Preparation method of sulfenyl full-soluble potassium-added monoammonium
Through the preparation method of sulfur-based fully dissolved potassium-monoammonium, the problem of lack of potassium-based monoammonium phosphate was solved, and efficient and environmentally friendly potassium-monoammonium production was achieved, reducing production costs and improving product quality and environmentally friendly sex.
Patent Information
- Application Number
- CN202411657646.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-20
- Publication Date
- 2025-02-18
AI Technical Summary
The lack of potassium in the existing fertilizer market has caused limited crop growth. The production process of blended potassium-ammonium is high, the nutrients are uneven, and the environmental impact is great, and it is not suitable for chlorine-banned crops.
A preparation method of sulfur-based fully dissolved potassium monoammonium is adopted. Potassium chloride reacts with sulfuric acid to form potassium bisulfate, and then mixes it with a phosphoric acid solution and undergoes neutralization reaction. After multiple concentration and neutralization treatments, the final The granular sulfur-based fully dissolved potassium-monoammonium is produced by the granulation process.
The potassium-monoammonium product has achieved high purity, high total nutrients and moderate potassium content, which reduces production costs, and has no waste slag emissions throughout the process, which is harmless to the environment and has good social and economic benefits.
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Figure CN119462304A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to fertilizer, in particular to a method for preparing a sulfur-based fully soluble potassium-added monoammonium fertilizer. Background Art
[0002] At present, there are many monoammonium phosphates in the fertilizer market, and the technology is very mature. It is mainly used as a raw material for compound fertilizer factories to produce compound fertilizers. The disadvantage of monoammonium phosphate is that it can only provide nitrogen and phosphorus to crops, and lacks potassium, which will affect crop growth and farmers' enthusiasm for direct fertilization. There are simple mixed potassium monoammonium phosphate and chlorine-based potassium monoammonium phosphate on the market. The production process of mixed potassium monoammonium phosphate is mainly to add potassium chloride and potassium sulfate. This production process is costly, the nutrients are seriously uneven, there are great risks in the fertilization process, and there are waste residues discharged in the production process, which has an impact on the environment; the chlorine-based potassium monoammonium phosphate has a high chloride content and is not suitable for use on chlorine-ban crops. Summary of the invention
[0003] The present invention aims to solve the above technical problems, thereby providing a method for preparing sulfur-based fully soluble potassium monoammonium, reducing the cost of potassium monoammonium and reducing the cost of crop planting.
[0004] The present invention solves the technical problem and adopts the following technical solution: A method for preparing a sulfur-based fully soluble potassium-added monoammonium salt comprises the following steps: S1, take 1 part of potassium chloride by mass, add it to a sulfuric acid solution accounting for 0.7-0.8 of potassium chloride by volume, control the reaction temperature to 100-120°C, control the reaction time to 1 hour, and the product is liquid A and gas B, wherein A is potassium hydrogen sulfate liquid and B is hydrogen chloride; S2, take a phosphoric acid solution with a volume of 10 times that of potassium chloride, add it to the liquid A in step S1, mix thoroughly, and form a mixed solution C, which is potassium hydrogen sulfate and phosphoric acid; S3, neutralizing the mixed solution C obtained in step S2 with ammonia, adjusting the degree of neutralization to between 0.9 and 1.0, and concentrating the slurry after the primary neutralization three times in sequence, and performing secondary neutralization on the obtained slurry and ammonia, adjusting the degree of neutralization to between 1.5 and 1.6, to obtain slurry D, which is a mixed solution of ammonium sulfate, monoammonium hydrogen phosphate, diammonium phosphate and potassium sulfate, with the addition of urea; S4. The D slurry obtained in step S3 is subjected to a granulation process to produce granular sulfur-based fully soluble potassium-added monoammonium.
[0005] Compared with the prior art, the present invention using the above technical solution has the following beneficial effects: 1) The potassium monoammonium product is a sulfur-based product with the advantages of high purity, high total nutrients, moderate potassium content, and low production cost; 2) There is no waste discharge in the whole process, no impact on the environment, and it has good social and economic benefits.
[0006] Further, the optimization scheme of the present invention is: The gas B is absorbed by water to become hydrochloric acid.
[0007] In step S2, potassium hydrogen sulfate accounts for 14.7% and phosphoric acid accounts for 83.2%.
