CN106588128B - Production method of large-particle ammonium sulfate - Google Patents
Production method of large-particle ammonium sulfate Download PDFInfo
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- CN106588128B CN106588128B CN201611115585.7A CN201611115585A CN106588128B CN 106588128 B CN106588128 B CN 106588128B CN 201611115585 A CN201611115585 A CN 201611115585A CN 106588128 B CN106588128 B CN 106588128B
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Abstract
A method for producing large-particle ammonium sulfate comprises the following steps: step 1: mixing the residue slurry generated in the process of producing industrial phosphoric acid by wet-process phosphoric acid, sulfuric acid and tail washing liquid according to the proportion of 0.5-3: 10: 0.1-3 to prepare mixed acid; step 2: adding gas ammonia or liquid ammonia or ammonia water into the mixed acid, and performing neutralization reaction to obtain ammonium sulfate slurry; and step 3: feeding the ammonium sulfate slurry into a granulator, granulating and drying; and 4, step 4: sieving and grading the large-particle ammonium sulfate obtained by granulation; and 5: sieving to obtain finished ammonium sulfate granules with the particle size of 2-4.5 mm, processing to obtain finished products, and packaging; step 6: and (3) circularly washing the screened dust-containing tail gas with water, adding sulfuric acid into washing water according to a ratio of 4-5: 1 to convert the washing water into dilute sulfuric acid, washing the granulated ammonia-containing tail gas, and washing the ammonia-containing tail gas with dilute sulfuric acid to obtain tail washing liquid containing sulfuric acid and ammonium sulfate for preparing mixed acid.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a production method for producing large-particle ammonium sulfate by matching slag slurry generated in the process of producing industrial phosphoric acid by wet-process phosphoric acid with sulfuric acid.
Background
Ammonium sulfate is a good sulfur-containing nitrogen fertilizer in agriculture, sulfur is a medium nutrient element required by crops, and the sulfur-containing fertilizer not only improves the crop yield, but also can improve the crop quality, and has a large domestic consumption in the United states, Japan and the like. Most of ammonium sulfate on the market is high-purity crystal ammonium sulfate, the diameter of the ammonium sulfate is below 1mm, and single ammonium sulfate is difficult to granulate to obtain large-particle ammonium sulfate. In the present day of agricultural high mechanization, small crystal ammonium sulfate can not meet the mechanization requirement. Therefore, the fertilizer can be used as a raw material for producing compound fertilizer and cannot be applied singly.
The cost of the process for producing industrial monoammonium phosphate by wet-process phosphoric acid is far lower than that of the production process of the traditional method, and the traditional method is basically replaced by the process at present, but the process has the defect that a matched agricultural monoammonium phosphate device or compound fertilizer device is needed to digest mother liquor and slag pulp generated in the production process. The nutrient content of the mother liquor is high, the direct production of the agricultural monoammonium phosphate or the compound fertilizer cannot affect the nutrient of the agricultural monoammonium phosphate or the compound fertilizer, but the impurity content in the slag slurry is high, the viscosity is strong, and the blending amount is large when the mother liquor is used for producing the agricultural monoammonium phosphate or the compound fertilizer, so that the nutrient of the agricultural monoammonium phosphate and the compound fertilizer is unqualified.
Disclosure of Invention
The invention aims to solve the technical problem of providing large-particle ammonium sulfate and a production method thereof, which can effectively utilize the characteristic that slurry generated in the process of producing industrial monoammonium phosphate by wet-process phosphoric acid has strong viscosity, and the slurry is used as a binder for producing the large-particle ammonium sulfate, so that the problem of difficult granulation of the pure ammonium sulfate is solved, and the residual nitrogen and phosphorus in the slurry are effectively utilized.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: the large-particle ammonium sulfate contains 19-20% of N, 22-23% of S, 1-3% of P2O5, 1-2% of water, 2-4.5 mm of particle size not less than 90% and strength not less than 40N.
