PCT/CN2016/073291
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French (fr)
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王冬林
展亚萍
吴传隆
丁永良
范倩玉
郑道敏
姚如杰
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重庆紫光化工股份有限公司
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
    • 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)]

Definitions

  • the invention belongs to the field of fine chemicals, and particularly relates to a glyphosate active composition and a preparation method thereof.
  • Glyphosate N-(phosphonomethyl)-glycine
  • Zhen Cao Ning Roundup, Dried Phosphate, Phosphonic Acid
  • Glyphosate is an efficient, broad-spectrum, low-toxic, safe organophosphorus herbicide that is very effective in preventing the perennial deep-rooted malignant weeds and is widely used in agriculture, forestry, and horticulture. Due to the expanding global GM crop planting area and the recovery and modernization of agriculture in the world, especially in developing countries, the demand for glyphosate has grown rapidly and has become the world's largest and fastest growing pesticide variety.
  • Glyphosate is generally used as an organic herbicide in the form of a liquid.
  • glyphosate herbicides are soluble granules (physically blended with plant-derived additives SD, SDP, etc.), soluble powders,
  • soluble tablet forms The use of soluble tablet forms is becoming more and more common, but the processing fluidity of glyphosate is not ideal.
  • the formulation is not good and affects its processing.
  • U.S. Patent 3,950,402 discloses the use of a noble metal supported on activated carbon as a catalyst and oxygen oxidation to extract glyphosate. Due to the use of special catalysts, the reaction yield is high, generally up to 95-96%, but the precious metal catalytic oxidation catalyst is expensive to prepare, and the catalyst is not easy to recover, and the reaction process is difficult to control.
  • No. 3,969,398 discloses the preparation of glyphosate by the oxidation of bisphosphonate with molecular oxygen using activated carbon as a catalyst. The method is characterized by low cost and high reaction yield.
  • CN101045735A discloses a reaction of oxidatively extracting glyphosate by using an oxygen-rich gas as an oxidant with a high specific surface area activated carbon as a catalyst.
  • the method solves the disadvantages of low-concentration double-glyphosate saturated solution, high energy consumption, reduced production cost, dissolving glyphosate under high temperature conditions and then separating and filtering activated carbon by hot filtration.
  • the disadvantage of the method is that the reaction mother liquid The formaldehyde in the reaction easily reacts with glyphosate to form methyl glyphosate, which reduces the reaction yield and product quality.
  • CN101508701A discloses a method for preparing glyphosate by oxidizing di-glyphos with oxygen, putting water, glyphosate and activated carbon into a pressure reaction, heating and stirring into a suspension, and then introducing oxygen to oxidize, and after the reaction is finished, the activated carbon is removed by hot filtration. The filtrate was concentrated by distillation under reduced pressure, cooled and crystallized, and filtered to give glyphosate product.
  • CN101337978A discloses a method for oxidizing glyphosate to glyphosate using activated carbon as a catalyst and an oxygen-rich gas as an oxidant. After the oxidation reaction is completed, the reaction solution is cooled and filtered to obtain a mixture of glyphosate solid and activated carbon, and then the mixture is mixed with water, heated to dissolve glyphosate and then filtered to remove activated carbon, and the filtrate is cooled and crystallized, and filtered to obtain glyphosate. Phosphine products.
  • the method separates the activated carbon by separating the glyphosate from the mother liquor containing formaldehyde first, and avoids the side reaction of glyphosate and formaldehyde to some extent, but the separation process still needs to be carried out at a high temperature and heated multiple times. Cooling, high energy consumption.
  • CN101531677A discloses a process for the preparation of glyphosate.
  • the glyphosate is mixed with the catalyst activated carbon in an aqueous medium, and is oxidized with oxygen.
  • the temperature is lowered, and the solid-liquid separation is carried out to obtain a filter cake containing glyphosate crystals and activated carbon, and the filter cake is added to the saturated solution of glyphosate.
  • the activated carbon and the glyphosate solution are separated, the glyphosate solution is cooled and crystallized, and the glyphosate product and the filtrate are separated, and the filtrate is applied as a saturated solution of glyphosate.
  • CN10169867A discloses a method for catalytically oxidizing diphosphonium to prepare glyphosate, which comprises glyphosate, water,
  • the activated carbon and the cocatalyst are mixed and stirred, and oxygen is oxidized.
  • the filter cake of glyphosate and activated carbon is cooled, and the filter cake is heated and dissolved, and the activated carbon is separated by filtration.
  • the filtrate is cooled and crystallized, and the glyphosate product is filtered.
  • the preparation method of glyphosate has the advantages of cumbersome preparation operation and high energy consumption, and the prepared glyphosate has low quality and unsatisfactory yield.
  • the existing glyphosate original drug processing fluidity is not ideal in the preparation of glyphosate soluble granules, soluble powder, soluble tablets, can be poor formulation, affecting its processing and molding.
  • Another object of the present invention is to provide a method for preparing the above glyphosate active composition, which can directly prepare the glyphosate active composition, has a simple process, and achieves environmentally friendly clean production, low energy consumption and high yield. .
  • a glyphosate active composition characterized in that it comprises the following components: glyphosate ⁇ 95%, 0 ⁇ glyphosate salt ⁇ 1%, the glyphosate salt is glyphosate ammonium salt, grass Any one or more of potassium glyphosate, glyphosate isopropylamine salt, glyphosate sodium salt, and glyphosate dimethylamine salt.
  • the existing glyphosate original drug processing fluidity is not ideal, the inventors accidentally discovered during the research process, adding the above amount of glyphosate salt to the glyphosate original drug, significantly improved the grass under the condition of ensuring its quality.
  • the fluidity of the original powder of glyphosate is good in formulation when the original powder is used to produce various soluble solid dosage forms, and the production needs are well satisfied to facilitate large-scale production and processing.
  • the glyphosate active composition of the present invention is characterized in that it comprises the following components: glyphosate ⁇ 95%, 0 ⁇ glyphosate salt ⁇ 1%, 0 ⁇ formaldehyde ⁇ 0.08%, 0 ⁇ Sodium hydroxide insoluble matter ⁇ 0.02%, the glyphosate salt is glyphosate ammonium salt, glyphosate potassium salt, glyphosate isopropylamine salt, glyphosate sodium salt, glyphosate dimethylamine salt Any one or several.
  • the glyphosate active composition of the invention is characterized in that it comprises the following components: glyphosate ⁇ 95%, 0.03% ⁇ glyphosate salt ⁇ 0.5%, 0 ⁇ formaldehyde ⁇ 0.08%, 0 ⁇ Sodium hydroxide insoluble matter ⁇ 0.02%, the glyphosate salt is glyphosate ammonium salt, glyphosate potassium salt, glyphosate isopropylamine salt, glyphosate sodium salt, glyphosate dimethylamine salt Any one or several.
  • the glyphosate active composition of the present invention is characterized in that it comprises the following components: glyphosate ⁇ 97%, 0.06% ⁇ glyphosate salt ⁇ 0.3%, 0 ⁇ formaldehyde ⁇ 0.08%, 0 ⁇ sodium hydroxide insoluble matter ⁇ 0.02%, the glyphosate salt is glyphosate ammonium salt, glyphosate potassium salt, glyphosate isopropylamine salt, glyphosate sodium salt, glyphosate II Any one or more of the methylamine salts.
  • the glyphosate salt of the present invention preferably employs any one or more of glyphosate ammonium salt, glyphosate potassium salt or glyphosate sodium salt.
  • the above glyphosate active composition can be prepared by directly mixing the glyphosate salt into the glyphosate powder, but the current glyphosate powder has poor processing fluidity, and the above amount of glyphosate salt is added.
