Crystal form of ammonium glyphosate and preparation method thereof

Abstract

The invention relates to the technical field of pesticides, and discloses a crystal form of ammonium glyphosate and a preparation method thereof, an X-ray diffraction pattern of the crystal form of ammonium glyphosate comprises at least one characteristic peak in 2theta of 10.196 + / -0.2 degrees, 18.339 + / -0.2 degrees, 20.207 + / -0.2 degrees, 20.857 + / -0.2 degrees, 22.483 + / -0.2 degrees, 22.845 + / -0.2 degrees, 23.416 + / -0.2 degrees, 24.868 + / -0.2 degrees, 26.811 + / -0.2 degrees, 28.878 + / -0.2 degrees or 34.057 + / -0.2 degrees, and the crystal form of ammonium glyphosate is tested to have the characteristic peak of 2theta of 10.196 + / -0.2 degrees, 18.339 + / -0.2 the crystal is regular and high in stability, the control effect reaches 96.79% after the herbicide is applied for 14 days, the control effect reaches 99.05% after the herbicide is applied for 28 days, and the weeding performance is excellent.

Description

Technical Field

[0001] This invention relates to the field of pesticide technology, specifically to a crystal form of glyphosate ammonium salt and its preparation method. Background Technology

[0002] Glyphosate is a broad-spectrum, non-selective herbicide, but its solubility in water is extremely low. In practical applications, glyphosate acid is usually formulated into water-soluble salts. Currently, the most widely used glyphosate-soluble salts are ammonium salts. Glyphosate ammonium salts generally refer to monoammonium salts of glyphosate; unless the context otherwise specifies, "glyphosate ammonium salt" here refers to the monoammonium salt of glyphosate. Its chemical formula is as follows:

[0003]

[0004] However, the crystal form of glyphosate ammonium salts on the market is currently unstable, with irregular crystal forms, disordered crystal growth, and a mixture of blocky, needle-like, and flaky shapes. At the same time, the crystals are prone to agglomeration and particle size increase. This structure affects the solubility and even leads to poor product flowability, which also has an impact on the formulation process. Summary of the Invention

[0005] This invention provides a crystal form of glyphosate ammonium salt and a method for preparing the same. The glyphosate ammonium salt has regular crystal structure and high stability, thus solving the problems mentioned in the background section.

[0006] The present invention provides the following technical solution: a crystal form of glyphosate ammonium salt, wherein the X-ray diffraction pattern of the crystal form of glyphosate ammonium salt contains at least one characteristic peak in 2θ selected from 10.196±0.2°, 18.339±0.2°, 20.207±0.2°, 20.857±0.2°, 22.483±0.2°, 22.845±0.2°, 23.416±0.2°, 24.868±0.2°, 26.811±0.2°, 28.878±0.2° or 34.057±0.2°.

[0007] As an optional crystal form of the glyphosate ammonium salt described in this invention, the X-ray diffraction pattern of the glyphosate ammonium salt crystal form further includes 10.196±0.2°, 11.291±0.2°, 14.347±0.2°, 18.339±0.2°, 19.331±0.2°, 20.207±0.2°, 20.857±0.2°, 22.483±0.2°, 22.845±0.2°, 23.416±0.2°, 24.868±0.2°, 25.445±0.2°, 26.811±0.2°, 27.141±0.2°, 27.804±0.2°, 28.878±0.2°, 29.767± At least three characteristic peaks in 2θ of 0.2°, 30.127±0.2°, 31.277±0.2°, 31.974±0.2°, 32.846±0.2°, 34.057±0.2°, 35.728±0.2°, 36.024±0.2°, 37.000±0.2°, 37.668±0.2°, 38.640±0.2°, 39.297±0.2°, 40.365±0.2°, 41.008±0.2°, 41.419±0.2°, 43.069±0.2°, 44.098±0.2°, 44.828±0.2°, 45.923±0.2°, or 46.222±0.2°.