The production method of the large-particle ammonium sulfate comprises the following steps:
step 1: mixing slag slurry generated in the process of producing industrial phosphoric acid by wet-process phosphoric acid or solid waste slag generated in the process of producing industrial phosphoric acid by wet-process phosphoric acid by filter pressing, and mixing the slag slurry, sulfuric acid and tail washing liquid according to the proportion of 0.5-3: 10: 0.1-3 to prepare mixed acid;
step 2: adding the mixed acid obtained in the step 1 into gas ammonia or liquid ammonia or ammonia water, carrying out neutralization reaction, and controlling the pH value to be 3.0-6.0 to obtain ammonium sulfate slurry;
and step 3: feeding the ammonium sulfate slurry obtained in the step (2) into a granulator, and granulating and drying the ammonium sulfate slurry and master batch in the granulator to obtain large-particle ammonium sulfate;
and 4, step 4: screening the ammonium sulfate granules obtained in the step (3), returning granules with the particle size of less than 2mm to the granulator to serve as a master batch, crushing granules with the particle size of more than 4.5mm, returning to the granulator to serve as the master batch, and directly supplementing large-particle ammonium sulfate crystals to the granulator to serve as the master batch;
and 5: carrying out post-treatment on finished ammonium sulfate particles with the particle size of 2-4.5 mm obtained by screening in the step 4 to obtain large-particle ammonium sulfate;
step 6: and (3) circularly washing the dust-containing tail gas screened in the step (3) with water, adding sulfuric acid into washing water according to a ratio of 4-5: 1 to convert the washing water into dilute sulfuric acid, washing the granulated ammonia-containing tail gas with the dilute sulfuric acid, washing the ammonia-containing tail gas with the dilute sulfuric acid to obtain tail washing liquid containing sulfuric acid and ammonium sulfate, and returning to the step (1) for preparing mixed acid.
Further, the slag slurry in the step 1 is slag slurry generated in the process of producing industrial phosphoric acid by wet-process phosphoric acid, or solid waste slag generated by filter pressing in the process of producing industrial phosphoric acid by wet-process phosphoric acid, wherein Fe2O3%+Al2O3The content of percent + MgO% is 10-30%, and the concentration of sulfuric acid is 50-99%.
Further, the ammonium sulfate granulation in the step 3 is a spraying coating granulation process, and the temperature in the granulator is less than or equal to 200 ℃.
Further, the concentration of the dilute sulfuric acid prepared for washing the ammonia-containing tail gas in the step 6 is 10-30%.
The production method of large-particle ammonium sulfate provided by the invention has the following beneficial effects:
1. effectively utilizes the slag slurry generated in the process of producing industrial monoammonium phosphate by wet-process phosphoric acid, and solves the problem of difficult granulation of pure ammonium sulfate.
2. The process conditions are easy to control, the operation is convenient, the product quality is good, elements such as nitrogen, phosphorus and the like in the slag slurry enter the large-particle ammonium sulfate product, the resources are effectively utilized, and no waste is generated.
Drawings
The invention is further illustrated by the following examples in conjunction with the accompanying drawings:
FIG. 1 is a process flow diagram of the method of the present invention.
Detailed Description
Example one
As shown in fig. 1, a method for producing large-particle ammonium sulfate comprises the following steps:
step 1: mixing the slag slurry generated in the process of producing industrial phosphoric acid by wet-process phosphoric acid or the solid waste slag generated by filter pressing in the process of producing industrial phosphoric acid by wet-process phosphoric acid, sulfuric acid and tail washing liquid according to the ratio of 1:10: 1, mixing the raw materials in a ratio to prepare mixed acid;
step 2: adding gas ammonia into the mixed acid obtained in the step 1, carrying out neutralization reaction, and controlling the pH value to be 3.0 to obtain ammonium sulfate slurry;
and step 3: feeding the ammonium sulfate slurry obtained in the step (2) into a granulator, granulating and drying the ammonium sulfate slurry and master batch in the granulator, and controlling the temperature in the granulator to be 160-180 ℃ to obtain large-particle ammonium sulfate;
and 4, step 4: screening the large-particle ammonium sulfate obtained in the step (3), returning particles with the particle size of less than 2mm to the granulator as a master batch, crushing particles with the particle size of more than 4.5mm, returning to the granulator as the master batch, and directly supplementing large-particle ammonium sulfate crystals into the granulator as the master batch;
and 5: performing post-treatment (cooling, coating and grading) on the finished ammonium sulfate granules with the particle size of 2-4.5 mm obtained by sieving in the step 4 to obtain finished products, and packaging;
step 6: after the screened dust-containing tail gas is circularly washed by water, adding sulfuric acid into washing water to convert into 20% dilute sulfuric acid, washing the granulated ammonia-containing tail gas by the dilute sulfuric acid, washing the ammonia-containing tail gas by the dilute sulfuric acid to obtain tail washing liquid containing sulfuric acid and ammonium sulfate, and returning to the step 1 for preparing mixed acid;
in step 1, Fe is contained in the slurry2O3%+Al2O3The percent + MgO percent is about 17 percent (about ten percent of upper and lower floating percent and mass percent), and the slag slurry contains 55 percent of water (mass percent).