[0008] The mass concentration of the sulfuric acid is 93% or 98%.
[0009] The volume concentration of the phosphoric acid solution is 22%-24%.
[0010] The three stages of concentration are triple-effect concentration, double-effect concentration and single-effect concentration, respectively. In each stage of concentration, steam is introduced into a heater to heat the slurry, and water in the slurry is flashed out in a flash chamber.
[0011] In the slurry D, ammonium sulfate accounts for 8.2%, diammonium phosphate accounts for 60%, monoammonium phosphate accounts for 15%, and potassium sulfate accounts for 12.2%.
[0012] In the primary neutralization reaction, the mass ratio of the mixed liquid C to ammonia is 14:1; in the secondary neutralization reaction, the mass ratio of the mixed liquid C to ammonia is 45:1. BRIEF DESCRIPTION OF THE DRAWINGS
[0013] Figure 1 is a flow chart of an embodiment of the present invention. DETAILED DESCRIPTION
[0014] The present invention is further described in detail below with reference to the accompanying drawings and embodiments. Embodiment 1
[0015] S1. Take 1 part of potassium chloride by mass and add it to 0.7 part of sulfuric acid by volume of potassium chloride. The mass concentration of sulfuric acid is 93%. Potassium chloride and sulfuric acid react in a reaction tank. Steam is introduced into the reaction tank. The reaction temperature is controlled at 100-120°C. The reaction time is controlled for 1 hour. The products are liquid A and gas B, wherein A is potassium hydrogen sulfate liquid, B is hydrogen chloride, and gas B becomes hydrochloric acid after being absorbed by water.
[0016] S2. Take a phosphoric acid solution with a volume ratio of 10 times that of potassium chloride, add it to the liquid A in step S1, mix thoroughly, and form a mixed solution C, where C is a potassium hydrogen sulfate solution.
[0017] S3. The mixed solution C obtained in step S2 is subjected to a neutralization reaction with ammonia, and the degree of neutralization is adjusted to between 0.9 and 1.0. The slurry after the first neutralization is a solution of monoammonium phosphate, potassium sulfate and ammonium sulfate, wherein: the proportion of monoammonium phosphate is 75%, the proportion of potassium sulfate is 15.6%, and the proportion of ammonium sulfate is 8.2%. The slurry is sequentially concentrated by three effects, two effects and one effects, and the obtained slurry is subjected to a second neutralization with ammonia, and the degree of neutralization is adjusted to between 1.3 and 1.5 to obtain slurry D. Slurry D is a mixed solution of ammonium sulfate, diammonium phosphate, diammonium phosphate and potassium sulfate, wherein: the proportion of ammonium sulfate is 8.6%, the proportion of diammonium phosphate is 60%, the proportion of monoammonium phosphate is 15%, and the proportion of potassium sulfate is 15.6%.
[0018] S4. The D slurry obtained in step S3 is subjected to a granulation process, which makes full use of the process of granular monoammonium phosphate granulation. The process of granular monoammonium phosphate granulation is a prior art. After granulation and screening, granular sulfur-based fully soluble potassium-added monoammonium phosphate is produced. Embodiment 2
[0019] S1, take 1 part of potassium chloride by mass, add it to 0.8 part of sulfuric acid by volume of potassium chloride, the mass concentration of sulfuric acid is 93%, potassium chloride and sulfuric acid react in a reaction tank, steam is introduced into the reaction tank, the reaction temperature is controlled at 100-120 ° C, the reaction time is controlled at 1, the product is liquid A and gas B, wherein A is potassium hydrogen sulfate liquid, B is hydrogen chloride, and gas B becomes hydrochloric acid after being absorbed by water; S3, take a phosphoric acid solution with a volume of 10 times that of potassium chloride, add it to the liquid A in step S1, mix thoroughly, and form a mixed solution C, where C is a potassium hydrogen sulfate solution; S3. The mixed solution C obtained in step S2 is subjected to a neutralization reaction with ammonia, and the degree of neutralization is adjusted to between 0.9 and 1.0. The slurry after the first neutralization is a solution of monoammonium phosphate, potassium sulfate and ammonium sulfate, wherein: the proportion of monoammonium phosphate is 71%, the proportion of potassium sulfate is 15.6%, and the proportion of ammonium sulfate is 8.3%. The slurry is sequentially concentrated by three effects, two effects and one effects, and the obtained slurry is subjected to a second neutralization with ammonia, and the degree of neutralization is adjusted to between 1.8 and 2.0 to obtain slurry D. Slurry D is a mixed solution of ammonium sulfate, diammonium phosphate, diammonium phosphate and potassium sulfate, wherein: the proportion of ammonium sulfate is 8.6%, the proportion of diammonium phosphate is 60%, the proportion of monoammonium phosphate is 15%, and the proportion of potassium sulfate is 15.6%.
