CN120423508A - A method for producing low-potassium industrial-grade ammonium phosphate using medium- and low-grade high-potassium phosphate ore - Google Patents
A method for producing low-potassium industrial-grade ammonium phosphate using medium- and low-grade high-potassium phosphate oreInfo
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- CN120423508A CN120423508A CN202510928902.XA CN202510928902A CN120423508A CN 120423508 A CN120423508 A CN 120423508A CN 202510928902 A CN202510928902 A CN 202510928902A CN 120423508 A CN120423508 A CN 120423508A
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- phosphoric acid
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Abstract
一种利用中低品位高钾磷矿生产低钾工业级磷酸铵的方法，包括：S1原料高钾矿配矿，硫酸法湿法磷酸生产粗磷酸并降温陈化，得到陈化酸。S2通过氨源与陈化酸发生中和反应，控制反应pH，反应后压滤反应料浆获得清液。S3多效蒸发浓缩清液，降温获取过饱和结晶晶浆体。S4通过pH调节剂调节过饱和晶浆液pH后过滤，干燥滤固物可获得低钾工业级磷酸二铵或用磷酸回调滤固物pH得低钾工业级磷酸一铵。该种方法能够有效解决成品工业级磷酸一铵中因原料矿石中钾含量高而导致的成品钾含量高的问题。本发明方案通过调整系统pH和重结晶的方式来降低钾元素含量，而且工艺流程简单，中间产生的所有滤液均可以回用，具有极高的产业化价值。
A method for producing low-potassium industrial-grade ammonium phosphate using medium- and low-grade high-potassium phosphate ore comprises the following steps: S1: blending the raw material high-potassium ore, producing crude phosphoric acid using a sulfuric acid wet-process phosphoric acid, and cooling and aging to obtain aged acid. S2: neutralizing the aged acid with an ammonia source to control the reaction pH, and filtering the reaction slurry after the reaction to obtain a clear liquid. S3: concentrating the clear liquid by multi-effect evaporation and cooling to obtain a supersaturated crystalline slurry. S4: adjusting the pH of the supersaturated slurry using a pH regulator, filtering, and drying the filtered solid to obtain low-potassium industrial-grade diammonium phosphate, or adjusting the pH of the filtered solid using phosphoric acid to obtain low-potassium industrial-grade monoammonium phosphate. This method can effectively solve the problem of high potassium content in the finished industrial-grade monoammonium phosphate due to the high potassium content in the raw material ore. The solution of the present invention reduces the potassium content by adjusting the system pH and recrystallization, and the process flow is simple. All filtrates produced in the process can be reused, thus having extremely high industrial value.
Description
Technical Field
The invention relates to the technical field of phosphate preparation, in particular to a method for producing low-potassium industrial grade ammonium phosphate by using medium-low-grade high-potassium phosphorite.
Background
The industrial monoammonium phosphate is also called monoammonium phosphate, and the crystal is a colorless transparent tetragonal system. Slightly soluble in alcohol and water, and the water solution is acidic, and the powdery product has certain hygroscopicity. Industrial monoammonium phosphate can not burn or explode when meeting acid and alkali, high temperature or oxidation-reduction substances, has good thermal stability, can be dehydrated at high temperature, and is easy to generate viscous chain compounds (ammonium polyphosphate, ammonium metaphosphate and the like).
The industrial monoammonium phosphate is a good fire extinguishing agent and fire retardant, is widely applied to the fire retardant of wood, paper and fabric, the main ingredients of forest fire extinguishing agents and dry powder fire extinguishing agents, and is also applied to dye industry and fiber processing dispersing agents, compounding agents of fire extinguishing paint, dry powder fire extinguishing agents, extinguishing agents of match stems and candle cores and the like.
In the food and pharmaceutical fields, as yeast food, leavening agents, buffering agents, dough conditioners, brewing fermentation aids, and also as additives for feed production. Industrial monoammonium phosphate can be used as phosphorus nutrition for yeast culture. It is also used in medicine production.