In step 1, the mass concentration of the sulfuric acid used is 50%.
In the step 6, after the density of the tail washing liquid is 1.20-1.25 g/ml, the tail washing liquid is taken out to be used for preparing the mixed acid in the step 1, and the slag slurry, the sulfuric acid and the tail washing liquid are mixed according to the volume ratio of 1:10: 1, mixing with acid.
The prepared large-particle ammonium sulfate has the N content of 18.5%, the S content of 22.8%, the P2O5 content of 1.5%, the water content of 1.1%, the particle size of 2-4.5 mm which is more than or equal to 90% and the strength which is more than or equal to 40N.
Example two
As shown in fig. 1, a method for producing large-particle ammonium sulfate comprises the following steps:
step 1: mixing the slurry generated in the process of producing industrial phosphoric acid by wet-process phosphoric acid, sulfuric acid and tail washing liquid according to the proportion of 1:10:0.6 to prepare mixed acid;
step 2: adding gas ammonia into the mixed acid obtained in the step 1, carrying out neutralization reaction, and controlling the pH value to be 4.0 to obtain ammonium sulfate slurry;
and step 3: feeding the ammonium sulfate slurry obtained in the step (2) into a granulator, granulating and drying the ammonium sulfate slurry and master batch in the granulator, and controlling the temperature in the granulator to be 180-200 ℃ to obtain large-particle ammonium sulfate;
and 4, step 4: screening the large-particle ammonium sulfate obtained in the step (3), returning particles with the particle size of less than 2mm to the granulator as a master batch, crushing particles with the particle size of more than 4.5mm, returning to the granulator as the master batch, and directly supplementing large-particle ammonium sulfate crystals into the granulator as the master batch;
and 5: performing subsequent further treatment (cooling, coating and grading) on the finished ammonium sulfate granules with the particle size of 2-4.5 mm obtained by sieving in the step 4 to obtain finished products, and packaging;
step 6: after the screened dust-containing tail gas is circularly washed by water, adding sulfuric acid into washing water to convert into 20% dilute sulfuric acid, washing the granulated ammonia-containing tail gas, washing the ammonia-containing tail gas by the dilute sulfuric acid to obtain tail washing liquid containing sulfuric acid and ammonium sulfate, and returning to the step 1 for preparing mixed acid;
in step 1, Fe is contained in the slurry2O3%+Al2O3The percent + MgO percent is approximately equal to 17 percent (the upper and lower floating percent is about fifteen percent, the mass percent), and the slag slurry contains 55 percent of water (the mass percent).
In step 1, the mass concentration of the sulfuric acid used is 60%.
And 6, after the density of the tail washing liquid is 1.20-1.25 g/ml, taking out the tail washing liquid for preparing the mixed acid in the step 1.
The prepared large-particle ammonium sulfate has the N content of 19.0 percent, the S content of 22.6 percent, the P2O5 content of 1.4 percent, the water content of 1.3 percent, the particle size of 2-4.5 mm which is more than or equal to 90 percent and the strength which is more than or equal to 40N.