  • the glyphosate powder is uniformly mixed and inconvenient to operate, and the glyphosate powder and the glyphosate salt are respectively dissolved in water, stirred and mixed, and crystallized, and the labor intensity is large and the water consumption is large.
  • the present invention provides the following glyphosate.
  • the phosphine preparation method realizes the direct preparation of the glyphosate active composition of the invention in one time, and has low energy consumption, low water consumption and high yield.
  • the preparation method of the above glyphosate active composition comprises the steps of synthesizing glyphosate by using glyphosate, oxidant, water and activated carbon catalyst as raw materials, separating activated carbon, cooling and crystallizing to obtain glyphosate, and the like, characterized in that the activated carbon is separated.
  • the glyphosate salt solution is glyphosate ammonium salt, grass a mixed solution of potassium glyphosate, glyphosate isopropylamine salt, glyphosate sodium salt, glyphosate dimethylamine salt
  • the glyphosate salt solution has a mass concentration of 5 to 35%
  • the mass ratio of the glyphosate-activated carbon mixture to the glyphosate salt solution is from 0.8 to 1.5:1.
  • the above glyphosate salt solution is respectively composed of glyphosate and ammonia, or isopropylamine, or dimethylamine, or sodium hydroxide, or potassium hydroxide, or sodium carbonate, or sodium hydrogencarbonate, or potassium carbonate, or hydrogen carbonate.
  • a corresponding glyphosate salt solution obtained by reacting an alkali or a basic salt such as potassium to form or other means known in the art.
  • the above glyphosate salt solution is preferably one or more of a glyphosate ammonium salt solution, a glyphosate potassium salt solution or a glyphosate sodium salt solution.
  • the glyphosate salt solution has a mass concentration of 12 to 25%.
  • the mass ratio of the above glyphosate-activated carbon mixture to the glyphosate salt solution is preferably from 1.0 to 1.2:1.
  • a method for preparing a glyphosate active composition is carried out as follows:
  • step 2) the reaction system of step 1) is cooled to 0 to 30 ° C, and a mixture of glyphosate-activated carbon is obtained;
  • step 3 The mixture obtained in the step 2) is added to the above glyphosate salt solution, heated at 85 to 95 ° C (preferably 85 to 90 ° C) to dissolve, and the activated carbon is separated by hot filtration, and the separated activated carbon is washed with hot water.
  • the cycle is applied to step 1), and the washing liquid is combined into the filtrate;
  • the method for preparing the above glyphosate active composition comprises the steps of synthesizing glyphosate using glyphosate, an oxidizing agent, water, an activated carbon catalyst as a raw material, separating activated carbon, cooling and crystallizing to obtain glyphosate, and the like, wherein:
  • the isolated activated carbon is a glyphosate-activated carbon mixture obtained by the step of synthesizing glyphosate, added to an aqueous alkali solution, heated until the glyphosate is dissolved, and the activated carbon is separated by hot filtration;
  • the alkali in the alkali water is reacted with glyphosate Forming one or more bases of glyphosate ammonium salt, glyphosate potassium salt, glyphosate isopropylamine salt, glyphosate sodium salt or glyphosate dimethylamine salt;
  • the aqueous alkali solution has a mass concentration of 15 ⁇ 30%, the m
  • the above base is preferably one or more bases which are reacted with glyphosate to form a glyphosate ammonium salt solution, a glyphosate potassium salt solution or a glyphosate sodium salt solution.
  • a method for preparing a glyphosate active composition is carried out as follows:
  • step 2) the reaction system of step 1) is cooled to 0 to 30 ° C, and a mixture of glyphosate-activated carbon is obtained;
  • step 3 The mixture obtained in the step 2) is added to an aqueous alkali solution, heated at 85 to 95 ° C (preferably 85 to 90 ° C) to dissolve, and the activated carbon is separated by hot filtration, and the separated activated carbon is washed with hot water and then recycled to the step.
  • aqueous alkali solution heated at 85 to 95 ° C (preferably 85 to 90 ° C) to dissolve, and the activated carbon is separated by hot filtration, and the separated activated carbon is washed with hot water and then recycled to the step.
  • the washing liquid is combined into the filtrate; the alkali in the alkali water is reacted with glyphosate to form glyphosate ammonium salt, glyphosate potassium salt, glyphosate isopropylamine salt, glyphosate sodium salt or
  • One or more bases of glyphosate dimethylamine salt the aqueous alkali solution has a mass concentration of 20 to 27%, and the molar ratio of the base to the glyphosate-activated carbon mixture in glyphosate is 0.3 to 1.2: 1;
  • the glyphosate active composition of the invention has good processing fluidity, and the angle of repose of the crystal particles of the glyphosate active composition of the invention is determined by an injection method (fixed funnel method), and the angle of repose is ⁇ ⁇ 30 degrees, which satisfies the production of glyphosate well.
  • the method of the invention adopts reasonable glyphosate purification separation step, compound material concentration and dosage ratio, and realizes the glyphosate active composition of the invention in one time; the process is simple and the yield is up to 88% or more, and the method of the invention Prior art hot melt method (hot solution method is a kind Compared with glyphosate prepared by dissolving glyphosate in a mixture of glyphosate and activated carbon with glyphosate saturated mother liquor or process water, and separating glyphosate by heating glyphosate and activated carbon, the method of the invention consumes less water, Each ton of product dissolves only consumes 5 to 10 tons of water, and the mother liquor circulation amount is 7 to 13 tons of water per ton of product.
  • the prior art hot-melt method consumes 19 to 22 tons of water per ton of product, and the mother liquor circulation amount is 20 to 23 tons of water per ton of product, the method of the invention reduces the amount of water by about 50% to 80%, and reduces the circulation amount of the mother liquor by about 40% to 70%;
  • the ammoniation method is a method of liquid ammonia or ammonia and grass
  • the phosphine reaction, the method of separating glyphosate and activated carbon, the ammoniation method needs to consume more acid and alkali, taking sulfuric acid and liquid ammonia as examples, respectively, it needs to consume about 0.50 t/t of sulfuric acid and about 0.17 t/t of liquid ammonia.
  • the method of the invention reduces the consumption of acid and alkali, and hardly produces inorganic salts containing glyphosate, and the raw material cost per ton of product is about 500 yuan/ton.
  • Example 1 is a process flow diagram of a method for preparing glyphosate of the present invention according to Example 2 of the present invention.
  • the existing glyphosate solid powder the glyphosate raw solid powder 200KG obtained by the glyphosate preparation method disclosed in Chinese Patent No. CN101993455A is added to the hot water of 90 ° C and continuously stirred. Until completely dissolved in 3200Kg water, about 1-1.5h, 0.6KG glyphosate potassium salt is dissolved in water, the two are mixed and stirred uniformly, crystallized by cooling to 20 ° C for 4h, and separated by centrifugation to obtain glyphosate.
  • the active composition is wet, washed with a small amount of water, and dried to obtain a glyphosate active composition.
  • the glyphosate-reactive composition obtained above was subjected to measurement of the angle of repose:
  • the angle of repose of the glyphosate sample prepared above was measured by an injection method (fixed funnel method). Pour the sample to be tested into the funnel, and gently and evenly fall into the center of the disc to form a cone. When the material is from the oblique side of the powder along the edge of the disc The feeding was stopped when the edge was free to fall, and the angle of repose was measured by a protractor. The three angles of repose were repeated: 28.2, 27.8, 28.4 degrees. It is indicated that the solid powder crystal particles are excellent in fluidity and good in formulation, and are suitable for use in the production of various solid preparations and storage and transportation.
