CN112758903B - Medium-low grade phosphorite pretreatment method - Google Patents
Medium-low grade phosphorite pretreatment method Download PDFInfo
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- CN112758903B CN112758903B CN202110110307.7A CN202110110307A CN112758903B CN 112758903 B CN112758903 B CN 112758903B CN 202110110307 A CN202110110307 A CN 202110110307A CN 112758903 B CN112758903 B CN 112758903B
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/01—Treating phosphate ores or other raw phosphate materials to obtain phosphorus or phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B11/00—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes
- C05B11/04—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid
- C05B11/06—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid using nitric acid (nitrophosphates)
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Abstract
The invention provides a pretreatment method of middle-low grade phosphate ore, which is characterized in that in the preparation of raw materials, the particle size of the raw materials is controlled to be 0.8-3 mm; in the acid liquid preparation process, the concentration of the acid liquid A is between 30 and 35 percent, and the concentration of the acid liquid B is between 40 and 45 percent; the treatment process comprises the following steps: pulverizing raw materials, mixing with water to obtain water slurry, adding acid solution A into the water slurry, controlling reaction temperature at 10-20 deg.C to obtain acid slurry A, adding acid solution B into the acid slurry A, and controlling reaction temperature at 10-20 deg.C to obtain acid slurry B; filtering the physalis alkekengi B for the first time to obtain a solid phase A and a liquid phase A; carrying out secondary filtration on the liquid phase A to obtain a solid phase B and a liquid phase B; collecting the solid phase A and the solid phase B to obtain concentrate, wherein P in the concentrate 2 O 5 The content of (B) is more than 30 percent. The pretreatment method has the advantages of strong practicability and wide applicability, and P in phosphorite can be treated by the method 2 O 5 The content is more than 30 percent, and the grade of the phosphorite is effectively improved.
Description
Technical Field
The invention relates to the technical field of medium and low grade phosphorite treatment, in particular to a medium and low grade phosphorite pretreatment method.
Background
The important and difficult-to-regenerate resources of phosphorus ore lead the phosphorus element to be widely dispersed in the nature along with the development of the phosphorus element and the preparation of downstream products, and because the phosphorus element is newly accumulated into the phosphorus ore for hundreds of millions of years, in 2010, 5 countries, such as China, germany, japan, english and American, take the phosphorus ore as rare natural resources to protect.
The phosphorite existing in nature occupies most low-grade phosphorite, takes second grade phosphorite and least high-grade phosphorite. In the process of mining and treating medium-grade and low-grade phosphorite, acidolysis treatment is a common treatment mode, and the medium-grade and low-grade phosphorite is rich in a large amount of associated elements such as magnesium element, iron element, calcium element and the like, so that acidolysis solution after acidolysis can contain magnesium ions, calcium ions, iron ions and the like, and the ions exist, so that a large amount of precipitates can be generated in subsequent crystallization treatment, and washing water for the precipitates can be increased.
At present, in order to reduce the amount of associated element ions in an acidolysis solution, the medium and low grade phosphorite is generally pretreated,the adopted method is a flotation process, the grade of the phosphorite is preliminarily improved, however, the content of impurities in the phosphorite is different and the compactness of the tissue is different due to different mineralization times, different burying positions and the like of the phosphorite, so that the difficulty of the flotation process is increased, and the pretreatment cost is increased; moreover, P in phosphorite obtained by flotation of phosphorite at present 2 O 5 The content of the concentrate reaches up to 25 percent, and the flotation pretreatment has high cost and poor applicability and the P in the concentrate 2 O 5 The content is only maintained in the region of medium-grade phosphorite, which is not beneficial to the subsequent phosphorite treatment.
Therefore, the method for treating the phosphorite has important significance for effectively improving the grade of the phosphorite and facilitating subsequent treatment of the phosphorite.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a pretreatment method of middle-low grade phosphorite, in the pretreatment method, acid liquor with different concentrations is added into the phosphorite in a gradient treatment mode, and the particle size and the reaction temperature of the phosphorite are controlled, so that the grade of the phosphorite is improved, and the subsequent treatment difficulty is reduced. The pretreatment method has the advantages of strong practicability and wide applicability, and P in phosphorite can be treated by the pretreatment method 2 O 5 The content is more than 30 percent, and the grade of the phosphorite is effectively improved.
