CN113479859B - Method for producing diammonium phosphate from phosphorite with high impurity content - Google Patents
Method for producing diammonium phosphate from phosphorite with high impurity content Download PDFInfo
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- CN113479859B CN113479859B CN202110654304.XA CN202110654304A CN113479859B CN 113479859 B CN113479859 B CN 113479859B CN 202110654304 A CN202110654304 A CN 202110654304A CN 113479859 B CN113479859 B CN 113479859B
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/28—Ammonium phosphates
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Abstract
The invention provides a method for producing diammonium phosphate by phosphorite with high impurity content, which comprises the working procedures of preparing phosphorite pulp, filtering, removing impurities, concentrating and granulating, the method can directly utilize the phosphorite with high impurity content to produce diammonium phosphate products with high-grade product indexes, adopts oxalic acid as an impurity removing agent, not only effectively removes metal ion impurities in dilute phosphoric acid, but also ensures nutrient P2O5The method has the advantages of low investment, strong adaptability to phosphorite, economy and contribution to realizing large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of fertilizer production, in particular to a method for producing diammonium phosphate by using phosphorite with high impurity content.
Background
China has large reserves of phosphorite, and is the second to live in the world, and the special characteristics are that the high-quality phosphorite is less and the high-impurity phosphorite is more. The cost of high-quality phosphorite remains high, the profit margin of enterprises is smaller and smaller, and the development and utilization of a new technology for producing diammonium phosphate chemical products from high-impurity phosphorite with low price and rich reserves are urgently needed to produce diammonium phosphate meeting the indexes of diammonium phosphate superior products, promote the upgrading of diammonium phosphate productivity and leave a resource-saving sustainable development road.
Ca as impurity in phosphoric acid in process of producing diammonium phosphate2+、Mg2+、Fe3+、Al3+The plasma metal ions can generate side reaction with ammonia and phosphoric acid in a certain pH value range, so that part of water-soluble P in the diammonium phosphate product2O5Conversion to insoluble P2O5Resulting in a low total available phosphorus. Therefore, in order to develop and utilize high-impurity phosphorite with low price and abundant reserves, the impurities are firstly removed to reduce the loss of available phosphorus.
Disclosure of Invention
The invention aims to provide a method for producing diammonium phosphate by using phosphorite with high impurity content, aiming at the defects in the prior art.
The invention relates to a method for producing diammonium phosphate by using phosphorite with high impurity content, which comprises the following steps:
s1, preparing phosphoric acid ore pulp: decomposing phosphorite with high impurity content by using sulfuric acid according to a wet-process phosphoric acid process to obtain phosphoric acid ore pulp;
s2, filtering: filtering the phosphoric acid ore pulp obtained in the step S1 by using a filter to obtain filtrate which is dilute phosphoric acid;
s3, removing impurities: adding an impurity removing agent into the diluted phosphoric acid obtained in the step S2, and naturally settling the formed precipitate in a settling tank;
s4, concentration: concentrating the diluted phosphoric acid without impurities obtained in step S3, and controlling the P content of the concentrated solution2O5The concentration is 44-47%, and a viscosity improver is added, and clarified concentrated phosphoric acid is obtained after clarification in a clarifying tank;
s5, granulating: and (4) conveying the concentrated phosphoric acid obtained in the step (S4) into a tubular reactor, reacting the phosphoric acid and ammonia gas in the tubular reactor to generate slurry, and spraying the slurry on the master batch in a granulator to form diammonium phosphate particles.
Further, the wet phosphoric acid process in step S1 is a dihydrate process.
Further, the impurity removing agent in step S2 is oxalic acid.
Further, the temperature in the settling tank in step S2 is 55 to 65 ℃.
Furthermore, the addition amount of the impurity removing agent is 5.0-10.0%.
Further, the viscosity improver in step S3 is aluminum phosphate.
Further, the neutralization degree value of the slurry in the tubular reactor in the step S5 is 1.5-1.6.
Further, the neutralization value range of the diammonium phosphate granules in the granulator in the step S5 is as follows: 1.8 to 1.9.