  • the glyphosate activated carbon mixture obtained above is added to 804 g of 16.9% glyphosate isopropylamine salt solution, heated to 95 ° C to dissolve, filtered while hot, cooled to 20 ° C for 4 h, and centrifuged to obtain glyphosate wet product. After washing with a small amount of water, the glyphosate active composition is dried, and the mother liquor is applied to the subsequent batch.
  • the white crystalline powder glyphosate active composition prepared by liquid chromatography was averaged as 97.68% of glyphosate, 0.63% of glyphosate isopropylamine salt, 0.02% of formaldehyde, and 0.005 of sodium hydroxide insoluble matter. %, residual impurities about 1.665%, nitrosyl glyphosate almost undetectable; angle of repose measurement: In this test, the angle of repose of the glyphosate sample prepared above was measured by an injection method (fixed funnel method). Pour the sample to be tested into the funnel, and gently and evenly fall into the center of the disc to form a cone. When the material falls freely from the oblique edge of the powder along the edge of the disc, the feeding is stopped, and the angle of repose is determined by a protractor. The measurement results are shown in Table 1.
  • the above-mentioned glyphosate active composition particles have an angle of repose ( ⁇ ) of about 27 degrees, which indicates that the solid powder crystal particles have excellent fluidity and good formulation, and are suitable for use in the production of solid preparations and storage and transportation.
  • the glyphosate activated carbon mixture obtained above was added to 716.5 g of an 18% glyphosate monosodium salt solution, heated to 95 ° C to dissolve, filtered while hot, cooled to 20 ° C for 4 h, and centrifuged to obtain a glyphosate wet product.
  • the glyphosate active composition is dried after washing with a small amount of water, and the mother liquor is applied to subsequent batches.
  • the white crystalline powder glyphosate active composition prepared by liquid chromatography was averaged as 97.69% of glyphosate, 0.12% of glyphosate sodium salt, 0.05% of formaldehyde, and 0.075% of sodium hydroxide insoluble matter. Nitroso glyphosate ⁇ 10 -4 % was almost undetectable, and residual impurities were about 2.06%.
  • Angle of repose measurement In this test, the angle of repose of the glyphosate sample prepared above was measured by an injection method (fixed funnel method). Pour the sample to be tested into the funnel, and gently and evenly fall into the center of the disc to form a cone. When the material falls freely from the oblique edge of the powder along the edge of the disc, the feeding is stopped, and the angle of repose is determined by a protractor. The measurement results are shown in Table 2.
  • the above-mentioned glyphosate active composition particles have an angle of repose ( ⁇ ) of about 28 degrees, which indicates that the solid powder crystal particles have excellent fluidity and good formulation, and are suitable for use in the production of solid preparations and storage and transportation.
  • the glyphosate activated carbon mixture obtained above was added to 635 g of 17.9% glyphosate monopotassium salt solution, heated to 92 ° C to dissolve, filtered while hot, cooled to 20 ° C for 4 h, and centrifuged to obtain glyphosate wet product. After washing with a small amount of water, the glyphosate active composition is dried, and the mother liquor is applied to the subsequent batch.
  • the white crystalline powder glyphosate active composition prepared by liquid chromatography was determined by liquid chromatography and was 97.61% of glyphosate, 0.05% of potassium glyphosate, 0.03% of formaldehyde, and 0.015% of sodium hydroxide insoluble matter. The nitroso glyphosate was almost undetectable, and the residual impurities were about 2.19%.
  • the angle of repose was measured: In this test, the angle of repose of the glyphosate sample prepared above was measured by an injection method (fixed funnel method). Pour the sample to be tested into the funnel, and gently and evenly fall into the center of the disc to form a cone. When the material falls freely from the oblique edge of the powder along the edge of the disc, the feeding is stopped, and the angle of repose is determined by a protractor. The measurement results are shown in Table 3.
  • the above-mentioned glyphosate active composition particles have an angle of repose ( ⁇ ) of about 30 degrees, which indicates that the solid powder crystal particles have excellent fluidity and good formulation, and are suitable for use in the production of solid preparations and storage and transportation.
  • the glyphosate activated carbon mixture obtained above is added to 773.5 g of 13.9% glyphosate ammonium salt solution, heated to 92 ° C to dissolve, filtered while hot, cooled to 20 ° C for 4 h, and centrifuged to obtain glyphosate wet product. After washing with a small amount of water, the glyphosate active composition is dried, and the mother liquor is applied to the subsequent batch.
  • the white crystalline powder glyphosate active composition prepared by the above liquid chromatography is 97.95% of glyphosate, 0.5% of glyphosate ammonium salt, 0.04% of formaldehyde, and 0.01% of sodium hydroxide insoluble matter. Residual impurities: about 1.50%; angle of repose measurement: In this test, the angle of repose of the glyphosate sample prepared above was measured by an injection method (fixed funnel method). Pour the sample to be tested into the funnel, and gently and evenly fall into the center of the disc to form a cone. When the material falls freely from the oblique edge of the powder along the edge of the disc, the feeding is stopped, and the angle of repose is determined by a protractor. The measurement results are shown in Table 4.
  • the above-mentioned glyphosate active composition particles have an angle of repose ( ⁇ ) of about 26 degrees, which indicates that the solid powder crystal particles have excellent fluidity and good formulation, and are suitable for use in the production of solid preparations and storage and transportation.
  • the glyphosate activated carbon mixture obtained above is added to 750 g of a 17% glyphosate dipotassium amine salt solution, heated to 90 ° C to dissolve, filtered while hot, cooled to 20 ° C for 4 h, and centrifuged to obtain a glyphosate wet product.
  • the glyphosate active composition is dried after washing with a small amount of water, and the mother liquor is applied to subsequent batches.
  • the white crystalline powder glyphosate active composition prepared by the above liquid chromatography is 98.31% of glyphosate, 0.3% of glyphosate dipotassiumamine salt, 0.01% of formaldehyde, and sodium hydroxide insoluble matter. 0.008%, residual impurities about 1.37%; angle of repose measurement:
  • angle of repose measurement In this test, the angle of repose of the glyphosate sample prepared above was measured by an injection method (fixed funnel method). Pour the sample to be tested into the funnel so that it gently and evenly falls into the center of the disc to form a cone that stops when the material falls freely from the oblique edge of the powder along the edge of the disc. The angle of repose was measured by a protractor, and the results are shown in Table 5.
  • the above-mentioned glyphosate active composition particles have an angle of repose ( ⁇ ) of about 28.5 degrees, which indicates that the solid powder crystal particles have excellent fluidity and good formulation, and are suitable for use in the production of various solid preparations and storage and transportation.
  • a method for preparing a glyphosate active composition is carried out as follows:
  • step 2) the reaction system of step 1) is cooled to 0 to 30 ° C, and a mixture of glyphosate-activated carbon is obtained;
  • the glyphosate salt (glyphosate ammonium salt, glyphosate potassium salt, glyphosate isopropylamine salt, glyphosate) at a concentration of 5 to 35% by mass Phosphine sodium salt, glyphosate II
  • the solution is dissolved at 85-95 ° C, and the activated carbon is separated by hot filtration. The separated activated carbon is washed with hot water and then recycled to step 1), and the washing liquid is combined.
  • the mass ratio of the glyphosate-activated carbon mixture to the glyphosate salt is 0.8 to 1.5:1;
  • step 5) Drying the glyphosate obtained in the step 4) to obtain a glyphosate active composition, and the obtained glyphosate salt solution is returned to the step 3) and continues to be used.