[0020] S4, the D slurry obtained in step S3 is subjected to a granulation process, which makes full use of the granulation process of granular monoammonium phosphate, and undergoes granulation and screening to produce granular sulfur-based fully soluble potassium-added monoammonium phosphate. Embodiment 3
[0021] S1, take 1 part of potassium chloride by mass, add it to 0.9 part of sulfuric acid by volume of potassium chloride, the mass concentration of sulfuric acid is 93%, potassium chloride and sulfuric acid react in a reaction tank, steam is introduced into the reaction tank, the reaction temperature is controlled at 100-120 ° C, the reaction time is controlled for 1 hour, the product is liquid A and gas B, wherein A is potassium hydrogen sulfate liquid, B is hydrogen chloride, and gas B becomes hydrochloric acid after being absorbed by water; S2, take a phosphoric acid solution with a volume of 10 times the potassium chloride, add it to the liquid A in step S1, mix thoroughly, and form a mixed solution C, where C is a potassium hydrogen sulfate solution; S3. The mixed solution C obtained in step S2 is subjected to a neutralization reaction with ammonia, and the degree of neutralization is adjusted to between 0.9 and 1.0. The slurry after the first neutralization is a solution of monoammonium phosphate, potassium sulfate and ammonium sulfate, wherein: the proportion of monoammonium phosphate is 71%, the proportion of potassium sulfate is 15.6% and the proportion of ammonium sulfate is 8.4%. The slurry is sequentially concentrated by three effects, two effects and one effects, and the obtained slurry is subjected to a second neutralization with ammonia, and the degree of neutralization is adjusted to between 1.5 and 1.6 to obtain slurry D. Slurry D is a mixed solution of ammonium sulfate, diammonium phosphate, diammonium phosphate and potassium sulfate, wherein: the proportion of ammonium sulfate is 8.3%, the proportion of diammonium phosphate is 60%, the proportion of monoammonium phosphate is 15%, and the proportion of potassium sulfate is 15.6%.
[0022] S4, the D slurry obtained in step S3 is subjected to a granulation process, which makes full use of the granulation process of granular monoammonium phosphate, and undergoes granulation and screening to produce granular sulfur-based fully soluble potassium-added monoammonium phosphate. Embodiment 4
[0023] S1, take 1 part of potassium chloride by mass, add it to 0.7 part of sulfuric acid by volume of potassium chloride, the mass concentration of sulfuric acid is 95%, potassium chloride and sulfuric acid react in a reaction tank, steam is introduced into the reaction tank, the reaction temperature is controlled at 100-120 ° C, the reaction time is controlled at 1.0 hour, the product is liquid A and gas B, wherein A is potassium hydrogen sulfate liquid, B is hydrogen chloride, and gas B becomes hydrochloric acid after being absorbed by water; S2, take a phosphoric acid solution with a volume of 10 times the potassium chloride, add it to the liquid A in step S1, mix thoroughly, and form a mixed solution C, where C is a potassium hydrogen sulfate solution; S3. The mixed solution C obtained in step S2 is subjected to a neutralization reaction with ammonia, and the degree of neutralization is adjusted to between 0.9 and 1.0. The slurry after the first neutralization is a solution of monoammonium phosphate, potassium sulfate and ammonium sulfate, wherein: the proportion of monoammonium phosphate is 71%, the proportion of potassium sulfate is 15.6%, and the proportion of ammonium sulfate is 8.2%. The slurry is sequentially concentrated by three effects, two effects and one effects, and the obtained slurry is subjected to a second neutralization with ammonia, and the degree of neutralization is adjusted to between 1.5 and 1.6 to obtain slurry D. Slurry D is a mixed solution of ammonium sulfate, monoammonium hydrogen phosphate, diammonium phosphate and potassium sulfate, wherein: the proportion of ammonium sulfate is 8.2%, the proportion of diammonium hydrogen phosphate is 60%, the proportion of monoammonium hydrogen phosphate is 15%, and the proportion of potassium sulfate is 15.6%.