[0008] As an optional crystal form of the glyphosate ammonium salt described in this invention, the X-ray diffraction pattern of the glyphosate ammonium salt crystal form further includes 10.196±0.2°, 11.291±0.2°, 14.347±0.2°, 17.585±0.2°, 18.339±0.2°, 19.331±0.2°, 20.207±0.2°, 20.857±0.2°, 21.880±0.2°, 22.483±0.2°, 22.845±0.2°, 23.416±0.2°, 24.329±0.2°, 24.868±0.2°, 25 0.445±0.2°, 26.811±0.2°, 27.141±0.2°, 27.804±0.2°, 28.878±0.2°, 29.767±0.2°, 30.127±0.2°, 31.277±0.2°, 31.974±0.2°, 32.846±0.2°, 34.057±0.2°, 35.728±0.2°, 36.024±0.2°, 37.000±0.2°, 37.668±0.2°, 38.181±0.2°, 38.640±0.2°, 39.297±0.2°, 40 0.365±0.2°, 41.008±0.2°, 41.419±0.2°, 42.075±0.2°, 42.688±0.2°, 43.069±0.2°, 44.098±0.2°, 44.828±0.2°, 45.923±0.2°, 46.222±0.2°, 46.7000±0.2°, 47.514±0.2°, 48.033±0.2°, 49.559±0.2°, 50.524±0.2°, 50.986±0.2°, 51.718±0.2°, 52.277±0.2° At least six characteristic peaks in 2θ of 53.686±0.2°, 54.418±0.2°, 55.902±0.2°, 56.422±0.2°, 57.099±0.2°, 58.271±0.2°, 58.860±0.2°, 61.192±0.2°, 61.742±0.2°, 63.132±0.2°, 63.727±0.2°, 64.982±0.2°, 67.421±0.2°, 68.881±0.2°, 70.322±0.2°, 73.912±0.2°, or 78.596±0.2°.

[0009] A method for preparing the crystal form of glyphosate ammonium salt, used to prepare the crystal form of any of the glyphosate ammonium salts described above, comprising:

[0010] Step 1, Neutralization Reaction: Glyphosate (≥95%) is added to a closed mixer as raw material. A solid ammonium-containing alkaline substance is added to the mixer all at once. The system temperature, stirring rate, pressure, and pH value are adjusted separately to carry out a three-stage reaction. The solid ammonium-containing alkaline substance includes at least one of ammonium carbonate ((NH4)2CO3) or ammonium bicarbonate (NH4HCO3). Its decomposition product, CO2, can buffer pH fluctuations. The closed mixer is a jacketed, high-speed mixer, equipped with: a pressure sensor with a range of 0-0.5MPa and an accuracy of ±0.01MPa; a temperature-resistant, measurement range of 2-10, and a response time of <5s insertion-type pH probe; and an automatic speed control system with a rotation speed range of 0-200r / min and an adjustment accuracy of ±5r / min.

[0011] After the reaction begins, the feed inlet is closed and the automatic control system is activated. The first stage is the decomposition initiation period: the jacket temperature is raised to 60-70℃, the initial stirring rate is 30-50 r / min, and the pressure and pH value are monitored in real time. When the pressure rises to 0.05-0.1 MPa and the pH value rises to 3.9-4.1, NH3 begins to be released. The stirring speed is maintained to promote the release and diffusion of NH3 and prevent NH3 from escaping too quickly.

[0012] The second stage is the peak reaction period: when the pressure rises to 0.1-0.2 MPa and the pH value reaches 3.5-4.5, NH3 and CO2 accumulate to the required amount. At this time, the stirring speed is increased to 80-120 r / min to carry out the reaction, balance the reaction efficiency and crystal form, and avoid local over-alkaliness.

[0013] The third stage is the final stage of the reaction: when the pressure drops to 0.05-0.1 MPa and the pH value stabilizes at 3.5-4.0, more than half of the NH3 has been consumed. At this time, the stirring rate is reduced to 20-50 r / min to carry out the reaction, reduce crystal breakage, and promote crystal growth.

[0014] Termination conditions: When the pressure is ≤0.05MPa and the pH value is stable for more than 5 minutes, the reaction is complete, and the jacket is cooled to 20-30℃.

[0015] Step 2, Discharge: To avoid the disorderly release of residual NH3 due to high speed, the pressure relief valve is controlled to have a pressure relief rate ≤0.02MPa / min, the stirring rate is 5-10r / min, and the material is discharged. The inlet temperature of the flash dryer is controlled to be 90-100℃ for drying, to obtain glyphosate ammonium salt crystals with a purity ≥95.5%. The glyphosate ammonium salt crystals are regular flaky with a D90 particle size of 100-200μm.