In agricultural production, industrial monoammonium phosphate is used as a basic raw material of fertilizer, such as N, P, K ternary compound fertilizer, and is mainly used for producing compound fertilizer and water-soluble fertilizer to be directly applied to farmlands. In the field of environmental protection, it is used for measuring water and sulfide in the atmosphere.
In the field of new energy, with the gradual development of new energy automobiles, the market share of electric core products taking ferric phosphate as a precursor of a positive electrode material is gradually increased, ammonium ferric phosphate is a main process for producing ferric phosphate, the requirements and quality requirements on industrial monoammonium phosphate are also increasingly high, and the industrial monoammonium phosphate with low impurity content, especially potassium content, is required to be produced in the market by the ammonium ferric phosphate process.
At present, monoammonium phosphate is mainly prepared by two methods of wet-process phosphoric acid and hot-process phosphoric acid, and wet-process phosphoric acid production is an effective method for treating phosphate ores. Wet process phosphoric acid reduces a lot of energy consumption compared to hot process phosphoric acid. With the increasing shortage of energy sources, low-energy wet-process phosphoric acid purification technology is gaining importance. The wet phosphoric acid is used for replacing the hot phosphoric acid to produce the industrial monoammonium phosphate, which has important significance for improving the technical content of the traditional monoammonium phosphate device, increasing the deep processing force of the wet phosphoric acid and improving the economic benefit.
However, the monoammonium phosphate prepared by the wet-process phosphoric acid has the technical problem of high K content introduced from raw materials, and in the field of new energy, the high K content of a finished product can cause adverse effects on the performance of a battery prepared subsequently.
Disclosure of Invention
Aiming at the technical problem that monoammonium phosphate prepared by wet-process phosphoric acid has high K content introduced from raw materials, the invention provides a method for producing low-potassium industrial-grade ammonium phosphate by using medium-low-grade high-potassium phosphorite.
A method for producing low-potassium industrial grade ammonium phosphate by using medium-low grade high-potassium phosphorite comprises the following steps:
s1, preparing high-potassium ore as a raw material, producing crude phosphoric acid by using wet phosphoric acid by a sulfuric acid method, cooling and aging to obtain aging acid;
s2, carrying out neutralization reaction on an ammonia source and aging acid, controlling the reaction pH, and carrying out filter pressing on the reaction slurry after the reaction to obtain clear liquid;
s3, concentrating clear liquid through multi-effect evaporation, and cooling to obtain supersaturated crystal slurry;
S4, adjusting the pH value of the supersaturated crystal slurry through a pH regulator, filtering, and drying the filtered solids to obtain low-potassium industrial grade diammonium phosphate or adjusting the pH value of the filtered solids back through phosphoric acid to obtain low-potassium industrial grade monoammonium phosphate.
Preferably, the mass fraction of the crude phosphoric acid P2O5 in the step S1 is 18% -26%.
Preferably, in the step S1, the cooling and ageing temperature is 45-75 ℃, and the cooling and ageing time is 8-12h.
Preferably, the ammonia source in step S2 is from one or more of liquid ammonia, aqueous ammonia and gaseous ammonia.
Preferably, the neutralization reaction in step S2 is controlled to have a pH in the range of 3.5 to 4.5.
Preferably, the temperature of the reduced crystallization in step S3 is 60-75deg.C.
Preferably, the pH adjuster in step S4 is one or more of liquid ammonia, aqueous ammonia and gaseous ammonia.
Preferably, the saturated crystal slurry pH in step S4 is adjusted to a range of 7-10.
Preferably, the phosphoric acid used for callback of the solid in step S4 is refined phosphoric acid with a mass fraction of 75% or 85%.
Preferably, the pH of the phosphoric acid callback filtrate in step S4 is in the range of 3.2-4.8.
