CN109896509B - Method for pre-treating and strengthening wet-process phosphoric acid extraction reaction - Google Patents
Method for pre-treating and strengthening wet-process phosphoric acid extraction reaction Download PDFInfo
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- CN109896509B CN109896509B CN201910322018.6A CN201910322018A CN109896509B CN 109896509 B CN109896509 B CN 109896509B CN 201910322018 A CN201910322018 A CN 201910322018A CN 109896509 B CN109896509 B CN 109896509B
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Abstract
The invention discloses a method for pre-treating and strengthening wet-process phosphoric acid extraction reaction, which takes a product which can be produced in large scale by a wet-process phosphoric acid production enterprise as a raw material of a pre-treating medicament, and has low price and rich source; the preparation is convenient by adding water for dilution; in the existing production device of a wet-process phosphoric acid plant, mild reaction conditions are adopted for pretreatment, so that the field industrialization is easy to realize; the used pre-decomposed medicament has no influence on the subsequent process; the method can obviously improve the recovery rate of phosphorus, has strong adaptability to phosphorite, stable operation and high operating rate, can realize harmless treatment and stacking after the obtained phosphogypsum is neutralized by a small amount of lime water, and greatly reduces the comprehensive utilization cost of the phosphogypsum, thereby having good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of phosphoric acid production, in particular to a method for pre-treating and strengthening wet-process phosphoric acid extraction reaction.
Background
Phosphoric acid is an important chemical raw material and is widely applied to industries such as chemical fertilizers, foods, coatings, electronic industry and the like. The wet-process phosphoric acid accounts for more than 90 percent of the total production amount of the phosphoric acid, wherein the wet-process phosphoric acid process is mainly a dihydrate method. But the recovery rate of phosphorus is lower when the wet-process phosphoric acid is produced by a dihydrate method, so that a large amount of phosphorus resources are wasted. The phosphorus remained in the phosphogypsum can cause the phosphorus content of the gypsum to be higher, is not beneficial to building material utilization, and can cause serious environmental pollution when being discharged into the environment.
In order to overcome the problem of low phosphorus recovery rate in the dihydrate method, researchers have developed a semi-water and dihydrate method process, and compared with the dihydrate method process, the semi-water and dihydrate method process has the advantages that the obtained product is phosphoric acid with higher concentration, the semi-water and dihydrate method process is more energy-saving if concentration is needed in the later period, and the phosphorus yield in the semi-water and dihydrate method process is higher. The method has the disadvantages that the investment and the operation are 2 times of those of a dihydrate method, the method has no great significance for manufacturers needing dilute phosphoric acid, and in the semiwater-dihydrate method, a semiwater reaction zone is easy to scale and the service life of equipment is shortened. Meanwhile, the semi-water and one-water method has narrow suitable conditions and unstable production.
The wet-process phosphoric acid produced by the dihydrate method is easy to cause the formation of a passive film, thereby causing incomplete decomposition of the ground phosphate rock and residual in gypsum to influence the yield of phosphorus. It is necessary to pretreat the phosphate rock particles to form a chemical environment and a phosphate rock particle structure which are beneficial to later-stage extraction. Further improves the recovery rate of phosphorus in the dihydrate method, reduces the content of phosphorus in the phosphogypsum, improves the economic benefit of a phosphoric acid plant and reduces the pollution to the environment.
Disclosure of Invention
The invention aims to provide a method for pre-treating and strengthening wet-process phosphoric acid extraction reaction aiming at the defects of the prior art, and the method is used for pre-treating raw materials by a pre-treating agent so as to improve the recovery rate of phosphorus and improve the high-quality byproduct phosphogypsum.
The invention provides a method for pre-treating and strengthening wet-process phosphoric acid extraction reaction, which comprises the following preparation steps:
s1, contacting and mixing the wet-process phosphoric acid raw material with a pretreatment agent to obtain ore pulp;
s2, carrying out oscillation and stirring pretreatment on the ore pulp to obtain pretreated ore pulp;
s3, placing the pretreated ore pulp into a phosphoric acid extraction reaction device, and performing extraction reaction under the condition of phosphoric acid by a dihydrate method to obtain extraction slurry;
s4, washing and filtering the extraction slurry to obtain a phosphoric acid product, phosphogypsum and reverse acid.
Further, the pretreatment agent in S1 contains 0.5wt% to 37.5wt% of an aqueous hydrochloric acid solution, 0.5wt% to 85wt% of an aqueous phosphoric acid solution, 0.5wt% to 68wt% of an aqueous nitric acid solution, and 0.5wt% to 98wt% of an aqueous sulfuric acid solution.
Further, the hydrochloric acid aqueous solution is prepared by mixing 10wt% -37.5wt% of hydrochloric acid and water; the phosphoric acid aqueous solution is prepared by mixing 40-98 wt% of phosphoric acid and water; the nitric acid aqueous solution is prepared by mixing 20-68 wt% of nitric acid and water; the sulfuric acid aqueous solution is prepared by mixing 40-98 wt% of sulfuric acid and water.