[0016] A method for preparing glyphosate ammonium salts by dynamically matching the stirring rate through real-time monitoring of the reaction system pressure and pH value achieves controllable crystal form, improved purity, and enhanced safety.

[0017] As an optional scheme for the preparation method of glyphosate ammonium salt crystal form according to the present invention, in step one, during the neutralization reaction, more than 95% glyphosate and a certain amount of water are mixed in a closed mixer, the stirring speed is controlled at 50-80 r / min, the pressure is controlled at around 0 MPa, and the mixture is mixed for 0-5 minutes until the material is uniform. Then, a solid ammonium-containing alkaline substance is added at one time to carry out the neutralization reaction. Water is used as a catalyst medium, and the weight ratio of glyphosate to water is 1:0-0.1.

[0018] As an optional method for preparing the crystal form of glyphosate ammonium salt according to the present invention, the molar ratio of glyphosate to ammonium ions is 1:1.01-1.1.

[0019] The present invention has the following beneficial effects:

[0020] 1. The crystal form of this glyphosate ammonium salt was tested and found to be regular and highly stable. The control efficacy reached 96.79% 14 days after application and 99.05% 28 days after application, demonstrating excellent weed control performance.

[0021] 2. The method for preparing the crystal form of glyphosate ammonium salt involves the coordinated adjustment of stirring rate, pressure, and pH value. By monitoring the state of the reaction system in real time, the optimal stirring strategy is intelligently matched and controlled in three stages. This achieves the effects of avoiding local unreacted areas, preventing excessive pH fluctuations, ensuring uniform crystal growth, stabilizing the crystal form, and reducing impurities.

[0022] 3. The method for preparing the crystal form of glyphosate ammonium salt completes the mixing-reaction-crystal form control in one step, without the need for complex equipment. Compared with the traditional liquid ammonia method, it reduces the number of steps by 30%, increases the reaction efficiency by 20%, and shortens the reaction time to 30-40 minutes.

[0023] 4. The preparation method of the glyphosate ammonium salt crystal form uses solid ammonium salt to replace liquid ammonia, eliminating the risk of high-pressure storage; the closed system + pressure control reduces NH3 emission by more than 90%, improves the operating environment, and greatly enhances safety and environmental protection, making it suitable for industrial production.

[0024] 5. The preparation method of the glyphosate ammonium salt crystal form, the pH value fluctuation is controlled within ±0.5 to avoid diammonium salt impurities caused by local excessive alkalinity; the product purity is ≥95.5%, the crystal powder is regular, the dissolution rate is improved, and the efficacy is enhanced. Attached Figure Description

[0025] Figure 1 This is a scanning electron microscope (SEM) image of the crystal form of glyphosate ammonium salt prepared in Example 1 of this application;

[0026] Figure 2 The image shows a scanning electron microscope (SEM) image of the crystal form of glyphosate ammonium salt prepared in Comparative Example 1 of this application.

[0027] Figure 3 The X-ray powder diffraction pattern of the crystal form of glyphosate ammonium salt prepared in Example 1 of this application is shown. Detailed Implementation

[0028] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] Although the preparation methods for glyphosate ammonium salts have been optimized over the years, existing processes, including conventional neutralization crystallization and high-purity preparation methods, still have some common or specific defects. The stirring rate is often controlled by a fixed value or empirical range, lacking a real-time response mechanism for key parameters during the reaction process, leading to:

[0030] Uneven local reaction: High-speed stirring may cause ammonia to escape too quickly, while low speed may easily create an overly alkaline local environment, generating impurities such as diammonium salts and triammonium salts, which adhere to the crystals, resulting in a rough surface. SEM observation shows obvious small particles adhering to the crystals.

[0031] Traditional processes cannot dynamically adjust shear force according to the material state, resulting in irregular crystal forms, disordered crystal growth, and a mixture of blocky, needle-like, and flaky crystals. At the same time, crystals are prone to agglomeration, leading to increased particle size. This structure affects solubility and can even cause poor product flowability, which also has an impact on formulation processing.