The invention has the following beneficial effects:
(1) compared with the prior art, the method can directly utilize the phosphorite with high impurity content to produce diammonium phosphate products with high-grade product indexes;
(2) oxalic acid is used as an impurity removing agent, so that metal ion impurities in dilute phosphoric acid are effectively removed, and nutrient P is ensured2O5The stability of (2);
(3) the method has the advantages of low investment, strong adaptability to phosphorite, economy and contribution to realizing large-scale industrial production.
Drawings
FIG. 1 is a schematic process flow diagram of the method for producing diammonium phosphate from phosphate ore with high impurity content according to the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be further described with reference to the accompanying drawings.
As shown in figure 1, the invention provides a method for producing diammonium phosphate by using phosphorite with high impurity content, which comprises the following steps:
s1, preparing phosphoric acid ore pulp: decomposing phosphorite with high impurity content by using sulfuric acid according to a wet-process phosphoric acid process to obtain phosphoric acid ore pulp;
s2, filtering: filtering the phosphoric acid ore pulp obtained in the step S1 by using a filter to obtain filtrate which is dilute phosphoric acid;
s3, removing impurities: adding an impurity removing agent into the diluted phosphoric acid obtained in the step S2, and naturally settling the formed precipitate in a settling tank;
s4, concentration: concentrating the diluted phosphoric acid without impurities obtained in step S3, and controlling the P content of the concentrated solution2O5The concentration is 44-47%, and a viscosity improver is added, and clarified concentrated phosphoric acid is obtained after clarification in a clarifying tank;
s5, granulating: and (4) conveying the concentrated phosphoric acid obtained in the step (S4) into a tubular reactor, reacting phosphoric acid and ammonia gas in the tubular reactor to generate slurry, and spraying the slurry on the master batch in a granulator to form diammonium phosphate particles.
The wet phosphoric acid process in step S1 has various processes, and may be: any one of a dihydrate process, a hemihydrate-dihydrate process, or a dihydrate-hemihydrate process, and in this embodiment, the wet-process phosphoric acid process is a dihydrate process.
In order to effectively remove metal ions such as Fe, Al, Mg, and the like in the dilute phosphoric acid and improve the quality of diammonium phosphate production, the impurity removing agent used in step S3 is various, in this embodiment, oxalic acid is added in a proportion of 5% to 10%, and because the temperature has a large influence on the precipitation of the metal oxalate, the dissociation degree of oxalic acid increases with the temperature, which is beneficial to the precipitation of the metal oxalate, but the solubility of the metal oxalate increases with the temperature, which in turn inhibits the precipitation of the metal, and in order to achieve the optimal precipitation effect, the temperature in the settling tank can be set to 55 ℃ to 65 ℃.
In order to further remove sulfate impurities, promote sulfate crystallization, reduce the viscosity of the concentrated solution and reduce the ion diffusion resistance, the P of the concentrated solution after the dilute phosphoric acid is concentrated can be controlled2O5The concentration is 44-47%, and in order to produce diammonium phosphate with good appearance quality, proper aluminum phosphate can be added to adjust Al in concentrated phosphoric acid2O3The viscosity of the concentrated phosphoric acid is improved to 33 to 38 mPas, and the binding effect of the gel is very beneficial to granulation.
In the step S5, the reaction of ammonia and phosphoric acid is carried out in a tubular reactor, so that the time for generating diammonium phosphate by the reaction of ammonia and phosphoric acid is shortened, the generation of double salts in ammonium phosphate slurry is reduced, and the content of N, P available nutrients in diammonium phosphate is increased; simultaneously, the neutralization degree of slurry in the two tubular reactors can be adjusted to be 1.5-1.6, so that the granulation balling rate is greatly improved, the production period of the tube reaction is prolonged, and the qualified neutralization degree of diammonium phosphate is reached through secondary ammoniation, so that the range is as follows: 1.8 to 1.9.
The method for producing diammonium phosphate from phosphate ore with high impurity content according to the present invention will be described in detail with reference to the following examples.