EXAMPLE III
As shown in fig. 1, a method for producing large-particle ammonium sulfate comprises the following steps:
step 1: mixing the slurry generated in the process of producing industrial phosphoric acid by wet-process phosphoric acid, sulfuric acid and tail washing liquid according to the proportion of 0.8:10:1 to prepare mixed acid;
step 2: adding gas ammonia into the mixed acid obtained in the step 1, carrying out neutralization reaction, and controlling the pH value to be 5.0 to obtain ammonium sulfate slurry;
and step 3: feeding the ammonium sulfate slurry obtained in the step (2) into a granulator, granulating and drying the ammonium sulfate slurry and master batch in the granulator, and controlling the temperature in the granulator to be 180-200 ℃ to obtain large-particle ammonium sulfate;
and 4, step 4: sieving and grading the large-particle ammonium sulfate obtained in the step (3), returning particles with the particle size of less than 2mm to a granulator to serve as a master batch, crushing particles with the particle size of more than 4.5mm, returning to the granulator to serve as the master batch, and directly supplementing large-particle ammonium sulfate crystals to the granulator to serve as the master batch;
and 5: performing post-treatment (cooling, coating and grading) on the finished ammonium sulfate granules with the particle size of 2-4.5 mm obtained by sieving in the step 4 to obtain finished products, and packaging;
step 6: after the screened dust-containing tail gas is circularly washed by water, adding sulfuric acid into washing water to convert into 20% dilute sulfuric acid, washing the granulated ammonia-containing tail gas by the dilute sulfuric acid, washing the ammonia-containing tail gas by the dilute sulfuric acid to obtain tail washing liquid containing sulfuric acid and ammonium sulfate, and returning to the step 1 for preparing mixed acid;
in step 1, Fe is contained in the slurry2O3%+Al2O3The percentage of MgO is approximately equal to 17 percent (mass percentage), and the slag slurry contains 55 percent of water (mass percentage).
In step 1, the mass concentration of the sulfuric acid used is 70%.
In the step 6, after the density of the tail washing liquid is 1.20-1.25 g/ml, the tail washing liquid is taken out to be used for preparing the mixed acid in the step 1, and the slag slurry, the sulfuric acid and the tail washing liquid are mixed according to the volume ratio of 1:10: 1, mixing with acid.
The prepared large-particle ammonium sulfate has the N content of 19.6 percent, the S content of 22.4 percent, the P2O5 content of 1.4 percent, the water content of 1.6 percent, the particle size of 2-4.5 mm which is more than or equal to 90 percent and the strength which is more than or equal to 40N.
Example four
As shown in fig. 1, a method for producing large-particle ammonium sulfate comprises the following steps:
step 1: mixing the slurry generated in the process of producing industrial phosphoric acid by wet-process phosphoric acid with sulfuric acid and tail washing liquid according to the proportion of 1:10:2 to prepare mixed acid;
step 2: adding gas ammonia into the mixed acid obtained in the step 1, carrying out neutralization reaction, and controlling the pH value to be 6.0 to obtain ammonium sulfate slurry;
and step 3: feeding the ammonium sulfate slurry obtained in the step (2) into a granulator, granulating and drying the ammonium sulfate slurry and master batch in the granulator, and controlling the temperature in the granulator to be 160-180 ℃ to obtain large-particle ammonium sulfate;
and 4, step 4: sieving and grading the large-particle ammonium sulfate obtained in the step (3), returning particles with the particle size of less than 2mm to a granulator to serve as a master batch, crushing particles with the particle size of more than 4.5mm, returning to the granulator to serve as the master batch, and directly supplementing large-particle ammonium sulfate crystals to the granulator to serve as the master batch;
and 5: performing subsequent further treatment (cooling, coating and grading) on the finished ammonium sulfate granules with the particle size of 2-4.5 mm obtained by sieving in the step 4 to obtain finished products, and packaging;
step 6: after the screened dust-containing tail gas is circularly washed by water, adding sulfuric acid into washing water to convert into 20% dilute sulfuric acid, washing the granulated ammonia-containing tail gas, washing the ammonia-containing tail gas by the dilute sulfuric acid to obtain tail washing liquid containing sulfuric acid and ammonium sulfate, and returning to the step 1 for preparing mixed acid;
in step 1, Fe is contained in the slurry2O3%+Al2O3The percentage of MgO is approximately equal to 17 percent (mass percentage), and the slag slurry contains 55 percent of water (mass percentage).
In step 1, the mass concentration of the sulfuric acid used is 60%.
In the step 6, after the density of the tail washing liquid is 1.20-1.25 g/ml, the tail washing liquid is taken out to be used for preparing the mixed acid in the step 1, and the slag slurry, the sulfuric acid and the tail washing liquid are mixed according to the volume ratio of 1:10: 1, mixing with acid.