[0032] Safety hazard: The risk of ammonia leakage and the pressure fluctuation of the reaction system lack linkage control, posing a safety hazard.

[0033] Therefore, there is an urgent need to establish an intelligent control system based on multi-parameter coupling to achieve precise control of the glyphosate ammonium salt preparation process. Since the stirring rate, pressure, and pH value all affect the morphology and purity of the product during the reaction, improper control can lead to localized over-alkali risk, reduced reaction efficiency, and decreased yield. Therefore, it is necessary to monitor the reaction system status in real time and intelligently match the optimal formation strategy. Research has found that during the reaction, the stirring rate needs to be dynamically adjusted based on pressure and pH value, ranging from 0-200 r / min; pressure reflects the internal pressure of the reaction system, indicating the rate of NH3 generation and consumption; pH value reflects the reaction progress and the risk of localized over-alkali. Based on this, the following examples are provided for illustration.

[0034] Example 1

[0035] A method for preparing the crystal form of glyphosate ammonium salt and the prepared glyphosate ammonium salt, wherein the raw material ratio is glyphosate:ammonium ion = 1:1.05, wherein the ammonium ions are provided by ammonium carbonate, and the specific method steps include:

[0036] Step 1, Neutralization reaction: Mix 97% glyphosate with water at a ratio of 1:0.05, control the stirring speed at 50 r / min, and control the pressure at around 0 MPa. After mixing for 3 minutes, carry out a three-stage neutralization reaction.

[0037] The three-stage neutralization reaction is as follows:

[0038] First stage, decomposition initiation period: reaction time 12 min, pressure increased from 0 to 0.045 MPa, pH value increased to 4.1, stirring rate 50 r / min.

[0039] The second stage, the peak reaction period: the reaction time is 16 min, the pressure is stabilized at 0.15 MPa, the pH value fluctuates between 3.5 and 4.0, and the stirring rate is 100 r / min.

[0040] The third stage, the final stage of the reaction: the reaction time is 12 min, the pressure is reduced to 0.05 MPa, the pH value fluctuates stably in a small range of 3.5-3.6, and the stirring rate is 30 r / min.

[0041] Step 2, Discharge: After the neutralization reaction is completed, open the pressure relief valve and control the pressure relief rate to ≤0.02MPa / min, while setting the stirring rate to 5r / min; after the material is discharged, control the inlet temperature to 95℃ and dry it in a flash dryer before discharging.

[0042] X-ray powder diffraction (XPD) was performed on the glyphosate salt product obtained in this embodiment, and the spectrum is shown below. Figure 3 As shown, the SEM image of glyphosate ammonium salt is as follows. Figure 1 As shown, at least one or more characteristic peaks with high intensity are observed in 2θ at 10.196±0.2°, 18.339±0.2°, 20.207±0.2°, 20.857±0.2°, 22.483±0.2°, 22.845±0.2°, 23.416±0.2°, 24.868±0.2°, 26.811±0.2°, 28.878±0.2°, and 34.057±0.2°. Their X-ray powder diffraction data are shown in the table below:

[0043]

[0044]

[0045] .

[0046] Using 79g of glyphosate ammonium salt prepared in Example 1, 4g of tallow amine polyether and 17g of ammonium sulfate were added to prepare 68% glyphosate ammonium salt soluble granules. After sample testing, the glyphosate content was 68.98%, the ammonium content was 12.93%, and the moisture content was 0.57%, all of which met the requirements.

[0047] The efficacy of glyphosate ammonium salt and 68% glyphosate ammonium salt soluble granules from Example 1, as well as commercially available 95.5% glyphosate ammonium salt and 68% glyphosate ammonium salt soluble granules, was compared in this study. The active ingredient was 60 g / mu (calculated as glyphosate), diluted with water to 30 L / mu, and applied to control weeds in wasteland. Four replicates were performed, with each plot covering 5 m². 2 The overall control effect of the herbicide on wasteland was statistically analyzed 14 and 28 days after application. The specific results are shown in the table below:

[0048]

[0049] Efficacy tests showed that the glyphosate ammonium salt and 68% glyphosate ammonium salt soluble granules in this embodiment had better weed control effects than commercially available products, demonstrating good weed control performance.