The method reduces the content of potassium element by adjusting the pH value of the system and recrystallizing, has simple process flow, can recycle all filtrate generated in the middle, has extremely high industrialization value, and can be directly used for preparing high-purity ferric phosphate.
Drawings
FIG. 1 is a flow chart of the operation of the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1]
A method for producing low-potassium industrial grade ammonium phosphate by using medium-low grade high-potassium phosphorite comprises the following steps:
1. And (3) preparing a medium-low-grade high-potassium phosphorite with the potassium content of more than or equal to 2000ppm, producing crude phosphoric acid with the mass fraction of P2O5 of 26% by a sulfuric acid method wet phosphoric acid method, cooling and aging at 60 ℃ for 8 hours, and obtaining the aging acid.
2. And (3) carrying out neutralization reaction on ammonia water and aging acid, controlling the pH value at the end point of the neutralization reaction to be 4.2, and filtering to obtain clear liquid.
3. Evaporating and concentrating the clear liquid, and cooling to 60 ℃ to obtain supersaturated crystal slurry.
4. And (3) regulating the pH value of the supersaturated crystal slurry to 9.41 by using ammonia water at 60 ℃, filtering and drying to obtain the low-potassium industrial grade diammonium phosphate.
Example 2 ]
1. And (3) preparing a medium-low-grade high-potassium phosphorite with the potassium content of more than or equal to 2000ppm, producing crude phosphoric acid with the mass fraction of P2O5 of 26% by a sulfuric acid method wet phosphoric acid method, cooling and aging at 60 ℃ for 8 hours, and obtaining the aging acid.
2. And (3) carrying out neutralization reaction on ammonia water and aging acid, controlling the pH at the end point of the neutralization reaction to be 3.8, and filtering to obtain clear liquid.
3. Evaporating and concentrating the clear liquid, and cooling to 70 ℃ to obtain supersaturated crystal slurry.
4. And (3) regulating the pH value of the supersaturated crystal slurry to 9.27 by using ammonia water at 70 ℃, filtering and drying to obtain the low-potassium industrial grade diammonium phosphate.
5. Dissolving low-potassium industrial grade diammonium phosphate with deionized water, adding phosphoric acid to adjust the pH to 4.2, evaporating, concentrating and filtering to obtain low-potassium industrial grade monoammonium phosphate.
Example 3 ]
A method for producing low-potassium industrial grade ammonium phosphate by using medium-low grade high-potassium phosphorite comprises the following steps:
1. And (3) preparing a medium-low-grade high-potassium phosphorite with the potassium content of more than or equal to 2000ppm, producing crude phosphoric acid with the mass fraction of P2O5 of 18% by a sulfuric acid method wet phosphoric acid method, cooling and aging at 70 ℃ for 12 hours, and obtaining the aging acid.
2. And (3) carrying out neutralization reaction on ammonia water and aging acid, controlling the pH value at the end point of the neutralization reaction to be 4.0, and filtering to obtain clear liquid.
3. Evaporating and concentrating the clear liquid, and cooling to 70 ℃ to obtain supersaturated crystal slurry.
4. And (3) regulating the pH value of the supersaturated crystal slurry to 8.77 by ammonia water at 70 ℃, filtering and drying to obtain the low-potassium industrial grade diammonium phosphate.
Example 4 ]
A method for producing low-potassium industrial grade ammonium phosphate by using medium-low grade high-potassium phosphorite comprises the following steps:
1. And (3) preparing a medium-low-grade high-potassium phosphorite with the potassium content of more than or equal to 2000ppm, producing crude phosphoric acid with the mass fraction of P 2O5 of 18% by a sulfuric acid method wet phosphoric acid method, cooling and aging at 70 ℃ for 12 hours to obtain the aging acid.
2. And (3) carrying out neutralization reaction on ammonia water and aging acid, controlling the pH value at the end point of the neutralization reaction to be 4.0, and filtering to obtain clear liquid.