The prepared large-particle ammonium sulfate has the N content of 19.8 percent, the S content of 22.0 percent, the P2O5 content of 1.6 percent, the water content of 2.0 percent, the particle size of 2-4.5 mm which is more than or equal to 90 percent and the strength which is more than or equal to 40N.
The specific implementation of the present invention is not limited by the above embodiments, and it is within the protection scope of the present invention as long as various insubstantial modifications are made by using the method concept and technical scheme of the present invention, or the concept and technical scheme of the present invention are directly applied to other occasions without modification.
Claims (1)
1. A production method of large-particle ammonium sulfate is characterized in that: the method comprises the following steps:
step 1: mixing slag slurry generated in the process of producing industrial phosphoric acid by using wet-process phosphoric acid or solid waste residues generated by filter pressing in the process of producing industrial phosphoric acid by using wet-process phosphoric acid, sulfuric acid and tail washing liquid according to the proportion of 0.5-3: 10: 0.1-3 to prepare mixed acid, wherein the slag slurry generated in the step 1 is slag slurry generated in the process of producing industrial phosphoric acid by using wet-process phosphoric acid or solid waste residues generated by filter pressing in the process of producing industrial phosphoric acid by using wet-process phosphoric acid, wherein Fe2O3%+Al2O3The content of percent + MgO is 10-30%, and the concentration of sulfuric acid is 50-99%;
step 2: adding the mixed acid obtained in the step 1 into gas ammonia or liquid ammonia or ammonia water, carrying out neutralization reaction, controlling the pH value to be 3.0-6.0, and obtaining ammonium sulfate slurry, wherein ammonium sulfate granulation in the step 3 is a spray coating granulation process, and the temperature in a granulator is less than or equal to 200 ℃;
and step 3: feeding the ammonium sulfate slurry obtained in the step (2) into a granulator, and granulating and drying the ammonium sulfate slurry and master batch in the granulator to obtain large-particle ammonium sulfate;
and 4, step 4: screening the ammonium sulfate granules obtained in the step (3), returning granules with the particle size of less than 2mm to the granulator to serve as a master batch, crushing granules with the particle size of more than 4.5mm, returning to the granulator to serve as the master batch, and directly supplementing large-particle ammonium sulfate crystals to the granulator to serve as the master batch;
and 5: carrying out post-treatment on finished ammonium sulfate particles with the particle size of 2-4.5 mm obtained by screening in the step 4 to obtain large-particle ammonium sulfate;
step 6: and (3) circularly washing the dust-containing tail gas screened in the step (3) with water, adding sulfuric acid into washing water according to a ratio of 4-5: 1 to convert the washing water into dilute sulfuric acid, washing the granulated ammonia-containing tail gas with the dilute sulfuric acid, washing the ammonia-containing tail gas with the dilute sulfuric acid to obtain tail washing liquid containing sulfuric acid and ammonium sulfate, returning to the step (1) for preparing mixed acid, wherein the concentration of the dilute sulfuric acid prepared for washing the ammonia-containing tail gas in the step (6) is 10-30%.
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| CN112403391A (en) * | 2020-10-16 | 2021-02-26 | 湖北三宁化工股份有限公司 | Binder for producing large-particle ammonium sulfate and preparation method thereof |
| CN114180994B (en) * | 2021-12-29 | 2022-08-09 | 连云港钧格环境科技有限公司 | Production process and equipment for large-particle ammonium sulfate product |
| CN114735720B (en) * | 2022-04-25 | 2023-08-18 | 云南云天化云峰化工有限公司 | Method and system for producing granular ammonium sulfate by rotary drum granulation through cyclic neutralization method |
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| CN104418626A (en) * | 2013-08-26 | 2015-03-18 | 山东聊城鲁西化工第五化肥有限公司 | Method for producing sulfur-based composite fertilizer by using monoammonium phosphate instead of phosphoric acid |
| CN103626528A (en) * | 2013-11-28 | 2014-03-12 | 瓮福（集团）有限责任公司 | Method for producing granular ammonium sulphate by using phosphorus-containing wastewater |
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