  • the glyphosate active composition prepared above has the following components: glyphosate 97% to 98.5%, 0 ⁇ glyphosate salt ⁇ 1%, 0 ⁇ formaldehyde ⁇ 0.08%, 0 ⁇ sodium hydroxide insoluble matter ⁇ 0.02% and Residual impurities, nitrosodium glyphosate is almost undetectable; its angle of repose ⁇ ⁇ 30 degrees, which satisfies the needs of various soluble solid dosage forms for producing glyphosate.
  • the yield of the above method is as high as 88% or more, the water consumption is small, only 5 to 10 tons of water per ton of product is consumed, and the circulating amount of mother liquor is 7 to 13 tons of water per ton of product. The energy consumption is low and the operation is simple and suitable for large-scale operation. Industrial production.
  • the above glyphosate activated carbon mixture is added to 150 g of water, 35 g of 26% aqueous ammonia is added dropwise, and the glyphosate is completely dissolved after the dropwise addition is completed to 60 ° C.
  • the glyphosate is completely filtered, and 26 g of 98% sulfuric acid is added dropwise to the filtrate to be acidified, and cooled to 20 ° C to be crystallized. 4h, the glyphosate wet product was obtained by centrifugation, washed with a small amount of water, and the product was dried to obtain 64.9 g of glyphosate product, the content was 95.85%, and the yield was 85.02%.
  • the obtained glyphosate product was subjected to an angle of repose measurement:
  • the angle of repose of the glyphosate sample prepared above was measured by an injection method (fixed funnel method). Pour the sample to be tested into the funnel, and gently and evenly fall into the center of the disc to form a cone. When the material falls freely from the oblique edge of the powder along the edge of the disc, the feeding is stopped, and the angle of repose is determined by a protractor. Repeated measurement of three angles of repose: 42.3, 42.0, 42.2 degrees, can be poor formulation, not suitable for use Production of soluble solid preparations.
  • the glyphosate activated carbon mixture is added to 1390 g of glyphosate saturated solution, heated to 90 ° C to dissolve, filtered while hot, cooled to 20 ° C for 4 h, centrifuged to obtain glyphosate wet product, the product after drying, the quality of 67.0 g, content 97.12%, yield 88.72%.
  • the hot solution method has a large amount of hot solution mother liquor dissolved in glyphosate compared to the method of the present invention.
  • the glyphosate saturated mother liquor per ton of product consumes 20.7 t/t
  • the method of the present invention is 7-13 t/ t, which is 1.6 to 2.9 times that of the process of the present invention, results in an increase in energy consumption in the dissolution and crystallization process, thereby increasing production costs.
  • the obtained glyphosate product was subjected to an angle of repose measurement: In this test, the angle of repose of the glyphosate sample prepared above was measured by an injection method (fixed funnel method). Pour the sample to be tested into the funnel, and gently and evenly fall into the center of the disc to form a cone.