3. Evaporating and concentrating the clear liquid, and cooling to 70 ℃ to obtain supersaturated crystal slurry.
4. And (3) regulating the pH value of the supersaturated crystal slurry to 8.77 by ammonia water at 70 ℃, filtering and drying to obtain the low-potassium industrial grade diammonium phosphate.
5. Dissolving low-potassium industrial grade diammonium phosphate with deionized water, adding phosphoric acid to adjust the pH to 4.2, evaporating, concentrating and filtering to obtain low-potassium industrial grade monoammonium phosphate.
< Comparative example >
A method for producing industrial grade ammonium phosphate by using medium-low grade high-potassium phosphorite comprises the following steps:
1. And (3) preparing the medium-low-grade high-potassium phosphorite with the potassium content of more than or equal to 2000ppm, and producing the crude phosphoric acid with the P 2O5 mass fraction of 26% by using the wet phosphoric acid of a sulfuric acid method.
2. And (3) carrying out neutralization reaction on ammonia water and crude phosphoric acid, controlling the pH at the end point of the neutralization reaction to be 4.2, and filtering to obtain clear liquid.
3. Evaporating and concentrating the clear liquid, and filtering to obtain industrial monoammonium phosphate.
The results of the detection and comparison of the K content of the low-potassium content industrial grade ammonium phosphate obtained in examples 1-4 and the K content of the industrial grade monoammonium phosphate obtained in the comparison example are shown in the following table 1:
from the table above, it can be seen that the purification process of examples 1 to 4 according to the present invention can effectively reduce the K content in industrial grade ammonium phosphate.
The above embodiments are only for illustrating the technical solution and features of the present invention, and are intended to be better implemented by those skilled in the art, but not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention are within the scope of the present invention, wherein the prior art is not specifically illustrated.
Claims (10)
1. The method for producing the low-potassium industrial grade ammonium phosphate salt by using the medium-low-grade high-potassium phosphorite is characterized by comprising the following steps of:
s1, preparing raw material high-potassium phosphorite, producing crude phosphoric acid by a sulfuric acid method wet phosphoric acid method, cooling and aging to obtain aging acid;
s2, carrying out neutralization reaction on an ammonia source and aging acid, controlling the reaction pH, and carrying out filter pressing on the reaction slurry after the reaction to obtain clear liquid;
s3, concentrating clear liquid through multi-effect evaporation, and cooling to obtain supersaturated crystal slurry;
S4, adjusting the pH value of the supersaturated crystal slurry through a pH regulator, filtering, and drying the filtered solids to obtain low-potassium industrial grade diammonium phosphate or adjusting the pH value of the filtered solids back through phosphoric acid to obtain low-potassium industrial grade monoammonium phosphate.
2. The method for producing low-potassium industrial grade ammonium phosphate by using medium-low-grade high-potassium phosphorite as claimed in claim 1, wherein the mass fraction of the crude phosphoric acid P 2O5 in the step S1 is 18% -26%.
3. The method for producing low-potassium industrial grade ammonium phosphate salt by using medium-low grade high-potassium phosphorite as claimed in claim 1, wherein the cooling aging temperature in the step S1 is 45-75 ℃, and the cooling aging time is 8-12h.
4. The method for producing low-potassium industrial grade ammonium phosphate salt by using medium-low grade high-potassium phosphorite according to claim 1, wherein the ammonia source in the step S2 is one or more of liquid ammonia, ammonia water and gaseous ammonia.
5. The method for producing low-potassium industrial grade ammonium phosphate by using medium-low grade high-potassium phosphorite as claimed in claim 1, wherein the neutralization reaction in the step S2 is controlled to have a pH value ranging from 3.5 to 4.5.
6. The method for producing low-potassium industrial grade ammonium phosphate salt by using medium-low grade high-potassium phosphorite as claimed in claim 1, wherein the temperature of the cooling crystallization in the step S3 is 60-75 ℃.