[0024] S4, the D slurry obtained in step S3 is subjected to a granulation process, which makes full use of the granulation process of granular monoammonium phosphate, and undergoes granulation and screening to produce granular sulfur-based fully soluble potassium-added monoammonium phosphate. Embodiment 5
[0025] S1, take 1 part of potassium chloride by mass, add it to 0.8 part of sulfuric acid by volume of potassium chloride, the mass concentration of sulfuric acid is 95%, potassium chloride and sulfuric acid react in a reaction tank, steam is introduced into the reaction tank, the reaction temperature is controlled at 100-120 ° C, the reaction time is controlled at 1.0 hour, the product is liquid A and gas B, wherein A is potassium hydrogen sulfate liquid, B is hydrogen chloride, and gas B becomes hydrochloric acid after being absorbed by water; S2, take a phosphoric acid solution with a volume of 10 times the potassium chloride, add it to the liquid A in step S1, mix thoroughly, and form a mixed solution C, where C is a potassium hydrogen sulfate solution; S3. The mixed solution C obtained in step S2 is subjected to a neutralization reaction with ammonia, and the degree of neutralization is adjusted to between 0.9 and 1.0. The slurry after the first neutralization is a solution of monoammonium phosphate, potassium sulfate and ammonium sulfate, wherein: monoammonium phosphate accounts for 71%), potassium sulfate accounts for 15.6%, and ammonium sulfate accounts for 8.3%. The slurry is sequentially concentrated by three effects, two effects and one effects, and the obtained slurry is subjected to a second neutralization with ammonia, and the degree of neutralization is adjusted to between 1.5 and 1.6 to obtain slurry D. Slurry D is a mixed solution of ammonium sulfate, monoammonium hydrogen phosphate, diammonium phosphate and potassium sulfate, wherein: ammonium sulfate accounts for 8.2%, diammonium hydrogen phosphate accounts for 60%, monoammonium hydrogen phosphate accounts for 15%, and potassium sulfate accounts for 15.6%.
[0026] S4, the D slurry obtained in step S3 is subjected to a granulation process, which makes full use of the granulation process of granular monoammonium phosphate, and undergoes granulation and screening to produce granular sulfur-based fully soluble potassium-added monoammonium phosphate. Embodiment 6
[0027] S1, 1 part of potassium chloride by mass is added to 0.9 part of sulfuric acid by volume of potassium chloride, the mass concentration of sulfuric acid is 95%, potassium chloride and sulfuric acid react in a reaction tank, steam is introduced into the reaction tank, the reaction temperature is controlled at 100-120°C, the reaction time is controlled at 1.0 hour, and the products are liquid A and gas B, wherein A is potassium hydrogen sulfate liquid, B is hydrogen chloride, and gas B is absorbed by water to become hydrochloric acid; S2, take a phosphoric acid solution with a volume of 10 times the potassium chloride, add it to the liquid A in step S1, mix thoroughly, and form a mixed solution C, where C is a potassium hydrogen sulfate solution; S3. The mixed solution C obtained in step S2 is subjected to a neutralization reaction with ammonia, and the degree of neutralization is adjusted to between 0.9 and 1.0. The slurry after the first neutralization is a solution of monoammonium phosphate, potassium sulfate and ammonium sulfate, wherein: monoammonium phosphate accounts for 71%, potassium sulfate accounts for 15.6%, and ammonium sulfate accounts for 8.4%. The slurry is sequentially concentrated by three effects, two effects and one effects, and the obtained slurry is subjected to a second neutralization with ammonia, and the degree of neutralization is adjusted to between 1.5 and 1.6 to obtain slurry D. Slurry D is a mixed solution of ammonium sulfate, monoammonium hydrogen phosphate, diammonium phosphate and potassium sulfate, wherein: ammonium sulfate accounts for 8.3%, monoammonium hydrogen phosphate accounts for 15%, diammonium phosphate accounts for 60%, and potassium sulfate accounts for 15.6%.