The technical scheme of the invention is as follows:
a method for pretreating middle-low grade phosphorite comprises preparing raw materials and preparing acid liquor;
in the preparation of raw materials, the raw materials are crushed, and the particle size of the raw materials is controlled to be 0.8-3 mm;
preparing acid liquor A and acid liquor B in the acid liquor preparation process; the concentration of the acid liquid A is 30-35%, and the concentration of the acid liquid B is 40-45%;
the treatment process comprises the following steps:
(1) Pulverizing the raw materials, mixing with water, and making into water slurry;
(2) Adding the acid liquor A into the water slurry, reacting the acid liquor A with substances in the raw materials, and controlling the reaction temperature to be between 10 and 20 ℃ to obtain acid slurry A for later use;
(3) Adding the acid liquor B into the acid pulp A, continuously reacting the acid liquor B with substances in the raw materials, and controlling the reaction temperature to be between 10 and 20 ℃ to obtain acid pulp B;
(4) Filtering the physalis alkekengi B for the first time to obtain a solid phase A and a liquid phase A; carrying out secondary filtration on the liquid phase A to obtain a solid phase B and a liquid phase B; collecting the solid phase A and the solid phase B, namely the concentrate obtained after pretreatment, and P in the concentrate 2 O 5 The content of (b) is more than 30%.
Further, the raw material is carbonate type middle-low grade phosphorite.
Further, the nitric phosphate fertilizer is obtained by performing acidolysis, filtering and washing, elution crystallization and decalcification on concentrate obtained by pretreating raw materials.
Furthermore, in the acidolysis process of the concentrate, the concentration of nitric acid is 58%; controlling the acidolysis temperature between 60 and 65 ℃; by using the concentration and controlling the acidolysis temperature, the phosphorus in the concentrate can be dissolved in the acidolysis solution, and the yield of the phosphorus is improved.
Furthermore, in the filtering process, a plate and frame filter is adopted for filtering, and the particle size of the medium-grade and low-grade phosphorite is limited in the pretreatment process, so that the problem that the filter aid is required to be added in the filtering stage to improve the filtering effect in the prior art can be effectively avoided, the filtering efficiency is improved, and the production cost is reduced.
Furthermore, in the process of elution crystallization, ethanol is used as an elution agent, so that the method has the advantages of environmental protection and no pollution.
Further, an ammonium sulfate method is adopted in the decalcification process, and ammonium sulfate is added as a decalcification agent to generate phosphogypsum; due to the pair F in the pretreatment process - Removing organic matters in the solution in the filtering process to ensure that the organic matters and F in the phosphogypsum - The content is low, thereby improving the application range of the phosphogypsum.
Compared with the prior art, the invention has the beneficial effects that:
1. the medium-low grade phosphorite is pretreated, so that the grade of the phosphorite is improved, and a high-quality ore source is directly provided for enterprises.
2. The invention providesThe pretreatment method uses nitric acid for pretreatment, is the same as the acid for subsequent concentrate treatment, avoids excessive impurities from being doped in acidolysis solution obtained in the concentrate treatment process, and reduces the amount of impurities in phosphogypsum; at the same time, after pretreatment, F in the obtained concentrate - The content is low, so that the F-content in the phosphogypsum is low, and the use limit of the phosphogypsum is reduced.
3. According to the pretreatment method provided by the invention, the particle size of the medium-grade and low-grade phosphorite is limited, so that the concentrate can be rapidly and efficiently filtered without adding a filter aid when being filtered after being subjected to acidolysis by 58% of nitric acid, and the filtering efficiency is improved.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, shall fall within the protection scope of the present invention.
Example 1
A method for pretreating middle-low grade phosphorite comprises preparing raw materials and preparing acid liquor;
in the preparation of raw materials, the raw materials are crushed, and the particle size of the raw materials is controlled to be 0.8-3 mm;
in the acid liquor preparation process, preparing acid liquor A and acid liquor B; the concentration of the acid liquor A is 32.5 percent, and the concentration of the acid liquor B is 45 percent;
the treatment process comprises the following steps:
(1) Pulverizing the raw materials, mixing with water, and making into water slurry;
(2) Adding the acid liquor A into the water slurry, reacting the acid liquor A with substances in the raw materials, and controlling the reaction temperature to be 15 ℃ to obtain acid slurry A for later use;
(3) Adding the acid liquor B into the acid pulp A, continuously reacting the acid liquor B with substances in the raw materials, and controlling the reaction temperature to be 12 ℃ to obtain acid pulp B;
(4) Filtering the physalis alkekengi B for the first time to obtain a solid phase A and a liquid phase A; carrying out secondary filtration on the liquid phase A to obtain a solid phase B and a liquid phase B; collecting a solid phase A and a solid phase B, namely the concentrate obtained after pretreatment;
when the raw material is medium-grade phosphorite, the raw material is pretreated by the method, the components of the concentrate obtained after the pretreatment are shown in table 1, and the components in the raw ore are also recorded in table 1.