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Abstract

一种草甘膦活性组合物，它包含以下组分：草甘膦≥95％，0<草甘膦盐≤1％，所述草甘膦盐为草甘膦铵盐、草甘膦钾盐、草甘膦异丙胺盐、草甘膦钠盐、草甘膦二甲胺盐中的任一种或几种，以质量百分含量计。本发明草甘膦活性组合物加工流动性好，采用注入法测定本发明草甘膦活性组合物结晶颗粒的休止角、θ≤30度，很好地满足了生产草甘膦各种可溶固体剂型的需要。本发明制备方法包括合成草甘膦，分离活性炭，冷却结晶得到草甘膦等步骤，所述分离活性炭是将合成草甘膦步骤所得的草甘膦-活性炭混合物，加入到草甘膦盐溶液中，加热溶解、趁热过滤分离出活性炭，所述草甘膦盐溶液5～35％，所述草甘膦-活性炭混合物与草甘膦盐溶液的质量比为0.8～1.5：1。

Description

一种草甘膦农药活性组合物及其制备方法 技术领域
本发明属于精细化工领域，具体涉及一种草甘膦活性组合物及其制备方法。
背景技术
草甘膦(N-(膦酰基甲基)-甘氨酸)又称：镇草宁、农达(Roundup)、草干膦、膦甘酸。其结构式如下：
Figure PCTCN2016073291-appb-000001
草甘膦是一种高效、广谱、低毒、安全的有机磷除草剂，对多年生的深根恶性杂草的防止非常有效，在农、林、园艺等方面应用广泛。由于全球转基因作物种植面积的不断扩大，以及全球农业特别是发展中国家农业的复苏和现代化，草甘膦的需求增长迅速，已成为世界上销量最大和增长速度最快的农药品种。
草甘膦作为有机除草剂一般以水剂形式使用，随着技术进步与使用的需要，草甘膦除草剂以可溶性粒剂(与植物源助剂SD、SDP等物理共混成型)、可溶性粉剂、可溶性片剂形式使用越来越普遍，但草甘膦原药加工流动性不理想在制备草甘膦可溶粒剂、可溶粉剂、可溶片剂时，可制剂性不好、影响其加工成型。
目前，生产草甘膦的方法很多，主要有甘氨酸法和亚氨基二乙酸法等。甘氨酸法1986年实现工业化生产，中国的产量较大。IDA法于上世纪90年代后期被开发并实现工业化生产，该方法使用亚氨基二乙腈或者二乙醇胺生产亚氨基二乙酸，然后与甲醛和亚磷酸缩合得到双甘膦，再氧化得到草甘膦。现有技术中，利用双甘膦氧化制备的方法很多，主要有双氧水活性炭法氧化法、空气 活性炭氧化法、富氧气体活性炭氧化法、过渡金属氧化法以及电解氧化法等。
US3950402公开了以贵金属负载于活性炭上做催化剂、氧气氧化支取草甘膦的方法。由于采用特殊的催化剂，因此反应收率较高，一般可达95-96％，但贵金属催化氧化法催化剂制备成本高，且催化剂不易回收，反应过程较难控制。
US3969398公开了以活性炭为催化剂，采用分子氧气氧化双甘膦制备草甘膦的方法。该方法的特点是成本低，反应收率较高。
CN101045735A公开了以高比表面积活性炭为催化剂，利用富氧气体为氧化剂进行氧化支取草甘膦的反应。该方法解决了以低浓度双甘膦饱和溶液进行反应、能耗高的缺点，降低了生产成本，采用高温条件将草甘膦溶解然后趁热过滤分离活性炭的方法，该方法的缺点是反应母液中的甲醛易与草甘膦反应生成甲基草甘膦，降低了反应收率和产品的品质。
CN101508701A公开一种氧气氧化双甘膦制备草甘膦的方法，将水、双甘膦和活性炭投入到压力反应中，加热搅拌成悬浮物，然后通入氧气氧化，反应结束趁热过滤除去活性炭，滤液减压蒸馏浓缩，冷却结晶、过滤得到草甘膦产品。
CN101337978A公开了以活性炭为催化剂、富氧气体为氧化剂，将双甘膦氧化成草甘膦的方法。氧化反应结束后，将反应液冷却、过滤得到草甘膦固体和活性炭的混合物，然后将此混合物与水混合，加热使草甘膦溶解然后趁热过滤除去活性炭，滤液冷却结晶、过滤得到草甘膦产品。此方法通过先将草甘膦与含甲醛的母液分开再热溶分离活性炭，在一定程度上避免了草甘膦与甲醛发生的副反应，但分离过程依然需要再高温下进行，且多次加热冷却，能耗较高。
CN101531677A公布了一种草甘膦的制备方法。将双甘膦与催化剂活性炭混于水相介质中，与氧气进行氧化反应，反应结束后降温、固液分离得到含草甘膦晶体和活性炭的滤饼，滤饼加入到草甘膦饱和溶液中，加热溶解后分离活性炭与草甘膦溶液，草甘膦溶液冷却、结晶，分离得到草甘膦产品和滤液，滤液作为草甘膦饱和溶液套用。
CN10169867A公开一种催化氧化双甘膦制备草甘膦的方法，将双甘膦、水、 活性炭、助催化剂混合搅拌，通入氧气氧化，反应结束后冷却得到草甘膦和活性炭的滤饼，滤饼加水热溶后过滤分离活性炭，滤液冷却结晶，过滤得草甘膦产品。
综上，目前草甘膦的制备方法存在着制备操作繁琐、能耗高，制得的草甘膦原药品质不高、收率不理想。同时，现有的草甘膦原药加工流动性不理想在制备草甘膦可溶粒剂、可溶粉剂、可溶片剂时，可制剂性不好、影响其加工成型。
发明内容
本发明的目的在于提供一种加工流动性好的草甘膦活性组合物。
本发明另一目的在于提供上述草甘膦活性组合物的制备方法，该制备方法实现了直接制得该草甘膦活性组合物、工艺简便，同时实现了环保清洁生产、低能耗、高收率。
本发明目的通过如下技术方案实现，以下没有特别说明、均以质量百分比/含量计：
一种草甘膦活性组合物，其特征在于，它包含以下组分：草甘膦≥95％，0<草甘膦盐≤1％，所述草甘膦盐为草甘膦铵盐、草甘膦钾盐、草甘膦异丙胺盐、草甘膦钠盐、草甘膦二甲胺盐中的任一种或几种。现有的草甘膦原药加工流动性不理想，发明人在研究过程中意外发现，在草甘膦原药中加入上述量的草甘膦盐，在保证了其品质情况下显著提高了草甘膦原药粉末的流动性，在后续采用该原药粉末生产各种可溶固体剂型时其可制剂性好、很好地满足了生产需要便于规模化生产加工。
为了品质更好，本发明草甘膦活性组合物，其特征在于，它包含以下组分：草甘膦≥95％、0<草甘膦盐≤1％、0<甲醛≤0.08％、0<氢氧化钠不溶物≤0.02％，所述草甘膦盐为草甘膦铵盐、草甘膦钾盐、草甘膦异丙胺盐、草甘膦钠盐、草甘膦二甲胺盐中的任一种或几种。
进一步提高品质，本发明草甘膦活性组合物，其特征在于：它包含以下组分：草甘膦≥95％、0.03％≤草甘膦盐≤0.5％、0<甲醛≤0.08％、0<氢氧化钠不溶物≤0.02％，所述草甘膦盐为草甘膦铵盐、草甘膦钾盐、草甘膦异丙胺盐、草甘膦钠盐、草甘膦二甲胺盐中的任一种或几种。
为了更进一步提高品质，优选地，本发明草甘膦活性组合物，其特征在于：它包含以下组分：草甘膦≥97％、0.06％≤草甘膦盐≤0.3％、0<甲醛≤0.08％、0<氢氧化钠不溶物≤0.02％，所述草甘膦盐为草甘膦铵盐、草甘膦钾盐、草甘膦异丙胺盐、草甘膦钠盐、草甘膦二甲胺盐中的任一种或几种。
为了使得本发明草甘膦活性组合物的加工流动性更理想，本发明草甘膦盐优选采用草甘膦铵盐、草甘膦钾盐或草甘膦钠盐的任一种或几种。
上述草甘膦活性组合物可以在草甘膦原药粉末中直接混合加入上述草甘膦盐制得，但目前草甘膦原药粉末加工流动性不理想、将上述量的草甘膦盐加入草甘膦原药粉末中混合均匀操作不便，需要将草甘膦原药粉及草甘膦盐分别溶于水、搅拌混匀、析晶，劳动强度大、耗水量多，本发明提供如下草甘膦制备方法，该方法实现了一次性直接制得本发明草甘膦活性组合物，同时能耗低、水耗低、收率高。