[0050] Example 2

[0051] A method for preparing the crystal form of glyphosate ammonium salt and the prepared glyphosate ammonium salt, wherein the raw material ratio is glyphosate:ammonium ion = 1:1.1, wherein the ammonium ions are provided by ammonium bicarbonate, and the specific method steps include:

[0052] Step 1, Neutralization Reaction: Add 96.5% glyphosate and ammonium bicarbonate to the mixer and directly carry out the three-stage neutralization reaction as follows:

[0053] First stage, decomposition initiation period: reaction time 15 min, pressure increased from 0 to 0.05 MPa, pH value increased to 4.0, stirring rate 30 r / min.

[0054] The second stage, the peak reaction period: the reaction time is 17 min, the pressure is stabilized at 0.2 MPa, the pH value fluctuates between 4.0 and 4.5, and the stirring rate is 120 r / min.

[0055] The third stage, the final stage of the reaction: the reaction time is 13 min, the pressure is reduced to 0.05 MPa, the pH value fluctuates stably in a small range of 3.8-3.9, and the stirring rate is 20 r / min.

[0056] Step 2, Discharge: After the neutralization reaction is completed, open the pressure relief valve and control the pressure relief rate to ≤0.02MPa / min, while setting the stirring rate to 10r / min; after the material is discharged, control the inlet temperature to 90℃ and dry it in a flash dryer before discharging.

[0057] Example 3

[0058] A method for preparing the crystal form of glyphosate ammonium salt and the prepared glyphosate ammonium salt, wherein the raw material ratio is glyphosate:ammonium ion = 1:1.03, wherein the ammonium ion is provided by a mixture of ammonium carbonate and ammonium bicarbonate in a 1:1 ratio. Specifically, the reaction steps include:

[0059] Step 1, Neutralization reaction: Mix 97.5% glyphosate with water at a ratio of 1:0.1, control the stirring speed at 80 r / min, and control the pressure at around 0 MPa. After mixing for 3 minutes, carry out a three-stage neutralization reaction.

[0060] The three-stage neutralization reaction is as follows:

[0061] First stage, decomposition initiation period: reaction time 18 min, pressure increased from 0 to 0.07 MPa, pH value increased to 4.1, stirring rate 40 r / min.

[0062] The second stage, the peak reaction period: the reaction time is 12 min, the pressure is stabilized at 0.1 MPa, the pH value fluctuates between 3.7 and 4.2, and the stirring rate is 100 r / min.

[0063] The third stage, the final stage of the reaction: the reaction time is 12 min, the pressure is reduced to 0.05 MPa, the pH value fluctuates stably in a small range of 3.7-3.8, and the stirring rate is 35 r / min.

[0064] Step 2, Discharge: After the neutralization reaction is completed, open the pressure relief valve and control the pressure relief rate to ≤0.02MPa / min, while setting the stirring rate to 7r / min; after the material is discharged, control the inlet temperature to 95℃ and dry it in a flash dryer before discharging.

[0065] Example 4

[0066] A method for preparing the crystal form of glyphosate ammonium salt and the prepared glyphosate ammonium salt, wherein the raw material ratio is glyphosate:ammonium ion = 1:1.01, wherein the ammonium ions are provided by ammonium bicarbonate, and the specific reaction steps include:

[0067] Step 1, Neutralization reaction: Mix 98% glyphosate with water at a ratio of 1:0.1, control the stirring speed at 50 r / min, and control the pressure at around 0 MPa. After mixing for 5 minutes, carry out a three-stage neutralization reaction.

[0068] The three-stage neutralization reaction is as follows:

[0069] First stage, decomposition initiation period: reaction time 14 min, pressure increased from 0 to 0.1 MPa, pH value increased to 3.9, stirring rate 50 r / min.

[0070] The second stage, the peak reaction period: the reaction time is 12 min, the pressure is stabilized at 0.12 MPa, the pH value fluctuates between 3.9 and 4.4, and the stirring rate is 90 r / min.

[0071] The third stage, the final stage of the reaction: the reaction time is 12 min, the pressure is reduced to 0.04 MPa, the pH value fluctuates stably in a small range of 3.9-4.0, and the stirring rate is 50 r / min.