TABLE 1 Effect of treating Medium grade phosphorus ore by the method of the present invention
| P 2 O 5 | CaO | MgO | F - | |
| Crude ore (%) | 26.35 | 49.63 | 3.52 | 3.17 |
| Concentrate (%) | 34.16 | 20.16 | 0.57 | 0.21 |
Example 2
A method for pretreating middle-low grade phosphorite comprises preparing raw materials and preparing acid liquor;
in the preparation of raw materials, the raw materials are crushed, and the particle size of the raw materials is controlled to be 0.8-3 mm;
preparing acid liquor A and acid liquor B in the acid liquor preparation process; the concentration of the acid liquor A is 30 percent, and the concentration of the acid liquor B is 43 percent;
the treatment process comprises the following steps:
(1) Pulverizing the raw materials, mixing with water, and making into water slurry;
(2) Adding the acid liquor A into the water slurry, reacting the acid liquor A with substances in the raw materials, and controlling the reaction temperature to be 20 ℃ to obtain acid slurry A for later use;
(3) Adding the acid liquor B into the acid pulp A, continuously reacting the acid liquor B with substances in the raw materials, and controlling the reaction temperature to be 20 ℃ to obtain acid pulp B;
(4) Filtering the physalis alkekengi B for the first time to obtain a solid phase A and a liquid phase A; carrying out secondary filtration on the liquid phase A to obtain a solid phase B and a liquid phase B; collecting a solid phase A and a solid phase B, namely the concentrate obtained after pretreatment;
when the raw material is low-grade phosphorite, the raw material is pretreated by the method, the components of the concentrate obtained after the treatment are shown in table 2, and the components in the raw ore are also recorded in table 2.
TABLE 2 Effect of treating Low grade phosphorus ore by the method of the present invention
| P 2 O 5 | CaO | MgO | F - | |
| Crude ore (%) | 22.04 | 54.65 | 4.17 | 3.64 |
| Concentrate (%) | 31.43 | 21.33 | 0.72 | 0.44 |
As can be seen from the combination of tables 1 and 2, after pretreatment, both low-grade phosphate ore and medium-grade phosphate ore can be treated to have higher grade, and P is used 2 O 5 The content is more than 30 percent; caO, mgO and F - The content of the nitro-phosphate is reduced, the reduction of the impurity amount provides a good mineral source foundation for the subsequent production of the nitro-phosphate with high content, and the subsequent treatment process and the treatment difficulty are shortened.
Example 3
Carrying out acidolysis treatment on the concentrate obtained in the embodiment 1 by using 58% nitric acid, controlling the temperature to be 62 ℃ in the treatment process, stirring at a stirring speed of 300r/min in the acidolysis process to ensure that the acidolysis is more thorough, filtering acidolysis solution after the acidolysis by using a plate and frame filter, washing filter residues after the filtration by using clean water for 3 times, and recycling the washing water to be mixed with the filtrate for subsequent treatment; the filtration rate was recorded and the composition of the residue was analyzed.
Comparative example 1
The difference from example 3 is that the particle size of the raw material (i.e. raw ore) is between 40-300 mesh.
Comparative example 2
The difference from example 3 is that the particle size of the raw material (i.e. raw ore) is between 40-300 mesh; during the filtering process of the acidolysis solution, humic acid as a filter aid is added.
The filtration rates and P2O5 contents in the filter residue of example 3, comparative example 1 and comparative example 2 were counted and shown in Table 3.
TABLE 3 filtration Rate and composition statistics
| P 2 O 5 (％) | Filtration Rate (m) 3 /m 2 .h) | |
| Example 3 | 0.42 | 65.8 |
| Comparative example 1 | 1.22 | 5.3 |
| Comparative example 2 | 0.87 | 63.4 |
As can be seen from Table 3, the filtration rate of comparative example 1 was slow and the residue P remained in the filtration cake under the condition of small particle size 2 O 5 More; the filtration rate was significantly increased after the addition of the filter aid in comparative example 2, which is similar to that of example 3, indicating that, in the present invention, the concentrate can be filtered by controlling the particle size of the raw material during the pretreatment processThe process provides a good filtration foundation, and can be equivalent to the filtration rate of the filter aid under the condition of not adding the filter aid, which shows that the pretreatment process provided by the invention has an indispensable effect in the production process of the nitrophosphate fertilizer.