上述草甘膦活性组合物的制备方法，包括以双甘膦、氧化剂、水、活性炭催化剂为原料合成草甘膦，分离活性炭，冷却结晶得到草甘膦等步骤，其特征在于：所述分离活性炭是将合成草甘膦步骤所得的草甘膦-活性炭混合物，加入到草甘膦盐溶液中，加热溶解、趁热过滤分离出活性炭；所述草甘膦盐溶液为草甘膦铵盐、草甘膦钾盐、草甘膦异丙胺盐、草甘膦钠盐、草甘膦二甲胺盐中的一种或几种混合溶液，所述草甘膦盐溶液的质量浓度为5～35％，所述草甘膦-活性炭混合物与草甘膦盐溶液的质量比为0.8～1.5：1。
上述的草甘膦盐溶液分别由草甘膦和氨、或异丙胺、或二甲胺、或氢氧化钠、或氢氧化钾、或碳酸钠、或碳酸氢钠、或碳酸钾、或碳酸氢钾等碱或碱性盐反应生成或本领域公知的其他方式获得的相应草甘膦盐溶液。
为了提高所制得的草甘膦活性组合物品质，优选地，上述草甘膦盐溶液优选草甘膦铵盐溶液、草甘膦钾盐溶液或草甘膦钠盐溶液中的一种或多种。
进一步优选地，上述草甘膦盐溶液的质量浓度为12～25％。
上述草甘膦-活性炭混合物与草甘膦盐溶液的质量比优选为1.0～1.2：1。
具体地说，一种草甘膦活性组合物的制备方法，按如下步骤进行：
1)以双氧水、空气或富氧气体为氧化剂，活性炭为催化剂，在水中将双甘膦氧化合成草甘膦；所述双甘膦与双氧水反应摩尔比1：1.6～2.4、双甘膦与活性炭质量比为1：0.08～0.2，或者空气与双甘膦反应、体系内保持压力0.4～0.6Mpa、双甘膦与活性炭质量比为1：0.08～0.2，或者富氧与双甘膦反应、体系内保持压力0.4～0.6Mpa、双甘膦与活性炭质量比为1：0.05～0.12；
2)将步骤1)的反应体系降温至0～30℃、分离得到草甘膦-活性炭的混合物；
3)将步骤2)所得的混合物加入到上述草甘膦盐溶液中，加热在85～95℃(优选85～90℃)溶解、趁热过滤分离出活性炭，分离出的活性炭用热水洗涤后循环套用至步骤1)，洗涤液合并入滤液中；
4)将步骤3)所得的滤液5～25℃下(优选5～15℃)冷却结晶，分离草甘膦和草甘膦盐溶液；
5)将步骤4)得到的草甘膦干燥制得本发明草甘膦活性组合物，得到的草甘膦盐溶液返回步骤3)继续使用。
或者，上述草甘膦活性组合物的制备方法，包括以双甘膦、氧化剂、水、活性炭催化剂为原料合成草甘膦，分离活性炭，冷却结晶得到草甘膦等步骤，其特征在于：所述分离活性炭是将合成草甘膦步骤所得的草甘膦-活性炭混合物，加入到碱水溶液中，加热直至草甘膦溶解、趁热过滤分离出活性炭；所述碱水中的碱为与草甘膦反应生成草甘膦铵盐、草甘膦钾盐、草甘膦异丙胺盐、草甘膦钠盐或草甘膦二甲胺盐的一种或多种碱；所述碱水溶液的质量浓度为15～30％，所述碱与草甘膦-活性炭混合物中草甘膦的摩尔比为0.3～1.2：1。
上述碱优选为与草甘膦反应生成草甘膦铵盐溶液、草甘膦钾盐溶液或草甘膦钠盐溶液的一种或多种碱。
具体地说，一种草甘膦活性组合物的制备方法，按如下步骤进行：
1)以双氧水、空气或富氧气体为氧化剂，活性炭为催化剂，在水中将双甘膦氧化合成草甘膦；所述双甘膦与双氧水反应摩尔比1：1.6～2.4、双甘膦与活性炭质量比为1：0.08～0.2，或者空气与双甘膦反应、体系内保持压力0.4～0.6Mpa、双甘膦与活性炭质量比为1：0.08～0.2，或者富氧与双甘膦反应、体系内保持压力0.4～0.6Mpa、双甘膦与活性炭质量比为1：0.05～0.12；
2)将步骤1)的反应体系降温至0～30℃、分离得到草甘膦-活性炭的混合物；
3)将步骤2)所得的混合物加入到碱水溶液中，加热在85～95℃(优选85～90℃)溶解、趁热过滤分离出活性炭，分离出的活性炭用热水洗涤后循环套用至步骤1)，洗涤液合并入滤液中；所述碱水中的碱为是可与草甘膦反应生成草甘膦铵盐、草甘膦钾盐、草甘膦异丙胺盐、草甘膦钠盐或草甘膦二甲胺盐的一种或多种碱，所述碱水溶液的质量浓度为20～27％，所述碱与草甘膦-活性炭混合物中草甘膦的摩尔比为0.3～1.2：1；
4)将步骤3)所得的滤液5～25℃下(优选5～15℃)冷却结晶，分离草甘膦和草甘膦盐溶液；
5)将步骤4)得到的草甘膦干燥制得本发明草甘膦活性组合物，得到的草甘膦盐溶液返回步骤3)继续使用。
本发明具有如下的有益效果：
本发明草甘膦活性组合物加工流动性好，采用注入法(固定漏斗法)测定本发明草甘膦活性组合物结晶颗粒的休止角、θ≤30度，很好地满足了生产草甘膦各种可溶固体剂型的需要。本发明方法采用合理的草甘膦纯化分离步骤、配合物料浓度及用量比例，实现了一次性制得本发明草甘膦活性组合物；同时工艺简便，收率高达88％以上，本发明方法与现有技术的热溶法(热溶法是一种 采用草甘膦饱和母液或工艺水溶解草甘膦和活性炭混合物中的草甘膦，趁热将草甘膦和活性炭分离的方法)制备分离纯化草甘膦相比，本发明方法耗水量小、每吨产品溶解只消耗5～10吨水、母液循环量为7～13吨水/每吨产品，而现有技术热溶法每吨产品热溶需消耗19～22吨水、母液循环量为20～23吨水/每吨产品，本发明方法减少了水用量约50％～80％、减少了母液循环量约40％～70％；氨化法是一种通过液氨或氨水与草甘膦反应，将草甘膦和活性炭分离的方法，氨化法需消耗较多酸和碱，以硫酸和液氨为例，分别需消耗硫酸约0.50t/t、液氨约0.17t/t，本发明方法减少了酸和碱的消耗，几乎不产生含草甘膦的无机盐，每吨产品节约原料成本约500元/吨。
附图说明
图1为本发明实施例2的本发明草甘膦制备方法的工艺流程图。
具体实施方式
以下优选实施例仅用以说明本发明的技术方案而非限制，通过以下优选实施例对本发明进行详细的描述，但本领域技术人员应当理解，可以在形式上和细节上对其作出各种各样的改变，而不偏离本发明权利要求书所限定的范围。
实施例1
将现有的草甘膦固体粉末、按中国专利CN101993455A公开的草甘膦制备方法制得的质量百分含量为95％左右的草甘膦原药固体粉末200KG加入90℃的热水不断搅拌、直至完全溶解于3200Kg水中、用时需约1-1.5h，将0.6KG草甘膦钾盐溶于水中，将两者混合搅拌均匀，在冷却至20℃结晶4h析晶，离心分离获得草甘膦活性组合物湿品，少量水洗涤，干燥得到草甘膦活性组合物。
将上述得到的草甘膦活性组合物进行休止角测定：本试验采用注入法(固定漏斗法)测定上述制备的草甘膦样品的休止角。将待测样品倒入漏斗，使其轻轻地、均匀地落入圆盘中心，形成一个圆锥体，当物料从粉体斜边沿圆盘边 缘中自由落下时停止加料，用量角器测定休止角，重复测定三次休止角分别为：28.2、27.8、28.4度。表明该固体粉末晶体颗粒流动性优异、可制剂性好，适合应用于生产各固体制剂及储藏运输。
实施例2
将800g双甘膦(PMIDA)(98.2％、3.46mol)、1450g水、120g活性炭依次加入四口瓶，在不断搅拌下升温至68℃，常压下开始滴加27.5％过氧化氢1000g，滴加完毕保温1h，冷却至5℃，结晶3h，分离获得草甘膦活性炭混合物816g，将草甘膦活性炭混合物平分为八份，备用。
将上述获得的一份草甘膦活性炭混合物加入804g16.9％草甘膦异丙胺盐溶液中，升温至95℃溶解，趁热过滤，冷却至20℃结晶4h，离心分离获得草甘膦湿产品，少量水洗涤后干燥得草甘膦活性组合物，母液套用至后续批次。
经液相色谱测定、取平均值，上述制得的白色结晶性粉末草甘膦活性组合物为草甘膦97.68％、草甘膦异丙胺盐0.63％、甲醛0.02％、氢氧化钠不溶物0.005％、残余杂质约1.665％、亚硝基草甘膦几乎检测不到；休止角测定：本试验采用注入法(固定漏斗法)测定上述制备的草甘膦样品的休止角。将待测样品倒入漏斗，使其轻轻地、均匀地落入圆盘中心，形成一个圆锥体，当物料从粉体斜边沿圆盘边缘中自由落下时停止加料，用量角器测定休止角，测定结果见表1。