Further, the pretreatment agent also comprises return acid produced in wet-process phosphoric acid production, return slurry produced in wet-process phosphoric acid production and phosphogypsum slag yard wastewater.
The pretreatment reagent adopts hydrochloric acid aqueous solution, phosphoric acid aqueous solution, nitric acid aqueous solution, sulfuric acid aqueous solution, acid returning, slurry returning and phosphogypsum slag yard wastewater, and can be added at one time or added step by step, which depends on the type and crushing degree of raw materials.
Further, the wet-process phosphoric acid raw material in the S1 is one or both of phosphoric ore pulp and phosphoric ore concentrate pulp.
Furthermore, the mass mixing ratio of the wet process phosphoric acid raw material and the pretreatment medicament in S1 is 1: 0.01-3.
Further, the pretreatment temperature in S2 is 0 to 90 ℃.
Further, the pretreatment time in S2 is 0.1-50 h.
According to the method for pre-treating and strengthening the wet-process phosphoric acid extraction reaction, the product which can be produced in large quantities by wet-process phosphoric acid production enterprises is taken as the raw material of the pre-treating medicament, so that the price is low, and the source is rich; the preparation is convenient by adding water for dilution; in the existing production device of a wet-process phosphoric acid plant, mild reaction conditions are adopted for pretreatment, so that the field industrialization is easy to realize; the used pre-decomposed medicament has no influence on the subsequent process; the method can obviously improve the recovery rate of phosphorus, has strong adaptability to phosphorite, stable operation and high operating rate, can realize harmless treatment and stacking after the obtained phosphogypsum is neutralized by a small amount of lime water, and greatly reduces the comprehensive utilization cost of the phosphogypsum, thereby having good industrial application prospect.
Detailed Description
The invention will be further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, various changes or modifications of the present invention may be made by those skilled in the art, and equivalents may fall within the scope of the claims of the present application. The proportions in the examples of the invention are by weight.
Comparative example
1) Weighing 82.4g of flotation concentrate, weighing 22mL of water, 68mL of phosphoric acid (9wt%) and 66.4mL of phosphoric acid (24wt%), mixing the above objects, placing the mixture in a 1000mL measuring cylinder, uniformly dropwise adding 50mL of concentrated sulfuric acid (30 min) to start an extraction reaction, then obtaining primary filter gypsum, weighing 20g of primary filter gypsum, adding 60g of water, placing the mixture in a conical flask, and oscillating the mixture for 3 times (27 ℃, 20 min) to obtain water-washed gypsum.
2) The 3 times water washed gypsum was assayed for phosphorus content.
3) The total phosphorus content of the undecomposed water-washed gypsum is 0.88%, the water-soluble phosphorus content is 0.53%, and the insoluble phosphorus content is 0.35%.
Example 1
1) 82.4g of flotation concentrate was weighed, 55.6g of a reagent mixture (comprising 30.25 wt% hydrochloric acid aqueous solution, 47% phosphoric acid aqueous solution, 63.5wt% nitric acid aqueous solution, 45wt% sulfuric acid aqueous solution, return acid from wet-process phosphoric acid production, return slurry from wet-process phosphoric acid production and phosphogypsum slag yard wastewater) was weighed, mixed and placed in a 250mL erlenmeyer flask and shaken in a shaker for 12h (27 ℃, 180 rpm) for pre-decomposition.
2) Pouring the pre-decomposed 12h ore pulp and 66.4mL phosphoric acid (24wt%) into a 1000mL measuring cylinder, uniformly dropwise adding 50mL concentrated sulfuric acid (30 min) to start extraction reaction, then obtaining primary filter gypsum, weighing 20g primary filter gypsum, adding 60g water, placing in a conical flask, and oscillating for 3 times (27 ℃, 20 min) to obtain water-washed gypsum.
3) The phosphorus content assay was performed on 3 times of the pre-decomposed 12h water-washed gypsum.
4) The total phosphorus content of the pre-decomposed 12h water washed gypsum is 0.51%, the water soluble phosphorus content is 0.33%, and the insoluble phosphorus content is 0.18%. Therefore, the pre-decomposition has great effect on reducing the phosphorus content in the phosphogypsum, and the phosphorus recovery rate is greatly improved due to the reduction of the phosphorus content in the waste gypsum.
Example 2
1) Weighing 80.1g of flotation concentrate, measuring 158.3g of mixed reagent (22.3 wt% hydrochloric acid aqueous solution, 18.6% phosphoric acid aqueous solution, 50wt% nitric acid aqueous solution, 66wt% sulfuric acid aqueous solution, return acid generated in wet-process phosphoric acid production, return slurry generated in wet-process phosphoric acid production and phosphogypsum slag yard wastewater), mixing the above substances, placing the mixture in a 250mL conical flask, and oscillating the mixture in a shaking table for 24 hours (27 ℃, 180 rpm) for pre-decomposition.