[0072] Step 2, Discharge: After the neutralization reaction is completed, open the pressure relief valve and control the pressure relief rate to ≤0.02MPa / min, while setting the stirring rate to 7r / min; after the material is discharged, control the inlet temperature to 100℃ and dry it in a flash dryer before discharging.

[0073] Comparative Example 1

[0074] A method for preparing the crystal form of glyphosate ammonium salt and the prepared glyphosate ammonium salt, wherein the raw material ratio is glyphosate:ammonium ion = 1:1.05, wherein the ammonium ions are provided by ammonium carbonate, as detailed below:

[0075] Preliminary mixing: The reaction time was 10 min. 96% glyphosate and water were added to an open reactor at a ratio of 1:0.1. The stirring speed was fixed at 60 r / min, and no pressure monitoring was performed.

[0076] Neutralization reaction: reaction time 30 min, ammonium carbonate added at once, stirring rate maintained at 80 r / min throughout, no segmented temperature control.

[0077] The reaction was carried out in an open environment, with ammonia gas escaping naturally. There was no pressure control and the pH value was not monitored.

[0078] Post-processing: The reaction time is 10 minutes. After the reaction is completed, the material is discharged directly without cooling. It is dried at 100℃ before being discharged.

[0079] The SEM image of glyphosate ammonium salt in this comparative example is shown below. Figure 2 As shown.

[0080] The glyphosate ammonium salt crystal products prepared in the examples and comparative examples were measured, and the results are shown in the table below:

[0081] .

[0082] The results show that the present invention, through dynamic control of pressure, pH value, and rotation speed, achieves mixing, reaction, and crystal form regulation in one step, resulting in crystals whose various indicators meet the standards. This invention, through the deep integration of raw material innovation and process optimization, successfully constructs a highly efficient and green production system. It not only significantly improves production efficiency and stabilizes product crystal form but also achieves synergistic development of environmental and economic benefits. This technical solution combines technological foresight, economic feasibility, and environmental friendliness.

[0083] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0084] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A crystal form of glyphosate ammonium salt, characterized in that, The X-ray diffraction pattern of the glyphosate ammonium salt crystal form contains at least one characteristic peak in 2θ at 10.196±0.2°, 18.339±0.2°, 20.207±0.2°, 20.857±0.2°, 22.483±0.2°, 22.845±0.2°, 23.416±0.2°, 24.868±0.2°, 26.811±0.2°, 28.878±0.2° or 34.057±0.2°.

2. The crystal form of glyphosate ammonium salt according to claim 1, characterized in that: The X-ray diffraction patterns of glyphosate ammonium salt crystal forms also include 10.196±0.2°, 11.291±0.2°, 14.347±0.2°, 18.339±0.2°, 19.331±0.2°, 20.207±0.2°, 20.857±0.2°, 22.483±0.2°, 22.845±0.2°, 23.416±0.2°, 24.868±0.2°, 25.445±0.2°, 26.811±0.2°, 27.141±0.2°, 27.804±0.2°, 28.878±0.2°, 29.767±0.2°, and 30.127±0. At least three characteristic peaks in 2θ of 0.2°, 31.277±0.2°, 31.974±0.2°, 32.846±0.2°, 34.057±0.2°, 35.728±0.2°, 36.024±0.2°, 37.000±0.2°, 37.668±0.2°, 38.640±0.2°, 39.297±0.2°, 40.365±0.2°, 41.008±0.2°, 41.419±0.2°, 43.069±0.2°, 44.098±0.2°, 44.828±0.2°, 45.923±0.2°, or 46.222±0.2°.