表1
Figure PCTCN2016073291-appb-000002
Figure PCTCN2016073291-appb-000003
上述草甘膦活性组合物颗粒休止角(θ)在27度左右，表明其固体粉末晶体颗粒流动性优异、可制剂性好，适合应用于生产各固体制剂及储藏运输。
实施例3
将800g双甘膦(PMIDA)(98.3％、3.46mol)、1450g水、120g活性炭依次加入四口瓶，在不断搅拌下升温至68℃，常压下开始滴加27.5％过氧化氢980g，滴加完毕保温1h，冷却至5℃，结晶3h，分离获得草甘膦活性炭混合物835g，将草甘膦活性炭混合物平分为八份，备用。
将上述获得的一份草甘膦活性炭混合物加入716.5g18％草甘膦单钠盐溶液中，升温至95℃溶解，趁热过滤，冷却至20℃结晶4h，离心分离获得草甘膦湿产品，少量水洗涤后干燥得草甘膦活性组合物，母液套用至后续批次。
经液相色谱测定、取平均值，上述制得的白色结晶性粉末草甘膦活性组合物为草甘膦97.69％、草甘膦钠盐0.12％、甲醛0.05％、氢氧化钠不溶物0.075％、亚硝基草甘膦≤10-4％几乎检测不到、残余杂质约2.06％；休止角测定：本试验采用注入法(固定漏斗法)测定上述制备的草甘膦样品的休止角。将待测样品倒入漏斗，使其轻轻地、均匀地落入圆盘中心，形成一个圆锥体，当物料从粉体斜边沿圆盘边缘中自由落下时停止加料，用量角器测定休止角，测定结果见表2。
表2
Figure PCTCN2016073291-appb-000004
Figure PCTCN2016073291-appb-000005
上述草甘膦活性组合物颗粒休止角(θ)在28度左右，表明其固体粉末晶体颗粒流动性优异、可制剂性好，适合应用于生产各固体制剂及储藏运输。
实施例4
将800g双甘膦(PMIDA)(98.5％、3.47mol)、1450g水、120g活性炭依次加入四口瓶，在不断搅拌下升温至68℃，常压下开始滴加27.5％过氧化氢1050g，滴加完毕保温1h，冷却至5℃，结晶3h，分离获得草甘膦活性炭混合物821g，将草甘膦活性炭混合物平分为八份，备用。
将上述获得的一份草甘膦活性炭混合物加入635g17.9％草甘膦单钾盐溶液中，升温至92℃溶解，趁热过滤，冷却至20℃结晶4h，离心分离获得草甘膦湿产品，少量水洗涤后干燥得草甘膦活性组合物，母液套用至后续批次。
经液相色谱测定、取平均值，上述制得的白色结晶性粉末草甘膦活性组合物为草甘膦97.61％、草甘膦钾盐0.05％、甲醛0.03％、氢氧化钠不溶物0.015％、亚硝基草甘膦几乎检测不到、残余杂质约2.19％；休止角测定：本试验采用注入法(固定漏斗法)测定上述制备的草甘膦样品的休止角。将待测样品倒入漏斗，使其轻轻地、均匀地落入圆盘中心，形成一个圆锥体，当物料从粉体斜边沿圆盘边缘中自由落下时停止加料，用量角器测定休止角，测定结果见表3。
表3
序号 双甘膦(g) 草甘膦(g) 含量(％) 收率(％) 休止角(θ)
1 100 67.4 98.36 90.44 30.7
2 100 68.3 98.28 91.58 30.4
3 100 69.2 97.07 91.64 29.8
4 100 69.8 97.57 92.91 30.0
5 100 69.8 97.49 92.83 30.2
6 100 69.5 97.33 92.28 30.5
7 100 69.7 97.41 92.63 29.6
8 100 68.8 97.36 91.38 30.3
上述草甘膦活性组合物颗粒休止角(θ)在30度左右，表明其固体粉末晶体颗粒流动性优异、可制剂性好，适合应用于生产各固体制剂及储藏运输。
实施例5
将800g双甘膦(PMIDA)(98.2％、3.46mol)、1450g水、120g活性炭依次加入四口瓶，在不断搅拌下升温至68℃，常压下开始滴加27.5％过氧化氢1020g，滴加完毕保温1h，冷却至5℃，结晶3h，分离获得草甘膦活性炭混合物859g，将草甘膦活性炭混合物平分为八份，备用。
将上述获得的一份草甘膦活性炭混合物加入773.5g13.9％草甘膦铵盐溶液中，升温至92℃溶解，趁热过滤，冷却至20℃结晶4h，离心分离获得草甘膦湿产品，少量水洗涤后干燥得草甘膦活性组合物，母液套用至后续批次。
经液相色谱测定、取平均值，上述制得的白色结晶性粉末草甘膦活性组合物为草甘膦97.95％、草甘膦铵盐0.5％、甲醛0.04％、氢氧化钠不溶物0.01％、残余杂质约1.50％；休止角测定：本试验采用注入法(固定漏斗法)测定上述制备的草甘膦样品的休止角。将待测样品倒入漏斗，使其轻轻地、均匀地落入圆盘中心，形成一个圆锥体，当物料从粉体斜边沿圆盘边缘中自由落下时停止加料，用量角器测定休止角，测定结果见表4。
表4
Figure PCTCN2016073291-appb-000006
上述草甘膦活性组合物颗粒休止角(θ)在26度左右，表明其固体粉末晶体颗粒流动性优异、可制剂性好，适合应用于生产各固体制剂及储藏运输。
实施例6
将800g双甘膦(PMIDA)(98.5％、3.47mol)、1200g水、85g活性炭依次加入氧化釜，在不断搅拌下升温至55-65℃，通入压缩空气，保持釜内压力在0.4-0.6MP，氧化反应完毕，冷却至5℃，结晶3h，分离获得草甘膦活性炭混合物833g，将草甘膦活性炭混合物平分为八份，备用。
将上述获得的一份草甘膦活性炭混合物加入750g17％草甘膦二钾胺盐溶液中，升温至90℃溶解，趁热过滤，冷却至20℃结晶4h，离心分离获得草甘膦湿产品，少量水洗涤后干燥得草甘膦活性组合物，母液套用至后续批次。
经液相色谱测定、取平均值，上述制得的白色结晶性粉末草甘膦活性组合物为草甘膦98.31％、草甘膦二钾胺盐0.3％、甲醛0.01％、氢氧化钠不溶物0.008％、残余杂质约1.37％；休止角测定：本试验采用注入法(固定漏斗法)测定上述制备的草甘膦样品的休止角。将待测样品倒入漏斗，使其轻轻地、均匀地落入圆盘中心，形成一个圆锥体，当物料从粉体斜边沿圆盘边缘中自由落下时停止加 料，用量角器测定休止角，测定结果见表5。
表5
序号 双甘膦(g) 草甘膦(g) 含量(％) 收率(％) 休止角(θ)
1 100 68.9 98.76 93.11 28.7
2 100 68.6 98.82 92.77 28.5
3 100 69.7 98.67 94.11 28.3
4 100 70.8 98.62 95.55 28.4
5 100 70.5 98.54 95.06 28.6
6 100 70.5 97.82 94.37 28.5
7 100 69.4 97.69 92.77 28.8
8 100 70.3 97.61 93.90 28.6
上述草甘膦活性组合物颗粒休止角(θ)在28.5度左右，表明其固体粉末晶体颗粒流动性优异、可制剂性好，适合应用于生产各固体制剂及储藏运输。
实施例7～10
一种草甘膦活性组合物的制备方法，按如下步骤进行：
1)以双氧水、空气或富氧气体为氧化剂，活性炭为催化剂，在水中将双甘膦氧化合成草甘膦；所述双甘膦与双氧水反应摩尔比1：1.6～2.4、双甘膦与活性炭质量比为1：0.08～0.2，或者空气与双甘膦反应、体系内保持压力0.4～0.6Mpa、双甘膦与活性炭质量比为1：0.08～0.2，或者富氧与双甘膦反应、体系内保持压力0.4～0.6Mpa、双甘膦与活性炭质量比为1：0.05～0.12；