[0028] S4, the D slurry obtained in step S3 is subjected to a granulation process, which makes full use of the granulation process of granular monoammonium phosphate, and undergoes granulation and screening to produce granular sulfur-based fully soluble potassium-added monoammonium phosphate.
[0029] Cost of the invention:
[0030] It can be seen from the table that the low-temperature conversion method has obvious cost advantages.
[0031] The present invention adopts low-cost wet-process phosphoric acid as a raw material, undergoes a desulfurization procedure, and reacts with sulfuric acid and potassium chloride in a sulfur-based spraying low-temperature conversion process to produce a potassium bisulfate mixed solution, which is then neutralized with ammonia to obtain monoammonium phosphate, potassium sulfate and ammonium sulfate solutions, which are concentrated and neutralized with ammonia again to produce a fertilizer mainly containing monoammonium phosphate and diammonium phosphate solutions, supplemented by potassium sulfate and ammonium sulfate, and then undergoes spraying coating granulation technology to produce a fertilizer with smooth particles. The sulfur-based potassium-ammonium product prepared by the present invention has the advantages of low cost, high purity, high total nutrients, and moderate potassium content, no waste residue discharge in the whole process, no impact on the environment, and good social and economic benefits.
Claims
1. A method for preparing a sulfur-based fully soluble potassium-added monoammonium salt, comprising the following steps: S1. Take 1 part of potassium chloride by mass and add it to a sulfuric acid solution with a volume fraction of 0.7-0.8 of potassium chloride. Control the reaction temperature to 100-120°C and the reaction time to 1 hour. The products are liquid A and gas B. A is potassium bisulfate liquid, B is hydrogen chloride; S2, take a phosphoric acid solution with a volume of 10 times that of potassium chloride, add it to the liquid A in step S1, mix thoroughly, and form a mixed solution C, which is potassium hydrogen sulfate and phosphoric acid; S3, neutralizing the mixed solution C obtained in step S2 with ammonia, adjusting the degree of neutralization to between 0.9 and 1.0, and concentrating the slurry after the primary neutralization three times in sequence, and performing secondary neutralization on the obtained slurry and ammonia, adjusting the degree of neutralization to between 1.5 and 1.6, to obtain slurry D, which is a mixed solution of ammonium sulfate, monoammonium hydrogen phosphate, diammonium phosphate and potassium sulfate, with the addition of urea; S4. The D slurry obtained in step S3 is subjected to a granulation process to produce granular sulfur-based fully soluble potassium-added monoammonium.
2. The method for preparing the sulfur-based fully soluble potassium-added monoammonium according to claim 1, characterized in that: The gas B is absorbed by water to become hydrochloric acid.
3. The method for preparing the sulfur-based fully soluble potassium-added monoammonium according to claim 1, characterized in that: In step S2, potassium hydrogen sulfate accounts for 14.7% and phosphoric acid accounts for 83.2%.
4. The method for preparing the sulfur-based fully soluble potassium-added monoammonium according to claim 1, characterized in that: The mass concentration of the sulfuric acid is 93% or 98%.
5. The method for preparing the sulfur-based fully soluble potassium-added monoammonium according to claim 1, characterized in that: The volume concentration of the phosphoric acid solution is 22%-24%.
6. The method for preparing the sulfur-based fully soluble potassium-added monoammonium according to claim 1, characterized in that: The three stages of concentration are triple-effect concentration, double-effect concentration and single-effect concentration, respectively. In each stage of concentration, steam is introduced into a heater to heat the slurry, and water in the slurry is flashed out in a flash chamber.
7. The method for preparing the sulfur-based fully soluble potassium-added monoammonium according to claim 1, characterized in that: In the slurry D, ammonium sulfate accounts for 8.2%, diammonium phosphate accounts for 60%, monoammonium phosphate accounts for 15%, and potassium sulfate accounts for 12.2%.
8. The method for preparing the sulfur-based fully soluble potassium-added monoammonium according to claim 1, characterized in that: In the primary neutralization reaction, the mass ratio of the mixed liquid C to ammonia is 14:1; in the secondary neutralization reaction, the mass ratio of the mixed liquid C to ammonia is 45:1.