3. The crystal form of glyphosate ammonium salt according to claim 1 or 2, characterized in that: The X-ray diffraction patterns of glyphosate ammonium salt crystal forms also include 10.196±0.2°, 11.291±0.2°, 14.347±0.2°, 17.585±0.2°, 18.339±0.2°, 19.331±0.2°, 20.207±0.2°, 20.857±0.2°, 21.880±0.2°, 22.483±0.2°, 22.845±0.2°, 23.416±0.2°, 24.329±0.2°, 24.868±0.2°, 25.445±0.2°, and 26.811±0.2°. °, 27.141±0.2°, 27.804±0.2°, 28.878±0.2°, 29.767±0.2°, 30.127±0.2°, 31.277±0.2°, 31.974±0.2°, 32.846±0.2°, 34.057±0.2°, 35.728±0.2°, 36.024±0.2°, 37.000±0.2°, 37.668±0.2°, 38.181±0.2°, 38.640±0.2°, 39.297±0.2°, 40.365±0.2°, 41. 008±0.2°, 41.419±0.2°, 42.075±0.2°, 42.688±0.2°, 43.069±0.2°, 44.098±0.2°, 44.828±0.2°, 45.923±0.2°, 46.222±0.2°, 46.7000±0.2°, 47.514±0.2°, 48.033±0.2°, 49.559±0.2°, 50.524±0.2°, 50.986±0.2°, 51.718±0.2°, 52.277±0.2°, 53.686± At least six characteristic peaks in 2θ of 0.2°, 54.418±0.2°, 55.902±0.2°, 56.422±0.2°, 57.099±0.2°, 58.271±0.2°, 58.860±0.2°, 61.192±0.2°, 61.742±0.2°, 63.132±0.2°, 63.727±0.2°, 64.982±0.2°, 67.421±0.2°, 68.881±0.2°, 70.322±0.2°, 73.912±0.2°, or 78.596±0.2°.

4. A method for preparing the crystal form of glyphosate ammonium salt, used to prepare the crystal form of glyphosate ammonium salt as described in any one of claims 1-3, characterized in that: include: Step 1, Neutralization reaction: Glyphosate is added to a closed mixer, and a solid ammonium-containing alkaline substance is added at once. The system temperature, stirring rate, pressure and pH value are adjusted respectively to carry out a three-stage reaction. The neutralization reaction ends when the pressure is ≤0.05MPa and the pH value is stable. Step 2, Discharge: Control the pressure relief valve and the stirring rate to output the material, and then dry it to obtain glyphosate ammonium salt crystals.

5. The method for preparing the crystal form of glyphosate ammonium salt according to claim 4, characterized in that: In step one, after adding glyphosate to a closed mixer, a certain amount of water is added. The glyphosate and water are mixed at a stirring speed of 50-80 r / min and a pressure of around 0 MPa for 0-5 minutes until the material is uniform. Then, a solid ammonium-containing alkaline substance is added at once for neutralization reaction. The weight ratio of glyphosate to water is 1:0-0.

1.

6. The method for preparing the crystal form of glyphosate ammonium salt according to claim 4 or 5, characterized in that: The first stage of the three-stage reaction is the decomposition initiation period: control the system temperature at 60-70℃, the initial stirring rate at 30-50 r / min, and maintain the stirring speed when the pressure rises to 0.05-0.1 MPa and the pH value rises to 3.9-4.

1.

7. The method for preparing the crystal form of glyphosate ammonium salt according to claim 4 or 5, characterized in that: The second stage of the three-stage reaction is the peak reaction period: when the pressure rises to 0.1-0.2 MPa and the pH value reaches 3.5-4.5, the stirring speed is increased to 80-120 r / min to carry out the reaction.

8. The method for preparing the crystal form of glyphosate ammonium salt according to claim 4 or 5, characterized in that: The third stage of the three-stage reaction is the final stage of the reaction: when the pressure drops to 0.05-0.1 MPa and the pH value stabilizes at 3.5-4.0, the stirring speed is reduced to 20-50 r / min to continue the reaction.

9. The method for preparing the crystal form of glyphosate ammonium salt according to claim 4 or 5, characterized in that: During discharge, the pressure relief valve is controlled to have a pressure relief rate of ≤0.02MPa / min, the stirring rate is 5-10r / min, and the material is output. The inlet temperature of the flash dryer is controlled to be 90-100℃ for drying, to obtain glyphosate ammonium salt crystals with a purity of ≥95.5%. The glyphosate ammonium salt crystals are regular flaky with a D90 particle size of 100-200μm.

10. The method for preparing the crystal form of glyphosate ammonium salt according to claim 4 or 5, characterized in that: Using glyphosate of 95% or higher as raw material, the molar ratio of glyphosate to ammonium ions is 1:1.01-1.1, and the solid ammonium-containing alkaline substances include ammonium carbonate and / or ammonium bicarbonate.

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