2)将步骤1)的反应体系降温至0～30℃、分离得到草甘膦-活性炭的混合物；
3)将步骤2)所得的草甘膦-活性炭混合物加入到质量浓度为5～35％的草甘膦盐(草甘膦铵盐、草甘膦钾盐、草甘膦异丙胺盐、草甘膦钠盐、草甘膦二 甲胺盐中的任一种或几种)溶液中，加热在85～95℃溶解、趁热过滤分离出活性炭，分离出的活性炭用热水洗涤后循环套用至步骤1)，洗涤液合并入滤液中；其中，草甘膦-活性炭混合物与草甘膦盐质量比为0.8～1.5：1；
4)将步骤3)所得的滤液5～25℃下冷却结晶，分离草甘膦和草甘膦盐溶液；
5)将步骤4)得到的草甘膦干燥制得草甘膦活性组合物，得到的草甘膦盐溶液返回步骤3)继续使用。
以上制得的草甘膦活性组合物成分为：草甘膦97％～98.5％、0<草甘膦盐≤1％、0<甲醛≤0.08％、0<氢氧化钠不溶物≤0.02％与残余杂质，亚硝基草甘膦几乎检测不到；其休止角θ≤30度，很好地满足了生产草甘膦各种可溶固体剂型的需要。以上方法收率高达88％以上，耗水量小、每吨产品热溶只消耗5～10吨水、母液循环量为7～13吨水/每吨产品，能耗低、操作简便适用于大规模工业化生产。
对比实施例1
将100g双甘膦(PMIDA)(98.2％、0.433mol)、180g水、15g活性炭依次加入四口瓶，在不断搅拌下升温至68℃，常压下开始滴加(27.5％)过氧化氢125g，滴加完毕保温1h，冷却至5℃，结晶3h，分离草甘膦活性炭混合物103.6g。
将上述草甘膦活性炭混合物加入150g水中，滴加35g26％氨水，滴加完毕升温至60℃使草甘膦全部溶解，趁热过滤，滴加26g98％硫酸至滤液中酸化，冷却至20℃结晶4h，离心分离获得草甘膦湿产品，少量水洗涤，产品干燥即得到草甘膦产品64.9g，含量95.85％，收率85.02％。将所得草甘膦产品进行休止角测定：本试验采用注入法(固定漏斗法)测定上述制备的草甘膦样品的休止角。将待测样品倒入漏斗，使其轻轻地、均匀地落入圆盘中心，形成一个圆锥体，当物料从粉体斜边沿圆盘边缘中自由落下时停止加料，用量角器测定休止角，重复测定三次休止角分别为：42.3、42.0、42.2度，可制剂性较差、不适合用 于可溶固体制剂的生产。
对比实施例2
将100g双甘膦(PMIDA)(98.5％、0.434mol)、150g水、10.6g活性炭依次加入氧化釜，在不断搅拌下升温至55-65℃，通入压缩空气，保持釜内压力在0.4-0.6MP，氧化反应完毕，冷却至5℃，结晶3h，分离草甘膦活性炭混合物105.2g。
将上述草甘膦活性炭混合物加入1390g草甘膦饱和溶液中，升温至90℃溶解，趁热过滤，冷却至20℃结晶4h，离心分离获得草甘膦湿产品，产品干燥后质量67.0g，含量97.12％，收率88.72％。该热溶法与本发明方法相比，使用溶解草甘膦的热溶母液量很大，本实例中每吨产品消耗草甘膦饱和母液20.7t/t，而本发明方法为7-13t/t，为本发明方法的1.6-2.9倍，导致溶解和结晶过程能耗增加，从而增加了生产成本。将所得草甘膦产品进行休止角测定：本试验采用注入法(固定漏斗法)测定上述制备的草甘膦样品的休止角。将待测样品倒入漏斗，使其轻轻地、均匀地落入圆盘中心，形成一个圆锥体，当物料从粉体斜边沿圆盘边缘中自由落下时停止加料，用量角器测定休止角，重复测定三次休止角分别为：47.5、47.7、47.3度，表明该固体粉末加工流动性不好、可制剂性较差、不适合用于可溶固体制剂的生产。

Claims (10)

  1. 一种草甘膦活性组合物，其特征在于，它包含以下组分：草甘膦≥95％，0<草甘膦盐≤1％，所述草甘膦盐为草甘膦铵盐、草甘膦钾盐、草甘膦异丙胺盐、草甘膦钠盐、草甘膦二甲胺盐中的任一种或几种，以质量百分含量计。
  2. 如权利要求1所述的草甘膦活性组合物，其特征在于，它包含以下组分：草甘膦≥95％、0<草甘膦盐≤1％、甲醛≤0.08％、氢氧化钠不溶物≤0.02％，所述草甘膦盐为草甘膦铵盐、草甘膦钾盐、草甘膦异丙胺盐、草甘膦钠盐、草甘膦二甲胺盐中的任一种或几种。
  3. 如权利要求2所述的草甘膦活性组合物，其特征在于，它包含以下组分：草甘膦≥95％、0.03％≤草甘膦盐≤0.5％、甲醛≤0.08％、氢氧化钠不溶物≤0.02％，所述草甘膦盐为草甘膦铵盐、草甘膦钾盐、草甘膦异丙胺盐、草甘膦钠盐、草甘膦二甲胺盐中的任一种或几种。
  4. 如权利要求3所述的草甘膦活性组合物，其特征在于，它包含以下组分：草甘膦≥97％、0.06％≤草甘膦盐≤0.3％、甲醛≤0.08％、氢氧化钠不溶物≤0.02％，所述草甘膦盐为草甘膦铵盐、草甘膦钾盐、草甘膦异丙胺盐、草甘膦钠盐、草甘膦二甲胺盐中的任一种或几种。
  5. 如权利要求1-4所述的草甘膦活性组合物，其特征在于：所述草甘膦盐为草甘膦铵盐、草甘膦钾盐、草甘膦钠盐的任一种或几种。
  6. 如权利要求1-5所述草甘膦活性组合物的制备方法，其特征在于：包括以双甘膦、氧化剂、水、活性炭催化剂为原料合成草甘膦，分离活性炭，冷却结晶得到草甘膦等步骤，其特征在于：所述分离活性炭是将合成草甘膦步骤所得的草甘膦-活性炭混合物，加入到草甘膦盐溶液或碱水溶液中，加热溶解、趁热过滤分离出活性炭；
    所述草甘膦盐溶液为草甘膦铵盐、草甘膦钾盐、草甘膦异丙胺盐、草甘膦钠盐、草甘膦二甲胺盐中的一种或几种混合溶液，所述草甘膦盐溶液的质量浓度为5～35％，所述草甘膦-活性炭混合物与草甘膦盐溶液的质量比为0.8～1.5： 1；
    所述碱水中的碱为与草甘膦反应生成草甘膦铵盐、草甘膦钾盐、草甘膦异丙胺盐、草甘膦钠盐或草甘膦二甲胺盐的一种或多种碱；所述碱水溶液的质量浓度为15～30％，所述碱与草甘膦-活性炭混合物中草甘膦的摩尔比为0.3～1.2：1。
  7. 如权利要求6所述草甘膦活性组合物的制备方法，其特征在于：所述草甘膦盐溶液为草甘膦铵盐溶液、草甘膦钾盐溶液、草甘膦钠盐溶液中的一种或多种；所述碱为与草甘膦反应生成草甘膦铵盐溶液、草甘膦钾盐溶液或草甘膦钠盐溶液的一种或多种碱。
  8. 如权利要求6或7所述草甘膦活性组合物的制备方法，其特征在于：所述草甘膦盐溶液的质量浓度为12～25％。
  9. 如权利要求6、7或8所述草甘膦活性组合物的制备方法，草甘膦-活性炭混合物与草甘膦盐溶液的质量比为1.0～1.2：1。
  10. 如权利要求6～9任一项所述草甘膦活性组合物的制备方法，按如下步骤进行：
    1)以双氧水、空气或富氧气体为氧化剂，活性炭为催化剂，在水中将双甘膦氧化合成草甘膦；
    2)将步骤1)的反应体系降温至0～30℃、分离得到草甘膦-活性炭的混合物；
    3)将步骤2)所得的混合物加入到上述草甘膦盐溶液或上述碱水溶液中，加热在85～95℃(优选85～90℃)溶解、趁热过滤分离出活性炭，分离出的活性炭用热水洗涤后循环套用至步骤1)，洗涤液合并入滤液中；
    4)将步骤3)所得的滤液5～25℃下(优选5～15℃)冷却结晶，分离草甘膦和草甘膦盐溶液；
    5)将步骤4)得到的草甘膦干燥制得本发明草甘膦活性组合物，得到的草甘膦盐溶液返回步骤3)继续使用。
PCT/CN2016/073291 2015-02-10 2016-02-03 一种草甘膦农药活性组合物及其制备方法 WO2016127890A1 (zh)

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