Although the present invention has been described in detail by referring to the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions should be within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present disclosure and the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (4)
1. The method for pretreating the medium-low grade phosphorite is characterized by comprising the steps of preparing raw materials and preparing acid liquor;
in the preparation of raw materials, the raw materials are crushed, and the particle size of the raw materials is controlled to be 0.8-3 mm;
in the acid liquor preparation process, preparing acid liquor A and acid liquor B; the concentration of the acid liquor A is 30-35%, and the concentration of the acid liquor B is 40-45%; the acid liquor A and the acid liquor B are both nitric acid;
the treatment process comprises the following steps:
(1) Pulverizing the raw materials, mixing with water, and making into water slurry;
(2) Adding the acid liquor A into the water slurry, reacting the acid liquor A with substances in the raw materials, and controlling the reaction temperature to be between 10 and 20 ℃ to obtain acid slurry A for later use;
(3) Adding the acid liquor B into the acid pulp A, continuously reacting the acid liquor B with substances in the raw materials, and controlling the reaction temperature to be between 10 and 20 ℃ to obtain acid pulp B;
(4) Filtering the physalis alkekengi B for the first time to obtain a solid phase A and a liquid phase A; carrying out secondary filtration on the liquid phase A to obtain a solid phase B and a liquid phase B; collecting the solid phase A and the solid phase B, namely the concentrate obtained after pretreatment, and P in the concentrate 2 O 5 The content of (A) is more than 30 percent;
the method comprises the steps of carrying out acidolysis, filtering washing, elution crystallization and decalcification on concentrate obtained by pretreating raw materials to obtain the nitrophosphate fertilizer, wherein in the acidolysis process of the concentrate, the concentration of nitric acid is 58%, and the acidolysis temperature is controlled to be 60-65 ℃.
2. The method for pretreating middle and low-grade phosphorus ore according to claim 1, wherein the raw material is carbonate type middle and low-grade phosphorus ore.
3. The method for pretreating middle and low grade phosphorus ore according to claim 1, wherein ethanol is used as the elution agent during the elution crystallization.
4. The method for pretreating middle-low grade phosphorus ore according to claim 1, wherein the decalcification process adopts ammonium sulfate method, and ammonium sulfate is added as decalcification agent to produce phosphogypsum.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1398331A (en) * | 1971-08-03 | 1975-06-18 | Montedison Spa | Preparation of phosphoric acid by the wet process |
| CN102126738A (en) * | 2011-01-20 | 2011-07-20 | 山东金正大生态工程股份有限公司 | Method for producing nitrophosphate fertilizer and co-producing gypsum through decomposing phosphorite with nitric acid |
| CN106395774A (en) * | 2016-09-09 | 2017-02-15 | 安徽六国化工股份有限公司 | Gradient technology method for wet process phosphoric acid production |
| CN106744753A (en) * | 2016-12-30 | 2017-05-31 | 贵州开磷集团股份有限公司 | A kind of method of phosphorus ore stagewise de-magging |
| CN109293402A (en) * | 2018-10-17 | 2019-02-01 | 贵州芭田生态工程有限公司 | The method and nitrophosphate fertilizer of automated production nitrophosphate fertilizer |
| CN110357054A (en) * | 2019-07-29 | 2019-10-22 | 四川大学 | The pretreated method of phosphorus ore |
-
2021
- 2021-01-27 CN CN202110110307.7A patent/CN112758903B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1398331A (en) * | 1971-08-03 | 1975-06-18 | Montedison Spa | Preparation of phosphoric acid by the wet process |
| CN102126738A (en) * | 2011-01-20 | 2011-07-20 | 山东金正大生态工程股份有限公司 | Method for producing nitrophosphate fertilizer and co-producing gypsum through decomposing phosphorite with nitric acid |
| CN106395774A (en) * | 2016-09-09 | 2017-02-15 | 安徽六国化工股份有限公司 | Gradient technology method for wet process phosphoric acid production |
| CN106744753A (en) * | 2016-12-30 | 2017-05-31 | 贵州开磷集团股份有限公司 | A kind of method of phosphorus ore stagewise de-magging |
| CN109293402A (en) * | 2018-10-17 | 2019-02-01 | 贵州芭田生态工程有限公司 | The method and nitrophosphate fertilizer of automated production nitrophosphate fertilizer |
| CN110357054A (en) * | 2019-07-29 | 2019-10-22 | 四川大学 | The pretreated method of phosphorus ore |
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Effective date of registration: 20230112 Address after: 276700 Xingda West Street, Linshu County, Linyi City, Shandong Province, No. 19 Applicant after: KINGENTA ECOLOGICAL ENGINEERING GROUP Co.,Ltd. Applicant after: KINGENTA NORSTERRA CHEMICAL Co.,Ltd. Applicant after: HEZE KINGENTA ECOLOGICAL ENGINEERING Co.,Ltd. Applicant after: HENAN YUYOU JINDADI TECHNOLOGY SERVICE CO.,LTD. Applicant after: Woft Compound Fertilizer Co.,Ltd. Address before: 276700 Xingda West Street, Linshu County, Linyi City, Shandong Province, No. 19 Applicant before: KINGENTA ECOLOGICAL ENGINEERING GROUP Co.,Ltd. Applicant before: KINGENTA NORSTERRA CHEMICAL Co.,Ltd. Applicant before: HEZE KINGENTA ECOLOGICAL ENGINEERING Co.,Ltd. |
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