Example 1
1000.0g of wet-process diluted phosphoric acid (25% P) was taken2O5) Filtering to remove phosphogypsum, transferring the filtrate to a settling tank, and adding oxalic acid (H) as impurity removing agent2C2O4) 5.0%, setting the temperature in the settling tank at 60 deg.C, collecting supernatant, and concentrating until the concentrate contains P2O5Adding aluminum phosphate, adjusting the viscosity to 33-38 mPa · s, conveying the obtained concentrated phosphoric acid into a tubular reactor, reacting the concentrated phosphoric acid with ammonia gas in the tubular reactor to generate slurry, adjusting the neutralization degree of the slurry to 1.56, spraying the slurry on a master batch in a granulator, and increasing the neutralization degree to 1.84 through secondary ammoniation to generate diammonium phosphate particles. The analysis indexes are as follows: total nutrient 63.9, available phosphorus 46.5, total N17.8, H2O％＝2.0。
Example 2:
1000.0g of wet-process diluted phosphoric acid (25% P) was taken2O5) Filtering to remove phosphogypsum, transferring the filtrate to a settling tank, and adding oxalic acid (H) as impurity removing agent2C2O4)7.0 percent, setting the temperature in the settling tank to be 60 ℃, taking supernatant fluid to concentrate until the concentrated solution contains P2O5Adding aluminum phosphate, adjusting the viscosity to 33-38 mPa · s, conveying the obtained concentrated phosphoric acid into a tubular reactor, reacting the concentrated phosphoric acid with ammonia gas in the tubular reactor to generate slurry, adjusting the neutralization degree of the slurry to 1.56, spraying the slurry on a master batch in a granulator, and increasing the neutralization degree to 1.84 through secondary ammoniation to generate diammonium phosphate particles. The analysis indexes are as follows: 64.1 percent of total nutrient, 46.3 percent of available phosphorus, 17.4 percent of total N and H2O％＝2.1。
Example 3:
1000.0g of wet-process diluted phosphoric acid (25% P) was taken2O5) Filtering to remove phosphogypsum, transferring the filtrate to a settling tank, and adding oxalic acid (H) as impurity removing agent2C2O4) 10.0%, setting the temperature in the settling tank to 60 ℃, and taking supernatantConcentrating until the concentrated solution contains P2O5Adding aluminum phosphate, adjusting the viscosity to 33-38 mPa · s, conveying the obtained concentrated phosphoric acid into a tubular reactor, reacting the concentrated phosphoric acid with ammonia gas in the tubular reactor to generate slurry, adjusting the neutralization degree of the slurry to 1.56, spraying the slurry on a master batch in a granulator, and increasing the neutralization degree to 1.84 through secondary ammoniation to generate diammonium phosphate particles. The analysis indexes are as follows: 64.3 percent of total nutrient, 46.4 percent of available phosphorus, 17.6 percent of total N and H2O％＝2.3。
The above is not relevant and is applicable to the prior art.
While certain specific embodiments of the present invention have been described in detail by way of illustration, it will be understood by those skilled in the art that the foregoing is illustrative only and is not limiting of the scope of the invention, as various modifications or additions may be made to the specific embodiments described and substituted in a similar manner by those skilled in the art without departing from the scope of the invention as defined in the appending claims. It should be understood by those skilled in the art that any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention are included in the scope of the present invention.
Claims (7)
1. A method for producing diammonium phosphate by using phosphorite with high impurity content is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing phosphoric acid ore pulp: decomposing phosphorite with high impurity content by using sulfuric acid according to a wet-process phosphoric acid process to obtain phosphoric acid ore pulp;
s2, filtering: filtering the phosphoric acid ore pulp obtained in the step S1 by using a filter to obtain filtrate which is dilute phosphoric acid;
s3, removing impurities: adding an impurity removing agent into the diluted phosphoric acid obtained in the step S2, and naturally settling the formed precipitate in a settling tank;
s4, concentration: concentrating the diluted phosphoric acid without impurities obtained in the step S3, controlling the concentration of P2O5 of the concentrated solution to be 44-47%, adding a viscosity improver aluminum phosphate, and clarifying in a clarifying tank to obtain clarified concentrated phosphoric acid;
s5, granulating: and (4) conveying the concentrated phosphoric acid obtained in the step (S4) into a tubular reactor, reacting phosphoric acid and ammonia gas in the tubular reactor to generate slurry, and spraying the slurry on the master batch in a granulator to form diammonium phosphate particles.