7. The method for producing low-potassium industrial grade ammonium phosphate salt by using medium-low grade high-potassium phosphorite as claimed in claim 1, wherein the pH regulator in the step S4 is one or more of liquid ammonia, ammonia water and gaseous ammonia.
8. The method for producing low-potassium industrial grade ammonium phosphate salt by using medium-low grade high-potassium phosphorite as claimed in claim 1, wherein the pH adjustment range of the saturated crystal slurry in the step S4 is 7-10.
9. The method for producing low-potassium industrial grade ammonium phosphate by using medium-low grade high-potassium phosphorite as claimed in claim 1, wherein the phosphoric acid used for the callback solid in the step S4 is refined phosphoric acid with the mass fraction of 75% or 85%.
10. The method for producing low-potassium industrial grade ammonium phosphate by using medium-low grade high-potassium phosphorite as claimed in claim 1, wherein the pH range of the phosphoric acid callback filter solid in the step S4 is 3.2-4.8.
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| CN202510928902.XA CN120423508A (en) | 2025-07-07 | 2025-07-07 | A method for producing low-potassium industrial-grade ammonium phosphate using medium- and low-grade high-potassium phosphate ore |
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| CN202510928902.XA CN120423508A (en) | 2025-07-07 | 2025-07-07 | A method for producing low-potassium industrial-grade ammonium phosphate using medium- and low-grade high-potassium phosphate ore |
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Citations (6)
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|---|---|---|---|---|
| CN102320585A (en) * | 2011-09-01 | 2012-01-18 | 贵州开磷（集团）有限责任公司 | Method for direct production of industrial-grade ammonium biphosphate by wet-process phosphoric acid |
| CN103569982A (en) * | 2013-11-08 | 2014-02-12 | 武汉工程大学 | Method for crystallizing large-grained industrial ammonium dihydrogen phosphate |
| CN111498821A (en) * | 2020-04-23 | 2020-08-07 | 湖北兴发化工集团股份有限公司 | Process and device for producing diammonium hydrogen phosphate and ammonium dihydrogen phosphate by taking phosphoric acid as raw material |
| CN115231536A (en) * | 2022-06-27 | 2022-10-25 | 佛山市德方纳米科技有限公司 | Preparation method of diammonium hydrogen phosphate and battery cathode material |
| CN115535976A (en) * | 2022-10-13 | 2022-12-30 | 中国科学院过程工程研究所 | A device system and method for resource recovery of potassium-containing phosphate rock |
| CN116425132A (en) * | 2023-04-21 | 2023-07-14 | 新洋丰农业科技股份有限公司 | Preparation method of high-quality industrial grade monoammonium phosphate |
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2025
- 2025-07-07 CN CN202510928902.XA patent/CN120423508A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320585A (en) * | 2011-09-01 | 2012-01-18 | 贵州开磷（集团）有限责任公司 | Method for direct production of industrial-grade ammonium biphosphate by wet-process phosphoric acid |
| CN103569982A (en) * | 2013-11-08 | 2014-02-12 | 武汉工程大学 | Method for crystallizing large-grained industrial ammonium dihydrogen phosphate |
| CN111498821A (en) * | 2020-04-23 | 2020-08-07 | 湖北兴发化工集团股份有限公司 | Process and device for producing diammonium hydrogen phosphate and ammonium dihydrogen phosphate by taking phosphoric acid as raw material |
| CN115231536A (en) * | 2022-06-27 | 2022-10-25 | 佛山市德方纳米科技有限公司 | Preparation method of diammonium hydrogen phosphate and battery cathode material |
| CN115535976A (en) * | 2022-10-13 | 2022-12-30 | 中国科学院过程工程研究所 | A device system and method for resource recovery of potassium-containing phosphate rock |
| CN116425132A (en) * | 2023-04-21 | 2023-07-14 | 新洋丰农业科技股份有限公司 | Preparation method of high-quality industrial grade monoammonium phosphate |
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