2) Pouring the pre-decomposed 24h ore pulp and 66.4mL slurry (containing 24wt% phosphoric acid) into a 1000mL measuring cylinder, uniformly dropwise adding 50mL concentrated sulfuric acid (30 min) to start extraction reaction, then obtaining primary filter gypsum, weighing 20g primary filter gypsum, adding 60g water, placing in a conical flask, and oscillating for 3 times (27 ℃, 20 min) to obtain water-washed gypsum.
3) The 24h predecomposed 3 times water washed gypsum was assayed for phosphorus content.
4) The total phosphorus content of the pre-decomposed 24h water washed gypsum is 0.59%, the water soluble phosphorus content is 0.28%, and the insoluble phosphorus content is 0.18%. Therefore, the pre-decomposition has great effect on reducing the phosphorus content in the phosphogypsum, and the phosphorus recovery rate is greatly improved due to the reduction of the phosphorus content in the waste gypsum.
Comparative example 3
1) Weighing 90.7g of flotation concentrate, measuring 262.8g of mixed reagent (12.8 wt% hydrochloric acid aqueous solution, 6.9% phosphoric acid aqueous solution, 51.3wt% nitric acid aqueous solution, 42.9wt% sulfuric acid aqueous solution, return acid generated in wet-process phosphoric acid production, return slurry generated in wet-process phosphoric acid production and phosphogypsum slag yard wastewater), mixing the above materials, placing the mixture in a 250mL conical flask, and oscillating the mixture in a shaking table for 24h (27 ℃, 180 rpm) for pre-decomposition.
2) Pouring the pre-decomposed 24h ore pulp and 66.4mL slurry (containing 24wt% phosphoric acid) into a 1000mL measuring cylinder, uniformly dropwise adding 50mL concentrated sulfuric acid (30 min) to start extraction reaction, then obtaining primary filter gypsum, weighing 20g primary filter gypsum, adding 60g water, placing in a conical flask, and oscillating for 3 times (27 ℃, 20 min) to obtain water-washed gypsum.
3) The 24h predecomposed 3 times water washed gypsum was assayed for phosphorus content.
4) The total phosphorus content of the pre-decomposed 24h water washed gypsum is 0.56%, the water soluble phosphorus content is 0.36%, and the insoluble phosphorus content is 0.20%. Therefore, the pre-decomposition has a certain effect on reducing the phosphorus content in the phosphogypsum, and the phosphorus recovery rate is improved because the phosphorus content in the waste gypsum is reduced.
Evaluation:
the data analysis of the detection results of the example 1, the example 2, the example 3 and the comparative example fully shows that the phosphorus content obtained by the method provided by the application is higher than that of the comparative example which is not pretreated, and the phosphorus content in the waste gypsum is lower than that of the comparative example, thereby further showing that the invention has great progress in the technical field.
The embodiments of the present invention have been described above by way of example, but the description is only a preferred embodiment of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the application of the present invention shall fall within the scope of the patent of the present invention.
Claims (5)
1. A method for pre-treating and strengthening wet-process phosphoric acid extraction reaction is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
s1, contacting and mixing the wet-process phosphoric acid raw material with a pretreatment agent to obtain ore pulp;
s2, carrying out oscillation and stirring pretreatment on the ore pulp to obtain pretreated ore pulp;
s3, placing the pretreated ore pulp into a phosphoric acid extraction reaction device, and performing extraction reaction under the condition of phosphoric acid by a dihydrate method to obtain extraction slurry;
s4, washing and filtering the extraction slurry to obtain a phosphoric acid product, phosphogypsum and a reverse acid;
the pretreatment agent in S1 comprises 0.5-37.5 wt% of hydrochloric acid aqueous solution, 0.5-85 wt% of phosphoric acid aqueous solution, 0.5-68 wt% of nitric acid aqueous solution, 0.5-98 wt% of sulfuric acid aqueous solution, return acid generated in wet-process phosphoric acid production, return slurry generated in wet-process phosphoric acid production and phosphogypsum slag yard wastewater;
the mass mixing ratio of the wet-process phosphoric acid raw material and the pretreatment medicament in S1 is 1: 0.01-3.
2. The method of claim 1, wherein the pre-treatment enhances the wet-process phosphoric acid extraction reaction, and comprises: the hydrochloric acid aqueous solution is prepared by mixing 10-37.5 wt% of hydrochloric acid and water; the phosphoric acid aqueous solution is prepared by mixing 40-98 wt% of phosphoric acid and water; the nitric acid aqueous solution is prepared by mixing 20-68 wt% of nitric acid and water; the sulfuric acid aqueous solution is prepared by mixing 40-98 wt% of sulfuric acid and water.
3. The method of claim 1, wherein the pre-treatment enhances the wet-process phosphoric acid extraction reaction, and comprises: the wet-process phosphoric acid raw material in the S1 is one or two of phosphoric ore pulp and phosphoric ore concentrate pulp.
4. The method of claim 1, wherein the pre-treatment enhances the wet-process phosphoric acid extraction reaction, and comprises: the pretreatment temperature in S2 is 0-90 ℃.
5. The method of claim 1, wherein the pre-treatment enhances the wet-process phosphoric acid extraction reaction, and comprises: the pretreatment time in S2 is 0.1-50 h.
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