2. The method for producing diammonium phosphate from phosphate ore with high impurity content according to claim 1, characterized in that: the wet phosphoric acid process in step S1 is a dihydrate process.
3. The method for producing diammonium phosphate from phosphate ore with high impurity content according to claim 1, characterized in that: the impurity removing agent in the step S2 is oxalic acid.
4. The method for producing diammonium phosphate from phosphate ore with high impurity content according to claim 3, characterized in that: the temperature in the settling tank in the step S2 is 55-65 ℃.
5. The method for producing diammonium phosphate from phosphate ore with high impurity content according to claim 3, characterized in that: the addition amount of the impurity removing agent is 5.0-10.0%.
6. The method for producing diammonium phosphate from phosphate ore with high impurity content according to claim 1, characterized in that: and the neutralization value range of the slurry in the tubular reactor in the step S5 is 1.5-1.6.
7. The method for producing diammonium phosphate from phosphate ore with high impurity content according to claim 1, characterized in that: the neutralization degree value range of the diammonium phosphate particles in the step S5 is as follows: 1.8 to 1.9.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1218997A (en) * | 1968-02-20 | 1971-01-13 | Freeport Sulphur Co | Production of ammonium phosphates |
| AR214229A1 (en) * | 1976-07-09 | 1979-05-15 | Stauffer Chemical Co | NEW PROCEDURE FOR THE PREPARATION OF AN ALUMINUM SODIUM PHOSPHATE |
| US4390509A (en) * | 1980-03-10 | 1983-06-28 | Agrico Chemical Company | Process for manufacturing ammonium phosphate utilizing an oxalic acid acidulating process |
| CN1039777A (en) * | 1988-07-26 | 1990-02-21 | 郭湘泗 | The manufacture method of diammonium phosphate |
| CN101134905A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method for improving solid content of catalytic cracking catalyst slurry |
| CN101613094A (en) * | 2009-07-24 | 2009-12-30 | 瓮福（集团）有限责任公司 | Method with the raffinate production diammonium phosphate of purifying phosphoric acid |
| CN104261371A (en) * | 2014-09-01 | 2015-01-07 | 云南云天化国际化工有限公司 | Method for producing diammonium phosphate from high-impurity phosphorite |
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- 2021-06-11 CN CN202110654304.XA patent/CN113479859B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1218997A (en) * | 1968-02-20 | 1971-01-13 | Freeport Sulphur Co | Production of ammonium phosphates |
| AR214229A1 (en) * | 1976-07-09 | 1979-05-15 | Stauffer Chemical Co | NEW PROCEDURE FOR THE PREPARATION OF AN ALUMINUM SODIUM PHOSPHATE |
| US4390509A (en) * | 1980-03-10 | 1983-06-28 | Agrico Chemical Company | Process for manufacturing ammonium phosphate utilizing an oxalic acid acidulating process |
| CN1039777A (en) * | 1988-07-26 | 1990-02-21 | 郭湘泗 | The manufacture method of diammonium phosphate |
| CN101134905A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method for improving solid content of catalytic cracking catalyst slurry |
| CN101613094A (en) * | 2009-07-24 | 2009-12-30 | 瓮福（集团）有限责任公司 | Method with the raffinate production diammonium phosphate of purifying phosphoric acid |
| CN104261371A (en) * | 2014-09-01 | 2015-01-07 | 云南云天化国际化工有限公司 | Method for producing diammonium phosphate from high-impurity phosphorite |
Non-Patent Citations (1)
| Title |
|---|
| 利用中低品位磷矿生产高品质磷酸一铵的工业试验;张战利 等;《化学生物与工程》;20180825;第35卷(第12期);全文 * |
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